Cyclopolymerization of Metalloid-Containing Alpha, Omega-Dienes. 1.3-Divinyltetramethyldisiloxane, 1,3-Divinyltetramethyl-Disilazane and 1.3-Divinylpentamethyldisilazane.

摘要

The di-tert-butyl peroxide-initiated cyclopolymerization of (CH2=CHMe2Si)2X (X = 0, NH, NMe) gives polymers of relatively low molecular weight. Their IR, 1H and 29Si NMR spectroscopy provided some structural information when they were compared with spectroscopic data for model cyclic and acyclic organosilicon compounds. These studies indicated the presence of 5- and 6-membered cyclic units in the polymer chain, possibly also of 7-membered cyclic and of acyclic units. The Si-NH-Si functions in the cyclopolymer derived from (CH2=CHMe2Si)2NH reacted readily with HF and HCl to open the ring and introduce SiMe2F and SiMe2Cl substituents, respectively, onto the polymer backbone. Reactions of the former with LiAlH4, MeLi, n-BuLi and CH2=CHMgBr converted them to SiMe2H, SiMe3, SiMe2Bu-n and SiMe2(CH=CH2) substituents, respectively.