Radiation-induced heterogeneous polymerization of acrylamide in acetone and acetone--water mixtures

International Nuclear Information System (INIS)

Wada, T.; Sekiya, H.; Machi, S.

1975-01-01

The effects of temperature, dose rate, and monomer concentration on the heterogeneous polymerization of acrylamide in acetone--water mixtures have been studied. Heterogeneous polymerization takes place in mixtures containing less than 60 vol-percent water. The polymerization is steady in acetone and nonsteady in mixtures containing 10 to 50 vol-percent water. The average rate of polymerization is highest in mixtures with about 20 vol-percent water. Polymer molecular weight increases with the increasing water content in the range 0 to 10 vol-percent and does not change in the range of 30 to 70 vol-percent water. For the polymerization in acetone and an acetone-water 60/40 mixture, the activation energies are 2.3 and -1.8 kcal/mole, the dose rate exponents of rate are 0.78 and 0.52, and the monomer concentration exponents of rate are 0.5 and 1.6, respectively. The polymer molecular weight increases with decreasing dose rate, decreasing temperature, and increasing monomer concentration. These results are discussed in connection with the mechanism of heterogeneous polymerization and the solvent effect

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.

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.

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

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)

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

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...

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

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.

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.

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).

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

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.

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

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

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.

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)

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.

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.

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.

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.

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

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.

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

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

Heterogeneous chromium catalysts

NARCIS (Netherlands)

2005-01-01

The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based

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.

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)

Polymerization of aliphatic alkynes with heterogeneous Mo catalysts supported on mesoporous molecular sieves

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Topka, Pavel; Sedláček, J.; Zedník, J.; Čejka, Jiří

2008-01-01

Roč. 46, č. 7 (2008), s. 2593-2599 ISSN 0887-624X R&D Projects: GA ČR GA203/05/2194; GA AV ČR IAA4040411; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkyne polymerization * conjugated polymers * metathesis * Mo heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.821, year: 2008

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

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.)

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

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.

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.

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.

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

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.

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.

First Principles Molecular Dynamics Study of Catalysis for Polyolefins: the Ziegler-Natta Heterogeneous System.

Directory of Open Access Journals (Sweden)

Michele Parrinello

2002-04-01

Full Text Available Abstract: We review part of our recent ab initio molecular dynamics study on the Ti-based Ziegler-Natta supported heterogeneous catalysis of α-olefins. The results for the insertion of ethylene in the metal-carbon bond are discussed as a fundamental textbook example of polymerization processes. Comparison with the few experimental data available has shown that simulation can reproduce activation barriers and the overall energetics of the reaction with sufficient accuracy. This puts these quantum dynamical simulations in a new perspective as a virtual laboratory where the microscopic picture of the catalysis, which represents an important issue that still escapes experimental probes, can be observed and understood. These results are then discussed in comparison with a V-based catalyst in order to figure out analogies and differences with respect to the industrially more successful Tibased systems.

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.

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)

Nature of active centers of catalytic system of VOCl/sub 3/ - Al(C/sub 2/H/sub 5/)/sub 2/Cl

Energy Technology Data Exchange (ETDEWEB)

Dubnikova, I L; Meshkova, I N [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1977-05-01

To investigate the nature of the active sites of the catalyst VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl during olefine polymerization, the following factors have been studied: composition and catalytic activity of homogeneous and heterogeneous components of the system, valent state of vanadium entering into the composition of the catalytic sites, effect of an organoaluminium component on the catalytic activity of the system, and the properties of the polymeric products being formed. It has been shown that the catalytic sites of the system VOCl/sub 3/-Al(C/sub 4/H/sub 5/)/sub 2/Cl are located, predominantly, in the heterogeneus phase of the catalyst. A conclusion has been made that heterogeneous catalytic sites are bimetal complexes of alkyl derivatives of vanadium trichloride and aluminuim alkylchlorides and that polycentral mechanism of catalysis of olefine polymerization in the presence of VOCl/sub 3/-Al(C/sub 2/H/sub 5/)/sub 2/Cl is caused by two types of active vanadium-aluminium complexes differing in the nature of an organoaluminium component.

Online observation of emulsion polymerization by fluorescence technique

CERN Document Server

Rudschuck, S; Fuhrmann, J

1999-01-01

An online observation of local polarity via fluorescence spectroscopy was used to study the formation and growth of polymer particles during an emulsifier-free heterogeneous polymerization. The reaction mixture consisted of styrene dispersed in water and the polymerization was initiated by a macro-initiator (hydrolyzed propene-maleic acid copolymer with t-butyl perester groups). Pyrenyl probes were attached to the backbone of the initiator to analyze the heterogeneous reaction. The experimental results allow a clear distinction of different time regions during the heterogeneous polymerization. Information about the heating period, the latex formation, the particle growth and the final stage of the polymerization process (gel point) were obtained. (11 refs).

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

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

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

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)

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

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.

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

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

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.

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.

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...

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.

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.

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.

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

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)

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)

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

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.

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

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.

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.

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

(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.

(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.

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

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.

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.

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.

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.

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.

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

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.)

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

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

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.

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

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.

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.

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.

Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts

KAUST Repository

Pelletier, Jeremie

2016-03-09

support taken as a X, L ligands in the Green formalism, the catalyst can be designed and generated by grafting the organometallic precursor containing the functional group(s) suitable to target a given transformation (surface organometallic fragments (SOMF)). The choice of these SOMF is based on the elementary steps known in molecular chemistry applied to the desired reaction. The coordination sphere necessary for any catalytic reaction involving paraffins, olefins, and alkynes also can thus be predicted. Only their most complete understanding can allow development of catalytic reactions with the highest possible selectivity, activity, and lifetime. This Account will examine the results of SOMC for hydrocarbon transformations on oxide surfaces bearing metals of group 4-6. The silica-supported catalysts are exhibiting remarkable performances for Ziegler-Natta polymerization and depolymerization, low temperature hydrogenolysis of alkanes and waxes, metathesis of alkanes and cycloalkanes, olefins metathesis, and related reactions. In the case of reactions involving molecules that do not contain carbon (water-gas shift, NH3 synthesis, etc.) this single site approach is also valid but will be considered in a later review. © 2016 American Chemical Society.

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.

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.

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

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

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.

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.

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.

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

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.

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.

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.

Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

Science.gov (United States)

Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

2014-07-07

A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

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

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)

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

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.

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.

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.

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.

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

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

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.

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.)

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

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)

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.

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.

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.

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

Heterogeneous in situ polymerization of polyaniline (PANI) nanofibers on cotton textiles: Improved electrical conductivity, electrical switching, and tuning properties.

Science.gov (United States)

Tissera, Nadeeka D; Wijesena, Ruchira N; Rathnayake, Samantha; de Silva, Rohini M; de Silva, K M Nalin

2018-04-15

Electrically conductive cotton fabric was fabricated by in situ one pot oxidative polymerization of aniline. Using a simple heterogeneous polymerization method, polyaniline (PANI) nano fibers with an average fiber diameter of 40-75 nm were grafted in situ onto cotton fabric. The electrical conductivity of the PANI nanofiber grafted fabric was improved 10 fold compared to fabric grafted with PANI nanoclusters having an average cluster size of 145-315 nm. The surface morphology of the cotton fibers was characterized using SEM and AFM. Electrical conductivity of PANI nanofibers on the cotton textile was further improved from 76 kΏ/cm to 1 kΏ/cm by increasing the HCl concentration from 1 M to 3 M in the polymerization medium. PANI grafted cotton fabrics were analyzed using FTIR, and the data showed the presence of polyaniline functional groups on the treated fabric. Further evidence was present for the chemical interaction of PANI with cellulose. Dopant level and morphology dependent electron transition behavior of PANI nanostructures grafted on cotton fabric was further characterized using UV-vis spectroscopy. The electrical conductivity of the PANI nano fiber grafted cotton fabric can be tuned by immersing the fabric in pH 2 and pH 6 solutions for multiple cycles. Copyright © 2018. Published by Elsevier Ltd.

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.

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

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.

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

2014-01-01

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

KAUST Repository

Kumar, Rajeev Ananda

2014-03-25

The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

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.

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.

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.

Fe(III)-functionalized carbon dots—Highly efficient photoluminescence redox catalyst for hydrogenations of olefins and decomposition of hydrogen peroxide

KAUST Repository

Bourlinos, Athanasios B.

2017-03-21

We present the first bottom-up approach to synthesize Fe(III)-functionalized carbon dots (CDs) from molecular precursors without the need of conventional thermal or microwave treatment and additional reagents. Specifically, sonication of xylene in the presence of anhydrous FeCl3 results in oxidative coupling of the aromatic substrate towards Fe(III)-functionalized CDs. The as-prepared CDs are spherical in shape with a size of 3–8 nm, highly dispersible in organic solvents and display wavelength-dependent photoluminescence (PL). The iron ions attached to the surface endow the CDs with superior catalytic activity for olefin hydrogenation with excellent conversion and selectivity (up to 100%). The Fe(III)-CDs are more effective in the hydrogenation of a series of electron donating or withdrawing olefin substrates compared to conventional homogeneous or heterogeneous Fe(III)-based catalysts. The as-prepared heterogeneous nanocatalyst can be used repeatedly without any loss of catalytic activity. Importantly, the stability of the new catalysts can be easily monitored by PL intensity or quantum yield measurements, which certainly opens the doors for real time monitoring in a range of applications. Additionally, to the best of our knowledge, for the first time, the oxidative property of Fe-CDs was also explored in decomposition of hydrogen peroxide in water with the first order rate constant of 0.7 × 10−2 min−1, proving the versatile catalytic properties of such hybrid systems.

Fe(III)-functionalized carbon dots—Highly efficient photoluminescence redox catalyst for hydrogenations of olefins and decomposition of hydrogen peroxide

KAUST Repository

Bourlinos, Athanasios B.; Rathi, Anuj K.; Gawande, Manoj B.; Hola, Katerina; Goswami, Anandarup; Kalytchuk, Sergii; Karakassides, Michael A.; Kouloumpis, Antonios; Gournis, Dimitrios; Deligiannakis, Yannis; Giannelis, Emmanuel P.; Zboril, Radek

2017-01-01

We present the first bottom-up approach to synthesize Fe(III)-functionalized carbon dots (CDs) from molecular precursors without the need of conventional thermal or microwave treatment and additional reagents. Specifically, sonication of xylene in the presence of anhydrous FeCl3 results in oxidative coupling of the aromatic substrate towards Fe(III)-functionalized CDs. The as-prepared CDs are spherical in shape with a size of 3–8 nm, highly dispersible in organic solvents and display wavelength-dependent photoluminescence (PL). The iron ions attached to the surface endow the CDs with superior catalytic activity for olefin hydrogenation with excellent conversion and selectivity (up to 100%). The Fe(III)-CDs are more effective in the hydrogenation of a series of electron donating or withdrawing olefin substrates compared to conventional homogeneous or heterogeneous Fe(III)-based catalysts. The as-prepared heterogeneous nanocatalyst can be used repeatedly without any loss of catalytic activity. Importantly, the stability of the new catalysts can be easily monitored by PL intensity or quantum yield measurements, which certainly opens the doors for real time monitoring in a range of applications. Additionally, to the best of our knowledge, for the first time, the oxidative property of Fe-CDs was also explored in decomposition of hydrogen peroxide in water with the first order rate constant of 0.7 × 10−2 min−1, proving the versatile catalytic properties of such hybrid systems.

