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Sample records for hexavinyl disiloxane hvds

  1. Controlled nanoclustering of magnetic nanoparticles using telechelic polysiloxane and disiloxane

    Energy Technology Data Exchange (ETDEWEB)

    Thong-On, Bandit; Rutnakornpituk, Boonjira; Wichai, Uthai; Rutnakornpituk, Metha, E-mail: methar@nu.ac.th [Naresuan University, Department of Chemistry, Faculty of Science (Thailand)

    2015-06-15

    Diacrylate-terminated polydimethylsiloxane (PDMS) and disiloxane were synthesized and used for controlling degree of nanoclustering of magnetite nanoparticles (MNPs). PDMS was synthesized via a ring-opening polymerization of octamethylcyclotetrasiloxane (D{sub 4}), followed by end functionalization with diacrylate groups. Diacrylate-terminated disiloxane was separately synthesized in a similar fashion without the use of D{sub 4} in the reaction. They were then reacted with amino-coated MNPs to obtain MNP-embedded siloxane nanoclusters. Transmission electron microscopy showed the formation of MNP-siloxane nanoclusters with the size of 70–200 nm. Degree of MNP nanoclustering can be adjusted by varying the MNP-to-siloxane ratio to obtain hydrodynamic size ranging from 200 to 2400 nm. Using the same ratio of MNPs to the siloxanes, PDMS resulted in the nanoclusters with smaller D{sub h} and more stable in toluene than those coated with disiloxane. These novel nanoclusters with controllable size might be ideal candidates for biomedical and other advanced applications after suitable surface modification.

  2. Secondary Amine Functional Disiloxanes as CO2 Sorbents

    Energy Technology Data Exchange (ETDEWEB)

    O' Brien, MJ; Farnum, RL; Perry, RJ; Genovese, SE

    2014-05-01

    A series of two different types of secondary amine functional disiloxanes were prepared and screened as CO2 capture solvents. The first group of materials contained RNHCH2CH2CH2 side chains where the R groups were C1-6 alkyls. When R was a primary alkyl group, these materials exhibited CO2 uptake values slightly in excess of theoretical. As the alkyl groups were changed to more sterically hindered secondary or tertiary alkyls, the uptake was less efficient. Heats of absorption values for these materials were generally in the range 2000-2200 kJ/kg of CO2, values significantly lower than those obtained for primary amine functional disiloxanes (2500-2700 kJ/kg of CO2). Also explored were a series of secondary amine functional disiloxanes with X-CH2CH2NH-CH2CH2CH2 - substituents. When X was an electron-donating group (RO-, R2N-, RO-CH2-) the CO2 uptake was also in excess of theoretical. Interestingly, these compounds were generally found to produce carbamate salts that were flowable, low-viscosity oils. Furthermore, the heat of absorption values determined for these materials were even lower. Most compounds gave values below 2000 kJ/kg of CO2. Overall the most promising results were obtained with a methoxyethylaminopropyl derivative, an ethoxyethylaminopropyl-containing material, and a dimethylaminoethylaminopropyl-based compound. These materials showed excellent CO2 uptake, had low heats of absorption, and produced carbamate salts that were flowable liquids even at room temperature.

  3. Study of carbamate-modified disiloxane in porous PVDF-HFP membranes: new electrolytes/separators for lithium-ion batteries.

    Science.gov (United States)

    Jeschke, Steffen; Mutke, Monika; Jiang, Zhongxiang; Alt, Burkhard; Wiemhöfer, Hans-Dieter

    2014-06-23

    A gel electrolyte membrane is obtained through the absorption of a carbamate-modified liquid disiloxane-containing lithium bis(trifluoromethane)sulfonimide (LiTFSI) by using macroporous poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) membranes. The porous membranes are prepared by means of a phase inversion technique. The resulting gel electrolyte membrane is studied by using differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, and microscope mapping through coherent anti-Stokes Raman scattering (CARS) confocal microscopy and impedance spectroscopy. The ionic conductivity of the gel electrolyte is 10(-4) S cm(-1) at 20 °C. FTIR spectroscopy reveals interactions between LiTFSI and the carbonyl moiety of the disiloxane. No interactions between LiTFSI and PVDF-HFP or between disiloxane and PVDF-HFP are detected by FTIR spectroscopy. Furthermore, the distribution of the α and β/γ phases of PVDF-HFP and the homogeneous distribution of disiloxane/LiTFSI in the gel electrolyte membranes are examined by FTIR mapping. CARS confocal microscopy is used to image the three-dimensional interconnectivity, which reveals a reticulated structure of macrovoids in the porous PVDF-HFP framework. Owing to properties such as electrochemical and thermal stability of the disiloxane-based liquid electrolyte and the mechanical stability of the porous PVDF-HFP membrane, the gel electrolyte membranes presented herein are promising candidates for applications as electrolytes/separators in lithium-ion batteries.

  4. Disiloxanes and Functionalized Silica Gels: One Route, Two Complementary Outcomes-Guanidinium and Pyridinium Ion-Exchangers.

    Directory of Open Access Journals (Sweden)

    Łukasz Tabisz

    Full Text Available Five novel disiloxane compounds comprising guanidinium and pyridinium moieties were obtained with high yields and purity. The verified synthetic pathways were then applied for modification of pre-functionalized silica gel, producing materials with the analogous organic side-chains. These halide-containing compounds and materials were then compared as to their ion-exchange properties: two disiloxanes proved to be effective in leaching different anions (nitrate, benzoate and ascorbate from solid to organic phase, and pyridinium-functionalized silica gels showed selectivity towards perchlorate ion, removing it from methanolic solutions with preference to other singly charged anions. The results presented demonstrate that both compounds and materials containing silicon-carbon bonds can be produced using the same methodology, but offer strikingly different application opportunities. Comparison of their properties provides additional insight into the binding mode of different anions and hints at how the transition from a flexible siloxane bridge to immobilization on solid surface influences anion-binding selectivity. Additionally, one of the siloxane dipodands was found to form a crystalline and poorly soluble nitrate salt (1.316 g/L, water, although it was miscible with a wide range of solvents as a hydrochloride. A possible explanation is given with the help of semi-empirical calculations. A simple, time- and cost-efficient automated potentiometric titration methodology was used as a viable analytical tool for studying ion-exchange processes for both compounds and materials, in addition to standard NMR, FT-IR and ESI-MS methods.

  5. Easily processable highly ordered Langmuir-Blodgett films of quaterthiophene disiloxane dimer for monolayer organic field-effect transistors.

    Science.gov (United States)

    Sizov, Alexey S; Anisimov, Daniil S; Agina, Elena V; Borshchev, Oleg V; Bakirov, Artem V; Shcherbina, Maxim A; Grigorian, Souren; Bruevich, Vladimir V; Chvalun, Sergei N; Paraschuk, Dmitry Yu; Ponomarenko, Sergei A

    2014-12-23

    Self-assembly of highly soluble water-stable tetramethyldisiloxane-based dimer of α,α'-dialkylquaterthiophene on the water-air interface was investigated by Langmuir, grazing incidence X-ray diffraction, and X-ray reflectivity techniques. The conditions for formation of very homogeneous crystalline monolayer Langmuir-Blodgett (LB) films of the oligomer were found. Monolayer organic field-effect transistors (OFETs) based on these LB films as a semiconducting layer showed hole mobilities up to 3 × 10(-3) cm(2)/(V s), on-off ratio of 10(5), small hysteresis, and high long-term stability. The electrical performance of the LB films studied is close to that for the same material in the bulk or in the monolayer OFETs prepared from water vapor sensitive chlorosilyl derivatives of quaterthiophene by self-assembling from solution. These findings show high potential of disiloxane-based LB films in monolayer OFETs for large-area organic electronics.

