Synthesis of Poly(silylenemethylenes) through Reactions Carried Out on Preformed Polymers. 2. Investigation of the Hydrosilation Route to Substituted Poly(silylenemethylenes)

Abstract

A series of polymers of the type [Si(CH3)(C3H6R)CH2] n where R = C3H7, NEt2, carbazole, and OC2H4OC2H4OCH3 were prepared by hydrosilation of the appropriate terminal olefin with the [Si(H)(CH3)CH2] n (1) polymer using Karsted's catalyst. It was found that hydrosilation of these olefins with 1 proceeds with a relatively high (80−95%) conversion of the polymer SiH groups. NMR and DSC data on these polymers as well as their relative thermal and oxidative stabilities are reported. The phenol-substituted polymers, [Si(CH3)(C3H6C6H4OH)X] n (5), where X = O (5e) or CH2 (5f), were also prepared and their stability toward base hydrolysis was evaluated. It was found that the polycarbosilane 5f shows superior hydrolytic stability relative to the polysiloxane 5e.

Modification of polysiloxane polymers for biomedical applications: a review

“…Hydrosilation,138 an addition reaction of SiH compounds to π‐unsaturated, vinyl or allyl groups, has attracted considerable attention in silicone polymer chemistry. This reaction has been widely used as a method of introducing various R groups onto polysiloxane chains through the platinum‐catalysed reaction of olefins with [Si(H)(CH 3 )O] n 139. In addition to its well‐known applications for room‐temperature vulcanization processes,140 this reaction has also been used for the synthesis of various siloxane‐containing side‐chain liquid‐crystalline polymers141 and for Starburst dendrimers 142.…”

Synthesis and Characterization of Water Soluble Saccharide Functionalized Polysiloxanes and Their Use as Polymer Surfactants for the Stabilization of Polycaprolactone Nanoparticles

“…Other deprotective methods for silyl ether linkage seemed to be inappropriate when applied for polysiloxane compounds because they lead to chain degradation. [32,33] Therefore, we tried this geltype resin based on two hypotheses: a) the Si-O-C bond is more labile than the Si-O-Si bond; b) at least in the early stages of the deprotection reaction, the modified polysiloxanes are not soluble in methanol. So we can assume that the siloxane bonds would not be significantly exposed to the catalyst active centers.…”

Organic/inorganic hybrid polymers

“…Using the thus developed route, a variety of further poly(silylene methylene) derivatives have been prepared, such as 19 -25 [126,127]. Also, some polymers [Si(Me)(C 3 H 6 R)CH 2 ] n were obtained by hydrosilylation, having R = C 3 H 7 , NEt 2 , carbazole, and OC 2 H 4 O-C 2 H 4 OCH 3 [128].…”