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

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.

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.

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

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....

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

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.

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

Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

Science.gov (United States)

Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

2002-05-15

Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

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.

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.).

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.

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.

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

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

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)

Polydiphenylacetylene with Schiff Base End Groups: Synthesis and Characterization

Science.gov (United States)

Kalinova, Radostina; Jossifov, Christo

The carbonyl-olefin exchange reaction is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis - 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 carbonyl-olefin exchange reaction. The question arises: is it possible the carbonyl-olefin exchange reaction to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction become an alternative of the existing carbonyl olefination reactions?

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.

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

Single-molecule resolution of protein dynamics on polymeric membrane surfaces: the roles of spatial and population heterogeneity.

Science.gov (United States)

Langdon, Blake B; Mirhossaini, Roya B; Mabry, Joshua N; Sriram, Indira; Lajmi, Ajay; Zhang, Yanxia; Rojas, Orlando J; Schwartz, Daniel K

2015-02-18

Although polymeric membranes are widely used in the purification of protein pharmaceuticals, interactions between biomolecules and membrane surfaces can lead to reduced membrane performance and damage to the product. In this study, single-molecule fluorescence microscopy provided direct observation of bovine serum albumin (BSA) and human monoclonal antibody (IgG) dynamics at the interface between aqueous buffer and polymeric membrane materials including regenerated cellulose and unmodified poly(ether sulfone) (PES) blended with either polyvinylpyrrolidone (PVP), polyvinyl acetate-co-polyvinylpyrrolidone (PVAc-PVP), or polyethylene glycol methacrylate (PEGM) before casting. These polymer surfaces were compared with model surfaces composed of hydrophilic bare fused silica and hydrophobic trimethylsilane-coated fused silica. At extremely dilute protein concentrations (10(-3)-10(-7) mg/mL), protein surface exchange was highly dynamic with protein monomers desorbing from the surface within ∼1 s after adsorption. Protein oligomers (e.g., nonspecific dimers, trimers, or larger aggregates), although less common, remained on the surface for 5 times longer than monomers. Using newly developed super-resolution methods, we could localize adsorption sites with ∼50 nm resolution and quantify the spatial heterogeneity of the various surfaces. On a small anomalous subset of the adsorption sites, proteins adsorbed preferentially and tended to reside for significantly longer times (i.e., on "strong" sites). Proteins resided for shorter times overall on surfaces that were more homogeneous and exhibited fewer strong sites (e.g., PVAc-PVP/PES). We propose that strong surface sites may nucleate protein aggregation, initiated preferentially by protein oligomers, and accelerate ultrafiltration membrane fouling. At high protein concentrations (0.3-1.0 mg/mL), fewer strong adsorption sites were observed, and surface residence times were reduced. This suggests that at high concentrations

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.

Copolymerization of 1-hexene and 1-dodecene with 1,3-butadiene by a versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system

Directory of Open Access Journals (Sweden)

Gustavo Monteiro da Silva

2014-01-01

Full Text Available The aim of this study was to incorporate an alpha-olefin (1-hexene or 1-dodecene in a high cis polybutadiene chain, using a neodymium versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system. The influence of alpha-olefin on polymerization reaction and polymer characteristics, using different weight ratios of butadiene/α-olefin, was evaluated. The copolymers were characterized by SEC, FTIR, NMR, TGA and viscosimetric analysis. The thermal stability of the polymer tended to increase with incorporation of alpha-olefins, while its microstructure was not affected. The weight average molecular mass (Mw tended to increase and the polymerization conversion tended to decrease with increasing alpha-olefins content. The copolymers showed a lower intrinsic viscosity than for the homopolymer. The results indicated that the alpha-olefins were incorporated in the polybutadiene chain.

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.

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.

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...

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)

Production of urethane group containing coatings by curing with ionizing radiation

International Nuclear Information System (INIS)

Spoor, H.; Demmler, K.

1975-01-01

A process is described for the manufacture of coatings by applying ionizing radiation to a composition which contains olefinically unsaturated polymeric materials having urethane groups and which has been applied to a substrate. The polymeric materials may be used in combination with olefinically unsaturated monomeric compounds and conventional additives. (U.S.)

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.

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.

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)

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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

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.

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.

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.

Polymeric peptide pigments with sequence-encoded properties

Energy Technology Data Exchange (ETDEWEB)

Lampel, Ayala; McPhee, Scott A.; Park, Hang-Ah; Scott, Gary G.; Humagain, Sunita; Hekstra, Doeke R.; Yoo, Barney; Frederix, Pim W. J. M.; Li, Tai-De; Abzalimov, Rinat R.; Greenbaum, Steven G.; Tuttle, Tell; Hu, Chunhua; Bettinger, Christopher J.; Ulijn, Rein V.

2017-06-08

Melanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments. In these structures, phenols are presented in a (supra-)molecular context dictated by the positions of the amino acids in the peptide sequence. Oxidative polymerization can be tuned in a sequence-dependent manner, resulting in peptide sequence–encoded properties such as UV absorbance, morphology, coloration, and electrochemical properties over a considerable range. Short peptides have low barriers to application and can be easily scaled, suggesting near-term applications in cosmetics and biomedicine.

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)

Comparison of techniques for the determination of conversion during suspension polymerization reactions

Directory of Open Access Journals (Sweden)

J. C. Santos

2008-06-01

Full Text Available The determination of conversion during suspension polymerization reactions is not an easy task due to the heterogeneity of the reaction medium and the tendency of particles to agglomerate rapidly when stirring is stopped. Usually, bulk polymerization in ampoules is employed to study the kinetics of suspension polymerization reactions. In this work, a comparison of different techniques for the determination of conversion during suspension polymerization reactions is presented. Results showed a good agreement between the conversion obtained by gravimetry during styrene suspension polymerization and on-line conversion monitoring data using fiber-optic based Raman Spectroscopy. Nevertheless, the polymerization rate of styrene bulk polymerization carried out in ampoules was higher than the real reaction rate of styrene suspension polymerization due to slightly higher reaction temperatures. Simulation results using the experimental temperature data in a mathematical model confirmed these results.

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

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.

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.

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.

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%

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

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.

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.

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.

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

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

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

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.

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.

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.

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.

(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.

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...

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...

Study on the effects of temperature, time and policy of pre polymerization on particle morphology in propylene slurry polymerization with heterogeneous ziegler-Natta catalysts

International Nuclear Information System (INIS)

Pircheraghi, G.; Pourmahdian, S.; Vatankhah, M.

2008-01-01

The effects of temperature, time and the strategy of pre polymerization were studied on the morphology of polypropylene particles. Propylene polymerization was carried out in slurry phase using fourth generation of Ziegler-Natta Catalyst, cyclohexylmethyl dimethoxysilane as external electron donor, and triethyl aluminum as co-catalyst. Pre polymerizations were carried out based on two strategies: isothermal and non-isothermal conditions. Particle imaging using SEM, bulk density, and particle size distribution was used to analyse the particle morphology. It was found that the variation of initial condition together with the change in the mechanism of particle fracture has a dominant effect on particle morphology. Each combination between the temperature and reaction time causes to have a special effect on the product particle morphology. It has become clear that in isothermal pre polymerization, spherical particles with identical properties were produced. In low temperature experiments particles with porous surface were observed. At increasing temperature, however, the pores disappeared. Non-isothermal pre polymerization produced different morphological types. In all experiments core shell structures were observed that seemed to be related to the structure of catalysts

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.

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)

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.

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

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

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)

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.

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...

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)

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.

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

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

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.

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.

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.

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.

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

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.

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.

Method to upgrade bio-oils to fuel and bio-crude

Science.gov (United States)

Steele, Philip H; Pittman, Jr., Charles U; Ingram, Jr., Leonard L; Gajjela, Sanjeev; Zhang, Zhijun; Bhattacharya, Priyanka

2013-12-10

This invention relates to a method and device to produce esterified, olefinated/esterified, or thermochemolytic reacted bio-oils as fuels. The olefinated/esterified product may be utilized as a biocrude for input to a refinery, either alone or in combination with petroleum crude oils. The bio-oil esterification reaction is catalyzed by addition of alcohol and acid catalyst. The olefination/esterification reaction is catalyzed by addition of resin acid or other heterogeneous catalyst to catalyze olefins added to previously etherified bio-oil; the olefins and alcohol may also be simultaneously combined and catalyzed by addition of resin acid or other heterogeneous catalyst to produce the olefinated/esterified product.

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.

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).

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).

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)

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.

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.)

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.

Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.

Science.gov (United States)

Negishi, Ei-ichi; Huang, Zhihong; Wang, Guangwei; Mohan, Swathi; Wang, Chao; Hattori, Hatsuhiko

2008-11-18

Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

Toward Green Acylation of (Heteroarenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones

Directory of Open Access Journals (Sweden)

Jie Liu

2017-11-01

Full Text Available Green Friedel–Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero­arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C–H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel–Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene as well as of natural products (eugenol and safrole. Furthermore, synthetic applications to drug molecules are showcased.

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

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)

Studies on radiation-induced graft polymerization

International Nuclear Information System (INIS)

Omichi, Hideki

1978-09-01

Radiation-induced graft polymerization is used extensively to improve physical properties of polymers, but few processes are now commercialized. The reason for this is partly inadequate basic research on the reaction and partly the difficulty in developing the grafting process with large radiation source. Firstly, new techniques are proposed of studying kinetics of the graft polymerization in heterogeneous system. Based on the grafting yield, the molecular weight of graft chains, and the amount of radicals given by ESR and activation analysis, kinetic parameters are obtained and the reaction mechanism of grafting process is discussed. Secondly, the development of grafting process of poly (vinyl chloride)-butadiene is described. By study of the reaction, process design, construction and operation of the pilot plant, and economic analysis of the process, this process with 60 Co gamma ray sources is shown to be industrially promising. (author)

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

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).

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.

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...

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...

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.

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.

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.

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.

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.

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.

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

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

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.

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

International Nuclear Information System (INIS)

Pan Yang; Zhao Junshu; Ji Yuanyuan; Yan Lei; Yu Shuqin

2006-01-01

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields 3 TMB* after rapid intersystem crossing from 1 TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), α-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property (π-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k q T values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k q S have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k q values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation

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.

