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Catalytic chain transfer polymerisation (cctp) of methyl methacrylate: Effect of catalyst structure and reaction conditions on chain transfer coefficient
Author(s) -
Haddleton David M.,
Maloney Darren R.,
Suddaby Kevin G.,
Muir Andrew V. G.,
Richards Stuart N.
Publication year - 1996
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19961110106
Subject(s) - catalysis , polymerization , chain transfer , chemistry , methyl methacrylate , activation energy , catalytic chain transfer , polymer chemistry , solvent , chain termination , active center , reaction rate constant , diffusion , radical polymerization , kinetics , organic chemistry , polymer , thermodynamics , physics , quantum mechanics
Catalytic chain transfer polymerisation of methyl methacrylate has been investigated by a range of cobalt(II) complexes. The effect of catalyst structure, reaction temperature and solvent has been examined. At 60°C in the absence of solvent, the chain transfer coefficient, Cs, for MMA and cobaloximes modified by bridging BF 2 groups e.g. 3 is found to be 40,900, this is constant over a wide mass range. Cs is lowered when catalysts of larger cross sectional area are used supporting a diffusion controlled process. Co‐ordinating solvents suppress Cs by competing for coordination of the Co(II) effectively reducing the concentration of active species. No conclusions can be drawn regarding the effect of temperature and thus the activation energy of the process. CCTP lowers the observed rate of polymerisation.