A Quantum-Chemical Approach to Understanding Reversible Addition Fragmentation Chain-Transfer Polymerization

Michelle L. Coote

doi:10.1071/CH04083

RESEARCH ARTICLE

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A Quantum-Chemical Approach to Understanding Reversible Addition Fragmentation Chain-Transfer Polymerization

Michelle L. Coote ^A

+ Author Affiliations

- Author Affiliations

^A Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia. Email: mcoote@rsc.anu.edu.au

Australian Journal of Chemistry 57(12) 1125-1132 https://doi.org/10.1071/CH04083
Submitted: 30 March 2004 Accepted: 22 July 2004 Published: 8 December 2004

Abstract

This article highlights some of the recent contributions that computational quantum chemistry has made to the understanding of the reversible addition fragmentation chain transfer (RAFT) polymerization process. These include recent studies of rate retardation in cumyl dithiobenzoate mediated polymerization of styrene and methyl acrylate and the xanthate mediated polymerization of vinyl acetate, and studies of the effects of substituents on the addition and fragmentation reactions in prototypical systems and polymer-related systems. The accuracy and applicability of theoretical procedures for studying free-radical polymerization are also discussed, and the methodology is evaluated using the homopropagation rate coefficient of methyl acrylate as a test case. The review concludes with a brief discussion of possible future developments in the field.

Acknowledgments

The author is thankful for generous allocations of computing time on the Compaq Alphaserver and the Linux Cluster of the Australian Partnership for Advanced Computing and the Australian National University Supercomputer Facility. Useful discussions with Prof. Leo Radom, and provision of an Australian Research Council postdoctoral fellowship are also gratefully acknowledged.

References

^* This is given by the formula k_tr = k_add[k_β/(k_β + k_–add)]. It should be noted that this formula is only correct if the quasi-steady-state assumption holds, if the adduct does not undergo side-reactions, and if the fragmentation step is irreversible. In real systems, and particularly in retarded polymerizations, the relationship between the observed transfer coefficient and the individual rate coefficients would be more complex.

A Quantum-Chemical Approach to Understanding Reversible Addition Fragmentation Chain-Transfer Polymerization

Abstract

Acknowledgments

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