Synthesis and microstructural characterization of low-molar-mass poly(vinylidene fluoride)

Copolymers based on 2,2,2-trifluoroethyl -fluoroacrylate (FATRIFE) and 2,2,2-trichlororoethyl -fluoroacrylate (FATRICE) were synthesized in good yields by radical process initiated by tert-butyl 2,2-dimethylperoxypropanoate. Molar composition of the obtained poly(FATRIFE-co-FATRICE) copolymers were assessed by means of 19 F nuclear magnetic resonance spectroscopy. The reactivity ratios, r i , of both comonomers were determined from the Kelen-Tüdos method (r FATRIFE = 0.56 ± 0.01 and r FATRICE = 0.11 ± 0.01 at 74°C) showing that FATRIFE is the more reactive monomer. Thermal and optical properties of the resulting polymers were examined. Thermogravimetric analyses showed good thermal stability, thermal decomposition occurring from 300 °C to 310 °C for all copolymers. Moreover, the glass transition temperature of copolymers varied from 113 °C to 127 °C, increasing with the molar ratio of FATRICE in the copolymers. The refractive indices were measured at 633, 1320 and 1550 nm, ranging from 1.375 to 1.4812 at 1550 nm and were found to increase linearly with the chlorine content of the copolymer, allowing a precise control of the refractive index.

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“…Acetonitrile induces very low transfer reactions [42][43][44] and solubilize both monomers and copolymers.…”

Section: Copolymerizationmentioning

confidence: 99%

Free radical copolymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate and tert‐butyl α‐trifluoromethylacrylate: Thermal and optical properties of the copolymers

Cracowski

Montembault

Hardy

et al. 2008

J. Polym. Sci. A Polym. Chem.

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“…In analogy the signals in the 19 F-NMR spectrum of PVDF between -91 and -96 ppm are attributed to the regular head to tail addition of monomers and the signals observed between -113 to -117 ppm (A and B signals in Fig. 18b, respectively) are attributed to the irregular monomer additions [73]. Calculations showed that PVDF polymerized at 115°C contained 8 mol.-% irregular monomer additions which was 2 -3 % higher than the average value (5.5 %) calculated for the product of polymerizations at 40°C.…”

Section: Characterization Of Pvdf Polymersmentioning

confidence: 91%

“…The amounts of irregular monomer additions were calculated by 1 H-NMR and 19 F-NMR spectrums measured with 600 MHz spectrometer in DMSO-d6 [73]. In 1 H-NMR spectra of PVDF the signal at 2.9 ppm is attributed to -F 2 -CH 2 -CF 2 -, resulting from the regular addition of the monomers, while the signal at 2.2 ppm is assigned to a -CF 2 -CH 2 -CH 2 -moieties that arose from irregular addition of the monomers (Fig.…”

Section: Characterization Of Pvdf Polymersmentioning

confidence: 99%

Polymerization of Vinylidene Difluoride in Supercritical Carbon Dioxide

Beginn

Najjar

Ellmann

et al. 2011

Chemie Ingenieur Technik

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The preparation of poly(vinylidene fluoride) in supercritical carbon dioxide is investigated with mixtures of carbon dioxide and vinylidene difluoride alone, as well as in the presence of macromolecular stabilizers my means of turbidimetry, and gravimetric measurements. The morphology of the obtained poly(vinylidene fluoride) powder, and the molecular weight distribution of the polymer was used to distinguish between homogeneous polymerization, precipitation polymerization, and dispersion polymerization due to the added macromolecular stabilizers. The effect of stabilizers and reaction conditions on the predominating locus of polymerization is discussed.

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“…Figure 2 represents the 19 F NMR spectrum of a poly(VDF-co-BDFO) copolymer from a feed content of VDF/BDFO with the molar ratio 90.8/9.2 (run #3 in Table 1). First, this spectrum showed a characteristic signal centered at À91.4 ppm (-CH 2 -CF 2 -CH 2 -) resulting from the headto-tail addition of VDF (i.e., normal VDF addition [33,42,[46][47][48] ). Moreover, a series of other signals, also assigned to the difluoromethylene of VDF, located at À94.8, À113.8 and À116.0 ppm, were attributed to the difluoromethylene group in -(CH 2 -CF 2 )-(CF 2 -CH 2 )-(CH 2 -CF 2 )-(CH 2 -, -(CH 2 -CF 2 )-(CF 2 -CH 2 )-(CH 2 -and -(CH 2 -CF 2 )-(CF 2 -CH 2 )-(CH 2 -CF 2 )-, respectively ( Table 2).…”

Section: Radical Homopolymerization Ofmentioning

confidence: 99%

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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Synthesis and microstructural characterization of low-molar-mass poly(vinylidene fluoride)

Cited by 69 publications

References 14 publications

Free radical copolymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate and tert‐butyl α‐trifluoromethylacrylate: Thermal and optical properties of the copolymers

Free radical copolymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate and tert‐butyl α‐trifluoromethylacrylate: Thermal and optical properties of the copolymers

Polymerization of Vinylidene Difluoride in Supercritical Carbon Dioxide

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

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