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1.
J. Daum G. Erdodi J. P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》2006,44(13):4053-4062
The synthesis and characterization of two groups of novel networks prepared from cyclolinear polysiloxanes are described. The first group of networks from cyclolinear polysiloxanes (N‐CLPSs) was synthesized by the hydrosilation of vinyl‐terminated cyclolinear polyorganosiloxanes [prepared from diacetoxydiethyltetramethylcyclotetrasiloxane (D4Et2OAc2) or diacetoxytriethylpentamethylcyclopentasiloxane (D5Et3OAc2)] with a copolymer of dimethylsiloxane and methylhydrosiloxane as the crosslinking agent. Hydrosilation was effected with a platinum carbonyl catalyst with a cyclovinylsiloxane moderator. The second group of networks (N‐eCLPSs) was prepared similarly with extended cyclolinear polysiloxanes. The mechanical properties of the novel networks were comparable to those of polydimethylsiloxane networks (N‐PDMS). The oxygen permeabilities were similar to or slightly higher than that of N‐PDMS. The glass‐transition temperatures of D4Et2OAc2‐ and D5Et3OAc2‐based N‐CLPSs were ?67.8 and ?90.8 °C, respectively, whereas the incorporation of polydimethylsiloxane spacers into similar N‐eCLPSs lowered their glass‐transition temperatures to ?109.7 and ?115.0 °C. Upon heating to 800 °C in air, N‐CLPSs yielded more residue than N‐eCLPSs, which in turn yielded more residue than N‐PDMS. These results may have been due to the presence of T units in the cyclic siloxane units, which may have inhibited chain degradation or the formation of volatile products. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4053–4062, 2006 相似文献
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Several series of multifunctional silicon-containing epoxide monomers and oligomers have been prepared using rhodium catalyzed hydrosilation reactions. Dialkyl and diarylsilanes can be condensed with vinyl epoxides to give high yields of the desired diepoxides while the hydrosilation of alkyl and aryl silanes yields a mixture of di and tri epoxy substituted products. The condensation of αω,? Si? H difunctional compounds with vinyl epoxides can be carried out regioselectively to give α-hydrogen-ω-epoxy intermediates, which can be further reacted with di and tri olefins bearing terminal double bonds to give a series of well characterized epoxy functional oligomers. An investigation of the photoinitiated cationic polymerization of the monomers and oligomers, which were prepared during the course of these studies, was carried out. © 1994 John Wiley & Sons, Inc. 相似文献
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J. V. Crivello Daoshen Bi 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3109-3119
Silicon-containing epoxide compounds bearing Si ? H groups can be readily prepared in high yields by the regioselective rhodium-catalyzed monohydrosilation of α,ω-dihydrogen functional siloxanes and silanes with vinyl epoxides. The remaining Si ? H groups in these compounds can be further selectively hydrosilated with unsaturated epoxides to give a series of unique ambifunctional monomers containing two different epoxide groups in the same molecule. The photopolymerization of these monomers has been studied using analytical techniques including real time infrared spectroscopy and differential scanning photocalorimetry. On photopolymerization, the new monomers yield interesting networks. © 1993 John Wiley & Sons, Inc. 相似文献
4.
Seven chiral thiazolidines bound rhodium complexes were synthesized and their catalytic asymmetric hydrosilation properties were investigated It was found through investigation that the configuration of newly formed chiral centre C2 of substituted chiral thiazolidines prepared from L-cysteine or its esters has no effect on the final results of catalytic asymmetric hydrosilation.The direct reason for causing this phenomenon is reported by the present quantitative results for the first time:the rapid racemation of chiral center C2 of chiral thiazolidine ligands takes place under the catalysis of rhodium(Ⅰ) complex [Rh(COD)CI]2 相似文献
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Comparison of octadecyl bonded titania phases 总被引:1,自引:0,他引:1
Summary The structure of a C18 phase based on titania (C18-A), synthesized by the method of solution polymerization, is investigated by diffuse reflectance infrared Fourier transform
(DRIFT) and solid-state nuclear magnetic resonance (NMR) spectroscopy. The findings are compared with the results of a second
C18 phase based on titania (C18-B) which was synthesized by the method of surface hydrosilation. The dynamic behavior of both phases is examined by1H MAS NMR detection of spinlattice relaxation times in the rotating frame (T1pH) and conventional spin-lattice relaxation times (T1). Due to a smaller ligand density, phase C18-A appears to be a somewhat more mobile than phase C18-B.
