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A Density Functional Theory Study of Poly (vinyl chloride) (PVC) Free Radical Polymerization
Author(s) -
Cuccato Danilo,
Dossi Marco,
Moscatelli Davide,
Storti Giuseppe
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.201000057
Subject(s) - branching (polymer chemistry) , vinyl chloride , density functional theory , polymerization , intramolecular force , reaction rate constant , radical polymerization , polymer , polymer chemistry , materials science , chemistry , molecule , computational chemistry , kinetics , kinetic chain length , thermodynamics , organic chemistry , copolymer , physics , quantum mechanics
Summary: Quantum chemistry was applied to the free radical polymerization of Vinyl Chloride with the aim of elucidating the reaction kinetics and especially the formation of structural defects and low molecular weight polymer. The radical reactions were studied using the Density Functional Theory. All calculations were performed with B3LYP functionals and in particular the 6‐31G(d,p) basis set was selected to evaluate the exchange and correlation energies. The computational method was first validated by predicting the rate constant of the propagation step and comparing the calculated values to experimental ones. Then intramolecular chain transfer, β‐scission and branching reactions were also investigated, due to their direct connection with the production of defects in the growing chains. A comparison of the evaluated kinetic constants of such secondary reactions with other computational evaluations and experimental data was finally made.