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Cobalt(II)-Mediated Alternating Radical Copolymerization of Tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate

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Cobalt(II)-Mediated Alternating Radical Copolymerization of Tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate polymers Article Bis(formylphenolato)cobalt(II)-Mediated Alternating Radical Copolymerization of tert-Butyl 2-Trifluoromethylacrylate with Vinyl Acetate Sanjib Banerjee 1,† ID , Ekaterina V. Bellan 2, Florence Gayet 2, Antoine Debuigne 3, Christophe Detrembleur 3, Rinaldo Poli 2,4,* ID , Bruno Améduri 1 ID and Vincent Ladmiral 1,* ID 1 Institut Charles Gerhardt Montpellier, University of Montpellier, CNRS, ENSCM, Place Eugène Bataillon, 34095 Montpellier CEDEX 5, France; [email protected] (S.B.); [email protected] (B.A.) 2 Laboratoire de Chimie de Coordination (LCC), Université de Toulouse, CNRS, UPS, INPT, 205 route de Narbonne, BP 44099, 31077 Toulouse CEDEX 4, France; [email protected] (E.V.B.); fl[email protected] (F.G.) 3 Center for Education and Research on Macromolecules (CERM), University of Liege, CESAM Research Unit, Sart-Tilman B6a, 4000 Liege, Belgium; [email protected] (A.D.); [email protected] (C.D.) 4 Institut Universitaire de France, 1, rue Descartes, 75231 Paris CEDEX 05, France * Correspondence: [email protected] (R.P.); [email protected] (V.L.) † Present address: Department of Chemistry, Indian Institute of Technology Bhilai, GEC Campus, Sejbahar, Raipur 492015, Chhattisgarh, India. Received: 7 November 2017; Accepted: 7 December 2017; Published: 12 December 2017 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. Keywords: alternating copolymers; cobalt complex; fluoropolymer; organometallic mediated radical polymerization; poly(vinyl acetate) 1. Introduction Fluoropolymers are unique materials, exhibiting outstanding properties, suitable for high-value added applications [1,2]. The incorporation of sequences of these polymers into a di- or multi-block [3] polymer architectures could lead to interesting materials of even greater value. Extensive research and development of different reversible deactivation radical polymerization (RDRP) techniques over the last two decades has enabled the facile synthesis of macromolecules with a high degree of complexity and well-defined architectures [4,5]. Although nitroxide-mediated radical polymerization (NMP) [6], atom transfer radical polymerization (ATRP) [7], iodine-transfer polymerization (ITP) [8–10] and reversible addition-fragmentation chain transfer (RAFT) polymerization [11–15] have been comparatively more studied, organometallic-mediated radical polymerization (OMRP) [16–20] has Polymers 2017, 9, 702; doi:10.3390/polym9120702 www.mdpi.com/journal/polymers Polymers 2017, 9, 702 2 of 11 Polymers 2017, 9, 702 2 of 11 polymerization [11–15] have been comparatively more studied, organometallic-mediated radical polymerization (OMRP) [16–20] has recently emerged as a potent RDRP technique for the recentlypolymerization emerged of as “less a potent activated RDRP monomers” technique for(LAMs) the polymerization, such as vinyl ofimidazolium “less activated salts monomers” [21,22] or (LAMs),vinyl amides such (such as vinyl as vinyl imidazolium pyrrolidone) salts [[23]21,22. Indeed,] or vinyl for amides these more (such difficult as vinyl monomers pyrrolidone), OMRP [23]. Indeed,and, in particular for these, morecobalt- difficultmediated monomers, radical polymerization OMRP and, (CMRP) in particular, [24] has cobalt-mediated proven very efficient, radical polymerizationopening synthetic (CMRP) routes [for24] homopolymers has proven very and efficient, block copolymers opening synthetic that could routes only for be homopolymers prepared with anda lower block level copolymers of control that or couldnot at only all by be preparedother RDRP with techniques. a lower level The of technique control or was not atpioneered all by other by RDRPWayland techniques. et al. [25] The using technique tetramesitylporphyrin was pioneered by for Wayland the controlled et al. [25 p]olymerization using tetramesitylporphyrin of acrylates, and for thesince controlled then several polymerization other CoII complexes of acrylates, with and different since then donor several atom other combinations CoII complexes and withcoordination