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

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

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

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.

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.)

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...

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�

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

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

Effects of aromatics, olefins and distillation temperatures (T50 & T90) on particle mass and number emissions from gasoline direct injection (GDI) vehicles

International Nuclear Information System (INIS)

Zhu, Rencheng; Hu, Jingnan; Bao, Xiaofeng; He, Liqiang; Zu, Lei

2017-01-01

Abstratct: Fuel quality is among the primary reasons for severe vehicle pollution. A limited understanding of the effects of gasoline properties on modern vehicle emissions is one obstacle for the establishment of stricter fuel standards in China. The goal of this study was to evaluate the effects of aromatic and olefin contents and T50 and T90 (defined as the 50%v and 90%v distillation temperatures) on tailpipe emissions from gasoline direct injection (GDI) vehicles compliant with China 4 standards. Both gaseous and particle emissions using different types of gasoline were measured. Changing aromatic and olefin contents had relatively small impacts on fuel consumption. Compared with olefins and T90, the regulated gaseous emissions were impacted more by aromatics and T50. Evident decreases of the particle mass (PM) and particle number (PN) emissions were noticed when the aromatic content and T90 decreased. Reducing the olefin content slightly decreased the PM emissions and increased the PN emissions. With decreasing T50, the PM emissions increased and the PN emissions slightly decreased. These results suggest that aromatic content and T90 should be decreased to reduce particle emissions from GDI vehicles. The information presented in this study provides some suggestions for how to improve gasoline quality in China. - Highlights: • Effect of aromatics, olefins, T50 and T90 on GDI vehicle emissions was investigated. • Aromatics and olefins had little impact on fuel consumption and CO 2 emissions. • Reducing the aromatic content and T90 significantly decreased PM and PN emissions. • Changing the olefin content and T50 had a minor impact on particle emissions. • Thresholds of aromatics and T90 should be tightened in future gasoline regulations.

Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

International Nuclear Information System (INIS)

Castillo, N.; Perez, R.; Martinez-Ortiz, M.J.; Diaz-Barriga, L.; Garcia, L.; Conde-Gallardo, A.

2010-01-01

Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO 2 in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO 2 were prepared by wetness impregnation techniques at different concentrations of Pt and Pd ∼1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO 2 were characterized by N 2 physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO 2 (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt x -Pd (1-x) /TiO 2 based system was then conducted to study the effects of metals on the nanostructure of the materials.

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.

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.

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.

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...

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....

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.

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.

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

Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization.

Science.gov (United States)

Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming

2018-03-02

A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

Surface modification of cation exchange membranes by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles

International Nuclear Information System (INIS)

Nemati, Mahsa; Hosseini, Sayed Mohsen; Bagheripour, Ehsan; Madaeni, Sayed Siavash

2016-01-01

Surface modification of polyvinylchloride based heterogeneous cation exchange membrane was performed by graft polymerization of PAA and PAA-co-PANI/MWCNTs nanoparticles. The ion exchange membranes were prepared by solution casting technique. Spectra analysis confirmed graft polymerization clearly. SEM images illustrated that graft polymerization covers the membranes by simple gel network entanglement. The membrane water content was decreased by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles on membrane surface. Membrane transport number and selectivity declined initially by PAA graft polymerization and then began to increase by utilizing of composite nanoparticles in modifier solution. The sodium and barium flux was improved sharply by PAA and PAAco- 0.01%wt PANI/MWCNTs graft polymerization on membrane surface and then decreased again by more increase of PANI/MWCNTs nanoparticles content ratio in modifier solution. The electrodialysis experiment results in laboratory scale showed higher dialytic rate in heavy metals removal for grafted-PAA and grafted-PAA-co-PANI/MWCNTs modified membrane compared to pristine one. Membrane areal electrical resistance was also decreased by introducing graft polymerization of PAA and PAA-co-PANI/MWCNTs NPs on membrane surface.

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.

Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

Science.gov (United States)

Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

2015-07-13

Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

Functional (co)polymers from carbenes: scope, mechanism & polymer properties

NARCIS (Netherlands)

Franssen, N.M.G.

2012-01-01

Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

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).

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

Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

Energy Technology Data Exchange (ETDEWEB)

Castillo, N., E-mail: necastillo@yahoo.co [Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Edificio B, 04510 Mexico DF (Mexico); Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico); Perez, R. [Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico, Campus Morelos, 62251 Cuernavaca Morelos (Mexico); Martinez-Ortiz, M.J.; Diaz-Barriga, L. [Instituto Politecnico Nacional - ESIQIE, UPALM Edif. 7, 07738 Mexico DF (Mexico); Garcia, L. [Instituto Politecnico Nacional - ESIT, UPALM, 07738 Mexico DF (Mexico); Conde-Gallardo, A. [Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico)

2010-04-16

Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO{sub 2} in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO{sub 2} were prepared by wetness impregnation techniques at different concentrations of Pt and Pd {approx}1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO{sub 2} were characterized by N{sub 2} physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO{sub 2} (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt{sub x}-Pd{sub (1-x)}/TiO{sub 2} based system was then conducted to study the effects of metals on the nanostructure of the materials.

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).

Langmuir-Blodgett films prepared from pre-formed cholestanic liquid-crystalline polymers

Energy Technology Data Exchange (ETDEWEB)

Tundo, P.; Hodge, P.; Valli, L.; Davis, F. (Venice Univ. (Italy). Dip. di Scienze Ambientali Lecce Univ. (Italy). Dip. di Scienza dei Materiali Manchester Univ. (United Kingdom). Dep. of Chemistry)

1992-01-01

A series of alternating copolymers of maleic anhydride and a-olefins functionalized through different alkyl chains with cholestanic groups were synthetised and derivatives prepared by reactions of the anhydride residues with methanol, water, dimethylamine and morpholine, respectively. The same starting functionalized a-olefins were used to prepare other suitable compounds in order to correlate the features of the liquid-crystalline behaviour of the mesogenic cholestanic group with the stability of the forthcoming polymeric or not polymeric Langmuir-Blodgett (LB) films. For some copolymers surface pressure against area per molecule isotherms are reported. In some multilayer (LB) films, the spacings between the layers were determined by the detection of BRAGG peaks by X-ray diffraction. The (LB) films of these polymers are closed packed, owing to either the polymeric skeleton or liquid-crystalline interaction.

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.

Conceptual design of coke-oven gas assisted coal to olefins process for high energy efficiency and low CO2 emission

International Nuclear Information System (INIS)

Man, Yi; Yang, Siyu; Zhang, Jun; Qian, Yu

2014-01-01

Highlights: • A novel coke-oven gas assisted coal to olefins (GaCTO) process is proposed. • GaCTO has higher energy efficiency and emits less CO 2 compared to coal-to-olefins process. • GaCTO proposes an idea of using redundant coke-oven gas for producing value added products. - Abstract: Olefins are one of the most important platform chemicals. Developing coal-to-olefins (CTO) processes is regarded as one of promising alternatives to oil-to-olefins process. However, CTO suffers from high CO 2 emission due to the high carbon contents of coal. In China, there is 7 × 10 10 m 3 coke-oven gas (COG) produced in coke plants annually. However, most of the hydrogen-rich COG is utilized as fuel or discharged directly into the air. Such situation is a waste of precious hydrogen resource and serious economic loss, which causes serious environmental pollution either. This paper proposes a novel co-feed process of COG assist CTO in which CH 4 of COG reacts with CO 2 in a Dry Methane Reforming unit to reduce emissions, while the Steam Methane Reforming unit produces H 2 -rich syngas. H 2 of COG can adjust the H/C ratio of syngas. The analysis shows that the energy efficiency of the co-feed process increases about 10%, while at the same time, life cycle carbon footprint is reduced by around 85% in comparison to the conventional CTO process. The economic sustainability of the co-feed process will be reached when the carbon tax would be higher than 150 CNY/t CO 2

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

Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

Energy Technology Data Exchange (ETDEWEB)

Wienand, A.; Reissig, H.U. (Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany))

1990-12-01

The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

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

Heterogeneous self-assembled media for biopolymerization

DEFF Research Database (Denmark)

Monnard, Pierre-Alain

2011-01-01

Heterogeneous media, such as micro-structured aqueous environments, could offer an alternative approach to the synthesis of biopolymers with novel functions. Structured media are here defined as specialized, self-assembled structures that are formed, e.g, by amphiphiles, such as liposomes, emulsion...... polymerization, the initial elongation rates clearly depended on the complementarity of the monomers with the templating nucleobases3. However, metal-ion catalyzed reactions deliver RNA analogs with heterogeneous linkages. Moreover, the usefulness of this medium in the form of quasi-compartmentalization extends...... beyond metal-ion catalysis reactions, as we have recently demonstrated the catalytic power of a dipeptide, SerHis, for the regioselective formation of phosphodiester bonds. These results in conjonction with the synthesis of nucleobases at -78˚C, the demonstration of ribozyme activity (RNA ligase ribozyme...

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique

Science.gov (United States)

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

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 (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH. PMID:28531106

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique

Directory of Open Access Journals (Sweden)

Paola Fanzio

2017-05-01

Full Text Available 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 (polyaniline. The patterning of the fluidic (microfluidic channels and conductive (wiring and electrodes functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique.

Science.gov (United States)

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

2017-05-20

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 (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin

Energy Technology Data Exchange (ETDEWEB)

Liu Peng [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Long Chao, E-mail: clong@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China); Li Qifen [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Qian Hongming [State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China); Li Aimin; Zhang Quanxing [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); State Environmental Protection Engineering Center for Organic Chemical Industrial Waste Water Disposal and Resources Reuse, Nanjing 210046 (China); Jiangsu Engineering Research Center for Organic Pollution Control and Resources Reuse, Nanjing 210046 (China)

2009-07-15

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin.

Science.gov (United States)

Liu, Peng; Long, Chao; Li, Qifen; Qian, Hongming; Li, Aimin; Zhang, Quanxing

2009-07-15

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin

International Nuclear Information System (INIS)

Liu Peng; Long Chao; Li Qifen; Qian Hongming; Li Aimin; Zhang Quanxing

2009-01-01

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

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

MODELING PARTICLE SIZE DISTRIBUTION IN HETEROGENEOUS POLYMERIZATION SYSTEMS USING MULTIMODAL LOGNORMAL FUNCTION

Directory of Open Access Journals (Sweden)

J. C. Ferrari

Full Text Available Abstract This work evaluates the usage of the multimodal lognormal function to describe Particle Size Distributions (PSD of emulsion and suspension polymerization processes, including continuous reactions with particle re-nucleation leading to complex multimodal PSDs. A global optimization algorithm, namely Particle Swarm Optimization (PSO, was used for parameter estimation of the proposed model, minimizing the objective function defined by the mean squared errors. Statistical evaluation of the results indicated that the multimodal lognormal function could describe distinctive features of different types of PSDs with accuracy and consistency.

