Synthesis and properties of a well-defined copolymer of chlorotrifluoroethylene and N-vinylpyrrolidone by xanthate-mediated radical copolymerization under ⁶⁰Co γ-ray irradiation

Abstract

RAFT/MADIX polymerization of CTFE and NVP under 60Co γ-ray irradiation with S-benzyl O-ethyl dithiocarbonate (BEDTC).

Cobalt-Mediated Radical Copolymerization of Chlorotrifluoroethylene and Vinyl Acetate

“…However, perfluoropolymers often suffer from poor solubility in common organic solvents and have difficult processing characteristics. As a result, an increasing amount of research in recent years have been focusing on the copolymerization of fluoroolefins and non-fluoro monomers to prepare semi-fluorinated polymers [6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25]. Iodine transfer terpolymerization (ITP) was developed in the late 1970s by Tatemoto et al [26] and believed to be a suitable controlled radical polymerization (CRP) method for the polymerization of some fluoroolefins, especially for vinylidene fluoride (VDF) [27,28,29].…”

“…In 2011, Liu et al achieved the living/controlled radical copolymerization of CTFE and butyl vinyl ether (BVE) at room temperature under 60 Co γ-ray irradiation with an O -ethyl xanthate [11]. Later in 2014, living/controlled radical copolymerization of CTFE and N -vinylpyrrolidone under 60 Co γ-ray irradiation with S-benzyl O -ethyl dithiocarbonate as the RAFT/MADIX agent at room temperature was reported [6]. As mentioned before, VDF has been involved in many CRP reactions.…”

A New Strategy for the Synthesis of Fluorinated Polyurethane

“…As we know, living/controlled radical polymerization is a powerful tool for the synthesis of well-defined polymers with predetermined molar mass, low dispersity, and various architectures [67,68,69,70]. Some successful works focusing on the living/controlled radical (co)polymerization for fluoroolefins, such as vinylidene fluoride (VDF), tetrafluoroethylene (TFE), 3,3,3-trifluoropropene (TFP), hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE), have been done in recent years [71,72,73,74,75,76,77,78,79,80,81]. RAFT/MADIX polymerization initiated by γ-rays seems to be very suitable for fluoroolefins.…”

“…Another fluorinated copolymer, poly(HFP-alt-BVE), was prepared under similar conditions in 2013 [77]. Later in 2014, RAFT/MADIX copolymerization of CTFE and N-vinylpyrrolidone under 60 Co γ-ray irradiation with S–benzyl O–ethyl dithiocarbonate (BEDTC) as the mediating agent was reported [78]. However, there is a problem that could not be ignored in the polymerization reactions irradiated by 60 Co γ-ray.…”

Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

“…In addition, 2-methylene-1,3-dioxepane was copolymerized with several fluoroalkenes (R f CHvCH 2 ) using azobis(isobutyronitrile) (AIBN) as an initiator: 1 H NMR spectroscopy proved that all the obtained polymers were effectively alternating copolymers of caprolactone and fluoroalkene. 45 Compared to conventional radical polymerization, the formation of (semi)fluorinated copolymers relying on controlled radical polymerizations (mainly ATRP, 46 NMP and RAFT/ MADIX 36,[47][48][49][50][51][52][53] ) still remain limited, although among these controlled radical polymerizations, RAFT/MADIX polymerization has been known to be one of the most versatile methods for providing structurally well-controlled macromolecules. 54 Destarac and co-workers 49 have reported the RAFT/MADIX copolymerization of vinyl trifluoroacetate with vinyl acetate or vinyl pivalate using a xanthate chain transfer agent (O-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate), also employing vinyl trifluoroacetate as a vinyl acetate co-monomer in the RAFT/MADIX process in order to increase the solubility of poly(vinyl esters) in supercritical CO 2 .…”