Torsional braid as a kinetic tool for the study of the polymerization of viscous materials. II. Catalytic effects in the polymerization of carboxylic acid-terminated polybutadiene prepolymers with tris[1-(2-methyl)aziridinyl]phosphine oxide



The torsional braid technique for studying the polymerization of viscous substances has been extended to a study of the homogenous catalytic behavior of a number of acidic and basic catalysts int he polymerization of carboxy-terminated polybutadiene with tris(methyl aziridinyl)phosphine oxide. No general catalytic behavior was observed. Specific catalysis was observed in the case of lithium oleate, where the gel time was decreased, and in the case of bis(tri-n-butyltin) oxide, where the gel time was increased. The average energy of activation for all of these polymerizations was 13.9 ± 0.5 kcal./mole. This energy of activation and the reaction environment, when compared with the data in the literature, strongly suggest that the explanation that a change in the rate-determining step occurs as a function of the polarity of the reaction medium fails to account for all of the results.