Determination of absolute rate constants for free radical polymerization of ethyl α‐fluoroacrylate and characterization of the polymer

The absolute rate constants for propagation (kp) and for termination (kt) of ethyl α‐fluoroacrylate (EFA) were determined by means of the rotating sector method; kp = 1120 and kt = 4.8 × 108 L/mol.s at 30°C. The monomer reactivity ratios for the copolymerizations with various monomers were obtained. By combining the kp values for EFA from the present study and those for common monomers with the monomer reactivity ratios, the absolute values of the rate constants for cross‐propagations were also evaluated. Reactivities of EFA and poly(EFA) radical, being compared with those of methyl acrylate and its polymer radical, were found to be little affected by the α‐fluoro substitution. Poly(EFA) prepared with the radical initiator was characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Although the glass transition temperature obtained by DSC for poly(EFA) resembled that of poly(ethyl α‐chloroacrylate), its TGA thermogram showed fast chain de polymerization to EFA that was distinct from complicated degradation of poly(ethyl α‐chloroacrylate).