Stereospecific polymerization of methacrylonitrile. III. Some new catalysts for isotactic polymethacrylonitrile

Abstract

AbstractSome classes of organometallic catalysts what induce stereospecific polymerization of methacrylonitrile have been found. They include organolithium aluminum compounds of the type LiAlR4, Li[R3AlOAlR2], and Li[R3AlN(R)AlR2], organosodium aluminum compounds of the type NaAlR4, organolithium zinc compounds of the type LiZnR3 and Li2ZnR4, organomagnesium aluminum compounds of the type RMg[AlR4] and Mg[AlR4]2, and organomagnesium compounds containing an MgN bond, such as magnified image and their related compounds. One of the features of the polymerization with these catalysts was that the crystalline polymers were formed at moderately high temperatures. Total conversion, solubility index, and molecular weight of the polymer increased with increasing polymerization temperature, as observed in the case of polymerization with diethylmagnesium catalyst. Catalysts with an MgN bond were found to be highly effective for the stereospecific polymerization. The acetone‐insoluble fractions of the polymers gave x‐ray diagrams identical to the crystalline polymer produced with diethylmagnesium. This indicates that the acetone‐insoluble crystalline polymers produced with these catalysts have an isotactic structure. The viscosity–molecular weight relationship for crystalline polymer was conveniently determined in Cl2CHCOOH at 30°C.; [η] = 2.27 × 10−4 M0.754.