Distributions of Molecular Weights and 3D Sizes of Hyperbranched Polymers Formed in Batch Self‐Condensing Vinyl Polymerization

Abstract

It is known that the step polymerization of AB 2 -type monomer leads to form random hyperbranched architecture, irrespective of the reactivity of the second B group. On the other hand, the hyperbranched structure formed in the self-condensing vinyl polymerization of AB* monomer is now shown to be nonrandom because of the persistent history-dependent connection through the A * group. The molecular weight distribution deviates from that of the random branched polymers. On the other hand, the nonrandom effect on the 3D architecture is rather small, and the expected g-ratio of the unperturbed mean-square radius of gyration 〈s 2 〉 0 of the branched molecule to that of a linear molecule for a given number k of branch points agrees well with the Zimm-Stockmayer equation that assumes random branching of primary chains having the most probable distribution.