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.

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.

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.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martínez, Juan Pablo

2016-04-10

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

2016-01-01

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Implications of the fluorescence for the conformational analysis of polymeric profisentinidins and procyanidins

Science.gov (United States)

Carin A. Heifer; Joo-Sang Sun; Mark A. Matties; Wayne L. Mattice; Richard W. Hemingway; Jan P. Steynberg; Lisa A. Kelly

1995-01-01

The common monomeric units in the polymeric procyanidins are catechin and epicatechin, which have a hydroxyl group at C(5). this hydroxyl group is absent in the profisetinidins. The fluorescence properties have been characterized for the profisentinidin monomer and dimers, and compared with previous results for the procyanidins. There is a measurable heterogeneity in...

Implications of the fluorescence for the conformational analysis of polymeric profisetinidins and procyanidins

Science.gov (United States)

Carin A. Helfer; Joo-Sang Sun; Mark A. Matties; Wayne L. Mattice; Richard W. Hemingway; Jan P. Steynberg; Lisa A. Kelly

1995-01-01

The common monomeric units in the polymeric proeyanidins are catechin and epicatechin, which have a hydroxyl group at C(5). This hydroxyl group is absent in the profisetinidins. The fluorescence properties have been characterized for the profisetinidin monomer and dimers, and compared with previous results for the procyanidins. There is a measurable heterogeneity in...

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

Energy Technology Data Exchange (ETDEWEB)

Pan Yang [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Zhao Junshu [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Ji Yuanyuan [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yan Lei [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yu Shuqin [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China)], E-mail: sqyu@ustc.edu.cn

2006-01-05

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields {sup 3}TMB* after rapid intersystem crossing from {sup 1}TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), {alpha}-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property ({pi}-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k{sub q}{sup T} values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k{sub q}{sup S} have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k{sub q} values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation.

Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies

Directory of Open Access Journals (Sweden)

Qingwen Wang

2013-03-01

Full Text Available Catalytic refining of bio-oil by reacting with olefin/alcohol over solid acids can convert bio-oil to oxygen-containing fuels. Reactivities of groups of compounds typically present in bio-oil with 1-octene (or 1-butanol were studied at 120 °C/3 h over Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA and Cs2.5H0.5PW12O40 supported on K10 clay (Cs2.5/K10, 30 wt. %. These compounds include phenol, water, acetic acid, acetaldehyde, hydroxyacetone, d-glucose and 2-hydroxymethylfuran. Mechanisms for the overall conversions were proposed. Other olefins (1,7-octadiene, cyclohexene, and 2,4,4-trimethylpentene and alcohols (iso-butanol with different activities were also investigated. All the olefins and alcohols used were effective but produced varying product selectivities. A complex model bio-oil, synthesized by mixing all the above-stated model compounds, was refined under similar conditions to test the catalyst’s activity. SSA shows the highest hydrothermal stability. Cs2.5/K10 lost most of its activity. A global reaction pathway is outlined. Simultaneous and competing esterification, etherfication, acetal formation, hydration, isomerization and other equilibria were involved. Synergistic interactions among reactants and products were determined. Acid-catalyzed olefin hydration removed water and drove the esterification and acetal formation equilibria toward ester and acetal products.

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.

III. Heterogeneous Polymerization. Modeling of emulsion polymerization, will it ever be possible? Part 2: Determination of Basic Kinetic data over the last ten years.

NARCIS (Netherlands)

Herk, van A.M.

2009-01-01

Modeling of Emulsion polymerization processes is based on the knowledge of fundamental kinetic and thermodynamic parameters. The most important kinetic parameters are propagation and termination rate coefficients. Ten years ago a paper has been published with the title Modeling of Emulsion

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.

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

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

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

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.

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

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

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.

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.

Enhanced catalytic performance for light-olefins production from chloromethane over hierarchical porous ZSM-5 zeolite synthesized by a growth-inhibition strategy

Science.gov (United States)

Liu, Qing; Wen, Dafen; Yang, Yanran; Fei, Zhaoyang; Zhang, Zhuxiu; Chen, Xian; Tang, Jihai; Cui, Mifen; Qiao, Xu

2018-03-01

Hierarchical porous ZSM-5 (HP-ZSM-5) zeolites were synthesized by hydrothermal crystallization method adding triethoxyvinylsilane as the growth-inhibitor at different hydrothermal crystallized temperatures. The properties of the obtained samples were characterized by XRD, SEM, N2-sorption, uptake of ethylene, 27Al MAS NMR, NH3-TPD, and Py-IR. It was found that the mesopore was introduced and the acidity was adjusted over HP-ZSM-5 samples successfully. The hydrothermal crystallized temperature had an important influence on the porous structure and surface properties. The catalytic performance for chloromethane to light-olefins (CMTO) were also investigated. Compared with ZSM-5 samples, HP-ZSM-5 samples exhibited enhanced stability and increased selectivity of light-olefins for CMTO reaction because of the introduction of the abundant mesopore and appropriate acidity. The lifetime (the duration of chloromethane conversion >98%) and selectivity of light-olefins reached 115 h and 69.3%, respectively.

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.

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

SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

Institute of Scientific and Technical Information of China (English)

Huai-chao Wang; Ming-zu Zhang; Pei-hong Ni; Jin-lin He; Ying Hao; Yi-xian Wu

2013-01-01

Two pH-responsive amphiphilic diblock copolymers,namely polyisobutylene-block-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA),were synthesized via oxyanion-initiated polymerization,and their multiple self-assembly behaviors have been studied.An exo-o1efin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end,and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+).PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer,resulting in a cationic diblock copolymer PIB-b-PDMAEMA.With the similar synthesis procedure,the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block.The functional PIB and block copolymers have been fully characterized by 1H-NMR,FT-IR spectroscopy,and gel permeation chromatography (GPC).These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent.Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles,vesicles with different particle sizes and cylindrical aggregates,depending on various factors including block copolymer composition,solvent polarity and pH value.

Heteropolytungstate nanoparticles: Microemulsion-mediated preparation and investigation of their catalytic activity in the epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com; Ghorbani, M.

2016-04-15

Highlights: • Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles were synthesized by using microemulsion system. • The nanoparticles have uniform size of about 25 nm and spherical morphologies. • The prepared nanoparticles act as reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}. - Abstract: Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles (Q = cetyltrimethylammonium cation) were synthesized in water-in-oil (w/o) microemulsion consisted of water/cetyltrimethylammonium bromide/n-butanol/isooctane. Reaction of Na{sub 2}WO{sub 4}, Na{sub 2}HPO{sub 4} and hydrochloric acid within water containing nanoreactors of reverse micelles resulted in the preparation of Q{sub 3}PW{sub 12}O{sub 40} nanoparticles. The resultant nanoparticles were analyzed by physicochemical methods such as FT-IR spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, thermogravimetric analyses (TGA-DTA), scanning and transmission electron microscopy and atomic force microscopy which show nearly uniform spherical nanoparticles with size of about 15 nm. Finally, catalytic activity of the Q{sub 3}PW{sub 12}O{sub 40} nanoparticles was examined in the epoxidation of olefins with H{sub 2}O{sub 2}. The prepared nanoparticles acted as recoverable and reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}.

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

Green's Function and Stress Fields in Stochastic Heterogeneous Continua

Science.gov (United States)

Negi, Vineet

Many engineering materials used today are heterogenous in composition e.g. Composites - Polymer Matrix Composites, Metal Matrix Composites. Even, conventional engineering materials - metals, plastics, alloys etc. - may develop heterogeneities, like inclusions and residual stresses, during the manufacturing process. Moreover, these materials may also have intrinsic heterogeneities at a nanoscale in the form of grain boundaries in metals, crystallinity in amorphous polymers etc. While, the homogenized constitutive models for these materials may be satisfactory at a macroscale, recent studies of phenomena like fatigue failure, void nucleation, size-dependent brittle-ductile transition in polymeric nanofibers reveal a major play of micro/nanoscale physics in these phenomena. At this scale, heterogeneities in a material may no longer be ignored. Thus, this demands a study into the effects of various material heterogeneities. In this work, spatial heterogeneities in two material properties - elastic modulus and yield stress - have been investigated separately. The heterogeneity in the elastic modulus is studied in the context of Green's function. The Stochastic Finite Element method is adopted to get the mean statistics of the Green's function defined on a stochastic heterogeneous 2D infinite space. A study of the elastic-plastic transition in a domain having stochastic heterogenous yield stress was done using Mont-Carlo methods. The statistics for various stress and strain fields during the transition were obtained. Further, the effects of size of the domain and the strain-hardening rate on the stress fields during the heterogeneous elastic-plastic transition were investigated. Finally, a case is made for the role of the heterogenous elastic-plastic transition in damage nucleation and growth.

Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary.

Science.gov (United States)

Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng

2017-06-01

Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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...

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.

Modélisation de réacteurs et procédés de polymérisation de propylène industriels

OpenAIRE

Feng , Lian-Fang

2006-01-01

In this thesis, rigorous steady and dynamic models have been developed for an industrial propylene polymerization process. They have then been used to develop new processes based on the existing one. For that purpose, this thesis has: ? reviewed the state of the art of the olefin Ziegler-Natta catalysts; ? analyzed classical propylene polymerization processes and their characteristics; ? analyzed the characteristics of industrial slurry and gas phase propylene polymerization reactors using re...

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.

Ion beam analysis of diffusion in heterogeneous materials

International Nuclear Information System (INIS)

Clough, A.S.; Jenneson, P.M.

1998-01-01

Ion-beam analysis has been applied to a variety of problems involving diffusion in heterogeneous materials. An energy loss technique has been used to study both the diffusion of water and the surface segregation of fluoropolymers in polymeric matrices. A scanning micro-beam technique has been developed to allow water concentrations in hydrophilic polymers and cements to be measured together with associated solute elements. It has also been applied to the diffusion of shampoo into hair. (orig.)

Ion beam analysis of diffusion in heterogeneous materials

Energy Technology Data Exchange (ETDEWEB)

Clough, A.S.; Jenneson, P.M. [Surrey Univ., Guildford (United Kingdom). Dept. of Physics

1998-04-01

Ion-beam analysis has been applied to a variety of problems involving diffusion in heterogeneous materials. An energy loss technique has been used to study both the diffusion of water and the surface segregation of fluoropolymers in polymeric matrices. A scanning micro-beam technique has been developed to allow water concentrations in hydrophilic polymers and cements to be measured together with associated solute elements. It has also been applied to the diffusion of shampoo into hair. (orig.) 13 refs.

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

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

NARCIS (Netherlands)

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

2010-01-01

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. FeCl3 reduced by 3

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.

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

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...

