Radical Copolymerization of <i>α</i>‐Trifluoromethylacrylic Acid with Vinylidene Fluoride and Vinylidene Fluoride/Hexafluoropropene

Souzy, Renaud; Améduri, Bruno; Boutevin, Bernard

doi:10.1002/macp.200300091

Cited by 59 publications

(120 citation statements)

References 43 publications

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“…Indeed, molar amount of FMB in the copolymer up to 94% was reached whereas it is known that FMB does not homopolymerize25 under radical conditions. This may arise from the high pressure generated in the vessel and a similar observation was noted on the radical copolymerization of α‐trifluoromethacrylic acid (MAF) with VDF for which the gaseous VDF induced a high pressure and hence could produce copolymers with a high amount of MAF29 considering that MAF does not homopolymerize. Except in the case of the radical copolymerization of CTFE with vinyl ethers, which leads to alternating copolymers,2, 3, 18–20 such a tendency is similar to those of other radical copolymerizations of CTFE with different comonomers.…”

Section: Resultssupporting

confidence: 53%

Opening up the JCN toolbox

Saper¹

2009

J of Comparative Neurology

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For more than a decade, the Journal of Comparative Neurology has had a firm policy that we did not publish "methods" papers. The point of this policy was that we wanted our research articles to focus on new findings that enlighten us about aspects of the structure, function, and development of neural systems. We did not want to become a repository for papers that simply championed a new method but did not otherwise advance the field in a scientific sense.Yet, over the years, we were presented periodically with papers that provided important methodological advances, which we thought deserved broad attention. In most cases, we were able to persuade the authors to apply the advance to a scientific problem, to produce new data that would justify publishing the paper in JCN. This process, however, always felt awkward, and the resulting papers often were more notable for the methodological advance than the scientific advances.At our Editorial Board meeting last Fall, we therefore agreed that JCN would change its policy on publishing papers that focus on methodology. We still do not want to publish papers that simply describe a method, but we do want to bring forward a new category of papers that we hope will change the ways in which we do our work in a more broad generic sense, the JCN Toolbox.The hallmark of a Toolbox paper is that it should review critically an area of neuroscience methodology, potentially providing additional new methods or improvements but always putting them into perspective in ways that we hope will allow our readers to challenge, and perhaps change and improve, their own work. The first paper published under this new policy appeared in JCN in January of this year (Lavanex From this point forward, we will denote Toolbox papers with that designation, so that they are easier to identify. The paper by van den Pol and colleagues in the current issue is the first to carry the Toolbox label. This study reviews the use of viral vectors for introducing new genes into the brain and demonstrates a novel method for rapidly introducing new genes into neurons and permitting electrophysiological observations on transfected cells. We hope that this method, and variations that will be stimulated by this paper, will have broad application. We have other papers in the Toolbox series in the works and hope that we can stimulate our colleagues to contribute their best ideas for improving the ways in which we do our science through this category of publication. The groundbreaking series of papers that can result would surely become "must-read" material for neuroscientists and attract new readers to JCN, furthering our mission to publish the most exciting research in systems neuroscience.

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Section: Resultssupporting

confidence: 53%

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Saper¹

2009

J of Comparative Neurology

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“…One monomer commonly used is vinylidene fluoride (VDF), because its copolymers exhibit useful properties, such as the chemical inertness, the resistance to acids and to chemical agents, piezo‐, pyroelectrical, and gas‐barrier properties, and low toxicity. In fact, VDF has been copolymerized with various fluorinated monomers,4 and the resulting copolymers bear functionality such as hydroxy,4 carboxylic acid,23 acetoxy,4 thioacetoxy,4 sulfonyl fluoride,4 nitrile,4 bromine,24 or a pentafluorosulfonyl25 group.…”

