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Ab Initio Calculation of the Propagation Kinetics in Free Radical Polymerization: Chain Length and Penultimate Effects
Author(s) -
Moscatelli Davide,
Dossi Marco,
Cavallotti Carlo,
Storti Giuseppe
Publication year - 2007
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.200751338
Subject(s) - ab initio , kinetics , chain (unit) , polymerization , radical polymerization , materials science , computational chemistry , chain propagation , chemistry , polymer chemistry , thermodynamics , polymer , organic chemistry , physics , classical mechanics , quantum mechanics
Summary: In this work, Quantum Chemistry is applied to investigate the propagation kinetics in free radical polymerization. Energies, structures and transition state geometries are determined using density functional theory, which combines good accuracy with reasonable computational demand. In particular, B3LYP functional is used to evaluate the exchange and correlation energy with the 6‐311+G(d,p) basis sets. The capabilities of the approach with respect to the prediction of the kinetic constants of elementary processes relevant to polymeric systems (propagation reactions) is first tested using literature experimental data as reference values.1 Namely, two different monomers of industrial relevance have been selected, acrylonitrile and styrene. For such systems, the effect of chain‐length on the propagation rate coefficient is examined. Finally, for the selected monomer pair, the relative reactivity (so‐called reactivity ratios) is also analyzed, in particular considering the penultimate effect.