  6. Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.

    Science.gov (United States)

    Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J; Arion, Vladimir B

    2015-06-15

    Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry.

  7. 隔板塔共沸精馏分离二氯甲烷-乙腈-水-硅醚体系%Separation of dichloromethane-acetonitrile-water-hexamethyl disiloxane with dividing wall column by azeotropic distillation

    Institute of Scientific and Technical Information of China (English)

    方静; 王宝东; 李春利; 李莉洁; 李艳鹏

    2013-01-01

    以二氯甲烷-乙腈-水-硅醚为分离体系,采用自制隔板塔小试装置,研究了共沸剂回流比和液相分配比等操作参数对隔板塔分离效果的影响.实验结果表明,当气相分配比Rv为0.5,共沸剂回流比为3时,液相分配比Rl在[0.12,0.2]范围内,隔板塔分离效果较好.在实验的基础上,采用Aspen Plus软件对隔板塔共沸精馏工艺进行模拟,考察了隔板塔共沸精馏工艺最佳操作区域及节能效果.模拟结果表明,特定分离要求下,隔板塔存在一个使再沸器热负荷最小的最佳操作区域,在此最佳操作区域内,Rl和Rv相互关联,呈一一对应关系;与三塔串联简单精馏工艺相比,完成相同的分离任务,隔板塔共沸精馏工艺再沸器节能32.74%,冷凝器热负荷减少33.70%,乙腈回收率由66.47%提高到96.01%,且大幅降低设备投资.%The separation of dichloromethane, acetonitrile, water, and hexamethyl disiloxane mixture with a self-made dividing wall column ( DWC) was investigated experimentally. The effects of manipulative parameters, such as azeotropic agent reflux ratio and liquid split, on the separation were discussed. According to the experimental results, the process of azeotropic distillation with DWC was simulated with Aspen Plus. The experimental results demonstrate that the separation effect is better in the range of liquid split (Rl) 0.12-0.2 at vapor split (Rv) of 0.5 and entrainer reflux ratio of 3. The simulation results illustrate the optimum operation region and energy saving effect. In the optimum operation region, the thermal load of DWC reboiler is the minimum under specific requirements of separation. In the best operation region, Rl and Rv interrelate with each other. The comparison of energy consumption with that of conventional distillation sequences shows that the reboiler duty is reduced by 32. 74%, the condenser duty is reduced by 33. 70%, the recovery rate of acetonitrile is increased from 66. 47% to

  8. Tetra­carbon­yl[bis­(diphenyl­phosphan­yl)tetra­methyl­disiloxane-κ2 P,P′]chromium(0)

    Science.gov (United States)

    Peulecke, Normen; Müller, Bernd H.; Spannenberg, Anke; Rosenthal, Uwe

    2012-01-01

    The title compound, [Cr(C28H32OP2Si2)(CO)4], was obtained by the ligand-exchange reaction of Cr(CO)6 with (Ph2PSiMe2)2O in refluxing toluene. The CrC4P2 coordination geometry is distorted octa­hedral, with a P—Cr—P bite angle of 99.22 (4)°. PMID:22346807

  9. EFFECTS OF SOME PHENYLETHYNYLSILICON COMPOUNDS ON HEAT-CURABLE SILICONE RUBBER Ⅲ 1,1,3,3-TETRAMETHYL- 1,3-DIPHENYLETHYNYL-DISILOXANE

    Institute of Scientific and Technical Information of China (English)

    FENG Shengyu; YU Shuqi; LI Shijun; ZHANG Shengyou; CHEN Jianhua; DU Zuodong

    1995-01-01

    We have shown that some phenylethynylsilicon compounds are good cure crosslinkers of heat-curable silicone rubber(HCSR). In this paper the effects of 1,1,3,3-tetramethyl1,3-diphenylethynyldisiloxane (TMDPDS) as a crosslinker on HCSR were studied. The vulcanizates with fine mechanical properties could be obtained with suitable amounts of TMDPDS. Sol fractions, and crosslinking density of vulcanizates and vulcanization retardation effect of TMDPDS on hydrosilation curing silicone rubber were also discussed.

  10. Minimization of Power Loss in Distribution Systems by Implementation of High Voltage Distribution System

    Directory of Open Access Journals (Sweden)

    PARWAL Arvind

    2013-05-01

    Full Text Available The loads in rustic area are preeminent pump sets used for various applications i.e. lift irrigation system. Minimal power factor and minimal load factor is found in loads. Further, being a factordissemination of loads, load density is found low. The present distribution system dwell of three-phase 11KV/433Volts distribution transformer with extended L.T Lines. In this system, voltage profile and reliability are poor. In this paper, HVDS is unveiled with smallcapacity distribution transformers. A simple load flow technique is used for solving distribution networks before and after implementation of HVDS. The advantages of implementing HVDS against LVDS system are discussed.

  11. Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

    Science.gov (United States)

    Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap

    2015-08-26

    We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.

  12. Brønsted acid-promoted azide–olefin [3 + 2] cycloadditions for the preparation of contiguous aminopolyols: The importance of disiloxane ring size to a diastereoselective, bidirectional approach to zwittermicin A

    Directory of Open Access Journals (Sweden)

    Hubert Muchalski

    2010-12-01

    Full Text Available We report the first study of substrate-controlled diastereoselection in a double [3 + 2] dipolar cycloaddition of benzyl azide with α,β-unsaturated imides. Using a strong Brønsted acid (triflic acid to activate the electron deficient imide π-bond, high diastereoselection was observed provided that a 1,1,3,3-tetraisopropoxydisiloxanylidene group (TIPDS is used to restrict the conformation of the central 1,3-anti diol. This development provides a basis for a stereocontrolled approach to the aminopolyol core of (−-zwittermicin A using a bidirectional synthesis strategy.

  13. Regio- and stereoselective hydrosilylation of immobilized terminal alkynes

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob; Henriksen, Jonas; Gotfredsen, Charlotte Held;

    2008-01-01

    Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane), in ...

  14. Digital Printing of μPlasmas to Selectively Improve Wetting Behavior of Functional Inks for Printed Electronics

    NARCIS (Netherlands)

    Dongen, Martijn van; Nieuwenhuis, Erik; Verbraeken, Lise; Verkuijlen, Renee; Bernards, Jan

    2012-01-01

    In this article we investigate the change in wetting behavior of inkjet printed materials on either hydrophilic or hydrophobic plasma treated patterns, to determine the minimum obtainable track width using selective patterned μPlasma printing. For Hexamethyl-Disiloxane (HMDSO)/N2 plasma, a decrease

  15. Digital Printing of μPlasmas to Selectively Improve Wetting Behavior of Functional Inks for Printed Electronics

    NARCIS (Netherlands)

    Erik Nieuwenhuis; ir Renee Verkuijlen; Lise Verbraeken; Dr Jan Bernards; ir Martijn van Dongen

    2012-01-01

    In this article we investigate the change in wetting behavior of inkjet printed materials on either hydrophilic or hydrophobic plasma treated patterns, to determine the minimum obtainable track width using selective patterned μPlasma printing. For Hexamethyl-Disiloxane (HMDSO)/N2 plasma, a decrease

  16. A bentonite-gold nanohybrid as a heterogeneous green catalyst for selective oxidation of silanes.

    Science.gov (United States)

    Maya, R J; John, Jubi; Varma, R Luxmi

    2016-08-23

    A highly efficient, environmentally benign and reusable heterogeneous bentonite-gold nanohybrid catalyst was designed and synthesized. This heterogeneous catalyst could efficaciously catalyse the oxidation of organosilanes to silanols. The reaction is 98.7% atom economical and the products were obtained in excellent yield without the formation of disiloxanes as byproducts. The catalyst was also well applicable for the gram scale preparation of silanols.

