Olefin Polymerization and Copolymerization with Alkylaluminum-lnitiator Systems. VII. Initiation by Electrophilic Halogens

Abstract

The discovery of initiation of cat ionic polymerization of isobutylene and styrene by electrophilic chlorine generated by the reaction of chlorine and trimethylaluminum in the temperature range -40 to -100° is reported. Bromine and trimethylaluminum is a very poor initiating system, and iodine and trimethylaluminum does not initiate the polymerization of either isobutylene or styrene. Polymerization of isobutylene initiated by chlorine and trimethylaluminum shows a linear plot of log M_v vs 1/T with an overall E_DPof ～1.9 kcal, mole. The molecular weights (M_w) of polystyrene obtained with the Cl₂/Me₃Al system appear to be the highest ever reported for cationic polymerization of this monomer under comparable conditions. The mechanism of initiation has been investigated by model experiments: The reaction between Cl₂/ Me₃Al and 2,2,4-trimethyl-l-pentene gave three chlorinated products (2-chloromechyl-4,4-dimethyl-l-pentene, 1-chloro-2,4,4-trimethyl-1-pentene, and 2-chioromethyl-2,4,4-trimethyl-pentane). The position of chlorine in these compounds indicate initiation by electrophilic chlorine, Cl. Some preliminary results obtained using diethylaluminum chloride-halogens as coinitiator-initiator systems are also described.