3-ene, and 1,1 -dimethyl-1 -germacyclopent-3-ene undergo ring-opening polymerization catalyzed by alkyllithium reagents in the presence of hexamethylphosphoramide or , , ', -tetramethylethylenediamine to yield respectively poly(l,l-dimethyl-l-sila-cis-pent-3-ene), poly(l-methyl-l-phenyl-l-sila-cis-pent-3-ene), poly(l,l-diphenyl-l-sila-cis-pent-3-ene), poly(l,l,3-trimethyll-sila-Cí's-pent-3-ene), and poly(l,l-dimethyl-l-germa-cts-pent-3-ene). These polymers have been characterized by , 13C, and MSi NMR spectroscopy. Their molecular weight distributions have been determined by gel permeation chromatography. Their thermal stability has been measured by thermogravimetric analysis. The mechanism of this novel ring-opening polymerization is discussed.

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Faraday Soe. 1953, 15, 226. Obraztsov, V. I.; Khrustaleva, A. A. Russ. J. Phys. Chem. (Engl. Trans.) 1973, 47, 461. Moskala, E. J.; Varnell, D. F.; Coleman, M. M. Polymer 1985, 26, 228. Fowkes, F. M.; Tishler, D. 0.; Wolfe, J. A.; Lannigan, L. A.; Ademu-John, C. M.; Halliwell, M. J.ABSTRACT Dichlorocarbene generated under phase-transfer catalysis conditions was added to poly(1,ldimethyl-lsila-cis-pent-3-ene) (I). Catalytic isomerization of I by photochemically generated phenylthio radicals gave poly(1,l-dimethyl-1-sila-cis (and trans)-pent-3-ene) (11). Dichlorocarbene was also added to 11. The microstructures of these dichlorocarbene adduct polymers were characterized by 'H, 13C, and =Si NMR. Their thermal stabilities were determined by thermogravimetric analysis. They were found to be considerably less stable than the starting polymers I or 11. These dichlorocarbene adduct polymers slowly undergo spontaneous depolymerization at room temperature. The mechanism of this process is considered.

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