  17. Highly Mass-Sensitive Thin Film Plate Acoustic Resonators (FPAR)

    Science.gov (United States)

    Arapan, Lilia; Alexieva, Gergana; Avramov, Ivan D.; Radeva, Ekaterina; Strashilov, Vesseline; Katardjiev, Ilia; Yantchev, Ventsislav

    2011-01-01

    The mass sensitivity of thin aluminum nitride (AlN) film S0 Lamb wave resonators is theoretically and experimentally studied. Theoretical predictions based on modal and finite elements method analysis are experimentally verified. Here, two-port 888 MHz synchronous FPARs are micromachined and subsequently coated with hexamethyl-disiloxane(HMDSO)-plasma-polymerized thin films of various thicknesses. Systematic data on frequency shift and insertion loss versus film thickness are presented. FPARs demonstrate high mass-loading sensitivity as well as good tolerance towards the HMDSO viscous losses. Initial measurements in gas phase environment are further presented. PMID:22163994

  18. Highly mass-sensitive thin film plate acoustic resonators (FPAR).

    Science.gov (United States)

    Arapan, Lilia; Alexieva, Gergana; Avramov, Ivan D; Radeva, Ekaterina; Strashilov, Vesseline; Katardjiev, Ilia; Yantchev, Ventsislav

    2011-01-01

    The mass sensitivity of thin aluminum nitride (AlN) film S0 Lamb wave resonators is theoretically and experimentally studied. Theoretical predictions based on modal and finite elements method analysis are experimentally verified. Here, two-port 888 MHz synchronous FPARs are micromachined and subsequently coated with hexamethyl-disiloxane(HMDSO)-plasma-polymerized thin films of various thicknesses. Systematic data on frequency shift and insertion loss versus film thickness are presented. FPARs demonstrate high mass-loading sensitivity as well as good tolerance towards the HMDSO viscous losses. Initial measurements in gas phase environment are further presented.

  19. Synthesis of lipase-catalysed silicone-polyesters and silicone-polyamides at elevated temperatures.

    Science.gov (United States)

    Frampton, Mark B; Zelisko, Paul M

    2013-10-18

    More and more enzymes are being explored as alternatives to conventional catalysts in chemical reactions. To utilize these biocatalysts to their fullest, it is incumbent on researchers to gain a complete understanding of the reaction conditions that particular enzymes will tolerate. To this end siloxane-containing polyesters and polyamides have been produced via N435-mediated catalysis at temperatures well above the normal denaturation temperature for free CalB. Low molecular weight disiloxane-based acceptors release the enzyme from its acylated state with equal proficiency while longer chain siloxanes favours polyester synthesis. The thermal tolerance of the enzyme catalyst is increased using longer chain diesters and generally more hydrophobic substrates.

  20. SYNTHESIS AND CHARACTERIZATION OF Si-CONTAINING POLYESTER-POLYETHER MULTIBLOCK COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    LI Zhenyi; ZHU Jin

    1996-01-01

    A series of Si-containing polyester-polyether multiblock copolymers were synthesized by transesterification and melt copolycondensation of organosilicon monomers [1, 1, 3, 3-tetramethyl-1, 3-bis (p-carbomethoxyphenyl) disiloxane] (I) or dimethyl bis (p-carbomethoxyphenyl) silane] (II) and dimethyl terephthalate (DMT), with 1, 4-butanediol, polytetramethylene glycol (PTMG) respectively. The organosilicon monomers were prepared by Grinard reaction, oxidation and esterification. The structures of the above monomers (Ⅰ), (Ⅱ) and the copolymers were characterized by MS anal. and 1H-NMR.

  1. Highly Mass-Sensitive Thin Film Plate Acoustic Resonators (FPAR

    Directory of Open Access Journals (Sweden)

    Ventsislav Yantchev

    2011-07-01

    Full Text Available The mass sensitivity of thin aluminum nitride (AlN film S0 Lamb wave resonators is theoretically and experimentally studied. Theoretical predictions based on modal and finite elements method analysis are experimentally verified. Here, two-port 888 MHz synchronous FPARs are micromachined and subsequently coated with hexamethyl-disiloxane(HMDSO-plasma-polymerized thin films of various thicknesses. Systematic data on frequency shift and insertion loss versus film thickness are presented. FPARs demonstrate high mass-loading sensitivity as well as good tolerance towards the HMDSO viscous losses. Initial measurements in gas phase environment are further presented.

  2. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    Directory of Open Access Journals (Sweden)

    M. Claeys

    2010-10-01

    Full Text Available Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil using a high-volume dichotomous sampler (HVDS and a Micro-Orifice Uniform Deposit Impactor (MOUDI within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia – Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate campaign. The campaign spanned the late dry season (biomass burning, a transition period, and the onset of the wet season (clean conditions. In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m−3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m−3 during the dry period versus 157 ng m−3 during the transition period and 52 ng m−3 during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of

  3. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    Directory of Open Access Journals (Sweden)

    M. Claeys

    2010-04-01

    Full Text Available Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil using a High-Volume dichotomous sampler (HVDS and a Micro-Orifice Uniform Deposit Impactor (MOUDI. The samplings were conducted within the framework of the LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia – Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate campaign, which took place from 9 September till 14 November 2002, spanning the late dry season (biomass burning, the transition period, and the onset of the wet season (clean conditions. In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including: (a levoglucosan, a tracer for biomass burning, (b malic acid, a tracer for the oxidation of semivolatile carboxylic acids, (c tracers for secondary organic aerosol (SOA from isoprene, i.e., the 2-methyltetrols (2-methylthreitol and 2-methylerythritol and the C5-alkene triols [2-methyl-1,3,4-trihydroxy-1-butene (cis and trans and 3-methyl-2,3,4-trihydroxy-1-butene], and (d sugar alcohols (arabitol, mannitol, and erythritol, tracers for fungal spores. The results obtained for levoglucosan are covered first with the aim to address its contrasting behavior with that of malic acid, the isoprene SOA tracers, and the fungal spore tracers. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m−3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the

  4. Inflation of the type I error: investigations on regulatory recommendations for bioequivalence of highly variable drugs.

    Science.gov (United States)

    Wonnemann, Meinolf; Frömke, Cornelia; Koch, Armin

    2015-01-01

    We investigated different evaluation strategies for bioequivalence trials with highly variable drugs on their resulting empirical type I error and empirical power. The classical 'unscaled' crossover design with average bioequivalence evaluation, the Add-on concept of the Japanese guideline, and the current 'scaling' approach of EMA were compared. Simulation studies were performed based on the assumption of a single dose drug administration while changing the underlying intra-individual variability. Inclusion of Add-on subjects following the Japanese concept led to slight increases of the empirical α-error (≈7.5%). For the approach of EMA we noted an unexpected tremendous increase of the rejection rate at a geometric mean ratio of 1.25. Moreover, we detected error rates slightly above the pre-set limit of 5% even at the proposed 'scaled' bioequivalence limits. With the classical 'unscaled' approach and the Japanese guideline concept the goal of reduced subject numbers in bioequivalence trials of HVDs cannot be achieved. On the other hand, widening the acceptance range comes at the price that quite a number of products will be accepted bioequivalent that had not been accepted in the past. A two-stage design with control of the global α therefore seems the better alternative.

