Radical copolymerization of vinylidene fluoride with perfluoroalkylvinyl ethers

Otazaghine, Belkacem; Sauguet, L.; Boucher, Mario; Améduri, Bruno

doi:10.1016/j.eurpolymj.2005.02.015

Cited by 35 publications

(45 citation statements)

References 24 publications

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“…Figure 4 shows the results of the estimated reactivity ratios and the comparison of the calculated polymer composition with experimental data for the example of vinylidene fluoride (VF2) and perfluoro(methyl vinyl)ether (PMVE) copolymerization. The reactivity ratio values we obtained are very different from those reported in the original paper 61. It is important to note that a nonlinear parameter estimation algorithm is the statistically preferred approach versus the traditional methods of linearizing the Mayo–Lewis equation (e.g., the linear Fineman–Ross method) as discussed in detail by Tidwell and Mortimer 62.…”

Section: Literature Reviewcontrasting

confidence: 86%

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Polymerization Reactor Modeling in Industry

Mueller

Richards

Congalidis

2011

Macro Reaction Engineering

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This paper provides an industrial perspective for the development of polymer reaction engineering models and their application to create new materials, products, and improved or novel processes. The challenges specific to polymer reactor modeling are discussed in the context of articles and books that the authors have found useful. Four components of a polymer reactor model (kinetics, thermodynamics, transport effects, and particle dynamics) are discussed with illustrative examples. Finally typical outputs of polymer reactor models are shown to demonstrate that a first principles model supported and validated by experiments can be a very powerful tool for fundamental understanding of polymer reactors and is a recommended alternative to empirical methods and experimentation alone.magnified image

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Section: Literature Reviewcontrasting

confidence: 86%

“… Calculated (line) and experimental64, 61 (symbols) VF2 mole fraction in VF2/PMVE copolymer as a function of VF2 mole fraction in monomer mixture; fitted values of reactivity ratios are given in the figure title. …”

Section: Literature Reviewmentioning

confidence: 99%

Polymerization Reactor Modeling in Industry

Mueller

Richards

Congalidis

2011

Macro Reaction Engineering

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“…This observation confirms that BDFO was not able to homopolymerize, and the same behavior was observed for the radical copolymerization of VDF with perfluoroalkylvinyl ether, [51,52] trifluorovinyloxyaryl monomers, [53,54] 2-pentafluorosulfanyl-1,1,2-trifluoroethene [55] and with HFP. [56] Nevertheless, according to Table 1, it can be clearly observed that BDFO is reactive enough to be incorporated in sufficient amounts into poly(VDF-co-BDFO) copolymers.…”

Section: As Shown In Equationsupporting

confidence: 71%

Radical Copolymerization of Vinylidene Fluoride with 8‐Bromo‐1H,1H,2H‐perfluorooct‐1‐ene: Microstructure, Crosslinking and Thermal Properties

Sauguet¹,

Améduri²,

Boutevin³

2007

Macro Chemistry & Physics

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An original synthesis of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene (BDFO) and its radical copolymerization with vinylidene fluoride (VDF), initiated by 2,5‐bis(tert‐butylperoxy)‐2,5‐dimethylhexane at 134 °C, are presented. The fluorinated bromoalkene was obtained by dehydrobromination of 1,8‐dibromo‐1H,1H,2H,2H‐perfluorooctane in a satisfactory yield. Although BDFO did not homopolymerize under radical initiation, it did copolymerize with VDF. The compositions of the resulting random type copolymers were calculated by means of 19F NMR spectroscopy and allowed the quantification of the respective amounts of both comonomers in the copolymers, showing good incorporation of the brominated monomer. Nevertheless, obtaining PVDF copolymers containing a high molar percentage of BDFO in good yields was difficult to achieve from initial molar ratios of BDFO higher than 9.2 mol‐%. Radical terpolymerization of VDF, BDFO and hexafluoropropene (HFP) was also successfully achieved. BDFO contents in these co‐ or terpolymers ranged from 3.6 to 12.2 mol‐%. The bromoalkene acted as a cure site monomer and the resulting poly(VDF‐co‐BDFO) copolymers were crosslinked via the bromine atom in the presence of a triallyl isocyanurate/peroxide system. The materials obtained led to more thermally stable copolymers than the uncured ones and their thermostabilities were compared to those of commercially available poly(VDF‐co‐HFP) copolymers crosslinked using diamines.magnified image

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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 vinylidene fluoride with perfluoroalkylvinyl ethers

Cited by 35 publications

References 24 publications

Polymerization Reactor Modeling in Industry

Polymerization Reactor Modeling in Industry

Radical Copolymerization of Vinylidene Fluoride with 8‐Bromo‐1H,1H,2H‐perfluorooct‐1‐ene: Microstructure, Crosslinking and Thermal Properties

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

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