OLEFIN POLYMERIZATION IN LIQUID SULFUR DIOXIDE INITIATED BY m-CHLOROPERBENZOIC ACID - 1. HOMOPOLYMERIZATION OF STYRENE AND alpha -METHYLSTYRENE.

In the reported experiments, homopolymerizations of styrene (Sty) and alpha -methylstyrene (AMS) in liquid sulfur dioxide were carried out in the temperature range from minus 10 degree C to minus 78 degree C, using m-chloroperbenzoic acid as initiator. It is shown, through the effect of initiator concentration, temperature, and time of reaction on the conversion and molecular weight of the polymers, that AMS is more reactive than Sty because it requires a smaller amount of initiator for the same conversion to be reached, although the molecular weight of the resulting polymer is lower. A linear relationship has been observed for Sty between the degree of polymerization and the intiator concentration. Within the experimental conditions employed, the presence of polysulfones has been discarded by elemental analysis. The polymerization reactions are considered to be cationic in mechanism.