Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Theis, A., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2006) Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX). Polymer, 47(4).

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Abstract

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25-3.25 (in the often employed expression kt(i,i)=kt0i-α) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of kt is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of kt as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of kt with conversion is more pronounced at increased chain lengths, with a strong decrease in kt exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800. © 2005 Elsevier Ltd. All rights reserved.

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ID Code: 99134
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :58
Export Date: 5 September 2016
CODEN: POLMA
Correspondence Address: Barner-Kowollik, C.; School of Chemical Engineering and Industrial Chemistry, Centre for Advanced Macromolecular Design, University of New South Wales, Sydney, NSW 2052, Australia; email: camd@unsw.edu.au
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Keywords: Living free radical polymerization (RAFT), Polymerization kinetics and mechanism, Vinyl acetate, Free radical polymerization, Living polymerization, Macromolecules, Monomers, Reaction kinetics, Esters, polymer science
DOI: 10.1016/j.polymer.2005.12.054
ISSN: 00323861
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 05 Oct 2016 04:59

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