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1.
Bogdan Marciniec Hieronim Maciejewski Karol Szubert Magdalena Kurdykowska 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):605-611
Summary. The hydrosilylation of 1-heptene, allyl glycidyl ether and, allyl polyether by heptamethylhydrotrisiloxane and poly(hydro,
methyl)(dimethyl)siloxane catalyzed by rhodium(I) complexes (particularly [{Rh(μ–OSiMe3)(cod)}2]) in imidazolium ionic liquids (especially [TriMIM]MeSO4) gives heptyl and glycidyloxy functional (poly)siloxanes and silicone polyethers with high yield and selectivity. The catalytic
system based on rhodium siloxide can be easily separated from the product and successfully reused up to five times. 相似文献
2.
Bogdan Marciniec Hieronim Maciejewski Karol Szubert Magdalena Kurdykowska 《Monatshefte für Chemie / Chemical Monthly》2006,100(1):605-611
The hydrosilylation of 1-heptene, allyl glycidyl ether and, allyl polyether by heptamethylhydrotrisiloxane and poly(hydro,
methyl)(dimethyl)siloxane catalyzed by rhodium(I) complexes (particularly [{Rh(μ–OSiMe3)(cod)}2]) in imidazolium ionic liquids (especially [TriMIM]MeSO4) gives heptyl and glycidyloxy functional (poly)siloxanes and silicone polyethers with high yield and selectivity. The catalytic
system based on rhodium siloxide can be easily separated from the product and successfully reused up to five times. 相似文献
3.
Kazuya Uenishi Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2008,46(12):4092-4102
Anionic copolymerizations of 3,4‐dihydrocoumarin (DHCM) and a series of glycidyl ethers (n‐butyl glycidyl ether, tert‐butyl glycidyl ether, and allyl glycidyl ether) with 2‐ethyl‐4‐methylimidazole as an initiator proceeded in a 1:1 alternating manner to give the corresponding polyesters, whose structures were confirmed by spectroscopic analyses and reductive scission of the ester bonds in the main chain with lithium aluminum hydride, followed by detailed analyses of the resulting fragments. The polyester obtained by the copolymerization of DHCM and allyl glycidyl ether inherited the allyl groups in the side chain, whose applicability to chemical modifications of the polyester was successfully demonstrated by a platinum‐catalyzed hydrosilylation reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4092–4102, 2008 相似文献
4.
Jianbo Zhao Xiaoli Sun Bing Xie Guoqing Wang Shiqiu Song Yu’An Sun 《Research on Chemical Intermediates》2009,35(5):625-631
Silica-supported chitosan–platinum complex was prepared and characterized by ICP-AES, FT-IR, and XPS, respectively. The complex
as catalyst was found to display high catalytic activity in the hydrosilylation reaction of allyl glycidyl ether with triethoxysilane
for the first time. It can be recovered by simple filtration and reused for six times without significant loss of activity. 相似文献
5.
P. A. Sitnikov A. G. Belykh M. S. Fedoseev I. I. Vaseneva A. V. Kuchin 《Russian Journal of General Chemistry》2009,79(12):2594-2598
The processes occurring during the modification of epoxy polymers by various polymorphic aluminum oxide modifications (γ-AlO(OH),
γ-Al2O3, α-Al2O3) with epoxy groups were studied by the methods of IR Fourier spectroscopy, chemical analysis, and differential scanning calorimetry
(DSC) by an example of a model compound (phenyl glycidyl ether). Two types of interactions were revealed: a direct chemical
reaction of phenyl glycidyl ether with the surface hydroxy groups of alyminum oxide, and phenyl glycidyl ether homopolymerization.
By processing by graphical method the data of chemical analysis on the diminishing in amount of epoxy groups in the course
of the polycondensation reaction the value of activation energy 106–110 kJ mol−1 of the process of phenyl glycidyl ether interaction with aluminum γ-oxide was determined. 相似文献
6.
Hydrosilylation of allyl glycidyl ether with triethoxysilane 总被引:1,自引:0,他引:1
E. A. Chernyshev Z. V. Belyakova L. K. Knyazeva N. N. Khromykh 《Russian Journal of General Chemistry》2007,77(1):55-61
Hydrosilylation of allyl glycidyl ether with triethoxysilane in presence of Speier’s catalyst leads to triethoxy(3-glycidoxypropyl)silane and triethoxy(2-glycidoxy-1-methylethyl)silane and is accompanied by isomerization of allyl glycidyl ether and cleavage of the oxirane ring and the ether bond. An effect of admixtures in allyl glycidyl ether on the process is revealed. Some other hydrosilylation catalysts and additives to Speier’s catalyst are studied 相似文献
7.
