期刊
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY
卷 32, 期 3, 页码 467-513出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/0144235X.2013.797277
关键词
quantum chemistry; molecular orbital calculations; density functional theory; kinetic modelling; radical polymerisation; free-radical copolymerisation; poly(vinyl chloride) defect structures; reversible addition fragmentation chain transfer (RAFT) polymerisation
资金
- Australian Research Council (ARC) under their Centres of Excellence Programme
- ARC Future Fellowship
Computational quantum chemistry can make valuable contributions to modelling and improving free radical polymerisation. At a microscopic level, it can assist in establishing reaction mechanisms and structure-reactivity trends; at a macroscopic level it can be used in the design and parameterisation of accurate kinetic models for process optimisation and control. This review outlines and critically evaluates various methodological approaches that have been employed in first principles prediction of rate coefficients in free radical polymerisation, examining in turn the choice of chemical model, electronic structure method, solvation modelling and the coupled issues of partition function evaluation and conformational analysis. It is shown that accurate and reliable predictions are possible but only if necessary precautions are taken into account. The practical value of accurate computational modelling of radical polymerisation kinetics is then illustrated through three representative case studies from the literature in which theory has been used to develop accurate kinetic models: free radical copolymerisation kinetics; defect structure formation in radical suspension polymerisation of vinyl chloride; and reversible addition fragmentation chain transfer polymerisation.
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