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RAFT Miniemulsion Polymerization Kinetics, 1 – Polymerization Rate
Author(s) -
Tobita Hidetaka
Publication year - 2009
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.200800069
Subject(s) - miniemulsion , polymerization , radical polymerization , emulsion polymerization , reversible addition−fragmentation chain transfer polymerization , polymer chemistry , kinetics , chemistry , monomer , chain transfer , raft , precipitation polymerization , bulk polymerization , kinetic chain length , chain growth polymerization , polymer , organic chemistry , physics , quantum mechanics
Abstract The polymerization kinetics of a RAFT‐mediated radical polymerization inside submicron particles (30 < D p < 300 nm) is considered. When the time fraction of active radical period, ϕ A , is larger than ca. 1%, the polymerization rate increases with reducing particle size, as for the cases of conventional emulsion polymerization. The rate retardation by the addition of RAFT agent occurs with or without intermediate termination in zero‐one systems. For the particles with D p < 100 nm, the statistical variation of monomer concentration among particles may not be neglected. It was found that this monomer‐concentration‐variation (MCV) effect may slow down the polymerization rate. An analytical expression describing the MCV effect is proposed, which is valid for both RAFT and conventional miniemulsion polymerizations.