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Design and control of hyperbranched (HB) polymer architecture by way of reactor operation is key to a successful production of higher-valued HB polymers, and it is essential in order to clarify the fundamental structural characteristics formed in representative types of reactors. In this article, the irreversible step growth polymerization of AB2 type monomer is investigated by a Monte Carlo simulation method, and the calculation was conducted for a batch and a continuous stirred-tank reactor (CSTR). In a CSTR, a highly branched core region consisting of units with large residence times is formed to give much more compact architecture, compared to batch polymerization. The universal relationships, unchanged by the conversion levels and/or the reactivity ratio, are found for the mean-square radius of gyration Rg2, and the maximum span length LMS. For batch polymerization, the g-ratio of Rg2 of the HB molecule to that for a linear molecule conforms to that for the random branched polymers represented by the Zimm-Stockmayer equation. A single linear equation represents the relationship between Rg2 and LMS, both for batch and CSTR. Appropriate process control in combination with the chemical control of the reactivity of the second B-group promises to produce tailor-made HB polymer architecture.

Universal Relationships in Hyperbranched Polymer Architecture for Batch and Continuous Step Growth Polymerization of AB2-Type Monomers