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)

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.

Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

Energy Technology Data Exchange (ETDEWEB)

Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.; Ramasamy, Karthikeyan K.; Kovarik, Libor; Bowden, Mark E.; Onfroy, Thomas; Dagle, Robert A.

2016-04-01

In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found to produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship between

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.

A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)-H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.

Science.gov (United States)

Liu, Jian-Biao; Tian, Ying-Ying; Zhang, Xin; Wang, Lu-Lin; Chen, De-Zhan

2018-04-03

The detailed mechanism of palladium-catalyzed γ-C(sp3)-H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)-H bond cleavage, alkene insertion and 'reductive β-hydride elimination'. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C-H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

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.

Borata-Wittig olefination reactions of ketones, carboxylic esters and amides with bis(pentafluorophenyl)borata-alkene reagents.

Science.gov (United States)

Wang, Tongdao; Kohrt, Sonja; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

2017-08-07

The strongly electrophilic borane derivative amino-CH 2 CH 2 CH 2 -B(C 6 F 5 ) 2 6 was α-CH deprotonated with LiTMP to give the borata-alkene {[amino-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ][Li + ]} 2 9 which underwent facile [2 + 2] cycloaddition reactions with benzophenone or fluorenone to yield the respective 1,2-oxaboretanides 11a,b. Compounds 9 and 11 were characterized by the X-ray diffraction. Thermolysis or hydrolysis of compounds 11a,b gave the corresponding borata-Wittig olefination products 12a,b. A variety of R-CH 2 -CH 2 -B(C 6 F 5 ) 2 boranes (conveniently generated by hydroboration of terminal alkenes R-CH[double bond, length as m-dash]CH 2 with Piers' borane [HB(C 6 F 5 ) 2 ]) were analogously deprotonated to give the respective borata-alkenes 16a-e (R: Ph-CH 2 -, n C 4 H 9 , t Bu, Cy, PhCH 2 CH 2 -). They underwent "non-classical" borata-Wittig olefination reactions with ethylformate to give the respective enolether carbonylation products, or their C 1 -elongated aldehydes (after hydrolysis). The borata-alkene [Ph-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ] [Li + HTMP] (16a) gave the respective "non-classical" borata-Wittig olefination products, the enolethers 25a,b and 27, respectively, upon treatment with methyl- or ethyl acetate or γ-butyrolactone.

Ozone impact minimization through coordinated scheduling of turnaround operations from multiple olefin plants in an ozone nonattainment area

Science.gov (United States)

Ge, Sijie; Wang, Sujing; Xu, Qiang; Ho, Thomas

2018-03-01

Turnaround operations (start-up and shutdown) are critical operations in olefin plants, which emit large quantities of VOCs, NOx and CO. The emission has great potentials to impact the ozone level in ozone nonattainment areas. This study demonstrates a novel practice to minimize the ozone impact through coordinated scheduling of turnaround operations from multiple olefin plants located in Houston, Texas, an ozone nonattainment area. The study considered two olefin plants scheduled to conduct turnaround operations: one start-up and one shutdown, simultaneously on the same day within a five-hour window. Through dynamic simulations of the turnaround operations using ASPEN Plus Dynamics and air quality simulations using CAMx, the study predicts the ozone impact from the combined effect of the two turnaround operations under different starting-time scenarios. The simulations predict that the ozone impact from planned turnaround operations ranges from a maximum of 11.4 ppb to a minimum of 1.4 ppb. Hence, a reduction of up to 10.0 ppb can be achieved on a single day based on the selected two simulation days. This study demonstrates a cost-effective and environmentally benign ozone control practice for relevant stakeholders, including environmental agencies, regional plant operators, and local communities.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

Science.gov (United States)

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η(5) -Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions.

Science.gov (United States)

Takahama, Yuji; Shibata, Yu; Tanaka, Ken

2015-06-15

The oxidative olefination of sp(2) C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η(5) -cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-deficient rhodium(III) catalyst, [Cp*RhCl2 ]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C-H bond cleavage step is thought to be the turnover-limiting step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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

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

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

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.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas

2017-09-25

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

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

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.)

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.

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.

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.

Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

Directory of Open Access Journals (Sweden)

Qingwen Wang

2013-09-01

Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

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

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.

Applications of functionalized polymers in catalysis. Progress report 3, July 15, 1979-July 1, 1980

Energy Technology Data Exchange (ETDEWEB)

Bergbreiter, D.E.

1980-07-01

Research on applications of polymers in catalysis has encompassed three areas: the use of functionalized polymers to detect soluble intermediates in heterogeneous Group VIII metal catalyzed arene hydrogenations; a study of olefin isomerization and hydrogenations catalyzed by polystyrene supported bis(cyclopentadienyl)titanium dichloride and an alkylmagnesium halide; and the acceleration in rate of an olefin hydrogenation catalyzed by homogeneous rhodium and ruthenium complexes as a result of absorption of triphenylphosphine by silver (I) polystyrenesulfonate. The first project found that polymer bound trapping agents were unable to detect soluble intermediates such as dienes, free radicals, or reducing agents in platinum-catalyzed benzene hydrogenation at 60 psi H/sub 2/ and 30/sup 0/C. The inability to detect diene intermediates was shown to be the result of the lower reactivity of the polymeric reagent versus an active catalyst. The polymer-supported titanium catalysts studied were unusual in that immobilization of a catalyst in this case altered the catalyst's specificity relative to its homogeneous counterpart. Preliminary results from the third project demonstrate the potential of simple functionalized polymers to improve existing homogeneously catalyzed reactions. Rate increases for olefin hydrogenations using C1Rh(Ph/sub 3/P)/sub 3/, HRh(CO)(Ph/sub 3/)/sub 3/, HRu(OAc)(Ph/sub 3/P), H/sub 2/Ru(Ph/sub 3/P)/sub 4/, Cl/sub 2/Ru(Ph/sub 3/P)/sub 3/, and Cl/sub 2/Ru(Ph/sub 3/P)/sub 4/ ranged from 25 to 3000%.

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.

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.

JP-8 and Other Military Fuels

Science.gov (United States)

2011-12-01

Fermentation Jet Fuel-Like Product sugarcane Alcohol Oligomerization Conventional Refinery ProcessesSugar switchgrass Dehydration Pyrolysis Fermentation...PolymerizationOlefins Lignocellulose corn stover forest waste Jet Fuel-Like ProductBio-CrudePyrolysis Hydroprocessing Unclassified Back Up Slides

Mena–GRASP65 interaction couples actin polymerization to Golgi ribbon linking

Science.gov (United States)

Tang, Danming; Zhang, Xiaoyan; Huang, Shijiao; Yuan, Hebao; Li, Jie; Wang, Yanzhuang

2016-01-01

In mammalian cells, the Golgi reassembly stacking protein 65 (GRASP65) has been implicated in both Golgi stacking and ribbon linking by forming trans-oligomers through the N-terminal GRASP domain. Because the GRASP domain is globular and relatively small, but the gaps between stacks are large and heterogeneous, it remains puzzling how GRASP65 physically links Golgi stacks into a ribbon. To explore the possibility that other proteins may help GRASP65 in ribbon linking, we used biochemical methods and identified the actin elongation factor Mena as a novel GRASP65-binding protein. Mena is recruited onto the Golgi membranes through interaction with GRASP65. Depleting Mena or disrupting actin polymerization resulted in Golgi fragmentation. In cells, Mena and actin were required for Golgi ribbon formation after nocodazole washout; in vitro, Mena and microfilaments enhanced GRASP65 oligomerization and Golgi membrane fusion. Thus Mena interacts with GRASP65 to promote local actin polymerization, which facilitates Golgi ribbon linking. PMID:26538023

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

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.

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.

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.

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...

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.

First principle chemical kinetics in zeolites: the methanol-to-olefin process as a case study.

Science.gov (United States)

Van Speybroeck, Veronique; De Wispelaere, Kristof; Van der Mynsbrugge, Jeroen; Vandichel, Matthias; Hemelsoet, Karen; Waroquier, Michel

2014-11-07

To optimally design next generation catalysts a thorough understanding of the chemical phenomena at the molecular scale is a prerequisite. Apart from qualitative knowledge on the reaction mechanism, it is also essential to be able to predict accurate rate constants. Molecular modeling has become a ubiquitous tool within the field of heterogeneous catalysis. Herein, we review current computational procedures to determine chemical kinetics from first principles, thus by using no experimental input and by modeling the catalyst and reacting species at the molecular level. Therefore, we use the methanol-to-olefin (MTO) process as a case study to illustrate the various theoretical concepts. This process is a showcase example where rational design of the catalyst was for a long time performed on the basis of trial and error, due to insufficient knowledge of the mechanism. For theoreticians the MTO process is particularly challenging as the catalyst has an inherent supramolecular nature, for which not only the Brønsted acidic site is important but also organic species, trapped in the zeolite pores, must be essentially present during active catalyst operation. All these aspects give rise to specific challenges for theoretical modeling. It is shown that present computational techniques have matured to a level where accurate enthalpy barriers and rate constants can be predicted for reactions occurring at a single active site. The comparison with experimental data such as apparent kinetic data for well-defined elementary reactions has become feasible as current computational techniques also allow predicting adsorption enthalpies with reasonable accuracy. Real catalysts are truly heterogeneous in a space- and time-like manner. Future theory developments should focus on extending our view towards phenomena occurring at longer length and time scales and integrating information from various scales towards a unified understanding of the catalyst. Within this respect molecular

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

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.

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.

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

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

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.

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.

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

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

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

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.

Olefin Metathesis with Ru-Based Catalysts Exchanging the Typical N-Heterocyclic Carbenes by a Phosphine–Phosphonium Ylide

Directory of Open Access Journals (Sweden)

Laia Arnedo

2017-03-01

Full Text Available Density functional theory (DFT calculations have been used to describe the first turnover of an olefin metathesis reaction calling for a new in silico family of homogenous Ru-based catalysts bearing a phosphine–phosphonium ylide ligand, with ethylene as a substrate. Equal to conventional Ru-based catalysts bearing an N-heterocyclic carbene (NHC ligand, the activation of these congeners occurs through a dissociative mechanism, with a more exothermic first phosphine dissociation step. In spite of a stronger electron-donating ability of a phosphonium ylide C-ligand with respect to a diaminocarbene analogue, upper energy barriers were calculated to be on average ca. 5 kcal/mol higher than those of Ru–NHC standards. Overall, the study also highlights advantages of bidentate ligands over classical monodentate NHC and phosphine ligands, with a particular preference for the cis attack of the olefin. The new generation of catalysts is constituted by cationic complexes potentially soluble in water, to be compared with the typical neutral Ru–NHC ones.

Prenylcoumarins in One or Two Steps by a Microwave-Promoted Tandem Claisen Rearrangement/Wittig Olefination/Cyclization Sequence.

