Copolymerization of α‐olefins with ω‐halo‐α‐olefins by use of Ziegler catalysts

The copolymerization of α‐olefins with ω‐halo‐α‐olefins by use of Ziegler catalysts has been investigated. It was found that ω‐halo‐α‐olefins deactivate the catalyst, thus resulting in low copolymer yield and reduced molecular weight. The deactivation is caused by hydrogen halide formation which is greatly facilitated in the case of the allyl halides and 6‐halo‐1‐hexenes. The different degrees of deactivation were interpreted by considering the ease of carbonium ion formation from the various ω‐halo‐α‐olefins. The copolymer yields were considerably improved when a catalytic amount of a Lewis base was added to the polymerization system. It is proposed that the added Lewis base, by decreasing the Lewis acid character of the catalyst, suppresses the decomposition of the ω‐halo‐α‐olefin leading to hydrogen halide formation. Depending on the Ziegler catalyst employed, the copolymers of α‐olefins and ω‐halo‐α‐olefins can be either crystalline or amorphous solids. The halogen, especially the bromine in the copolymers, is reactive in nucleophilic substitution reactions. Reaction with amines gave polymers which could be dyed by acid dyes.