Origin of inhibition effects in the reversible addition fragmentation chain transfer (RAFT) polymerization of methyl acrylate

Perrier, S., Barner-Kowollik, C., Quinn, J. F., Vana, P., & Davis, T. P. (2002) Origin of inhibition effects in the reversible addition fragmentation chain transfer (RAFT) polymerization of methyl acrylate. Macromolecules, 35(22).

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The reversible addition fragmentation chain transfer (RAFT) bulk polymerization of a fast propagating monomer (methyl acrylate, MA) has been studied using 1-phenylethyl dithiobenzoate (1-PEDB) and 2-(2-cyanopropyl) dithiobenzoate (CPDB) as RAFT agents at 60 °C. Rate retardation with increasing initial RAFT agent concentrations is common to both 1-PEDB- and CPDB-mediated MA polymerizations and occurs in comparable magnitude. A pronounced inhibition period is observed in 1-PEDB-mediated MA polymerizations, whereas the corresponding CPDB-mediated polymerizations show considerably less inhibition. The cause for this inhibition may either be associated with the leaving group of the initial RAFT agent or with the slow fragmentation of the initial intermediate macroRAFT radical. The present experimental data suggest that slow fragmentation is the probable cause for inhibition. We conclude that the radical intermediate formed by addition of radicals to the initial RAFT agent is different in stability than the macroRAFT radical formed analogously from macroRAFT agent. The inhibition period is effectively reduced by the use of CPDB as the initial RAFT agent in methyl acrylate polymerizations.

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ID Code: 99058
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :314
Export Date: 5 September 2016
Correspondence Address: Davis, T.P.; Centre for Adv. Macromolecular Des., Sch. of Chem. Eng. and Indust. Chem., University of New South Wales, Sydney, NSW 2052, Australia; email: t.davis@unsw.edu.au
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Keywords: Reversible addition fragmentation chain transfer (RAFT), Acrylic monomers, Addition reactions, Computer simulation, Reaction kinetics, Free radical polymerization
DOI: 10.1021/ma0203445
ISSN: 00249297
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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