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Sample records for olefin polymerization reactor

  1. Olefin metathesis and metathesis polymerization

    CERN Document Server

    Ivin, K J

    1997-01-01

    This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

  2. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  3. Catalytic olefin polymerization with early transition metal compounds

    OpenAIRE

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

  4. Catalytic polymerization of olefins in supercritical carbon dioxide

    NARCIS (Netherlands)

    Kemmere, M.F.; Vries, de T.J.; Keurentjes, J.T.F.

    2004-01-01

    A novel process is being developed for the catalytic polymerization of olefins in supercritical carbon dioxide (sc CO2), for which potential applications will mainly be in the production of EPDM and other elastomers. For this purpose, the Brookhart catalyst has been tested for the homopolymerization

  5. Surface science of single-site heterogeneous olefin polymerization catalysts

    OpenAIRE

    Kim, Seong H.; Somorjai, Gabor A.

    2006-01-01

    This article reviews the surface science of the heterogeneous olefin polymerization catalysts. The specific focus is on how to prepare and characterize stereochemically specific heterogeneous model catalysts for the Ziegler–Natta polymerization. Under clean, ultra-high vacuum conditions, low-energy electron irradiation during the chemical vapor deposition of model Ziegler–Natta catalysts can be used to create a “single-site” catalyst film with a surface structure that produces only isotactic ...

  6. NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

    CERN Document Server

    1998-01-01

    The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

  7. Olefin polymerization from single site catalysts confined within porous media

    Science.gov (United States)

    Kasi, Rajeswari M.

    Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

  8. Olefin copolymerization using atom transfer radical polymerization (ATRP)

    NARCIS (Netherlands)

    Venkatesh, R.; Klumperman, B.

    2003-01-01

    Olefin copolymers of alpha-olefins with polar monomers with various architectures remain an ultimate goal in polyolefin engineering. The present paper is a more detailed study on the copolymn. of alpha-olefins (1-octene) with acrylates (Me acrylate). Comparison of reaction kinetics between free

  9. Production of jet fuel range paraffins by low temperature polymerization of gaseous light olefins using ionic liquid

    International Nuclear Information System (INIS)

    Jiang, Peiwen; Wu, Xiaoping; Zhu, Lijuan; Jin, Feng; Liu, Junxu; Xia, Tongyan; Wang, Tiejun; Li, Quanxin

    2016-01-01

    Graphical abstract: A novel catalytic transformation of light olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. - Highlights: • A novel transformation of light olefins to jet fuel range paraffins was demonstrated. • The synthetic fuels can be produced by atmospheric olefin polymerizations. • C 8 –C 15 iso-paraffins from light olefins was achieved with a selectivity of 80.6%. - Abstract: This work demonstrated a novel catalytic transformation of gaseous olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. The production of the desired C 8 –C 15 iso-paraffins with the selectivity of 80.6 C mol% was achieved by the room-temperature polymerizations of gaseous light olefins using the [BMIM] Al 2 Cl 7 ionic liquid. The influences of the reaction conditions on the olefinic polymerizations were investigated in detail. The properties of hydrocarbons in the synthetic fuels were determined by the GC–MS analyses combined with 1 H NMR, and 13 C NMR analyses. The formation of C 8 –C 15 hydrocarbons from gaseous light olefins was illustrated by the identified products and the functional groups. This transformation potentially provides a useful avenue for the production of the most important components of iso-paraffins required in jet fuels.

  10. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1982-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  11. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1981-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  12. STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

    Science.gov (United States)

    2013-03-28

    production of polyethylene (PE) and polypropylene (PP) topped 53 billion pounds in 2011.1 This extreme demand has ensured that olefin polymerization...is an ideal starting monomer as it is a liquid at room temperature facilitating rapid screening and data collection without the need for cumbersome...elastomers, binders, thermoplastic elastomers, rheology modifiers, permeation selective membranes, and high strength, light-weight structural materials

  13. Effects of the Linking of Cyclopentadienyl and Ketimide Ligands in Titanium Half-sandwich Olefin Polymerization Catalysts

    Czech Academy of Sciences Publication Activity Database

    Varga, Vojtěch; Večeřa, M.; Gyepes, R.; Pinkas, Jiří; Horáček, Michal; Merna, J.; Lamač, Martin

    2017-01-01

    Roč. 9, č. 16 (2017), s. 3160-3172 ISSN 1867-3880 R&D Projects: GA ČR(CZ) GA14-08531S; GA ČR(CZ) GA17-13778S Institutional support: RVO:61388955 Keywords : ketimide ligands * olefin polymerization catalysts * cyclopentadienyl Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 4.803, year: 2016

  14. Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong

    2006-01-01

    Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

  15. Nonthermal plasma reactors for the production of light hydrocarbon olefins from heavy oil

    Directory of Open Access Journals (Sweden)

    G. Prieto

    2003-03-01

    Full Text Available During the last decade, nonthermal plasma technology was applied in many different fields, focusing attention on the destruction of harmful compounds in the air. This paper deals with nonthermal plasma reactors for the conversion of heavy oil into light hydrocarbon olefins, to be employed as gasoline components or to be added in small amounts for the catalytic reduction of nitrogen oxide compounds in the treatment of exhaust gas at power plants. For the process, the plate-plate nonthermal plasma reactor driven by AC high voltage was selected. The reactor was modeled as a function of parameter characteristics, using the methodology provided by the statistical experimental design. The parameters studied were gap distance between electrodes, carrier gas flow and applied power. Results indicate that the reactions occurring in the process of heavy oil conversion have an important selective behavior. The products obtained were C1-C4 hydrocarbons with ethylene as the main compound. Operating the parameters of the reactor within the established operative window of the system and close to the optimum conditions, efficiencies as high as 70 (mul/joule were obtained. These values validate the process as an in-situ method to produce light olefins for the treatment of nitrogen oxides in the exhaust gas from diesel engines.

  16. Alkylation of mixed olefins with isobutane in a stratco chemical reactor

    Energy Technology Data Exchange (ETDEWEB)

    Vichailak, M. [ABB Lummus Global Inc., Houston, TX (United States); Hopper, J.R.; Yaws, C.L. [Lamar Univ., Beaumont, TX (United States); Pike, R.W. [Louisiana State Univ., Baton Rouge, LA (United States)

    1996-12-31

    The 17 reaction model for the sulfuric acid alkylation of isobutane with propylene as proposed by Langley and Pike has been used to simulate the effluent refrigeration reactor. The simulation conditions selected to minimize the formation of light and heavy by-product were determined to be: Temperature: 9 - 10 {degrees}C,- Isobutane/Olefin Ratio: 8 - 10; % Volume of Acid: 50 %. The reactor effluent composition from the simulation program has been used to compare with several sets of published data with reasonable agreement. This model has been extrapolated to simulate the alkylation of isobutane with butylenes and amylenes. The model will be optimized with commercial data. 9 refs., 6 figs., 1 tab.

  17. N-Heterocyclic Olefins as Initiators for the Polymerization of (Meth)Acrylic Monomers: A Combined Experimental and Theoretical Approach

    KAUST Repository

    Naumann, Stefan

    2017-08-25

    The zwitterionic organopolymerization of four different acrylic monomers (N,N-dimethylacrylamide, methyl acrylate, methyl methacrylate and tert-butyl methacrylate) based on neutral initiators, so-called N-heterocyclic olefins (NHOs), is presented. Scope and underlying (deactivation-)mechanisms where studied in a combined experimental and computational effort. From a range of differently structured NHOs it emerged that imidazole-, in contrast to imidazoline- and benzimidazole-derivatives, readily polymerize the selected monomers. While the additive-free reactions proceed with a relatively low degree of control to yield largely atactic material, for the acrylamide the addition of LiCl as µ-type ligand has been shown to result in a rapid and quantitative monomer consumption. The thus generated poly(N,N-dimethyl acrylamide) was found to be highly isotactic (>90% isotactic dyads) with high molecular weight (Mn = 250 000 – 650 000 g/mol, ÐM = 1.3- 1.6). Complementing DFT calculations considered the zwitterionic chain growth with respect to competing side reactions, namely spirocycles and enamine formation. It was found that NHOs with unsaturated backbone better support the zwitterionic chain growth, with the spirocycles acting as dormant species that slow down but do not quench the polymerization process. Contrasting this, enamine formation irreversibly terminates the polymerization and is found to be energetically favored. This pathway can be blocked by introduction of substituents on the exocyclic carbon of the NHO, resulting in structures like 2-isopropylidene-1,3,4,5-tetramethylimidazoline (4) which consequently deliver the most controlled polymerizations. Finally, a good correlation of the initiation energy barrier with the buried volume (%VBur) and the Parr electrophilicity index is described, allowing for a quick and reliable screening of potential monomers based on these two readily accessible parameters.

  18. FINAL TECHNICAL REPORT Synthetic, Structural and Mechanistic Investigations of Olefin Polymerization Catalyzed by Early Transition Metal Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Bercaw, John E. [California Institute of Technology

    2014-05-23

    The goal of this project is to develop new catalysts and provide understanding of ligand effects on catalyst composition in order to guide development of superior catalyst systems for polymerization of olefins. Our group is designing and synthesizing new “LX2”,“pincer” type ligands and complexing early transition metals to afford precatalysts. In a collaboration with Hans Brintzinger from the University of Konstanz, we are also examining the structures of the components of catalyst systems obtained from reaction of zirconocene dichlorides with aluminum alkyls and aluminum hydrides. Such systems are currently used commercially to produce polyolefins, but the nature of the active and dormant species as well as the mechanisms of their interconversions are not understood. New information on catalyst design and performance may lead to new types of polymers and/or new chemical transformations between hydrocarbons and transition metal centers, ultimately contributing to the development of catalytic reactions for the production of fuels, commodity and polymeric materials.

  19. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

    Science.gov (United States)

    Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

    2010-01-01

    In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

  20. Olefin copolymerization via controlled radical polymerization : copolymerization of methyl methacrylate and 1-octene

    NARCIS (Netherlands)

    Venkatesh, R.; Klumperman, B.

    2004-01-01

    The atom transfer radical (co)polymerization (ATRP) of methyl methacrylate (MMA) with 1-octene was investigated. Well controlled homopolymer of MMA was obtained with 2,2,2-trichoroethanol (TCE) and p-toluenesulfonyl chloride (pTsCl), although, uncontrolled copolymerization occurred when pTsCl was

  1. Mechanism of Propylene Oxide Polymerization Promoted by N-Heterocyclic Olefins

    KAUST Repository

    Al-Ghamdi, Miasser

    2017-01-11

    We report a mechanistic DFT investigation of the organopolymerization of propylene oxide (PO) promoted by N-heterocyclic olefins (NHOs) in combination with benzylic alcohol (BnOH). Calculations support the experimentally based hypothesis of two competing pathways, namely, the anionic and zwitterionic pathways. The former is based on an acid–base cooperativity between BnOH and the NHO, promoting ring opening of PO by BnO–. The latter occurs through the formation of a zwitterionic adduct by nucleophilic attack of the exocyclic carbon atom of the NHO on the PO, with the concerted ring opening of PO. The two initiating species cannot interconvert, and chain elongation can proceed from both initiation adducts. Potential energy surfaces were computed for a set of NHOs to clarify the effects of the steric and electronic properties of the NHO on the system reactivity. The results achieved represent useful insight toward the synthesis of PPO with better properties with respect to the polymer obtained with the experimental tested systems because the computationally proposed NHO system is the only one that favors the mechanism leading to higher molecular weight.

  2. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura

    2018-04-24

    Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.

  3. Recent advances on polymeric membranes for membrane reactors

    KAUST Repository

    Buonomenna, M. G.

    2012-06-24

    Membrane reactors are generally applied in high temperature reactions (>400 °C). In the field of fine chemical synthesis, however, much milder conditions are generally applicable and polymeric membranes were applied without their damage. The successful use of membranes in membrane reactors is primary the result of two developments concerning: (i) membrane materials and (ii) membrane structures. The selection of a suited material and preparation technique depends on the application the membrane is to be used in. In this chapter a review of up to date literature about polymers and configuration catalyst/ membranes used in some recent polymeric membrane reactors is given. The new emerging concept of polymeric microcapsules as catalytic microreactors has been proposed. © 2012 Bentham Science Publishers. All rights reserved.

  4. Modelagem do Processo de Fragmentação de Catalisadores Suportados Durante a Pré-polimerização de Olefinas Modeling of Catalyst Fragmentation During Olefin Pre-polymerizations

    Directory of Open Access Journals (Sweden)

    Douglas M. Merquior

    2002-01-01

    Full Text Available Uma metodologia é proposta para descrever a morfologia das partículas de polímero que são obtidas durante os momentos iniciais da polimerização de olefinas via catálise heterogênea. O método é baseado na análise matemática da capacidade da partícula em liberar a energia mecânica acumulada no seu interior devido à rápida produção de polímero. O balanço entre as quantidades de energia acumulada e liberada é calculado com o auxílio de um modelo dinâmico da reação de pré-polimerização. A combinação da metodologia proposta com o modelo dinâmico permitiu a análise dos mecanismos de fragmentação, indicando a morfologia da partícula de polímero produzida em função do tamanho da partícula e da temperatura do reator.A model-based methodology is proposed for describing the morphology of the polymer particles that are obtained during the very early stages of the olefin polymerization. The method is based on the analysis of the particle capacity to release the amount of energy that is accumulated in its interior during the polymerization, due to the fast polymer production. The balance between the accumulated and released amounts of energy is calculated with the help of a dynamic pre-polymerization reaction model. The combination of the fragmentation criteria and of the polymerization model allows the analysis of the prepolymerization step, indicating the morphology of the final polymer particles as a function of the catalyst particle diameter and reactor temperature.

  5. α 'agostic' assistance in Ziegler-Natta polymerization of olefins. Deuterium isotopic perturbation of stereochemistry indicating coordination of an α C-H bond in chain propagation

    International Nuclear Information System (INIS)

    Piers, W.E.; Bercaw, J.E.

    1990-01-01

    The well-defined, homogeneous Ziegler-Natta olefin polymerization systems that have been reported recently provide an unprecedented opportunity to investigate the mechanism of this important process. While a consensus appears to be developing that in all these systems the active catalysts are the 14-electron, d 0 (or d 0 f n ) metallocene alkyls, Cp 2 MR (M = lanthanide or group 3 transition metal) or [Cp 2 MR] + (M = group 4 transition metal), the mechanism for chain propagation and the geometry of the transition state for olefin insertion into the metal-carbon bond have not yet been unequivocally established. In a cleverly conceived experiment, Grubbs et al. probed for an α agostic interaction in the transition state for olefin insertion. Racemic 1-d 1 -5-hexenylchlorotitanocene was prepared and found to undergo AlCl 2 (CH 2 CH 3 )-induced cyclization to a mixture of cis- and trans-2-d 1 -cyclopentylmethyl stereoisomers. Any α agostic assistance in the insertion step is expected to favor the trans product (vide infra). Hydrolysis and 2 H NMR analysis of the resultant mixture of deuteriomethylcyclopentanes revealed a 1.00 ± 0.05 ratio of trans:cis products, arguing against an α agostic assisted insertion in their system, however. The scandium hydride, {(η 5 -C 5 Me 4 ) 2 SiMe 2 }Sc(PMe 3 )H ('OpSc(PMe 3 )H'), cleanly catalyzes the hydrocyclization of 1,5-hexadiene to methylcyclopentane. The authors have adapted this catalytic hydrocyclization reaction along the lines of the Grubbs experiment to probe for α agostic assistance with the scandium system

  6. Computational fluid dynamic modeling of fluidized-bed polymerization reactors

    Energy Technology Data Exchange (ETDEWEB)

    Rokkam, Ram [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    Polyethylene is one of the most widely used plastics, and over 60 million tons are produced worldwide every year. Polyethylene is obtained by the catalytic polymerization of ethylene in gas and liquid phase reactors. The gas phase processes are more advantageous, and use fluidized-bed reactors for production of polyethylene. Since they operate so close to the melting point of the polymer, agglomeration is an operational concern in all slurry and gas polymerization processes. Electrostatics and hot spot formation are the main factors that contribute to agglomeration in gas-phase processes. Electrostatic charges in gas phase polymerization fluidized bed reactors are known to influence the bed hydrodynamics, particle elutriation, bubble size, bubble shape etc. Accumulation of electrostatic charges in the fluidized-bed can lead to operational issues. In this work a first-principles electrostatic model is developed and coupled with a multi-fluid computational fluid dynamic (CFD) model to understand the effect of electrostatics on the dynamics of a fluidized-bed. The multi-fluid CFD model for gas-particle flow is based on the kinetic theory of granular flows closures. The electrostatic model is developed based on a fixed, size-dependent charge for each type of particle (catalyst, polymer, polymer fines) phase. The combined CFD model is first verified using simple test cases, validated with experiments and applied to a pilot-scale polymerization fluidized-bed reactor. The CFD model reproduced qualitative trends in particle segregation and entrainment due to electrostatic charges observed in experiments. For the scale up of fluidized bed reactor, filtered models are developed and implemented on pilot scale reactor.

  7. Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    A. S. Almeida

    2008-06-01

    Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.

  8. FLUIDDYNAMIC ASPECTS OF GAS-PHASE ETHYLENE POLYMERIZATION REACTOR DESIGN

    Directory of Open Access Journals (Sweden)

    Guardani R.

    1998-01-01

    Full Text Available The relative importance of design variables affecting the fluiddynamic behavior of a fluidized bed reactor for the gas-phase ethylene polymerization is discussed, based on mathematical modeling. The three-phase bubbling fluidized bed model is based on axially distributed properties for the bubble, cloud and emulsion phases, combined with correlations for population balance and entrainment. Under the operating conditions adopted in most industrial processes, the reactor performance is affected mainly by the reaction rate and solids entrainment. Simulation results indicate that an adequate design of the freeboard and particle collecting equipment is of primary importance in order to produce polymeric particles with the desired size distribution, as well as to keep entrainment and catalyst feed rates at adequate levels.

  9. Optimization and control of a continuous polymerization reactor

    Directory of Open Access Journals (Sweden)

    L. A. Alvarez

    2012-12-01

    Full Text Available This work studies the optimization and control of a styrene polymerization reactor. The proposed strategy deals with the case where, because of market conditions and equipment deterioration, the optimal operating point of the continuous reactor is modified significantly along the operation time and the control system has to search for this optimum point, besides keeping the reactor system stable at any possible point. The approach considered here consists of three layers: the Real Time Optimization (RTO, the Model Predictive Control (MPC and a Target Calculation (TC that coordinates the communication between the two other layers and guarantees the stability of the whole structure. The proposed algorithm is simulated with the phenomenological model of a styrene polymerization reactor, which has been widely used as a benchmark for process control. The complete optimization structure for the styrene process including disturbances rejection is developed. The simulation results show the robustness of the proposed strategy and the capability to deal with disturbances while the economic objective is optimized.

  10. molecular weight control of a batch suspension polymerization reactor

    International Nuclear Information System (INIS)

    Shahrokhi, M.; Fanaei, M. A.

    2002-01-01

    This paper concerns molecular weight control of a batch polymerization reactor where suspension polymerization of methyl methylacrylate (MMA) takes place. For this purpose, a cascade control structure with two control loops has been selected. The slave loop is used for temperature control using on-line temperature measurements, and the master loop controls the average molecular weights based on its estimated values. Two different control algorithms namely proportional-integral (PI) controller and globally linearizing controller (GLC) have been used for temperature control. An estimator, which has the structure of an extended Kalman filter(EKF), is used for estimating monomer conversion and average molecular weights of polymer using reactor temperature measurements. The performance of proposed control algorithm is evaluated through simulation and experimental studies. The results indicate that a constant average molecular weight cannot be achieved in case of strong gel effect. However, the polydispersity of product will be lower in comparison to isothermal operation. It is also shown that in case of mo dek mismatch, the performance of cascade control is superior compared to the case where only reactor temperature is controlled based on desired temperature trajectory obtained through cascade strategy

  11. Experimental and theoretical studies on hydrogenation of olefins in multiphase fixed bed reactors

    Energy Technology Data Exchange (ETDEWEB)

    Battsengel, B.; Datsevitch, L.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2003-07-01

    Multi phase reactors like trickle bed systems are frequently used for gas-liquid reactions. In general, they have complex mass and heat transfer characteristics; scale-up is therefore difficult. The present work focuses on the role of mass transfer on the effective reaction rate, taking catalytic octene hydrogenation as a model reaction. The reaction rate in a trickle bed reactor is by a factor of about 20 smaller than (theoretically) in the absence of any mass transfer limitations. Based on the experimental results, the so-called pre-saturation concept is presented, where only the liquid saturated with hydrogen is fed into the reactor. The effective reaction rate in this two phase system (liquid and solid cat.) is equal or even higher than in a trickle bed reactor. Scale-up problems do not occur, and the pre-saturation concept has also other advantages (lower energy consumption), as discussed in detail in this paper. (orig.)

  12. Design and Implementation of a Novel Quench Flow Reactor for the Study of Nascent Olefin Polymerisation

    NARCIS (Netherlands)

    Di Martino, Audrey; Broyer, Jean Pierre; Schweich, Daniel; de Bellefon, Claude; Weickert, G.; McKenna, Timothy F.L.

    2007-01-01

    A novel stopped flow reactor system is described in the current work, along with the underlying design philosophy. While the concept of stopped flow technology is not recent, this system is the first to be designed with the objective of studying particle morphology, and to work at extremely short

  13. Numerical simulation of scale-up effects of methanol-to-olefins fluidized bed reactors

    DEFF Research Database (Denmark)

    Lu, Bona; Zhang, Jingyuan; Luo, Hao

    2017-01-01

    )-based drag models are combined in simulations. The fluidization characteristics in terms of flow structures, velocity distribution, mass fractions of gaseous product and coke distribution are presented against available experimental data for different-sized reactors. It is found that typical hydrodynamic...

  14. Olefin Autoxidation in Flow

    OpenAIRE

    Neuenschwander Ulrich; Jensen Klavs F.

    2014-01-01

    Handling hazardous multiphase reactions in flow brings not only safety advantages but also significantly improved performance due to better mass transfer characteristics. In this paper we present a continuous microreactor setup capable of performing olefin autoxidations with O2 under solvent free and catalyst free conditions. Owing to the transparent reactor design consumption of O2 can be visually followed and exhaustion of the gas bubbles marks a clear end point along the channel length coo...

  15. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.

    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  16. Direct Wittig Olefination of Alcohols.

    Science.gov (United States)

    Li, Qiang-Qiang; Shah, Zaher; Qu, Jian-Ping; Kang, Yan-Biao

    2018-01-05

    A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination products. By the strategy of simultaneously in situ generation of ylides and aldehydes, for the first time, alcohols are directly transferred to olefins with no need of prepreparation of either aldehydes or ylides. Thus, the di/monocontrollable olefination of diols is accomplished. This synthetically practical method has been applied in the gram-scale synthesis of pharmaceuticals, such as DMU-212 and resveratrol from alcohols.

  17. Mechanocatalytic polymerization and cross-linking in a polymeric matrix

    NARCIS (Netherlands)

    Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

    2013-01-01

    A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

  18. Modeling of a Buss-Kneader as a Polymerization Reactor for Acrylates. Part II: Methyl Methacrylate Based Resins

    NARCIS (Netherlands)

    Troelstra, E.J; van Dierendonck, L.L.; Janssen, L.P.B.M.; Renken, A.

    2002-01-01

    The Buss-Kneader has proven to be a suitable reactor for the polymerization of acrylates. In this second part, the polymerization of methyl methacrylate and the ter-polymerization of methyl methacrylate (MMA), hydroxyethyl methacrylate and n-butylmethacrylate is carried out in a pilot Buss-Kneader.

  19. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  20. Recent advances on polymeric membranes for membrane reactors

    KAUST Repository

    Buonomenna, M. G.; Choi, Seung Hak

    2012-01-01

    . The successful use of membranes in membrane reactors is primary the result of two developments concerning: (i) membrane materials and (ii) membrane structures. The selection of a suited material and preparation technique depends on the application the membrane

  1. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura; Barone, Vincenzo; Talarico, Giovanni

    2018-01-01

    by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement

  2. Alkylation of isobutane with light olefins catalyzed by zeolite beta

    NARCIS (Netherlands)

    Nivarthy, G.S.; Feller, A.P.; Seshan, Kulathuiyer; Lercher, J.A.

    2000-01-01

    Alkylation of isobutane with ethene and propene was studied over an H-BEA catalyst in a well-stirred reactor. Under similar conditions of space velocity and paraffin-to-olefin feed ratio, lower initial olefin conversions were observed with ethene or propene than those reported earlier for butene.

  3. Catalytic and Noncatalytic Conversion of Methane to Olefins and Synthesis Gas in an AC Parallel Plate Discharge Reactor

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Khodagholi

    2013-01-01

    Full Text Available Direct conversion of methane to ethylene, acetylene, and synthesis gas at ambient pressure and temperature in a parallel plate discharge reactor was investigated. The experiments were carried out using a quartz reactor of outer diameter of 9 millimeter and a driving force of ac current of 50 Hz. The input power to the reactor to establish a stable gas discharge varied from 9.6 to maximum 15.3 watts (w. The effects of ZSM5, Fe–ZSM5, and Ni–ZSM5 catalysts combined with corona discharge for conversion of methane to more valued products have been addressed. It was found that in presence or absence of a catalyst in gas discharge reactor, the rate of methane and oxygen conversion increased upon higher input power supplied to the reactor. The effect of Fe–ZSM5 catalyst combined with gas discharge plasma yields C2 hydrocarbons up to 21.9%, which is the highest productions of C2 hydrocarbons in this work. The effect of combined Ni–ZSM5 and gas discharge plasma was mainly production of synthesis gas. The advantage of introducing ZSM5 to the plasma zone was increase in synthesis gas and acetylene production. The highest energy efficiency was 0.22 mmol/kJ, which belongs to lower rate of energy injection to the reactor.

  4. Cylindrical micelles of a POSS amphiphilic dendrimer as nano-reactors for polymerization.

    Science.gov (United States)

    Weng, Jing-Ting; Yeh, Tso-Fan; Samuel, Ashok Zachariah; Huang, Yi-Fan; Sie, Jyun-Hao; Wu, Kuan-Yi; Peng, Chi-How; Hamaguchi, Hiro-O; Wang, Chien-Lung

    2018-02-15

    A low generation amphiphilic dendrimer, POSS-AD, which has a POSS core and eight amphiphilic arms, was synthesized and used as a nano-reactor to produce well-defined polymer nano-cylinders. Confirmed by small-angle X-ray scattering (SAXS), Raman and NMR spectrometry, monodispersed cylindrical micelles that contain a hydrophilic cavity with a diameter of 2.09 nm and a length of 4.26 nm were produced via co-assembling POSS-AD with hydrophilic liquids, such as H 2 O and HEMA in hydrophobic solvents. Taking the HEMA/POSS-AD cylindrical micelles as nano-reactors, polymerization of HEMA within the micelles results in polymer nano-cylinders (POSS-ADNPs) with a diameter of 2.24 nm and a length of 5.02 nm. The study confirmed that despite the inability to maintain specific shape in solution, low generation dendrimers form well-defined nano-containers or nano-reactors, which relies on co-assembling with hydrophilic guest molecules. These nano-reactors are robust enough to maintain their shape during the polymerization of the guest molecules. Polymer nano-cylinders with dimensions less than 10 nm can thus be produced from the HEMA/POSS-AD micelles. Since the chemical structure of low-generation dendrimers and the contents of the co-assembled nano-reactors can be easily adjusted, the concept holds the potential for the further developments of low-generation amphiphilic dendrimers.

  5. An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions

    International Nuclear Information System (INIS)

    Ruan, Guihua; Wu, Zhenwei; Huang, Yipeng; Wei, Meiping; Su, Rihui; Du, Fuyou

    2016-01-01

    A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of N_α-benzoyl-L-arginine ethyl ester to N_α-benzoyl-L-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas. - Graphical abstract: Schematic illustration of preparation of hypercrosslinking polyHIPE immobilized enzyme reactor for on-column protein digestion. - Highlights: • A reactor was prepared and used for enzyme immobilization and continuous on-column protein digestion. • The new polyHIPE IMER was quite suit for protein digestion with good properties. • On-column digestion revealed that the IMER was easy regenerated by HCl without any structure destruction.

  6. An easily regenerable enzyme reactor prepared from polymerized high internal phase emulsions

    Energy Technology Data Exchange (ETDEWEB)

    Ruan, Guihua, E-mail: guihuaruan@hotmail.com [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Guangxi Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area, Guilin University of Technology, Guilin 541004 (China); Wu, Zhenwei; Huang, Yipeng; Wei, Meiping; Su, Rihui [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Du, Fuyou, E-mail: dufu2005@126.com [Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guangxi 541004 (China); Guangxi Collaborative Innovation Center for Water Pollution Control and Water Safety in Karst Area, Guilin University of Technology, Guilin 541004 (China)

    2016-04-22

    A large-scale high-efficient enzyme reactor based on polymerized high internal phase emulsion monolith (polyHIPE) was prepared. First, a porous cross-linked polyHIPE monolith was prepared by in-situ thermal polymerization of a high internal phase emulsion containing styrene, divinylbenzene and polyglutaraldehyde. The enzyme of TPCK-Trypsin was then immobilized on the monolithic polyHIPE. The performance of the resultant enzyme reactor was assessed according to the conversion ability of N{sub α}-benzoyl-L-arginine ethyl ester to N{sub α}-benzoyl-L-arginine, and the protein digestibility of bovine serum albumin (BSA) and cytochrome (Cyt-C). The results showed that the prepared enzyme reactor exhibited high enzyme immobilization efficiency and fast and easy-control protein digestibility. BSA and Cyt-C could be digested in 10 min with sequence coverage of 59% and 78%, respectively. The peptides and residual protein could be easily rinsed out from reactor and the reactor could be regenerated easily with 4 M HCl without any structure destruction. Properties of multiple interconnected chambers with good permeability, fast digestion facility and easily reproducibility indicated that the polyHIPE enzyme reactor was a good selector potentially applied in proteomics and catalysis areas. - Graphical abstract: Schematic illustration of preparation of hypercrosslinking polyHIPE immobilized enzyme reactor for on-column protein digestion. - Highlights: • A reactor was prepared and used for enzyme immobilization and continuous on-column protein digestion. • The new polyHIPE IMER was quite suit for protein digestion with good properties. • On-column digestion revealed that the IMER was easy regenerated by HCl without any structure destruction.

  7. Kinetics of vinyl acetate emulsion polymerization in a pulsed tubular reactor: comparison between experimental and simulation results

    Directory of Open Access Journals (Sweden)

    Sayer C.

    2002-01-01

    Full Text Available A new reactor, the pulsed sieve plate column (PSPC, was developed to perform continuous emulsion polymerization reactions. This reactor combines the enhanced flexibility of tubular reactors with the mixing behavior provided by sieved plates and by the introduction of pulses that is important to prevent emulsion destabilization. The main objective of this work is to study the kinetics of vinyl acetate (VA emulsion polymerization reactions performed in this PSPC. Therefore, both experimental studies and reaction simulations were performed. Results showed that it is possible to obtain high conversions with rather low residence times in the PSPC.

  8. Synthesis of uniformly labelled organic compounds by polymerization of 14C ethylene

    International Nuclear Information System (INIS)

    Dauphin, J.-F.

    1972-01-01

    The synthesis of 14 C uniformly labelled compounds is described. By polymerization of 14 C ethylene, linear olefins with a double bond at α position were obtained. From these olefins, uniformly labelled alkanes, alcohols and acids were prepared [fr

  9. Chemical Reactor Automation as a way to Optimize a Laboratory Scale Polymerization Process

    Science.gov (United States)

    Cruz-Campa, Jose L.; Saenz de Buruaga, Isabel; Lopez, Raymundo

    2004-10-01

    The automation of the registration and control of variables involved in a chemical reactor improves the reaction process by making it faster, optimized and without the influence of human error. The objective of this work is to register and control the involved variables (temperatures, reactive fluxes, weights, etc) in an emulsion polymerization reaction. The programs and control algorithms were developed in the language G in LabVIEW®. The designed software is able to send and receive RS232 codified data from the devices (pumps, temperature sensors, mixer, balances, and so on) to and from a personal Computer. The transduction from digital information to movement or measurement actions of the devices is done by electronic components included in the devices. Once the programs were done and proved, chemical reactions of emulsion polymerization were made to validate the system. Moreover, some advanced heat-estimation algorithms were implemented in order to know the heat caused by the reaction and the estimation and control of chemical variables in-line. All the information gotten from the reaction is stored in the PC. The information is then available and ready to use in any commercial data processor software. This work is now being used in a Research Center in order to make emulsion polymerizations under efficient and controlled conditions with reproducible results. The experiences obtained from this project may be used in the implementation of chemical estimation algorithms at pilot plant or industrial scale.

  10. Design of a self-tuning regulator for temperature control of a polymerization reactor.

    Science.gov (United States)

    Vasanthi, D; Pranavamoorthy, B; Pappa, N

    2012-01-01

    The temperature control of a polymerization reactor described by Chylla and Haase, a control engineering benchmark problem, is used to illustrate the potential of adaptive control design by employing a self-tuning regulator concept. In the benchmark scenario, the operation of the reactor must be guaranteed under various disturbing influences, e.g., changing ambient temperatures or impurity of the monomer. The conventional cascade control provides a robust operation, but often lacks in control performance concerning the required strict temperature tolerances. The self-tuning control concept presented in this contribution solves the problem. This design calculates a trajectory for the cooling jacket temperature in order to follow a predefined trajectory of the reactor temperature. The reaction heat and the heat transfer coefficient in the energy balance are estimated online by using an unscented Kalman filter (UKF). Two simple physically motivated relations are employed, which allow the non-delayed estimation of both quantities. Simulation results under model uncertainties show the effectiveness of the self-tuning control concept. Copyright © 2011 ISA. Published by Elsevier Ltd. All rights reserved.

  11. Development of polymeric applications for sodium cooled Fast Breeder Reactors: Chronicles of inception, progress and achievements

    International Nuclear Information System (INIS)

    Sinha, N.K.; Raj, Baldev

    2010-01-01

    The collaborative programme on development of important polymeric applications of Indian FBRs is chronicled from the days of motivation to its present state. Failure of inflatable seals of FBTR RPs (1985) and adoption of all-elastomer sealing concept for PFBR RPs (early 1990s), coupled with the unique characteristics of elastomeric materials, led to inception of the programme at IGCAR (1998) which involved DMSRDE as the first partner (1999). The planned initiative, which eventually involved more than 15 other Indian agencies, resulted in complete development of FKM backup seals for PFBR RPs which has been installed in reactor recently. Coated FKM and EPDM inflatable seals for PFBR and FBTR RPs have been developed, produced and evaluated up to ∼2 m diameter. Development methodologies for other critical polymeric applications of PFBR, FBTR and FCF have been formulated. Accomplishments and novelties of the development include EPDM and FKM compounds and designs for inflatable and backup seals, a common FEA procedure for elastomeric ring seals, PECVD based Teflon-like coating technology up to 7 m seal diameter, seal production process by cold feed extrusion and continuous cure, a robust quality control framework and the new facilities developed to support the programme. Future developments are focused on delivery of validated inflatable seals, life assessment and development of new elastomeric compounds which include silicone rubber and perfluoroelastomer, PECVD based coating on stainless steel and development of adhesionless joining of FKM. The achievements and future research will standardize the design and development of the elastomeric seals of Indian FBRs, PHWRs and AHWR based on a few well-characterized compounds, a common FEA method and PECVD based coating technology which can result in a universal design code.

  12. High temperature initiator-free RAFT polymerization of methyl methacrylate in a microwave reactor

    NARCIS (Netherlands)

    Paulus, R.M.; Becer, C.R.; Hoogenboom, R.; Schubert, U.S.

    2009-01-01

    The reversible additionfragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) was investigated under microwave irradiation. At first, a comparison was made between microwave and thermal heating for the RAFT polymerization of MMA with azobis(isobutyronitrile) (AIBN) as

  13. The characteristics of extracellular polymeric substances and soluble microbial products in moving bed biofilm reactor-membrane bioreactor.