Section: Introductionmentioning

confidence: 99%

Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Boyer

Améduri

2009

J. Polym. Sci. A Polym. Chem.

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The synthesis of poly(VDF-co-TFMA) copolymers (where VDF and TFMA stand for vinylidene fluoride and a-trifluoromethacrylic acid, respectively) by iodine transfer polymerization without any surfactant is presented. First, the synthesis and the control of the copolymerization of VDF and TFMA were investigated in the presence of two chain transfer agents, 1-perfluorohexyl iodide (C 6 F 13 I) and 1,4-diodoperfluorobutane (IC 4 F 8 I). TFMA monomer was incorporated in the copolymer in good yields. Moreover, the molecular weights of the resulting poly(VDF-co-TFMA) copolymers were in good agreement with the theoretical values for feed of TFMA/VDF ratios that ranged from 50/50 to 0/100 mol %, showing that TFMA does not disturb the controlled radical polymerization of VDF. The microstructures of the produced copolymers were characterized by 1 H and 19 F NMR to assess the amount of each comonomer, and the molecular weights and the end-groups of the copolymers. The results on the control of the copolymerization were compared to those obtained with and without the presences of TFMA and surfactant. The addition of a low amount of TFMA improved the control of the polymerization of VDF without using any surfactant. Also, the size of particles, assessed by light scattering, was smaller than 200 nm. The addition of TFMA in low proportions, that is, 5 to 10 mol %, enabled us to stabilize the particle size and to decrease the size by one order of magnitude. The emulsifying behavior of TFMA (in low amount in the copolymer, that is, \10 mol %) was similar to those achieved when a surfactant was added. Indeed, neither sedimentation nor destabilization was observed after several days. The reactivity ratios for r TFMA and r VDF were 0 and 1.6 at 80 C, respectively. V V C 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: [4710][4711][4712][4713][4714][4715][4716][4717][4718][4719][4720][4721][4722] 2009

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“…These values can be compared with the reactivity of other fluoromonomers able to be copolymerized with VDF (Table 5)21, 26–48 and with the values arising from the radical copolymerization of TFE with F 2 CCFOR F SO 2 F ( r TFE = 8.0 and r

_{C F_{2} CFOR F SO_{2} F}

= 0.08 at 45 °C,49 which evidences that the homopropagation of PFSVE did not occur), showing that VDF is less reactive than TFE, with respect to PFSVE.…”

Section: Resultsmentioning

confidence: 97%

Fluorinated copolymers and terpolymers based on vinylidene fluoride and bearing sulfonic acid side‐group

Sauguet

Améduri

Boutevin

2007

J. Polym. Sci. A Polym. Chem.

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The radical co‐ and terpolymerization of perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride (PFSVE) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF or VF2), hexafluoropropene (HFP), chlorotrifluoroethylene (CTFE), and bromotrifluoroethylene (BrTFE) is presented. Although PFSVE could not homopolymerize under radical initiation, it could be copolymerized in solution under a radical initiator with VDF, while its copolymerizations with HFP or CTFE led to oligomers in low yields. The terpolymerizations of PFSVE with VDF and HFP, with VDF and CTFE, or with VDF and BrTFE also led to original fluorinated terpolymers bearing sulfonyl fluoride side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature and the amount of the radical initiators, of the nature of solvents (fluorinated or nonhalogenated), and of the initial amounts of fluorinated comonomers. The different mol % contents of comonomers in the co‐ and terpolymers were assessed by 19F NMR spectroscopy. A wide range of co‐ and terpolymers containing mol % of PFSVE functional monomer ranging from 10 to 70% was produced. The kinetics of copolymerization of VDF with PFSVE enabled to assess the reactivity ratios of both comonomers: rVDF = 0.57 ± 0.15 and rPFSVE = 0.07 ± 0.04 at 120 °C. The thermal and physicochemical properties were also studied. Moreover, the glass transition temperatures (Tgs) of poly(VDF‐co‐PFSVE) copolymers containing different amounts of VDF and PFSVE were determined and the theoretical Tg of poly(PFSVE) homopolymer was deduced. Then, the hydrolysis of the SO2F into SO3H function was investigated and enabled the synthesis of fluorinated copolymers bearing sulfonic acid functions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1814–1834, 2007

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Radical Copolymerization of α‐Trifluoromethylacrylic Acid with Vinylidene Fluoride and Vinylidene Fluoride/Hexafluoropropene

Cited by 59 publications

References 43 publications

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Iodine transfer copolymerization of vinylidene fluoride and α‐trifluoromethacrylic acid in emulsion process without any surfactants

Fluorinated copolymers and terpolymers based on vinylidene fluoride and bearing sulfonic acid side‐group

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