Kinetics of anionic copolymerization. Determination of absolute rate constants

Lack of termination in the “Living” polymer systems enables one to determine directly the absolute rate constant of propagation and of copolymerization. Anionic polymerizations in tetrahydrofuran are usually very fast, and a flow technique was developed to determine the rate of these reactions. The method is described and its use illustrated by studies on the following systems: styrene–p-methylstyrene, styrene–p-methoxystyrene, and styrene-2-vinylpyridine. The results indicate that the polarity of the reacting monomer is the dominant factor in determining the value of the copolymerization rate constant as long as the polarities of the monomers involved are similar. However, the results obtained on the system styrene–2-vinylpyridine clearly demonstrate that the terminal carbanion plays a major role when the polarities of the two monomers are very different. The technique can also be used to study the effect of the penultimate unit of a chain on the rate constant of propagation or copolymerization. Moreover, the chain length of the “living” polymer can be caried and its effect of the rate constant determined.