Radical‐initiated homo‐ and copolymerization of α‐methylene‐γ‐butyrolactone

The kinetics of α‐methylene‐γ‐butyrolactone (α‐MBL) homopolymerization was investigated in N,N‐dimethylformamide (DMF) with azobis(isobutyronitrile) as initiator. The rate of polymerization (Rp) was expresed by Rp = k[AIBN]0.54[α‐MBL]1.1 and the overall activation energy was calculated as 76.1 kJ/mol. Kinetic constants for α‐MBL polymerization were obtained as follows: kp/kt1/2 = 0.161 L1/2 mol−1/2·s−1/2; 2fkd = 2.18 × 10−5 s−1. The relative reactivity ratios of α‐MBL(M2) copolymerization with styrene (r1 = 0.14, r2 = 0.87) were obtained. Applying the Q–e scheme led to Q = 2.2 and e = 0.65. These Q and e values for α‐MBL are higher than those for MMA