AbstractThe kinetics of radical homopolymerization of 2,2,3,4,4,4‐hexafluorobutyl methacrylate (HFBMA) and 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (OFPMA) was investigated in four different solvents. The rate of polymerization (Rp) of both monomers was found to increase with increasing donor number of the solvents, the increase being more marked in the case of OFPMA. This is probably associated with the leveling of the electron density of the double bonds of HFBMA and OFPMA by the influence of solvents as well as with the gel effect in the polymerization. Copolymerization parameters for HFBMA and OFPMA with butyl acrylate, styrene and methyl methacrylate were determined in benzene at 60°C and the values of resonance and polarity terms,Qande, were also establi