Center for Molecular Modeling - B. Van den Bossche

Ab Initio Study of Free-Radical Polymerization: Defect Structures in Poly(vinyl chloride)

wim — Mon, 03 Oct 2011 07:30:58 +0000

K. Van Cauter, B. Van den Bossche, V. Van Speybroeck, M. Waroquier

Macromolecules

40 (4), 1321-1331

2007

Abstract

The main reaction routes that lead to the formation of structural defects in PVC are studied on a theoretical basis with the BMK/6-311+G(3df,2p)//B3LYP/6-31+G(d) method. All studied reactions can be classified into four classes: the reactions following a head-to-head addition, intramolecular H-transfer (backbiting), and chain transfer reactions to polymer and to monomer. The head-to-tail propagation is the reference reaction for estimating the probability of the reaction routes leading to defect formation. Variations of chain length of the reacting polymer chain were taken into account in the calculations, leading to more than 100 studied reactions. The ab initio kinetic parameters, combined with typical monomer and polymer concentrations during suspension polymerization, serve as an input for the calculation of the defect concentrations that can be compared to the experimental data. This work supports the overall mechanism of defect formation during vinyl chloride polymerization as established experimentally.

DOI

http://dx.doi.org/10.1021/ma062174s

Private attachment

07 macromolecules 40(4)1321 van cauter.pdf

Formation of Structural Defects in Poly(Vinyl Chloride): a Microscopic Investigation

wim — Tue, 18 Oct 2011 08:12:01 +0000

K. Van Cauter, B. Van den Bossche, V. Van Speybroeck, M. Waroquier

Poster

Conference / event / venue

International Symposium on Radical Polymerization: Kinetics and Mechanism

Il Ciocco (Lucca) Tuscany, Italy

Sunday, 3 September, 2006 to Friday, 8 September, 2006

Bart Van Den Bossche

wim — Thu, 25 Aug 2011 12:51:04 +0000

Molecular modeling of elementary reactions leading to structural defects in PVC polymerisation / Moleculaire modellering van elementaire reacties die leiden tot structurele defecten bij PVC polymerisatie

wim — Wed, 24 Aug 2011 13:29:37 +0000

B. Van den Bossche

Master of Science in Civil Chemical Engineering

2006

Supervisors

Prof. Dr. Michel Waroquier, Prof. Dr. Guy B. Marin