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A Systematic Kinetic Study in Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) with Germanium, Tin, Phosphorus, and Nitrogen Catalysts
Author(s) -
Goto Atsushi,
Wakada Tsutomu,
Fukuda Takeshi,
Tsujii Yoshinobu
Publication year - 2010
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200900532
Subject(s) - catalysis , chemistry , polymerization , polymer chemistry , styrene , tin , reaction rate constant , monomer , germanium , chain transfer , bulk polymerization , radical polymerization , photochemistry , kinetics , copolymer , organic chemistry , polymer , silicon , physics , quantum mechanics
This paper reports a systematic kinetic study on the reversible activation processes and polymerization rates in the reversible chain transfer catalyzed living radical polymerizations (RTCPs) of styrene (St) and methyl methacrylate with germanium (Ge), tin (Sn), phosphorus (P), and nitrogen (N) catalysts. The pseudo‐first‐order activation rate constant k act significantly depended on monomers and the elements and substituents of the catalysts. For the St polymerization at 80 °C, k act increased in the order of PI 3 (P catalyst) < p ‐tolyl germanium triiodide (tolyl‐GeI 3 ) (Ge catalyst) < N ‐iodosuccinimide (NIS) (N catalyst) < SnI 4 (Sn catalyst) < GeI 4 (Ge catalyst) at the same catalyst concentration. The polymerization rate was somewhat retarded in the studied systems due to the cross‐termination between the propagating radical and the catalyst radical in situ formed in the polymerization.