Abstract: | Bulk polymerization of chloroprene was studied at 25°C in a wide does rate range. Variations of the rate of polymerization (Rp) and molecular weight as a function of does rate were essentially the same as those in several monomers that are capab;e of radical and cationic polymerizations. The polymerization proceeds with radical mechanism at low dose rate ans with radical and cationic mechanism concurrently at high dose rate. The number-average molecular weight of the high-dose-rate was ca. 2400. Microstructure of the polymers was mainly of trans-1,4 unit with small fraction of cis-1,4 and 3,4-vinyl unit. Fractions of the vinyl unit and the inverted unit in trans-1,4 sequence which increased at high does rate inflected the change of dominant mechanism of polymerization. |