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Polymers 2017, 9(12), 702; https://doi.org/10.3390/polym9120702

Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

1
Institut Charles Gerhardt Montpellier, University of Montpellier, CNRS, ENSCM, Place Eugène Bataillon, 34095 Montpellier CEDEX 5, France
2
Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, CNRS, UPS, INPT, 205 route de Narbonne, BP 44099, 31077 Toulouse CEDEX 4, France
3
Center for Education and Research on Macromolecules (CERM), University of Liege, CESAM Research Unit, Sart-Tilman B6a, 4000 Liege, Belgium
4
Institut Universitaire de France, 1, rue Descartes, 75231 Paris CEDEX 05, France
Present address: Department of Chemistry, Indian Institute of Technology Bhilai, GEC Campus, Sejbahar, Raipur 492015, Chhattisgarh, India.
*
Authors to whom correspondence should be addressed.
Received: 7 November 2017 / Revised: 3 December 2017 / Accepted: 7 December 2017 / Published: 12 December 2017
(This article belongs to the Special Issue Fluorinated Polymers)
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Abstract

The organometallic-mediated radical polymerization (OMRP) of vinyl acetate (VAc) and its OMR copolymerization (OMRcoP) with tert-butyl 2-trifluoromethylacrylate (MAF-TBE) mediated by Co(SAL)2 (SAL = 2-formylphenolato or deprotonated salicylaldehyde) produced relatively well-defined PVAc and poly(VAc-alt-MAF-TBE) copolymers at moderate temperature (<40 °C) in bulk. The resulting alternating copolymer was characterized by 1H-, 13C- and 19F-nuclear magnetic resonance (NMR) spectroscopies, and by size exclusion chromatography. The linear first-order kinetic plot, the linear evolutions of the molar mass with total monomer conversion, and the relatively low dispersity (Đ~1.55) of the resulting copolymers suggest that this cobalt complex provides some degree of control over the copolymerization of VAc and MAF-TBE. Compared to the previously investigated cobalt complex OMRP mediators having a fully oxygen-based first coordination sphere, this study emphasizes a few peculiarities of Co(SAL)2: a lower ability to trap radical chains as compared to Co(acac)2 and the absence of catalytic chain transfer reactions, which dominates polymerizations carried in the presence of 9-oxyphenalenone cobalt derivative. View Full-Text
Keywords: alternating copolymers; cobalt complex; fluoropolymer; organometallic mediated radical polymerization; poly(vinyl acetate) alternating copolymers; cobalt complex; fluoropolymer; organometallic mediated radical polymerization; poly(vinyl acetate)
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Banerjee, S.; Bellan, E.V.; Gayet, F.; Debuigne, A.; Detrembleur, C.; Poli, R.; Améduri, B.; Ladmiral, V. Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate. Polymers 2017, 9, 702.

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