The chromatographic capability of the phase C18-A is demonstrated by the separation of samples containing benzene derivates or anilines. The elution order is analogous to
the phase C18-B, but for both test mixtures the polarity of the mobile phase has to be increased. Phase C18-A is classified as being polymeric by the Sander and Wise test, whereas phase C18-B shows intermediate retention behavior. 相似文献
8.
Chungkyun Kim Kyounghan Jeong Inkyung Jung 《Journal of polymer science. Part A, Polymer chemistry》2000,38(15):2749-2759
Dendritic carbosilanes based on phenylethynylmethylsilanes (PhCC)4−nMenSi (n = 0–2) as cores were synthesized. The building blocks of the dendrimers consist of double bonds ( PhCCHMeSi ) in the inner shell and triple bonds [(PhCC)2MeSi ] on the outmost periphery. The synthetic methods used the iterative alkynylation and hydrosilation cycle, which was composed of lithium phenylacethylide and dichloromethylsilane. The limiting generation of the dendrimer for the four branching type (PhCC)4Si at a core molecule has 32 phenylethynyl groups on the third generation, 48 for the three branching type (PhCC)3MeSi on the fourth generation, and 64 for the two branching type (PhCC)2Me2Si on the fifth generation. The dendrimers were characterized by the use of NMR, Maldi mass, SEC, DSC, UV as well as elemental analysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2749–2759, 2000 相似文献
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Chungkyun Kim Sungkyung Kang 《Journal of polymer science. Part A, Polymer chemistry》2000,38(4):724-729
A method for synthesizing growth ring‐type dendritic macromolecules starting from siloxane polymer with Si H bonds [Me3SiO(MeSiOH)nSiMe3] as the core and dichlorovinylsilane, dichloromethylsilane, lithium phenylacethylide, and allylmagnesium bromide as the building blocks is described. The siloxane polymer was produced to the second dendritic generation by the repetition of hydrosilation and alkenylation as well as by an alkynylation process. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 724–729, 2000 相似文献
10.
Novel polyisobutylene/poly(dimethylsiloxane) bicomponent networks. I. Synthesis and characterization
Melissa A. Sherman Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》1998,36(11):1891-1899
The synthesis of novel polyisobutylene (PIB)/poly(dimethylsiloxane) (PDMS) bicomponent networks is described. The synthesis strategy (see Figure 1) was to prepare well-defined and -characterized allyl-tritelechelic polyisobutylenes [ϕ(PIB—C—C=C)3] and SiH-ditelechelic poly(dimethylsiloxanes) (HSi–PDMS–SiH) and then crosslink these moieties by hydrosilation. The ϕ(PIB—C—C=C)3 was prepared by living isobutylene polymerization followed by end-quenching with allyltrimethylsilane, whereas the HSi–PDMS–SiH was obtained by equilibrium polymerization of octamethylcyclotetrasiloxane and tetramethyldisiloxane. The detailed structures of the starting polymers were characterized by GPC and 1H-NMR spectroscopy. A series of PIB/PDMS bicomponent networks of varying compositions and average molecular weights between crosslinks (M c) of ∼ 20,000 g/mol were assembled. Optimum crosslinking conditions were defined in terms of H2PtCl6 catalyst concentration, nature of solvent, time, temperature, and stoichiometry of ∼ CH2CH=CH2/∼SiH groups, allowing for the convenient synthesis of well-defined model bicomponent networks. Swelling studies and elemental analysis confirm the correctness of the synthetic strategy. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1891–1899, 1998 相似文献