Proton-conducting polymer electrolyte membranes based on fluoropolymers incorporating perfluorovinyl ether sulfonic acids and fluoroalkenes Synthesis and characterizations

International audienceThis paper presents the synthesis of new polymer electrolyte membranes based on fluoropolymers incorporating aromatic perfluorovinyl ether sulfonic acids. A novel synthetic route describing the preparation of perfluorovinyl ether monomer containing sulfonic functionalities, 4-[(alpha,beta,beta-trifluorovinyl)oxy]benzene sulfonic acid (TFVOBSA), is reported. The radical (co) and terpolymerization of 4-[(alpha,beta,beta-trifluorovinyl)oxy]benzene sulfonyl chloride (TFVOBSC) with 1,1-difluoroethylene (or vinylidene fluoride, VDF), hexafluoropropene (HFP), and perfluoromethyl vinyl ether (PMVE) is described. The terpolymers of TFVOBSC with VDF and HFP, or VDF and PMVE, were hydrolyzed and led also to original fluorinated terpolymers bearing sulfonic acid aromatic side-group. The terpolymers were characterized by 1H and 19F NMR spectroscopies, SEC, DSC and TGA. Membranes incorporating these functional fluoropolymers were prepared and the electrochemical (IEC, proton conductivity, swelling rates) properties were studied and discussed

Poly(fluoroacrylate)s with tunable surface hydrophobicity via radical copolymerization of 2,2,2-trifluoroethyl α-fluoroacrylate and 2-(trifluoromethyl)acrylic acid

International audienceThe synthesis of poly(fluoroacrylate)s with tunable wettability and improved adhesion for potential applicationas functional coatings was achieved via radical copolymerization of 2,2,2-trifluoroethylα-fluoroacrylate (FATRIFE) with 2-(trifluoromethyl)acrylic acid (MAF), an adhesion-promoting monomer.These copolymerizations, initiated by tert-butyl peroxypivalate at varying comonomer feed ([FATRIFE]0/[MAF]0) ratios led to a series of poly(FATRIFE-co-MAF) copolymers with different molar compositions infair to good conversions (32–87%) depending on the MAF feed content. The microstructures of the synthesizedpoly(FATRIFE-co-MAF) copolymers were determined by 19F NMR spectroscopy. Even at MAFfeed contents higher than 50%, MAF incorporation into the copolymers was lower than 50%, since MAFdoes not undergo any homopolymerization under radical polymerization conditions. The reactivity ratiosof the (FATRIFE; MAF) monomer pair were also determined (rFATRIFE = 1.65 ± 0.07 and rMAF = 0 at 56 °C)evidencing the formation of statistical copolymers. Initiation involving a highly branched perfluorinatedradical that released a •CF3 radical enabled the demonstration of the regioselective attack of the latterradical onto the CH2 of FATRIFE. The resulting poly(FATRIFE-co-MAF) copolymers exhibited various glasstransition temperatures (Tgs) depending on their compositions. Tg values increased with increasing MAFcontents in the copolymer. In addition, their thermal stability (the temperature for 10% weight loss in air,Td10%) increased with increasing FATRIFE content in the copolymer and reached 348 °C (for that containing93 mol% FATRIFE). Finally, a high copolymer MAF content led to both a good adhesion onto metalsubstrates and to improved hydrophilicity, as revealed by the decrease of the water contact angle from107° (for a reference PFATRIFE homopolymer) to 81° (for a copolymer containing 42 mol% MAF)

Free Radical Copolymerization of 2,2,2-Trifluoroethyl a-Fluoroacrylate and tert-Butyl a-Trifluoromethylacrylate: Thermal and Optical Properties of the Copolymers

International audienceThe radical copolymerization of 2,2,2-trifluoroethyl a-fluoroacrylate (FATRIFE) with tert-butyl a-trifluoromethylacrylate (MAF-TBE) initiated by tertbutyl 2,2-dimethylperoxypropanoate was investigated in acetonitrile solution. A series of poly(FATRIFE-co-MAF-TBE) copolymers were synthesized with MAF-TBE compositions, determined by 19F NMR, ranging from 12 to 44 mol %. MAF-TBE incorporation was less than 50 mol % as this monomer underwent no radical homopolymerization. The obtained copolymers exhibited number-average molecular weights and polydispersity indexes ranging from 1.5 3 104 to 9.6 3 104 g/mol and from 1.5 to 3.1, respectively. The reactivity ratios were determined by the Kelen-Tu¨ dos method (rFATRIFE ¼ 1.71 6 0.01 and rMAF-TBE ¼ 0 at 74 8C) leading to random copolymers and alternating copolymers when the MAF-TBE molar ratio in copolymer is close to 50 mol %. Thermal and optical properties of the resulting polymers were examined. Glass transition temperatures of copolymers were varying from 89 to 108 8C. Modifying the compositions of these copolymers allowed a precise control over the refractive index measured at 633, 1320, and 1550 n

Synthesis and characterization of novel functional vinyl ethers that bear various groups

The synthesis of new functionalized vinyl ethers (VEs) by transetherification reaction between ethyl vinyl ether (EVE) and different alcohols is presented. An air-stable palladium catalyst generated in situ efficiently catalyzed the reaction leading to various VEs in a single step with good alcohol conversion (50–82%) and good VE yields (up to 75%). The reaction conditions were optimized in terms of the initial EVE/alcohol molar ratio, alcohol concentration, solvent, presence and nature of the ligand, amount of the catalyst, and choice of the metal precursor. All VEs were characterized using $^{1}$H and $^{13}$C NMR spectroscopy

Micromechanics of root development in soil

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Synthesis and characterization of novel functional vinyl ethers that bear various groups

The synthesis of new functionalized vinyl ethers (VEs) by transetherification reaction between ethyl vinyl ether (EVE) and different alcohols is presented. An air-stable palladium catalyst generated in situ efficiently catalyzed the reaction leading to various VEs in a single step with good alcohol conversion (50–82%) and good VE yields (up to 75%). The reaction conditions were optimized in terms of the initial EVE/alcohol molar ratio, alcohol concentration, solvent, presence and nature of the ligand, amount of the catalyst, and choice of the metal precursor. All VEs were characterized using $^{1}$H and $^{13}$C NMR spectroscopy

Recent development in the radical copolymerization of fluoroolefins and especially of vinylidene fluoride

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Recent Advances in the Telomerization of Vinylidene fluoride and application Therefrom

International audienceTelomerization involves a telogen or a transfer agent (X-Y), and one or more (n) molecules of a polymerizable compound M (called taxogen or monomer), under radical polymerization conditions, leading to X-(M)n-Y telomers, Various examples of telomerization of vinylidene fluoride, VDF (H2C=CF2) involving different X-Y transfer agents (hydroxylated, phosphonated3, halogenated have been investigated. The kinetics of telomerization enabled us to assess the transfer constants to the telogens and an increasing series regarding the efficiency of these transfer agents is supplied, correlated with the bond dissociation energy of the cleavable bond of the telogens: CF3CH2O

Challenges and Issues of Fluoropolymers

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