  5. SYNTHESIS OF NOVEL LIQUID CRYSTALLINE POLY(METH)ACRYLATES CONTAINING SILOXANE SPACER AND TERPHENYLENE MESOGENIC UNIT

    Institute of Scientific and Technical Information of China (English)

    Zhi-qian Zang; Yu-fei Luo; Dong Zhang; Xin-hua Wan; Qi-feng Zhou

    2000-01-01

    Novel side-chain liquid-crystalline poly(meth)acrylates were synthesized using 1-(3-hydroxyl-propyl)-3-[(4"cyano-p-terphenyloxycarbonyl)alkyl]-1, 1,3,3-tetramethyldisiloxane as the key intermediate. The polymers used a disiloxane moiety as decoupling spacer with cyano-p-terphenyl as mesogenic unit. The products were characterized by NMR, GPC,DSC and polarizing optical microscopy. All the polymers with cyano-p-terphenyl mesogens formed a stable mesophase.However, if the mesogenic unit is replaced by cyano-p-biphenyl, the liquid crystalline character will be lost. The results also showed that the decoupling is incomplete even if a complex and very flexible decoupling spacer is deliberately incorporated to obtain the highest possible decoupling effect.

  6. THE EFFECT OF THE ACID CATALYST ON THE PREPARATION OF MQ SILICONE RESINS

    Institute of Scientific and Technical Information of China (English)

    Wei Huang; Ying Huang; Yun-zhao Yu

    1999-01-01

    MQ silicone resins were prepared through hydrolytic condensation of ethyl polysilicate or tetraethoxysilane and hexamethyl disiloxane. The unit ratio of the MQ resins was determined by 29Si-NMR.The relationship of the unit ratio of the product resins with that in the feed was studied. When the reaction was catalyzed by aqueous hydrochloric acid, and the unit ratio of M to Q in the feed was more than 1, the unit ratio of the product was usually lower than that of the feed. The MQ silicon with an unit ratio of M/Q>2 could not be obtained. However, if the reaction was catalyzed by concentrated sulfuric acid and the reverse hydrolysis process was employed, MQ silicone resin with very high M/Q ratio was successfully prepared.

  7. Development of TiO2 and TiO2/Fe-based polymeric nanocomposites by single-step laser pyrolysis

    Science.gov (United States)

    Alexandrescu, R.; Morjan, I.; Dumitrache, F.; Scarisoreanu, M.; Fleaca, C. T.; Morjan, I. P.; Barbut, A. D.; Birjega, R.; Prodan, G.

    2013-08-01

    Polymer-based nanocomposites provided with inorganic cores were simultaneously manufactured by the single-step laser pyrolysis. A comparative study was performed on two types of nanocomposites, starting from two different systems: TiO2/methyl methacrylate (MMA) and TiO2/Fe/hexamethyl disiloxane (HMDSO) polymer. The reactive mixture contained TiCl4 as Ti precursor and alternatively, Fe(CO)5 (in case of TiO2/Fe mixture). The analytical techniques used for the characterization indicate distinct morphologies for the obtained nanostructures. Polyhedral and almost spherical nanoparticles in a coalescent matrix and very rare individual core-shell particles are noticed for the TiO2/MMA nanocomposites. Instead, nanoparticles presenting core-shell structures were often present in the TiO2/Fe/HMDSO polymeric nanocomposites.

  8. 2-Acetyl­amino-1,3,4,6-tetra-O-(tri­methyl­silyl)-2-de­oxy-α-d-gluco­pyran­ose

    Science.gov (United States)

    Cheng, Zhao-Dong; Cui, Yan-Li; Mao, Jian-Wei

    2013-01-01

    The title compound, C20H47NO6Si4, was synthesized by per-O-tri­methyl­silylation of N-acetyl-d-glucosa­mine using chloro­tri­methyl­silane in the presence of hexa­methyl­disiloxane. The tri­methyl­silyl group and acetamido group are located on the same side of the pyran ring, showing an α-configuration glycoside. One of the tri­methyl­silyl groups is disordered over two orientations, with site-occupancy factors of 0.625 (9) and 0.375 (9). In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into supra­molecular chains along the a-axis direction. PMID:23795087

  9. 一种新型双子有机硅表面活性剂的合成及表征%Synthesis and characterization of a new organic silicon gemini surfactant

    Institute of Scientific and Technical Information of China (English)

    梁静; 徐群; 高跃岳; 王丽艳; 王平朗

    2013-01-01

    Organic silicon gemini surfactant was synthesized with N- ethyl-N- propyl methyl dimethoxy silane, hexamethyl disiloxane,benzaldehyde and glycol diglycidyl ether as raw material via three steps reaction.Interme-diate and product structure were characterized by IR and 1HNMR and confirmed as the target product.%利用氨乙基氨丙基甲基二甲氧基硅烷、六甲基二硅氧烷、苯甲醛和乙二醇二缩水甘油醚等为原料,经三步反应合成目标产物双子有机硅表面活性剂。利用IR和1HNMR对中间体和产物进行结构表征,证明所得为目标产物。

  10. New World and Old World Alphaviruses Have Evolved to Exploit Different Components of Stress Granules, FXR and G3BP Proteins, for Assembly of Viral Replication Complexes

    Science.gov (United States)

    Kim, Dal Young; Reynaud, Josephine M.; Rasalouskaya, Aliaksandra; Akhrymuk, Ivan; Mobley, James A.; Frolov, Ilya; Frolova, Elena I.

    2016-01-01

    The positive-strand RNA viruses initiate their amplification in the cell from a single genome delivered by virion. This single RNA molecule needs to become involved in replication process before it is recognized and degraded by cellular machinery. In this study, we show that distantly related New World and Old World alphaviruses have independently evolved to utilize different cellular stress granule-related proteins for assembly of complexes, which recruit viral genomic RNA and facilitate formation of viral replication complexes (vRCs). Venezuelan equine encephalitis virus (VEEV) utilizes all members of the Fragile X syndrome (FXR) family, while chikungunya and Sindbis viruses exploit both members of the G3BP family. Despite being in different families, these proteins share common characteristics, which determine their role in alphavirus replication, namely, the abilities for RNA-binding and for self-assembly into large structures. Both FXR and G3BP proteins interact with virus-specific, repeating amino acid sequences located in the C-termini of hypervariable, intrinsically disordered domains (HVDs) of viral nonstructural protein nsP3. We demonstrate that these host factors orchestrate assembly of vRCs and play key roles in RNA and virus replication. Only knockout of all of the homologs results in either pronounced or complete inhibition of replication of different alphaviruses. The use of multiple homologous proteins with redundant functions mediates highly efficient recruitment of viral RNA into the replication process. This independently evolved acquisition of different families of cellular proteins by the disordered protein fragment to support alphavirus replication suggests that other RNA viruses may utilize a similar mechanism of host factor recruitment for vRC assembly. The use of different host factors by alphavirus species may be one of the important determinants of their pathogenesis. PMID:27509095

  11. A Study on the Effect of Plasma Treatment for Waste Wood Biocomposites

    Directory of Open Access Journals (Sweden)

    MiMi Kim

    2013-01-01

    Full Text Available The surface modification of wood powder by atmospheric pressure plasma treatment was investigated. The composites were manufactured using wood powder and polypropylene (wood powder: polypropylene = 55 wt% : 45 wt%. Atmospheric pressure plasma treatment was applied under the condition of 3 KV, 17±1 KHz, 2 g/min. Helium was used as the carrier gas and hexamethyl-disiloxane (HMDSO as the monomer to modify the surface property of the waste wood biocomposites by plasma polymerization. The tensile strengths of untreated waste wood powder (W3 and single species wood powder (S3 were about 18.5 MPa and 21.5 MPa while those of plasma treated waste wood powder (PW3 and plasma treated single species wood powder (PS3 were about 21.2 MPa and 23.4 MPa, respectively. Tensile strengths of W3 and S3 were improved by 14.6% and 8.8%, respectively. From the analyses of mechanical properties and morphology, we conclude that the interfacial bonding of polypropylene and wood powder can be improved by atmospheric pressure plasma treatment.

