Abstract
AbstractThe solution polymerization of methacrylic anhydride, a monomer which undergoes predominantly inter‐intramolecular propagation, shows kinetics similar to vinyl polymerization. The overall rate of polymerization is proportional to the square root of the initiator concentration and to the 3/2 power of the monomer concentration. The apparent, overall energy of activation was found to be 23.0 kcal./mole when azobisisobutyronitrile was used as the initiator. The value of Ep − Et/2 obtained is 8.0 kcal./mole. This compares with the value of Ep − Et/2 found for methacrylic acid in the same solvent (DMF) of 9.8 kcal./mole. Both values are in the range of values for other vinyl monomers. The polymer obtained from reactions carried out at monomer concentrations of 17% and lower were completely soluble, showed low amounts of residual unsaturation, and did not appear to be branching to a measureable extent. At higher monomer concentrations, gel was formed, and the polymers showed higher residual unsaturation levels. Poly(methacrylic anhydride) hydrolyzed to the polyacid did not show any enhancement in crystallinity over the polyacid prepared directly from methacrylic acid. Both show only low orders of crystalline content.
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