Abstract

A new Monte Carlo simulation method is proposed for the step polymerization of AB2‐type monomer conducted in a continuous flow stirred‐tank reactor (CSTR). The effect of the second B group reactivity, represented by the reactivity ratio r is investigated. The degree of branching (DB) at large degree of polymerization (P) limit, DBP→∞ does not change with the mean residence time . The value of DBP→∞ becomes larger by increasing r and is larger than the corresponding batch polymerization. The weight fraction distribution at high molecular weight tail follows a power law , and a simple formula to predict the power exponent α is proposed. The relationship between the radius of gyration 〈s2〉0 and P does not change with , and large polymers obtained in a CSTR are much more compact than those formed in batch polymerization. CSTR is advantageous to synthesize compact HB polymers, especially with a smaller r‐value.

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