Random and sequential radical cotelomerizations of 3,3,3‐trifluoropropene (H2CCHCF3) with vinylidene fluoride (F2CCH2)

Kostov, G.; Boschet, Frédéric; Brandstadter, Stephan M.; Améduri, Bruno

doi:10.1002/pola.23455

Cited by 21 publications

(29 citation statements)

References 54 publications

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“…Actually, the released bulky perfluorinated alkene (Scheme 1) is too hindered to undergo any radical (co)polymerization with styrene or trifluoromethyl styrene, as evidenced by the absences of the signals at ca. −82 and −78 ppm assigned to CF 3 end‐groups in CF 3 CF 2 and CF(CF 3 ) 2 , respectively [54] and that of CF(CF 3 ) 2 expected at −184 ppm [54] . In addition, our results confirm the absence of any trifluoromethylation of the benzylic side of toluene as reported by Sato et al [43] …”

Section: Resultssupporting

confidence: 88%

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

Briou

Gimello

Totée

et al. 2020

Chemistry A European J

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The radical polymerization of styrene(St) initiated by at rifluoromethyl radicalg enerated from ap erfluorinated highly branched persistentr adical (PPFR) is presented with an isolated yield above7 0%.T he releaseo fCCF 3 radical occurred from at emperature above 85 8C. Deeper 1 Ha nd 19 FNMR spectroscopieso ft he resultingf luorinated polystyrenes (CF 3-PSts)e videnced the presence of both CF 3 endgroup of the PSt chain and the trifluoromethylation of the phenylr ing (in meta-positionm ainly).[ PPFR] 0 /[St] 0 initial molar ratios of 3:1, 3:10 and 3:100 led to variousm olar massesr anging from 1750t o5 400 gmol À1 in 70-86 %y ields. MALDI-TOF spectrometry of such CF 3-PSts highlighted polymeric distributions which evidenced differences between m/z fragments of 104 and 172 corresponding to styrene and trifluoromethyl styreneu nits,r espectively.S uch CF 3-PSt polymers werea lso compared to conventional PSts produced from the radical polymerization of St initiatedb yaperoxydicarbonate initiator.Amechanism of the polymerization is presented showing the formation of at rifluoromethyl styrene first, followed by its radical (co)polymerization with styrene. The thermal properties (thermals tability and glass transition temperature, T g)o ft hesep olymers were also compared and revealed am uch better thermals tabilityo ft he CF 3-PSt (10 %w eight loss at 356-376 8C) and a T g of around 70 8C.

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Section: Resultssupporting

confidence: 88%

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

Briou

Gimello

Totée

et al. 2020

Chemistry A European J

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“…We have found that r VDF = 1.20 ± 0.50 and r BDFE = 0.40 ± 0.15 at 75 °C showing that VDF is more reactive than BDFE and showing also that they are statistic copolymers as most of the copolymers of VDF 7. (a), 8 (c), 35–57 Compared with the reactivity ratios of other fluoromonomers able to copolymerize with VDF (Table 4), the value of the reactivity ratio of BDFE was found to be between that of HCFCF 2 (0.50) and that of F 2 CCF(CH 2 ) 3 SAc (0.41) (Table 4) but r VDF is much lower ( r VDF = 0.70 or 0.60, respectively vs. 1.20 in that present study). These values can be compared with the reactivity of other fluoromonomers able to copolymerize with VDF (Table 4),7 (a), 8 (c), 35–57 and with the values arising from the radical copolymerization of TFE with BDFE ( r TFE = 0.82; r BDFE = 0.24) 20…”

Section: Resultsmentioning

confidence: 83%

Radical copolymerization of vinylidene fluoride with 1‐bromo‐2,2‐difluoroethylene

