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Experimental Validation of Intermediate Termination in RAFT Polymerization with Dithiobenzoate via Comparison of Miniemulsion and Bulk Polymerization Rates
Author(s) -
Suzuki Kiyoshi,
Nishimura Yuko,
Kanematsu Yuta,
Masuda Yoshie,
Satoh Shuzaemon,
Tobita Hidetaka
Publication year - 2012
Publication title -
macromolecular reaction engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 32
eISSN - 1862-8338
pISSN - 1862-832X
DOI - 10.1002/mren.201100054
Subject(s) - miniemulsion , raft , reversible addition−fragmentation chain transfer polymerization , polymerization , radical polymerization , polymer chemistry , chain transfer , chemistry , styrene , materials science , copolymer , organic chemistry , polymer
To understand if either of two controversial models for the retardation by RAFT agents is applicable, styrene polymerization using dithiobenzoate as the RAFT agent is carried out in both bulk and miniemulsion systems with the same rates of radical generation and the same RAFT agent concentrations. Miniemulsion polymerization with average diameters of the miniemulsion droplets of ≈107 nm is by far faster than in bulk, and the obtained rate of polymerization agrees well with the calculated results assuming a bimolecular termination between propagating radical and intermediate radical, generated by the addition reaction of propagating radical to the RAFT agent, which shows that the intermediate termination is the major reason for rate retardation by the RAFT agent.