  12. Computer simulation of liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    McBride, C.

    1999-01-01

    Molecular dynamics simulation performed on modern computer workstations provides a powerful tool for the investigation of the static and dynamic characteristics of liquid crystal phases. In this thesis molecular dynamics computer simulations have been performed for two model systems. Simulations of 4,4'-di-n-pentyl-bibicyclo[2.2.2]octane demonstrate the growth of a structurally ordered phase directly from an isotropic fluid. This is the first time that this has been achieved for an atomistic model. The results demonstrate a strong coupling between orientational ordering and molecular shape, but indicate that the coupling between molecular conformational changes and molecular reorientation is relatively weak. Simulations have also been performed for a hybrid Gay-Berne/Lennard-Jones model resulting in thermodynamically stable nematic and smectic phases. Frank elastic constants have been calculated for the nematic phase formed by the hybrid model through analysis of the fluctuations of the nematic director, giving results comparable with those found experimentally. Work presented in this thesis also describes the parameterization of the torsional potential of a fragment of a dimethyl siloxane polymer chain, disiloxane diol (HOMe[sub 2]Si)[sub 2]O, using ab initio quantum mechanical calculations. (author)

  13. Computer simulation of liquid crystals

    Energy Technology Data Exchange (ETDEWEB)

    McBride, C

    1999-09-01

    Molecular dynamics simulation performed on modern computer workstations provides a powerful tool for the investigation of the static and dynamic characteristics of liquid crystal phases. In this thesis molecular dynamics computer simulations have been performed for two model systems. Simulations of 4,4`-di-n-pentyl-bibicyclo[2.2.2]octane demonstrate the growth of a structurally ordered phase directly from an isotropic fluid. This is the first time that this has been achieved for an atomistic model. The results demonstrate a strong coupling between orientational ordering and molecular shape, but indicate that the coupling between molecular conformational changes and molecular reorientation is relatively weak. Simulations have also been performed for a hybrid Gay-Berne/Lennard-Jones model resulting in thermodynamically stable nematic and smectic phases. Frank elastic constants have been calculated for the nematic phase formed by the hybrid model through analysis of the fluctuations of the nematic director, giving results comparable with those found experimentally. Work presented in this thesis also describes the parameterization of the torsional potential of a fragment of a dimethyl siloxane polymer chain, disiloxane diol (HOMe{sub 2}Si){sub 2}O, using ab initio quantum mechanical calculations. (author)

  14. Comparison of GC-MS and GC-FID Results for the Determination of C2/C6 Substitution Ratio of Hydroxyethyl Starch 130/0.4%羟乙基淀粉130/0.4的C2/C6置换比例的GC-MS和GC-FID法测定结果比较

    Institute of Scientific and Technical Information of China (English)

    彭茗; 陆丹; 刘瑾; 杨永健

    2013-01-01

    将羟乙基淀粉130/0.4相继用酸水解、六甲基二硅氧烷衍生化后,分别采用GC-MS和GC-FID法测定并比较羟乙基淀粉C2位和C6位的羟乙基置换比例.结果显示,GC-FID法重复性好、进样精密度高,结果可靠;由于存在C2位和C6位衍生物离子化效率的差异,GC-MS法不适合用作该项目的定量方法,但可作为辅助的色谱峰定性工具.%Hydroxyethyl starch 130/0.4 was hydrolyzed by acid and trimethylsilylized by hexamethyl disiloxane successively. The resulting sample solution was utilized to determine C2/C6 substitution ratio by GC-MS and GC-FID method. The results showed that the GC-FID method had high repeatability, precision and reliability. However, the GC-MS method was unsuited for the quantitative analysis of C2/C6 substitution ratio, due to the discrepancy in ionization efficiency of the C2- and C6-derivatives. Nevertheless, it was a supplementary tool for identifying chromatographic peaks.

  15. Solution processed white light photodetector based N, N′-di (2-ethylhexyl)-3,4,9,10-perylene diimide thin film phototransistor

    Energy Technology Data Exchange (ETDEWEB)

    Tozlu, Cem, E-mail: tozlu.cem@gmail.com [Department of Energy System Engineering, Faculty of Engineering, Karamanoğlu Mehmetbey University, 70100 Karaman (Turkey); Kus, Mahmut [Department of Chemical Engineering, Selcuk University, Konya 42075 (Turkey); Advanced Technology Research and Application Center, Selcuk University, Konya 42075 (Turkey); Can, Mustafa [Department of Engineering Sciences, Faculty of Engineering, Izmir Katip Celebi University, Cigli, 35620 Izmir (Turkey); Ersöz, Mustafa [Advanced Technology Research and Application Center, Selcuk University, Konya 42075 (Turkey); Department of Chemistry, Selcuk University, Konya 42075 (Turkey)

    2014-10-31

    In this study, a solution-processed n-type photo-sensing organic thin film transistor was investigated using polymeric dielectric under different white light illuminations. N, N′-di (2-ethylhexyl)-3,4,9,10-perylene diimide and divinyl tetramethyl disiloxane-bis (benzo-cyclobutene) were used as a soluble active organic semiconductor and as a dielectric material, respectively. Stable amplification was observed in the visible region without gate bias by the device. The electrical characterization results showed that an n-type phototransistor with a saturated electron mobility of 0.6 × 10{sup −3} cm{sup 2}/V·s and a threshold voltage of 1.8 V was obtained. The charge carrier density of the channel of the device exhibited photo-induced behaviors that strongly affected the electrical properties of the transistor. The photosensitivity and photoresponsivity values of the device were 63.82 and 24 mA/W, respectively. These findings indicate that perylene diimide is a promising material for use on organic based phototransistors. - Highlights: • A solution processed n-type organic phototransistor was fabricated. • The geometry of device allows to be used double sided photo-sensor to detect light. • The accumulation of charge carrier is effected strongly by illumination intensity. • The current amplification was observed clearly under illumination without gate bias.

  16. 新型耐热、疏水MQ硅树脂的合成与性能研究%Synthesis and Performance Study of a Novel MQ Silicon Resin with High Heat Resist and Hydrophobic Property

    Institute of Scientific and Technical Information of China (English)

    刘方猛; 许苗军; 李斌

    2012-01-01

    A novel MQ silicon resin (1) was synthesized by hydrolysis condensation reaction under a-cidic conditions from tetraethoxysilane, hexamethyl-disiloxane and divinyltetramethyldisiloxane. The structure was characterized by 'H NMR, FT-IR, and XRD. The wettibility and thermal stability of 1 were investigated by static contact angle and thermogravimetric analysis, respectively. The results showed that the water contact angle of lwas 139° and 5% weight loss temperature was 456 °C. 1 exhibited hydrophobic property and high thermal stability.%以正硅酸乙酯、六甲基二硅氧烷和四甲基二乙烯基二硅氧烷为原料,通过在酸性条件的水解缩合反应合成了一种新型的MQ硅树脂(1),其结构经1H NMR,FT-IR和XRD表征.用静态接触角和热重分析分别研究了1的润湿性和热稳定性.结果表明:1的接触角为139°,具有良好的疏水性能;1失重5wt%的温度为456℃,具有高的热稳定性.