Kostov¹,

Sauguet²,

Améduri³

et al. 2010

J. Polym. Sci. A Polym. Chem.

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The radical copolymerization of vinylidene fluoride (VDF) and 1-bromo-2,2-difluoroethylene (BDFE) in 1,1,1,3,3-pentafluorobutane solution at different monomer molar ratios (ranging from 96/4 to 25/75 mol %) and initiated by tert-butylperoxypivalate (TBPPI, mainly) is presented. Poly(VDF-co-BDFE) copolymers of various aspects (from white powders to yellow viscous liquids) were produced depending on the copolymer compositions. The microstructures of the obtained copolymers were characterized by 19 F and 1 H NMR spectroscopy and by elementary analysis and these techniques enabled one to assess the contents of both comonomers in the produced copolymers. VDF was shown to be more incorporated in the copolymer than BDFE. From the extended Kelen and Tudos method, the kinetics of the radical copolymerization led to the determination of the reactivity ratios, r i , of both comonomers (r VDF ¼ 1.20 6 0.50 and r BDFE ¼ 0.40 6 0.15 at 75 C) showing that VDF is more reactive than BDFE. Alfrey-Price's Q and e values of BDFE monomer were calculated to be 0.009 (from Q VDF ¼ 0.008) or 0.019 (from Q VDF ¼ 0.015) and þ1.22 (vs. e VDF ¼ 0.40) or þ1.37 (vs. e VDF ¼ 0.50), respectively, indicating that BDFE is an electron-accepting monomer. Statistic cooligomers were produced with molar masses ranging from 1,800 to 5,500 g/mol (assessed by GPC with polystyrene standards). A further evidence of the successful copolymerization was shown by the selective reduction of bromine atoms in poly(VDF-co-BDFE) cooligomers that led to analog PVDF. The thermal properties of the poly(VDF-co-BDFE) cooligomers were also determined and those containing a high VDF amount exhibited a high thermal stability. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3964-3976, 2010.

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“…We considered R 0 as the ratio of the initial CTA concentration to the initial overall VDF concentration (i.e., the total VDF initial moles by volume of the liquid phase) [ 36 ]. …”

Section: Resultsmentioning

confidence: 99%

“…We considered R0 as the ratio of the initial CTA concentration to the initial overall VDF concentration (i.e., the total VDF initial moles by volume of the liquid phase) [36]. David and Gosselain's law [33] enabled us to assess the transfer constant to 2-mercaptoethanol of 40 at 140 °C.…”

Section: Kinetics Of Radical Telomerisation Of Vdf With 2-mercaptoethanolmentioning

confidence: 99%

Unexpected Radical Telomerisation of Vinylidene Fluoride with 2-Mercaptoethanol

2021

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The radical telomerisation of vinylidene fluoride (VDF) with 2-mercaptoethanol as chain transfer agent (CTA) was studied to synthesise fluorinated telomers which bear a hydroxy end-group, such as H(VDF)nS(CH2)2OH, under thermal (di-tert-butyl peroxide as the initiator) or photochemical initiations. A careful structural study of a typical H-VDF-S(CH2)2OH telomer was performed by 1H and 19F NMR spectroscopy. These analytical methods allowed us to explore the selective addition of the thiyl radical onto the hydrogenated side of VDF, and the telomer containing one VDF unit was obtained selectively. Surprisingly, for higher [VDF]o initial concentrations, a monoadduct telomer was produced as well as PVDF homopolymer. This feature was related to the fast consumption of the CTA. The kinetics of radical telomerisation led to a quite high transfer constant of the CTA (40 at 140 °C) that evidences the formation of a monoadduct as the only telomer formed.

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Random and sequential radical cotelomerizations of 3,3,3‐trifluoropropene (H₂CCHCF₃) with vinylidene fluoride (F₂CCH₂)

Abstract: The synthesis of original co-telomers based on 3,3,3-trifluoropropene (TFP) and vinylidene

Cited by 21 publications

References 54 publications

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

May Trifluoromethylation and Polymerization of Styrene Occur from a Perfluorinated Persistent Radical (PPFR)?

Radical copolymerization of vinylidene fluoride with 1‐bromo‐2,2‐difluoroethylene

Unexpected Radical Telomerisation of Vinylidene Fluoride with 2-Mercaptoethanol

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