Anionic polymerization of vinylsilanes VII：（阴离子聚合的多七世）.pdfVIP

Polymer Bulletin 39,287-293 (1997) Polymer Bulletin © Springer-Verlag 1997 Anionic polymerization of vinylsilanes VII Effects of N,N, N,N-tetramethylethylenediamine on the polymerization of tetravinylsilane Yasuhiro Suga, Yukiko Itoh, Jun-ichi Oku *, Mikio Takaki Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso -cho, Showa-ku, Nagoya 466, Japan Received: 29 March 1997/Revised version: 14 July 1997/Accepted: 18 July 1997 Summary The anionic polymerization of tetravinylsilane (TeVS) was carried out in the presence and absence of N,N,N,N- tetramethylethylenediamine (TMEDA). Without TMEDA, the polymerization proceeded extremely slowly and the polymer yield was still low even after an extended polymerization time. When TMEDA was added to the system, the polymerization was remarkably accelerated and gelation was suppressed. Such polymerization behavior of TeVS is closely similar to that of methyltrivinylsilane under similar conditions. The effects of TMEDA are explained by its coordination to the propagating end that increases the selectivity in the reaction of the propagating end with vinyl groups. Introduction We have studied the anionic cyclopolymerization of multivinylsilanes, namely dimethyldivinylsilane (DMDVS), methyltrivinylsilane (MTVS), and bis(dimethylvinyl- silyl)methane (BVSM) (1-3). The addition of N,NN,N- tetramethylethylenediamine (TMEDA) to the polymerization system of multivinylsilanes causes various interesting effects. For example, the anionic polymerization of BVSM hardly proceeds without TMEDA, while that with n-butyllithium (n-BuLi)/TMEDA affords the polymer having six- membered ring structure as a repeating cyclic unit through cyclopolymerization (1). The polymerization of MTVS with sec-butyllithium (s-BuLi) is remarkably accelerated by the addition of TMEDA to the polymerization syst