The reactions of aromatic azomethines with methyldichlorosilane, phenyldichlorosilane, and dimethylchlorosilane, performed in the presence of Speier's, Wilkinson's, and Karstedt's catalysts and a series of Pt(II) complexes LL'PtCl2, give hydrosilylation and reduction products whose ratio depends on the catalyst used. The highest yield of hydrosilylation products is attained with Pt(II) complexes as catalysts. 相似文献
8.
Metha Rutnakornpituk 《European Polymer Journal》2005,41(5):1043-1052
Synthesis of the statistical epoxidized polycyanopropylmethylsiloxane-co-polydimethylsiloxanes (PCPMS-co-PDMS) has been demonstrated. The modified polysiloxanes were prepared via a two-step method; (1) the ring-opening polymerization of octamethylcyclotetrasiloxane (D4) and tetramethylcyclotetrasiloxane (D4H), (2) hydrosilylation reaction of the polysiloxane prepolymers with allyl cyanide and allyl glycidyl ether. Molar ratios of D4H and D4 were varied to produce the modified polysiloxanes with differences in polarity. 1H-NMR, 29Si-NMR, 13C-NMR and FTIR were used to monitor the formation of the modified polysiloxanes and DSC was used to study their thermal behaviors (Tg, −118 to −68 °C). The use of the modified polysiloxanes as an elastomeric component in epoxy-novolac networks was also investigated. TEM and their transition temperatures suggested that the epoxy-novolac networks with high content of PDMS modifiers exhibited microphase separation. The fracture toughness properties of the networks with the polysiloxane modifiers were improved over the controls without polysiloxanes. 相似文献
9.
J. V. Crivello Whan-Gi Kim 《Journal of polymer science. Part A, Polymer chemistry》1994,32(9):1639-1648
The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using 1H- and, 13C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF3OEt2 followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc. 相似文献
10.
Mu-Shih Lin Chung-Song Huang 《Journal of polymer science. Part A, Polymer chemistry》1992,30(11):2303-2312
Allyl cellulose was synthesized by reacting cellulose with allyl bromide in homogeneous LiCl/DMAc solution containing NaOH powder. The degree of substitution (DS) per anhydroglucose (AHG) unit was determined by titrating the allyl cellulose with bromine in chloroform solution, and an allyl DS of 2.80 was found. Glycidyl cellulose was then prepared by reacting this allyl cellulose with peracetic acid in methylene chloride at ambient temperature for 6 days. The measured reaction rate constant was 1.33 × 10?3 min?1. The glycidyl cellulose thus obtained with a glycidyl DS of 2.58 was determined by titrating the product with perchloric acid in conjunction with tetrabutylammonium iodide. The 2.58 of glycidyl DS was also confirmed by 1H-NMR integration. Both allyl cellulose and glycidyl cellulose were analyzed and characterized with FTIR, 1H-NMR, 13C-NMR, TGA, and GPC. During epoxidation of allyl cellulose, possible side reaction leading to ester formation was evidenced from the continuous increase of vC? O at 1735 cm?1 in FTIR analyses. In addition, a bimodal distribution and a decreased molecular weight for glycidyl cellulose were found from GPC data, which might suggest a possible chain scission at the cellulosic ether linkage. © 1992 John Wiley & Sons, Inc. 相似文献
11.
4-氧杂-6,7-二氯庚基三甲氧基硅烷依次与二苯膦钾、气相法二氧化硅、三氯化铑作用,合成了聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铑配合物。它对烯烃与取代烯烃的硅氢化反应具有良好的催化活性。 相似文献
12.
Jan ukaszczyk Katarzyna Jaszcz Witold Kuran Tomasz Listo 《Macromolecular bioscience》2001,1(7):282-289
Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt2 and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO2 or by the terpolymerization of AGE, IGE and CO2 were oxidized with m‐chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss. 相似文献
13.
A. B. Terent'ev T. T. Vasil'eva N. A. Kuz'mina N. S. Ikonnikov S. A. Orlova E. I. Mysov Yu. N. Belokon' 《Russian Chemical Bulletin》1997,46(12):2096-2098
Allyl dibromoacetate, allyl α-bromopropionate, and allyl phenylbromoacetate undergo cyclization in benzene in the presence
of increased concentration of Fe(CO)5—DMF as the initiating system to give the corresponding bromo-substituted butyrolactones.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2210–2212, December, 1997. 相似文献
14.
D. N. Bazhin T. I. Gorbunova A. Ya. Zapevalov V. I. Saloutin 《Russian Chemical Bulletin》2007,56(8):1534-1536
Addition of polyfluoroalkyl iodides to the double bond of allyl glycidyl ether occurred under mild conditions (20–25 °C, MeCN/H2O, Na2S2O4, NaHCO3) with retention of the oxirane ring.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1476–1478, August, 2007. 相似文献
15.