Science.gov (United States)

Schultze, Christiane; Schmidt, Bernd

2018-05-04

The one-pot synthesis of 8-prenylcoumarins from 1,1-dimethylallylated salicylaldehydes and the stabilized ylide [(ethoxycarbonyl)methylene]triphenylphosphorane under microwave conditions was found to have a limited scope. The sequence suffers from a difficult and sometimes low-yielding synthesis of the precursors and from a competing deprenylation upon microwave irradiation. This side reaction occurs in particular with electron rich arenes with two or more alkoxy groups at adjacent positions, a prominent substitution pattern in naturally occurring 8-prenylcoumarins. Both limitations of this one-step sequence were overcome by a two-step synthesis consisting of a microwave-promoted tandem allyl ether Claisen rearrangement/Wittig olefination and a subsequent olefin cross metathesis with 2-methyl-2-butene. The cross metathesis step proceeds with a high selectivity and yields exclusively the desired prenyl, rather than the alternative crotyl substituent. Several naturally occurring 8-prenylcoumarins that were previously inaccessible have been synthesized in good overall yields along this route.

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.

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

Science.gov (United States)

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

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.

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.

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.

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.

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.

Remote meta-C-H olefination of phenylacetic acids directed by a versatile U-shaped template.

Science.gov (United States)

Deng, Youqian; Yu, Jin-Quan

2015-01-12

meta-C-H olefination of phenylacetic acid derivatives has been achieved using a commercially available nitrile-containing template. The identification of N-formyl-protected glycine as the ligand (Formyl-Gly-OH) was crucial for the development of this reaction. Versatility of the template approach in accommodating macrocyclopalladation processes with different ring sizes is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

KAUST Repository

Bahri-Laleh, Naeimeh

2012-11-01

Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

The Rearrangement of 1-Methylcyclohex-1-ene during the Hydrodesulfurization of FCC Gasoline over Supported Co(Ni)Mo/Al2O3 Sulfide Catalysts: the Isolation and Identification of Branched Cyclic C7 Olefins

Czech Academy of Sciences Publication Activity Database

Žáček, Petr; Kaluža, Luděk; Karban, Jindřich; Storch, Jan; Sýkora, Jan

2014-01-01

Roč. 112, č. 2 (2014), s. 335-346 ISSN 1878-5190 R&D Projects: GA ČR GAP106/11/0902 Institutional support: RVO:67985858 ; RVO:61388963 Keywords : hydrodesulfurization * olefin hydrogenation * branched cyclic olefins Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.170, year: 2014

Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C–H Bond Activation

Science.gov (United States)

Yi, Chae S.; Lee, Do W.

2010-01-01

Summary The cationic ruthenium-hydride complex [(η6-C6H6)(PCy3)(CO)RuH]+BF4− was found to be a highly effective catalyst for the intermolecular olefination reaction of arylketones with cycloalkenes. The preliminary mechanistic analysis revealed that electrophilic ruthenium-vinyl complex is the key species for mediating both vinyl C–H bond activation and the dehydrative olefination steps of the coupling reaction. PMID:20567607

Polymeric membranes containing silver salts for propylene/propane separation

Directory of Open Access Journals (Sweden)

L. D. Pollo

2012-06-01

Full Text Available The separation of olefin/paraffin mixtures is one of the most important processes of the chemical industry. This separation is typically carried out by distillation, which is an energy and capital intensive process. One promising alternative is the use of facilitated transport membranes, which contain specific carrier agents in the polymer matrix that interact reversibly with the double bond in the olefin molecule, promoting the simultaneous increase of its permeability and selectivity. In this study, polyurethane (PU membranes were prepared using two different silver salts (triflate and hexafluorantimonate. The membranes were structurally characterized and their performance for the separation of propylene/propane mixtures was evaluated. The results of the characterization analyses indicated that the triflate salt was the most efficient carrier agent. The membranes containing this salt showed the best performance, reaching an ideal selectivity of 10 and propylene permeability of 188 Barrer.

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.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

Science.gov (United States)

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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...

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

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)

Ligand-enabled ortho-C–H olefination of phenylacetic amides with unactivated alkenes† †Electronic supplementary information (ESI) available: Data for new compounds and experimental procedures. See DOI: 10.1039/c7sc04827k

Science.gov (United States)

Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui

2017-01-01

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(sp2)–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. PMID:29675177

Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

Energy Technology Data Exchange (ETDEWEB)

Aghamohammadi, Sogand [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Haghighi, Mohammad, E-mail: haghighi@sut.ac.ir [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Charghand, Mojtaba [Chemical Engineering Faculty, Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of); Reactor and Catalysis Research Center (RCRC), Sahand University of Technology, P.O. Box 51335-1996, Sahand New Town, Tabriz (Iran, Islamic Republic of)

2014-02-01

Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH{sub 3}-TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH{sub 3}-TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive

Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance

International Nuclear Information System (INIS)

Aghamohammadi, Sogand; Haghighi, Mohammad; Charghand, Mojtaba

2014-01-01

Graphical abstract: In this research nanostructured CeAPSO-34 was synthesized to explore the effect of TEAOH and morpholine on its physiochemical properties and MTO performance. Prepared catalysts were characterized with XRD, FESEM, BET, FTIR and NH3-TPD techniques. The results indicated that the nature of the template determines the physiochemical properties of CeAPSO-34 due to different rate of crystal growth. The catalyst obtained by using morpholine showed longer life time as well as sustaining light olefins selectivity at higher values. Furthermore, a comprehensive thermodynamic analysis of overall reactions network was carried out to address the major channels of methanol to olefins conversion. - Highlights: • Introduction of Ce into SAPO-34 framework. • Comparison of CeAPSO-34 synthesized using morpholine and TEAOH. • The nature of the template determines the physiochemical properties of CeAPSO-34. • Morpholine enhances catalyst lifetime in MTO process. • Presenting a complete reaction network for MTO process. - Abstract: TEAOH and morpholine were employed in synthesis of nanostructured CeAPSO-34 molecular sieve and used in methanol to olefins conversion. Prepared samples were characterized by XRD, FESEM, EDX, BET, FTIR and NH 3 -TPD techniques. XRD patterns reflected the higher crystallinity of the catalyst synthesized with morpholine. The FESEM results indicated that the nature of the template determines the morphology of nanostructured CeAPSO-34 due to different rate of crystal growth. There was a meaningful difference in the strength of both strong and weak acid sites for CeAPSO-34 catalysts synthesized with TEAOH and morpholine templates. The catalyst synthesized with morpholine showed higher desorption temperature of both weak and strong acid sites evidenced by NH 3 -TPD characterization. The catalyst obtained using morpholine template had the longer lifetime and sustained desired light olefins at higher values. A comprehensive thermodynamic

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.

Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

KAUST Repository

Chinnusamy, Tamilselvi R.

2012-05-09

The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

Directory of Open Access Journals (Sweden)

Jianbo Tan

2017-12-01

Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

Reduction of titanocene dichloride with dysprosium: access to a stable titanocene(ii) equivalent for phosphite-free Takeda carbonyl olefination.

Science.gov (United States)

Bousrez, G; Déchamps, I; Vasse, J-L; Jaroschik, F

2015-05-28

The reduction of titanocene dichloride with dysprosium yields a new titanocene(ii) equivalent without the need for further stabilising ligands. This reagent can be employed in combination with dithioacetals for the olefination of different carbonyl groups and allows for a simplified all-in-one procedure.

"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...

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.

Modeling of molecular weight and molecular weight distribution in slurry polymerization of propylene by Ziegler-Natta catalysts

International Nuclear Information System (INIS)

Khorasani, R.; Pourmahdian, S.

2007-01-01

The Precise prediction of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts needs good knowledge of parameters affecting on polymerization. molecular weight and molecular weight distribution are among important characteristics of a polymer determining physical-mechanical properties. broadening of molecular weight distribution is an important and well known characteristic of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts, So it is important to understand the origin of broad molecular weight. Two main factors in broadening molecular weight, namely mass transfer resistances and multiplicity of active sites, are discussed in this paper and a model including these factors is presented. Then we calculate molecular weight and molecular weight distribution by the model and compare our results with

Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-03-01

Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

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.

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.

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.

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)

Catalytic Enantioselective Synthesis of 3,4-Unsubstituted Thiochromenes through Sulfa-Michael/Julia-Kocienski Olefination Cascade Reaction.

Science.gov (United States)

Simlandy, Amit Kumar; Mukherjee, Santanu

2017-05-05

A highly enantioselective cascade sulfa-Michael/Julia-Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate and furnishes a wide range of 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters.

Science.gov (United States)

Wang, Sunewang Rixin; Radosevich, Alexander T

2015-08-07

A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

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.

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

Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

Science.gov (United States)

Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

2017-03-01

Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

Catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable OsO(4)2- in ionic liquid [bmim][PF6].

Science.gov (United States)

Branco, Luís C; Afonso, Carlos A M

2002-12-21

The use of the solvent systems water/ionic liquid or water/ionic liquid/tert-butanol provides a recoverable, reusable, robust and simple system for the asymmetric dihydroxylation of olefins, based on the immobilization of the osmium-ligand catalyst in the ionic liquid phase.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-04

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 with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation.

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

Science.gov (United States)

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

2016-12-23

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 with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety-unusual for a thiolase-are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys 143 ) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C 12 and C 14 ) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ 117 ) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

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

Science.gov (United States)

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 with the first substrate produces a covalent cysteine-thioester tethered acyl group that is transferred to the second substrate through formation of a carbon-carbon bond. Although the basics of thiolase chemistry are precedented, the mechanism by which OleA accommodates two substrates with extended carbon chains and a coenzyme moiety—unusual for a thiolase—are unknown. Gaining insights into this process could enable manipulation of the system for large scale olefin production with hydrocarbon chains lengths equivalent to those of fossil fuels. In this study, mutagenesis of the active site cysteine in Xanthomonas campestris OleA (Cys143) enabled trapping of two catalytically relevant species in crystals. In the resulting structures, long chain alkyl groups (C12 and C14) and phosphopantetheinate define three substrate channels in a T-shaped configuration, explaining how OleA coordinates its two substrates and product. The C143A OleA co-crystal structure possesses a single bound acyl-CoA representing the Michaelis complex with the first substrate, whereas the C143S co-crystal structure contains both acyl-CoA and fatty acid, defining how a second substrate binds to the acyl-enzyme intermediate. An active site glutamate (Gluβ117) is positioned to deprotonate bound acyl-CoA and initiate carbon-carbon bond formation. PMID:27815501

Nanostructural Features of Radiation Cured Networks for High Performance Composites: From Incurred Heterogeneities to Tailored Nanocomposites

International Nuclear Information System (INIS)

Krzeminski, Mickael; Ranoux, Guillaume; Coqueret, Xavier; Molinari, Michael; Chabbert, Brigitte; Aguié, Véronique; Defoort, Brigitte