  17. The Utilization of Low Frequency Raman Spectra of Gases for the Study of Molecules with Large Amplitude Vibration

    Institute of Scientific and Technical Information of China (English)

    James R. Durig; Sarah Xiao-hua Zhou; Joshua Klaassen; Arindam Ganguly

    2009-01-01

    The utilization of the Raman spectra of the low frequency bending mode for three quasi-linear molecules, disiloxane, (SiH3)2 O; methylisocyanate, CH3NCO; and dimethy lisocyanate, (CH3)2SiHNCO for observing the low frequency anharmonic bending vibration is demonstrated which is superior to the corresponding far infrared spectra. From the observed frequencies from the Raman spectra the potential function governing the heavy atom motion to linearity has been obtained from which the barrier has been determined. These experimental values are compared to the ab ini-tio predicted values. Also low frequency Raman spectra of the ring puckering vibration of chlorocy-clobutane, c-C4H7Cl, bromocyclobutane, c-C4H7Br, and aminocyclobutane, c-C4H7NH2, have been utilized to obtain the potential function governing the ring inversion for these molecules. The deter-mined barriers to planarity are compared to those obtained from MP2 (full) ab initio and density functional theory B3LYP calculations by utilizing a variety of basis sets. For all of these studies it is shown that the Raman spectra are superior to the infrared spectra for determining the frequencies of the excited state transitions.

  18. Synthesis and evaluation of C-ether formulations for use as high temperature lubricants and hydraulic fluids

    Science.gov (United States)

    Clark, F. S.; Green, R. L.; Miller, D. R.

    1974-01-01

    The formulation and evaluation of C-ether fluids for use in the hydraulic and lubrication systems of the space shuttle and advanced air breathing engines were studied to lower the pour point of a reference C-ether from -29 C to -40 C without changing its evaporation loss. Use of disiloxanes mixed with C-ethers gave a -40 C pour point fluid with little change in the desired evaporation loss or in oxidative stability. A second -40 C pour point fluid containing only C-ethers was also developed. A screening program tested lubrication additives for C-ethers and the new fluids. Six additive packages were chosen for evaluation in 316 C bearing tests, two for evaluation in 260 C pump tests. The goal of the bearing test was a 100 hour run. The rig was a specially designed 80-mm axially loaded ball bearing. The C-ether base fluid ran only one hour at 316 C before cage wear failure occurred. The best additive blends ran 47, 94 and 100 hours. The 96 hour test gave excessive deposits. The 100 hour test had no wear failures; an unexplained loss of cage silver occurred from areas of direct fluid impingement on the cage.

  19. Synthesis and Characterization of Ferroelectric Liquid Crystalline Organosiloxanes Containing 4-(4-undecanyloxy bi-phenyl-1-carboxyloxyphenyl (2S,3S-2-chloro-3-methylvalerate and 4-(4-undecanyloxybenzoyloxybiphenyl (2S,3S-2-chloro-3-methylvalerate

    Directory of Open Access Journals (Sweden)

    Chih-Hung Lin

    2013-10-01

    Full Text Available A series of new organosiloxane ferroelectric liquid crystalline (FLC materials have been synthesized, and their mesomorphic and physical properties have been characterized. Four new disiloxanes and trisiloxanes, containing biphenyl 4-hydroxybenzoate and phenyl 4-hydroxybiphenylcarboxylate as mesogenic units and eleven methylene unit as spacers and (2S,3S-2-chloro-3-methylvalerate unit as chiral end groups. The molecule, using three phenyl ring as a mesogenic unit, formulates much wider liquid crystalline phase temperature ranges than that of a two phenyl ring unit. The phenyl arrangement differences of mesogenic unit result in the greater differences of the liquid crystal phase formation. The siloxane molecule induction is helpful to the more regular smectic phase formation and smectic phase stabilization, such as chiral SC (SC* and SB phases. The siloxane molecule is helpful to reduce the phase transition temperature and broaden the liquid crystal temperature range of the SC* phase and, simultaneously, it will not induce chain crystallization phenomenon and dilute the Ps value. The synthesis and characterization of the new FLCs materials, which exhibit a room temperature SC* phase and higher spontaneous polarization are presented.

  20. The novel silicon-containing epoxy/PEPA phosphate flame retardant for transparent intumescent fire resistant coating

    Science.gov (United States)

    Shi, Yanchao; Wang, Guojian

    2016-11-01

    A series of novel silicon-containing epoxy/PEPA phosphate flame retardants (EPPSi) were synthesized by polyphosphoric acid (PPA), caged bicyclic phosphate 1-oxo-4-hydroxymethyl-2,6,7-trioxa-L-phosphabicyclo [2.2.2] octane (PEPA), and different ratios of silicon-containing epoxy 1,1,3,3-tetramethyl-1,3-bis(3-(oxiran-2-ylmethoxy)propyl)disiloxane (TMSEP) to 1,4-butanediol diglycidyl ether (BDE). The chemical structure of EPPSi was confirmed by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). Afterwards, the transparent intumescent fire resistant coatings were prepared by mixing EPPSi and melamine formaldehyde resin. The influence of silicon on the fire protection of coatings was intensively investigated by fire protection test, intumescence ratio, scanning electron microscope (SEM), compressive strength test, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and real-time FTIR. It was found that the fire resistant coatings obtained the best fire protection when the ratio of TMESP/BDE was 20/100, while excessive TMSEP made the fire protection of coatings deceased sharply. The intumescence ratio, compressive strength test and SEM result showed that a synergistic effect existed between phosphorus and silicon, which improved the foam structure and compressive strength of the char layer significantly. XPS result proved the out-migration effect of silicon. The high concentration silicon on surface played an important protecting role for the inner char residue and improved the fire protection of the coatings. TGA result demonstrated that silicon enhanced the thermo-oxidation resistance of coatings efficiently. Furthermore, real-time FTIR revealed the intumescent process of the fire resistant coatings according to the chemical structure changes of char residue.

  1. Reactivity of the Sterically Demanding Siloxanediol Mes2 Si(OH)(μ-O)Si(OH)Mes2 Towards Water and Ether Molecules.

    Science.gov (United States)

    Roesch, Philipp; Warzok, Ulrike; Enke, Martin; Müller, Robert; Schattenberg, Caspar; Schalley, Christoph A; Kaupp, Martin; Braun, Thomas; Wittwer, Philipp

    2017-07-29

    A series of isotopologues of the siloxanediol Mes2 Si(OH)(μ-O)Si(OH)Mes2 (3 a) (Mes=2,4,6-trimethylphenyl) were synthesized by reactions of the corresponding disiloxane precursors Mes2 Si(μ-O)2 SiMes2 (2 a), Mes2 Si(μ-(17) O)2 SiMes2 (2 b) or Mes2 Si(μ-(18) O)2 SiMes2 (2 c) with an excess of H2 O, H2(17) O or H2(18) O. NMR and IR signal assignments for the siloxanediols in benzene are supported by quantum-chemical calculations, which indicate small energy differences between trans and cis conformers, the latter of which exhibits an intramolecular hydrogen bond. (1) H NMR as well as IR data suggest the presence of a mixture of both conformers in C6 D6 . Hydrogen-bonded adducts of Mes2 Si(OH)(μ-O)Si(OH)Mes2 with ethers such as diethylether, dimethoxyethane or dioxane were observed in the solid state, where they form polymeric chain-like structures. The latter appear to be stable only in the crystal. (17) O{(1) H} NMR and IR data in THF solution suggest an interaction of 3 a with at least one THF molecule, whereas diethylether appears not to interact. Water adducts form neither in solution nor in the solid state as indicated by NMR and ATR IR data. (17) O{(1) H} NMR and ESI-MS experiments illustrate the remarkably high stability of the siloxanediols towards water and show no evidence for intra- or intermolecular oxygen-exchange reactions. In marked contrast, a stepwise exchange of all three oxygen atoms-including the one in the Si-O-Si bridge-occurred in the gas phase, when [Mes2 Si((18) OH)(μ-(18) O)Si((18) O)Mes2 ](-) was treated with H2 O in the hexapole of an ESI FT-ICR mass spectrometer. The scrambling between the bridging and the other oxygen atoms likely proceeds through cyclic Si2 O2 intermediates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and characterization of novel polysiloxanes. I. Telechelic cyanate esters. II. Hindered alkyl siloxanes