    Science.gov (United States)

    Duan, Liang; Jiang, Wei; Song, Yonghui; Xia, Siqing; Hermanowicz, Slawomir W

    2013-11-01

    The characteristics of extracellular polymeric substances (EPS) and soluble microbial products (SMP) in conventional membrane bioreactor (MBR) and in moving bed biofilm reactor-membrane bioreactors (MBBR-MBR) were investigated in long-term (170 days) experiments. The results showed that all reactors had high removal efficiency of ammonium and COD, despite very different fouling conditions. The MBBR-MBR with media fill ratio of 26.7% had much lower total membrane resistance and no obvious fouling were detected during the whole operation. In contrast, MBR and MBBR-MBR with lower and higher media fill experienced more significant fouling. Low fouling at optimum fill ratio may be due to the higher percentage of small molecular size (100 kDa) of EPS and SMP in the reactor. The composition of EPS and SMP affected fouling due to different O-H bonds in hydroxyl functional groups, and less polysaccharides and lipids. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Novel Formulation of Adaptive MPC as EKF Using ANN Model: Multiproduct Semibatch Polymerization Reactor Case Study.

    Science.gov (United States)

    Kamesh, Reddi; Rani, Kalipatnapu Yamuna

    2017-12-01

    In this paper, a novel formulation for nonlinear model predictive control (MPC) has been proposed incorporating the extended Kalman filter (EKF) control concept using a purely data-driven artificial neural network (ANN) model based on measurements for supervisory control. The proposed scheme consists of two modules focusing on online parameter estimation based on past measurements and control estimation over control horizon based on minimizing the deviation of model output predictions from set points along the prediction horizon. An industrial case study for temperature control of a multiproduct semibatch polymerization reactor posed as a challenge problem has been considered as a test bed to apply the proposed ANN-EKFMPC strategy at supervisory level as a cascade control configuration along with proportional integral controller [ANN-EKFMPC with PI (ANN-EKFMPC-PI)]. The proposed approach is formulated incorporating all aspects of MPC including move suppression factor for control effort minimization and constraint-handling capability including terminal constraints. The nominal stability analysis and offset-free tracking capabilities of the proposed controller are proved. Its performance is evaluated by comparison with a standard MPC-based cascade control approach using the same adaptive ANN model. The ANN-EKFMPC-PI control configuration has shown better controller performance in terms of temperature tracking, smoother input profiles, as well as constraint-handling ability compared with the ANN-MPC with PI approach for two products in summer and winter. The proposed scheme is found to be versatile although it is based on a purely data-driven model with online parameter estimation.

  15. Olefin metathesis in air

    Directory of Open Access Journals (Sweden)

    Lorenzo Piola

    2015-10-01

    Full Text Available Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

  16. Isobutane/olefin-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Waitkamp, J.; Maixner, S.

    1983-11-01

    Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

  17. Metylcyclohexane conversion to light olefins

    Directory of Open Access Journals (Sweden)

    SCOFIELD C.F.

    1998-01-01

    Full Text Available This study consists in the evaluation of the catalytic properties of zeolites with different structures in the conversion of methylcyclohexane to light olefins. Results obtained suggest that the steric constrictions of the catalysts used play an important role in hydrogen transfer reactions. Higher selectivities for light olefins (C3= and C4= were observed for zeolites having more closed structures, like MFI and ferrerite, when compared to those having more open ones, like beta, omega and faujasite.

  18. Metylcyclohexane conversion to light olefins

    OpenAIRE

    SCOFIELD, C.F.; BENAZZI, E.; CAUFFRIEZ, H.; MARCILLY, C.

    1998-01-01

    This study consists in the evaluation of the catalytic properties of zeolites with different structures in the conversion of methylcyclohexane to light olefins. Results obtained suggest that the steric constrictions of the catalysts used play an important role in hydrogen transfer reactions. Higher selectivities for light olefins (C3= and C4=) were observed for zeolites having more closed structures, like MFI and ferrerite, when compared to those having more open ones, like beta, omega and fa...

  19. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  20. Multienzyme Immobilized Polymeric Membrane Reactor for the Transformation of a Lignin Model Compound

    Directory of Open Access Journals (Sweden)

    Rupam Sarma

    2018-04-01

    Full Text Available We have developed an integrated, multienzyme functionalized membrane reactor for bioconversion of a lignin model compound involving enzymatic catalysis. The membrane bioreactors were fabricated through the layer-by-layer assembly approach to immobilize three different enzymes (glucose oxidase, peroxidase and laccase into pH-responsive membranes. This novel membrane reactor couples the in situ generation of hydrogen peroxide (by glucose oxidase to oxidative conversion of a lignin model compound, guaiacylglycerol-β-guaiacyl ether (GGE. Preliminary investigation of the efficacy of these functional membranes towards GGE degradation is demonstrated under convective flow mode. Over 90% of the initial feed could be degraded with the multienzyme immobilized membranes at a residence time of approximately 22 s. GGE conversion product analysis revealed the formation of oligomeric oxidation products upon reaction with peroxidase, which may be a potential hazard to membrane bioreactors. These oxidation products could further be degraded by laccase enzymes in the multienzymatic membranes, explaining the potential of multi enzyme membrane reactors. The multienzyme incorporated membrane reactors were active for more than 30 days of storage time at 4 °C. During this time span, repetitive use of the membrane reactor was demonstrated involving 5–6 h of operation time for each cycle. The membrane reactor displayed encouraging performance, losing only 12% of its initial activity after multiple cycles of operation.

  1. Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water.

    Science.gov (United States)

    Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

    We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, "ready for use" MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours.

  2. Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water

    OpenAIRE

    Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

    2014-01-01

    We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, “ready for use” MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours.

  3. Synthesis of interlocked molecules by olefin metathesis

    Science.gov (United States)

    Clark, Paul Gregory

    A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic

  4. Rh(III)-catalyzed olefination of N-sulfonyl imines: synthesis of ortho-olefinated benzaldehydes.

    Science.gov (United States)

    Zhang, Tao; Wu, Lamei; Li, Xingwei

    2013-12-20

    Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes has been achieved for the synthesis of ortho-olefinated benaldehydes. This reaction proceeds via a chelation assisted C-H olefination/in situ hydrolysis process.

  5. hf alkylation in the 1980's: the role of isobutane/olefin ratio

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.

    1978-08-01

    Research devoted to maximizing no-lead octane numbers in motor fuel is reported. Results of the studies are the basis for the following conclusions: 1. Isobutane alkylate made from either propylene, butene-2, or C/sub 3/--C/sub 4/ mixed olefins is a low sensitivity, high motor octane product. Typically, C/sub 3/--C/sub 4/ mixed olefin alkylate has a clear motor octane number of about 92.2 and a clear Research octane number of about 93.5. 2. In separate studies with propylene, butene-2 and C/sub 3/--C/sub 4/ mixed olefins, increasing the isobutane-to-olefin ratio suppressed the formation of high molecular weight residue, indicating a substantial reduction in the role of olefin polymerization to large ions. The overall result of increasing ratio was an improvement in selectivity to high-octane components in the alkylate. 3. When alkylating isobutane with propylene, increasing the ratio resulted in a decrease in the concentration of C/sub 7/-fraction (primary product) and an increase in the C/sub 8/-fraction (from chain initiation and subsequent hydrogen transfer). At the same time, the production of chain-termination-product propane also increased. 4. When alkylating isobutane with C/sub 3/--C/sub 4/ mixed olefins, increasing the ratio showed the same trend obtained in separate alkylation tests with propylene and butene-2. As the ratio increased, the concentration of C/sub 7/-fraction (primary propylene--isobutane product) decreased and the concentration of C/sub 8/-fraction increased markedly. Thus, increasing isobutane-to-olefin ratio exerted a strong effect on alkylate quality in the area of about 5 to 1 to 20 to 1; this effect diminished at ratios 20:1.

  6. Tacticities study of high poly-α-olefins, from poly-1-hexene to poly-1-octadecene, obtained with metallocenes catalysts

    International Nuclear Information System (INIS)

    Silva, Luciano F. da; Galland, Griselda B.

    2003-01-01

    High poly-α-olefins such as poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, poly-1-tetradecene, poly-1-hexadecene and poly-1-octadecene were obtained with the homogeneous iso specific catalyst rac-Et[Ind]ZrCl 2 /MAO and with the homogeneous syndiospecific catalyst Me 2 C[Cp(9-Flu)]ZrCl 2 /MAO at the polymerization temperatures of 0 deg C, 30 deg C and 60 deg C. The polymers were analyzed by 13 C NMR to study the influence of the α - olefins sizes, the catalysts type and the polymerization temperatures in their tacticities. The stereospecific control of both catalytic systems decreased with the increase of the reaction temperature and with the α-olefin size. (author)

  7. Decarbonisation of olefin processes using biomass pyrolysis oil

    International Nuclear Information System (INIS)

    Sharifzadeh, M.; Wang, L.; Shah, N.

    2015-01-01

    Highlights: • Decarbonization of olefin processes using biomass pyrolysis oil was proposed. • The decarbonization is based on integrated catalytic processing of bio-oil. • The retrofitted process features significant economic and environmental advantages. - Abstract: An imperative step toward decarbonisation of current industrial processes is to substitute their petroleum-derived feedstocks with biomass and biomass-derived feedstocks. For decarbonisation of the petrochemical industry, integrated catalytic processing of biomass pyrolysis oil (also known as bio-oil) is an enabling technology. This is because, under certain conditions, the reaction products form a mixture consisting of olefins and aromatics, which are very similar to the products of naphtha hydro-cracking in the conventional olefin processes. These synergies suggest that the catalytic bio-oil upgrading reactors can be seamlessly integrated to the subsequent separation network with minimal retrofitting costs. In addition, the integrated catalytic processing provides a high degree of flexibility for optimization of different products in response to market fluctuations. With the aim of assessing the techno-economic viability of this pathway, five scenarios in which different fractions of bio-oil (water soluble/water insoluble) were processed with different degrees of hydrogenation were studied in the present research. The results showed that such a retrofit is not only economically viable, but also provides a high degree of flexibility to the process, and contributes to decarbonisation of olefin infrastructures. Up to 44% reductions in greenhouse gas emissions were observed in several scenarios. In addition, it was shown that hydrogen prices lower than 6 $/kg will result in bio-based chemicals which are cheaper than equivalent petrochemicals. Alternatively, for higher hydrogen prices, it is possible to reform the water insoluble phase of bio-oil and produce bio-based chemicals, cheaper than

  8. New Trends in Olefin Production

    Directory of Open Access Journals (Sweden)

    Ismaël Amghizar

    2017-04-01

    Full Text Available Most olefins (e.g., ethylene and propylene will continue to be produced through steam cracking (SC of hydrocarbons in the coming decade. In an uncertain commodity market, the chemical industry is investing very little in alternative technologies and feedstocks because of their current lack of economic viability, despite decreasing crude oil reserves and the recognition of global warming. In this perspective, some of the most promising alternatives are compared with the conventional SC process, and the major bottlenecks of each of the competing processes are highlighted. These technologies emerge especially from the abundance of cheap propane, ethane, and methane from shale gas and stranded gas. From an economic point of view, methane is an interesting starting material, if chemicals can be produced from it. The huge availability of crude oil and the expected substantial decline in the demand for fuels imply that the future for proven technologies such as Fischer-Tropsch synthesis (FTS or methanol to gasoline is not bright. The abundance of cheap ethane and the large availability of crude oil, on the other hand, have caused the SC industry to shift to these two extremes, making room for the on-purpose production of light olefins, such as by the catalytic dehydrogenation of propane.

  9. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    Energy Technology Data Exchange (ETDEWEB)

    Albright, L.F. [Purdue Univ., West Lafayette, IN (United States); Kranz, K.E.; Masters, K.R. [STRATCO, Inc., Leawood, KS (United States)

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  10. Production of olefins from bioethanol. Catalysts, mechanism

    Directory of Open Access Journals (Sweden)

    Kusman Dossumov

    2012-12-01

    Full Text Available This review describes methods of catalytic obtaining from bioethanol of valuable industrial products – olefins, particularly ethylene. Аmong olefins, ethylene is the most popular key raw material of petrochemical synthesis. The scope of appllication of ethylene is almost unlimited in petrochemical products: polyethylene, ethylbenzene, styrene, ethylene dichloride, vinyl chloride etc. It also examines catalysts for the production of olefins and their properties. The most promising and commercially advantageous process of ethylene production by catalytic dehydration of ethanol on catalysts based on modified alumina. And this review discusses the mechanisms of catalytic conversion of ethanol to ethylene.

  11. Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

    International Nuclear Information System (INIS)

    Matsuda, O.; Kostov, G.K.; Tabata, Y.; Machi, S.

    1979-01-01

    Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with α-olefins were carried out in bulk by γ-ray irradiation at 25 0 C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r 1 (FAN) and r 2 (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system

  12. Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

    International Nuclear Information System (INIS)

    Kawaguchi, M.; Watanabe, T.; Matsuda, O.; Tabata, Y.; Machi, S.

    1981-01-01

    Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25 0 C, a dose rate of 1 x 10 6 rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene were nearly 1/2 over a wide range of the monomer compositions. The Mayo-Lewis method gave negative r 1 (FVA) and r 1 (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model

  13. Alternative Test Method for Olefins in Gasoline

    Science.gov (United States)

    This action proposes to allow for an additional alternative test method for olefins in gasoline, ASTM D6550-05. The allowance of this additional alternative test method will provide more flexibility to the regulated industry.

  14. Myoglobin-Catalyzed Olefination of Aldehydes.

    Science.gov (United States)

    Tyagi, Vikas; Fasan, Rudi

    2016-02-12

    The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. (Z)-Selective Takai olefination of salicylaldehydes.

    Science.gov (United States)

    Geddis, Stephen M; Hagerman, Caroline E; Galloway, Warren R J D; Sore, Hannah F; Goodman, Jonathan M; Spring, David R

    2017-01-01

    The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high ( E )-selectivity; however, herein we report the highly ( Z )-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

  16. Direct catalytic olefination of alcohols with sulfones.

    Science.gov (United States)

    Srimani, Dipankar; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

    2014-10-06

    The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. New unit for sulfuric acid alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Khadzhiev, S.N.; Baiburskii, V.L.; Deineko, P.S.; Gruzdev, A.S.; Tagavov, I.T.

    1987-01-01

    The authors describe and illustrate a sulfuric acid alkylation unit with a horizontal contact. As a result of the use of this design solution, the isobutane/olefin ratio is 10/1 in comparison with 4/1 to 5/1 in the other types of units, namely vertical reactors and cascade tank reactors. The unit was designed to process the butane-butylene cut (BBC) and part of the propane-propylene cut (PPC) from the G-43-107 cat cracker. The unit design includes provisions for controlled caustic washing of the feed and dehydration in an electric field. The authors present the basic data obtained in the three months of unit operation after startup, in comparison with the operating indexes of a sulfuric acid alkylation unit.

  18. Sixtieth Anniversary of Ziegler-Natta Catalysts and Stereospecific Polymerization

    Directory of Open Access Journals (Sweden)

    Janović Z.

    2015-07-01

    Full Text Available This review article highlights the history of the discoveries of organometallic catalysts and stereospecific polymerization of α-olefins, dienes and a number of vinyl monomers by Karl Ziegler and Giulio Natta sixty years ago, their developments and recent progress. As one of the most important achievements in the field of catalysis, macromolecular science and polymer materials, their inventors were awarded the Nobel Prize in Chemistry in 1963 “for their discoveries in the field of chemistry and technology of high polymers”. These discoveries have stimulated an intensive, both basic and applied research all over the world, up to the present times, leading to great development of the polymer industry. The important biographical data and scientific advancements of K. Ziegler and G. Natta are presented as well. Karl Ziegler, a German scientist, Director of Max Planck Institute for Coal Research in Mülheim, besides many scientific achievements, in 1953 discovered a new process for the polymerization of ethylene into linear polyethylene under mild conditions by using titanium chloride and alkyl aluminium catalytic system that was superior to all existing polymerization. Giulio Natta, an Italian scientist, Director of the Department of Industrial Chemistry at Polytechnic, University of Milan, besides many achievements in petrochemical processes, in 1954 obtained for the first time isotactic polypropylene and Montecatini Co. started its production already in 1958. He conducted pioneering studies on the chain microstructure of synthetic organic polymers and postulated the mechanisms of stereospecific polymerizations. Since the discovery of the Zeigler-Natta catalyst, stereospecific polymerization and processes, significant developments have occurred. The breakthrough in polymerization processes such as fluid bed, liquid phase loop reactor and reactor granule technology led to significant development and growth of polyolefin production. In the 1980s

  19. The progress of SINOPEC methanol-to-olefins (S-MTO) technology

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hongxing; Xie, Zaiku; Zhao, Guoliang [SINOPEC Shanghai Research Institute of Petrochemical Technology (China)

    2013-11-01

    It is widely recognized that naphtha steam crackers and FCC units are the main current sources of ethylene and propylene. On the condition of high oil price, olefin producers are striving to develop new economical routes to produce ethylene and propylene with low-cost feedstocks. Methanol to olefins (MTO) has aroused great attention in recent years, and SINOPEC has developed a new kind of MTO process named S-MTO which features high olefins selectivity, high methanol conversion and low catalyst consumption. Puyang Zhongyuan 200 KTA S-MTO has been in steady operation for more than 17 months. The catalyst used in the process is based on a silicoaluminophosphate, SAPO-34, which has very high carbon selectivity to low carbon olefins. Results from the commercial plant show that S-MTO process converts methanol to ethylene and propylene at about 81% carbon selectivity. The carbon selectivity approaches 92% if butenes are also accounted for as part of the product. Typically, the ratio of propylene to ethylene can range from 0.6 to 1.3. When combined with OCC (Olefin Catalytic Cracking) process to convert the heavier olefins, the overall yield of ethylene and propylene can increase to 85% {proportional_to} 87% and propylene-ethylene ratios of more than 1.5 are achievable. Other co-products include very small amounts of C1-C4 paraffins, hydrogen, CO and CO{sub 2}, as well as heavier oxygenates only with ppm level. Because of the quick deactivation of MTO catalyst, a kind of high efficiency fast fluidized bed reactor is adopted. The activity of deactivated catalyst is recovered by burning the coke in the regenerator. This paper gives an updated introduction of S-MTO technology developed by SINOPEC SRIPT. (orig.)

  20. Polymerization catalysts containing electron-withdrawing amide ligands

    Science.gov (United States)

    Watkin, John G.; Click, Damon R.

    2002-01-01

    The present invention describes methods of making a series of amine-containing organic compounds which are used as ligands for group 3-10 and lanthanide metal compounds. The ligands have electron-withdrawing groups bonded to them. The metal compounds, when combined with a cocatalyst, are catalysts for the polymerization of olefins.

  1. Synthesis of Fluoroolefins via Julia-Kocienski Olefination

    OpenAIRE

    Zajc, Barbara; Kumar, Rakesh

    2010-01-01

    The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

  2. Synthesis of Fluoroolefins via Julia-Kocienski Olefination.

    Science.gov (United States)

    Zajc, Barbara; Kumar, Rakesh

    2010-01-01

    The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

  3. Radiation-induced copolymerization of methyl trifluoroacrylate with α-olefins

    International Nuclear Information System (INIS)

    Matsuda, O.; Watanabe, T.; Tabata, Y.; Machi, S.

    1978-01-01

    Paper describes the radiation-induced bulk copolymerization of methyl trifluoroacrylate with various α olefins; propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and isobutylene. MTFA (purity above 98%) was synthesized by method described in literature. Reagent grade α-olefins were used. An equimolar mixture of MTFA and α-olefin was charged into the reactor. Trace amounts of oxygen were purged by the freeze-thaw technique. Irradiation was carried out with gamma rays from a 60 Co source under vapor pressure of the monomers at 25 0 C. The product was precipitated and washed with methanol to remove unreacted monomers, and dried under vacuum at 60 0 C. Infrared spectra of the copolymers were measured; compositions were determined from elemental analysis. Reactivity of the α-olefins appears to be related to the electron density at the double bond. All copolymers were found to have almost equimolar compositions and were soluble in polar solvents such as tetrahydrofuran and acetone. Copolymerization was inhibited completely by the addition of 1,1-diphenyl-2-picrihydrazil, but not by water, indicating that the copolymerization proceeds via a radical mechanism. 1 table; 2 figures

  4. Gamma radiolysis of 3-methylpentane. Effect of added olefins on the formation of C12-olefins

    International Nuclear Information System (INIS)

    Laet, M. de; Tilquin, B.

    1991-01-01

    Contributions of congruent (parent derived) olefins to the formation of unsaturated heavy products (C 12 H 24 ) are investigated. Effects of dose or of olefinic additives on the G yield values are studied by capillary gas chromatography. The dose dependence is explained by transfer of positive charge to congruent olefins (C 6 H 12 ) even though their concentrations build up linearly with dose. γ Irradiation of 3-methylpentane containing pentenes or butenes (0.2-2 mol %) provides good examples of transfer of energy, however the results are unexpected. C-H scission in the radiolysis of solid 3-methylpentane is also reviewed. (author)

  5. Olefin metathesis in nano-sized systems

    Directory of Open Access Journals (Sweden)

    Denise Méry

    2011-01-01

    Full Text Available The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM, cross metathesis (CM, enyne metathesis reactions (EYM – for reactions in water without a co-solvent and (ii construction and functionalization of dendrimers by CM reactions.

  6. (Z-Selective Takai olefination of salicylaldehydes

    Directory of Open Access Journals (Sweden)

    Stephen M. Geddis

    2017-02-01

    Full Text Available The Takai olefination (or Takai reaction is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E-selectivity; however, herein we report the highly (Z-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

  7. Assessment of extent and degree of thermal damage to polymeric materials in the Three Mile Island Unit 2 reactor building

    International Nuclear Information System (INIS)

    Alvares, N.J.

    1986-01-01

    This paper describes assumptions and procedures used to perform thermal damage analysis caused by post loss-of-coolant-accident (LOCA) hydrogen deflagration at Three Mile Island Unit 2 Reactor. Examination of available photographic evidence yields data on the extent and range of thermal and burn damage. Thermal damage to susceptible material in accessible regions of the reactor building was distributed in non-uniform patterns. No clear explanation for non-uniformity was found in examined evidence, e.g., burned materials were adjacent to materials that appear similar but were not burned. Because these items were in proximity to vertical openings that extend the height of the reactor building, the authors assume the unburned materials preferentially absorbed water vapor during periods of high, local steam concentration. A control pendant from the polar crane located in the top of the reactor building sustained asymmetric burn damage of decreasing degree from top to bottom. Evidence suggests the polar-crane pendant side that experienced heaviest damage was exposed to intense radiant energy from a transient fire plume in the reactor containment volume. Simple hydrogen-fire-exposure tests and heat transfer calculations approximate the degree of damage found on inspected materials from the containment building and support for an estimated 8% pre-fire hydrogen

  8. Assessment of extent and degree of thermal damage to polymeric materials in the Three Mile Island Unit 2 Reactor building

    International Nuclear Information System (INIS)

    Alvares, N.J.

    1985-06-01

    This paper describes assumptions and procedures used to perform thermal damage analysis caused by post loss-of-coolant-accident (LOCA) hydrogen deflagration at Three Mile Island Unit 2 Reactor. Examination of available photographic evidence yields data on the extent and range of thermal and burn damage. Thermal damage to susceptible material in accessible regions of the reactor building was distributed in non-uniform patterns. No clear explanation for non-uniformity was found in examined evidence, e.g., burned materials were adjacent to materials that appear similar but were not burned. Because these items were in proximity to vertical openings that extend the height of the reactor building, we assume the unburned materials preferentially absorbed water vapor during periods of high, local steam concentration. A control pendant from the polar crane located in the top of the reactor building sustained asymmetric burn damage of decreasing degree from top to bottom. Evidence suggests the polar-crane pendant side that experienced heaviest damage was exposed to intense radiant energy from a transient fire plume in the reactor containment volume. Simple hydrogen-fire-exposure tests and heat transfer calculations approximate the degree of damage found on inspected materials from the containment building and support for an estimated 8% pre-fire hydrogen

  9. Microfluidic Manufacturing of Polymeric Nanoparticles: Comparing Flow Control of Multiscale Structure in Single-Phase Staggered Herringbone and Two-Phase Reactors.

    Science.gov (United States)

    Xu, Zheqi; Lu, Changhai; Riordon, Jason; Sinton, David; Moffitt, Matthew G

    2016-12-06

    We compare the microfluidic manufacturing of polycaprolactone-block-poly(ethylene oxide) (PCL-b-PEO) nanoparticles (NPs) in a single-phase staggered herringbone (SHB) mixer and in a two-phase gas-liquid segmented mixer. NPs generated from two different copolymer compositions in both reactors and at three different flow rates, along with NPs generated using a conventional bulk method, are compared with respect to morphologies, dimensions, and internal crystallinities. Our work, the first direct comparison between alternate microfluidic NP synthesis methods, shows three key findings: (i) NP morphologies and dimensions produced in the bulk are different from those produced in a microfluidic mixer, whereas NP crystallinities produced in the bulk and in the SHB mixer are similar; (ii) NP morphologies, dimensions, and crystallinities produced in the single-phase SHB and two-phase mixers at the lowest flow rate are similar; and (iii) NP morphologies, dimensions, and crystallinities change with flow rate in the two-phase mixer but not in the single-phase SHB mixer. These findings provide new insights into the relative roles of mixing and shear in the formation and flow-directed processing of polymeric NPs in microfluidics, informing future reactor designs for manufacturing NPs of low polydispersity and controlled multiscale structure and function.

  10. Synthesis and characterization of tantalum organometallic complexes. Catalytic activity for olefins

    International Nuclear Information System (INIS)

    Baley, A.S.

    1990-11-01

    Synthesis of monoaryloxy (alcoxy) neopentyl compounds is investigated. The tantalum-oxygen bond is formed by two parallel ways from TaCl 5 or TaR 2 Cl 3 with R = neopentyl and the tantalum carbon bond from a neopentyl derivative of the main series. Some compounds were isolated and characterized by NMR, elemental analysis and sometimes X-ray structure, some others are characterized in solution only. Catalytic effect is tested by ethylene dimerization and olefin polymerization. Reactivity of tantalum aryloxy neopentyl in respect to complexing and chelating ligands is studied for preparation of neopentylidene complexes

  11. Assessment of Extent and Degree of Thermal Damage to Polymeric Materials in the Three Mile Island Unit 2 Reactor Building

    International Nuclear Information System (INIS)

    Alvares, N. J.

    1984-02-01

    Thermal damage to susceptible materials in accessible regions of the TMI-2 reactor building shows damage-distribution patterns that indicate non-uniform intensity of exposure. No clear explanation for non-uniformity is found in existing evidence; e.g., in some regions a lack of thermally susceptible materials frustrates analysis. Elsewhere, burned materials are present next to materials that seem similar but appear unscathed-leading to conjecture that the latter materials preferentially absorb water vapor during periods of high local steam concentration. Most of the polar crane pendant shows heavy burns on one half of its circumferential surface. This evidence suggests that the polar crane pendant side that experienced heaviest burn damage was exposed to intense radiant energy from a transient fire plume in the reactor containment volume. Tests and simple heat-transfer calculations based on pressure and temperature records from the accident show that the atmosphere inside the reactor building was probably 8% hydrogen in air, a value not inconsistent with the extent of burn damage. Burn-pattern geography indicates uniform thermal exposure in the dome volume to the 406-ft level (about 6 ft below the polar crane girder), partial thermal exposure in the volume between the 406- and 347-ft levels as indicated by the polar crane cable, and lack of damage to most thermally susceptible materials in the west quadrant of the reactor building; some evidence of thermal exposure Is seen in the free volume between the 305- and 347-ft levels. (author)

  12. Olefin Recovery from Chemical Industry Waste Streams

    Energy Technology Data Exchange (ETDEWEB)

    A.R. Da Costa; R. Daniels; A. Jariwala; Z. He; A. Morisato; I. Pinnau; J.G. Wijmans

    2003-11-21

    The objective of this project was to develop a membrane process to separate olefins from paraffins in waste gas streams as an alternative to flaring or distillation. Flaring these streams wastes their chemical feedstock value; distillation is energy and capital cost intensive, particularly for small waste streams.

  13. Cyclic olefin copolymer-silica nanocomposites foams

    Czech Academy of Sciences Publication Activity Database

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

  14. Synthesis of pterostilbene by Julie Olefination

    Science.gov (United States)

    A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

  15. Techno-economic analysis of the coal-to-olefins process in comparison with the oil-to-olefins process

    International Nuclear Information System (INIS)

    Xiang, Dong; Qian, Yu; Man, Yi; Yang, Siyu

    2014-01-01

    Highlights: • Present the opportunities and challenges of coal-to-olefins (CTO) development. • Conduct a techno-economic analysis on CTO compared with oil-to-olefins (OTO). • Suggest approaches for improving energy efficiency and economic performance of CTO. • Analyze effects of plant scale, feedstock price, CO 2 tax on CTO and OTO. - Abstract: Olefins are one of the most important oil derivatives widely used in industry. To reduce the dependence of olefins industry on oil, China is increasing the production of olefins from alternative energy resources, especially from coal. This study is concerned with the opportunities and obstacles of coal-to-olefins development, and focuses on making an overall techno-economic analysis of a coal-to-olefins plant with the capacity of 0.7 Mt/a olefins. Comparison is made with a 1.5 Mt/a oil-to-olefins plant based on three criteria including energy efficiency, capital investment, and product cost. It was found that the coal-based olefins process show prominent advantage in product cost because of the low price of its feedstock. However, it suffers from the limitations of higher capital investment, lower energy efficiency, and higher emissions. The effects of production scale, raw material price, and carbon tax were varied for the two production routes, and thus the operational regions were found for the coal-to-olefins process to be competitive

  16. Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer

    International Nuclear Information System (INIS)

    Ferreto, Helio Fernando Rodrigues

    2006-01-01

    The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

  17. Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Yu-Ting; Huber, George W.

    2011-06-03

    The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysis–mass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/Al ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO₂, aromatics, and olefins at temperatures from 400 to 600 °C. Aromatics (e.g., benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C₁₂{sub +} oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 min of time on-stream. We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO₂, allene, C₂–C₆ olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 °C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450–600 °C). At low temperatures (450 °C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include Diels–Alder condensation (e.g., two furans form benzofuran and water

  18. Assessment of thermal damage to polymeric materials by hydrogen deflagration in the Three Mile Island Unit 2 Reactor Building

    International Nuclear Information System (INIS)

    Alvares, N.J.

    1985-05-01

    Thermal damage to susceptible material in accessible regions of the reactor building was distributed in non-uniform patterns. No clear explanation for non-uniformity was found in examined evidence, e.g., burned materials were adjacent to materials that appear similar but were not burned. Because these items were in proximity to vertical openings that extend the height of the reactor building, we assume the unburned materials preferentially absorbed water vapor during periods of high, local steam concentration. Simple hydrogen-fire-exposure tests and heat transfer calculations duplicate the degree of damage found on inspected materials from the containment building. These data support estimated 8% pre-fire hydrogen concentration predictions based on various hydrogen production mechanisms

  19. Radiation-induced terpolymerization of methyl α,β,β-trifluoroacrylate with tetrafluoroethylene and α-olefin

    International Nuclear Information System (INIS)

    Matsuda, O.; Watanabe, T.; Tabata, Y.; Machi, S.

    1980-01-01

    Radiation-induced terpolymerizations of methyl α,β,β-trifluoroacrylate (MTFA) with tetrafluoroethylene (TFE) and α-olefins, such as ethylene, propylene, and isobutylene, were carried out in bulk at 25 0 C for the purpose of controlling the content of ester group in the MTFA-α-olefin alternating copolymers. These monomers polymerized to form alternating terpolymers which contained 50 mole % α-olefin in a wide range of monomer composition. The content of MTFA, namely, the ester group in polymer, can be varied without destruction of the alternating structures between fluoroolefins (MTFA, TFE) and α-olefin by changing the MTFA/TFE ratio in the monomer mixture. The relative reactivities of MTFA and TFE in the terpolymerization were discussed according to kinetic treatments by free propagating and complex mechanisms. The relation between the MTFA/TFE ratio in the monomer mixture and that in terpolymer was explained favorably by the complex mechanism. It was also concluded that the relative reactivity of MTFA is larger than that of TFE in the terpolymerizations

  20. A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Doshi, B.M.

    1978-01-01

    A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

  1. Conversion of olefins to liquid motor fuels

    Science.gov (United States)

    Rabo, Jule A.; Coughlin, Peter K.

    1988-01-01

    Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

  2. Thermal 18F atom addition to olefins

    International Nuclear Information System (INIS)

    Rogers, P.J.M.

    1986-01-01

    The addition of thermal 18 F atoms to olefins was investigated using various substrate molecules. The 18 F atoms were produced by the 19 F(n,2n) 18 F nuclear reaction with >10 5 eV of energy which is removed by multiple collisions with SF 6 molecules before reaction occurs with an olefin. By varying the SF 6 /substrate mole ratio it was demonstrated that the fraction of non-thermal reactions is dependent upon the frequency of non-reactive energy reducing collisions with SF 6 . The rate constants for addition and abstraction reactions with propene, cis-1-chloropropene and trans-1-chloropropene were determined. The substitution of a C1 atom for the olefinic H atom in the C 1 position does not affect the rate of 18 F bond formation but it changes the orientation of attack. The 18 F atom prefers the terminal carbon-in propene and propene-d 6 by a factor of 1.35 while the preference is less than 0.5 for the terminal carbon in cis-1-chloropropene and trans-1-chloropropene. The addition of 18 F atoms to olefins creates vibrationally excited fluoroalkyl radicals which can either decompose or stabilize by collision with another molecule. The rate constants for decomposition of excited CH 3 CHCHC1F radicals formed by 18 F addition to cis-1-chloropropene and trans-1-chloropropene are competitive with C 1 -C 2 bond rotation. The 18 F atoms add to the parent molecule with retention of geometry and a memory of the geometry persists as demonstrated by the cis-1-fluoropropene/trans-1-fluoropropene decomposition product ratio

  3. Olefin recovery from FCC off-gas can pay off

    International Nuclear Information System (INIS)

    Brahn, M.G.

    1992-01-01

    This paper reports on olefins recovery from refinery FCC offgas streams which offers an attractive cash flow from olefins from a tail-gas stream that has typically been consumed as refinery fuel. Such recovery schemes can be employed in refineries or olefins plants, and can be tailored to fit individual requirements. Mobil Chemical Co. has operated such a dephlegmator-based off-gas recovery unit at its Beaumont, Tex., olefin plant since 1987. It reported that the project was paid out within 11 months of initial start-up

  4. Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

    Science.gov (United States)

    Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2011-05-06

    The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

  5. The olefin metathesis reaction: reorganization and cyclization of organic compounds

    International Nuclear Information System (INIS)

    Frederico, Daniel; Brocksom, Ursula; Brocksom, Timothy John

    2005-01-01

    The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances. (author)

  6. Alternative routes to olefins. Chances and challenges

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Delhomme, C.; Ponceau, M. [Linde AG, Pullach (Germany)

    2013-11-01

    In the future, conventional raw materials which are used for the production of olefins will get shorter and more expensive and alternative raw materials and production routes will gain importance. Natural gas, coal, shale oil or bio-mass are potential sources for the production of olefins, especially ethylene and propylene, as major base chemicals. Several potential production routes were already developed in the past, but cost, energy and environmental considerations might make these unattractive or unfeasible in comparison to traditional processes (e.g. steam cracking). Other processes such as methanol to olefins processes were successfully developed and first commercial units are running. In addition, combination of traditional processes (e.g. coal/biomass gasification, Fischer-Tropsch and steam cracking) might enable new pathways. Besides, dehydration of ethanol is opening direct routes from biomass to 'green' ethylene. However, for these 'bio-routes', feedstock availability and potential land use conflict with food production (sugar cane, wheat,..) still need to be evaluated. finally, new oxidative routes, including processes such as oxidative coupling of methane or oxidative dehydrogenation, are still at an early development stage but present potential for future industrial applications. (orig.) (Published in summary form only)

  7. Application of a silver–olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    International Nuclear Information System (INIS)

    Everitt, D T; Coope, T S; Trask, R S; Bond, I P; Wass, D F

    2015-01-01

    A silver–olefin based coordination polymer was prepared in a simple, one step process to act as an initiator to facilitate the ring-opening polymerization of epoxides. Thermal analysis found the complex to be capable of curing a range of commercially available epoxy resins used in the manufacture of conventional composite materials. Curing of the oligomeric diglycidyl ether bisphenol A resin, Epon 828, in combination with a non-toxic solvent, ethyl phenylacetate, was studied by differential scanning calorimetry. The mechanical characterization of the resultant cured polymers was conducted by single lap shear tests. Tapered double cantilever beam (TDCB) test specimens containing 2.5 pph of silver–olefin initiator, both with and without embedded microcapsules, were analyzed for their healing performance. Healing efficiency values were found to be strongly dependent on the applied healing temperature. A mean recovery of 74% fracture load was found in TDCB samples after being healed at 70 °C for 48 h. (paper)

  8. Reactor

    International Nuclear Information System (INIS)

    Toyama, Masahiro; Kasai, Shigeo.

