KINETICS OF THE BULK RADICAL POLYMERIZATI ON OF FLUOROALKYL METHACRYLATE MONOMERS

Kinetics of the bulk radical polymerization of the fluoroalkyl methacr ylate monomers of the series CH2=C(CH3)-COO-CH2-(CF2-CF2)(n)-H (n = 1- 3) was studied within a wide range of conversions. At the initial stag es, the rate of polymerization and the molecular masses of poly(fluoro alkyl methacrylate)s increase with the length of fluoroalkyl radical o f the monomer, This is associated with a drop in the rate constant of bimolecular chain termination in this series. During the further polym erization, the gel effect is observed for all members of the series. T he onset of autoacceleration shifts to higher conversions, and the ext ent of the gel effect manifestation falls down with increasing the len gth of fluoroalkyl radical of the monomer. The specific features of th e gel effect in the series of fluoroalkyl methacrylates are related to decreasing influence of the topological network of entanglements on t he passage from lower to higher members of the series.