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Experimental Method to Discriminate RAFT Models between Intermediate Termination and Slow Fragmentation via Comparison of Rates of Miniemulsion and Bulk Polymerization
Author(s) -
Suzuki Kiyoshi,
Kanematsu Yuta,
Miura Takashi,
Minami Masayuki,
Satoh Shuzaemon,
Tobita Hidetaka
Publication year - 2014
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.201300150
Subject(s) - miniemulsion , polymerization , chain transfer , raft , reversible addition−fragmentation chain transfer polymerization , polymer chemistry , materials science , bulk polymerization , chemistry , styrene , radical polymerization , copolymer , polymer , organic chemistry
A simple model discrimination method for RAFT polymerization mechanism, proposed on a theoretical basis, is applied to the polystyryl dithiobenzoate‐mediated styrene polymerization. It is confirmed that the intermediate termination (IT) is the major reason for the rate retardation. The method utilizes the theoretical finding that the IT model shows a significantly larger polymerization rate in miniemulsion compared with the corresponding bulk polymerization, while the slow fragmentation model does not change the polymerization rate. The miniemulsion polymerization rate increases as the droplet size is made smaller, which agrees reasonably well with the theoretical prediction. The present model discrimination method is easy to apply, and would provide great insight into both basic and applied research in RAFT polymerization.