Weizhi Wang 《European Polymer Journal》2003,39(6):1117-1123
UV-curable polydimethylsiloxane epoxy acrylate (PSEA) was synthesized by hydrosilylation of allyl glycidyl ether with hydrogen-containing polydimethylsiloxane to give polydimethylsiloxane-type epoxy resin which modified with acrylic acid. The curing speed and the double bond conversion in the UV cured film were influenced by the purity of PSEA with Fourier transform infrared spectroscopy (FT-IR) measurements. The influences of the synthetic process, such as, the reaction temperature, the concentration of reactants and the catalyst which determined the purity and activity of resins were discussed in detail. The structures of this resin were characterized by 1H-NMR and FT-IR spectra. The molecular weight was checked by gel permeation chromatography, and Mn is 45,000. The properties of the cured film were also investigated by thermogravimetric analyzer, dynamical thermal mechanical analysis, and etc. For example, tensile strength (6.9 Mpa), elongation (20%), hardness (A; 18), water absorption (24 h; 2%), weight loss (40 min, 300 °C; 5%) and etc. 相似文献
16.
Qing‐Fa Si Xin Wang Xiao‐Dong Fan Sheng‐Jie Wang 《Journal of polymer science. Part A, Polymer chemistry》2005,43(9):1883-1894
Two UV‐curable hyperbranched poly(siloxysilane)s ( I and III ) containing vinyl and allyl end groups were synthesized via polyhydrosilylation with methylbis(methylethylvinylsiloxy)silane and methylbis(dimethylallylsiloxy)silane monomers. A cationic UV‐curable hyperbranched polymer ( II‐Ep ) with epoxy end groups was prepared via the hydrosilylation of hyperbranched polymer II with Si? H terminated groups and glycidyl methacrylate, and II was also obtained via the polyhydrosilylation of AB2‐type monomer methylvinylbis(methylethylsiloxy)silane. All hydrosilylation reactions were catalyzed by Pt/C or chloroplatinic acid. Three AB2‐type monomers were synthesized via the hydrolysis of functional chlorosilane, which was prepared with Grignard reagents and dichlorosilane. The molecular structures of the polymers were characterized with 1H NMR, Fourier transform infrared, and gel permeation chromatography, and the UV‐curing behaviors of the polymers under different atmospheres and with different photoaccelerators were also investigated. The thermostability of uncured and cured polymers was examined with thermogravimetric analysis, and the data indicated that the orders of the onset decomposition temperatures for the cured polymers and the residue weights were as follows: III (380 °C) > I (320 °C) > II‐Ep (280 °C) and I (70.4%) > III (64.1%) > II‐Ep (60.9%), respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1883–1894, 2005 相似文献
17.
Z. V. Belyakova M. G. Pomerantseva L. A. Efimova E. A. Chernyshev P. A. Storozhenko 《Russian Journal of General Chemistry》2010,80(4):728-733
The reaction of hydrosilylation of allyl esters XOCH2CH=CH2 (X = MeCO, CF3CO, C3F7CO) and PhOCH2CH=CH2 with hydrosilanes HSiY3 (Y = Cl, OEt) in the presence of the Speier catalyst, the Speier catalyst with additives, and of various nickel complexes
was studied. The catalytic hydrosilylation reaction in the presence of the Speier catalyst is accompanied by the reduction.
Additives to the Speier catalyst (vinyltriethoxysilane and some ethers) allow to suppress considerably the reduction reaction.
In the presence of the studied nickel complexes mainly reduction and isomerization reactions occurred. The best nickel catalysts
of hydrosilylation were the mixtures of NiCl2 or Ni(acac)2 with phosphine oxides. In contrast to allyl esters, the hydrosilylation of simple olefins proceeds easier, the content of
the product of hydrosilylation in the reaction mixture reaches 94.3%. 相似文献
18.
19.
合成了7,11-二硒杂苯并-13-冠-4及其铂配合物,并从底物的性质、反应温度、催化剂用量以及化学气氛四个方面考察了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性。与单硒杂冠醚配合物相比,该配合物对某些烯烃的催化活性较高,但催化反应需要的温度也较高. 相似文献
20.
Anne‐Laure Brocas Gabriel Cendejas Sylvain Caillol Alain Deffieux Stephane Carlotti 《Journal of polymer science. Part A, Polymer chemistry》2011,49(12):2677-2684
Poly(allyl glycidyl ether) and poly(allyl glycidyl ether‐co‐epichlorohydrin) were prepared by monomer‐activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i‐Bu3Al]/[NOct4Br] = 2?4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living‐like manner gradient‐type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate‐free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献