different donorgeometries atom have combinations been reported. and coordination However, geometriesthe controlled have polymerization been reported. However,of LAMs theseems controlled so far polymerizationrestricted to complexes of LAMs seemssupported so far restrictedby chelating to complexes oxygen- supportedbased ligands, by chelating like the oxygen-based archetypic ligands,bis(acety likelacetonate)cobalt(II) the archetypic bis(acetylacetonate)cobalt(II) complex, Co(acac)2 (1a), first complex,introduced Co(acac) by Debuigne2 (1a), et first al. introduced[26] for the bycontrolled Debuigne polymerization et al. [26] for of the vinyl controlled acetate polymerization (VAc). To the ofbest vinyl of our acetate knowledge, (VAc). To investigations the best of our of knowledge,other CoII complexes investigations entirely of other supported CoII complexes by oxygen entirely atoms supportedin OMRP byhas oxygen, so far, atoms been limited in OMRP to has,the so1,1,1 far,-trifluoro been limited- and to the1,1,1,5,5,5 1,1,1-trifluoro--hexafluoropentan and 1,1,1,5,5,5-hexafluoropentan-2,4-dionates-2,4-dionates (1b and 1c) (1b[27]and, to1c )[27the], to2,2,6,6 the 2,2,6,6-tetramethylheptan-3,5-dionate-tetramethylheptan-3,5-dionate (1d) ([28]1d)[ and28] andto the to the 9-oxyphenalenone 9-oxyphenalenone derivative derivative ( (22))[ [29]29] (Scheme(Scheme1 1).). Scheme 1.1. SchematicSchematic representationsrepresentations of of the the cobalt(II) cobalt(II) complexes: complexes: bis(acetylacetonato)cobalt(II) bis(acetylacetonato)cobalt(II) (1a );(1a bis); (1,1,1-trifluoro-acetylacetonato)cobalt(II)bis (1,1,1-trifluoro-acetylacetonato)cobalt(II) (1b); bis(1,1,1,5,5,5-hexafluoropentan-2,4-dionato)-cobalt(II)(1b); bis(1,1,1,5,5,5-hexafluoropentan-2,4-dionato)- (cobalt(II)1c); bis(2,2,6,6-tetramethylheptan-3,5-dionato)cobalt(II) (1c); bis(2,2,6,6-tetramethylheptan-3,5-dionato)cobalt(II) (1d); bis(9-oxyphenalenonato)-cobalt(II) (1d); bis(9-oxyphenalenonato) (2),- and;cobalt(II) bis(2-formylphenolato)cobalt(II) (2), and; bis(2-formylphenolato)cobalt(II) (3). (3). We areare interestedinterested inin expandingexpanding thethe availableavailable arrayarray ofof cobalt(II)cobalt(II) complexescomplexes asas OMRPOMRP mediatorsmediators and toto understand understand how how the metalthe metal coordination coordination sphere sphere affects theaffects metal the controlling metal controlling ability, potentially ability, providingpotentially access providing to the access controlled to the polymerization controlled polymerization of new challenging of new monomers challenging such monomers as the fluorinated such as olefinsthe fluorinated [30,31]. Theolefins focus [30,31] of the. The present focus articleof the present is the assessment, article is the for assessment, the first time, for the of the first air-stable time, of the air-stable bis(2-formylphenolato)cobalt(II) complex (Co(SAL)2, 3, Scheme 1), where the bis(2-formylphenolato)cobalt(II) complex (Co(SAL)2, 3, Scheme1), where the 2-formylphenolate is the deprotonated2-formylphenolate form ofis salicylaldehyde.the deprotonated This form complex of salicylaldehyde. has already been This described complex in the has literature already [32 been,33] anddescribed is quite in easily the literature synthesized. [32,33] Its performancesand is quite ineasily the bulksynthesized. polymerization Its performances of VAc and in in the the bulk copolymerizationpolymerization of of VAcVAc and andtert -butylin the 2-trifluoromethylacrylate bulk copolymerization (MAF-TBE) of VAc are and evaluated tert-butyl here. The2-trifluoromethylacrylate combination of these (MAF two monomers-TBE) are evaluated was recently here. shown The combination to radically of polymerize these two inmonomers a strictly alternatingwas recently fashion shown (theirto radically reactivity polymerize ratios arein a essentiallystrictly alternating zero) [34 fashion] and to(their be reactivity well controlled ratios are by essentially zero) [34] and to be well controlled by Co(acac)2 [35]. Fluorinated copolymers containing Co(acac)2 [35]. Fluorinated copolymers containing 2-(trifluoromethyl)acrylic acid (MAF) and alkyl 2-trifluoromethacrylates2-(trifluoromethyl)acrylic (MAF-esters) acid (MAF) mayand alkyl have applications2-trifluoromethacrylates in molecularly (MAF
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