    1978-01-01

    Purpose: To provide a lmfbr type reactor wherein effusion of coolants through a loop contact portion is reduced even when fuel assemblies float up, and misloading of reactor core constituting elements is prevented thereby improving the reactor safety. Constitution: The reactor core constituents are secured in the reactor by utilizing the differential pressure between the high-pressure cooling chamber and low-pressure cooling chamber. A resistance port is formed at the upper part of a connecting pipe, and which is connect the low-pressure cooling chamber and the lower surface of the reactor core constituent. This resistance part is formed such that the internal sectional area of the connecting pipe is made larger stepwise toward the upper part, and the cylinder is formed larger so that it profiles the inner surface of the connecting pipe. (Aizawa, K.)

  9. Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

    Science.gov (United States)

    Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

    2012-12-01

    Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Reactor

    International Nuclear Information System (INIS)

    Ikeda, Masaomi; Kashimura, Kazuo; Inoue, Kazuyuki; Nishioka, Kazuya.

    1979-01-01

    Purpose: To facilitate the construction of a reactor containment building, whereby the inspections of the outer wall of a reactor container after the completion of the construction of the reactor building can be easily carried out. Constitution: In a reactor accommodated in a container encircled by a building wall, a space is provided between the container and the building wall encircling the container, and a metal wall is provided in the space so that it is fitted in the building wall in an attachable or detatchable manner. (Aizawa, K.)

  11. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

    Jiang, J.; Wu, Zhenning; Benter, Maike

    2008-01-01

    , external electrode, and electrodeless microwave or high frequency reactors. [3] Softplasma™ is an internal electrode plasma setup powered by low frequenc~ gower supply. It was developed in late 90s for surface treatment of silicone rubber. [ ]- 5] It is a low pressure, low electron density, 3D homogenous......In the late 19th century, the first depositions - known today as plasma polymers, were reported. In the last century, more and more research has been put into plasma polymers. Many different deposition systems have been developed. [1, 2] Shi F. F. broadly classified them into internal electrode...... plasma. In this study, we are presenting the surface modification"pf polymers by plasma polymerization using Softplasma™. Softplasma™ can be used for two major types of polymerization: polymerization of vinyl monomers, where plasma acts as initiator; chemical vapour deposition, where plasma acts...

  12. Surface-enhanced light olefin yields during steam cracking

    NARCIS (Netherlands)

    Golombok, M.; Kornegoor, M.; Brink, van den P.; Dierickx, J.; Grotenbreg, R.

    2000-01-01

    Various papers have shown enhanced olefin yields during steam cracking when a catalytic surface is introduced. Our studies reveal that increased light olefin yields during catalytic steam cracking are mainly due to a surface volume effect and not to a traditional catalytic effect. Augmentation of

  13. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  14. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  15. Polyolefin nanocomposites in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

    2011-07-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  16. Polyolefin nanocomposites in situ polymerization

    International Nuclear Information System (INIS)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul

    2011-01-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  17. Rhodium(I) catalysis in olefin photoreactions

    International Nuclear Information System (INIS)

    Salomon, R.G.; El Sanadi, N.

    1975-01-01

    The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

  18. A method for producing lower olefins

    Energy Technology Data Exchange (ETDEWEB)

    Lemayev, N.V.; Grigorovich, V.A.; Isayev, V.A.; Liakumovich, A.G.; Mitrofanov, A.I.; Orekhov, A.I.; Trifonov, S.V.; Vernov, P.A.

    1983-01-01

    In the known method for producing lower olefins by pyrolysis of a hydrocarbon raw material in the presence of an initiator which contains ammonia, in order to increase the output of the target products, morpholine or piperidine are additionally introduced into the initiator in a volume of 0.00001 to 0.1 percent each, converted for the raw material. The compounds to be added may be introduced into the pyrolysis zone by dissolving them in the hydrocarbon raw material or in water, which forms vapors with dilution of the raw material being subjected to pyrolysis. The increase in the outputs of the lower olefins in the process through the use of additives may be explained by the synergistic effect of the mixture of ammonia, morpholine and piperidine used. With benzine pyrolysis without the additives the output of ethylene is 24.1 percent; in comparable conditions with additives of ammonia or morpholine alone, or of piperidine alone, the outputs are 24.0, 26.2 and 25.8 percent, respectively. With the joint presence of ammonia and piperidine, the output of ethylene reaches 27.2 percent and with the addition of ammonia and morpholine, it reaches 27.4 percent.

  19. Synthesis and essay of an Ionomer like catalyst of olefins epoxidation

    International Nuclear Information System (INIS)

    Boyaca Mendivelso, Alejandro; Tempesti, Ezio

    1995-01-01

    The purpose of the present work is the preparation of an ionomer with base in Molybdenum and to evaluate its activity like catalyst of olefins epoxidation like alternative of synthesis of catalysts of the Hawk process. A polymer is synthesized with available functional groups to stabilize the metal starting from sodium molybdate; the characterization is made by atomic absorption, spectroscopy to GO, and X.P.S. The characterization indicates that indeed it is possible to stabilize the Mo in the main polymeric. The evaluation in reaction in liquid phase allows similar conversions to those of a homogeneous catalyst. The selective epoxidation of olefins for alkyl hydroperoxides, it has acquired great importance inside the industrial processes obtaining of propylene oxide due to the recent use of the terbutilic alcohol (co-produced together with the epoxide), as preservative in gasoline free of lead. In the environment of these processes, and in particular in the Hawk process possibilities of technological innovation, in the concerning to the heterogenization of conventional catalysts, at the moment used in homogeneous phase. The present work collaborate to some tentative that look for to generate alternative of preparation of catalysts for the process Hawk, synthesizing and testing the activity of an ionomer like epoxidation catalyst, which tries to reproduce the chemical structure of the complexes organ-metallic pear to suppress the separation stages and necessary recovery facilitating its recurrent reutilization with eventual economic repercussions in the industrial process. It is described the procedure of synthesis of the ionomer, the characterization and the evaluation of the activity in reaction under diverse conditions. Of the made characterization it comes off that the heterogenization of catalysts for olefins epoxidation, according to the Hawk process, is possible by means of the preparation of polymers modified appropriately. Likewise the evaluation in

  20. Density variations in a reactor during liquid full dimerization

    NARCIS (Netherlands)

    Golombok, M.; Bruijn, J.

    2000-01-01

    In a liquid full plug flow reactor during lower olefin dimerization, the assumption of constant density is not valid—the volume of a plug changes as it proceeds along the reactor. The observed kinetics depend on the density variation in the reactor as the conversion proceeds towards a distribution

  1. Production and use of light olefins. Preprints of the conference

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Buzzoni, R.; Leitner, W.; Lercher, J.A.; Lichtscheidl, J.; Nees, F.; Santacesaria, E. (eds.)

    2009-07-01

    Within the conference of the German Society for Petroleum and Coal Science and Technology e.V. (Hamburg, Federal Republic of Germany) in Berlin (Federal Republic of Germany) at 28th to 30th September, 2009, the following lectures were held: (1) Steamcracking - State of the Art (H. Zimmermann); (2) Diversify Feedstock Options to Olefin Production (Q. Ling et al.); (3) Syngas to lower olefins (E. Schwab et al.); (4) STAR process registered for the on-purpose production of propylene (K. Bueker); (5) The catalytic activity of zinc oxide supported on aerosil for C-H activation of light alkanes (S. Arndt et al.); (6) Novel catalytic approaches for the oxidative dehydrogenation of ethane (D. Hartmann); (7) A comparison of the active sites structures of homogeneous and heterogeneous olefin polymerisation catalysts (A. Zecchina); (8) Catalytic strategies in metathesis (C. Coperet); (9) Multi-technology integrated production and consumption of olefins (J. Popp et al.); (10) Olefin oligomerization for the production of fuels and petrochemicals (H. Olivier-Bourbigou et al.); (11) Dieselization of the world - How to increase diesel yield in a refinery (A. Dueker); (12) Isomerization of butenes: LyondellBasell's Isomplus technology development (T. Zak et al.); (13) Valuable products from butadiene, carbon dioxide and further base chemicals (A. Behr); (14) The partial oxidation of propene to propylene oxide using N{sub 2}O as an oxidant (T. Thoemmes); (15) Alternative feedstocks for olefin production: What role will ethanol play? (B.R. Maughon); (16) Production of light olefins from renewable resources - The effect of deoxygenation degree on yields of light olefins (D. Kubicka et al.); (17) Recovery of low olefins from refinery offgases (M. Bender).

  2. Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

    Science.gov (United States)

    Li, Kuo-Tseng; Wu, Ling-Huey

    2017-05-05

    Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

  3. SAXS observation of structural evolution of heated olefin

    International Nuclear Information System (INIS)

    Sun Minhua; Mou Hongchen; Wang Yuxi; Li Demin; Wang Aiping; Ma Congxiao; Cheng Weidong; Wang Dan; Liu Jia

    2007-01-01

    Structural evolution of olefin during its heating process was observed with SAXS method at Beijing Synchrotron Radiation Facility. The mean square fluctuation of electron density increased from 468.5 nm -2 at 22 degree C to 2416 nm -2 at 100 degree C, while the electronic gyration radius decreased from 11.61 nm at 22 degree C to 11.16 nm at 100 degree C. Therefore, the olefin softens as a result of the increased thermal motion of the molecules, rather than the shrinking size of fundamental structural units of olefin. (authors)

  4. Reactions of dihydridotetrakis(triphenylphosphine)ruthenium(II) with olefins and isolation of new ruthenium-olefin complexes

    International Nuclear Information System (INIS)

    Komiya, Sanshiro; Yamamoto, Akio

    1976-01-01

    Dihydridotetrakis(triphenylphosphine)ruthenium (II), RuH 2 (PPh 3 ) 4 , reacts with olefins (ethylene, propylene, stylene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh 3 ) 3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH 4 (PPh 3 ) 3 , releasing alkane at room temperature, Under hydrogen atmosphere catalytic hydrogenation of the olefins smoothly takes place with RuH 2 (PPh 3 ) 4 . (Ethylene)tris(triphenylphosphine)ruthenium(0) reacts with methyl iodide to give propylene and a trace of butadiene along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C-H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C 2 H 4 )(PPh 3 ) 3 with methyl-d 3 iodide and ethyl iodide, and of Ru(C 3 H 6 )(PPh 3 ) 3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C 2 H 4 )(PPh 3 ) 3 with CD 3 I released CD 4 and CD 2 H 2 together with CD 3 H suggesting the involvement of α-hydrogen abstraction. (auth.)

  5. Elektroaktive polymerer

    DEFF Research Database (Denmark)

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

  6. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)

    2011-07-01

    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  7. Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

    National Research Council Canada - National Science Library

    Low, Tammy K

    2006-01-01

    .... Our research goals consisted of employing olefin metathesis in the synthesis of peptidomimetics, and studying the feasibility of this method in dynamic combinatorial chemistry and molecular imprinting of nerve agents...

  8. Olefin copolymerization via reversible addition-fragmentation chain transfer

    NARCIS (Netherlands)

    Venkatesh, R.; Staal, B.B.P.; Klumperman, B.

    2004-01-01

    Successful statistical copolymn. of an a-olefin (1-octene) with an acrylate (Bu acrylate, BA) and with a methacrylate (Me methacrylate, MMA), employing reversible addn.-fragmentation chain transfer (RAFT) mediated polymn. has been accomplished

  9. Direct observation of OH production from the ozonolysis of olefins

    Science.gov (United States)

    Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

    Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

  10. Olefins and chemical regulation in Europe: REACH.

    Science.gov (United States)

    Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

    2015-11-05

    REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

  11. Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

    Science.gov (United States)

    2006-08-01

    organic, and biochemistry, lectured in chemistry of weapons, and researched on ionic liquids and nucleic acid derivatives. She discovered her joy of...Products from oligomerization of the dimer scaffold or olefin isomerization are excluded from these projected numbers.97,98 The number of...Figure 3-8). This is excluding any olefin isomerization products or oligomerization of the cyclic scaffold. If stereoisomers are considered, then

  12. Reactors

    DEFF Research Database (Denmark)

    Shah, Vivek; Vaz Salles, Marcos António

    2018-01-01

    The requirements for OLTP database systems are becoming ever more demanding. Domains such as finance and computer games increasingly mandate that developers be able to encode complex application logic and control transaction latencies in in-memory databases. At the same time, infrastructure...... engineers in these domains need to experiment with and deploy OLTP database architectures that ensure application scalability and maximize resource utilization in modern machines. In this paper, we propose a relational actor programming model for in-memory databases as a novel, holistic approach towards......-level function calls. In contrast to classic transactional models, however, reactors allow developers to take advantage of intra-transaction parallelism and state encapsulation in their applications to reduce latency and improve locality. Moreover, reactors enable a new degree of flexibility in database...

  13. Fully-polymeric pH sensor realized by means of a single-step soft embossing technique

    NARCIS (Netherlands)

    Fanzio, P.; Skolimowski, Maciej; Tanzi, Simone; Sasso, L.

    2017-01-01

    We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer

  14. Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes.

    Science.gov (United States)

    Li, Xuting; Gong, Xue; Zhao, Miao; Song, Guoyong; Deng, Jian; Li, Xingwei

    2011-11-04

    Rhodium(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides has been achieved at the peri position. Three categories of olefins have been successfully applied. Activated olefins reacted to afford five-membered azacycles as a result of oxidative olefination-hydroamination. Unactivated olefins reacted to give the olefination product. 2-fold oxidative C-C and C-N coupling was achieved for allylbenzenes. © 2011 American Chemical Society

  15. A method for producing light olefines

    Energy Technology Data Exchange (ETDEWEB)

    Kavada, N.; Katsuno, K.

    1982-11-04

    A method is proposed for producing light olefins from MeOH in the presence of a catalyst (Kt), a crystalline silicate which includes silicon, an alkaline and or alkaline earth metal, titanium(4+) and phosphorus(5+), whose composition is described by the formula p(019 plus or minus 0.3)M2/mO with pZ4/nO2 with SiO2, where M is the alkaline or alkaline earth metal, Z = titanium(4+) or phosphorus(5+), m is the valency of the metal, n is the valency of Z and O is less than p is less than or equal to 0.1. A high selectivity of MeOH to C2 to C4 olefins is achieved in the presence of the catalyst. Silicon powder, silica gel, colloidal silicon, liquid glass or silicates of alkaline metals in a ratio of SiO2 to M2O of 1 to 5 is used as the source of the first component. Hydroxides or silicates of potassium and sodium (best sodium) and nitrates or chlorides of alkaline earth metals (best calcium) are used as the source of the second component. Water soluble compounds of titanium(4+) (best Ti(SO4)2, TiBr4 and TiI4) and phosphorus(5+) (best H3PO4, Na3PO4) are used as the source of the third component. Heterocyclic compounds (best morpholine, oxazolidine and their derivatives, which are taken in a molar ratio of crystallization agent to SiO2 of 0.01 to 50 (best at 0.1 to 10), are used as the crystallization agent (ArK). The catalyst is prepared through heating in an autoclave at a temperature of 80 to 300 degrees (best at 120 to 200 degrees) at atmospheric pressure for 10 to 50 hours with mixing of the mixture of the three components, water and the crystallization agent. The forming crystalline product is cooled, poured off, washed with water, dried for several hours at a temperature of at least 100 degrees and roasted in air for 2 to 48 hours at 300 to 700 degrees.

  16. La production des oléfines. Etat de la technique et développement dans le domaine des réacteurs chimiques et des procédés Olefin Production. State of Technology and Developement in the Field of Chemical Reactors and Processes

    Directory of Open Access Journals (Sweden)

    Amouyal R.

    2006-11-01

    Full Text Available La production des oléfines légères : éthylène, propylène et butadiène est actuellement entièrement basée sur le vapocraquage d'hydrocarbures dans des fours tubulaires. L'industrie doit faire face à un problème de coûts de production croissants, en grande partie dû au renchérissement des hydrocarbures et de l'énergie. D'autres procédés que le vapocraquage ont été proposés pour favoriser la diversification sur le plan des matières premières ; certains ont même été exploités industriellement. Le présent article fait le point sur l'état des développements en cours concernant plus particulièrement les procédés suivants : - craquage autothermique ; - craquage par caloporteur solide ; - craquage cyclique ; - craquage catalytique ; - prétraitement de charges lourdes ; - oléfines à partir de gaz de synthèse ; - oléfines à partir de biomasse. The production of light olefins (ethylene, propylene and butadien is now based entirely on hydrocarbon steam cracking in pipe stills. The industry must face the problem of increasing production costs, largely due to the higher costs of hydrocarbons and energy. Processes other than steam cracking have been proposed to promote diversification with regard to raw materials, and some such processes have even operated industrially. This article sums up the state of ongoing developments concerning in particular the following processes: a autothermal cracking; b cracking by a solid heat carrier; c cyclic cracking; d catalytic cracking ; e preprocessing of heavy feeds; f olefins from synthetic gas; g olefins from biomass.

  17. Reactor

    International Nuclear Information System (INIS)

    Fujibayashi, Toru.

    1976-01-01

    Object: To provide a boiling water reactor which can enhance a quake resisting strength and flatten power distribution. Structure: At least more than four fuel bundles, in which a plurality of fuel rods are arranged in lattice fashion which upper and lower portions are supported by tie-plates, are bundled and then covered by a square channel box. The control rod is movably arranged within a space formed by adjoining channel boxes. A spacer of trapezoidal section is disposed in the central portion on the side of the channel box over substantially full length in height direction, and a neutron instrumented tube is disposed in the central portion inside the channel box. Thus, where a horizontal load is exerted due to earthquake or the like, the spacers come into contact with each other to support the channel box and prevent it from abnormal vibrations. (Furukawa, Y.)

  18. Proceedings of the DGMK-Conference 'Creating value from light olefins - production and conversion'. Authors' manuscripts

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G; Kraemer, H J; Weitkamp, J [eds.

    2001-07-01

    Main topics of the conference were: production of light olefin by steamcracking and catalytic cracking processes, catalysts, methanol to olefin processes, oxidative dehydrogenation, partial oxidation, selective oxidation of alkanes with various catalysts. (uke)

  19. Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

    KAUST Repository

    Dong, G.; Teo, P.; Wickens, Z. K.; Grubbs, R. H.

    2011-01-01

    Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive

  20. Reactivity of olefin and allyl ligands in π-complexes of metals

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

  1. Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.

    Science.gov (United States)

    Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong

    2014-01-03

    A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

  2. Kinetically based NMR method of measuring blending octane number of olefins

    NARCIS (Netherlands)

    Golombok, M.; Bruijn, J.; Morley, C.

    1995-01-01

    Olefins are highly nonlinear octane blenders so that standard GC analyses are poor predictors of blend quality. Engine rating is the only way of measuring olefin octane number nonlinearity. It is thus not possible to rapidly assess the quality of the product obtained from an olefin-producing

  3. Ionic liquids for separation of olefin-paraffin mixtures

    Science.gov (United States)

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2013-09-17

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  4. Allene or alkyne treatment of olefin conversion catalysts

    International Nuclear Information System (INIS)

    Banks, R.L.

    1986-01-01

    This patent describes a disproportionation process which comprises contacting at least one olefin from the group consisting of: acyclic mono- and polyenes having at least 3 up to 10 carbon atoms per molecule, and cycloalkyl and aryl derivatives thereof; cyclic mono- and polyenes having at least 4 to 10 carbon atoms per molecule, and alkyl and aryl derivatives thereof; mixtures of two or more of the above olefins; and mixtures of ethylene with one or more of the above olefins capable of undergoing disproportionation with a tungsten oxide on silica disproportionation catalyst system under disproportionation conditions, the improvement comprising contacting the catalyst with an activating amount of at least one alkyne conforming to the formula: R-C=C-R wherein each R is independently H or a C/sub 1/-C/sub 6/ carbon radical per mole of tungsten oxide

  5. Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

    Energy Technology Data Exchange (ETDEWEB)

    Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)

    1995-12-31

    A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

  6. Olefination reactions of phosphorus-stabilized carbon nucleophiles.

    Science.gov (United States)

    Gu, Yonghong; Tian, Shi-Kai

    2012-01-01

    A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

  7. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

    2014-01-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  8. Methylenation of perfluoroalkyl ketones using a Peterson olefination approach.

    Science.gov (United States)

    Hamlin, Trevor A; Kelly, Christopher B; Cywar, Robin M; Leadbeater, Nicholas E

    2014-02-07

    An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3-trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl substituents and is easily scaled up. The alkenes prepared can be readily transformed into a variety of other perfluoroalkyl-containing compounds.

  9. Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

    Science.gov (United States)

    Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

    2010-03-20

    We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

  10. Modelling the Load Torques of Electric Drive for Polymerization Process

    Directory of Open Access Journals (Sweden)

    Andrzej Popenda

    2007-01-01

    Full Text Available The problems of mathematical modelling the load torques on shaft of driving motor designed for applications in polymerization reactors are presented in the paper. The real load of polymerization drive is determined as a function of angular velocity. Mentioned function results from friction in roll-formed slide bearing as well as from friction of ethylene molecules with mixer arms in polymerization reactor chamber. Application of mathematical formulas concerning the centrifugal ventilator is proposed to describe the mixer in reactor chamber. The analytical formulas describing the real loads of polymerization drive are applied in mathematical modelling the power unit of polymerization reactor with specially designed induction motor. The numerical analysis of transient states was made on the basis of formulated mathematical model. Examples of transient responses and trajectories resulting from analysis are presented in the paper.

  11. Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

    Science.gov (United States)

    dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

    2015-03-01

    Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

    Science.gov (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

    2017-04-07

    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  13. Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization

    KAUST Repository

    Jian, Zhongbao

    2016-10-14

    A single-step route to telechelic polyethylene (PE) is enabled by selective insertion polymerization. PdII-catalyzed copolymerization of ethylene and 2-vinylfuran (VF) generates α,ω-di-furan telechelic polyethylene. Orthogonally reactive exclusively in-chain anhydride groups are formed by terpolymerization with carbic anhydride. Combined experimental and theoretical DFT studies reveal the key for this direct approach to telechelics to be a match of the comonomers’ different electronics and bulk. Identified essential features of the comonomer are that it is an electron-rich olefin that forms an insertion product stabilized by an additional interaction, namely a π–η3 interaction for the case of VF.

  14. Polyolefin polymerization catalyst and method of production use

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, K.E.; Hawley, G.R.; Godbehere, D.W.

    1991-01-29

    This patent describes a process for the preparation of a catalyst suitable for the polymerization of an {alpha}-olefin. It comprises: forming a first component by reacting reactants comprising a magnesium dihalide, a phenol, an alkylbenzoate, and a titanium tetrahydrocarbyloxide; reacting the first component with an organoaluminum halide comprising ethylaluminum sesquichloride to produce a solid product; and then contacting the resulting solid product with an activating liquid comprising titanium tetrachloride and trichlorosilane in a confined zone under pressure of at least about 70 psi.

  15. New models of radical polymerization with branching and scission predicting molecular weight distribution in tubular and series of continuous stirred tank reactors allowing for multiradicals and gelation

    NARCIS (Netherlands)

    Yaghini, N.; Iedema, P.D.

    2015-01-01

    Modeling of the mol. wt. distribution (MWD) of low-​d. Polyethylene (ldPE) has been carried out for a tubular reactor under realistic non-​isothermal conditions and for a series of CSTR's. The model allows for the existence of multiradicals and the occurrence of gelation. The deterministic model is

  16. Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae

    NARCIS (Netherlands)

    Jongedijk, E.J.; Cankar, K.; Ranzijn, J.; Krol, van der A.R.; Bouwmeester, H.J.; Beekwilder, M.J.

    2015-01-01

    Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a

  17. Methanol conversion to lower olefins over RHO type zeolite

    KAUST Repository

    Masih, Dilshad; Imai, Hiroyuki; Yokoi, Toshiyuki; Kondo, Junkonomura; Tatsumi, Takashi

    2013-01-01

    Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET

  18. Ozonolysis of Model Olefins-Efficiency of Antiozonants

    NARCIS (Netherlands)

    Huntink, N.M.; Datta, Rabin; Talma, Auke; Noordermeer, Jacobus W.M.

    2006-01-01

    In this study, the efficiency of several potential long lasting antiozonants was studied by ozonolysis of model olefins. 2-Methyl-2-pentene was selected as a model for natural rubber (NR) and 5-phenyl-2-hexene as a model for styrene butadiene rubber (SBR). A comparison was made between the

  19. The asymmetric Schrock olefin metathesis catalysts. A computational study

    NARCIS (Netherlands)

    Goumans, T.P.M.; Ehlers, A.W.; Lammertsma, K.

    2005-01-01

    The mechanism of the transition metal catalyzed olefin metathesis reaction with the Schrock catalyst is investigated with pure (BP86) and hybrid (B3LYP) density functional theory. On the free-energy surface there is no adduct between ethylene and model catalyst (MeO)

  20. Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Čejka, Jiří

    2013-01-01

    Roč. 257, 21-22 (2013), s. 3107-3124 ISSN 0010-8545 R&D Projects: GA AV ČR IAA400400805; GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Olefin metathesis * mesoporous molecular sieves * Heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.098, year: 2013

  1. Radiation-induced copolymerization of hexafluoroacetone with α-olefins

    International Nuclear Information System (INIS)

    Matsuda, O.; Watanabe, S.; Okamoto, J.; Machi, S.; Tabata, Y.

    1977-01-01

    The copolymerization of hexafluoroacetone with higher α-olefins above butene, such as 1-pentene (I), 1-hexene (II), 1-octene (III), 2-methyl-1-butene (IV), 2-methyl-1-pentene (V), 3-methyl-1-butene (VI), and 4-methyl-1-pentene (VII) was studied at relatively low temperatures by γ-ray irradiation. Copolymerization of II, IV, V, and VII with hexafluoroacetone was found to scarcely take place at -78 0 C in bulk, but the addition of trichlorotrifluoroethane in amounts to yield equimolar mixtures resulted in conversion of 15.7 percent for IV and of 2.1 to 4.0 percent for the other α-olefins. Higher conversion of V at -78 0 C than at 0 0 C suggest that copolymerization may take place via an ionic mechanism. The effects of various additives on the copolymerization are reported. Infrared spectral studies indicated that the double bond of the α-olefins is opened to form a polymer. The C--O double bond of the hexafluoroacetone and the α-olefin double bond are opened to form the copolymer

  2. Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio

    2011-01-01

    A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

  3. Olefination of carbonyl compounds: modern and classical methods

    Energy Technology Data Exchange (ETDEWEB)

    Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2004-10-31

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  4. Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

    Science.gov (United States)

    Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

    2017-08-30

    Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

  5. Olefination of carbonyl compounds: modern and classical methods

    Science.gov (United States)

    Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.

    2004-10-01

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  6. Access to Functionalized Steroid Side Chains via Modified Julia Olefination

    Science.gov (United States)

    Izgu, Enver Cagri; Burns, Aaron C.; Hoye, Thomas R.

    2011-01-01

    Various functionalized steroidal side chains were conveniently accessed by a modified Julia olefination strategy using a common sulfone donor and an appropriate α-branched aldehyde acceptor. For the coupling of these hindered classes of reaction partners (and in contrast to typically observed trends), the benzothiazolyl(BT)-sulfone anion gave superior outcomes compared to the phenyltetrazolyl(PT)-sulfone anion. PMID:21244047

  7. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

    2015-01-01

    microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  8. Reactions of rhodium(I) carbonyl chloride with olefins

    International Nuclear Information System (INIS)

    Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.

    1987-01-01

    The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

  9. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1988-01-01

    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  10. Synthesis of polyalkylacrylate nanolatexes by microemulsion polymerization method

    Directory of Open Access Journals (Sweden)

    A.M. Al-Sabagh

    2012-12-01

    Full Text Available The paper concerns with the radical polymerization of [octadecyl acrylate (ODA, isooctyl acrylate (iso-OA and α-olefins 1-Octene (n-O]. These microemulsions were stabilized by sodium dodecyl sulfate (SDS and initiated by water-soluble initiator potassium persulfate (KPS. The nanolatex particle sizes were determined by transmission electron microscope (TEM. They were situated between 10 and 100 nm. The microstructures were confirmed by FT-IR and molecular weights determined by Gel permeation chromatography (GPC. The obtained M. wt. were (≈70 × 103, 101 × 103 and 153 × 103 g/mol. The polydispersity, molecular weights, and particle sizes were discussed in the light of micelle formation and shape of the alkyl group via emulsion polymerization.

  11. Propene bulk polymerization kinetics: Role of prepolymerization and hydrogen

    NARCIS (Netherlands)

    Pater, J.T.M.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2003-01-01

    An experimental setup for the polymerization of liquid propylene was used to carry out main polymerizations with and without a prepolymerization step. Two types of prepolymerization are introduced: at a constant temperature and at rapidly increasing reactor temperatures. With the present catalyst

  12. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    Science.gov (United States)

    Schrodi, Yann [Agoura Hills, CA

    2011-11-29

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  13. Ternary catalyst-olefin-hydroperoxide complexes and their contribution to epoxidation

    International Nuclear Information System (INIS)

    Svitych, R.B.; Rzhevskaya, N.N.; Buchachenko, A.L.; Yablonskij, O.P.; Petukhov, A.A.; Belyaev, V.A.

    1976-01-01

    Electron and NMR spectroscopy have been used for studying the complex formation of catalysts (Mo 5+ , Mn 2+ , Co 2+ ) in double and triple systems: metal-olefin and metal-olefin-hydroperoxide. It has been established that ions of metals form complexes with olefins in the first sphere. The formation has been proved of ternary complexes metal-olefin-hydroperoxide. The structure of the complexes has been proposed with olefins in the first and hydroperoxide in the second sphere of the metal ion. The structure explains known kinetic regularities of epoxydation and the mechanism of the formation of final products, oxide and alcohol. It has been shown that the best catalysts for epoxydation of olefins with hydroperoxides must be the compounds of the metals with an electron state of ion d 0 [ru

  14. Physical properties of metallocenes propene-higher α-olefins copolymers

    International Nuclear Information System (INIS)

    Lovisi, Humberto; Santa Maria, Luiz Claudio de; Coutinho, Fernanda M.B.

    2001-01-01

    In this work, new copolymers of propene/1-hexene (PHC) and propene/1-octene (POC) were synthesized by using a highly iso specific metallocenes catalyst system based on rac-Me 2 Si(2-ethyl,4-phenyl,1-indenyl) 2 ZrCl 2 , in the homogeneous and heterogeneous forms, methylaluminoxane (MAO) activated. An investigation about the copolymerization of propene with 1-hexene and 1-octene using this catalyst system illustrates the potential for the tailoring of propene/higher α-olefin copolymers with controlled thermal and mechanical properties by varying the comonomer concentration in the polymerization feed. Both catalyst systems showed high activity and produced random copolymers with very low or no detectable crystallinity. It was observed that properties such as enthalpy of crystallization (ΔHc), crystallization temperature (Tc), melting temperature (Tm), glass transition temperature (Tg) and elastic modulus (E') decreased in a linear pattern with increasing comonomer content in the copolymer. The effect of the short chain branch length was also investigated and it was observed that, compared to 1-hexene, much less 1-octene was necessary to disrupt the crystalline structure and impart rubbery behaviour to the copolymers. (author)

  15. A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

    KAUST Repository

    Leitgeb, Anita; Abbas, Mudassar E.; Fischer, Roland C.; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

    2012-01-01

    An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

  16. Pd(II)-Catalyzed Olefination of sp3 C–H Bonds

    Science.gov (United States)

    Wasa, Masayuki; Engle, Keary M.; Yu, Jin-Quan

    2010-01-01

    The first Pd(II)-catalyzed sp3 C–H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding γ lactams. Notably, this method was effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C–H olefination of cyclopropane substrates. PMID:20187642

  17. Direct olefination of fluorinated benzothiadiazoles: a new entry to optoelectronic materials.

    Science.gov (United States)

    Xiao, Yu-Lan; Zhang, Bo; He, Chun-Yang; Zhang, Xingang

    2014-04-14

    Fluorinated olefin-containing benzothiadiazoles have important applications in optoelectronic materials. Herein, we reported the direct olefination of fluorinated benzothiadiazoles, as catalyzed by palladium. The reaction proceeds under mild reaction conditions and shows high functional-group compatibility. A preliminary study of the properties of the resulting symmetrical and unsymmetrical olefin-containing fluorinated benzothiadiazoles in red-light-emitting dyes has also been conducted. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The activation mechanism of Fe-based olefin metathesis catalysts

    KAUST Repository

    Poater, Albert

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

  19. The activation mechanism of Fe-based olefin metathesis catalysts

    KAUST Repository

    Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

    2014-01-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

  20. Methanol conversion to lower olefins over RHO type zeolite

    KAUST Repository

    Masih, Dilshad

    2013-07-01

    Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET specific surface area (812 m2 g-1), micropore volume (0.429 cm3 g-1), and acid amount (2.53 mmol g-1). Scanning electron microscopy observations showed small crystallites of about 1 μm. The zeolite was active for MTO reaction with 100% methanol conversions at 623-723 K, whereas selectivity to lower olefins changed with time. © 2013 Elsevier B.V.

  1. Methyltrioxorhenium as catalyst of a novel aldehyde olefination

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, W.A. (Technische Univ. Muenchen, Garching (Germany). Anorganisch-Chemisches Inst.); Wang Mei (Academia Sinica, Dalian Inst. of Chemical Physics (China))

    1991-12-01

    From aldehydes or cyclic ketones, diazoalkanes, and teritiary phosphanes, olefins may be prepared with MTO as catalyst. In particular, diazoacetates and -malonates (R{sup 2}, R{sup 3} = H, CO{sub 2}Et, or 2 x CO{sub 2}Me) can be transformed into olefins with aliphatic and aromatic aldehydes (R{sup 1} = iPr, trans-PhCH=CH, Ph, 4-NO{sub 2}C{sub 6}H{sub 4}, etc.). Readily accessible starting materials, easy handling, mild reaction conditions, and good yields characterize the new synthesis method. (R' = Ph, 3-C{sub 6}H{sub 4}SO{sub 3}Na, nBu.) (orig.).

  2. A three-membered ring approach to carbonyl olefination.

    Science.gov (United States)

    Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno

    2017-10-23

    The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

  3. Retrofit with membrane the Paraffin/Olefin separation

    Energy Technology Data Exchange (ETDEWEB)

    Motelica, A.; Bruinsma, O.S.L.; Kreiter, R.; Den Exter, M.J.; Vente, J.F. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

    2012-10-15

    Olefins, such as ethylene, propylene, and butadiene, are among the most produced intermediates in petrochemical industry. They are produced from a wide range of hydrocarbon feedstocks (ethane, propane, butane, naphtha, gas oil) via a cracking process. The last step in this process is the separation of olefins from other hydrocarbons, which is traditionally performed with distillation. As the physicochemical properties, such as volatility and boiling point, of the compounds are very similar, the purification becomes capital and energy intensive. For example, the top of an ethylene/ethane distillation column needs to be chilled to -30C and this requires large amount of electric energy consumption. The separation of butadiene from the C4-fraction is performed with the aid of an additional solvent. This solvent has to be regenerated at the cost of additional high temperature steam. To overcome these separation disadvantages of olefin/paraffin separation, different separation methods have been investigated and proposed in recent years. Suggested options are based on better heat integration of the overall process, or on novel separation systems such as Heat Integrated Distillation Columns, membrane separation, adsorption-desorption systems or on hybrid separation methods, for example, distillation combined with membrane separation.

  4. Developing linear-alpha-olefins technology. From laboratory to a commercial plant

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Woehl, A.; Mueller, W.; Boelt, H. [Linde AG, Pullach (Germany)

    2011-07-01

    Linear {alpha}-Olefins (LAOs) are used in several applications in chemical industry. Together with SABIC (Saudi Basic Industries Corporation) Linde jointly developed the {alpha}-SABLIN technology for a full range LAO plant as well as a 1-Hexene selective ''On Purpose'' technology (LAO OP) to cover the rapidly increasing demand for this specific comonomer. The {alpha}-SABLIN as well as the OP technology are both homogenously catalyzed systems. This is raising special challenges concerning process and reactor design compared to much more established heterogeneous systems in chemical industry. E.g., the reactor concept is a bubble-column which allows efficient mixing as well as cooling of the reaction mixture. The development of the process was based on laboratory experiments which - based on an initial conceptual design for a large scale technical process - were first transformed into a pilot device before the commercial plant was designed, engineered and successfully started up and declared as commercialized. Today the {alpha}-SABLIN technology is the only LAO technology with a commercial reference which is free for licensing. A lot of experience and knowledge from the {alpha}-SABLIN development and commercial operation was gained. Although newly developed OP technology is based on a different catalytic system, this experience is now utilized and transformed within the commercialization of this new technological development. (orig.)

