Alternating radical copolymerization of vinyl acetate and tert-butyl-2-trifluoromethacrylate. (July 2018)

• Record Type: Journal Article
• Authors: Banerjee, Sanjib; Ladmiral, Vincent; Totée, Cédric; Améduri, Bruno
• Is Part Of: European polymer journal. Volume 104(2018)
• Page Start: 164
• Page End: 169
• Publication Date: 2018-07
• Subjects: Alternating copolymerization -- Fluoropolymer -- Radical polymerization -- Thermal properties -- Vinyl acetate; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2018.04.037
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Alternating radical copolymerization of vinyl acetate and tert -butyl-2-trifluoromethacrylate was achieved using an azo initiator. Highlights: Alternating copolymerization of a fluoromonomer with a polar monomer was achieved. Strictly 1:1 alternance throughout the entire monomer feed range (0.05–0.95). Reactivity ratios of both the monomers were determined to very close zero. Abstract: Alternating conventional radical copolymerization of tert -butyl-2-trifluoromethacrylate (a non-homopolymerizable fluoromonomer under radical conditions) with vinyl acetate, initiated by 2, 2′-azo-bis(4-methoxy-2, 4-dimethyl valeronitrile) at 40 °C is presented. The study of the kinetics of the copolymerization using various [VAc]0 /[MAF-TBE]0 feeds showed that an equimolar feed of comonomers led to the highest apparent copolymerization rate ( kapp = 4 × 10 −4 s −1 ). The resulting copolymers had a nearly perfect alternating structure over a very wide range of comonomer feed compositions ( fMAF-TBE = 0.05–0.95) until complete consumption of one of the monomers. The reactivity ratios were measured to be: rMAF-TBE = 0 and rVAc = 0.014 at 40 °C and the Alfrey and Price parameters for MAF-TBE were calculated ( QMAF-TBE = 1.18 and eMAF-TBE = 1.84).