    Science.gov (United States)

    Fu, Zhidong

    Two aspects of novel polysiloxane chemistry have been explored in this work: (1) the synthesis and characterization of polysiloxanes functionalized with terminal cyanate ester groups for use as low flammability impact modifiers for commercial phenolic cyanate ester resins (CERs) and (2) the synthesis and characterization of polydiethylsiloxane and polycyclotetramethylenesiloxane. CERs have been proposed as a potentially useful matrix material for commercial aircraft manufacture. However, commercial CERs do not currently have the appropriate fracture toughness for practical applications. Prior studies have shown that siloxanes offer excellent flame suppression and can improve the CERs impact properties. In this work, a series of new siloxanes terminated with cyanate-reactive groups, including bis[1,3-(4--cyanatophenyl)]-1,1,3,3-tetramethyldisiloxane (11), alpha,o-(4-cyanatophenyl) oligodimethylsiloxane (12), and alpha,o-(4-cyanatophenyl) oligo(dimethyl- co-diphenylsiloxane) (13), have been synthesized from corresponding diphenols. The intermediates and products were characterized by 1H NMR, 13C NMR, FTIR, GC-MS, and GPC. To synthesize the diphenols, a new route to synthesize disiloxane terminated with THP protected diphenols (dimer) was established. The synthesized dimer was used to equilibrate with D4 and/or D4'' to make desired siloxane oligomers. The mechanism of the equilibration of the dimer with D4 were studied. The synthesized CER monomers were polymerized by a cyclotrimerization reaction. The cured compound 11 is a brittle solid with Tg of 274°C. The cured 12 (oligodimethyl-siloxane) and 13 (oligodimethylsiloxane- co-diphenylsiloxane) are elastomers with Tg of -110°C and -8°C, respectively. The curing processes and intermediates were studied by dynamic and isothermal differential scanning calorimetry, GPC, IR and 13C NMR. The synthesized CER monomers were used as impact modifiers to blend and co-cure with the commercial CERs, Primaset PT-30. SEM shows

  3. Palladium-catalyzed cross-coupling reactions of organosilanols and their salts: practical alternatives to boron- and tin-based methods.

    Science.gov (United States)

    Denmark, Scott E; Regens, Christopher S

    2008-11-18

    In the panoply of modern synthetic methods for forming carbon-carbon and carbon-heteroatom bonds, the transition metal-catalyzed cross-coupling of organometallic nucleophiles with organic electrophiles enjoys a preeminent status. The preparative utility of these reactions is, in large measure, a consequence of the wide variety of organometallic donors that have been conscripted into service. The most common of these reagents are organic derivatives of tin, boron, and zinc, which each possess unique advantages and shortcomings. Because of their low cost, low toxicity, and high chemical stability, organosilanes have emerged as viable alternatives to the conventional reagents in recent years. However, unlike the tin- and zinc-based reactions, which require no activation, or the boron-based reactions, which require only heating with mild bases, silicon-based cross-coupling reactions often require heating in the presence of a fluoride source; this has significantly hampered the widespread acceptance of organosilanes. To address the "fluoride problem", we have introduced a new paradigm for palladium-catalyzed, silicon-based cross-coupling reactions that employs organosilanols, a previously underutilized class of silicon reagents. The use of organosilanols either in the presence of Brønsted bases or as their silanolate salts represents a simple and mild alternative to the classic fluoride-based activation method. Organosilanols are easily available by many well-established methods for introducing carbon-silicon bonds onto alkenes, alkynes, and arenes and heteroarenes. Moreover, we have developed four different protocols for the generation of alkali metal salts of vinyl-, alkenyl-, alkynyl-, aryl-, and heteroarylsilanolates: (1) reversible deprotonation with weak Brønsted bases, (2) irreversible deprotonation with strong Brønsted bases, (3) isolation of the salts from irreversible deprotonation, and (4) silanolate exchange with disiloxanes. We have demonstrated the

  4. Development and design of nanomaterial reagents in conjunction with new methods for their synthetic applications

    Science.gov (United States)

    Kwaramba, Farai Brian

    selectivity. The most commonly employed silicon tethers have been disiloxanes followed by siloxanes, then silanes. Of these methods the synthesis and utilization of tethered silyl-alkynes was limited. To address this gap, this work developed methodology to prepare tethered silyl alkynes through a hydrosilylation reaction. It was established that [IrCl(COD)]2 in the presence of excess COD can selectively catalyze the hydrosilylation of alkenes with alkynyl-silanes. This approach overrides traditional hydrosilylation catalysts' reactivity trends.

  5. Synthesis and Application of Fluorine-Containing Silicone Water-Repellent Finishing Agent%含氟有机硅拒水整理剂的合成及应用

    Institute of Scientific and Technical Information of China (English)

    袁京; 李战雄; 樊丹

    2013-01-01

    Mixed cyclosiloxane was prepared by catalytic condensation, with tridecafluorooctyloxa-propylmethyldichlorosilane and dimethyldichlorosilane as raw materials. Fluorine-containing silicone water-repellent finishing agent was prepared by ring-opening polymerization, with divinyl tetramethyl disiloxane as blocking agent. Three different fluorine content of fluorine-containing silicones were synthesized, and the hydrogen silicone as crosslinker was applied to water repellent finishing of cotton fabric. The structural properties of products were characterized by FT-IR and 1H-NMR. The effect of finishing efficiency on the type and amount of finishing agent was studied. The results show that the water-repellent effect of cotton fabrics is significant after finished with the water-repellent finishing agent. When the concentration is 15g/L, the water repellency rating can be up to five Level. Compared with the methyl silicone finishing agent, the water repellency and washability of the cotton fabric finished by the fluorine-containing silicone finishing agent are better.%以十三氟辛氧丙基甲基二氯硅烷和二甲基二氯硅烷为原料,通过催化缩合制备了混合环硅氧烷,再加入四甲基二乙烯基二硅氧烷作为封端剂,通过开环聚合制备了3种不同氟含量的氟硅拒水整理剂,并以氢基硅油作交联剂应用于棉织物整理.通过红外光谱(FT-IR)和核磁共振(1H-NMR)表征了产物的结构,研究了整理剂的种类及用量对整理效果的影响.结果表明,该拒水整理剂对棉织物的拒水效果明显,当浓度为15 g/L时,拒水等级均可达到5级.与甲基有机硅整理剂相比,含氟有机硅整理剂整理后的棉织物具有更好的拒水性和耐洗性.

  6. The novel silicon-containing epoxy/PEPA phosphate flame retardant for transparent intumescent fire resistant coating

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yanchao [School of Materials Science and Engineering, Tongji University, 4800 Cao' an Road, Shanghai 201804 (China); Wang, Guojian, E-mail: wanggj@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, 4800 Cao' an Road, Shanghai 201804 (China); Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, 4800 Cao' an Road, Shanghai 201804 (China)

