Addition of Dichlorocarbene to Poly(1,1-dimethyl-1-silia-cis-pent-3-ene) and Poly(1,1-dimethyl-1-silia-cis (and trans)-pent-3-ene). Characterization of Microstructures by 13C and 29Si NMR

摘要

Dichlorocarbene generated under phase transfer catalysis conditions was added to poly(1,1-dimethyl-1-sila-cis-pent-3-ene) (I). Catalytic isomerization of I by photochemically generated phenylthio radicals gave poly(1,1-dimethyl-1-sila-cis (and trans)-pent-3-ene) (II). Dichlorocarbene was also added to II. The microstructures of these dichlorocarbene adduct polymers were characterized by 1H, 13C, and 29Si NMR. Their thermal stabilities were determined by thermogravimetric analysis. They were found to be considerably less stable than the starting polymers I or II. These dichlorocarbene adduct polymers slowly undergo spontaneous depolymerization at room temperature. The mechanisms of this process is considered. Keywords: Dichlorocarbene adduct, Decomposition, Microstructure, Carbenes, Polymers, Silanes, Reprints. (MJM)