The mechanism of the spontaneous polymerization of 4‐vinylpyiridine on quaternization or protonation has been investigated. Results indicate that initiation is caused by the nucleophilic attack of 4‐vinylpyridine on the double bond of 4‐vinylpyridinium ion. It was shown that halide ions do not contribute significantly to the initiation. In the case of acid salts of 4‐vinylpyridine a hydrogen‐transfer polymerization occurred to give an ionene polymer with pyridinium units in the main chain. The “matrix” polymerization of 4‐vinylpyridine on poly(phosphoric acid) or poly(acrylic acid) also resulted in ionene formation. Conditions under which stable 4‐vinylpyridinium salts can be obtained are discussed.
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Salamone et al. (1971) studied this question.
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