  5. Life cycle assessment of energy consumption and GHG emissions of olefins production from alternative resources in China

    International Nuclear Information System (INIS)

    Xiang, Dong; Yang, Siyu; Li, Xiuxi; Qian, Yu

    2015-01-01

    Highlights: • Conduct a life cycle energy use and GHG emissions of olefins production processes. • Analyse effects of carbon capture and efficiency on alternative olefins production. • Analyse life cycle performance of Chinese olefins industry in three key periods. • Present the advantages and challenges of alternative olefins routes. - Abstract: Olefins are important platform chemicals widely used in industry. In terms of the short supply of oil resources, natural gas and coal are two significant alternative feedstocks. In this paper, energy consumption and GHG emissions of olefins production are analysed with life cycle assessment methods. Results showed the energy consumption and GHG emissions of natural gas-to-olefins are roughly equivalent to those of oil-to-olefins, while coal-to-olefins suffers from higher energy consumption and serious GHG emissions, including 5793 kg eq. CO 2 /t olefins of direct emissions and 5714 kg eq. CO 2 /t olefins of indirect emissions. To address the problem, the effect of carbon capture on coal-to-olefins is investigated. In comprehensive consideration of energy utilization, environmental impact, and economic benefit, the coal-to-olefins with 80% CO 2 capture of the direct emissions is found to be an appropriate choice. With this carbon capture configuration, the direct emissions of the coal-to-olefins are reduced to 1161 kg eq. CO 2 /t olefins. However, the indirect emissions are still not captured, which should be strictly monitored and significantly reduced. Finally, a scenario analysis is conducted to estimate resource utilization and GHG emissions of olefins production of China in 2020. Several suggestions are also proposed for policy making on the sustainable development of olefins industry

  6. Conceptual design and system analysis of a poly-generation system for power and olefin production from natural gas

    International Nuclear Information System (INIS)

    Qian Yu; Liu Jingyao; Huang Zhixian; Kraslawski, Andrzej; Cui Jian; Huang Yinlun

    2009-01-01

    In this paper, a novel poly-generation system for olefin and power production from natural gas is proposed, which integrates hydrocarbon production and the combined cycle power generation. Economic and technological evaluation based on the internal rate of return (IRR) and exergy efficiency is performed. The energy integration results in the proposed poly-generation system for simultaneous production of chemical products (ethylene and propylene) and electricity being more thermodynamically efficient and economically viable than single purpose power generation and chemical products production plants. IRR and exergy efficiency of the proposed poly-generation system are higher than that of natural gas methanol to olefin (NGMTO) system, 18.9% and 49.9%, respectively. The biggest exergy destruction segments, their causes, and possible measures for improvement are investigated simulation and thermodynamic analysis. To analyze the effect of unreacted syngas recycle on the exergy efficiency and economic gains from the proposed poly-generation system, its thermoeconomic optimization model is built by combining economic with thermodynamic analysis. Optimization analysis shows that when 78% of the unreacted syngas is recycled back to the reactor in the methanol synthesization process, the thermoeconomic performance of the poly-generation system is at its optimum.

  7. Estimation of the Polymerization Rate of Liquid Propylene Using Adiabatic Reaction Calorimetry and Reaction Dilatometry

    NARCIS (Netherlands)

    Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter

    2007-01-01

    The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization

  8. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

    Science.gov (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

    2015-08-21

    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  9. "Click" i polymerer 2

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  10. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  11. 76 FR 5319 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

    Science.gov (United States)

    2011-01-31

    ... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... gasoline. This proposed rule will provide flexibility to the regulated community by allowing an additional... A. Alternative Test Method for Olefins in Gasoline III. Statutory and Executive Order Reviews A...

  12. 76 FR 65382 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

    Science.gov (United States)

    2011-10-21

    ... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... gasoline. This final rule will provide flexibility to the regulated community by allowing an additional... Method for Olefins in Gasoline III. Statutory and Executive Order Reviews A. Executive Order 12866...

  13. Oxidative cracking of n-hexane: a catalytic pathway to olefins

    NARCIS (Netherlands)

    Boyadjian, C.A.

    2010-01-01

    Steam cracking, the major, current existing route for light olefin production, is the most energy consuming process in the chemical industry. The need for an energy efficient processes, urged substantial research work for the development of new catalytic technologies for light olefin production.

  14. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  15. Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

    Science.gov (United States)

    Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

    2017-02-01

    A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

    Science.gov (United States)

    Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su

    2016-11-18

    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF 3 -substituted allylic carbonate is described. This reaction provides direct access to linear CF 3 -allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF 3 -allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

  17. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir

    2015-11-28

    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

  18. Adsorption heats of olefins on supported MoO3/Al2O3 catalists

    International Nuclear Information System (INIS)

    Grinev, V.E.; Madden, M.; Khalit, V.A.; Aptekar', E.L.; Aldag, A.; Krylov, O.V.

    1983-01-01

    Adsorption heats of C 2 H 4 , C 3 H 6 and C 4 H 8 on supported MoO 3 /Al 2 O 3 catalysts containing 6, 10 and 15 wt. % of MoO 3 at 25, 77 and 195 deg are determimed. Adsorption heat of an olefin increases with a growing length of its carbonic chain. The number of adsorbed olefin molecules grows with an increase in the MoO 3 concentration, while initial adsorption heats decrease. The number of adsorbed olefins is proportional to mean rate of molybdenum reduction in catalysts. Adsorption heats of oxygen on the surface of the catalysts with preliminarily adsorbed olefins are determined. It is shown that adsorption of oxygen and olefins proceeeds both on the same and on different centres of the surface. Mechanisms of surface interactions are discussed

  19. Hydroformylation of olefins and reductive carbonylation of aryl halides with syngas formed ex situ from dehydrogenative decarbonylation of hexane-1,6-diol

    DEFF Research Database (Denmark)

    Christensen, Stig Holden; Olsen, Esben Paul Krogh; Rosenbaum, Jascha

    2014-01-01

    A variety of primary alcohols have been investigated as convenient substrates for the ex situ delivery of carbon monoxide and molecular hydrogen in a two-chamber reactor. The gaseous mixture is liberated in one chamber by an iridium-catalysed dehydrogenative decarbonylation of the alcohol...... and then consumed in the other chamber in either a rhodium-catalysed hydroformylation of olefins or a palladium-catalysed reductive carbonylation of aryl halides. Hexane-1,6-diol was found to be the optimum alcohol for both reactions where moderate to excellent yields were obtained of the product aldehydes...

  20. Synthesis of thermoplastic poly(ester-olefin elastomers

    Directory of Open Access Journals (Sweden)

    Tanasijević Branka

    2004-01-01

    Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

  1. Transmissive Olefination Route to Putative “Morinol I” Lignans

    Science.gov (United States)

    Yao, Lihua; Pitta, Bhaskar; Ravikumar, P. C.; Purzycki, Matthew; Fleming, Fraser F.

    2012-01-01

    A series of morinol-type lignans were rapidly assembled using a Grignard-based transmissive olefination. In combination with palladium-catalyzed arylations, the strategy provides stereoselective access to (7Z, 7′E), (7E, 7′E), (7E, 7′Z) morinol diastereomers and the (7Z, 8′E) and (7E, 8′E) conjugated analogs. Critical for the E/Z-stereoselectivity is a new, general method for converting alkenenitriles to alkenemethanols that circumvents the enal E/Z isomerization commonly encountered during conventional i-Bu2AlH reduction. PMID:22432777

  2. Radiation chemical addition of dimethylformamide to α-olefins

    International Nuclear Information System (INIS)

    Dederichs, B.; Saus, A.; Lennertz, A.M.

    1977-10-01

    With n-hexene-1, n-octene-1 and n-decene-1 the radiation-initiated addition of demethyl formamide to α-olefins is described for the fist time. N,N-dimethyl alkane carbonic acid amides and N-methyl-N-alkyl formamides are formed in a ratio of about 50:50. The addition reaction is investigated in depencence of a solvent, of the ratio of the reaction, temperature, reaction time and dose rate. Mechanistic considerations are performed by radiolysis experiments of dimethyl formamide. (orig.) [de

  3. A Generic Model for Prediction of Separation Performance of Olefin/Paraffin Mixture by Glassy Polymer Membranes

    Directory of Open Access Journals (Sweden)

    A.A. Ghoreyshi

    2008-02-01

    Full Text Available The separation of olefin/paraffin mixtures is an important process in petrochemical industries, which is traditionally performed by low temperature distillation with a high-energy consumption, or complex extractive distillationand adsorption techniques. Membrane separation process is emerging as an alternative for traditional separation processes with respect to low energy and simple operation. Investigations made by various researchers on polymeric membranes it is found that special glassy polymers render them as suitable materials for olefin/paraffin mixture separation. In this regard, having some knowledge on the possible transport mechanism of these processes would play a significant role in their design and applications. In this study, separation behavior of olefin/paraffin mixtures through glassy polymers was modeled by three different approaches: the so-called dual transport model, the basic adsorption-diffusion theory and the general Maxwell-Stefan formulation. The systems chosen to validate the developed transport models are separation of ethane-ethylene mixture by 6FDA-6FpDA polyimide membrane and propane-propylene mixture by 6FDA-TrMPD polyimide membrane for which the individual sorption and permeation data are available in the literature. Acritical examination of dual transport model shows that this model fails clearly to predict even the proper trend for selectivities. The adjustment of pemeabilities by accounting for the contribution of non-selective bulk flow in the transport model introduced no improvement in the predictability of the model. The modeling results based on the basic adsorption-diffusion theory revealed that in this approach only using mixed permeability data, an acceptable result is attainable which fades out the advantages of predictibility of multicomponent separation performance from pure component data. Finally, the results obtained from the model developed based on Maxwell-Stefan formulation approach show a

  4. Separation of Olefin/Paraffin Mixtures with Carrier Facilitated Membrane Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Merkel, T.C.; Blanc, R.; Zeid, J.; Suwarlim, A.; Firat, B.; Wijmans, H.; Asaro, M. (SRI); Greene, M.(Lummus)

    2007-03-12

    This document describes the results of a DOE funded joint effort of Membrane Technology and Research Inc. (MTR), SRI International (SRI), and ABB Lummus (ABB) to develop facilitated transport membranes for olefin/paraffin separations. Currently, olefin/paraffin separation is done by distillation—an extremely energy-intensive process because of the low relative volatilities of olefins and paraffins. If facilitated transport membranes could be successfully commercialized, the potential energy savings achievable with this membrane technology are estimated to be 48 trillion Btu per year by the year 2020. We discovered in this work that silver salt-based facilitated transport membranes are not stable even in the presence of ideal olefin/paraffin mixtures. This decline in membrane performance appears to be caused by a previously unrecognized phenomenon that we have named olefin conditioning. As the name implies, this mechanism of performance degradation becomes operative once a membrane starts permeating olefins. This project is the first study to identify olefin conditioning as a significant factor impacting the performance of facilitated olefin transport membranes. To date, we have not identified an effective strategy to mitigate the impact of olefin conditioning. other than running at low temperatures or with low olefin feed pressures. In our opinion, this issue must be addressed before further development of facilitated olefin transport membranes can proceed. In addition to olefin conditioning, traditional carrier poisoning challenges must also be overcome. Light, hydrogen, hydrogen sulfide, and acetylene exposure adversely affect membrane performance through unwanted reaction with silver ions. Harsh poisoning tests with these species showed useful membrane lifetimes of only one week. These tests demonstrate a need to improve the stability of the olefin complexing agent to develop membranes with lifetimes satisfactory for commercial application. A successful effort

  5. Experimental investigation into fast pyrolysis of biomass using an entrained flow reactor

    Science.gov (United States)

    Bohn, M.; Benham, C.

    1981-02-01

    Pyrolysis experiments were performed with steam as a carrier gas and two different feedstocks - wheat straw and powdered material derived from municipal solid waste (ECO-II TM). Reactor wall temperature was varied from 7000 to 1400 C. Gas composition data from the ECO-II tests were comparable to previously reported data but ethylene yield appeared to vary with reactor wall temperature and residence time. The important conclusion from the wheat straw tests is that olefin yields are about one half that obtained from ECO-II. Evidence was found that high olefin yields from ECO-II are due to the presence of plastics in the feedstock.

  6. Heterogeneous catalytic epoxidation of C/sub 8/-C/sub 1/4 olefins by tert. -butyl hydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Dahlmann, J; Hoeft, E; Boeden, H F; Dilcher, H

    1979-09-01

    Heterogeneous catalytic epoxidation of C/sub 8/-C/sub 14/ olefins by tert.-butyl hydroperoxide (TBHP) avoids large product losses to side reactions, associated with the use of homogeneous catalysts, such as Mo(CO)/sub 6/. With an unsupported MoO/sub 3/ catalyst, 48% TBHP conversion was achieved after one hour (vs. 24% after two hours for Mo(CO)/sub 6/) in 1-octene epoxidation at 90/sup 0/C and 2:1:3 octene/TBHP/toluene (solvent) molar ratio. The use of silica-supported catalysts, such as Bi/sub 9/PMo/sub 12/O/sub 52//30% SiO/sub 2/ (ACN, an industrial catalyst for acrylonitrile), MoO/sub 3//30% SiO/sub 2/ (D-1), 3MoO/sub 3/-Sb/sub 2/O/sub 5//50% SiO/sub 2/ (D-2), or 2MoO/sub 3/-As/sub 2/O/sub 3//50% SiO/sub 2/ (D-3) increased the conversion to 68, 67, 70, and 73%, respectively, with up to 95-99% selectivities for the epoxide. Under optimum conditions of 3:1 olefin/TBHP, 110/sup 0/C, and 2-4 g/l. catalyst, TBHP conversions in epoxidation of 1-tetradecene in a batch reactor over ACN, D-2, and D-3 after two hours were 94, 88, and 91%, respectively, but they decreased to 52, 78, and 79%, respectively, after five two-hour operating cycles. In epoxidation of 1-decene or a mixture of decene isomers (a model for the industrial olefin mixtures obtained by paraffin dehydrogenation via the Parex process) carried out in a continuous flow reactor over the D-3 catalyst at 90/sup 0/-110/sup 0/C, stable catalytic activities with TBHP conversions of approx. 90% and 90-96% selectivities for epoxides were observed for about 900 hr.

  7. New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins

    Energy Technology Data Exchange (ETDEWEB)

    Frolov, V.M.; Parenago, O.P.; Shuikina, L.P.

    1978-12-01

    New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins were obtained by reacting aqueous palladium, rhodium, or nickel chloride (0.005-0.05 mole/l.) at 50/sup 0/C, in an argon atmosphere with chelating nitrogen compounds, i.e., o-phenanthroline, ..cap alpha..,..cap alpha..'-dipyridyl, sodium ethylenediaminetetracetate, morpholine, branched polyethylene imines, or amino acids such as glycine, ..cap alpha..-alanine, ..beta..-phenyl-..cap alpha..-alanine, tyrosine, or histidine, and treating the complexes so obtained with sodium borohydride at 1:1-1:5 NaBH/sub 4/-metal ratios, in an aqueous medium. Palladium-based complexes showed the highest activities (20-98Vertical Bar3< conversion) and selectivities (98-100Vertical Bar3<) in heterogeneous hydrogenation of cyclopentadiene, butadiene, 1-hexyne, 1,3-cyclohexadiene, or 1,3-cyclooctadiene at 20/sup 0/-60/sup 0/C and 0.5-15 atm hydrogen, carried out in a kinetic circulation reactor or a metallic autoclave. Thus, a catalytic system based on PdCl/sub 2/ and ..beta..-phenyl-..cap alpha..-alanine converted 98Vertical Bar3< of cyclopentadiene to cyclopentene with 99Vertical Bar3< selectivity. The palladium-based catalyst did not deactivate on the contact with air.

  8. Study of Syngas Conversion to Light Olefins by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Hossein Atashi

    2013-01-01

    Full Text Available The effect of adding MgO to a precipitated iron-cobalt-manganese based Fischer-Tropsch synthesis (FTS catalyst was investigated via response surface methodology. The catalytic performance of the catalysts was examined in a fixed bed microreactor at a total pressure of 1–7 bar, temperature of 280–380°C, MgO content of 5–25% and using a syngas having a H2 to CO ratio equal to 2.The dependence of the activity and product distribution on MgO content, temperature, and pressure was successfully correlated via full quadratic second-order polynomial equations. The statistical analysis and response surface demonstrations indicated that MgO significantly influences the CO conversion and chain growth probability as well as ethane, propane, propylene, butylene selectivity, and alkene/alkane ratio. A strong interaction between variables was also evidenced in some cases. The decreasing effect of pressure on alkene to alkane ratio is investigated through olefin readsorption effects and CO hydrogenation kinetics. Finally, a multiobjective optimization procedure was employed to calculate the best amount of MgO content in different reactor conditions.

  9. Nanodispersed Suspensions of Zeolite Catalysts for Converting Dimethyl Ether into Olefins

    Science.gov (United States)

    Kolesnichenko, N. V.; Yashina, O. V.; Ezhova, N. N.; Bondarenko, G. N.; Khadzhiev, S. N.

    2018-01-01

    Nanodispersed suspensions that are effective in DME conversion and stable in the reaction zone in a three-phase system (slurry reactor) are obtained from MFI zeolite commercial samples (TsVM, IK-17-1, and CBV) in liquid media via ultrasonic treatment (UST). It is found that the dispersion medium, in which ultrasound affects zeolite commercial sample, has a large influence on particle size in the suspension. UST in the aqueous medium produces zeolite nanoparticles smaller than 50 nm, while larger particles of MFI zeolite samples form in silicone or hydrocarbon oils. Spectral and adsorption data show that when zeolites undergo UST in an aqueous medium, the acid sites are redistributed on the zeolite surface and the specific surface area of the mesopores increases. Preliminary UST in aqueous media of zeolite commercial samples (TsVM, IK-17-1, and CBV) affects the catalytic properties of MFI zeolite nanodispersed suspensions. The selectivity of samples when paraffins and olefins form is largely due to superacid sites consisting of OH groups of hydroxonium ion H3O+.

  10. Hydroxycarbonylation of olefins and alcohols in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Eliseev, O.L.; Bondarenko, T.N.; Stepin, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2006-07-01

    Palladium-catalysed hydroxycarbonylation of olefins and alcohols proceeds in ionic liquid media. Terminal and internal olefins, cyclohexene, styrene, methanol, ethanol, n-butanol, cyclohexanol, benzyl alcohol and 1-phenylethanol were tested as substrates for the reaction. A number of molten salts were applied as a reaction medium and tetrabutylammonium bromide (m.p. 103 C) seemed to be the best. Carbon monoxide pressure of 2 MPa and reaction temperature of 110 C are suitable conditions to furnish the reaction in 2 hours in the presence of palladium acetate as a precursor. Triphenylphosphine added as a ligand reduces reaction rate. The critical role of counter anion in molten salt was also recognised. Yield of acids decreased in the order: Br{sup -} > Cl{sup -} > BF{sub 4} {approx}PF{sub 6}{sup -}. A two-route reaction scheme is proposed to explain the regularities of styrene and 1-phenylethanol hydroxycarbonylation. The catalytic system can be used repeatedly by simple extraction of products with diethyl ether. Nine cycles were carried out without loss of activity. (orig.)

  11. Direct, enantioselective α-alkylation of aldehydes using simple olefins.

    Science.gov (United States)

    Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

    2017-11-01

    Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

  12. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  13. How much life is left in your olefin unit

    International Nuclear Information System (INIS)

    Baas, J.; Warner, R.

    1992-01-01

    Highly attractive economics in the olefin industry has justified increasing capacity via plant expansion and using aging olefin units beyond expected limitations. If these existing units are to operate well beyond their design life, what type of analysis and information is necessary to make this decision? What technologies or methods should be used for continued safe and controlled operation of these not so new units. This paper reports that the plant's mechanical integrity is the focal point of this analysis and decision-making method. Plant life expectancy study (PLES) looks at an operating plant's mechanical integrity from several vantage points. Four basic principles, such as plant history, process upsets and operating records, assessment of plant fires, and how to conduct records, assessment of plant fires, and how to conduct inspection and testing, provide the basis of how well a plant has been operated and maintained. Furthermore, the analysis includes a critical component inventory. These items address additional potential-failure causes, such as creep, fatigue, toughness, corrosion, erosion and carburization/oxidation

  14. Techno-economic analysis and comparison of coal based olefins processes

    International Nuclear Information System (INIS)

    Xiang, Dong; Yang, Siyu; Qian, Yu

    2016-01-01

    Highlights: • The coal based Fischer–Tropsch-to-olefins (CFTO) process is proposed and analyzed. • The CFTO suffers from lower energy efficiency and serious CO 2 emissions. • Approaches for improving techno-economic performance of the CFTO are obtained. - Abstract: Traditional olefins production is heavily dependent on oil. In the background of the scarcity of oil and richness of coal in China, olefins production from coal has been attracting more attention of the chemical process industry. The first coal based methanol-to-olefins (CMTO) plant has been commercialized in China. For shorter process route and lower capital cost, Fischer–Fropsch has been put forward in the last few years. The coal based Fischer–Tropsch-to-olefins (CFTO) process is designed in this paper and then its techno-economic and environmental performance was detailed studied in this paper, in comparison with the CMTO. Results show that at the present olefins selectivity, the CFTO suffers from relative lower energy efficiency and higher CO 2 emissions. In economic aspect, the capital investment and product cost of the CFTO are roughly equivalent to that of the CMTO. Although the conversion route of the CFTO is shorter, its techno-economic performance is still inferior to that of the CMTO. It is also found that increase of olefins selectivity by cracking oil or decrease of CO 2 selectivity by improving catalyst could significantly improve the performance of the CFTO.

  15. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser

    2016-10-11

    Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

  16. Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer; Estudo da sintese de copolimero olefinico a base de politetrafluoroetileno (PTFE) por meio da enxertia induzida por radiacao gama

    Energy Technology Data Exchange (ETDEWEB)

    Ferreto, Helio Fernando Rodrigues

    2006-07-01

    The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

  17. X-ray structure determination of new monomers to establish their polymerizability: copolymerization of two tetrasubstituted electrophilic olefins with electron-rich styrenes giving polymers with an average 1.25 functional groups per chain carbon atom

    International Nuclear Information System (INIS)

    Hall, H.K. Jr.; Reineke, K.E.; Ried, J.H.; Sentman, R.C.; Miller, D.

    1982-01-01

    X-ray crystal structure determination for two tetrasubstituted electrophilic olefins, tetramethyl ethylenetetracarboxylate TMET and dimethyl dicyanofumarate DDCF, revealed two fundamentally different molecular structures. TMET is a nonplanar molecule that possesses two opposite ester groups planar and the others above and below the molecular plane. In contrast, DDCF is a molecule for which both ester groups lie in the plane of the double bond and nitrile groups. DDCF underwent thermal spontaneous copolymerization with electron-rich styrenes to give 1:1 alternating copolymers in moderate yields and molecular weights. These copolymers, which result from the first copolymerization of a tetrasubstituted olefin, possess an average functionality of 1.25 per chain carbon atom. Polymerization is made possible by low steric hindrance and the high delocalization in the propagating radical. The yields were limited by competing cycloaddition reaction. The corresponding diethyl ester also copolymerized, but not so well. Neither electrophilic olefin homopolymerized under γ-irradiation. TMET did not copolymerize at all when treated under identical conditions

  18. In vivo and in vitro olefin cyclopropanation catalyzed by heme enzymes

    Science.gov (United States)

    Coelho, Pedro S; Brustad, Eric M; Arnold, Frances H; Wang, Zhan; Lewis, Jared C

    2015-03-31

    The present invention provides methods for catalyzing the conversion of an olefin to any compound containing one or more cyclopropane functional groups using heme enzymes. In certain aspects, the present invention provides a method for producing a cyclopropanation product comprising providing an olefinic substrate, a diazo reagent, and a heme enzyme; and admixing the components in a reaction for a time sufficient to produce a cyclopropanation product. In other aspects, the present invention provides heme enzymes including variants and fragments thereof that are capable of carrying out in vivo and in vitro olefin cyclopropanation reactions. Expression vectors and host cells expressing the heme enzymes are also provided by the present invention.

  19. Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

    Science.gov (United States)

    Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

    2017-10-17

    The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Ligand-Enabled γ-C(sp(3))-H Olefination of Amines: En Route to Pyrrolidines.

    Science.gov (United States)

    Jiang, Heng; He, Jian; Liu, Tao; Yu, Jin-Quan

    2016-02-17

    Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp(3))-H olefination reactions. The use of Ns protecting group to direct C(sp(3))-H activation of alkyl amines is also a significant step toward practical C-H functionalizations of alkyl amines.

  1. Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides.

    Science.gov (United States)

    Mitra, Prithiba; Shome, Brateen; De, Saroj Ranjan; Sarkar, Anindya; Mal, Dipakranjan

    2012-04-14

    The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone. This journal is © The Royal Society of Chemistry 2012

  2. Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

    KAUST Repository

    Dong, G.

    2011-09-15

    Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

  3. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng

    2015-09-01

    In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

  4. Simulação numérica aplicada para avaliar o efeito da pré-polimerização no comportamento de reatores tubulares Numerical simulation to evaluate the effect from pre-polymerization on the behavior of tubular reactors

    Directory of Open Access Journals (Sweden)

    André L. Nogueira

    2007-09-01

    Full Text Available O presente estudo utiliza um modelo matemático fenomenológico para simular um sistema de polimerização contínuo em dois estágios. Este sistema é composto por um reator contínuo tipo tanque agitado (CSTR, para pré-polimerização do monômero (primeiro estágio, associado em série a um reator tubular para conduzir a reação até elevados valores de conversão (segundo estágio. Um modelo detalhado, considerando variações axiais e radiais, assim como operação não-isotérmica, foi utilizado para simular o comportamento do reator tubular em diferentes situações. Um modelo de caracterização também foi desenvolvido para fornecer estimativas do peso molecular médio e do índice de polidispersão do polímero. Os resultados mostram que reações de polimerização conduzidas em sistemas contínuos de dois estágios fornecem um polímero com propriedades menos heterogêneas do que um polímero obtido em um sistema reacional composto por apenas um reator tubular. Além disso, quanto maior a viscosidade da mistura reacional alimentada ao reator tubular, mais homogêneo é o polímero obtido.The present study uses a phenomenological model to simulate a continuous, two-stage polymerization process. This system is composed by a continuous stirred tank reactor (CSTR for monomer pre-polymerization (first stage, connected to a tubular reactor (second stage to carry out the reaction up to high conversion values. A comprehensive non-isothermal 2-D model (axial and radial variations was used to predict the tubular reactor behavior. A polymer characterization model was also developed to provide estimates of the polymer average molecular weight and polydispersity. According to the results, polymerization reactions carried out in a continuous two-stage system provide a polymer with less heterogeneous properties than the one obtained in a single tubular reactor. Besides, it is possible to produce a more homogeneous polymer increasing the viscosity

  5. Radiation-chemical alkylation of olefines with adamantane

    International Nuclear Information System (INIS)

    Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

    1977-01-01

    Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

  6. The FCC process as a producer of light olefins

    International Nuclear Information System (INIS)

    Yung, K.Y.; Yanik, S.; O'Connor, P.; Pouwels, C.

    1992-01-01

    To reduce emissions from the gasoline engine, aromatics content and vapor pressure of the motor gasoline pool will be reduced and a minimum amount of oxygen will be mandated. This reformulation will limit the application of high octane components like benzene, toluene and butanes and will require the use of oxygenates. To compensate for the loss in octane, the use of alkylate and, of course also oxygenates will grow. The Fluid Catalytic Cracking Unit is, as producer of (olefinic) propanes, butanes and pentanes, an important feedstock producer for alkylate and oxygenate producing process. Hence, process adjustments and FCC catalyst formations to increase the yield of above desirable light products are of prime importance and will be dealt with in this paper

  7. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    KAUST Repository

    Rouen, Mathieu; Queval, Pierre; Borre, Etienne; Falivene, Laura; Poater, Albert; Berthod, Mikael; Hugues, Francois; Cavallo, Luigi; Basle, Olivier; Olivier-Bourbigou, Helene; Mauduit, Marc

    2016-01-01

    The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

  8. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  9. Gum forming olefinic precursors in motor gasoline: a model compound study

    Energy Technology Data Exchange (ETDEWEB)

    Nagpal, J.M.; Joshi, G.C.; Singh, J.; Rastogi, S.N. (Indian Institute of Petroleum, Dehradun (India))

    1994-01-01

    The source of the cracked components in motor gasoline are generally (Fluid Catalytic Cracking) FCC and thermal cracking naphthas incorporated in the gasoline pool. The FCC olefins are predominant in isostructures, while thermal cracking naphthas obtained from visbreaking and coking operations contain substantial amounts of cyclic structures. The contribution of various olefinic structures present in these naphthas are likely to vary. The gum forming tendencies of different types of olefinic structures have been studied by taking model compounds in a known sample matrix through potential gum measurements under accelerated test conditions. Peroxide number values have also been determined on aged sample. Cyclic and dicyclic structures have been found to contribute maximum, towards gum formation tendencies. Branching generally increases the gum formation. However, position of branching plays an important role besides the double bond. Synergistic effects of dienes with straight chain and branched olefins have also been studied. 11 refs., 10 figs., 2 tabs.

  10. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    KAUST Repository

    Rouen, Mathieu

    2016-10-14

    The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

  11. Esterase-sensitive sulfur dioxide prodrugs inspired by modified Julia olefination.

    Science.gov (United States)

    Wang, Wenyi; Wang, Binghe

    2017-09-12

    Sulfur dioxide (SO 2 ) is an endogenously produced gaseous molecule, and is emerging as a potential gasotransmitter. Herein, we describe the first series of esterase-sensitive prodrugs inspired by modified Julia olefination as SO 2 donors.

  12. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  13. Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

    Science.gov (United States)

    Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

    2017-05-01

    Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

  14. Extreme ultraviolet (EUV) degradation of poly(olefin sulfone)s: Towards applications as EUV photoresists

    International Nuclear Information System (INIS)

    Lawrie, Kirsten; Blakey, Idriss; Blinco, James; Gronheid, Roel; Jack, Kevin; Pollentier, Ivan; Leeson, Michael J.; Younkin, Todd R.; Whittaker, Andrew K.

    2011-01-01

    Poly(olefin sulfone)s, formed by the reaction of sulfur dioxide (SO 2 ) and an olefin, are known to be highly susceptible to degradation by radiation and thus have been identified as candidate materials for chain scission-based extreme ultraviolet lithography (EUVL) resist materials. In order to investigate this further, the synthesis and characterisation of two poly(olefin sulfone)s namely poly(1-pentene sulfone) (PPS) and poly(2-methyl-1-pentene sulfone) (PMPS), was achieved and the two materials were evaluated for possible chain scission EUVL resist applications. It was found that both materials possess high sensitivities to EUV photons; however; the rates of outgassing were extremely high. The only observed degradation products were found to be SO 2 and the respective olefin suggesting that depolymerisation takes place under irradiation in a vacuum environment. In addition to depolymerisation, a concurrent conversion of SO 2 moieties to a sulfide phase was observed using XPS.

  15. Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

    International Nuclear Information System (INIS)

    Desrosiers, M.F.; Trifunac, A.D.

    1986-01-01

    The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

  16. Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae.

    Science.gov (United States)

    Jongedijk, Esmer; Cankar, Katarina; Ranzijn, Jorn; van der Krol, Sander; Bouwmeester, Harro; Beekwilder, Jules

    2015-01-01

    Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a (+)-limonene synthase from Citrus limon. Both proteins were expressed either with their native plastid targeting signal or in a truncated form in which the plastidial sorting signal was removed. The yeast host strain for expression was AE9 K197G, which expresses a mutant Erg20 enzyme. This enzyme catalyses the formation of geranyl diphosphate, which is the precursor for monoterpenes. Several methods were tested to capture limonene produced by the yeast. Extraction from the culture medium by pentane, or by the addition of CaCl2 followed by solid-phase micro-extraction, did not lead to detectable limonene, indicating that limonene is rapidly lost from the culture medium. Volatile terpenes such as limonene may also be trapped in a dodecane phase added to the medium during fermentation. This method resulted in recovery of 0.028 mg/l (+)-limonene and 0.060 mg/l (-)-limonene in strains using the truncated Citrus and Perilla synthases, respectively. Trapping the headspace during culture of the limonene synthase-expressing strains resulted in higher titres, at 0.12 mg/l (+)-limonene and 0.49 mg/l (-)-limonene. These results show that the volatile properties of the olefins produced require specific methods for efficient recovery of these molecules from biotechnological production systems. Copyright © 2014 John Wiley & Sons, Ltd.

  17. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  18. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  19. An Improved Protocol for the Aldehyde Olefination Reaction Using (bmim ( as Reaction Medium

    Directory of Open Access Journals (Sweden)

    Vivek Srivastava

    2013-01-01

    Full Text Available [Ru(CODCl2]/CuCl2·2H2O/LiCl catalytic system works efficiently in ionic liquid media for aldehyde olefination reaction. It offers good yield and selectivity with the added advantage of 5 times recyclability for [Ru(CODCl2] /CuCl2·2H2O/LiCl catalytic system. We also successfully reduced the reaction time from 12 hours to 9 hours for the aldehyde olefination reaction.

  20. Stereoselective Wittig Olefination as a Macrocyclization Tool. Synthesis of Large Carbazolophanes.

    Science.gov (United States)

    Myśliwiec, Damian; Lis, Tadeusz; Gregoliński, Janusz; Stępień, Marcin

    2015-06-19

    Z-Selective Wittig olefination was applied to the synthesis of large carbazolophanes containing up to eight heteroaromatic subunits. A number of strategies were devised and tested, showing that cyclooligomerization yields can be significantly improved by using one-component schemes involving heterobifunctional reactants. [4]- and [6]Carbazolophanes were characterized in the solid state, revealing compact, highly folded structures. Electronic and steric effects of substitution and chain length on the Wittig olefination rates and Z-selectivities were explored theoretically using DFT calculations.

  1. Ligand-Promoted C(sp(3) )-H Olefination en Route to Multi-functionalized Pyrazoles.

    Science.gov (United States)

    Yang, Weibo; Ye, Shengqing; Schmidt, Yvonne; Stamos, Dean; Yu, Jin-Quan

    2016-05-17

    A Pd-catalyzed/N-heterocycle-directed C(sp(3) )-H olefination has been developed. The monoprotected amino acid ligand (MPAA) is found to significantly promote Pd-catalyzed C(sp(3) )-H olefination for the first time. Cu(OAc)2 instead of Ag(+) salts are used as the terminal oxidant. This reaction provides a useful method for the synthesis of alkylated pyrazoles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

    1992-03-25

    Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

  3. Palladium catalyzed selective distal C-H olefination of biaryl systems.

    Science.gov (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

    2016-11-29

    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  4. Zeolitic imidazolate frameworks with optimized pore structure for olefin/paraffin-separation

    Energy Technology Data Exchange (ETDEWEB)

    Paula, C.; Boehme, U.; Hartmann, M. [Erlangen-Nuernberg Univ. (Germany). Erlangen Catalysis Resource Center

    2013-11-01

    In the chemical industry, the largest part of energy is spent on separation processes such as the separation of olefin/paraffin mixtures from steam cracker effluents by low-temperature rectification. A suitable alternative to this energy and cost intensive process is separation by selective adsorption with suitable microporous adsorbent. In this work, different ZIFs (Zeolitic Imidazolate Frameworks) have been explored with respect to their separation of olefins and paraffins. The studied materials (e.g. ZIF-8 (SOD-Topology), ZIF-71 (RHO-Topology)) were selected because of their low diameter of the largest pore entrance (0.29 to 4.2 nm) which is close to the kinetic diameter of the C{sub 2} to C{sub 4} olefins and paraffins under study. In contrast to other MOF- or zeolite-based adsorbents, in ZIF-8 and ZIF-71, the paraffin is preferentially adsorbed, which is evident from the single-component adsorption isotherms at different temperature. In the corresponding mixture breakthrough curves, the olefin breaks through first and the alkane even displaces the olefin from the pores. Thus, ZIF-8 and ZIF-71 are interesting candidates for the envisaged paraffin/olefin separation. Whether the observed separation behavior is due to the structural properties of the studied ZIFs or a consequence of peculiar chemical properties is subject to further studies. (orig.) (Published in summary form only)

  5. Olefins-selective asymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations

    KAUST Repository

    Xu, Liren

    2012-12-01

    In this paper, the development of asymmetric carbon molecular sieve (CMS) hollow fiber membranes and advanced processes for olefin/paraffin separations based on the CMS membranes are reported. Membrane-based olefin/paraffin separations have been pursued extensively over the past decades. CMS membranes are promising to exceed the performance upper bound of polymer materials and have demonstrated excellent stability for gas separations. Previously, a substructure collapse phenomenon was found in Matrimid ® precursor derived CMS fiber. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM precursors were selected as potential new precursors for carbon membrane formation. Defect-free asymmetric 6FDA-DAM and 6FDA/BPDA-DAM hollow fibers were successfully fabricated from a dry-jet/wet-quench spinning process. Polymer rigidity, glass-rubber transition and asymmetric morphology were correlated. CMS hollow fiber membranes produced from 6FDA-polymer precursors showed significant improvement in permeance for ethylene/ethane and propylene/propane separations. Further studies revealed that the CMS membranes are olefins-selective, which means the membranes are able to effectively separate olefins (ethylene and propylene) from paraffins (ethane and propane). This unique feature of CMS materials enables advanced hybrid membrane-distillation process designs. By using the olefins-selective membranes, these new processes may provide advantages over previously proposed retrofitting concepts. Further applications of the membranes are explored for hydrocarbons processes. Significant energy savings and even reduced footprint may be achieved in olefins production units. © 2012 Elsevier B.V.

