Effect of ortho-Substituents on the Free-Radical Polymerization of N-Phenylmethacrylamides and on the Thermal Stability of the Polymers

Ceiling temperatures (T_c) and reactivities of N-phenylmethacrylamide (PMAm) and o-substituted PMAm's in free-radical polymerization and the thermal stability of the polymers obtained were investigated. Although PMAm and o-substituted analogs gave the same T_c, 123°C at 0.64 mol/L in N,N-dimethylformamide, that of 2,6-dimethyl-PMAm was found to be as low as 65°C. These findings are interpreted in terms of steric hindrance as a consequence of the bulkiness of the 2- and 6-substituents and of the rigid and planar structure expected for the polymers. In copolymerization with styrene, the o-monosubstituted PMAm's were estimated to be more reactive than PMAm by a factor of about 3 except for o-phenyl-PMAm. The enhanced reactivity of the PMAm with a relatively small o-substituent is explained by ground-state strain of the monomer tending toward a planar structure. 2,6-Dimethyl-PMAm and o-phenyl-PMAm showed lower and slightly higher reactivities than PMAm, respectively, probably due to the blocking effect of these substituents against the approaching polymer radical. Enhancement of thermal degradation owing to the substitution was confirmed by means of thermogravimetric analyses of the polymers. The polymers from the 2,6-dimethyl-substituted and the o-monosubstituted PMAm' exhibited similar maximum-degradation-rate temperatures.