Polymerization initiated by the charge‐transfer complex of styrene and maleic anhydride in the presence of cumene and of cumene and liquid sulfur dioxide

A polymerization was induced with a charge‐transfer type of complex consisting of styrene and maleic anhydride in the presence a solvent such as ethyl benzene, cumene, or p‐cymene. No polymer was obtained either when the solvent was missing from the polymerization system or when benzene, toluene, or xylene, which are relatively stable to hydrogen abstraction, was added to the polymerization system. An effective initiation, however, took place when cumene or p‐cymene, each of which has a labile hydrogen on an α carbon, was added. On the basis of elementary analysis and infrared spectroscopy the formation of copolymer containing substantially equimolar amounts of styrene and maleic anhydride was ascertained. This polymerization was inhibited by the addition of DPPH, suggesting that the system styrene–maleic anhydride–cumene functions much as a conventional free‐radical initiator. On the other hand, when a solution of cumene and liquid sulfur dioxide was added to the polymerization system, polystyrene was obtained. This polymerization was inhibited by the addition of a base such as dimethyl‐formamide or dimethyl sulfoxide, indicating that the polymerization proceeds through carbonium ion intermediates. The addition of ethyl benzene or of p‐cymene brought about the same result as cumene. It is conceivable that the polymerization is induced by the abstraction of hydrogen attached at the α position of cumene by means of the charge‐transfer complex of styrene and maleic anhydride.