  6. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  7. Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols.

    Science.gov (United States)

    Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata

    2016-02-04

    Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

  8. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  9. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt...

  10. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

    2015-01-01

    . In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

  11. About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

    Directory of Open Access Journals (Sweden)

    Hatice Mutlu

    2010-12-01

    Full Text Available We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS.

  12. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  13. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  14. Modeling of free radical polymerization up to high conversion. II. Development of a mathematical model.

    NARCIS (Netherlands)

    Tefera shibeshe, N.; Tefera, N.; Weickert, G.; Westerterp, K.R.

    1997-01-01

    In free radical polymerization diffusion-controlled processes take place simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical

  15. Proceedings of the DGMK-Conference 'Creating value from light olefins - production and conversion'. Authors' manuscripts

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Kraemer, H.J.; Weitkamp, J. (eds.)

    2001-07-01

    Main topics of the conference were: production of light olefin by steamcracking and catalytic cracking processes, catalysts, methanol to olefin processes, oxidative dehydrogenation, partial oxidation, selective oxidation of alkanes with various catalysts. (uke)

  16. (Electro)Mechanical Properties of Olefinic Block Copolymers

    Science.gov (United States)

    Spontak, Richard

    2014-03-01

    Conventional styrenic triblock copolymers (SBCs) swollen with a midblock-selective oil have been previously shown to exhibit excellent electromechanical properties as dielectric elastomers. In this class of electroactive polymers, compliant electrodes applied as active areas to opposing surfaces of an elastomer attract each other, and thus compress the elastomer due to the onset of a Maxwell stress, upon application of an external electric field. This isochoric process is accompanied by an increase in lateral area, which yields the electroactuation strain (measuring beyond 300% in SBC systems). Performance parameters such as the Maxwell stress, transverse strain, dielectric breakdown, energy density and electromechanical efficiency are determined directly from the applied electric field and resulting electroactuation strain. In this study, the same principle used to evaluate SBC systems is extended to olefinic block copolymers (OBCs), which can be described as randomly-coupled multiblock copolymers that consist of crystallizable polyethylene hard segments and rubbery poly(ethylene-co-octene) soft segments. Considerations governing the development of a methodology to fabricate electroresponsive OBC systems are first discussed for several OBCs differing in composition and bulk properties. Evidence of electroactuation in selectively-solvated OBC systems is presented and performance metrics measured therefrom are quantitatively compared with dielectric elastomers derived from SBC and related materials.

  17. Separation of products of alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Ward, J.

    1979-03-15

    The alkylation (A1) of isobutane (I) by propylene, butylene and amylenes is carried out at 24-52 degrees, pressure sufficient to maintain the liquid phase, and a molar ratio of I to olefins (O1) 10:1-15:1. The bulk ratio of catalysts to hydrocarbons in the reaction zone was 0.5:1-10:1; when using HF-K-T as the catalysts, it should contain less than 5 percent water and greater than or equal to 65 percent titrated HF. The hydrocarbon products (UP) from the alkylation zone are added after separating the catalyst in a fractionation tower; distillation is carried out at 38-49 degrees and 1.03-1.3 NPa. The head fraction containing I and less than 50 molar percent C3H8 and also fraction I at the point below the input side of the UP which contains less than 8 molar percent C3H8 and fraction n-C4H10 at the point below the point of discharge of fraction I is drained from the tower. The alkylate is discharged at the bottom of the tower. According to the patent the tower operates at low pressure. This improves relative volatility of individual components and reduces heat consumption. The best results are obtained when a head fraction or the concentration C3H8 approximately 25 molar percent is discharged.

  18. Catalyst compositions useful for olefin isomerization and disproportionation

    International Nuclear Information System (INIS)

    Drake, C.A.

    1987-01-01

    A process is described for the double bond isomerization of an aliphatic olefinic hydrocarbon feed which comprises contacting the feed under isomerization conditions with a catalyst prepared by: (a) impregnating an alumina support having a surface area of at least 200 m/sup 2//g and a pore volume of at least 0.45 cm/sup 3//g with: 1 up to 20 wt. % of at least one magnesium compound convertible to the oxide, based on the weight of support and calculated as the metal; 0 up to 5 wt. % of at least one alkali metal compound convertible to the oxide, based on the weight of support and calculated as the metal; and 0 up to 5 wt. % of at least one zirconium compound convertible to the oxide, based on the weight of support and calculated as the metal; and (b) heating the alumina support impregnated in accordance with step (a) in an oxygen-containing atmosphere under conditions suitable to convert at least a portion of the magnesium, alkali metal, and zirconium compounds to the oxide form

  19. Radiation degradation of poly(olefin sulphone)s - Fundamental research to practical applications

    International Nuclear Information System (INIS)

    Bowden, M.J.; O'Donnell, J.H.

    1985-01-01

    The degradation of poly(olefin sulphone)s by high energy radiation, particularly by γ-rays and electron beams, provides an example of the application of fundamental science to high technology industry. Scientific interest in the radiation degradation of these polymers was first aroused by the discovery that they underwent highly specific bond scission in the backbone chain as the primary result of absorption of high energy radiation and in fact they were the first polymers in which such an effect had been demonstrated. This conclusion was initially based mainly on evidence from electron spin resonance spectroscopy and was subsequently verified by studies of molecular weight changes. These studies showed that the poly(olefin sulphone)s not only degraded by main chain scission but were also among the most radiation-sensitive polymers known. The extremely high sensitivity of poly(olefin sulphone)s to radiation-induced main-chain scission has found application in the field of microelectronics. Electron beam writing on poly(olefin sulphone) films is used to produce lithographic masks for the manufacture of integrated circuits on silicon wafers. Poly(1-butene sulphone) (PBS) is currently used in the production of a substantial proportion of the masks for the industry. The fundamental aspects of the radiation degradation of poly(olefin sulphone)s and the practical applications to high technology are reviewed. (author)

  20. Optimization of catalytic glycerol steam reforming to light olefins using Cu/ZSM-5 catalyst

    International Nuclear Information System (INIS)

    Zakaria, Z.Y.; Amin, N.A.S.; Linnekoski, J.

    2014-01-01

    Highlights: • Glycerol steam reforming to light olefin using Cu/ZSM-5 process was optimized. • Response surface methodology and multi-objective genetic algorithm were employed. • Second order polynomial model produced adequately fitted experimental data. • Thermodynamic study inferred high temperature requirement for ethylene formation. • Turn-over-frequency at optimized responses is higher than the non-optimized process. - Abstract: Response surface methodology (RSM) and multi-objective genetic algorithm was employed to optimize the process parameters for catalytic conversion of glycerol, a byproduct from biodiesel production, to light olefins using Cu/ZSM-5 catalyst. The effects of operating temperature, weight hourly space velocity (WHSV) and glycerol concentration on light olefins selectivity and yield were observed. Experimental results revealed the data adequately fitted into a second-order polynomial model. The linear temperature and quadratic WHSV terms gave significant effect on both responses. Optimization of both the responses indicated that temperature favouring high light olefin formation lied beyond the experimental design range. The trend in the temperature profile concurred commensurately with the thermodynamic analysis. Multi-objective genetic algorithm was performed to attain a single set of processing parameters that could produce both the highest light olefin selectivity and yield. The turn-over-frequency (TOF) of the optimized responses demonstrated a slightly higher value than the one which was not optimized. Combination of RSM, multi-objective response and thermodynamic is useful to determine the process optimal operating conditions for industrial applications

  1. Direct Olefination of Alcohols with Sulfones by Using Heterogeneous Platinum Catalysts.

    Science.gov (United States)

    Siddiki, S M A Hakim; Touchy, Abeda Sultana; Kon, Kenichi; Shimizu, Ken-Ichi

    2016-04-18

    Carbon-supported Pt nanoparticles (Pt/C) were found to be effective heterogeneous catalysts for the direct Julia olefination of alcohols in the presence of sulfones and KOtBu under oxidant-free conditions. Primary alcohols, including aryl, aliphatic, allyl, and heterocyclic alcohols, underwent olefination with dimethyl sulfone and aryl alkyl sulfones to give terminal and internal olefins, respectively. Secondary alcohols underwent methylenation with dimethyl sulfone. Under 2.5 bar H2, the same reaction system was effective for the transformation of alcohol OH groups to alkyl groups. Structural and mechanistic studies of the terminal olefination system suggested that Pt(0) sites on the Pt metal particles are responsible for the rate-limiting dehydrogenation of alcohols and that KOtBu may deprotonate the sulfone reagent. The Pt/C catalyst was reusable after the olefination, and this method showed a higher turnover number (TON) and a wider substrate scope than previously reported methods, which demonstrates the high catalytic efficiency of the present method. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. RAFT polymerization and some of its applications.

    Science.gov (United States)

    Moad, Graeme; Rizzardo, Ezio; Thang, San H

    2013-08-01

    Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Use of water in aiding olefin/paraffin (liquid + liquid) extraction via complexation with a silver bis(trifluoromethylsulfonyl)imide salt

    International Nuclear Information System (INIS)

    Wang, Yu; Thompson, Jillian; Zhou, Jingjing; Goodrich, Peter; Atilhan, Mert; Pensado, Alfonso S.; Kirchner, Barbara; Rooney, David; Jacquemin, Johan; Khraisheh, Majeda

    2014-01-01

    Highlights: • Silver-based ILs used as olefin extracting agents for olefin/paraffin mixtures. • Each extraction process is based on the olefin complexation and solvation. • The presence of water influences positively each extraction process. • Each extraction process was evaluated by DFT calculations, NMR, IR and Raman. • LLE data were then correlated by using the UNIQUAC model. - Abstract: This paper describes the extraction of C 5 –C 8 linear α-olefins from olefin/paraffin mixtures of the same carbon number via a reversible complexation with a silver salt (silver bis(trifluoromethylsulfonyl)imide, Ag[Tf 2 N]) to form room temperature ionic liquids [Ag(olefin) x ][Tf 2 N]. From the experimental (liquid + liquid) equilibrium data for the olefin/paraffin mixtures and Ag[Tf 2 N], 1-pentene showed the best separation performance while C 7 and C 8 olefins could only be separated from the corresponding mixtures on addition of water which also improves the selectivity at lower carbon numbers like the C 5 and C 6 , for example. Using infrared and Raman spectroscopy of the complex and Ag[Tf 2 N] saturated by olefin, the mechanism of the extraction was found to be based on both chemical complexation and the physical solubility of the olefin in the ionic liquid ([Ag(olefin) x ][Tf 2 N]). These experiments further support the use of such extraction techniques for the separation of olefins from paraffins

  4. Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant.

    Science.gov (United States)

    Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan

    2015-03-01

    The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

  5. (E)-Specific direct Julia-olefination of aryl alcohols without extra reducing agents promoted by bases.

    Science.gov (United States)

    Yao, Chuan-Zhi; Li, Qiang-Qiang; Wang, Mei-Mei; Ning, Xiao-Shan; Kang, Yan-Biao

    2015-05-04

    An unprecedented base-promoted direct olefination of aryl alcohols with sulfones via a Julia-type reaction has been described. No extra reductants are needed for Julia reaction since alcohols work as double sources of aldehydes and the hydride. Generally high yields were given for both terminal and highly (E)-selective internal olefins.

  6. Radiation induced emulsion polymerization

    International Nuclear Information System (INIS)

    Stannett, V.T.; Stahel, E.P.

    1990-01-01

    High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

  7. Comparative toxicity of various ozonized olefins to bacteria suspended in air

    Energy Technology Data Exchange (ETDEWEB)

    Dark, P A; Nash, T

    1970-01-01

    Air containing olefin vapor was treated with known amounts of ozone simulating natural concentrations. The bactericidal effect of the mixture was tested using microthreads sprayed with washed cultures of Escherichia coli var. communis or Micrococcus albus, aerosol strain. With 20 different olefins a wide range of activity was found, those in which the double bond formed part of a ring being the most bactericidal; gasoline vapor was about as active as the average open-chain olefin. The two organisms behaved similarly at the experimental relative humidity of 80%. The estimated amount of bactericidal substance present was only about one hundreth of that required to give the same kill with a 'conventional' air disinfectant; a simple physical explanation is proposed for this enhanced effect.

  8. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    KAUST Repository

    Poater, Albert

    2015-09-29

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  9. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    KAUST Repository

    Poater, Albert; Cavallo, Luigi

    2015-01-01

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  10. Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

    Science.gov (United States)

    Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

    2017-01-09

    Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Ligand-Enabled Reactivity and Selectivity in a Synthetically Versatile Aryl C–H Olefination*

    Science.gov (United States)

    Wang, Dong-Hui; Engle, Keary M.; Shi, Bing-Feng; Yu, Jin-Quan

    2010-01-01

    The Mizoroki–Heck reaction, which couples aryl halides with olefins, has been widely used to stitch together the carbogenic cores of numerous complex organic molecules. Given that the position-selective introduction of a halide onto an arene is not always straightforward, direct olefination of aryl C–H bonds would obviate the inefficiencies associated with generating halide precursors or their equivalents; however, methods for carrying out such a reaction have suffered from narrow substrate scope and low positional selectivity. Here we report an operationally simple, atom-economical, carboxylate-directed Pd(II)-catalyzed C–H olefination reaction with phenylacetic acid and 3-phenylpropionic acid substrates, using oxygen at atmospheric pressure as the oxidant. The positional selectivity can be tuned by introducing amino acid derivatives as ligands. We demonstrate the versatility of the method through direct elaboration of commercial drug scaffolds and efficient synthesis of 2-tetralone and naphthoic acid natural product cores. PMID:19965380

  12. Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes.

    Science.gov (United States)

    Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui; Dai, Hui-Xiong; Yu, Jin-Quan

    2018-02-07

    Although chelation-assisted C-H olefination has been intensely investigated, Pd(ii)-catalyzed C-H olefination reactions are largely restricted to acrylates and styrenes. Here we report a quinoline-derived ligand that enables the Pd(ii)-catalyzed olefination of the C(sp 2 )-H bond with simple aliphatic alkenes using a weakly coordinating monodentate amide auxiliary. Oxygen is used as the terminal oxidant with catalytic copper as the co-oxidant. A variety of functional groups in the aliphatic alkenes are tolerated. Upon hydrogenation, the ortho -alkylated product can be accessed. The utility of this reaction is also demonstrated by the late-stage diversification of drug molecules.

  13. General regularities of olefin epoxidation by hydroperoxide catalyzed by V, W and Ti compounds

    International Nuclear Information System (INIS)

    Sapunov, V.N.; Sharykin, V.G.; Logvinov, A.S.; Litvintsev, I.Yu.; Lebedev, N.N.

    1983-01-01

    The kinetic analysis of cyclohexane epoxidation by ethylbenzene hydroperoxide when catalyzed by titanium- and tungsten cyclohexandiolates has shown that the reaction follows the main regularities of hydroperoxide epoxidation previously established for catalysis by molybdenum- and vanadiUm compounds. The catalyst activity varies depending on the metal nature and forms the following series: Mo>V>W>Ti, which agrees with their π-acceptor capacity. During the cyclohexane epoxidation on all catalysts the hydroperoxide activities vary according to the following series: ethylbenzene hydroperoxide>cumene>tertiarybutyl>tertiaryamyl. Correlation relationships between the olefine structure, characterized by th constants, and the reactivity of olefines are foUnd. The reaction sensitivity during catalysis by WV, and Ti cyclohexandiolates is -1.2, -1.0- and -1.3, respectively. The mechanism of hydroperoxide epoxidation of olefine is discussed

  14. At the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.

    Science.gov (United States)

    Rangheard, Claudine; de Julián Fernández, César; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; de Vries, Johannes G

    2010-09-28

    The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and alkynes. Olefin hydrogenation is relatively fast at 5 bar using 5 mol% of catalyst. The catalyst is also active for terminal olefins and 1,1' and 1,2-cis disubstituted olefins while trans-olefins react much slower. 1-Octyne is hydrogenated to mixtures of 1-octene and octane. Kinetic studies led us to propose a mechanism for this latter transformation where octane is obtained by two different pathways. Characterization of the nanoparticles via TEM, magnetic measurements and poisoning experiments were undertaken to understand the true nature of our catalyst.

  15. First examples of intramolecular addition of primary amidyl radicals to olefins

    Energy Technology Data Exchange (ETDEWEB)

    Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

    2005-07-01

    This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

  16. Nitrogen-Doped Carbon Encapsulated Nickel/Cobalt Nanoparticle Catalysts for Olefin Migration of Allylarenes

    DEFF Research Database (Denmark)

    Kramer, Søren; Mielby, Jerrik Jørgen; Buss, Kasper Spanggård

    2017-01-01

    Olefin migration of allylarenes is typically performed with precious metal-based homogeneous catalysts. In contrast, very limited progress has been made using cheap, earth-abundant base metals as heterogeneous catalysts for these transformations - in spite of the obvious economic and environmental...... advantages. Herein, we report on the use of an easily prepared heterogeneous catalyst material for the migration of olefins, in particular allylarenes. The catalyst material consists of nickel/cobalt alloy nanoparticles encapsulated in nitrogen-doped carbon shells. The encapsulated nanoparticles are stable...

  17. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert

    2014-05-25

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  18. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert; Correa, Andrea; Pump, Eva; Cavallo, Luigi

    2014-01-01

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  19. Kinetics of H-D exchange in olefins with complicating reactions

    International Nuclear Information System (INIS)

    Trokhimets, A.I.

    1979-01-01

    The kinetics of H-D-exchange is considered for olefins under conditions when simple and complicated exchange occur together with hydrogenation. If hydrogenation takes place in the system, it is theoretically impossible to derive the integrated rate equation for the accumulation of deuterium in the olefin. The variation of the concentration of different deuteroolefins during the process can be calculated numerically. A method is proposed for evaluating the contribution of individual steps to the overall process and determining the rate constants of the most important reactions. (author)

  20. Synthetic lubricants based on copolymers of n-butyl methacrylate and α-olefins

    Directory of Open Access Journals (Sweden)

    Đakov Tatjana A.

    2002-01-01

    Full Text Available Synthetic fluids obtained by the copolymerization of α -olefins with alkyl esters of unsaturated carboxylic acids have a unique combination of properties of non-polar poly-a-olefins (PAOs and polar esters in a single molecule. These compounds are characterized by superior thermal, oxidative and hydrolytic stability, miscibility with mineral and synthetic base oils solubility of additives and neutral elastomer behavior. Depending on the molar masses and comonomer ratios in the copolymer molecule, synthetic fluids with a wide range of properties are obtained. These compounds are valuable components in lubricating oil formulations for different applications.

  1. Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination.

    Science.gov (United States)

    Breit, Bernhard

    1998-03-02

    Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  2. Inflation of a Polymeric Menbrane

    DEFF Research Database (Denmark)

    Kristensen, Susanne B.; Larsen, Johannes R.; Hassager, Ole

    1998-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane.......We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane....

  3. Hydro-Metathesis of Long-Chain Olefin (1-decene) using Well-Defined Silica-Supported Tungsten (VI), Molybdenum (VI) and Tantalum (V) Catalysts

    KAUST Repository

    Saidi, Aya

    2016-11-01

    Nowadays, catalysis lies at the heart of economy growth mainly in the petroleum industry. Catalysis can offer real and potential solutions to the current challenges for a long-term sustainable energy, green chemistry, and environmental protection. In this context, one of the most important and future prosperity promising catalytic applications in the petrochemical field is hydrocarbons metathesis; it consists on the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels. Olefin metathesis has become one of the standard methodologies for constructing C-C bonds in many organic transformation reactions. This owed to the numerous types of metathesis reactions that have been developed, for example, enyne, ring-opening and closing, self and cross metathesis, etc. But the one step conversion of olefin to alkanes has not been studied much. Recently, only one such a work has been published for the hydro-metathesis of propylene by tantalum hydride supported on KCC-1 in dynamic reactor. With this knowledge, we thought to study the hydro-metathesis using liquid olefin (1-decene). Another aspect of using 1-decene comes from our previous experience on metathesis of n-decane where the first step is the conversion of decane to 1-decene and subsequently to different chain length alkanes with W-alkyl/alkylidene catalyst. In this way, it would be easy for us to use different catalysts and compare them with parent catalyst concerning TON. We found 100% conversion with TON of 1010 using supported WMe6 onto SiO2-700 [(≡Si-O-)WMe5] against the previous results for n-decane showing 20% conversion and TON of 153. In this work, we disclose the hydro-metathesis reaction of 1-decene using well-defined silica supported W(VI), Mo(VI) and Ta(V) alkyl catalysts in batch reactor condition. This work is divided into three major sections; first chapter contains an introduction to the field of catalysis and surface organometallic chemistry. In second chapter

  4. Polymerized and functionalized triglycerides

    Science.gov (United States)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  5. Polymerization by radiation. Application

    International Nuclear Information System (INIS)

    Romero, M.; Fernandez Miranda, J.

    1997-01-01

    Achieved results of the research work done in the field of radiation polymerization are summarized. Developing new chromatographic matrices, the radiation grafting of Glycidyl methacrylate on the surface of Low Density Polyethylene beads was studied. The dependence of both, the grafted degree and width of the grafted layer, with the radiation dose applied, is presented

  6. RAFT polymerization mediated bioconjugation strategies

    OpenAIRE

    Bulmuş, Volga

    2011-01-01

    This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

  7. The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-10-14

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  8. The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

    KAUST Repository

    Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

    2014-01-01

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  9. Stability of cracked naphthas from thermal and catalytic processes and their additive response. Part II. Composition and effect of olefinic structures

    Energy Technology Data Exchange (ETDEWEB)

    Nagpal, J.M.; Joshi, G.C.; Rastogi, S.N. [Indian Institute of Petroleum, Dehradun (India)

    1995-05-01

    Olefinic concentrates were separated from two naphthas, one from fluid catalytic cracking (FCC) and one thermal crackate, using column chromatography. The composition and structure of the olefins were determined by a combination of analytical techniques. FCC naphthas contain relatively higher levels of conjugated dienes. The monoolefins are highly branched. The thermal crackates have higher levels of {alpha}-olefins and abound in mono-, di-, tri- and conjugated cyclic olefins. Stability tests on these olefinic concentrates blended in low-S,N straight-run naphtha showed that cyclic olefins are very active gum formers. Representative commercial antioxidants (hindered phenols and phenylenediamines) both gave good responses to different olefin concentrate test blends. Hindered phenols had a marginally better effect. 14 refs., 5 figs., 3 tabs.

  10. N-Heterocyclic Olefins as Initiators for the Polymerization of (Meth)Acrylic Monomers: A Combined Experimental and Theoretical Approach

    KAUST Repository

    Naumann, Stefan; Mundsinger, Kai; Cavallo, Luigi; Falivene, Laura

    2017-01-01

    . Scope and underlying (deactivation-)mechanisms where studied in a combined experimental and computational effort. From a range of differently structured NHOs it emerged that imidazole-, in contrast to imidazoline- and benzimidazole-derivatives, readily

  11. Polymerization of an acetoxyvinyl substituted chlorocyclophosphazene

    NARCIS (Netherlands)

    Bosscher, G; Jekel, AP; vandeGrampel, JC

    The vinyl acetate derivative, gem-isopropyl-2-(alpha-acetoxyvinyl)tetrachlorocyclotriphosphazene (1), has been used in radical homopolymerization and copolymerization reactions with methyl methacrylate, (MMA) and styrene. The 1,1-disubstituted olefin did not undergo radical homopolymerization.

  12. Prediction of properties of new halogenated olefins using two group contribution approaches

    DEFF Research Database (Denmark)

    Montagud, Maria E. Mondejar; Cignitti, Stefano; Abildskov, Jens

    2017-01-01

    The increasingly restrictive regulations for substances with high ozone depletion and global warming potentials are driving the search for new sustainable fluids with low environmental impact. Recent research works have pointed out the great potential of fluorine- and chlorine-based olefins as re...

  13. RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

    Science.gov (United States)

    In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

  14. Steam cracking and methane to olefins: Energy use, CO2 emissions and production costs

    NARCIS (Netherlands)

    Ren, T.; Patel, M.K.|info:eu-repo/dai/nl/18988097X; Blok, K.|info:eu-repo/dai/nl/07170275X

    2008-01-01

    While most olefins (e.g., ethylene and propylene) are currently produced through steam cracking routes, they can also possibly be produced from natural gas (i.e., methane) via methanol and oxidative coupling routes. We reviewed recent data in the literature and then compared the energy use, CO2

  15. Ru-Based Complexes with Quaternary Ammonium Tags Immobilized on Mesoporous Silica as Olefin Metathesis Catalysts

    Czech Academy of Sciences Publication Activity Database

    Pastva, Jakub; Skowerski, K.; Czarnocki, S. J.; Žilková, Naděžda; Čejka, Jiří; Bastl, Zdeněk; Balcar, Hynek

    2014-01-01

    Roč. 4, č. 9 (2014), s. 3227-3236 ISSN 2155-5435 R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : olefin metathesis * heterogeneous catalysts * mesoporous molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.312, year: 2014

  16. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  17. Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

    KAUST Repository

    Morandi, Bill

    2013-01-16

    Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

  18. Immobilisation of homogeneous olefin polymerisation catalysts. Factors influencing activity and stability

    NARCIS (Netherlands)

    Severn, J.R.; Chadwick, J.C.

    2013-01-01

    The activity and stability of homogeneous olefin polymerisation catalysts, when immobilised on a support, are dependent on both chemical and physical effects. Chemical factors affecting catalyst activity include the ease of formation of the active species, which is strongly dependent on the

  19. Catalysts for production of lower olefins from synthesis gas: A review

    NARCIS (Netherlands)

    Torres Galvis, H.M.; de Jong, K.P.

    2013-01-01

    C2 to C4 olefins are traditionally produced from steam cracking of naphtha. The necessity for alternative production routes for these major commodity chemicals via non-oil-based processes has driven research in past times during the oil crises. Currently, there is a renewed interest in producing

  20. Omega-functionalized fatty acids, alcohols, and ethers via olefin metathesis

    Science.gov (United States)

    Methyl 17-hydroxy stearate was converted to methyl octadec-16-enoate using copper sulfate adsorbed on silica gel. This compound, possessing unsaturation at the opposite end of the chain from the carboxylate, served as a useful substrate for the olefin metathesis reaction. As a result, several fatt...

  1. Mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Baiburskii, V.L.; Khadzhiev, S.N.; Ovsyannikov, V.P.

    1992-05-10

    The authors attempted here to examine the mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid in terms of an initial stage of activation of isoparaffin. The version of formation of tert-alkyl cations and the role of the catalyst in this stage were analyzed. 10 refs., 1 fig., 1 tab.

  2. Synthesis of 7-Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

    DEFF Research Database (Denmark)

    Håkansson, Anders Eckart; Palmelund, Anders; Holm, H.

    2006-01-01

    from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product....

  3. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

    Science.gov (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani

    2016-08-18

    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  4. Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes

    International Nuclear Information System (INIS)

    Ren Tao; Patel, Martin; Blok, Kornelis

    2006-01-01

    Steam cracking for the production of light olefins, such as ethylene and propylene, is the single most energy-consuming process in the chemical industry. This paper reviews conventional steam cracking and innovative olefin technologies in terms of energy efficiency. It is found that the pyrolysis section of a naphtha steam cracker alone consumes approximately 65% of the total process energy and approximately 75% of the total exergy loss. A family portrait of olefin technologies by feedstocks is drawn to search for alternatives. An overview of state-of-the-art naphtha cracking technologies shows that approximately 20% savings on the current average process energy use are possible. Advanced naphtha cracking technologies in the pyrolysis section, such as advanced coil and furnace materials, could together lead to up to approximately 20% savings on the process energy use by state-of-the-art technologies. Improvements in the compression and separation sections could together lead to up to approximately 15% savings. Alternative processes, i.e. catalytic olefin technologies, can save up to approximately 20%

  5. Ether-Directed ortho-C–H Olefination with a PdII/MPAA Catalyst**

    Science.gov (United States)

    Li, Gang; Leow, Dasheng; Wan, Li; Yu, Jin-Quan

    2013-01-01

    Weak coordination is powerful! A PdII-catalyzed olefination of ortho-C–H bonds of arenes directed by weakly coordinating ethers is developed using mono-protected amino acid (MPAA) ligands. This finding provides a method for chemically modifying ethers, which are abundant in natural products and drug molecules. PMID:23239120

  6. Copper(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones.

    Science.gov (United States)

    Xu, Shuai; Gao, Yunpeng; Chen, Ri; Wang, Kang; Zhang, Yan; Wang, Jianbo

    2016-03-25

    The Cu(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones via metal carbene intermediates is reported. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of carbon-carbon double bonds. Mechanistically, Cu(I) carbene formation and subsequent carbene migratory insertion are proposed as the key steps.

  7. Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

    Science.gov (United States)

    Kim, Pilho; Barry, Clifton E.; Dowd*, Cynthia S.

    2006-01-01

    Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of desired product to deformylated product. PMID:16699591

  8. Polymer PCF Bragg grating sensors based on poly(methyl methacrylate) and TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, Ian P; Webb, David J; Kalli, Kyriacos

    2011-01-01

    mode PCF with a core diameter of 6μm based on TOPAS cyclic olefin copolymer. Bragg grating inscription was achieved using a 30mW continuous wave 325nm helium cadmium laser. Both TOPAS and PMMA fibre have a large attenuation of around 1dB/cm in the 1550nm spectral region, limiting fibre lengths...

  9. Pd(II)-Catalyzed Olefination of Electron-Deficient Arenes Using 2,6-Dialkylpyridine Ligands

    Science.gov (United States)

    Zhang, Yang-Hui; Shi, Bing-Feng; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed meta-olefination of highly electron deficient arenes is achieved through the use of a rationally designed mutually repulsive ligand. The combination of directed and non-directed C–H functionalization of arenes provides a versatile route for the synthesis of highly sought-after 1,2,4-trisubstituted arenes. PMID:19296661

  10. Modified Julia Olefination on Anhydrides: Extension and Limitations. Application to the Synthesis of Maculalactone B.

    Science.gov (United States)

    Dussart, Nicolas; Trinh, Huu Vinh; Gueyrard, David

    2016-10-07

    The preparation of exo-enol esters from cyclic anhydrides is reported using a modified Julia olefination. The reaction is highly stereoselective. The Smiles rearrangement can be performed in a one-pot process, giving a straightforward access to exo-enol lactones. Furthermore, the reaction was extended to semistabilized sulfones, and this methodology was applied to the synthesis of maculalactone B.

  11. Improved olefinic fat suppression in skeletal muscle DTI using a magnitude-based dixon method.

    Science.gov (United States)

    Burakiewicz, Jedrzej; Hooijmans, Melissa T; Webb, Andrew G; Verschuuren, Jan J G M; Niks, Erik H; Kan, Hermien E

    2018-01-01

    To develop a method of suppressing the multi-resonance fat signal in diffusion-weighted imaging of skeletal muscle. This is particularly important when imaging patients with muscular dystrophies, a group of diseases which cause gradual replacement of muscle tissue by fat. The signal from the olefinic fat peak at 5.3 ppm can significantly confound diffusion-tensor imaging measurements. Dixon olefinic fat suppression (DOFS), a magnitude-based chemical-shift-based method of suppressing the olefinic peak, is proposed. It is verified in vivo by performing diffusion tensor imaging (DTI)-based quantification in the lower leg of seven healthy volunteers, and compared to two previously described fat-suppression techniques in regions with and without fat contamination. In the region without fat contamination, DOFS produces similar results to existing techniques, whereas in muscle contaminated by subcutaneous fat signal moved due to the chemical shift artefact, it consistently showed significantly higher (P = 0.018) mean diffusivity (MD). Because fat presence lowers MD, this suggests improved fat suppression. DOFS offers superior fat suppression and enhances quantitative measurements in the muscle in the presence of fat. DOFS is an alternative to spectral olefinic fat suppression. Magn Reson Med 79:152-159, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

  12. Catalyst Design and Development for the Direct Production of Lower Olefins from Synthesis Gas

    NARCIS (Netherlands)

    Xie, J.

    2017-01-01

    The increase in global demand for lower olefins (ethylene, propylene, and butylenes) coupled with the regional diversification of carbon raw materials bring about opportunities and challenges for emerging technologies. Crude oil has been the primary carbon feedstock for the past 50 years, but

  13. Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

    Science.gov (United States)

    Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

    2010-01-01

    A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

  14. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  15. Cobalt carbide nanoprisms for direct production of lower olefins from syngas

    Science.gov (United States)

    Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

    2016-10-01

    Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

  16. Radiation polymerization of tetrafluoroethylene

    International Nuclear Information System (INIS)

    Kadoi, H.; Lugao, A.B.; Oikawa, H.

    1984-01-01

    Tetrafluoroethylene (TFE) monomer was obtained by means of the pyrolysis of chlorodifluoromethane (R-22). The experiments were carried out in quartz tube with temperature between 700 0 and 800 0 C. The principal reaction of the pyrolysis is considered to be: 2CHClF2 ----> C 2 F 4 +2HCl. However, by-products such as HF, C 3 F 6 , C 2 HClF 4 , C 4 F 8 etc are also produced in the pyrolysis process. The conversions of R-22 varied from 30 to 50%, depending upon the temperature, pressure and flow rate of R-22 in the furnace. Finally the TFE monomer of purity higher than 99.98% was obtained by fractional distillation in low temperatures ranging from -10 0 to -30 0 C. The bulk polymerization of this monomer induced by γ-rays from 3000Ci cobalt-60 source was studied at various temperatures (room temperature, 0 0 , -23 0 and -78 0 C). The monomers were introduced into stainless steel vessels of 15 and 60 ml volume under vacuum. The control of polymerization reaction was rather hard at temperatures higher than -23 0 C due to the difficulty of removing the heat of reaction. However, the polymerization at -78 0 C was very easy to control. The white polymer particles were obtained in agglomerated state. The IR spectra of the polymers were consistent with those of commercial products. The melting points of samples were between 326 0 and 331 0 C. (Author) [pt

  17. Optimal control of batch emulsion polymerization of vinyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Damslora, Andre Johan

    1998-12-31

    The highly exothermic polymerization of vinyl chloride (VC) is carried out in large vessels where the heat removal represents a major limitation of the production rate. Many emulsion polymerization reactors are operated in such a way that a substantial part of the heat transfer capacity is left unused for a significant part of the total batch time. To increase the reaction rate so that it matches the heat removal capacity during the course of the reaction, this thesis proposes the use of a sufficiently flexible initiator system to obtain a reaction rate which is high throughout the reaction and real-time optimization to compute the addition policy for the initiator. This optimization based approach provides a basis for an interplay between design and control and between production and research. A simple model is developed for predicting the polymerization rate. The model is highly nonlinear and open-loop unstable and may serve as an interesting case for comparison of nonlinear control strategies. The model is fitted to data obtained in a laboratory scale reactor. Finally, the thesis discusses optimal control of the emulsion polymerization reactor. Reduction of the batch cycle time is of major economic importance, as long as the quality parameters are within their specifications. The control parameterization had a major influence on the performance. A differentiable spline parameterization was applied and the optimization is illustrated in a number of cases. The best performance is obtained when the reactor temperature is obtained when the optimization is combined with some form of closed-loop control of the reactor temperature. 112 refs., 48 figs., 4 tabs.

