Abstract
(4-Vinylphenyl)dimethylvinylsilane (VS) was anionically polymerized to yield poly[(4-vinylphenyl)dimethylvinylsilane] (PVS). The styryl group of VS was polymerized and silylvinyl group of VS remained unreacted during the anionic polymerization. However, a slight amount of the silylvinyl group of VS should be subject to anionic polymerization. To suppress two side reactions related to the silylvinyl group, the influence of initiators, solvents and polymerization time on anionic polymerization was studied in detail. When n-butyllithium was used as initiator, the resultant polymer conversion rate was 60% and the corresponding GPC chromatogram showed a broad peak. This is because during chain propagation, the styryl living end was deactivated by a labile proton of the silylmethyl group of the side chain (abstraction mechanism). When cumylpotassium and cumylcesium were used as initiators, the polymer conversion rates were nearly 100% and corresponding GPC chromatograms showed double and/or triple peaks because after chain propagation had completely finished, the styryl living end reacted with the silylvinyl group of the side chain of a different polymer molecule (addition mechanism). When a mixture of diethyl ether/4,4-dimethyl-1,3-dioxane (1,3-DX) was used as solvent, PVS yielded a sharp GPC chromatogram containing a small shoulder at the higher molecular weight side. The size of this shoulder increased with polymerization time. Thus, VS was polymerized by cumylcesium in a 1:2 mixture of diethyl ether/1,3-DX for 30 minutes to yield four polymers with Mn from 2.50×104 to 1.36×105, and Mw/Mn less than 1.08. Upon exposure to a deep ultraviolet light having a wavelength of 290 nm, gel of PVS was observed in the exposed area.
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Se, K., Matsumura, K., Kazama, T. et al. Preparation and Characterization of Poly[(4-vinylphenyl)dimethylvinylsilane] via Anionic Living Polymerization. Polym J 29, 434–441 (1997). https://doi.org/10.1295/polymj.29.434
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DOI: https://doi.org/10.1295/polymj.29.434