Premium
Quantum Chemistry: A Powerful Tool in Polymer Reaction Engineering
Author(s) -
Dossi Marco,
Storti Giuseppe,
Moscatelli Davide
Publication year - 2011
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.201000056
Subject(s) - methyl methacrylate , copolymer , acrylonitrile , methyl acrylate , polymerization , polymer chemistry , methacrylate , radical polymerization , styrene , kinetics , polymer , reaction rate constant , materials science , chemistry , computational chemistry , organic chemistry , physics , quantum mechanics
Abstract Summary: The potentials of computational techniques based on quantum mechanics, to support and complement the experimental analysis, are examined. Mechanisms and reaction paths involved in the free radical polymerization of widely used monomers are studied through a computational approach based on Density Functional Theory (DFT). First, the attention is focused on the initiation kinetics in order to evaluate the role of the initiators in the polymerization process. Methyl acrylate, methyl methacrylate, acrylonitrile, and styrene homopolymerization using different initiators are studied. Then, propagation kinetics is investigated. In particular, the propagation kinetic rate constants for different kinds of acrylates, methacrylates and acetates are calculated and compared with experimental data reported in the literature. The same computational approach is applied to the study of secondary reactions (backbiting, beta‐scission) occurring during free radical polymerizations. Finally, the same methodologies are applied to copolymer systems, with emphasis on the evaluation of the role of penultimate effect. The copolymers vinyl acetate/methyl methacrylate and styrene/methyl methacrylate are investigated as system characterized by weak and strong penultimate effect, respectively.