  18. Radiation chemistry of polymeric system

    International Nuclear Information System (INIS)

    Machi, Sueo; Ishigaki, Isao

    1978-01-01

    Among wide application of radiation in the field of polymer chemistry, practices of polymerization, graft polymerization, bridging, etc. are introduced hereinafter. As for the radiation sources of radiation polymerization, in addition to the 60 Co-γ ray with long permeation distance which has been usually applied, electron beam accelerators with high energy, large current and high reliability have come to be produced, and the liquid phase polymerization by electron beam has attracted attention industrially. Concerning polymerizing reactions, explanations were given to electron beam polymerization under high dose rate, the polymerization in supercooling state or under high pressure, and emulsifying polymerization. As for radiation bridging, radiation is applied for the bridging of hydrogel, acceleration of bridging and improvement of radiation resistance. It is also utilized for reforming membranes by graft polymerization, and synthesis of polymers for medical use. Application of fixed enzymes in the medical field has been investigated by fixing various enzymes by low temperature γ-ray polymerization with glassy monomers such as HEMA. (Kobatake, H.)

  19. Fragmentation of delta-diketones by electron impact. Olefin elimination and formation of an enol acetate ion

    International Nuclear Information System (INIS)

    Morizur, J.P.; Mercier, J.; Casals, P.F.

    1985-01-01

    Under electron impact delta-diketones lose an olefin. The mechanism and structure of the resulting ion have been established by several techniques: substitution, Mike and Cid spectra and thermochemical data [fr

  20. Manganese oxide as a promoter for C2-C4 olefin production in the hydrogenation of carbon dioxide

    International Nuclear Information System (INIS)

    Kim, C.; Chen, K.; Hanson, F.V.; Oblad, A.G.; Tsai, Y.

    1986-01-01

    A number of active research and development programs have been initiated to explore the potential of CO hydrogenation process as a source of low molecular weight (C 2 -C 4 ) olefins. Metal catalysts such as Co-Mn, Ni-zeolite, Rd and Mo have been evaluated for low molecular weight olefin selectivity. The coprecipitated Fe-Mn system (Mn/Fe=9/1) was reported to be highly olefin selective. Recently, many investigators reported supporting evidence for the promotional effect of Mn for precipitated Fe catalysts. In this study, Raney Fe promoted with Mn has been evaluated for C 2 -C 4 olefin selectivity in the hydrogenation of CO relative to coprecipitated Fe-Mn catalysts. Catalyst characterization, including BET surface area, X-ray diffraction, selective chemisorption and ESCA, has been carried to provide insight into the role of manganese in both the Coprecipitated and Raney catalyst systems

  1. On the impact of olefins and aromatics in the methanol-to-hydrocarbon conversion over H-ZSM-5 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sun, X.; Mueller, S.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

    2012-07-01

    Methanol-to-hydrocarbons processes using HZSM-5 archetype acidic zeolites or zeotype SAPO-34 catalysts are regarded as a vital suite of conversion technologies to bypass petroleum-based routes for the production of specific fuels and petrochemical commodities. Special significance of the methanol chemistry originates from its versatility enabling selective transformations towards various products. Industry demonstrated successfully implementations of Methanol-To-Gasoline, Methanol-To-Olefin, and Methanol-To-Propylene processes, although the typical single-pass selectivity remained limited and recycling is necessary. Considerable fundamental research efforts both from experimental and computational sides contributed to unravel the underlying complex reaction mechanism. The indirect hydrocarbon pool mechanism, in which Broensted acid sites combined with adsorbed light olefins or lower methylbenzenes act as active centers, is generally accepted to explain the formation of light olefins. As olefin and aromatics populated catalytic sites show different reactivity in terms of activity and selectivity to ethylene or propylene, one could envision optimizing the product distribution by suitable co-feeding of specific hydrocarbons. The present work addresses three questions with an experimental study conducted under realistic MTP operation conditions: (1) How are ethylene and propylene formed at molecular level? (2) Which reaction pathway leads to the formation of undesired hydrogen transfer products? (3) Does olefin or aromatics co-feeding change the selectivity to ethylene or propylene? Xylenes and various olefins were co-fed with methanol to achieve a detailed understanding of the reaction mechanism over acidic HZSM-5 zeolites. Results suggest, that an olefin homologation/cracking route (olefin cycle) accounts for the autocatalytic (-like) nature and the majority of methanol consumption rather than the route involving aromatic intermediates (aromatics cycle). Co

  2. Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

    OpenAIRE

    Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

    2016-01-01

    Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction wi...

  3. Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

    Science.gov (United States)

    Chang, Chi-Hao; Chou, Chih-Ming

    2018-04-06

    This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

  4. Highly Convergent Total Synthesis of (+)-Lithospermic Acid via a Late-Stage Intermolecular C–H Olefination

    Science.gov (United States)

    Wang, Dong-Hui; Yu, Jin-Quan

    2011-01-01

    The total synthesis of (+)-lithospermic acid is reported, which exploits two successive C–H activation reactions as the key steps. Rh-catalyzed carbene C–H insertion reaction using Davies’ catalyst built the dihydrobenzofuran core, and a late-stage intermolecular C–H olefination coupled the olefin unit with the dihydrobenzofuran core to construct the molecule in a highly convergent manner. PMID:21443224

  5. Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates.

    Science.gov (United States)

    Feng, Chao; Feng, Daming; Loh, Teck-Peng

    2013-07-19

    Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

  6. Packaging based on polymeric materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2005-01-01

    Full Text Available In the past two years the consumption of common in the developed countries world wide (high tonnage polymers for packaging has approached a value of 50 wt.%. In the same period more than 50% of the packaging units on the world market were made of polymeric materials despite the fact that polymeric materials present 17 wt.% of all packaging materials. The basic properties of polymeric materials and their environmental and economical advantages, providing them such a position among packaging materials, are presented in this article. Recycling methods, as well as the development trends of polymeric packaging materials are also presented.

  7. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  8. Synthesis of magnetic polymeric microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I [M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow (Russian Federation)

    2010-05-13

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  9. Synthesis of magnetic polymeric microspheres

    International Nuclear Information System (INIS)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I

    2010-01-01

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  10. The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

    Science.gov (United States)

    Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

    2018-07-01

    Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. Propagation/depropagation equilibrium and structural factors in the radiation degradation of poly(olefin sulfone)s

    International Nuclear Information System (INIS)

    Bowmer, T.N.; O'Donnell, J.H.

    1981-01-01

    The principal volatile products observed after γ irradiation of nine different poly(olefin sulfone)s in the solid state were the two comonomers, i.e., the respective olefin and sulfur dioxide. An exponential increase in yield, G (volatile products), with increasing irradiation temperature, T/sub irr/, was observed for each copolymer through the ceiling temperature, T/sub c/, for the corresponding propagation/depropagation equilibrium. Thus the G value increased by ca. 3 orders of magnitude from T/sub irr/ = 0.7 T/sub c/ to T/sub irr/ = 1.3 T/sub c/ for all of the poly(olefin sulfone)s. Depropagation sensitivity was considered to be best measured by G(SO 2 ) since radiation induced, cationic homopolymerization of the product olefin occurred to a variable extent. Five of the poly(olefin sulfone)s had similar rates of depropagation at their respective T/sub c's/ but the polysulfones of 1-hexene, cyclohexene and 2-butene showed anomalously high depropagation rates. This may be related to greater steric hinderance to segmental chain mobility in the polysulfones of the 1,2 disubstituted olefins. Poly(1-hexene sulfone) appears to be anomalous, as in other respects

  12. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

    Science.gov (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

    2017-01-18

    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  13. First principles study of propene polymerization in Ziegler-Natta heterogeneous catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Boero, M.; Parrinello, M.; Hueffer, S.; Weiss, H.

    2000-01-26

    In this work the authors address the problem of isotacticity in a realistic heterogeneous Ziegler-Natta system by means of ab initio molecular dynamics. A previously identified 5-fold catalytic center was selected and examined for its ability to select the appropriate olefin enantioface in the chain growth process. The first steps in the propene polymerization process were studied to determine the energetics of the initial complexation phase for the different stereochemical orientations of the incoming propene. Then the authors analyze the subsequent insertions which represent the crucial issue for the formation of a stereospecific polymer chain, and find that the 5-fold catalytic center possesses a huge degree of stereoselectivity. The role of the agostic interaction was examined which can switch from {alpha} to {beta} and allow, even in the presence of a substrate, process that can lead to chain termination.

  14. Femtosecond laser ablation of polymeric substrates for the fabrication of microfluidic channels

    International Nuclear Information System (INIS)

    Suriano, Raffaella; Kuznetsov, Arseniy; Eaton, Shane M.; Kiyan, Roman; Cerullo, Giulio; Osellame, Roberto; Chichkov, Boris N.; Levi, Marinella; Turri, Stefano

    2011-01-01

    This manuscript presents a study of physical and chemical properties of microchannels fabricated by femtosecond laser processing technology in thermoplastic polymeric materials, including poly(methyl methacrylate) (PMMA), polystyrene (PS) and cyclic olefin polymer (COP). By surface electron microscopy and optical profilometry, the dimensions of microchannels in the polymers were found to be easily tunable, with surface roughness values comparable to those obtained by standard prototyping techniques such as micromilling. Through colorimetric analysis and optical microscopy, PMMA was found to remain nearly transparent after ablation while COP and PS darkened significantly. Using infrared spectroscopy, the darkening in PS and COP was attributed to significant oxidation and dehydrogenation during laser ablation, unlike PMMA, which was found to degrade by a thermal depolymerization process. The more stable molecular structure of PMMA makes it the most viable thermoplastic polymer for femtosecond laser fabrication of microfluidic channels.

  15. Effects of Polymeric Dielectric Morphology on Pentacene Morphology and Organic TFT Characteristics

    Directory of Open Access Journals (Sweden)

    Ye Rongbin

    2016-01-01

    Full Text Available In this paper, we report on the effects of the polymeric dielectric morphology on pentacene morphology and organic thin film transistor (TFT characteristics. The morphology and thickness of cyclo-olefin polymer (COP dielectric could be controlled by selecting a solvent. Higher the solvent’s boiling point is, thinner and smother COP films could be obtained. Using the solvent of trimethylcyclohexane, the spin-coated COP films of ca. 330 nm with the peak-to-valley of 7.35 nm and the roughness of root mean square of 0.58 nm were obtained, and pentacene TFT showed high mobility of 2.0 cm2V-1s-1, which originated from highly ordering of pentacene thin films deposited on the smoother and thinner COP films.

  16. A novel approach to the design and operation scheduling of heterogeneous catalytic reactors

    International Nuclear Information System (INIS)

    Ghodasara, Kamlesh; Smith, Robin; Hwang, Sungwon

    2014-01-01

    A number of studies have been conducted to reduce the overall level of catalyst deactivation in heterogeneous catalytic reactors, and improve the performance of reactors, such as yield, conversion or selectivity. The methodology generally includes optimization of the following: (1) operating conditions of the reaction system, such as feed temperature, normal operating temperature, pressure, and composition of feed streams; (2) reactor design parameters, such as dimension of the reactor, side stream distribution along the axis of the reactor beds, the mixing ratio of inert catalyst at each bed; and (3) catalyst design parameters, such as the pore size distribution across the pellet, active material distribution, size and shape of the catalyst, etc. Few studies have examined optimization of the overall catalyst reactor performance throughout the catalyst lifetime, considering catalyst deactivation. Furthermore, little attention has been given to the impact of various configurations of reactor networks and scheduling of the reactor operation (i.e., online and offline-regeneration) on the overall reactor performance throughout the catalyst lifetime. Therefore, we developed a range of feasible sequences of reactors and scheduling of reactors for operation and regeneration, and compared the overall reactor performance of multiple cases. Furthermore, a superstructure of reactor networks was developed and optimized to determine the optimum reactor network that shows the maximum overall reactor performance. The operating schedule of each reactor in the network was considered further. Lastly, the methodology was illustrated using a case study of the MTO (methanol to olefin) process

  17. Key product development based on cyclo olefin polymer for LCD-TV

    Science.gov (United States)

    Konishi, Yuichiro; Kobayashi, Masahi; Arakawa, Kouhei

    2006-09-01

    Cyclo Olefin Polymer (COP), which was developed by Zeon Corporation, is well known and used as an optical plastic in optical markets, having unique properties such as high light transmission, low water absorption, low birefringence etc. Optes Inc, who is ZEON CORPORATION's affiliate optical parts manufacturer, has succeeded in the development of high performance optical base films. These are used for retardation and polarizing films in LCD's (Liquid Crystal Displays), made from Cyclo Olefin Polymer with own film extrusion technologies. The Optical base film developed by Optes Inc has superior properties compared with those of existing products such as polycarbonate (PC), polyethylene terephthalate (PET) and Triacetate Cellulose (TAC) base in terms of low birefringence, high optical isotropy and high dimensional stability under high humidity and temperature conditions.

  18. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, César A.

    2013-05-08

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  19. Synthesis and characterization of new magnetically recoverable molybdenum nanocatalyst for epoxidation of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Masteri-Farahani, M., E-mail: mfarahany@yahoo.com [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of); Kashef, Z. [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of)

    2012-04-15

    New heterogeneous molybdenum catalyst was prepared through covalent attachment of a Schiff base ligand on the surface of silica coated magnetite nanoparticles via aminopropyl spacer and subsequent complexation with MoO{sub 2}(acac){sub 2}. The prepared nanocatalyst was characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies and vibrating sample magnetometry. Catalytic epoxidation of some olefins and allylic alcohols by prepared nanocatalyst using tert-butyl hydroperoxide and cumene hydroperoxide as oxidants was achieved with good activities and selectivities. - Highlights: Black-Right-Pointing-Pointer Silica coated magnetite nanoparticles were modified with a Schiff base ligand. Black-Right-Pointing-Pointer Next reaction with MoO{sub 2}(acac){sub 2} afforded magnetically recoverable nanocatalyst. Black-Right-Pointing-Pointer The prepared nanocatalyst catalyzed the epoxidation of olefins with TBHP.

  20. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, Cé sar A.; Poater, Albert; Lé bl, Tomá š; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  1. Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

    Science.gov (United States)

    Meng, Xiangtao; Edgar, Kevin J

    2015-11-05

    Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Improving energy efficiency of an Olefin plant – A new approach

    International Nuclear Information System (INIS)

    Tahouni, Nassim; Bagheri, Narges; Towfighi, Jafar; Hassan Panjeshahi, M.

    2013-01-01

    Highlights: • The retrofit of an Olefin plant is studied to improve the overall energy efficiency. • Three levels of retrofit and optimization of this process are suggested. • A simultaneous method is presented to optimize low-temperature separation processes. - Abstract: Low-temperature gas separation processes are the most important gas separation routes. There is a complex interaction between core process (separation columns), associated heat exchanger network and refrigeration cycles in sub ambient processes. The aim of this paper is performing a comprehensive retrofit study of an Olefin plant (as an industrial example) to improve the overall energy efficiency. In this regard, the effect of improving column operating parameters and refrigeration cycles are first evaluated separately. Then, column operating parameters and refrigeration cycles as well as heat exchanger network are optimized simultaneously using genetic algorithm or simulated annealing. Having compared all results, one can conclude that simultaneous optimization leads to higher efficiency of the overall system

  3. Sustainable solid catalyst alkylation of commercial olefins by regeneration with supercritical isobutane

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2005-12-01

    Supercritical isobutane regeneration of a USY zeolite alkylation catalyst was examined in a continuous, automated reaction / regeneration system. Two feeds were studied; a synthetic isobutane / 2-butene blend, and a commercial refinery isoparaffin / olefin blend. The refinery blend was minimally treated, containing a variety of light olefins, and contaminants, including butadiene, oxygenates and sulfur, which are well known to cause severe catalyst deactivation. Synthetic feed experiments showed that high levels of butene conversion was maintained for more than 200 hours time on stream, and that product quality and catalyst maintenance was relatively stable over the course of the experiment using a 3 hour reaction / 3 hour regeneration cycle. Catalyst activity maintenance was lower when the commercial feed was employed. High levels of alkene conversion were maintained for 78 hours and 192 hours using a 3 hour reaction / 3 hour regeneration cycle and a 2 hour reaction / 2 hour regeneration cycle, respectively.

  4. A Wittig-olefination-Claisen-rearrangement approach to the 3-methylquinoline-4-carbaldehyde synthesis.

    Science.gov (United States)

    Kulkarni, Mukund G; Desai, Mayur P; Birhade, Deekshaputra R; Shaikh, Yunus B; Dhatrak, Ajit N; Gannimani, Ramesh

    2012-01-01

    Efficient syntheses are described for the synthetically important 3-methylquinoline-4-carbaldehydes 6a-h from o-nitrobenzaldehydes 1a-h employing a Wittig-olefination-Claisen-rearrangement protocol. The Wittig reaction of o-nitrobenzaldehydes with crotyloxymethylene triphenylphosphorane afforded crotyl vinyl ethers 2a-h, which on heating under reflux in xylene underwent Claisen rearrangement to give 4-pentenals 3a-h. Protection of the aldehyde group of the 4-pentenals as acetals 4a-h and subsequent oxidative cleavage of the terminal olefin furnished nitroaldehydes 5a-h. Reductive cyclization of these nitroaldehydes yielded the required 3-methylquinoline-4-carbaldehydes 6a-h in excellent yields. Therefore, an efficient method was developed for the preparation of 3-methylquinoline-4-carbaldehydes from o-nitrobenzaldehydes in a simple five-step procedure.

  5. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Cleavage of olefinic double bonds by mediated anodic oxidation

    International Nuclear Information System (INIS)

    Baeumer, U.-St.; Schaefer, H.J.

    2003-01-01

    Seven alkenes, e.g. 1-decene, methyl oleate, cyclododecene, norbornene, are cleaved by indirect anodic oxidation with IO 4 - /RuCl 3 as mediator to carboxylic acids. The best performance was achieved with two alternative ex cell-methods. Periodate is regenerated from iodate in a divided cell at a PbO 2 /Ti-anode. In the chemical reactor alkene and the produced carboxylic acid are immobilized in a chromatography column on Chromosorb W and oxidized with IO 4 - /RuO 4 in CH 3 CN/water. In the alternative version the alkene is oxidized in an emulsion generated by sonication and the organic phase is retained in the reactor by a separator. Acids and diacids are obtained in 61-91% chemical yield and good current yields. The amount of consumed periodate can be reduced to less than 5% of the amount needed for the chemical oxidation. The mediated anodic cleavage of alkenes is altogether an interesting alternative to ozonolysis

  7. Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

    Science.gov (United States)

    Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

    2013-03-06

    A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

  8. Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

    Energy Technology Data Exchange (ETDEWEB)

    McCann, Ronán [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin 9 (Ireland); Bagga, Komal; Groarke, Robert [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); Stalcup, Apryll [Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); School of Chemical Sciences, Dublin City University, Dublin 9 (Ireland); Vázquez, Mercedes, E-mail: mercedes.vazquez@dcu.ie [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); School of Chemical Sciences, Dublin City University, Dublin 9 (Ireland); Brabazon, Dermot [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin 9 (Ireland)

    2016-11-30

    Highlights: • Rapid single-step microchannel fabrication on optically transparent cyclic olefin polymer using IR Nd:YAG laser. • Ability to tailor channel depth between 12–47 μm demonstrated for single laser pass. • Use of multiple laser passes showed capability for finer depth control. • Potential applications in lab-on-chip and microfluidic devices. - Abstract: This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

  9. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora

    2016-07-21

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  10. InCl3/NaClO: a reagent for allylic chlorination of terminal olefins

    International Nuclear Information System (INIS)

    Pisoni, Diego S.; Gamba, Douglas; Fonseca, Carlos V.; Costa, Jesse S. da; Petzhold, Cesar L.; Oliveira, Eduardo R. de; Ceschi, Marco A.

    2006-01-01

    Indium trichloride promotes the chlorination of terminal olefins in the presence of sodium hypochlorite with good results. Carvone was chosen as a model compound to examine some of the general features of this reaction, such as stoichiometry, temperature, reaction time and product conversion. Treatment of β-pinene with sodium hypochlorite in the presence of indium trichloride resulted in a facile rearrangement to selectively yield perillyl chloride, which is an important precursor for C-7 oxygenated limonenes. (author)

  11. Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

    International Nuclear Information System (INIS)

    McCann, Ronán; Bagga, Komal; Groarke, Robert; Stalcup, Apryll; Vázquez, Mercedes; Brabazon, Dermot

    2016-01-01

    Highlights: • Rapid single-step microchannel fabrication on optically transparent cyclic olefin polymer using IR Nd:YAG laser. • Ability to tailor channel depth between 12–47 μm demonstrated for single laser pass. • Use of multiple laser passes showed capability for finer depth control. • Potential applications in lab-on-chip and microfluidic devices. - Abstract: This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

  12. Constructing Multiply Substituted Arenes Using Sequential Pd(II)-Catalyzed C–H Olefination**

    Science.gov (United States)

    Engle, Keary M.; Wang, Dong-Hui; Yu, Jin-Quan

    2011-01-01

    Complementary catalytic systems have been developed in which the reactivity/selectivity balance in Pd(II)-catalyzed ortho-C–H olefination can be modulated through ligand control. This allows for sequential C–H functionalization for the rapid preparation of 1,2,3-trisubstituted arenes. Additionally, a rare example of iterative C–H activation, in which a newly installed functional group directs subsequent C–H activation has been demonstrated. PMID:20632344

  13. Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

    KAUST Repository

    Fava, Eleonora; Nakajima, Masaki; Nguyen, Anh L. P.; Rueping, Magnus

    2016-01-01

    A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

  14. Electrochemical energy storage by polyaniline nanofibers: high gravity assisted oxidative polymerization vs. rapid mixing chemical oxidative polymerization.

    Science.gov (United States)

    Zhao, Yibo; Wei, Huige; Arowo, Moses; Yan, Xingru; Wu, Wei; Chen, Jianfeng; Wang, Yiran; Guo, Zhanhu

    2015-01-14

    Polyaniline (PANI) nanofibers prepared by high gravity chemical oxidative polymerization in a rotating packed bed (RPB) have demonstrated a much higher specific capacitance of 667.6 F g(-1) than 375.9 F g(-1) of the nanofibers produced by a stirred tank reactor (STR) at a gravimetric current of 10 A g(-1). Meanwhile, the cycling stability of the electrode is 62.2 and 65.9% for the nanofibers from RPB and STR after 500 cycles, respectively.

  15. Characterization and properties of plasma polymerized 2-vinylpyridine

    International Nuclear Information System (INIS)

    Bieg, K.W.; Ottesen, D.K.; Brower, K.L.

    1979-11-01

    The chemical structure, aging, thermal, and adhesive behavior of plasma-deposited 2-vinylpyridine has been investigated. The molecular structure of the plasma polymer is significantly different from the conventional, linear polymer and is strongly dependent on plasma reactor variables. Additional cyano, methyl, and olefinic groups were identified in the plasma polymer, and aromaticity retention was reduced at the more severe (low pressure, high rf power) reactor conditions studied. Post-deposition oxidation occurred, which followed approximately first order kinetics initially (ΔE approx. 11.6 Kcal/mole, with approx. 25% conversion of aromatic rings to an aromatic ketone in 4.5 months at 23 0 C). Oxidation was significantly reduced in vacuum, inert gas, and hydrogen atmospheres. Thermal weight loss began at relatively low temperatures and appeared to accompany an exothermic, irreversible cross-linking reaction which began at about 100 0 C. Principle low temperature decomposition products were low molecular weight gases (primarily, CO 2 ) and 2-methylpyridine. A quantitative tensile-pull adhesion test was developed. Using this technique, the plasma polymer-aluminum cohesive bond strength was found to be 480 psi and was degraded at high humidity levels

  16. Surface functionalization of cyclic olefin copolymer (COC) with evaporated TiO{sub 2} thin film

    Energy Technology Data Exchange (ETDEWEB)

    El Fissi, Lamia, E-mail: lamia.elfissi@uclouvain.be [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium); Vandormael, Denis [SIRRIS Liege Science Park, 4102 Seraing (Belgium); Houssiau, Laurent [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Francis, Laurent A. [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium)

    2016-02-15

    Highlights: • TiO{sub 2}/COC (cyclic olefin copolymer) hybrid material for BioMEMS applications. • Thin layer of TiO{sub 2} was deposed on cyclic olefin copolymer using physical vapor deposition (PVD) technique. • The coating possess the highest level of adhesion with an excellent morphology of the hybrid material (TiO{sub 2}/COC). - Abstract: Cyclic olefin copolymer (COC) is a new class of thermoplastic polymers used for a variety of applications ranging from bio-sensing to optics. However, the hydrophobicity of native COC hampers the further development and application of this material [1]. In this work, we report the structural, morphological, and optical properties of the TiO{sub 2}/COC hybrid material, which provides a desirable substrate for optical devices and subsequent surface modifications. The TiO{sub 2} film on COC substrate was deposited by the evaporation method, and it was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), profilometry and atomic force microscope (AFM). Using an UV-vis spectrophotometer, we found that the transmittance of the TiO{sub 2}/COC hybrid material in the visible domain reached 80%. The TiO{sub 2}/COC hybrid appeared to be stable in most of the assessed polar solvents and acid/basic solutions. The new TiO{sub 2}/COC hybrid material and the robust fabrication method are expected to enable a variety of BioMEMS applications.

  17. Energy and materials flows in the production of olefins and their derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Gaines, L.L.; Shen, S.Y.

    1980-08-01

    Production of olefins and their derivatives uses almost 3.5% of the oil and gas consumed annually in the United States. It is estimated that their production requires an input energy of 2 Q, which is 50% of the energy used in the production of all petrochemicals. Substantial amounts of this energy could be recovered through recycling. For example, recycling of a single plastic product, polyester soft drink bottles, could have recovered about 0.014 Q in 1979. (About 1.4 Q is used to produce plastic derivatives of olefins). Petrochemical processes use fuels as feedstocks, as well as for process energy, and a portion of this energy is not foregone and can be recovered through combustion of the products. The energy foregone in the production of ethylene is estimated to be 7800 Btu/lb. The energy foregone in plastics production ranges from 12,100 Btu/lb for the new linear low-density polyethylene to 77,200 Btu/lb for nylon 66, which is about 60% of the total energy input for that product. Further investigation of the following areas could yield both material and energy savings in the olefins industry: (1) recycling of petrochemical products to recover energy in addition to that recoverable through combustion, (2) impact of feedstock substitution on utilization of available national resources, and (3) effective use of the heat embodied in process steam. This steam accounts for a major fraction of the industry's energy input.

  18. Positive ion scavenging by olefins in trans-decalin: TRMC and product analysis studies

    International Nuclear Information System (INIS)

    Warman, J.M.; Leng, H.C. de; Haas, M.P. de; Anisimov, O.A.

    1990-01-01

    The rate constants for scavenging of the mobile positive ion in trans-decalin have been measured using the time-resolved microwave conductivity (TRMC) pulse radiolysis technique for a series of olefins and cyclopropane. For the olefins the values vary from ≤2 x 10 8 dm 3 /mol/s for ethylene to 1.6 x 10 11 dm 3 /mol/s for cyclohexene. Steady-state (γ) radiolysis of solutions of isobutene in trans-decalin results in the formation of isobutane and C 8 and C 14 products which display different dependences on solute concentration. The results are explained in terms of the formation of a complex between the solvent radical cation and isobutene which can dissociate, within a timescale of approx. 1 ns, to give isobutane or on neutralisation leads to the formation of C 14 condensation products. The C 8 products which are formed above 5 x 10 -2 mol/dm 3 are attributed to reaction of the complex with isobutene to form the olefin dimer cation. Cyclopropane is unreactive, i.e. k 8 dm 3 /mol/s, towards the mobile positive ion in trans-decalin (author)

  19. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    Science.gov (United States)

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  20. Co-Aromatization of Methane with Olefins: The Role of Inner Pore and External Surface Catalytic Sites

    Energy Technology Data Exchange (ETDEWEB)

    Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); He, Peng [University of Calgary; Jarvis, Jack [University of Calgary; Meng, Shijun [University of Calgary; Wang, Aiguo [University of Calgary; Kou, Shiyu [University of Calgary; Gatip, Richard [University of Calgary; Liu, Lijia [Soochow University; Song, Hua [University of Calgary

    2018-04-22

    The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, which might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.

  1. Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

    KAUST Repository

    Caporaso, Lucia; Loria, Marianna; Mazzeo, Mina; Michiue, Kenji; Nakano, Takashi; Fujita, Terunori; Cavallo, Luigi

    2012-01-01

    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

  2. Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

    KAUST Repository

    Caporaso, Lucia

    2012-11-13

    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

  3. Collaborative Research: Polymeric Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Shenqiang [Temple Univ., Philadelphia, PA (United States). College of Engineering

    2017-04-20

    The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamental understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.

  4. Polymerization with freezing

    International Nuclear Information System (INIS)

    Ben-Naim, E; Krapivsky, P L

    2005-01-01

    Irreversible aggregation processes involving reactive and frozen clusters are investigated using the rate equation approach. In aggregation events, two clusters join irreversibly to form a larger cluster; additionally, reactive clusters may spontaneously freeze. Frozen clusters do not participate in merger events. Generally, freezing controls the nature of the aggregation process, as demonstrated by the final distribution of frozen clusters. The cluster mass distribution has a power-law tail, F k ∼k -γ , when the freezing process is sufficiently slow. Different exponents, γ = 1 and 3, are found for the constant and the product aggregation rates, respectively. For the latter case, the standard polymerization model, either no gels, or a single gel, or even multiple gels, may be produced

  5. Nuclear reactors

    International Nuclear Information System (INIS)

    Barre, Bertrand

    2015-10-01

    After some remarks on the nuclear fuel, on the chain reaction control, on fuel loading and unloading, this article proposes descriptions of the design, principles and operations of different types of nuclear reactors as well as comments on their presence and use in different countries: pressurized water reactors (design of the primary and secondary circuits, volume and chemistry control, backup injection circuits), boiling water reactors, heavy water reactors, graphite and boiling water reactors, graphite-gas reactors, fast breeder reactors, and fourth generation reactors (definition, fast breeding). For these last ones, six concepts are presented: sodium-cooled fast reactor, lead-cooled fast reactor, gas-cooled fast reactor, high temperature gas-cooled reactor, supercritical water-cooled reactor, and molten salt reactor

  6. Polymeric micelles for drug targeting.

    Science.gov (United States)

    Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh

    2007-11-01

    Polymeric micelles are nano-delivery systems formed through self-assembly of amphiphilic block copolymers in an aqueous environment. The nanoscopic dimension, stealth properties induced by the hydrophilic polymeric brush on the micellar surface, capacity for stabilized encapsulation of hydrophobic drugs offered by the hydrophobic and rigid micellar core, and finally a possibility for the chemical manipulation of the core/shell structure have made polymeric micelles one of the most promising carriers for drug targeting. To date, three generations of polymeric micellar delivery systems, i.e. polymeric micelles for passive, active and multifunctional drug targeting, have arisen from research efforts, with each subsequent generation displaying greater specificity for the diseased tissue and/or targeting efficiency. The present manuscript aims to review the research efforts made for the development of each generation and provide an assessment on the overall success of polymeric micellar delivery system in drug targeting. The emphasis is placed on the design and development of ligand modified, stimuli responsive and multifunctional polymeric micelles for drug targeting.

  7. Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

    [1]Ewen, J. A., Novel method for plastic production, Science (in Chinese), 1997, 9: 34.[2]Brintzinger, H. H., Fischer, D., Waymouth, R. M. et al., Stereospecific olefin polymerization with chiral metallocene catalysts, Angewandte Chemie International Edition in English, 1995, 34(11): 1143.[3]Matyjaszewski, K., Atom transfer radical polymerization, role of various components and reaction conditions, Polym. Prep., 1997, 38(2): 736.[4]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, atom transfer radical polymerization in the presence of transition-metal complex, J. Am. Soc., 1995, 117: 5614.[5]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 1995, 28: 7901.[6]Koto, M., Kamigaito, M., Sawamoto, M. et al., Polymerization of methyl methacrylate with the carbon tetrachloride/dichloro-tris(triphenyphosphine) ruthenium(II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possible of living radical polymerization, Macromolecules, 1995, 28: 1721.[7]Ando, T., Kato, M., Living radical polymerization of methyl methacrylate with Ruthenium complex: formation of polymers with controlled molecular weights and very narrow distributions, Macromolecules, 1996, 29: 1070.[8]Granel, C., Dubios, P., Jerome, R. et al., Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides, Macromolecules, 1996, 29: 8576.[9]Granel, C., Moineau, G., Lecome, P. et al., (Meth)acrylates pseudo-living radical polymerization in the presence of transition metal complexes: the kharasch reaction revisited, Polym. Prep., 1997, 38(1): 450.[10]Ando, T., Kamigaito, M., Sawamoto, M., Iron(II) chloride complex for living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30: 4507.[11

  8. Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

    KAUST Repository

    Riache, Nassima; Callens, Emmanuel; Espinas, Jeff; Dé ry, Alexandre; Samantaray, Manoja; Dey, Raju; Basset, Jean-Marie

    2015-01-01

    Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

  9. Maximizing light olefins production in fluid catalytic cracking (FCC) units; Maximizacao de olefinas leves em unidades de craqueamento catalitico fluido

    Energy Technology Data Exchange (ETDEWEB)

    Pimenta, Ricardo D.M.; Pinho, Andrea de Rezende [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    The Fluid Catalytic Cracking (FCC) process is widely spread over the ten PETROBRAS refineries in its thirteen industrial units. The importance of the FCC process resides on its high gasoline output, being the main supplier of this important product to the system. Additionally, FCC process is the main source of light hydrocarbons in the LPG range, including light olefins. The increasing demand for ethylene, propylene and butylenes was encouraging to concentrate the research efforts on studies about alternatives for the traditional FCC process. In the present work, the proposals from main licensors (UOP, KBR, Stone and Webster) for a light-olefins-driven FCC process (Petrochemical FCC) will be compared. Furthermore, the catalytic route for light olefins production in FCC units is also described. An additive based on ZSM- 5 zeolite, which is produced following a PETROBRAS proprietary technology, is being largely applied into the catalyst inventories of all FCC units. An analysis of different scenarios was performed to estimate the maximum potential of light olefins production from the highest possible ZSM-5 additive usage. More specifically for the case of ethylene, which production is also boosted by the same type of additive, studies are being conducted with the objective of recovering it from a C2 stream using specific units to do the splitting (UPGR). The search for increasing light olefins production in the refining processes is in line with PETROBRAS strategic plan which targeted for the company a more intense activity in the Brazilian petrochemical market (author)

  10. The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

    International Nuclear Information System (INIS)

    Miyazaki, Tetsuo

    1991-01-01

    The formation of olefin cations in the radiolysis of 2,3-dimethylbutane (DMB) was studied by ESR at 4.2 and 77 K. When a DMB-SF 6 mixture is γ-irradiated at 77 K, tetramethylethylene (TME) cations are formed remarkably. The formation of the TME cations, however, is suppressed at 4.2 K. When the DMB-SF 6 mixture is γ-irradiated at 4.2 K and then warmed to 77 K, TME cations are formed by thermal annealing. The TME cations are not formed by a charge transfer to olefinic impurities or olefinic products in radiolysis, but by H 2 elimination from parent DMB cations in the ground state. The remarkable formation of olefin cations at 77 K corresponds to the large yields of unsaturated dimers in the radiolysis of DMB at 77 K. The suppression of olefin cation formation at 4.2 K corresponds to the low yields of unsaturated dimers in the radiolysis of DMB at 4.2 K. (author)

  11. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  12. Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas

    NARCIS (Netherlands)

    Oschatz, M; van Deelen, T W; Weber, J L; Lamme, W S; Wang, G; Goderis, B; Verkinderen, O; Dugulan, A I; de Jong, K P

    2016-01-01

    Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon

  13. Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

    Science.gov (United States)

    Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

    2014-09-14

    An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

  14. De fysica van polymere materialen

    NARCIS (Netherlands)

    Struik, L.C.E.

    1987-01-01

    Rede, uitgesproken ter gelegenheid van de aanvaarding van het ambt van buitengewoon hoogleraar in de fysica van polymere materialen aan de Universitelt Twente op donderdag 22 januarì 1987 door Dr.lr. L.C.E. Struik.

  15. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Gnanou, Yves

    2014-01-01

    .e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  16. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  17. Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

    NARCIS (Netherlands)

    Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

    2000-01-01

    Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

  18. H Reactor

    Data.gov (United States)

    Federal Laboratory Consortium — The H Reactor was the first reactor to be built at Hanford after World War II.It became operational in October of 1949, and represented the fourth nuclear reactor on...

  19. Electroactivity in Polymeric Materials

    CERN Document Server

    2012-01-01

    Electroactivity in Polymeric Materials provides an in-depth view of the theory of electroactivity and explores exactly how and why various electroactive phenomena occur. The book explains the theory behind electroactive bending (including ion-polymer-metal-composites –IPMCs), dielectric elastomers, electroactive contraction, and electroactive contraction-expansion cycles.  The book also balances theory with applications – how electroactivity can be used – drawing inspiration from the manmade mechanical world and the natural world around us.  This book captures: A complete introduction to electroactive materials including examples and recent developments The theory and applications of numerous topics like electroactive bending of dielectric elastomers and electroactive contraction and expansion New topics, such as biomimetic applications and energy harvesting This is a must-read within the electroactive community, particularly for professionals and graduate students who are interested in the ...

