The homopolymerization of both free and aluminum alkyls complexed 4‐vinylpyridine (4VP) in the presence of Ziegler‐Natta catalysts, based on TiCl3“ARA” and aluminum or zinc alkyls, has been performed. The copolymerization of free or complexed 4VP with chiral α‐olefins or styrene (St), using the same catalysts, has also been investigated. Spectroscopic and solubility data of the polymers obtained are consistent with the presence in the above‐mentioned catalysts of several species having different reactivity and stereochemistry. Data, based on fractionation and composition of the resulting polymeric products, are reported supporting a polymerization mechanism different from that connected with a free radical initiation.
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Carlo Carlini (1980) studied this question.
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