    2016-11-01

    Highlights: • The novel halogen-free flame retardant containing silicon and caged bicyclic phosphate was synthesized. • A novel transparent intumescent fire resistant coating was developed by the P-Si synergistic flame retardant and melamine formaldehyde resin. • Excellent fire protection of the transparent intumescent fire resistant coating. • The P-Si synergistic flame retardant could improve the thermo-oxidation resistance of transparent fire resistant coating. - Abstract: A series of novel silicon-containing epoxy/PEPA phosphate flame retardants (EPPSi) were synthesized by polyphosphoric acid (PPA), caged bicyclic phosphate 1-oxo-4-hydroxymethyl-2,6,7-trioxa-L-phosphabicyclo [2.2.2] octane (PEPA), and different ratios of silicon-containing epoxy 1,1,3,3-tetramethyl-1,3-bis(3-(oxiran-2-ylmethoxy)propyl)disiloxane (TMSEP) to 1,4-butanediol diglycidyl ether (BDE). The chemical structure of EPPSi was confirmed by Fourier transform infrared spectroscopy (FTIR) and {sup 1}H nuclear magnetic resonance spectroscopy ({sup 1}H NMR). Afterwards, the transparent intumescent fire resistant coatings were prepared by mixing EPPSi and melamine formaldehyde resin. The influence of silicon on the fire protection of coatings was intensively investigated by fire protection test, intumescence ratio, scanning electron microscope (SEM), compressive strength test, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and real-time FTIR. It was found that the fire resistant coatings obtained the best fire protection when the ratio of TMESP/BDE was 20/100, while excessive TMSEP made the fire protection of coatings deceased sharply. The intumescence ratio, compressive strength test and SEM result showed that a synergistic effect existed between phosphorus and silicon, which improved the foam structure and compressive strength of the char layer significantly. XPS result proved the out-migration effect of silicon. The high concentration silicon on surface played

  7. Influence Principle of Mechanical Properties of Additional RTV Silicone Rubber%加成型室温硫化硅橡胶力学特性的影响规律

    Institute of Scientific and Technical Information of China (English)

    赵翠峰; 蒋立纯; 贺攀; 方仕江

    2011-01-01

    以端乙烯基硅油为基础胶、低含氢硅油为交联荆、处理气相法白炭黑为填料、铂-二乙烯基四甲基二硅氧烷配合物为催化剂,制备了加成型室温硫化硅橡胶.考察了端乙烯基硅油黏度、处理气相法白炭黑用量、含氢硅油中的Si-H基与乙烯基硅油中的SiCH-CH2基的量之比(简称A值)对硅橡胶力学特性的影响.结果表明,随着端乙烯基硅油黏度的增加,硅橡胶的拉伸强度、拉断伸长率和撕裂强度分别出现峰值;处理气相法白发黑使硅橡胶的硬度先增后降;较佳工艺为:端乙烯基聚硅氧烷的黏度为5 Pa·s、处理气相法白炭黑用量为25份(按乙烯基硅油用量为100份计)、A值在l~3.6之间.按此条件制成的硅橡胶的邵尔A硬度为34度、拉伸强度4.78~5.09 MPa、撕裂强度4.97 kN/m、拉断伸长率为107%.%The additional room temperature vulcanizing silicone rubber was prepared by using polydime-thyl siloxane terminated by vinyl group as basic components, hydrogen-containing silicone oil as a cross-linking reagent and the complex pound of platinum and divinyltetramethyl disiloxane as catalyst. The effect of the viscosity of basic components, the hydrogen content of hydrogen-containing silicone oil, the filler amount and the A value (the ratio of Si-H/SiCH =CH2 of hydrogen-containing silicone oil and vinyl silicone oil) on the properties of silicone rubber were experimentally examined. Results showed that the tensile strength, the elongation and the tear strength appeared maximum values respectively as the viscosity of basic components was increased. The hardness of the silicone rubber was increased and then decreased with the increase of additional filler. The vulcanized silicone rubber was of excellent mechanical properties while the viscosity of the vinyl silicone oil was 5 Pa·s, and the treatment of fumed silica was about 25 phr ( based on vinyl silicone oil consumption) , and A value was between 1 and

  8. Preparation and Properties of High Refractive Index LED Encapsulation Rubber with Long Life%高折射率、长寿命 LED 灌封胶的制备及性能

    Institute of Scientific and Technical Information of China (English)

    叶文波; 汤胜山

    2015-01-01

    以甲基苯基混合环体、八甲基环四硅氧烷、四甲基四乙烯基环四硅氧烷、四甲基二乙烯基二硅氧烷等为原料制得甲基苯基硅油;以苯基三氯基硅烷、二苯基二氯硅烷、二甲基二氯硅烷和二甲基乙烯基氯硅烷等为原料,制得甲基乙烯基苯基有机硅树脂;以二苯基二甲氧基硅烷、苯基三甲氧基硅烷、四甲基环四硅氧烷为原料制得苯基交联剂。按甲基乙烯基苯基硅油、甲基苯基乙烯基硅树质量比和nSi—H/nVi筛选出符合LED芯片封装基本要求的灌封胶,其折射率为1.5441,操作黏度(25℃)4000~5500 mPa・s,固化后的初始邵尔D硬度为33~37度,可见光(550 nm)透光率大于85%。耐热老化性能测试研究表明,150℃热老化1000 h后,硬度增幅为5度,无黄变现象,在550 nm的透光率大于80%。进一步的光通量测试研究表明,点灯测试1000 h后,该灌封胶的光衰<2%。表明该款灌封胶具有高折射率和较长的应用寿命。%Phenyl methyl silicone fluid was prepared with methylphenyl cyclics mixture, octamethyl cy-clotetrasiloxane, tetramethyl tetravinyl cyclotetrasiloxane, tetramethyl divinyl disiloxane.Then methyl vinyl phenyl silicone resin was prepared with phenyl trichlorosilane, diphenyl dichlorosilane, dimethyl dichloride si-lane and dimethyl vinyl chlorosilane.At last, the phenyl crosslinkers were prepared with diphenyl dimethoxy silane, phenyl trimethoxy silane, and tetramethyl cyclotetrasiloxane.By varying the mass ratios of vinyl methyl phenyl silicone oil and methyl vinyl phenyl silicone resin and Si-H/Vi molar ratio, the optimal composition meeting LED chip packaging was selected.The material has a viscosity of 4000-5500mPa・ s (25 °C) , a re-fractive index of 1.5441 , an initial degree of hardness shore D 33-37°after curing, the visible light trans-mittance (550nm) over 85%.Research of the heat aging testing shows that after thermal

  9. IMPROVED ANTIFOAM AGENT STUDY END OF YEAR REPORT, EM PROJECT 3.2.3

    Energy Technology Data Exchange (ETDEWEB)

    Lambert, D.; Koopman, D.; Newell, J.

    2011-09-30

    issues above is that DWPF had three antifoam needs in FY2011: (1) Determine the cause of the poor Antifoam 747 performance during caustic boiling; (2) Determine the decomposition products of Antifoam 747 during CPC processing; and (3) Improve the effectiveness of Antifoam 747, in order to minimize the amount used. Testing was completed by Illinois Institute of Technology (IIT) and Savannah River National Laboratory (SRNL) researchers to address these questions. The testing results reported were funded by both DWPF and DOE/EM 31. Both sets of results are reported in this document for completeness. The results of this research are summarized: (1) The cause for the poor Antifoam 747 performance during caustic boiling was the high hydrolysis rate, cleaving the antifoam molecule in two, leading to poor antifoam performance. In testing with pH solutions from 1 to 13, the antifoam degraded quickly at a pH < 4 and pH > 10. As the antifoam decomposed it lost its spreading ability (wetting agent performance), which is crucial to its antifoaming performance. During testing of a caustic sludge simulants, there was more foam in tests with added Antifoam 747 than in tests without added antifoam. (2) Analyses were completed to determine the composition of the two antifoam components and Antifoam 747. In addition, the decomposition products of Antifoam 747 were determined during CPC processing of sludge simulants. The main decomposition products were identified primarily as Long Chain Siloxanes, boiling point > 400 C. Total antifoam recovery was 33% by mass. In a subsequent study, various compounds potentially related to antifoam were found using semi-volatile organic analysis and volatile organic analysis on the hexane extractions and hexane rinses. These included siloxanes, trimethyl silanol, methoxy trimethyl silane, hexamethyl disiloxane, aliphatic hydrocarbons, dioctyl phthalate, and emulsifiers. Cumulatively, these species amounted to less than 3% of the antifoam mass. The