This article presents the results of a systematic synthesis study of elastomeric crosslinkable polysilicon olefins, the related thermal crosslinking kinetics, and the main permeability parameters recorded for inorganic gases (He, N2, O2, and CO2) and C1-C 7 hydrocarbons. Poly(vinyl allyl dimethylsilane) (PVADMS; glass-transition temperature < 273°K) was obtained by the anionic polymerization of bifunctional vinyl allyl dimethylsilane monomer. The polymers were amorphous, high molecular compounds with mixed carbo-heterochain structures containing double bonds capable of intermolecular crosslinking under a thermal treatment. Thus, thermally crosslinked polymers exhibited a high resistance toward exposure to organic vapors, unlike noncrosslinked PVADMS. IR spectroscopy was used to investigate the polymer structural changes induced by the thermal treatment. An original technique based on a differential method was used to measure gas permeability during thermal crosslinking. PVADMS possessed higher permeability for C1-C7 hydrocarbons than for inorganic gases (excluding CO2), even after crosslinking. Permeability coefficients ranging from 140 to 1780 Barrer for He and CH 4 were found before crosslinking; the thermal crosslinking induced a nonlinear permeability decrease that could be correlated with the disappearance of the double bonds in the polymer structures, that is, cis-CH=CH-, trans-CH=CH-, and CH2=CH- in the side-chain position. According to the found properties, PVADMS could be used as a prospective material for the preparation of highly permeable selective membranes suitable for lower hydrocarbon and volatile organic compound recovery from various chemical and petrochemical process streams.