2011-01-01

The radiation-induced polymerization of multiacrylates is suspected to generate heterogeneous networks at various dimension scales. In order to gain an insight into the polymer microstructure, a combination of analytic methods was used to quantify polymer segment mobility in the different domains [4,5]. Model epoxy or ethoxylated bis-phenol A diacrylates, EPAC and ETAC respectively, were used as precursors of representative networks for our investigations

Nanostructural Features of Radiation Cured Networks for High Performance Composites: From Incurred Heterogeneities to Tailored Nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Krzeminski, Mickael [Institut de Chimie Moléculaire de Reims (France); EADS Astrium, BP 20011, 33165 Saint Médard en Jalles Cedex (France); Ranoux, Guillaume; Coqueret, Xavier [Institut de Chimie Moléculaire de Reims (France); Molinari, Michael [Laboratoire des Microscopies et d’Etude des Nanostructures (France); Chabbert, Brigitte; Aguié, Véronique [UMR INRA Fractionnement des Agro-ressources et Environnement, Université de Reims Champagne Ardenne - 51687 Reims (France); Defoort, Brigitte [EADS Astrium, BP 20011, 33165 Saint Médard en Jalles Cedex, (France)

2011-07-01

The radiation-induced polymerization of multiacrylates is suspected to generate heterogeneous networks at various dimension scales. In order to gain an insight into the polymer microstructure, a combination of analytic methods was used to quantify polymer segment mobility in the different domains [4,5]. Model epoxy or ethoxylated bis-phenol A diacrylates, EPAC and ETAC respectively, were used as precursors of representative networks for our investigations.

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.

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.

Synthesis, characterizations and catalytic studies of a new two-dimensional metal-organic framework based on Co-carboxylate secondary building units

Science.gov (United States)

Bagherzadeh, Mojtaba; Ashouri, Fatemeh; Đaković, Marijana

2015-03-01

A metal-organic framework [Co3(BDC)3(DMF)2(H2O)2] was synthesized and structurally characterized. X-ray single crystal analysis revealed that the framework contains a 2D polymeric chain through coordination of 1,4-benzenedicarboxylic acid linker ligand to cobalt centers. The polymer crystallize in monoclinic P21/n space group with a=13.989(3) Å, b=9.6728(17) Å, c=16.707(3) Å, and Z=2. The polymer features a framework based on the perfect octahedral Co-O6 secondary building units. The catalytic activities of [Co3(BDC)3(DMF)2(H2O)2]n for olefins oxidation was conducted. The heterogeneous catalyst could be facilely separated from the reaction mixture, and reused three times without significant degradation in catalytic activity. Furthermore, no contribution from homogeneous catalysis of active species leaching into reaction solution was detected.

Mechanistic Studies on Chabazite-Type Methanol-to-Olefin Catalysts: Insights from Time-Resolved UV/Vis Microspectroscopy Combined with Theoretical Simulations

NARCIS (Netherlands)

Van Speybroeck, V.; Hemelsoet, K.L.J.; De Wispelaere, K.; Qian, Q.|info:eu-repo/dai/nl/34138609X; Van der Mynsbrugge, J.; De Sterck, B.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397; Waroquier, M.

2013-01-01

The formation and nature of active sites for methanol conversion over solid acid catalyst materials are studied by using a unique combined spectroscopic and theoretical approach. A working catalyst for the methanol-to-olefin conversion has a hybrid organic–inorganic nature in which a cocatalytic

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.

N-Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts To Generate α,β-Unsaturated Ketones.

Science.gov (United States)

Rajkiewicz, Adam A; Kalek, Marcin

2018-04-06

An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

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.

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

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.

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.

Techno-economic assessment of different routes for olefins production through the oxidative coupling of methane (OCM) : Advances in benchmark technologies

NARCIS (Netherlands)

Spallina, V.; Campos Velarde, I.; Medrano, J.A.; Godini, H.; Gallucci, F.; van Sint Annaland, M.

2017-01-01

This paper addresses the techno-economic assessment of two technologies for olefins production from naphtha and natural gas. The first technology is based on conventional naphtha steam cracking for the production of ethylene, propylene and BTX at polymer grade. The unused products are recovered in a

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.

Investigation of Shear-Thinning Behavior on Film Thickness and Friction Coefficient of Polyalphaolefin Base Fluids With Varying Olefin Copolymer Content

Energy Technology Data Exchange (ETDEWEB)

Zolper, Thomas J.; He, Yifeng; Delferro, Massimiliano; Shiller, Paul; Doll, Gary; LotfizadehDehkordi, Babak; Ren, Ning; Lockwood, Frances; Marks, Tobin J.; Chung, Yip-Wah; Greco, Aaron; Erdemir, Ali; Wang, Qian

2016-08-11

This study investigates the rheological properties, elastohydrodynamic (EHD) film-forming capability, and friction coefficients of low molecular mass poly-alpha-olefin (PAO) base stocks with varying contents of high molecular mass olefin copolymers (OCPs) to assess their shear stability and their potential for energy-efficient lubrication. Several PAO-OCP mixtures were blended in order to examine the relationship between their additive content and tribological performance. Gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize the molecular masses and structures, respectively. Density, viscosity, EHD film thickness, and friction were measured at 303 K, 348 K, and 398 K. Film thickness and friction were studied at entrainment speeds relevant to the boundary, mixed, and full-film lubrication regimes. The PAO-OCP mixtures underwent temporary shear-thinning resulting in decreases in film thickness and hydrodynamic friction. These results demonstrate that the shear characteristics of PAO-OCP mixtures can be tuned with the OCP content and provide insight into the effects of additives on EHD characteristics.

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

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.

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.

Probing functional groups at the gas-aerosol interface using heterogeneous titration reactions: a tool for predicting aerosol health effects?

Science.gov (United States)

Setyan, Ari; Sauvain, Jean-Jacques; Guillemin, Michel; Riediker, Michael; Demirdjian, Benjamin; Rossi, Michel J

2010-12-17

The complex chemical and physical nature of combustion and secondary organic aerosols (SOAs) in general precludes the complete characterization of both bulk and interfacial components. The bulk composition reveals the history of the growth process and therefore the source region, whereas the interface controls--to a large extent--the interaction with gases, biological membranes, and solid supports. We summarize the development of a soft interrogation technique, using heterogeneous chemistry, for the interfacial functional groups of selected probe gases [N(CH(3))(3), NH(2)OH, CF(3)COOH, HCl, O(3), NO(2)] of different reactivity. The technique reveals the identity and density of surface functional groups. Examples include acidic and basic sites, olefinic and polycyclic aromatic hydrocarbon (PAH) sites, and partially and completely oxidized surface sites. We report on the surface composition and oxidation states of laboratory-generated aerosols and of aerosols sampled in several bus depots. In the latter case, the biomarker 8-hydroxy-2'-deoxyguanosine, signaling oxidative stress caused by aerosol exposure, was isolated. The increase in biomarker levels over a working day is correlated with the surface density N(i)(O3) of olefinic and/or PAH sites obtained from O(3) uptakes as well as with the initial uptake coefficient, γ(0), of five probe gases used in the field. This correlation with γ(0) suggests the idea of competing pathways occurring at the interface of the aerosol particles between the generation of reactive oxygen species (ROS) responsible for oxidative stress and cellular antioxidants.

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process.

Science.gov (United States)

Gusev, Andrey A; Psarras, Antonios C; Triantafyllidis, Konstantinos S; Lappas, Angelos A; Diddams, Paul A

2017-10-21

ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC) process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam), FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives) are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated) activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n -Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C 12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F) ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas) olefins as the nature (Brønsted-to-Lewis ratio) of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at higher

Effect of Steam Deactivation Severity of ZSM-5 Additives on LPG Olefins Production in the FCC Process

Directory of Open Access Journals (Sweden)

Andrey A. Gusev

2017-10-01

Full Text Available ZSM-5-containing catalytic additives are widely used in oil refineries to boost light olefin production and improve gasoline octanes in the Fluid Catalytic Cracking (FCC process. Under the hydrothermal conditions present in the FCC regenerator (typically >700 °C and >8% steam, FCC catalysts and additives are subject to deactivation. Zeolites (e.g., Rare Earth USY in the base catalyst and ZSM-5 in Olefins boosting additives are prone to dealumination and partial structural collapse, thereby losing activity, micropore surface area, and undergoing changes in selectivity. Fresh catalyst and additives are added at appropriate respective levels to the FCC unit on a daily basis to maintain overall targeted steady-state (equilibrated activity and selectivity. To mimic this process under accelerated laboratory conditions, a commercial P/ZSM-5 additive was hydrothermally equilibrated via a steaming process at two temperatures: 788 °C and 815 °C to simulate moderate and more severe equilibration industrial conditions, respectively. n-Dodecane was used as probe molecule and feed for micro-activity cracking testing at 560 °C to determine the activity and product selectivity of fresh and equilibrated P-doped ZSM-5 additives. The fresh/calcined P/ZSM-5 additive was very active in C12 cracking while steaming limited its activity, i.e., at catalyst-to-feed (C/F ratio of 1, about 70% and 30% conversion was obtained with the fresh and steamed additives, respectively. A greater activity drop was observed upon increasing the hydrothermal deactivation severity due to gradual decrease of total acidity and microporosity of the additives. However, this change in severity did not result in any selectivity changes for the LPG (liquefied petroleum gas olefins as the nature (Brønsted-to-Lewis ratio of the acid/active sites was not significantly altered upon steaming. Steam deactivation of ZSM-5 had also no significant effect on aromatics formation which was enhanced at

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.

Nanoporous Polymeric Grating-Based Biosensors

KAUST Repository

Gao, Tieyu; Hsiao, Vincent; Zheng, Yue Bing; Huang, Tony Jun

2012-01-01

We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

Nanoporous Polymeric Grating-Based Biosensors

KAUST Repository

Gao, Tieyu

2012-05-02

We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

Determination of polymerization particle morphology using synchrotron computed microtomography

International Nuclear Information System (INIS)

Jones, K.W.; Spanne, P.; Lindquist, W.B.; Conner, W.C.; Ferrero, M.

1991-10-01

Polymerization of monomers over heterogeneous catalysts results in the fragmentation of the catalysts and subsequent transport in the polymer particles that are produced. Characterization of the process using nondestructive synchrotron computed microtomography techniques makes possible measurement of the distribution of the catalyst fragments in an individual particle and, in addition, gives an estimate of the particle porosity and surface area. The present experiment was carried out using the x-ray microscopy facility at the Brookhaven National Synchrotron Light Source (NSLS) X26 beam line. The tomographic sections were analyzed using autocorrelation techniques to determine porosity and surface area values. The results are compared to values obtained using conventional methods. This procedure makes possible the extraction of quantitative information about porosity and specific area from the tomograms. 9 refs., 7 figs., 1 tab

Determination of mineral oil aromatic hydrocarbons in edible oils and fats by online liquid chromatography-gas chromatography-flame ionization detection - Evaluation of automated removal strategies for biogenic olefins.