  20. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Directory of Open Access Journals (Sweden)

    Tanveer Mahamadali Shaikh

    2013-08-01

    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  1. Argentation gas chromatography revisited: Separation of light olefin/paraffin mixtures using silver-based ionic liquid stationary phases.

    Science.gov (United States)

    Nan, He; Zhang, Cheng; Venkatesh, Amrit; Rossini, Aaron J; Anderson, Jared L

    2017-11-10

    Silver ion or argentation chromatography utilizes stationary phases containing silver ions for the separation of unsaturated compounds. In this study, a mixed-ligand silver-based ionic liquid (IL) was evaluated for the first time as a gas chromatographic (GC) stationary phase for the separation of light olefin/paraffin mixtures. The selectivity of the stationary phase toward olefins can be tuned by adjusting the ratio of silver ion and the mixed ligands. The maximum allowable operating temperature of these stationary phases was determined to be between 125°C and 150°C. Nuclear magnetic resonance (NMR) spectroscopy was used to characterize the coordination behavior of the silver-based IL as well as provide an understanding into the retention mechanism of light olefins. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Ligand-Enabled γ-C(sp3)–H Olefination of Amines: En Route to Pyrrolidines

    Science.gov (United States)

    Jiang, Heng; He, Jian; Liu, Tao

    2016-01-01

    Pd(II)-catalyzed olefination of γ-C(sp3)–H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp3)–H olefination reaction. The use of Ns protecting group to direct C(sp3)–H activation of alkyl amine is also a significant step towards practical C–H functionalizations of alkyl amines. PMID:26796676

  3. Cyclic olefin homopolymer-based microfluidics for protein crystallization and in situ X-ray diffraction

    International Nuclear Information System (INIS)

    Emamzadah, Soheila; Petty, Tom J.; De Almeida, Victor; Nishimura, Taisuke; Joly, Jacques; Ferrer, Jean-Luc; Halazonetis, Thanos D.

    2009-01-01

    A cyclic olefin homopolymer-based microfluidics system has been established for protein crystallization and in situ X-ray diffraction. Microfluidics is a promising technology for the rapid identification of protein crystallization conditions. However, most of the existing systems utilize silicone elastomers as the chip material which, despite its many benefits, is highly permeable to water vapour. This limits the time available for protein crystallization to less than a week. Here, the use of a cyclic olefin homopolymer-based microfluidics system for protein crystallization and in situ X-ray diffraction is described. Liquid handling in this system is performed in 2 mm thin transparent cards which contain 500 chambers, each with a volume of 320 nl. Microbatch, vapour-diffusion and free-interface diffusion protocols for protein crystallization were implemented and crystals were obtained of a number of proteins, including chicken lysozyme, bovine trypsin, a human p53 protein containing both the DNA-binding and oligomerization domains bound to DNA and a functionally important domain of Arabidopsis Morpheus’ molecule 1 (MOM1). The latter two polypeptides have not been crystallized previously. For X-ray diffraction analysis, either the cards were opened to allow mounting of the crystals on loops or the crystals were exposed to X-rays in situ. For lysozyme, an entire X-ray diffraction data set at 1.5 Å resolution was collected without removing the crystal from the card. Thus, cyclic olefin homopolymer-based microfluidics systems have the potential to further automate protein crystallization and structural genomics efforts

  4. The Research on Modeling and Simulation of TFE Polymerization Process

    Directory of Open Access Journals (Sweden)

    Jing Gao Sun

    2014-01-01

    Full Text Available PTFE (polytetrafluoroethylene is the fluorinated straight-chain polymer, made by the polymerization of tetrafluoroethylene monomer; it is used widely because of its excellent performance and can be obtained by the polymerization of body, solutions, suspensions, and emulsions. But only the last two are the main ways. This research paper makes simulation based on Polymer Plus. It uses the emulsion polymerization method at background to carry out a semibatch reactor system. Upon the actual production conditions, simulation process under the steady state conditions is used to analyze the effects of the changes on operating conditions; the corresponding dynamic model is created to analyze the impact of the changes of conditions on the entire system. Moreover, the amount of APS which plays an important part in this reaction is discussed for getting the most suitable amount of initiator. Because of less research work on this job, it is so difficult to find the related data from the literature. Therefore, this research will have a great significance for the process of the tetrafluoroethylene emulsion polymerization in the future.

  5. Kinetic advantages of using microwaves in the emulsion polymerization of MMA

    Energy Technology Data Exchange (ETDEWEB)

    Costa, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Santos, A.F.; Fortuny, M. [Programa de Mestrado em Engenharia de Processos, Universidade Tiradentes, Instituto de Tecnologia e Pesquisa, Av. Murilo Dantas, 300, CEP: 49032-490, Aracaju, SE (Brazil); Araujo, P.H.H. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Sayer, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil)], E-mail: csayer@enq.ufsc.br

    2009-03-01

    Microwave irradiation has been an interesting alternative for heating systems and several chemical reactions. In polymerization processes, microwaves can enhance reaction rates or improve specific characteristics of the formed polymer. In this work, the use of microwave irradiation in emulsion polymerization reactions has been studied, using a commercial microwave reactor, which is able to perform syntheses under controlled conditions of temperature and power. Methyl methacrylate emulsion polymerization reactions were faster, resulting in smaller polymer particles, in comparison to the conventional heating method (reactions in a jacketed reactor). Different effects were observed in the emulsion polymerization of butyl acrylate. To study the effect of high power microwave irradiation upon the emulsion polymerization, a pulsed irradiation strategy was developed, in which the samples were repeatedly heated within short intervals of time (about 27 s) at the maximum microwave power. A significant reduction of the total time of irradiation was observed in reactions carried out under the pulsed scheme, showing the kinetic advantages of using microwaves in emulsion polymerization processes.

  6. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  7. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. New synthesis of photocurable silanes and polysiloxanes bearing heterocyclic or olefinic functions

    International Nuclear Information System (INIS)

    Youssef, B.; Lecamp, L.; Garin, S.; Bunel, C.

    1999-01-01

    In this work, we described the synthesis of silanes and polysiloxanes bearing cationic photopolymerizable groups. Two new methods were used. The first one is the reaction between 3-mercapto-propyl-1-triethoxysilane (1) and chloromethylated olefins by a phase transfer catalysis. The second one is the radical addition of (1) or poly(dimethylsiloxane-co-methylmercaptopropylsiloxane) (9) to allyl or vinyl substituted heterocyclic monomers. These methods led to the expected adducts with an excellent yield. The polysiloxanes bearing heterocyclic functional groups linked through thioether bonds were photocurable by cationic route. Under UV light intensity of 17.5 mW/cm 2 , these polymers harden after 15 or 20 s

  9. Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters

    Directory of Open Access Journals (Sweden)

    Fabio Benedetti

    2016-06-01

    Full Text Available The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral β-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

  10. Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins' Bicyclic Sugar Moiety.

    Science.gov (United States)

    Cachatra, Vasco; Almeida, Andreia; Sardinha, João; Lucas, Susana D; Gomes, Ana; Vaz, Pedro D; Florêncio, M Helena; Nunes, Rafael; Vila-Viçosa, Diogo; Calhorda, Maria José; Rauter, Amélia P

    2015-11-20

    2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.

  11. A new approach to ferrocene derived alkenes via copper-catalyzed olefination

    Directory of Open Access Journals (Sweden)

    Vasily M. Muzalevskiy

    2015-11-01

    Full Text Available A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

  12. A new approach to ferrocene derived alkenes via copper-catalyzed olefination.

    Science.gov (United States)

    Muzalevskiy, Vasily M; Shastin, Aleksei V; Demidovich, Alexandra D; Shikhaliev, Namiq G; Magerramov, Abel M; Khrustalev, Victor N; Rakhimov, Rustem D; Vatsadze, Sergey Z; Nenajdenko, Valentine G

    2015-01-01

    A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

  13. Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters.

    Science.gov (United States)

    Benedetti, Fabio; Berti, Federico; Fanfoni, Lidia; Garbo, Michele; Regini, Giorgia; Felluga, Fulvia

    2016-06-21

    The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral β-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

  14. Palladium-Catalyzed Tandem Oxidative Arylation/Olefination of Aromatic Tethered Alkenes/Alkynes.

    Science.gov (United States)

    Gao, Yang; Gao, Yinglan; Wu, Wanqing; Jiang, Huanfeng; Yang, Xiaobo; Liu, Wenbo; Li, Chao-Jun

    2017-01-18

    We describe herein a palladium-catalyzed tandem oxidative arylation/olefination reaction of aromatic tethered alkenes/alkynes for the synthesis of dihydrobenzofurans and 2 H-chromene derivatives. This reaction features a 1,2-difunctionalization of C-C π-bond with two C-H bonds using O 2 as terminal oxidant at room temperature. The products obtained are valuable synthons and important scaffolds in biological agents and natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

    Science.gov (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

    2017-12-01

    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  16. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    Science.gov (United States)

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-04

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel.

  17. Pd(II)-Catalyzed Ortho- or Meta-C–H Olefination of Phenol Derivatives

    Science.gov (United States)

    Dai, Hui-Xiong; Li, Gang; Zhang, Xing-Guo; Stepan, Antonia F.

    2013-01-01

    A combination of weakly coordinating auxiliaries and ligand acceleration allows for the development of both ortho- and meta-selective C–H olefination of phenol derivatives. These reactions demonstrate the feasibility of directing C–H functionalizations when functional groups are distal to target C–H bonds. The meta-C–H functionalization of electron-rich phenol derivatives is unprecedented and orthogonal to previous electrophilic substitution of phenols in terms of regioselectivity. These methods are also applied to functionalize α-phenoxyacetic acids, a fibrate class of drug scaffolds. PMID:23614807

  18. An adaptive self-healing ionic liquid nanocomposite membrane for olefin-paraffin separations.

    Science.gov (United States)

    Pitsch, Fee; Krull, Florian F; Agel, Friederike; Schulz, Peter; Wasserscheid, Peter; Melin, Thomas; Wessling, Matthias

    2012-08-16

    An adaptive self-healing ionic liquid nanocomposite membrane comprising a multi-layer support structure hosting the ionic salt [Ag](+) [Tf(2) N](-) is used for the separation of the olefin propylene and the paraffin propane. The ionic salt renders liquid like upon complexation with propylene, resulting in facilitated transport of propylene over propane at benchmark-setting selectivity and permeance levels. The contacting with acetylene causes the ionic salt to liquefy without showing evidence of forming explosive silver acetylide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Electrochromatography on acrylate-based monolith in cyclic olefin copolymer microchip: an attractive technology.

    Science.gov (United States)

    Ladner, Y; Cretier, G; Faure, K

    2015-01-01

    Electrochromatography (EC) on a porous monolithic stationary phase prepared within the channels of a microsystem is an attractive alternative for on-chip separation. It combines the separation mechanisms of electrophoresis and liquid chromatography. Moreover, the porous polymer monolithic materials have become popular as stationary phase due to the ease and rapidity of fabrication via free radical photopolymerization. Here, we describe a hexyl acrylate (HA)-based porous monolith which is simultaneously in situ synthesized and anchored to the inner walls of the channel of a cyclic olefin copolymer (COC) device in only 2 min. The baseline separation of a mixture of neurotransmitters including six amino acids and two catecholamines is realized.

  20. Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

    Directory of Open Access Journals (Sweden)

    Shaheen M. Sarkar

    2014-01-01

    Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

  1. Dismantlable Thermosetting Adhesives Composed of a Cross-Linkable Poly(olefin sulfone) with a Photobase Generator.

    Science.gov (United States)

    Sasaki, Takeo; Hashimoto, Shouta; Nogami, Nana; Sugiyama, Yuichi; Mori, Madoka; Naka, Yumiko; Le, Khoa V

    2016-03-02

    A novel photodetachable adhesive was prepared using a photodepolymerizable cross-linked poly(olefin sulfone). A mixture of a cross-linkable poly(olefin sulfone), a cross-linking reagent, and a photobase generator functioned as a thermosetting adhesive and exhibited high adhesive strength on quartz plates comparable to that obtained for commercially available epoxy adhesives. The cured resin was stable in the absence of UV light irradiation but completely lost its adhesive strength upon exposure of glued quartz plates to UV light in conjunction with heating to 100 °C.

  2. Exploring new generations of ruthenium olefin metathesis catalysts: The reactivity of a bis-ylidene ruthenium complex by DFT

    KAUST Repository

    Poater, Albert; Credendino, Raffaele; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    Density functional theory calculations were used to predict the behaviour of a potential novel architecture of olefin metathesis catalysts, in which one of the neutral ligands of classical Ru-based catalysts, e.g. a phosphine or an N-heterocyclic carbene, is replaced by an alkylidene group. Introduction of a second alkylidene ligand favors dissociation of the remaining phosphine and the overall energy profile for the metathesis using ethylene as the probe substrate reveals that the proposed bis-alkylidene complexes might match the requirements of a good performing olefin metathesis catalyst. © 2013 The Royal Society of Chemistry.

  3. Pd(II)-catalyzed di-o-olefination of carbazoles directed by the protecting N-(2-pyridyl)sulfonyl group.

    Science.gov (United States)

    Urones, Beatriz; Gómez Arrayás, Ramón; Carretero, Juan Carlos

    2013-03-01

    Despite the significance of carbazole in pharmacy and material science, examples of the direct C-H functionalization of this privileged unit are quite rare. The N-(2-pyridyl)sulfonyl group enables the Pd(II)-catalyzed ortho-olefination of carbazoles and related systems, acting as both a directing and readily removable protecting group. This method features ample structural versatility, affording typically the double ortho-olefination products (at C1 and C8) in satisfactory yields and complete regiocontrol. The application of this procedure to related heterocyclic systems, such as indoline, is also described.

  4. Aerobic Pd-Catalyzed sp3 C–H Olefination: A Route to Both N-Heterocyclic Scaffolds and Alkenes

    Science.gov (United States)

    Stowers, Kara J.; Fortner, Kevin C.

    2011-01-01

    This communication describes a new method for the Pd/polyoxometalate-catalyzed aerobic olefination of unactivated sp3 C–H bonds. Nitrogen heterocycles serve as directing groups, and air is used as the terminal oxidant. The products undergo reversible intramolecular Michael addition, which protects the mono-alkenylated product from over-functionalization. Hydrogenation of the Michael adducts provides access to bicyclic nitrogen-containing scaffolds that are prevalent in alkaloid natural products. Additionally, the cationic Michael adducts undergo facile elimination to release α,β-unsaturated olefins, which can be elaborated in numerous C–C and C–heteroatom bond-forming reactions. PMID:21476513

  5. Advances in Process Intensification through Multifunctional Reactor Engineering

    Energy Technology Data Exchange (ETDEWEB)

    O' Hern, Timothy [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Engineering Sciences Center; Evans, Lindsay [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Materials Sciences and Engineering Center; Miller, Jim [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Materials Sciences and Engineering Center; Cooper, Marcia [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Energetic Components Realization Center; Torczynski, John [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Pena, Donovan [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Gill, Walt [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Engineering Sciences Center

    2011-02-01

    This project was designed to advance the art of process intensification leading to a new generation of multifunctional chemical reactors utilizing pulse flow. Experimental testing was performed in order to fully characterize the hydrodynamic operating regimes associated with pulse flow for implementation in commercial applications. Sandia National Laboratories (SNL) operated a pilot-scale multifunctional reactor experiment for operation with and investigation of pulse flow operation. Validation-quality data sets of the fluid dynamics, heat and mass transfer, and chemical kinetics were acquired and shared with Chemical Research and Licensing (CR&L). Experiments in a two-phase air-water system examined the effects of bead diameter in the packing, and viscosity. Pressure signals were used to detect pulsing. Three-phase experiments used immiscible organic and aqueous liquids, and air or nitrogen as the gas phase. Hydrodynamic studies of flow regimes and holdup were performed for different types of packing, and mass transfer measurements were performed for a woven packing. These studies substantiated the improvements in mass transfer anticipated for pulse flow in multifunctional reactors for the acid-catalyzed C4 paraffin/olefin alkylation process. CR&L developed packings for this alkylation process, utilizing their alkylation process pilot facilities in Pasadena, TX. These packings were evaluated in the pilot-scale multifunctional reactor experiments established by Sandia to develop a more fundamental understanding of their role in process intensification. Lummus utilized the alkylation technology developed by CR&L to design and optimize the full commercial process utilizing multifunctional reactors containing the packings developed by CR&L and evaluated by Sandia. This hydrodynamic information has been developed for multifunctional chemical reactors utilizing pulse flow, for the acid-catalyzed C4 paraffin/olefin alkylation process, and is now accessible for use in

  6. Development of water-borne thermosetting paint by radiation-induced emulsion polymerization

    International Nuclear Information System (INIS)

    Makuuchi, K.; Katakai, A.; Nakayama, H.

    1981-01-01

    In previous papers the features of γ-ray induced emulsion polymerization were studied to use the emulsion as vehicles for water-borne paint. In this paper, the physical properties of thermosetting paints made with emulsions containing N-(n-butoxymethyl)acrylamide (NBM) and hydroxyl and carboxyl functionality were investigated. Since NBM moieties can react with amide, hydroxyl, and carboxyl groups, NBM copolymer emulsions prepared in this study have the self-crosslinking capability. As far as it was investigated, it was difficult to prepare a stable emulsion containing 10% of NBM by the conventional emulsion polymerization by using a water soluble radical initiator such as persulfate. In addition to 1-liter reactor, a pilot-scale plant of 70 liters reactor was used for γ-ray induced emulsion polymerization. Experimental details are given, and results are discussed. (author)

  7. Comparison between rice husk ash and commercial silica as filler in polymeric composites

    International Nuclear Information System (INIS)

    Fernandes, I.J.; Calheiro, D.; Santos, E.C.A. dos; Oliveira, R.; Rocha, T.L.A.C.; Moraes, C.A.M.

    2014-01-01

    The use of rice husk ash (RHA) as filler in polymeric materials has been studied in different polymers. Research reported that RHA may successfully replace silica. The silica production process using ore demands high energy input and produces considerable amounts of waste. Therefore, the replacement of silica by RHA may be economically and environmentally advantageous, reducing environmental impact and adding value to a waste material. In this context, this study characterizes and compares RHA of different sources (travelling grate reactor and fluidized bed reactor) with commercially available silicas to assess performance as filler in polymeric materials. Samples were characterized by X-ray fluorescence, loss on ignition, X-ray diffraction, grain size, specific surface area and specific weight. The results show that RHA may be used as a filler in several polymeric materials.(author)

  8. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  9. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    International Nuclear Information System (INIS)

    Brisset, Florian; Vieillard, Julien; Berton, Benjamin; Morin-Grognet, Sandrine; Duclairoir-Poc, Cécile; Le Derf, Franck

    2015-01-01

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique

  10. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    Energy Technology Data Exchange (ETDEWEB)

    Brisset, Florian, E-mail: florian.brisset@etu.univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Vieillard, Julien, E-mail: julien.vieillard@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Berton, Benjamin, E-mail: benjamin.berton@univ-rouen.fr [EA 3233 SMS, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Morin-Grognet, Sandrine, E-mail: sandrine.morin@univ-rouen.fr [EA 3829 MERCI, Université de Rouen, 1 rue du 7ème Chasseurs, BP281, 27002 Evreux Cedex (France); Duclairoir-Poc, Cécile, E-mail: cecile.duclairoir@univ-rouen.fr [EA 4312 LMSM, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France); Le Derf, Franck, E-mail: franck.lederf@univ-rouen.fr [UMR CNRS 6014 COBRA, FR 3038, Université de Rouen, 55 rue Saint Germain, 27000 Evreux (France)

    2015-02-28

    Graphical abstract: - Highlights: • An effective method to modify cyclic olefin copolymer surface. • The surface of COC was modified by covalent grafting of aryl diazonium salts. • The wettability of COC surface was modulated by diazonium salts. • Photoinitiation and chemical reduction have to be combined to graft diazonium salt on COC surface. - Abstract: Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique.

  11. Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

    Science.gov (United States)

    Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

    2011-01-04

    Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

  12. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin

    2017-01-05

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  13. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin; Hamieh, Ali Imad Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D’ Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

    2017-01-01

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  14. Mesoporous catalysts for the synthesis of clean diesel fuels by oligomerisation of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Catani, Roberto; Rossini, Stefano [Snamprogetti SpA, Via F. Maritano 26, 20092 , MI S. Donato Milanese (Italy); Mandreoli, Monica; Vaccari, Angelo [Dipartimento di Chimica Industriale e dei Materiali, Universita di Bologna, INSTM-UdR di Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy)

    2002-07-03

    Si/Al MCM-41 type mesoporous compounds, as such or containing small amounts of metal (Ni, Rh or Pt), were investigated in the synthesis of clean diesel fuels by oligomerisation of orphan olefin streams. Very good catalytic performances were obtained with C{sub 4} and C{sub 5} olefins, while almost no conversion occurred with ethylene. The activity increased with increasing reaction pressure, temperature and contact time, while high Si/Al ratios had a negative effect on both activity and catalyst stability. The presence of small amount of metal inside the mesoporous structure did not significantly modify the catalytic activity, although specific effects were detected for each element. Since the evaluation of the cetane number by H-NMR gave rise to values about 20% lower than the actual value, a new and more complex algorithm is proposed to calculate the cetane number. Using the proposed algorithm, a good correlation index was found between calculated and motor values for pure compounds. Further study is necessary to move from pure compounds to experimental mixtures.

  15. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  16. Polymeric media for tritium fixation

    International Nuclear Information System (INIS)

    Franz, J.A.; Burger, L.L.

    1975-01-01

    The synthesis and leach testing of several polymeric media for tritium fixation are presented. Tritiated bakelite, poly(acrylonitrile) and polystyrene successfully fixed tritium. Tritium leach rates at the tracer level appear to be negligible. Advantages and disadvantages of the processes are discussed, and further bench-scale investigations underway are reported. Rough cost estimates are presented for the different media and are compared with alternate approaches such as deep-well injection and long-term tank storage. Polymeric media costs are high compared to deep-well storage and are of the same order of magnitude per liter of water as for isotopic enrichment. With this limitation, polymeric media can be economically feasible only for highly concentrated tritiated wastes. It is recommended that the bakelite and polystyrene processes be examined on a larger scale to permit more accurate cost analysis and process design. (auth)

  17. H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

    Czech Academy of Sciences Publication Activity Database

    Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

    2017-01-01

    Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol-to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

  18. Comparison of mesoporous SSZ-13 and SAPO-34 zeolite catalysts for the methanol-to-olefins reaction

    NARCIS (Netherlands)

    Wu, L.; Hensen, E.J.M.

    2014-01-01

    Several approaches to improve the catalytic performance of SSZ-13 and SAPO-34 for application as acid catalysts in the methanol-to-olefins (MTO) reaction were explored. Silylation of mesoporous SSZ-13 with a Si/Al ratio of 20 zeolite resulted in increased lifetime in the MTO reaction. Lowering the

  19. Kinetics of olefin arylation by bis(triphenylphosphine) diacetatopalladium(II) (PPAP) and trans-cis isomerization of the latter

    Energy Technology Data Exchange (ETDEWEB)

    Ryabov, A.D.; Yatsimirskii, A.K.

    1979-01-01

    In the absence of olefins, at 70/sup 0/C, PPAP dissolved in glacial acetic acid rapidly decomposed into triphenylphosphine (TPP) oxide, biphenyl, and metallic palladium, after an induction period of about ten minutes. At lower temperatures in this solvent, pure trans-PPAP was converted into the more stable cis-isomer. The conversion was 70-80Vertical Bar3<, increased with temperature (25/sup 0/-45/sup 0/C), and was inhibited by free TPP. Interaction of PPAP with styrene in glacial acetic acid at 70/sup 0/C occurred with an induction period and gave stilbene (80Vertical Bar3< yield) and TPP oxide. The induction period was independent of the concentration of PPAP or olefin and coincided with that in PPAP decomposition in the absence of olefin. Similar regularities were observed in PPAP interaction with p-methoxystyrene and p-nitrostyrene. Apparently, the induction period involves Pd(II) reduction to a phenypalladium(0) species stabilized by TPP and is followed by rapid transfer of phenyl from palladium to olefin.

  20. Experimental study of the retention properties of a cyclo olefin polymer pillar array column in reversed-phase mode

    NARCIS (Netherlands)

    Illa, Xavi; de Malsche, Wim; Gardeniers, Johannes G.E.; Desmet, Gert; Romano-Rodriguez, Albert

    2010-01-01

    Experimental measurements to study the retention capacity and band broadening under retentive conditions using micromachined non-porous pillar array columns fabricated in cyclo olefin polymer are presented. In particular, three columns with different depths but with the same pillar structure have

  1. Bio-inspired iron and manganese complexes derived from mixed N,O ligands for the oxidation of olefins

    NARCIS (Netherlands)

    Moelands, M.A.H.

    2014-01-01

    This Thesis describes the synthesis and structural analysis of bio-inspired iron and manganese complexes used for the catalytic oxidation of olefin substrates. The development of catalytic systems for oxidation chemistry that are based on first row transition metals and that apply a green oxidant

  2. H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

    Czech Academy of Sciences Publication Activity Database

    Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

    2017-01-01

    Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol -to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

  3. Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite

    Directory of Open Access Journals (Sweden)

    Xuan Hoan Vu

    2015-10-01

    Full Text Available The catalytic cracking of triglyceride-rich biomass toward C2–C4 olefins was evaluated over a hierarchically textured nano-ZSM-5/SBA-15 analog composite (ZSC-24 under fluid catalytic cracking (FCC conditions. The experiments were performed on a fully automated Single-Receiver Short-Contact-Time Microactivity Test unit (SR-SCT-MAT, Grace Davison at 550 °C and different catalyst-to-oil mass ratios (0–1.2 g∙g−1. The ZSC-24 catalyst is very effective for transformation of triglycerides to valuable hydrocarbons, particularly lower olefins. The selectivity to C2–C4 olefins is remarkably high (>90% throughout the investigated catalyst-to-oil ratio range. The superior catalytic performance of the ZSC-24 catalyst can be attributed to the combination of its medium acid site amount and improved molecular transport provided by the bimodal pore system, which effectively suppresses the secondary reactions of primarily formed lower olefins.

  4. Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

    NARCIS (Netherlands)

    Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

    1982-01-01

    Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

  5. Oxidative Heck Reaction as a Tool for Para-selective Olefination of Aniline: A DFT Supported Mechanism.

    Science.gov (United States)

    Moghaddam, Firouz Matloubi; Pourkaveh, Raheleh; Karimi, Ashkan

    2017-10-06

    This study describes the first para-selective palladium-catalyzed alkenylation of tertiary amines. This regioselective C-H activation was conducted without any chelation moieties. A series of olefins were reacted under mild reaction conditions at 60 °C, and the corresponding products were obtained in good yields with high selectivity.

  6. Rhenium-catalyzed dehydrogenative olefination of C(sp(3))-H bonds with hypervalent iodine(III) reagents.

    Science.gov (United States)

    Gu, Haidong; Wang, Congyang

    2015-06-07

    A dehydrogenative olefination of C(sp(3))-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

  7. A selective C-H insertion/olefination protocol for the synthesis of α-methylene-γ-butyrolactone natural products.

    Science.gov (United States)

    Lloyd, Matthew G; D'Acunto, Mariantonietta; Taylor, Richard J K; Unsworth, William P

    2016-02-07

    A regio- and stereoselective one-pot C-H insertion/olefination protocol has been developed for the late stage installation of α-methylene-γ-butyrolactones into conformationally restricted cyclohexanol-derivatives. The method has been successfully applied in the total synthesis of eudesmanolide natural product frameworks, including α-cyclocostunolide.

  8. Synthesis of 2-Alkenylquinoline by Reductive Olefination of Quinoline N-Oxide under Metal-Free Conditions.

    Science.gov (United States)

    Xia, Hong; Liu, Yuanhong; Zhao, Peng; Gou, Shaohua; Wang, Jun

    2016-04-15

    Synthesis of 2-alkenylquinoline by reductive olefination of quinoline N-oxide under metal-free conditions is disclosed. Practically, the reaction could be performed with quinoline as starting material via a one-pot, two-step process. A possible mechanism is proposed that involves a sequential 1,3-dipolar cycloaddition and acid-assisted ring opening followed by a dehydration process.

  9. Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

    Science.gov (United States)

    2015-01-01

    Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids. PMID:24666182

  10. Palladium-Catalyzed C-H Functionalization Using Guanidine as a Directing Group: Ortho Arylation and Olefination of Arylguanidines

    Science.gov (United States)

    Shao, Jiaan; Chen, Wenteng; Giulianotti, Marc A.; Houghten, Richard A.; Yu, Yongping

    2012-01-01

    Palladium-catalyzed C-H functionalization using guanidine as the directing group was achieved under mild reaction conditions. Various guanidine derivatives were produced in moderate to good yields by using simple unactivated arenes or ethyl acrylate as the source of arylation or olefination respectively. PMID:23095022

  11. Amine-Controlled Divergent Reaction: Iminolactonization and Olefination in the Presence of a Cu(I) Catalyst.

    Science.gov (United States)

    Nishikata, Takashi; Itonaga, Kohei; Yamaguchi, Norihiro; Sumimoto, Michinori

    2017-05-19

    α-Bromoamides and styrenes underwent iminolactonization reactions (carbooxygenation), in which simultaneous C-C and C-O formation occurred in the presence of a copper catalyst with triethylamine as the base. Conversely, olefination reactions occurred in the presence of a Cu catalyst with piperidine as the base. The selectivities in those reactions were very high.

  12. Olefination of Electron-Deficient Alkenes with Allyl Acetate: Stereo- and Regioselective Access to (2Z,4E)-Dienamides.

    Science.gov (United States)

    Li, Feifei; Yu, Chunbing; Zhang, Jian; Zhong, Guofu

    2016-09-16

    A Ru-catalyzed direct olefination of electron-deficient alkenes with allyl acetate via C-H bond activation is disclosed. By using N,N-disubstituted aminocarbonyl as the directing group, this external oxidant-free protocol resulted in high reaction efficiency and good stereo- and regioselectivities, which opens a novel synthetic passway for access to (Z,E)-butadiene skeletons.

  13. Synthesis of a [(14) C]-steroid intermediate: an application of a nonstabilized Horner-Wadsworth-Emmons olefination approach.

    Science.gov (United States)

    Rivera, Nelo R; Ren, Sumei; Hesk, David

    2015-01-01

    Radiolabeled steroid derivative 1 was successfully prepared using a Horner-Wadsworth-Emmons approach: a [(14) C]-label was efficiently incorporated into the C-18 position of the molecule. Previously published procedures employing other olefination methods are either not applicable due to unavailability of [(14) C]-precursors or suffer from poor reactivity. Copyright © 2015 John Wiley & Sons, Ltd.

  14. Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant.

    Science.gov (United States)

    Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng

    2017-04-18

    The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

  15. On-demand photoinitiated polymerization

    Science.gov (United States)

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  16. Pentafluorosulfanyl Substituents in Polymerization Catalysis.

    Science.gov (United States)

    Kenyon, Philip; Mecking, Stefan

    2017-10-04

    Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

  17. Radiation Induced Polymerization of Pyrrole

    International Nuclear Information System (INIS)

    Sarada Idris; Ratnam, C.T.; Ahmad Ashrif Abu Bakar

    2016-01-01

    We demonstrate the polymerization of pyrrole by gamma irradiation. The pyrrole films were exposed to gamma ray from cobalt 60 source at doses ranging from 0 to 150 kGy. The films were subjected to structural and morphological analyses by using FTIR, SEM and AFM techniques. Similar studies were also made on pristine pyrrole film which serve as control. Results revealed that pyrrole has been successfully polymerized through irradiation induced reactions. The SEM images depicted the formation of cauliflower shape upon gamma irradiation. The structural changes of pyrrole also evidenced by FTIR spectra. Surface topography and roughness of pyrrole before and after gamma irradiation found to show significant differences. (author)

  18. Reactor Physics

    International Nuclear Information System (INIS)

    Ait Abderrahim, A.

    2002-01-01

    SCK-CEN's Reactor Physics and MYRRHA Department offers expertise in various areas of reactor physics, in particular in neutron and gamma calculations, reactor dosimetry, reactor operation and control, reactor code benchmarking and reactor safety calculations. This expertise is applied in the Department's own research projects in the VENUS critical facility, in the BR1 reactor and in the MYRRHA project (this project aims at designing a prototype Accelerator Driven System). Available expertise is also used in programmes external to the Department such as the reactor pressure steel vessel programme, the BR2 materials testing reactor dosimetry, and the preparation and interpretation of irradiation experiments by means of neutron and gamma calculations. The activities of the Fuzzy Logic and Intelligent Technologies in Nuclear Science programme cover several domains outside the department. Progress and achievements in these topical areas in 2001 are summarised

  19. Reactor Physics

    Energy Technology Data Exchange (ETDEWEB)

    Ait Abderrahim, A

    2001-04-01

    The Reactor Physics and MYRRHA Department of SCK-CEN offers expertise in various areas of reactor physics, in particular in neutronics calculations, reactor dosimetry, reactor operation, reactor safety and control and non-destructive analysis of reactor fuel. This expertise is applied in the Department's own research projects in the VENUS critical facility, in the BR1 reactor and in the MYRRHA project (this project aims at designing a prototype Accelerator Driven System). Available expertise is also used in programmes external to the Department such as the reactor pressure steel vessel programme, the BR2 reactor dosimetry, and the preparation and interpretation of irradiation experiments by means of neutron and gamma calculations. The activities of the Fuzzy Logic and Intelligent Technologies in Nuclear Science programme cover several domains outside the department. Progress and achievements in these topical areas in 2000 are summarised.

  20. Reactor Physics

    Energy Technology Data Exchange (ETDEWEB)

    Ait Abderrahim, A

    2002-04-01

    SCK-CEN's Reactor Physics and MYRRHA Department offers expertise in various areas of reactor physics, in particular in neutron and gamma calculations, reactor dosimetry, reactor operation and control, reactor code benchmarking and reactor safety calculations. This expertise is applied in the Department's own research projects in the VENUS critical facility, in the BR1 reactor and in the MYRRHA project (this project aims at designing a prototype Accelerator Driven System). Available expertise is also used in programmes external to the Department such as the reactor pressure steel vessel programme, the BR2 materials testing reactor dosimetry, and the preparation and interpretation of irradiation experiments by means of neutron and gamma calculations. The activities of the Fuzzy Logic and Intelligent Technologies in Nuclear Science programme cover several domains outside the department. Progress and achievements in these topical areas in 2001 are summarised.

  1. Reactor Physics

    International Nuclear Information System (INIS)

    Ait Abderrahim, A.

    2001-01-01

    The Reactor Physics and MYRRHA Department of SCK-CEN offers expertise in various areas of reactor physics, in particular in neutronics calculations, reactor dosimetry, reactor operation, reactor safety and control and non-destructive analysis of reactor fuel. This expertise is applied in the Department's own research projects in the VENUS critical facility, in the BR1 reactor and in the MYRRHA project (this project aims at designing a prototype Accelerator Driven System). Available expertise is also used in programmes external to the Department such as the reactor pressure steel vessel programme, the BR2 reactor dosimetry, and the preparation and interpretation of irradiation experiments by means of neutron and gamma calculations. The activities of the Fuzzy Logic and Intelligent Technologies in Nuclear Science programme cover several domains outside the department. Progress and achievements in these topical areas in 2000 are summarised

  2. Multi hollow needle to plate plasmachemical reactor for pollutant decomposition

    International Nuclear Information System (INIS)

    Pekarek, S.; Kriha, V.; Viden, I.; Pospisil, M.

    2001-01-01

    Modification of the classical multipin to plate plasmachemical reactor for pollutant decomposition is proposed in this paper. In this modified reactor a mixture of air and pollutant flows through the needles, contrary to the classical reactor where a mixture of air and pollutant flows around the pins or through the channel plus through the hollow needles. We give the results of comparison of toluene decomposition efficiency for (a) a reactor with the main stream of a mixture through the channel around the needles and a small flow rate through the needles and (b) a modified reactor. It was found that for similar flow rates and similar energy deposition, the decomposition efficiency of toluene was increased more than six times in the modified reactor. This new modified reactor was also experimentally tested for the decomposition of volatile hydrocarbons from gasoline distillation range. An average efficiency of VOC decomposition of about 25% was reached. However, significant differences in the decomposition of various hydrocarbon types were observed. The best results were obtained for the decomposition of olefins (reaching 90%) and methyl-tert-butyl ether (about 50%). Moreover, the number of carbon atoms in the molecule affects the quality of VOC decomposition. (author)

  3. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

    In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

  4. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

  5. Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8.

