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1.
J. V. Crivello Daoshen Bi 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3121-3132
Using rhodium and platinum catalyzed regioselective hydrosilation, a series of α-hydrogen-ω-epoxy silane and siloxane compounds have been prepared in good yields. These intermediates have been further condensed with vinyltrimethoxysilane in subsequent hydrosilation reactions to prepare an interesting new class of ambifunctional monomers containing both epoxy and trimethoxysilane groups. It was further shown that these same compounds could be synthesized by a simplified “one-pot” two-step procedure. An investigation of the simultaneous cationic ring-opening polymerization of the epoxy groups and the acid-catalyzed condensation of the trimethoxysilyl groups was carried out. © 1993 John Wiley & Sons, Inc. 相似文献
2.
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
3.
J. V. Crivello Daoshen Bi 《Journal of polymer science. Part A, Polymer chemistry》1993,31(11):2729-2737
The discovery that the rhodium-catalyzed hydrosilation of unsaturated epoxides with compounds containing two Si? H functional groups proceeds in a discrete, stepwise fashion, has made possible the synthesis of a series of interesting compounds containing both Si? H and epoxy groups in the same molecule. These compounds can be used both as an interesting new class of epoxy monomers as well as intermediates for the preparation of a wide variety of novel monomers which incorporate epoxide as well as other types of polymerizable functional groups © 1993 John Wiley & Sons, Inc. 相似文献
4.
P. H. Chung J. V. Crivello M. Fan 《Journal of polymer science. Part A, Polymer chemistry》1993,31(7):1741-1746
Regioselective platinum and rhodium catalysts were employed for the preparation of novel silicon-containing polyethers. First, silicon-containing monomers bearing cycloaliphatic epoxy groups were prepared by a rhodium-catalyzed regioselective hydrosilation. Then these monomers were polymerized using a platinum-catalyzed, cationic, ring-opening polymerization to give the linear polyethers. The obtained polyethers were compared with polymers prepared by photoinitiated cationic ring-opening polymerization using onium salt photoinitiators and found to be identical. © 1993 John Wiley & Sons, Inc. 相似文献
5.
J. V. Crivello Daoshen Bi 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2563-2572
The hydrosilation of α,ω-dihydrogen functional oligopolydimethylsiloxanes with epoxy compounds containing vinyl groups has been found to take place regioselectively in such a manner that compounds can be isolated in high yields in which only one Si? H group has been reacted. Three different α,ω-dihydrogen functional oligopolydimethysiloxanes with different chain lengths were monohydrosilated and the resulting epoxide monomers characterized. The rate of hydrosilation at the first Si? H functional group has been shown to be considerably faster than at the second site and from these kinetic studies, activation energies for each hydrosilation step were calculated. Mechanisms are considered which offer an explantion for these observations. © 1993 John Wiley & Sons, Inc. 相似文献
6.
Abstract The use of novel chemo- and regioselective hydrosilation reactions to prepare several series of ambifunctional silicon-containing epoxy monomers and oligomers is described. These monomers can be polymerized using traditional cationic initiators or by employing onium salt photoinitiators. 相似文献
7.
Myoungsouk Jang James V. Crivello 《Journal of polymer science. Part A, Polymer chemistry》2003,41(19):3056-3073
A series of difunctional silicon‐containing monomers were prepared with a novel method consisting of the monohydrosilation of an α,ω‐difunctional Si? H‐terminated siloxane with a vinyl‐functional epoxide or oxetane followed by the dehydrodimerization of the resulting Si? H‐functional intermediate. This method used simple, readily available starting materials and could be conducted as a streamlined one‐pot, two‐step synthesis. This novel method was also applied to the synthesis of several epoxy–silicone oligomers. The reactivities of these new monomers and oligomers were examined with Fourier transform real‐time infrared spectroscopy and optical pyrometry. Those monomers containing epoxycyclohexyl groups displayed excellent reactivity in cationic ring‐opening polymerization in the presence of lipophilic onium salt photoinitiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3056–3073, 2003 相似文献
8.
