Abstract
AbstractIt is known that the step polymerization of AB2‐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 〈s2〉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.
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