Abstract
Poly(methyl methacrylate) (PMMA) and MMA—α-methylstyrene block copolymer were reacted with polystyryl anion in mixed solvents of tetrahydrofuran (THF)—methylcyclohexane at −78°C. The changes in the concentration of the living end with the reaction time were measured photometrically. By using the analytical method of successive reactions, the rate constant of each step-wise process (k0, k1, ···, kj, ···, kn), where kj means the rate constant to form the j-th branched graft copolymer from the (j−1)-th branched graft copolymer, was estimated from the rate constant observed (kobs). It was found that kn decreased rapidly with increasing number of polystyrene branches on the PMMA molecule. The tendency of the rate constant to decrease with the progress of the reaction became more clear when the molecular weight of polystyryl anion and the volume fraction of methylcyclohexane increased. These results are discussed in some detail.
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