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Computational Radical Polymerization
Michelle L. Coote
ARC Centre of Excellence in Free Radical Chemistry and Biotechnology
Research School of Chemistry
Australian National University
Canberra ACT 0200, Australia
Computational quantum chemistry is rapidly establishing itself as a powerful tool for
studying the mechanism and kinetics of radical polymerization processes. Unlike
experiment, it allows for the direct calculation of the rate coefficients of individual
reactions within a complicated multi-step process, without empirical parameters or
(kinetic) model-based assumptions. It also provides useful mechanistic information, such as transition state geometries, charge distributions and radical stabilization energies.
However, to obtain accurate results for these radical reactions, high-level composite
procedures are required, and these are currently too computationally intensive to be
applied to polymeric systems. We have been working toward adapting computational
chemistry for radical polymerization, through the selection of accurate yet economic
methods, and the design of suitable model systems capable of mimicking the behaviour of real polymeric systems.
Recently, we reported the first chemically accurate computational predictions of propagation rate coefficients in free-radical polymerization and the first ab initio simulation of an entire polymerization process. We have also utilized our computational approach in the design of a new class of multipurpose RAFT agent, a new type of controlled radical polymerization process and a new method for incorporating phosphorus atoms into the backbones of olefinic polymers. In this talk we outline our computational methodology, discuss its accuracy and outstanding problems, and highlight some of its applications.