Hydrosilylation polymerization

Hu, J. Son, D. Y. Halogenated Siloxane-Containing Polymers via Hydrosilylation Polymerization. In Silicones and Silicone-Modified Materials Clarson, S. J., Fitzgerald, J. J., Owen, M. J., Smith, S. D., Eds. ACS Symposium Series 729 American Chemical Society Washington, DC, 2000 pp 226-240. 

Scheme 14.4 Synthesis of poly(phenylene-silylene-ethylene)s via hydrosilylation polymerization process.

Hydrosilylation-polymerization provides a new approach to the syntheses of macromonomers such as poly(arylene-silylethylene) and poly(aralkylene-silylethylene) (274) that possess reactive ethenyl and SiH termini for further manipulations through self-polyaddition of 273 promoted by Speier s catalyst (equation 103)272. 

The hydrosilylation-polymerization of 1,3-diethenyltetramethyldisiloxane (276) with 1,3-dihydrotetramethyldisiloxane (275) proceeds smoothly in the presence of Karstedt s catalyst to give high molecular weight poly[(l,l,3,3-tetramethyldisiloxanyl)ethylene] (277) (equation 104)273-274. 

In a similar manner, the hydrosilylation-polymerization of diallyl bisphenol A (278) with 275 in the presence of a platinum catalyst affords polymer 279 that possesses a relatively high glass transition temperature for siloxane polymers (Tg = 28-34 °C) and... 

Hydrosilylation was also applied to the preparation of thiophene-terminated dimethyl-siloxane macromonomer, which is used for the synthesis of thiophene-dimethylsiloxane graft copolymers by oxidative polymerization281. Polycarbosilanes have been prepared by hydrosilylation-polymerization of l,4-bis(ethenylmethylphenylsilyl)benzene with 1,4-bis(methylphenylsilyl)benzene in various ratios282. 

As been shown by Weber, simultaneous hydrosilylation-polymerization can be accomplished with a Pt-catalyst <1995BSF551>, as shown in Scheme 20. 

In 1994, Rubinsztajn reported the hyperbranched hydrosilylation polymerization of the AB3 carbosiloxane monomers 9 and 10181. Since intramolecular cyclization of these monomers would lead to more highly strained five-membered rings, it was expected that intermolecular reaction would be preferred. This was indeed the case, and molecular weights were highest when polymerizations were performed in bulk. Furthermore, slow addition of monomer resulted in polymers of much higher molecular weight. Functionalization of the polymers could be performed via hydrosilylation reactions, although these... 

Frechel and coworkers reported the hydrosilylation polymerization of the AB2 and AB3 carbosiloxy monomers 13, 14 and 15184-187. After polymerization in bulk, soluble polymers were obtained in 55-69% yields. Molecular weight analysis revealed the... 

Vasilenko and coworkers reported the hydrosilylation polymerization of AB2 monomers containing extremely long spacers between the SiH and vinyl groups (19)189. For the monomer with n = 10, polymers of 15,000-30,000 molecular weight were obtained in neat polymerizations. In solution, the monomer apparently cyclized intramolecularly. In the monomers with = 50 or 100, crosslinked polymers were obtained in neat polymerizations, but soluble polymers were obtained in solution polymerizations. 

Abstract Double-decker shaped silsesquioxane was synthesized by hydrolysis and condensation of trimetoxyphenylsilane in the presence of sodium hydroxide and it led to macromonomers having carbon functionalized groups. Then, these were polymerized by hydrosilylation polymerization, and their properties were measured. 

Seine M et al. (2006) Hydrosilylation polymerization of double-decker-shaped silsesquioxane having hydrosilane with diynes. Macromolecules 39 3473-3475... 

Synthesis and Properties of Silicones and Silicone-Modified Materials R 115 J.M. Mabry, M.K. Runyon, J.K. Paulasaari and W.P. Weber, Ru-Catalysed Hydrosilylation Polymerization An Overview of RuH2(CO)(PPh3)3 - Catalysed Hydrosilylation Copolymerizations of a,(o-Diketones with a,(o-Dihydrido-oligodimethylsiloxanes and Polymerizations of co-Dimethylsilyloxy Ketones , p. 50 Vol. 854, 2003... 

Synthesis of Hybrid Silicones Through Hydrosilylation of cr, oi-Dienes. Hydrosilylation Polymerization... 

More recently, Dvornic et al. [64,65] used the hydrosilylation polymerization method between 1,1,3,3-tetramethyl disiloxane and 1,3-divinyl 1,1,3,3-tetramethyl disiloxane and succeeded in obtaining the first hybrid siUcones, called here polycarbosiloxanes, with a high molecular weight (up to 76 000), according to the following reaction ... 

Finally, the platinum-catalyzed hydrosilylation polymerization was also used very recently by Cassidy et al. [82,83] to prepare fluorine containing silicon-organic hybrid polymers in supercritical carbon dioxide (SCCO2) (cf. Scheme 32). 

Monomers chosen for hydrosilylation polymerization (Ml = 1,3-diisopiopenylbenzene, M2 = 5-vinylnorbomene, M3 = bisphenol A diallyl ether, M4 = 2,2 -diallyloxybiphenyl, MS = 2,3-diallyloxynaphthalene). 

The hydrosilylation processes of carbon-carbon multiple bonds, applied in the field of polymer chemistry and materials science, are described in part three (section 4) of this article. It includes functionalization (and cross-linking) of polysiloxanes and (poly)silsesquioxanes as well as hydrosilylation polymerization of difunctional organosilicon monomers besides the application of hydrosilylation in the synthesis of silicon-containing dendrimers and hybrid organic-inorganic materials. 

Ruthenium dihydride complex [Ru(H)2(CO)(PPh3)3], activated by treatment with st3rrene, catalyzes several hydrosilylation polymerization processes, such as the reaction of tereftaldehyde with 1,3-tetramethyldisiloxane and hydrosilylation of poly(l-hydrido-l,3,3,5,5-pentamethyltrisiloxane) with benzophenone (221,222). [Ru3(CO)i2] was found catalytically active in the hydrosilylation of acetophenone with HSi(OEt)3 (222). The same cluster and several ruthenium carbonyl complexes efficiently catalyze the reduction of linear and cyclic amides with trisubstituted silanes to give the corresponding amines (224). Activated diruthenium and triruthenium carbonyls catalyze the hydrosilylation of ketones, as well as that of aldehydes wdth different silanes (225). First-generation Grubbs... 

Hydrosilylation polymerization may be carried out by means of the following processes ... 

Many other difiinctional organosilicon monomers containing both alkenyl groups and Si—H bonds in the molecule have also been successfully used in the platinum-catalyzed hydrosilylation polymerization (353-355) (Scheme 35). 

Halogenated Siloxane-Containing Polymers via Hydrosilylation Polymerization... 

Hydrosilylation polymerization has proven to be an extremely effective method for the synthesis of many types of organosilicon polymers. For example, hydrosilylation polymerization has been utilized extensively in the synthesis of both poly(carbosilanes) (14-23) and poly(carbosiloxanes) (i-5). These polymerizations... 

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