James V. Crivello Saoshi Liu 《Journal of polymer science. Part A, Polymer chemistry》2000,38(3):389-401
A series of epoxy alcohols were prepared by simple, straightforward methods. These compounds were very reactive monomers that polymerized rapidly on UV irradiation in the presence of cationic photoinitiators. The kinetics of the cationic photopolymerization of these monomers were studied with diaryliodonium salt photoinitiators and real‐time IR spectroscopy. The rate of epoxide ring‐opening polymerization was enhanced markedly by the presence of the hydroxy group. Using model compounds, the monomers were shown to polymerize via an activated monomer mechanism. Simple epoxy alcohols polymerized to give polymers with a hyperbranched structure. The novel monomers also were observed to accelerate the rate of the photopolymerization of mono‐ and multifunctional epoxides. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 389–401, 2000 相似文献
9.
Certain complexes of platinum, rhodium, iridium and cobalt are capable of initiating cationic vinyl and ring-opening polymerizations in the presence of a Si-H containing cocatalyst. An investigation has shown that two distinctly different mechanisms are involved, however, in both cases cationic polymerization can be explained by the formal attack of an electrophilic silicon species on the monomers. Since the transition metal complexes listed above also are catalysts for hydrosilation reactions, it is possible to carry out simultaneous cationic polymerizations and hydrosilation reactions to prepare novel and interesting polymers and oligomers. 相似文献
10.
John R. Ebdon 《Macromolecular Symposia》1994,84(1):45-54
Telechelic acrylic oligomers possessing terminal carboxylic acid, ketone, aldehyde or hydroxy groups can be synthesised in good yields by the ozonolysis of free radical copolymers of the appropriate acrylic monomer with a small amount of a 1,3-diene, such as butadiene, 2,3-dimethyl-butadiene or 2,3-diphenyl-butadiene. The oligomers so-prepared have high end-functionalities (>98%), controllable average molecular weights, relatively narrow molecular weight distributions, and can be chain extended by a variety of means to give back high molecular weight polymers. Oligomers with perfect α-phenyl ketone-ω-carboxylic acid functionality can be prepared by ozonolysing copolymers containing low concentrations of units derived from phenyl acetylene. Photolysis of copolymers of an alkyl vinyl ketone with monomers such as styrene yield, directly, oligomers with polymerisable unsaturated end-groups, i.e. macromonomers. 相似文献
11.
R. B. Jayaraman J. V. Facinelli J. S. Riffle S. E. George 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1543-1552
Methods for preparing saturated polyolefin oligomers with Si(SINGLE BOND)H, epoxy groups, and with dihydroxy groups have been developed. Anionic polymerization of butadiene, then termination of the chains with chlorodimethylsilane leads to controlled molecular weight oligomers with silane functionality, and wherein the microstructure can be tailored. Hydrogenation of these materials proceeds smoothly using colloidal nickel catalysts to yield the corresponding saturated materials, which are stable to conditions used for melt polyesterifications. Hydrosilation of allyl glycidyl ether with the Si(SINGLE BOND)H end groups produces epoxy functional oligomers, and subsequent hydrolysis of the epoxy rings yields oligomers with a dihydroxy group at one end. Melt copolymerization of the olefin macromers with 1,4-butanediol and 1,4-dimethylcyclohexanedicarboxylate in the presence of titanium isopropoxide affords poly(ester-g-olefin) graft copolymers. These copolymers are under study as model interfacial agents for polyester/polyolefin blends and as suspension agents for polyester particles in nonpolar media. © 1996 John Wiley & Sons, Inc. 相似文献
12.
