Solvent effects, diffusion control and mechanistic aspects of catalytic chain transfer polymerization

S.C.J. Pierik, R. Vollmerhaus, A.M. Herk, van

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Abstract

In the cobalt-catalyzed chain transfer polymn. of Me methacrylate, Bu methacrylate, and 2-ethylhexyl methacrylate in toluene, it was found that the chain transfer consts. (CT) were independent of solvent concn. and therefore of soln. viscosity, and did not differ from the bulk polymn. values. For a diffusion-controlled system, theor. calcns. predict an increase in CT when the soln. viscosity is lowered. This points at a non-diffusion-controlled catalytic chain transfer step. These results were obtained when the solvent was thoroughly purified using a Grubbs-type set-up, whereas a large redn. in CT was found in unpurified solvent. Similar results were obtained for Bu acetate. Therefore it is concluded that the decrease of CT in non-purified solvents is not related to the solvent itself, but to solvent impurities. Further we found that Me methacrylate-ended radicals do not covalently bind to the catalyst, in contrast to styrene- and acrylate-ended radicals. [on SciFinder (R)]
Original languageEnglish
Pages (from-to)1090-1101
JournalMacromolecular Chemistry and Physics
Volume204
Issue number8
DOIs
Publication statusPublished - 2003

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