Science.gov (United States)

Nestola, Marco; Schmidt, Torsten C

2017-07-07

The determination of mineral oil aromatic hydrocarbons (MOAH) in foodstuffs gained in importance over the last years as carcinogenicity cannot be excluded for certain MOAH. The existence of olefins in foodstuffs, such as edible oils and fats, can be problematic for the determination of MOAH by LC-GC-FID. Removal of these interfering substances by HPLC based on polarity differences is not possible. During gas chromatographic separation heavily overloaded peaks are observed rendering the detection of small mineral oil contaminations almost impossible. Therefore, removal of these olefins is necessary before subjection of the sample to LC-GC-FID. Epoxidation of olefins to increase their polarity proved to be a valuable tool in the past. Precision and trueness of the results as shown in a collaborative trial, however, are relying on exact reaction conditions. Additionally, it is known that certain MOAH are oxidized during epoxidation and therefore get lost. In the scope of this work, hydroboration, bromohydrin reaction, and epoxidation were examined for their potential for derivatization of unsaturated hydrocarbons with increased robustness and higher recovery of MOAH. Epoxidation by meta-chloroperoxybenzoic acid (mCPBA) delivered the best removal of olefins. Factors influencing this reaction were enlightened. Adaption of the reaction conditions and time-controlled automation increased the recovery of polycyclic MOAH. Good precision (RSD r oils spiked with a lubricating mineral oil (at 24.5mg/kg of MOAH). The trueness of the method was verified by analyzing collaborative trial samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Regioselective C2 Oxidative Olefination of Indoles and Pyrroles through Cationic Rhodium(III)-Catalyzed C-H Bond Activation.

Science.gov (United States)

Li, Bin; Ma, Jianfeng; Xie, Weijia; Song, Haibin; Xu, Shansheng; Wang, Baiquan

2013-09-02

Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles with broad substrate scope and tolerance is reported. The catalytic reaction proceeds with excellent regio- and stereoselectivity. The directing group N,N-dimethylcarbamoyl was crucial for the reaction and could be removed easily. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction of uranium(IV) and its mixtures with an olefin or an alkyne in tetrahydrofuran solutions by solvated electrons

International Nuclear Information System (INIS)

Koulkes-Pujo, A.M.; Le Marechal, J.F.; Le Motais, B.; Folcher, G.

1985-01-01

The reduction of UCl 4 and its mixtures with different olefins (stilbene, St, diphenylethylene, DPE, acenaphtylene, Ac or with diphenylacetylene (DPA) was studied by pulse radiolysis of tetrahydrofuran (THF) solutions. U(III) was formed by U(IV) reaction either with the solvated electrons created by THF radiolysis or with the transitory anions St - and DPA - . In the latter case, the reaction proceeds via a first step leading to [St-U(IV)] - or [DPA-U(IV)] - . In the case of DPE - the first species, [DPE-U(IV)] - , does not lead to U(III) but is destroyed by THF(H) + giving DPE(H). and U(IV). Ac - does not react with U(IV). A mechanistic scheme of this electron attachment is discussed as well as its implication in catalytic hydrogenation of olefins in LiAlH 4 -UCl 4 solutions. It is concluded that the catalytic effect observed is rather the result of a hydride transfer from a uranium transient compound to the alkenes. 22 references, 8 figures, 1 table

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

KINETICS OF SUSPENDED EMULSION POLYMERIZATION OF METHYL METHACRYLATE

Institute of Scientific and Technical Information of China (English)

Yong-zhong Bao; Cheng-xi Wang; Zhi-ming Huang; Zhi-xue Weng

2004-01-01

The kinetics of suspended emulsion polymerization of methyl methacrylate (MMA), in which water acted as the dispersed phase and the mixture of MMA and cyclohexane as the continuous phase, was investigated. It showed that the initial polymerization rate (Rp0) and steady-state polymerization rate (Rp) were proportional to the mass ratio between water and oil phase, and increased as the polymerization temperature, the potassium persulphate concentration ([I]) and the Tween20 emulsifier concentration ([S]) increased. The relationships between the polymerization rate and [I] and [S] were obtained as follows: Rp0 ∝ [I]0.73[S]0.32 and Rp ∝ [I]0.71[S]0.23. The above exponents were close to those obtained from normal MMA emulsion polymerization. It also showed that the average molecular weight of the resulting poly(methyl methacrylate) decreased as the polymerization temperature, [I] and [S] increased. Thus, MMA suspended emulsion polymerization could be considered as a combination of many miniature emulsion polymerizations proceeding in water drops and obeyed the classical kinetics of MMA emulsion polymerization.

Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

Science.gov (United States)

Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

2018-03-07

The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

Institute of Scientific and Technical Information of China (English)

Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

2000-01-01

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

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.

(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.

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....

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.

Rh(III) -Catalyzed C-H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant.

Science.gov (United States)

Jiang, Quandi; Zhu, Changlei; Zhao, Huaiqing; Su, Weiping

2016-02-04

Phthalide skeletons have been synthesized for the first time through a Rh(III) -catalyzed C-H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate-to-excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric membrane materials for artificial organs.

Science.gov (United States)

Kawakami, Hiroyoshi

2008-01-01

Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

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.

THE EFFECTS OF N-2-HYDROXYETHYL-N-METHYL-P-TOLUIDINE ON METHYL METHACRYLATE RADICAL POLYMERIZATION AND ACRYLONITRILE PHOTOINDUCED POLYMERIZATION

Institute of Scientific and Technical Information of China (English)

QIU Kunyuan; ZHANG Zhanghua; FENG Xinde

1992-01-01

The effects of N-2-hydroxyethyl-N-methyl-p-toluidine (HMT) on MMA polymerization using organic peroxide as an initiator and on AN photoinduced polymerization have been investigated respectively. The kinetics of polymerization and the overall activation energy of polymerization were determined. Based on kinetics study and the end group analysis of the polymer obtained by UV spectrum method, the initiation mechanism is proposed.

Olefins transformation catalysis by zirconium and tungsten complexes in organic and non-aqueous ionic media; Catalyse de transformation des olefines par les complexes du zirconium et du tungstene en milieux organique et ionique non aqueux

Energy Technology Data Exchange (ETDEWEB)

Laurent-Gerot, P

1997-06-30

Molten salts are suitable solvents for biphasic catalysis: melting butyl-1 methyl-3 imidazolium chloride and aluminium chloride gives a polar and aprotic ionic liquid which is not miscible with hydrocarbons but dissolves organometallic complexes. Two types of complexes have been tested in molten salts with ethyl-aluminium dichloride: zirconium complexes to synthesize light {alpha} olefins from ethene; mono-imido complexes of tungsten VI (Cl{sub 4}W = NAr) to dimerize ethene in but-1 ene and propene in dimethyl-2,3-but-1-ene. For both of these complexes, biphasic catalysis principle is always respected: the active species is present only in the ionic phase and not in the organic phase. The first complexes, biphasic principle is always respected: the active species is present only in the ionic phase and not in the organic phase. The first complexes oligomerize ethene in molten salts with low activity and the {alpha} olefins selectivity is weak. Mono-imido complexes of tungsten VI are proved to be equivalent to the systems composed with WCl{sub 6} and aniline, and they dimerize ethene in but-1 ene and propene in dimethyl-2,3-but-1 ene more efficiently in organic medium than in ionic liquid. The characterization of the active species of the system Cl{sub 4}W=NAr / EtAlCl{sub 2} shows that it is the corresponding mono-imido complex of tungsten 4. (author) 129 refs.

Mena-GRASP65 interaction couples actin polymerization to Golgi ribbon linking.

Science.gov (United States)

Tang, Danming; Zhang, Xiaoyan; Huang, Shijiao; Yuan, Hebao; Li, Jie; Wang, Yanzhuang

2016-01-01

In mammalian cells, the Golgi reassembly stacking protein 65 (GRASP65) has been implicated in both Golgi stacking and ribbon linking by forming trans-oligomers through the N-terminal GRASP domain. Because the GRASP domain is globular and relatively small, but the gaps between stacks are large and heterogeneous, it remains puzzling how GRASP65 physically links Golgi stacks into a ribbon. To explore the possibility that other proteins may help GRASP65 in ribbon linking, we used biochemical methods and identified the actin elongation factor Mena as a novel GRASP65-binding protein. Mena is recruited onto the Golgi membranes through interaction with GRASP65. Depleting Mena or disrupting actin polymerization resulted in Golgi fragmentation. In cells, Mena and actin were required for Golgi ribbon formation after nocodazole washout; in vitro, Mena and microfilaments enhanced GRASP65 oligomerization and Golgi membrane fusion. Thus Mena interacts with GRASP65 to promote local actin polymerization, which facilitates Golgi ribbon linking. © 2016 Tang et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2016-01-01

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju

2016-04-13

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

Double role of the hydroxy group of phosphoryl in palladium(II)-catalyzed ortho-olefination: a combined experimental and theoretical investigation.

Science.gov (United States)

Liu, Liu; Yuan, Hang; Fu, Tingting; Wang, Tao; Gao, Xiang; Zeng, Zhiping; Zhu, Jun; Zhao, Yufen

2014-01-03

Density functional theory calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dimethyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C-H bond activation, transmetalation, reductive elimination, and recycling of catalyst, each of which is constituted from different steps. Our calculations reveal that the hydroxy group of phosphoryl plays a crucial role almost in all steps, which can not only stabilize the intermediates and transition states by intramolecular hydrogen bonds but also act as a proton donor so that the η(1)-CH3COO(-) ligand could be protonated to form a neutral acetic acid for easy removal. These findings explain why only the methyl hydrogen benzylphosphonates and methyl hydrogen phenylphosphates were found to be suitable reaction partners. Our mechanistic findings are further supported by theoretical prediction of Pd-catalyzed ortho-olefination using methyl hydrogen phenylphosphonate, which is verified by experimental observations that the desired product was formed in a moderate yield.

Characterization behavior of some polymeric composite ion exchangers

International Nuclear Information System (INIS)

El-Zahhar, A.A; Ahdel-Aziz, H.M.; Siyam, T.

2005-01-01

Polymeric composite resins were prepared by template polymerization process in aqueous solution. Thermogravimetric analysis (TGA), differential thermal analysis (DTA) and The X-ray diffraction patterns (XRD) were performed to evaluate the physico chemical properties of the different polymeric composite resins. The TGA and DTA clarify high thermal stability of prepared polymeric composite resins. XRD of prepared polymeric composite shows that there is crystalline structure of some resins while other are amorphous one

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.