Sang Hern Kim Hee‐Gweon Woo Joon‐Seop Kim Hyun‐Woo Lee Whan‐Gi Kim 《Journal of polymer science. Part A, Polymer chemistry》2001,39(17):2937-2942
4‐Fluorophenylsulfonylphenyl‐terminated polysulfone and 4‐fluorobenzoylphenyl ketone were prepared with bisphenol A and an excess of bis‐(4‐fluorophenyl)sulfone or 4,4′‐difluorobenzophenone, respectively, at 160 °C using potassium carbonate in N,N‐dimethylacetamide. The resulting polymers were reacted with 4‐hydroxystyrene to synthesize vinyl‐terminated polysulfones and ketones. The silicon‐containing polysulfones and ketones were prepared from the vinyl‐terminated polymer precursor and various H‐functional silanes or siloxanes. The synthesis of silicon‐containing polymers was achieved by hydrosilation with a rhodium catalyst. It was shown that the hydrosilation reaction proceeds with 55:45 chemoselectivity. The resulting polymers were investigated by 1H NMR spectroscopy, DSC, and thermogravimetric analysis. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2937–2942, 2001 相似文献
13.
James V. Crivello 《Journal of polymer science. Part A, Polymer chemistry》2009,47(7):1825-1835
A novel catalytic method for carrying out the cationic polymerizations has been developed based on a redox initiator system in which the reducing component is delivered to the reaction mixture in the vapor state. The redox couple consists of a diaryliodonium salt that is dissolved in the monomer and a noble metal catalyst is added. The silane reducing agent is introduced to the reaction mixture in the vapor state using air as the carrier gas. Reduction of the diaryliodonium salt by the silane results in the liberation of a Brønsted superacid that initiates cationic polymerizations. A study of the effects of variations in the structures of the diaryliodonium salt, the silane, and the type of noble metal catalyst was carried out. In principle, the initiator system is applicable to all types of cationically polymerizable monomers and oligomers including: the ring‐opening polymerizations of such heterocyclic monomers as epoxides and oxetanes and, in addition, the polymerization of vinyl ether monomers such as vinyl ethers. The use of this initiator system for carrying out commercially attractive cross‐linking polymerizations for coatings, composites, and encapsulations is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1825–1835, 2009 相似文献
14.
Manoj K. Kolel‐Veetil Teddy M. Keller 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):147-155
The Karstedt catalyst‐catalyzed ambient‐condition hydrosilation reactions in hexane of a monomeric vinyl‐containing carboranylenesiloxane, 1 , and three‐branched siloxane crosslinker monomers were discovered to produce elastomeric network polymers at very rapid rates of formation. The flexible and transparent films of the saturated elastomeric network polymers were observed to possess low glass‐transition temperatures (below ?35 °C). Similar hydrosilation reactions at two different reactant ratios involving a diethynyl‐containing carboranylenesiloxane, 2 , and the siloxane crosslinkers produced partially hydrosilated and completely hydrosilated polymeric networked systems, which were transparent and elastomeric at room temperature. The glass‐transition temperatures of all the polymeric systems formulated from 2 were below 0 °C. The elastomeric polymeric networks from 1 and 2 were found to have degradation temperatures in the range of 500–550 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 147–155, 2006 相似文献
15.
Peter Zarras 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):701-713
Several vinylbenzyltri-n-alkylammonium salts were prepared via the Menshutkin reaction in high yields by the reaction of vinyl benzyl chloride (VBC) and tertiary amines. Additional salts based on 2-ionene oligomers were synthesized via a sequential Menshutkin reaction. The 2-ionene oligomers were further reacted with VBC to afford the vinyl benzyl chloride-2-ionene halide monomers in nearly quantitative yield. The monomers were polymerized in either aqueous or organic solvents with azo initiators in high yield with correspondingly high inherent viscosities. The polymers were measured spectrophotometrically for their bile acid sequestering activity with an in vitro enzymatic reaction. Several of the measured polymers exhibited 15–28% greater activity relative to cholestyramine. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 701–713, 2004 相似文献
16.
The Wolf-Ziegler reaction carried out in CCl4 or chlorobenzene on unsaturated acids was found to give the isomeric mono, di or tri bromide products corresponding to a decarboxylation process, instead of the expected allylic substitution reaction. Some of the compounds thus prepared can constitute key intermediates in further synthesis and they are required in great quantities. 相似文献
17.
