Soluble poly(divinylbenzene): Reaction mechanism for the anionic polymerization of divinylbenzene with lithium diisopropylamide as catalyst

This paper presents results of the studies on the mechanism of initiation, propagation and chain transfer reactions in the recently found polymerization of 1,4‐ and/or 1,3‐divinylbenzene (DVB), initiated with lithium diisopropylamide/diisopropylamine. Initiation was confirmed to take place by addition reaction of the alkylamino group to the DVB molecule. The population of the triad tacticity of the soluble poly(DVB) suggested the steric course of the polymerization to proceed according to Bernoullian statistics with respect to the diad placements, m and r. The chain transfer reaction was found to take place via the free amine, the chain transfer reactivity of a primary amine being higher than that of a secondary amine. Comparative studies on the reactivity and selectivity of sodium diisopropylamide toward styrene and DVB were also carried out with respect to lithium diisopropylamide as reference.