Silane Based Radical Polymerization: Functionalized Homopolymers and Copolymers

Abstract

<p> This thesis presents a study on silane based polymerization in two parts. </p> <p> In Part A, diphenylvinylsilane (1) underwent oligomerization with initiation by azo(bisisobutyronitrile) (AIBN) or benzoyl peroxide (BPO). The vinyl groups were preferentially consumed under either set of conditions. Several products were isolated; these included oligomers 3, an AIBN adduct 4, a dimer 5, and a trimer 6. The residual SiH moieties could be subsequently coupled hydrosilylatively with alkynes or vinylsilicones. The efficiency of the radical reactions was very low. 15% starting material was recovered even with 200 mol% of initiating radicals added to the reaction mixture. The relative radical reactivities of the two functional groups is discussed.</p> <p> In Part B, 1 was radically copolymerized with styrene and methyl methacrylate (MMA). From the results of infrared and 1H NMR it was determined that 1 participated in copolymerization via a vinyl type polymerization and not in the form of a hydrogen-transfer type polymerization. Residual SiH groups along the backbone of the polymer remained reactive. A vinylsilicone and 9-vinylanthracene were grafted onto the copolymer from MMA and 1 by hydrosilylation and radical methods, respectively.</p>