James V. Crivello 《Journal of polymer science. Part A, Polymer chemistry》2009,47(21):5639-5651
Diaryliodonium salts undergo facile reduction by the dialkylborane, 9‐BBN. The combination of these two reagents constitutes a redox couple that can be employed as a convenient and versatile initiator system for the cationic polymerizations of styrenic monomers, vinyl ethers and the ring‐opening polymerizations of cyclic ethers and acetals including; epoxides, oxetanes, tetrahydrofuran, and 1,3,5‐trioxane. The polymerizations of these monomers can be carried out in either neat monomer or under solution conditions. Typically, the redox cationic polymerizations of the above monomers are rapid and exothermic. Optical pyrometry (infrared thermography) was employed as a convenient method with which to monitor and optimize the aforementioned redox initiated cationic polymerizations. Studies of the effects of variations in the structure and concentrations of the diaryliodonium salt and 9‐BBN on the polymerizations of various monomers were carried out. A mechanism for the redox cationic initiation of the polymerizations was proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5639–5651, 2009 相似文献
18.
Janet A. Kling Harry J. Ploehn 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1107-1118
Colloidal polystyrene particles with surface epoxy groups have been synthesized through surfactant-free emulsion copolymerization of styrene with glycidyl methacrylate; and through copolymerization of glycidyl methacrylate (GMA) and methyl methacrylate as shells around existing polystyrene seed particles. We developed two titration methods to quantify the number of epoxy groups that survived the polymerization processes. The styrene-GMA copolymer particles were judged to be unsatisfactory as model colloidal materials due to their size polydispersity and unknown internal distribution of epoxy groups. The core-shell particles had high epoxy surface densities with at least 60% of the initial epoxy groups surviving the synthesis process. Transmission electron microscopy shows that the thickness of the epoxy-rich shell is less than expected based on the volume of monomers added, suggesting that some of the monomer forms water-soluble oligomers. Photon correlation spectroscopy measurements imply that the shell is swollen with water and consists of polymer configurations which extend out into solution. The morphological details vary consistently with the GMA content, and hence the hydrophilicity, of the shell polymer. © 1995 John Wiley & Sons, Inc. 相似文献
19.
James V. Crivello Shengqian Kong 《Journal of polymer science. Part A, Polymer chemistry》1999,37(15):3017-3025
A series of aryl 1-propenyl ethers (ArPE) were prepared by the isomerization of the corresponding allyl aryl ethers (AArE) and used for photoinduced cationic polymerization studies. Attempted polymerization reactions using diaryliodonium salts as photoinitiators generally resulted in low yields of oligomers. Further studies revealed that these compounds have much lower reactivity in cationic vinyl polymerization as compared to their alkyl analogues. Moreover, side reactions resulting from chain transfer due to Friedel–Crafts alkylations take place and compete with vinyl polymerization. These side reactions are responsible for the low molecular weights observed in the cationic photopolymerization of aryl 1-propenyl ether monomers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3017–3025, 1999 相似文献
20.
Hideyuki Itoh Atsushi Kameyama Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(2):217-225
New hybrid vinyl monomers with both cationic- and radical-polymerizable vinyl groups were synthesized by the reaction of bis[1(chloromethyl)-2-(vinyloxy)ethyl]terephthalate ( 3 ) with unsaturated carboxylic acids using 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU) as a base. The reaction of 3 with methacrylic acid 4a was carried out using DBU in DMSO at 70°C for 24 h to give an 86% yield of the hybrid vinyl monomer ( 5a ). Polycondensation of 3 with unsaturated dicarboxylic acids was also performed using DBU to give hybrid vinyl oligomers with radical polymerizable C (DOUBLE BOND) C groups (VR) in the main chain and cationic polymerizable vinyl ether moieties (VC) on the side chain. The photopolymerization of these hybrid vinyl compounds proceeded smoothly in bulk using either a cationic photoinitiator such as a sulfonium salt or a radical photoinitiator such as acyl phosphine oxide under UV irradiation. © 1996 John Wiley & Sons, Inc. 相似文献