Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Investigation of the Experimental Factors Affecting the Trithiocarbonate-Mediated RAFT Polymerization of Methyl Acrylate

Murray R. Wood A , David J. Duncalf B , Paul Findlay B , Steven P. Rannard B and Sébastien Perrier A C
+ Author Affiliations
- Author Affiliations

A Department of Colour and Polymer Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, England.

B Unilever Research & Development, Port Sunlight Laboratories, Quarry Road East, Bebington, Wirral, L63 3JW, England.

C Corresponding author. Email: s.perrier@leeds.ac.uk

Australian Journal of Chemistry 60(10) 772-778 https://doi.org/10.1071/CH07171
Submitted: 24 May 2007  Accepted: 21 August 2007   Published: 9 October 2007

Abstract

The reversible addition–fragmentation chain transfer polymerization of acrylates, using methyl acrylate (MA) as a monomer model, mediated by a trithiocarbonate was tested under several conditions where the experimental parameters were systematically altered. The most significant parameter in controlling the rate and control of the polymerization was found to be the ratio of chain transfer agent (CTA) to initiator. Decreasing this ratio increased the rate of polymerization and had little noticeable effect on the control over molecular weight distribution. A ratio of CTA to initiator of unity was shown to give the best compromise between rate and control of the polymerization. Targeted degrees of polymerization (equivalent to ratios of monomer to CTA) had negligible effect on the rate of polymerization and polydispersity index (PDI). Performing the polymerization in the presence of solvent (up to 41.2% (w/w) in toluene) had no negative effect on the rate of polymerization. Indeed, marginally higher conversions and lower PDIs than for bulk polymerization were achieved for similar reaction times. A higher amount of toluene (66.6% (w/w)) induced a lower rate of polymerization, but the evolution of molecular weight and PDI were unaffected. Polymerizations performed in the presence of toluene, N,N-dimethylformamide, and methyl ethyl ketone showed that solvent polarity and aromaticity had no observable effect on the rate of polymerization and over the control of molecular weight distribution. The optimum conditions for the polymerization of MA, mediated by 2-ethylthiocarbonylsulfanyl-propionic acid ethyl ester at 50°C were found to be [CTA]/[AIBN] = 1/1 and ~40% solvent (w/w).


Acknowledgements

The authors acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) and Unilever (MW).


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