Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 57, Issue 18, Pages 1938-1946Publisher
WILEY
DOI: 10.1002/pola.29329
Keywords
block copolymer; colloids; kinetics (polym; ); livingness; miniemulsion; reversible addition fragmentation chain transfer (RAFT); segregation
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Funding
- Australian Research Council [DP170100081]
- UNSW Mark Wainwright Analytical Centre
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It is demonstrated that the degree of livingness (chain-end fidelity) in RAFT polymerization for a given degree of polymerization can be markedly increased in miniemulsion polymerization relative to the corresponding homogeneous bulk system. Polymerization of styrene was conducted using a poly(methyl methacrylate) benzodithioate as macroRAFT agent in both miniemulsion and bulk. The substantially higher polymerization rate in miniemulsion, which is attributed to the segregation effect (compartmentalization) causing a reduction in the rate of bimolecular termination, makes it possible to reach a given degree of polymerization in a significantly shorter time than in the corresponding bulk system. As a consequence, fewer initiating radicals are required throughout the polymerization, leading to higher livingness in the more rapid miniemulsion system. It is demonstrated how this approach facilitates synthesis of high-molecular-weight block copolymers comprising slowly propagating monomers such as styrene and methacrylates. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1938-1946
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