    Science.gov (United States)

    Böhme, Ulrike; Barth, Benjamin; Paula, Carolin; Kuhnt, Andreas; Schwieger, Wilhelm; Mundstock, Alexander; Caro, Jürgen; Hartmann, Martin

    2013-07-09

    Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.

  6. Efficient and Selective Syntheses of (all-E)- and (6E,10Z)-2′-O-Methylmyxalamides D via Pd-Catalyzed Alkenylation—Carbonyl Olefination Synergy

    Science.gov (United States)

    Wang, Guangwei; Huang, Zhihong; Negishi, Ei-ichi

    2008-01-01

    Highly efficient and selective syntheses of both (all-E) and (6E,10Z)-isomers of 2′-O-methylmyxalamide D (2 and 3), in which the crucial conjugated pentaene moieties were assembled in ≥98% stereoselectivity through the use of two Pd-catalyzed alkenylation reactions, the Horner—Wadsworth—Emmons (HWE) olefination, and either the Corey—Schlessinger—Mills modified (CSM-modified) Peterson olefination for 2 or the Still—Gennari olefination for 3, are reported. Either 2 or 3 was prepared in 16% yield in seven steps from propargyl alcohol. PMID:18593171

  7. Reactor operation

    CERN Document Server

    Shaw, J

    2013-01-01

    Reactor Operation covers the theoretical aspects and design information of nuclear reactors. This book is composed of nine chapters that also consider their control, calibration, and experimentation.The opening chapters present the general problems of reactor operation and the principles of reactor control and operation. The succeeding chapters deal with the instrumentation, start-up, pre-commissioning, and physical experiments of nuclear reactors. The remaining chapters are devoted to the control rod calibrations and temperature coefficient measurements in the reactor. These chapters also exp

  8. Reactor safeguards

    CERN Document Server

    Russell, Charles R

    1962-01-01

    Reactor Safeguards provides information for all who are interested in the subject of reactor safeguards. Much of the material is descriptive although some sections are written for the engineer or physicist directly concerned with hazards analysis or site selection problems. The book opens with an introductory chapter on radiation hazards, the construction of nuclear reactors, safety issues, and the operation of nuclear reactors. This is followed by separate chapters that discuss radioactive materials, reactor kinetics, control and safety systems, containment, safety features for water reactor

  9. Continuous ARGET ATPR of methyl methacrylate and butyl acrylate in a stirred tank reactor

    NARCIS (Netherlands)

    Chan, N.; Meuldijk, J.; Cunningham, M.F.; Hutchinson, R.A.

    2013-01-01

    ARGET ATRP (activator regenerated by electron transfer atom transfer radical polymerization) of butyl acrylate (BA) and methyl methacrylate (MMA) was successfully adapted from a batch process to a continuous stirred tank reactor (CSTR) with 50 ppm copper. A series of batch polymerizations were first

  10. Olefins hydro-formylation catalysed by rhodium complexes using ionic liquids; Hydroformylation des olefines par les complexes du rhodium dans les liquides ioniques

    Energy Technology Data Exchange (ETDEWEB)

    Favre, F.

    2000-10-26

    Biphasic long chain olefins hydro-formylation catalysed by rhodium complexes using ionic liquids allows a selective reaction and an easy separation of the products from the catalyst. This study reports the synthesis of ionic liquids that were used as the catalyst's solvent. Their physical and chemical properties (melting point, solubility of organic substrates) can be varied with the structure of the organic cation (imidazolium, pyridinium, pyrrolydinium) and with its substituents (nature, length, number). It depends also on the nature of the inorganic anion (hexa-fluoro-phosphate, tetrafluoroborate, tri-fluoro-acetate, triflate, bistriflylamidure...). The use of phosphorus ligands bearing ionic functions proved to be efficient to maintain the onerous rhodium catalyst in the ionic liquid phase. Phosphines, phosphites and phosphinites including anionic (sulfonate, carboxylate) or cationic (imidazolium, pyridinium, guanidinium, phosphonium) groups have been synthesised. Finally, the influences of the ligand and of the ionic liquid on the catalytic system performances are described. Selectivities in aldehydes and reaction rates proved to be highly dependent on the nature of the ligand and of the ionic liquid. The different possibilities of recycling the ionic phase containing the rhodium catalyst have been also studied. (author)

  11. Novel polymeric materials from triglycerides

    Science.gov (United States)

    Triglycerides are good platforms for new polymeric products that can substitute for petroleum-based materials. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a number of reactions in efforts to produce a wide range of value-added products. In this ...

  12. Novel solid state polymeric batteries

    Energy Technology Data Exchange (ETDEWEB)

    Patrick, A.; Glasse, M.; Latham, R.; Linford, R.

    1986-01-01

    AC conductivity measurements have been performed on a number of polymeric electrolytes containing Mg, Ca, Sr and Zn perchlorates and Mg and Ca thiocyanates. The electrolytes were characterized using DSC. Results are reported of preliminary tests of cells incorporating anodes of the above metals. 11 refs.

  13. Reactive surfactants in heterophase polymerization

    NARCIS (Netherlands)

    Guyot, A.; Tauer, K.; Asua, J.M.; Es, van J.J.G.S.; Gauthier, C.; Hellgren, A.C.; Sherrington, D.C.; Montoya-Goni, A.; Sjöberg, M.; Sindt, O.; Vidal, F.F.M.; Unzue, M.; Schoonbrood, H.A.S.; Schipper, E.T.W.M.; Lacroix-Desmazes, P.

    1999-01-01

    This paper summarizes the work carried out during 3 years in a Network of the program "Human Capital and Mobility" of the European Union CHRX 93-0159 entitled "Reactive surfactants in heterophase polymerization for high performance polymers". A series of about 25 original papers will be published in

  14. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

    Bennet, D.B.; Li, X.; Adams, N.W.; Kim, S.W.; Hoes, C.J.T.; Hoes, C.J.T.; Feijen, Jan

    1991-01-01

    The development of a biodegradable polymeric drug delivery system for the narcotic antagonist naltrexone may improve patient compliance in the treatment of opiate addiction. Random copolymers consisting of the ¿-amino acids N5-(3-hydroxypropyl--glutamine and -leucine were synthesized with equimolar

  15. Preparations of spherical polymeric particles from Tanzanian ...

    African Journals Online (AJOL)

    Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

  16. Nanoscale elastic modulus variation in loaded polymeric micelle reactors.

    Science.gov (United States)

    Solmaz, Alim; Aytun, Taner; Deuschle, Julia K; Ow-Yang, Cleva W

    2012-07-17

    Tapping mode atomic force microscopy (TM-AFM) enables mapping of chemical composition at the nanoscale by taking advantage of the variation in phase angle shift arising from an embedded second phase. We demonstrate that phase contrast can be attributed to the variation in elastic modulus during the imaging of zinc acetate (ZnAc)-loaded reverse polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock co-polymer micelles less than 100 nm in diameter. Three sample configurations were characterized: (i) a 31.6 μm thick polystyrene (PS) support film for eliminating the substrate contribution, (ii) an unfilled PS-b-P2VP micelle supported by the same PS film, and (iii) a ZnAc-loaded PS-b-P2VP micelle supported by the same PS film. Force-indentation (F-I) curves were measured over unloaded micelles on the PS film and over loaded micelles on the PS film, using standard tapping mode probes of three different spring constants, the same cantilevers used for imaging of the samples before and after loading. For calibration of the tip geometry, nanoindentation was performed on the bare PS film. The resulting elastic modulus values extracted by applying the Hertz model were 8.26 ± 3.43 GPa over the loaded micelles and 4.17 ± 1.65 GPa over the unloaded micelles, confirming that phase contrast images of a monolayer of loaded micelles represent maps of the nanoscale chemical and mechanical variation. By calibrating the tip geometry indirectly using a known soft material, we are able to use the same standard tapping mode cantilevers for both imaging and indentation.

  17. Glycine Polymerization on Oxide Minerals

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  18. Glycine Polymerization on Oxide Minerals.

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  19. Nuclear reactors

    International Nuclear Information System (INIS)

    Middleton, J.E.

    1977-01-01

    Reference is made to water cooled reactors and in particular to the cooling system of steam generating heavy water reactors (SGHWR). A two-coolant circuit is described for the latter. Full constructural details are given. (U.K.)

  20. Reactor decommissioning

    International Nuclear Information System (INIS)

    Lawton, H.

    1984-01-01

    A pioneering project on the decommissioning of the Windscale Advanced Gas-cooled Reactor, by the UKAEA, is described. Reactor data; policy; waste management; remote handling equipment; development; and recording and timescales, are all briefly discussed. (U.K.)

  1. RA Reactor

    International Nuclear Information System (INIS)

    1978-02-01

    In addition to basic characteristics of the RA reactor, organizational scheme and financial incentives, this document covers describes the state of the reactor components after 18 years of operation, problems concerned with obtaining the licence for operation with 80% fuel, problems of spent fuel storage in the storage pool of the reactor building and the need for renewal of reactor equipment, first of all instrumentation [sr

  2. Multiregion reactors

    International Nuclear Information System (INIS)

    Moura Neto, C. de; Nair, R.P.K.

    1979-08-01

    The study of reflected reactors can be done employing the multigroup diffusion method. The neutron conservation equations, inside the intervals, can be written by fluxes and group constants. A reflected reactor (one and two groups) for a slab geometry is studied, aplying the continuity of flux and current in the interface. At the end, the appropriated solutions for a infinite cylindrical reactor and for a spherical reactor are presented. (Author) [pt

  3. Nuclear reactor

    International Nuclear Information System (INIS)

    Hattori, Sadao; Sato, Morihiko.

    1994-01-01

    Liquid metals such as liquid metal sodium are filled in a reactor container as primary coolants. A plurality of reactor core containers are disposed in a row in the circumferential direction along with the inner circumferential wall of the reactor container. One or a plurality of intermediate coolers are disposed at the inside of an annular row of the reactor core containers. A reactor core constituted with fuel rods and control rods (module reactor core) is contained at the inside of each of the reactor core containers. Each of the intermediate coolers comprises a cylindrical intermediate cooling vessels. The intermediate cooling vessel comprises an intermediate heat exchanger for heat exchange of primary coolants and secondary coolants and recycling pumps for compulsorily recycling primary coolants at the inside thereof. Since a plurality of reactor core containers are thus assembled, a great reactor power can be attained. Further, the module reactor core contained in one reactor core vessel may be small sized, to facilitate the control for the reactor core operation. (I.N.)

  4. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

    International Nuclear Information System (INIS)

    Volovik, S.V.; Dyadyusha, G.G.; Staninets, V.I.

    1987-01-01

    On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate

  5. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    KAUST Repository

    Żukowska, Karolina

    2015-08-20

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  6. Deformation mechanism under essential work of fracture process in polycyclo-olefin materials

    Directory of Open Access Journals (Sweden)

    2008-06-01

    Full Text Available The fracture toughness of a glassy polycyclo-olefin (PCO was investigated by the essential work of fracture (EWF method using a double-edge notched specimens. It was shown that the PCO follows the EWF concept in the temperature range between room temperature and glass transition temperature Tg where the ligament yielding appear at a maximum point on the stress-displacement curves and subsequently the necking and tearing processes take place in the post yielding region. The essential work of fracture required for the ligament yielding drops as the temperature approaches Tg. The non-essential work of fracture attributed to tearing process after yielding is consumed to expand the plastic region and causes molecular chains to orient to the stretching direction.

  7. [Experimental research on alcohols, aldehydes, aromatic hydrocarbons and olefins emissions from alcohols fuelled vehicles].

    Science.gov (United States)

    Zhang, Fan; Wang, Jian-Hai; Wang, Xiao-Cheng; Wang, Jian-Xin

    2013-07-01

    Using two vehicles fuelled with pure gasoline, M15, M30 and pure gasoline, E10, E20 separately, 25 degrees C normal temperature type I emission test, -7 degrees C low temperature type VI emission test and type IV evaporation emission test were carried out. FTIR, HPLC and GC-MS methods were utilized to measure alcohols, aldehydes, aromatic hydrocarbons and olefins emissions. The test results indicate that at the low as well as normal ambient temperature, as the alcohols proportion increasing in the fuel, unburned methanol, formaldehyde, acetaldehyde increase proportionally, benzene, toluene, ethylene, propylene, 1,3-butadiene and isobutene decrease slightly. The unregulated emissions at the low ambient temperature are significantly higher than those at the normal ambient temperature. The difference of HC emissions in the entire process of evaporative emission tests of E10, gasoline and M15 fuels is slight. There is a small difference of unregulated emissions in the diurnal test of three fuels.

  8. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    KAUST Repository

    Żukowska, Karolina; Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi; Slugovc, Christian

    2015-01-01

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  9. Light olefins from synthesis gas using ruthenium on rare earth oxide catalysts

    International Nuclear Information System (INIS)

    Bruce, L.; Hardin, S.; Hoang, M.; Turney, T.

    1988-01-01

    The interaction of ruthenium carbonyl, Ru/sub 3/(CO)/sub 12/ with rare earth oxides of high surface area, >50m/sup 2/g/sup -1/, has been studied. [Ru/sub 3/(μ H)(CO)/sub 10/(μ-OM=)] is formed on holmia, but on lanthana only [Ru(CO)/sub 2/]/sub n/ species are observed. Reduction of the carbonyl ligands takes place at <573K to give catalysts for the hydrogenation of carbon monoxide with activity and selectivity dependent on the particular rare earth oxide and pretreatment. Over ceria, the product is up to 55 wt% C2-5 olefins. A similar selectivity is obtained over lanthana only after redispersion through a reduction-oxidation-reduction cycle

  10. Surface activation of cyclo olefin polymer by oxygen plasma discharge: a molecular dynamics study

    International Nuclear Information System (INIS)

    Soberon, Felipe

    2014-01-01

    Thermoplastic substrates made of cyclo olefin polymer (COP) are treated with oxygen plasma discharges to introduce polar groups at the surface. This is the first step in the process of surface functionalization of COP substrates used in biosensor devices. A molecular dynamics model of basic COP structure is implemented using the second-generation reactive empirical bond order (REBO) potentials for hydrocarbon–oxygen interactions. The model includes covalent bond and Van der Waals interactions. The bombardment of a COP surface with mono-energetic atomic oxygen ions, energy in the range 1-35 eV, is simulated and reported here. The dynamics of the substrate modification reveals that the substrate top layer is de-hydrogenated and subsequently builds up an oxygen–carbon matrix layer, ∼10 Å thick. Analysis of the modified substrates indicates that surface yield is predominantly peroxide groups. (paper)

  11. Effect of norbornene content on laser ablation of cyclic olefin copolymers

    International Nuclear Information System (INIS)

    Leech, Patrick W.

    2010-01-01

    The ablation of cyclic olefin copolymers (COC) by 5 ns/248 nm laser has been examined as a function of norbornene content (61-82 wt.%). The dependence of ablation rate on laser fluence, repetition rate and pulse number has been determined over the range of composition of the copolymers. The ablation rate has increased logarithmically with laser fluence in accordance with the Beer-Lambert relationship. An increase in norbornene content has resulted in an increase in ablation rate and a decrease in threshold fluence. These trends have been attributed to a higher intramolecular rigidity of the chain structure in COC with increasing norbornene content. The morphology of the ablated surfaces was characterised by the formation of voids at high norbornene contents.

  12. Dual Ligand-Enabled Nondirected C-H Olefination of Arenes.

    Science.gov (United States)

    Chen, Hao; Wedi, Philipp; Meyer, Tim; Tavakoli, Ghazal; van Gemmeren, Manuel

    2018-02-23

    The application of the Pd-catalyzed oxidative C-H olefination of arenes, also known as the Fujiwara-Moritani reaction, has traditionally been limited by the requirement for directing groups on the substrate or the need to use the arene in large excess, typically as a (co)solvent. Herein the development of a catalytic system is described that, through the combined action of two complementary ligands, makes it possible to use directing-group-free arenes as limiting reagents for the first time. The reactions proceed under a combination of both steric and electronic control and enable the application of this powerful reaction to valuable arenes, which cannot be utilized in excess. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Vacuum ultraviolet-induced surface modification of cyclo-olefin polymer substrates for photochemical activation bonding

    International Nuclear Information System (INIS)

    Kim, Young-Jong; Taniguchi, Yoshinao; Murase, Kuniaki; Taguchi, Yoshihiro; Sugimura, Hiroyuki

    2009-01-01

    The surface of cyclo-olefin polymer (COP) was treated with vacuum ultraviolet (VUV) light at 172 nm wavelength to improve the wettability and adhesion properties. Through VUV treatment in air, the terminal groups of the COP surface were oxidized into oxygen functional groups, containing C-O, C=O, and COO components, making the COP surface hydrophilic. The extent of oxygenation was evaluated by XPS and FTIR-ATR spectra, and it was shown that the surface properties, hydrophilicity, and functionalization were dependent on both VUV irradiation distance and irradiation time, which have an effect on the concentration of oxygen functional groups. VUV-light treatment with a short irradiation distance was more effective in introducing oxygen functional groups.

  14. Heat integration of an Olefins Plant: Pinch Analysis and mathematical optimization working together

    Directory of Open Access Journals (Sweden)

    M. Beninca

    2011-03-01

    Full Text Available This work explores a two-step, complexity reducing methodology, to analyze heat integration opportunities of an existing Olefins Plant, identify and quantify reduction of energy consumption, and propose changes of the existing heat exchanger network to achieve these goals. Besides the analysis of plant design conditions, multiple operational scenarios were considered to propose modifications for handling real plant operation (flexibility. On the strength of plant complexity and large dimension, work methodology was split into two parts: initially, the whole plant was evaluated with traditional Pinch Analysis tools. Several opportunities were identified and modifications proposed. Modifications were segregated to represent small and independent portions of the original process. One of them was selected to be re-analyzed, considering two scenarios. Reduction of problem dimension allowed mathematical methodologies (formulation with decomposition, applying LP, MILP and NLP optimization methods to synthesize flexible networks to be applied, generating a feasible modification capable of fulfilling the proposed operational scenarios.

  15. The Mechanism of Rh-Catalyzed Transformation of Fatty Acids to Linear Alpha olefins

    Directory of Open Access Journals (Sweden)

    Sondre H. Hopen Eliasson

    2017-12-01

    Full Text Available Linear alpha olefins (LAOs are key commodity chemicals and petrochemical intermediates that are currently produced from fossil resources. Fatty acids are the obvious renewable starting material for LAOs, which can be obtained via transition-metal-catalyzed decarbonylative dehydration. However, even the best catalysts that have been obtained to date, which are based on palladium, are not active and stable enough for industrial use. To provide insight for design of better catalysts, we here present the first computationally derived mechanism for another attractive transition-metal for this reaction, rhodium. By comparing the calculated mechanisms and free energy profiles for the two metals, Pd and Rh, we single out important factors for a facile, low-barrier reaction and for a stable catalyst. While the olefin formation is rate limiting for both of the metals, the rate-determining intermediate for Rh is, in contrast to Pd, the starting complex, (PPh32Rh(COCl. This complex largely draws its stability from the strength of the Rh(I–CO bond. CO is a much less suitable ligand for the high-oxidation state Rh(III. However, for steric reasons, rhodium dissociates a bulkier triphenylphosphine and keeps the carbonyl during the oxidative addition, which is less favorable than for Pd. When compared to Pd, which dissociates two phosphine ligands at the start of the reaction, the catalytic activity of Rh also appears to be hampered by its preference for high coordination numbers. The remaining ancillary ligands leave less space for the metal to mediate the reaction.

  16. Nuclear power reactors

    International Nuclear Information System (INIS)

    1982-11-01

    After an introduction and general explanation of nuclear power the following reactor types are described: magnox thermal reactor; advanced gas-cooled reactor (AGR); pressurised water reactor (PWR); fast reactors (sodium cooled); boiling water reactor (BWR); CANDU thermal reactor; steam generating heavy water reactor (SGHWR); high temperature reactor (HTR); Leningrad (RMBK) type water-cooled graphite moderated reactor. (U.K.)

  17. Investigations into Alternative Desorption Agents for Amidoxime-Based Polymeric Uranium Adsorbents

    Energy Technology Data Exchange (ETDEWEB)

    Gill, Gary A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kuo, Li-Jung [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Strivens, Jonathan E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wood, Jordana R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wai, Chien [LCW Supercritical Technologies, Inc., Seattle, WA (United States); Pan, Horng-Bin [Univ. of Idaho, Moscow, ID (United States)

    2015-06-01

    Amidoxime-based polymeric braid adsorbents that can extract uranium (U) from seawater are being developed to provide a sustainable supply of fuel for nuclear reactors. A critical step in the development of the technology is to develop elution procedures to selectively remove U from the adsorbents and to do so in a manner that allows the adsorbent material to be reused. This study investigates use of high concentrations of bicarbonate along with targeted chelating agents as an alternative means to the mild acid elution procedures currently in use for selectively eluting uranium from amidoxime-based polymeric adsorbents.

  18. Research reactors

    International Nuclear Information System (INIS)

    Merchie, Francois

    2015-10-01

    This article proposes an overview of research reactors, i.e. nuclear reactors of less than 100 MW. Generally, these reactors are used as neutron generators for basic research in matter sciences and for technological research as a support to power reactors. The author proposes an overview of the general design of research reactors in terms of core size, of number of fissions, of neutron flow, of neutron space distribution. He outlines that this design is a compromise between a compact enough core, a sufficient experiment volume, and high enough power densities without affecting neutron performance or its experimental use. The author evokes the safety framework (same regulations as for power reactors, more constraining measures after Fukushima, international bodies). He presents the main characteristics and operation of the two families which represent almost all research reactors; firstly, heavy water reactors (photos, drawings and figures illustrate different examples); and secondly light water moderated and cooled reactors with a distinction between open core pool reactors like Melusine and Triton, pool reactors with containment, experimental fast breeder reactors (Rapsodie, the Russian BOR 60, the Chinese CEFR). The author describes the main uses of research reactors: basic research, applied and technological research, safety tests, production of radio-isotopes for medicine and industry, analysis of elements present under the form of traces at very low concentrations, non destructive testing, doping of silicon mono-crystalline ingots. The author then discusses the relationship between research reactors and non proliferation, and finally evokes perspectives (decrease of the number of research reactors in the world, the Jules Horowitz project)

  19. Reactor physics and reactor computations

    International Nuclear Information System (INIS)

    Ronen, Y.; Elias, E.

    1994-01-01

    Mathematical methods and computer calculations for nuclear and thermonuclear reactor kinetics, reactor physics, neutron transport theory, core lattice parameters, waste treatment by transmutation, breeding, nuclear and thermonuclear fuels are the main interests of the conference

  20. Homogeneous dihydroxylation of olefins catalyzed by OsO(4)(2-) immobilized on a dendritic backbone with a tertiary nitrogen at its core position.

    Science.gov (United States)

    Fujita, Ken-Ichi; Inoue, Kensuke; Tsuchimoto, Teruhisa; Yasuda, Hiroyuki

    2012-01-01

    OsO(4)(2-) immobilized on a poly(benzyl ether) dendrimer with a tertiary nitrogen at its core position efficiently catalyzed the homogeneous dihydroxylation of olefins with a low level of osmium leaching. The dendritic osmium catalyst could be applied to the wide range of olefins. Furthermore, the dendritic osmium catalyst was recovered by reprecipitation and then reused up to five times.

  1. OsO(4) in ionic liquid [Bmim]PF(6): a recyclable and reusable catalyst system for olefin dihydroxylation. remarkable effect of DMAP.

    Science.gov (United States)

    Yao, Qingwei

    2002-06-27

    [reaction: see text] The combination of the ionic liquid [bmim]PF(6) and DMAP provides a most simple and practical approach to the immobilization of OsO(4) as catalyst for olefin dihydroxylation. Both the catalyst and the ionic liquid can be repeatedly recycled and reused in the dihydroxylation of a variety of olefins with only a very slight drop in catalyst activity.

  2. On the nature of acidic centers in the deep oxidation of olefins over CdMoO/sub 4/: temperature-programmed desorption/Mass spectrometer investigation

    Energy Technology Data Exchange (ETDEWEB)

    Forzatti, P. (Politec. Milano); Kotzev, N.; Gencheva, L.; Pasquon, I.; Shopov, D.; Villa, P.L.

    1980-10-01

    Propylene and 1-butene were adsorbed at room temperature on cadmium molybdate, a poorly selective catalyst for olefin oxidation Temperature-programed desorption occurred at low temperature (145/sup 0/C for propylene, 100/sup 0/C for butene) from a reversibly adsorbed species on A sites, and at high temperature (400/sup 0/C for both olefins) from B sites in dissociated form. The A-sites were apparently vacancies or surface defects, which were destroyed when the cata

  3. Distributions of imidacloprid, imidacloprid-olefin and imidacloprid-urea in green plant tissues and roots of rapeseed (Brassica napus) from artificially contaminated potting soil.

    Science.gov (United States)

    Seifrtova, Marcela; Halesova, Tatana; Sulcova, Klara; Riddellova, Katerina; Erban, Tomas

    2017-05-01

    Imidacloprid-urea is the primary imidacloprid soil metabolite, whereas imidacloprid-olefin is the main plant-relevant metabolite and is more toxic to insects than imidacloprid. We artificially contaminated potting soil and used quantitative UHPLC-QqQ-MS/MS to determine the imidacloprid, imidacloprid-olefin and imidacloprid-urea distributions in rapeseed green plant tissues and roots after 4 weeks of exposure. In soil, the imidacloprid/imidacloprid-urea molar ratios decreased similarly after the 250 and 2500 µg kg -1 imidacloprid treatments. The imidacloprid/imidacloprid-urea molar ratios in the root and soil were similar, whereas in the green plant tissue, imidacloprid-urea increased more than twofold compared with the root. Although imidacloprid-olefin was prevalent in the green plant tissues, with imidacloprid/imidacloprid-olefin molar ratios of 2.24 and 1.47 for the 250 and 2500 µg kg -1 treatments respectively, it was not detected in the root. However, imidacloprid-olefin was detected in the soil after the 2500 µg kg -1 imidacloprid treatment. Significant proportions of imidacloprid-olefin and imidacloprid-urea in green plant tissues were demonstrated. The greater imidacloprid supply increased the imidacloprid-olefin/imidacloprid molar ratio in the green plant tissues. The absence of imidacloprid-olefin in the root excluded its retransport from leaves. The similar imidacloprid/imidacloprid-urea ratios in the soil and root indicated that the root serves primarily for transporting these substances. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  4. An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4.

    Science.gov (United States)

    Nicolaou, K C; Adsool, Vikrant A; Hale, Christopher R H

    2010-04-02

    PhI(OAc)(2) in the presence of OsO(4) (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with alpha-hydroxy ketones as byproduct. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO(4) (cat.), 2,6-lutidine, and PhI(OAc)(2).

  5. Biomimetic Aerobic C–H Olefination of Cyclic Enaminones at Room Temperature: Development toward the Synthesis of 1,3,5-Trisubstituted Benzenes

    Science.gov (United States)

    Yu, Yi-Yun

    2014-01-01

    A green and mild protocol for the dehydrogenative olefination of cyclic enaminones was devised via palladium catalysis at room temperature using oxygen as the terminal oxidant. The synthetic utility of the olefinated cyclic enaminones afforded a series of unique 1,3,5-trisubstituted benzenes via an unanticipated Diels-Alder tandem reaction. The broad substrate scope and good yields achieved with this new protocol provide an alternative pathway for arene functionalization. PMID:25071423

  6. Biomimetic Aerobic C-H Olefination of Cyclic Enaminones at Room Temperature: Development toward the Synthesis of 1,3,5-Trisubstituted Benzenes.

    Science.gov (United States)

    Yu, Yi-Yun; Georg, Gunda I

    2014-04-14

    A green and mild protocol for the dehydrogenative olefination of cyclic enaminones was devised via palladium catalysis at room temperature using oxygen as the terminal oxidant. The synthetic utility of the olefinated cyclic enaminones afforded a series of unique 1,3,5-trisubstituted benzenes via an unanticipated Diels-Alder tandem reaction. The broad substrate scope and good yields achieved with this new protocol provide an alternative pathway for arene functionalization.

  7. Click polymerization for the synthesis of reduction-responsive polymeric prodrug

    Science.gov (United States)

    Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

    2018-05-01

    Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

  8. Synthesis of o-Alkenylated 2-Arylbenzoxazoles via Rh-Catalyzed Oxidative Olefination of 2-Arylbenzoxazoles: Scope Investigation, Structural Features, and Mechanism Studies.

    Science.gov (United States)

    Zhou, Quan; Zhang, Jing-Fan; Cao, Hui; Zhong, Rui; Hou, Xiu-Feng

    2016-12-16

    2-Arylbenzazoles are promising molecules for potential applications in medicine and material areas. Efficient protocols for direct regioselective functionalization of 2-arylbenzoxazoles are in high demand. Herein, we disclose a general method for selective ortho-olefination of 2-arylbenzo[d]oxazoles with alkenes enabled by versatile Cp*Rh(III) in high yields. This protocol features broad functional group tolerance and high regioselectivity. Intermolecular competition studies and kinetic isotope effect experiments imply that the oxidative olefination process occurs via an electrophilic C-H activation pathway. The molecular structure of the m-fluoro-substituted olefination product confirms regioselective C-H activation/olefination at the more hindered site in cases where the meta F atom or heteroatom substituent existed. Apparent torsion angles were observed in the structures of mono- and bis-olefination products, which resulted in distinct different chemical shifts of olefinic protons. Additionally, two gram-scale reactions and further transformation experiments demonstrate that this method is practical for synthesis of ortho-alkenylated 2-arylbenzoxazole derivatives.

  9. Research reactors

    International Nuclear Information System (INIS)

    Kowarski, L.

    1955-01-01

    It brings together the techniques data which are involved in the discussion about the utility for a research institute to acquire an atomic reactor for research purposes. This type of decision are often taken by non-specialist people who can need a brief presentation of a research reactor and its possibilities in term of research before asking advises to experts. In a first part, it draws up a list of the different research programs which can be studied by getting a research reactor. First of all is the reactor behaviour and kinetics studies (reproducibility factor, exploration of neutron density, effect of reactor structure, effect of material irradiation...). Physical studies includes study of the behaviour of the control system, studies of neutron resonance phenomena and study of the fission process for example. Chemical studies involves the study of manipulation and control of hot material, characterisation of nuclear species produced in the reactor and chemical effects of irradiation on chemical properties and reactions. Biology and medicine research involves studies of irradiation on man and animals, genetics research, food or medical tools sterilization and neutron beams effect on tumour for example. A large number of other subjects can be studied in a reactor research as reactor construction material research, fabrication of radioactive sources for radiographic techniques or applied research as in agriculture or electronic. The second part discussed the technological considerations when choosing the reactor type. The technological factors, which are considered for its choice, are the power of the reactor, the nature of the fuel which is used, the type of moderator (water, heavy water, graphite or BeO) and the reflector, the type of coolants, the protection shield and the control systems. In the third part, it described the characteristics (place of installation, type of combustible and comments) and performance (power, neutron flux ) of already existing

  10. SCATTERING FROM RAMIFIED POLYMERIC SYSTEMS

    Directory of Open Access Journals (Sweden)

    M.Benhamou

    2004-01-01

    Full Text Available Here, of great interest to us is a quantitative study of the scattering properties from ramified polymeric systems of arbitrary topology. We consider three types of systems, namely ramified polymers in solution, ramified polymer blends, or ternary mixtures made of two ramified polymers of different chemical nature immersed in a good solvent. To achieve the goal of the study, use is made of the Random Phase Approximation. First we determine the exact expression of the form factor of an ideal ramified polymer of any topology, from which we extract the exact expression of its gyration radius. Using the classical Zimm's formulae and the exact form factor, we determine all scattering properties of these three types of ramified polymeric systems. The main conclusion is that ramification of the chains induces drastic changes of the scattering properties.

  11. Catalysts for liquid phase oxidation of olefins and sulfur compounds; Catalyseurs pour l'oxydation en phase liquide d'olefines et de composes soufres

    Energy Technology Data Exchange (ETDEWEB)

    Palomeque Santiago, J.F.

    2002-07-01

    Several basic, acid and acid-base catalysts were studied for the epoxidation of olefins activated or not and dibenzo-thiophene.Hydrotalcite activation by thermic treatment and in situ re-hydration improves catalytic activity for 2-cyclohexene-1-one and isophorone. Bronsted basic sites were found to be more active than Lewis sites. Total conversion of 2-cyclohexene-1-one is reached in 1.5 h in polar solvents. W{sub 7}O{sub 24}{sup 6-} Iso-poly-anion was exchanged onto a meixnerite by a new preparation method, A meso-porous solid was obtained with good catalytic properties for cyclohexene epoxidation 100% selective to epoxide. W{sub 7}O{sub 24}{sup 6-} and WO{sub 5}{sup 2-} anions and phenyl and dodecyl-phospho-tungstates were grafted on hydrotalcites. Due to the acid-base characteristics of these solid catalysts, cyclohexene yields products of allylic reactions. Mg-La, and Mg-Al-La mixed oxides were synthesized and mixed phases were gotten. Their basic characteristics account for hydrogen peroxide decomposition which prevents DBT oxidation reaction to sulfone. On the contrary, Mg-Al re-hydrated hydrotalcites are very active for this reaction and remove 100% of sulfur compounds in 1 hour. New catalyst W-ZrO{sub 2} were synthesized with high acid properties. stable structure with temperature and high DBT conversion in less than 5 minutes of reaction. These catalytic systems can be applied for hydrocarbon desulfurization of fuels like naphtha, gas oil and kerosene. (author)

  12. Polymeric nanoparticles for optical sensing.

    Science.gov (United States)

    Canfarotta, Francesco; Whitcombe, Michael J; Piletsky, Sergey A

    2013-12-01

    Nanotechnology is a powerful tool for use in diagnostic applications. For these purposes a variety of functional nanoparticles containing fluorescent labels, gold and quantum dots at their cores have been produced, with the aim of enhanced sensitivity and multiplexing capabilities. This work will review progress in the application of polymeric nanoparticles in optical diagnostics, both for in vitro and in vivo detection, together with a discussion of their biodistribution and biocompatibility. © 2013.

  13. Studies in reactive extrusion processing of biodegradable polymeric materials

    Science.gov (United States)

    Balakrishnan, Sunder

    Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends

  14. Polymeric Coatings for Combating Biocorrosion

    Science.gov (United States)

    Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

    2018-03-01

    Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

  15. Non-equilibrium supramolecular polymerization.

    Science.gov (United States)

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  16. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    Science.gov (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-04-19

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

  17. Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Piaoran [Case Western Reserve Univ., Cleveland, OH (United States); Cao, Peng -Fei [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Su, Zhe [Case Western Reserve Univ., Cleveland, OH (United States); Advincula, Rigoberto [Case Western Reserve Univ., Cleveland, OH (United States)

    2017-03-23

    Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L–1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.

  18. Allylic chlorination of terpenic olefins using a combination of MoCl{sub 5} and NaOCl

    Energy Technology Data Exchange (ETDEWEB)

    Boualy, Brahim; Firdoussi, Larbi El; Ali, Mustapha Ait; Karim, Abdellah, E-mail: elfirdoussi@ucam.ac.m [Universite Cadi Ayyad, Marrakech (Morocco). Faculte des Sciences Semlalia. Lab. de Chimie de Coordination

    2011-07-01

    MoCl{sub 5} is applied as efficient agent in allylic chlorination of terpenic olefins in the presence of NaOCl as chlorine donor. Various terpenes are converted to the corresponding allylic chlorides in moderate to good yield under mild and optimized reaction conditions. Different molybdenum precursors are also studied. Among them, MoO{sub 3} gives good yield, but after a longer reaction time. (author)

  19. Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

    Science.gov (United States)

    Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

    2018-03-26

    Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Iodine-Catalyzed Direct Olefination of 2-Oxindoles and Alkenes via Cross-Dehydrogenative Coupling (CDC) in Air.

    Science.gov (United States)

    Huang, Hong-Yan; Wu, Hong-Ru; Wei, Feng; Wang, Dong; Liu, Li

    2015-08-07

    A direct intermolecular olefination of sp(3) C-H bond between 2-oxindoles and simple alkenes via a Cross-Dehydrogenative Coupling (CDC) strategy has been developed. In the absence of additional base, moderate to excellent yields have been obtained by using a catalytic amount of iodine with atmospheric oxygen as the reoxidant. Based on the observation of a radical capture experiment, the transformation is proposed to proceed via a radical process.