Living/controlled free radical copolymerization of chlorotrifluoroethene and butyl vinyl ether under 60Co γ-ray irradiation in the presence of S-benzyl O-ethyl dithiocarbonate

Abstract

Living/controlled free radical copolymerization of chlorotrifluoroethene and butyl vinyl ether has been successfully achieved at room temperature under (60)Co γ-ray irradiation in the presence of S-benzyl O-ethyl dithiocarbonate. The alternating and block copolymers have been obtained with well-defined molecular weights and narrow molecular weight distributions.

Conventional and RAFT Copolymerization of Tetrafluoroethylene with Isobutyl Vinyl Ether

“…Furthermore, such low Ð values are compared to higher ones achieved by RAFT copolymerization of CTFE 24 (or HFP 25 ) with VEs, initiated by 60 Co irradiation. Tobolsky's law, relating conversion to reaction time, is supplied in equation (11) ln…”

“…TFE (co)polymers are usually synthesized via radical (co)polymerization 12,13 , and a number of methods are available to conduct controlled radical polymerization (also known as reversible-deactivation radical polymerization, RDRP) [14][15][16] . Significant studies have been reported in the last couple of decades on the controlled homo-and copolymerization of fluoroolefins using iodine transfer polymerization (ITP) [17][18][19][20][21] and Reversible addition-fragmentation chain transfer (RAFT/MADIX) methods [22][23][24][25][26][27][28][29] . RAFT/MADIX polymerization proceeds via a degenerative chain transfer (DT) mechanism in which a double equilibrium favors the control of the polymerization with high efficiency (Scheme 1) [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] .…”

“…Significant studies have been reported in the last couple of decades on the controlled homo-and copolymerization of fluoroolefins using iodine transfer polymerization (ITP) [17][18][19][20][21] and Reversible addition-fragmentation chain transfer (RAFT/MADIX) methods [22][23][24][25][26][27][28][29] . RAFT/MADIX polymerization proceeds via a degenerative chain transfer (DT) mechanism in which a double equilibrium favors the control of the polymerization with high efficiency (Scheme 1) [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] . Recently, O-ethyl-S-(1methyloxycarbonyl)ethyl xanthate as chain transfer agent (CTA) has been successfully applied in the RDRP of vinylidene fluoride (VDF) 22,23,[27][28][29]38 , and the limits to which VDF lends itself to controlled polymerization has been explored.…”

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].…”

“…Later on, another similar copolymerization process of perfluoro(methyl vinyl ether) and VDF was presented by Girard et al [9]. 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].…”