Chain transfer kinetics of acid/base switchable n-aryl- n-pyridyl dithiocarbamate RAFT agents in methyl acrylate, n-vinylcarbazole and vinyl acetate polymerization
Abstract
The structures of the "Z" and "R" substituents of a RAFT agent (Z-C(S)S-R) determine a RAFT agent's ability to control radical polymerization. In this paper we report new acid/base switchable N-aryl-N-pyridyl dithiocarbamates (R = -CH 2CN, Z = -N(Py)(Ar)) which vary in substituent at the 4-position of the aryl ring and the use of these to control molecular weight and dispersity. In their protonated form, the new RAFT agents are more effective in controlling polymerization of the more activated monomer, methyl acrylate (MA), whereas in their neutral form they provide more effective control of the polymerization of less activated monomers, N-vinyl carbazole (NVC) and vinyl acetate (VAc). For each polymerization, the apparent chain transfer coefficient (C trapp) shows a good correlation with Hammett parameters. Dithiocarbamates with more electron-withdrawing aryl ring substituents have the higher C trapp. This demonstrates the influence of polar effects on C trapp and supports the hypothesis that the activity of these RAFT agents is determined by the availability of the lone pair of the dithiocarbamate nitrogen.Citation
Keddie, D.J., Guerrero-Sanchez, C. , Moad, G., Mulder, R.J., Rizzardo, E. and Thang, S.H. (2012) Chain transfer kinetics of acid/base switchable n-aryl- n-pyridyl dithiocarbamate RAFT agents in methyl acrylate, n-vinylcarbazole and vinyl acetate polymerization. Macromolecules, 45(10), pp. 4205–4215.Publisher
American Chemical SocietyJournal
MacromoleculesAdditional Links
https://pubs.acs.org/doi/10.1021/ma300616gType
Journal articleLanguage
enDescription
This is an accepted manuscript of an article published by American Chemistry Society in Macromolecules on 14/05/2012, available online: https://doi.org/10.1021/ma300616g ©American Chemical Society. The accepted version of the publication may differ from the final published version.ISSN
0024-9297EISSN
1520-5835Sponsors
The authors gratefully acknowledge the Capability Development Fund of CSIRO Materials Science and Engineering for financial support.ae974a485f413a2113503eed53cd6c53
10.1021/ma300616g
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