RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

Lily A. Dayter; Kate A. Murphy; Devon A. Shipp

doi:10.1071/CH13375

RESEARCH ARTICLE

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RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

Lily A. Dayter ^A , Kate A. Murphy ^A and Devon A. Shipp ^A ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry and Biomolecular Science, and Center for Advanced Materials Processing, Clarkson University, Potsdam, NY 13699-5810, USA.

^B Corresponding author. Email: dshipp@clarkson.edu

Australian Journal of Chemistry 66(12) 1564-1569 https://doi.org/10.1071/CH13375
Submitted: 18 July 2013 Accepted: 27 September 2013 Published: 25 October 2013

Abstract

A single reversible addition–fragmentation chain transfer (RAFT) agent, malonate N,N-diphenyldithiocarbamate (MDP-DTC) is shown to successfully mediate the polymerization of several monomers with greatly differing reactivities in radical/RAFT polymerizations, including both vinyl acetate and styrene. The chain transfer constants (C_tr) for MDP-DTC for both these monomers were evaluated; these were found to be ~2.7 in styrene and ~26 in vinyl acetate, indicating moderate control over styrene polymerization and good control of vinyl acetate polymerization. In particular, the MDP-DTC RAFT agent allowed for the synthesis of block copolymers of these two monomers without the need for protonation/deprotonation switching, as has been previously developed with N-(4-pyridinyl)-N-methyldithiocarbamate RAFT agents, or other end-group transformations. The thermal properties of the block copolymers were studied using differential scanning calorimetry, and those with sufficiently high molecular weight and styrene composition appear to undergo phase separation. Thus, MDP-DTC may be useful for the production of other block copolymers consisting of monomers with highly dissimilar reactivities.

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RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

Abstract

References

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