Synthesis of 3,3,3-trifluoropropene telomers and their modification into fluorosurfactants

Boschet, Frédéric; Kostov, G.; Améduri, Bruno; Jackson, Andrew C.; Boutevin, Bernard

doi:10.1039/c1py00394a

Cited by 21 publications

(12 citation statements)

References 32 publications

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“…C 3 F 7 OCF 2 CF 2 CH 2 CH 2 SO 3 H, C 6 F 13 CH 2 CF 2 CH 2 CH 2 SO 3 H), sulfamido betaine and sulfamido amine oxide surfactants derived from C 3 F 7 OCF 2 CF 2 CH 2 CH 2 SO 2 Cl and C 4 F 9 (CH 2 CF 2 ) (1 or 2) CH 2 CH 2 SO 2 Cl have been synthesized [411,412], as well as oligo(vinylidene fluoride) telomers C n F 2n+1 (CH 2 CF 2 ) x CH 2 COOH (n = 2, 4; x = 2) [413]. Various surfactants that combine an F-isopropyl terminal group with pending CF 3 groups located on alternate carbons along the hydrophobic backbone had surface tensions comparable to that of PFOA [414]. Sequential block copolymerization of vinylidene fluoride, trifluoropropene and vinyl acetate led to surfactants that combine a terminal C 6 F 13 chain, isolated CF 2 groups in the backbone and pending CF 3 groups [415].…”

Section: There Is a Need For Genuine Breakthrough Products And Technomentioning

confidence: 94%

Per- and polyfluorinated substances (PFASs): Environmental challenges

Krafft

Riess²

2015

Current Opinion in Colloid & Interface Science

232

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Section: There Is a Need For Genuine Breakthrough Products And Technomentioning

confidence: 94%

Per- and polyfluorinated substances (PFASs): Environmental challenges

Krafft

Riess²

2015

Current Opinion in Colloid & Interface Science

232

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“…Because of the presence of degradable methylene and methyne groups, the TFP unit has been used as a starting material to synthesize nonbioaccumulable fluorinated materials. 36 The fluorosurfactant synthesis was achieved from the radical telomerization of 3,3,3-trifluoropropene (TFP) with 2iodoperfluoropropane 31,35,36 (initiated by di-tert-butylperoxide), followed by chemical modification of the resulting monoadduct telomer. The overall synthesis route for this surfactant is shown in Scheme 1.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Fluoropolymer Nanoparticles Prepared Using Trifluoropropene Telomer Based Fluorosurfactants

Lopez

Améduri

et al. 2020

Langmuir

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A fluorosurfactant based on 3,3,3-trifluoropropene (TFP) telomer was synthesized as an environmentally friendly alternative to perfluorooctanoic acid (PFOA) using TFP and 2-iodoperfluoropropane ((CF3)2CF–I) as starting materials. TFP telomerization was initiated by addition of di-tert-butylperoxide in the presence of (CF3)2CF–I as a chain transfer agent. The surfactant was obtained by modification of the iodine end-group on the TFP telomer to form an allylic functionality followed by the addition of thioglycolic acid via a thiol–ene reaction. The resulting fluorosurfactant exhibited a lower critical micellar concentration (CMC = 0.87 g·L–1) than that of PFOA (CMC = 3.0 g·L–1). This surfactant was used to prepare fluoropolymer nanoparticles by solvent evaporation from a solution composed of the surfacant and poly[2-(perfluorobutyl)ethyl methacrylate]. The oil-in-water emulsion was initially formed due to the adsorption of the surfactant molecules at the oil/water interface and subsequently converted into a nanoparticle suspension after solvent evaporation. Because of the strong hydrophobic interactions between the fluorinated surfactant tail and fluoropolymer, the obtained nanoparticle suspension was quite stable against water dialysis.

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“…Hence, a growing interest in the synthesis of short perfluoroalkyl chain surfactants was noted, [33][34][35][36] especially since the 3M company developed perfluorobutane sulfonyl compounds. [37][38][39] Various strategies to synthesize potentially non-bio accumulable alternatives to PFOA have been reported: 40 (1) chemicals bearing either a CF 3 O or (CF 3 ) 2 N end-group, 41 (2) compounds produced from small perfluorinated chains with non-ionic oligoethylene oxide or carbohydrate, 36,42 (3) carboxylate gemini surfactants, 43,44 (4) vinylidene fluoride (VDF) telomers with short 1-iodoperfluoroalkane where methylene groups may act as "weak" degradable points, 45,46 (5) 3,3,3-trifluoropropene (TFP) telomers from either 1-iodoperfluoroalkanes or other chain transfer agents, 47 (6) VDF and TFP cotelomers, 48 and (7) compounds derived from oligo(hexafluoropropylene oxide), oligo(HFPO). 49 Interestingly, these perfluorooligoethers were shown to be nontoxic and nonbioaccumulable 50 and thus offer further opportunities to synthesize more environmentally friendly fluorinated surfactants.…”

Section: Introductionmentioning

confidence: 99%

A new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide) diblock surfactant obtained by radical reactions

et al. 2015

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The synthesis and characterization of a new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide), oligo(HFPO)-b-oligo(PEG), diblock co-oligomer are presented. First, the model reactions dealing with the radical addition of 1-iodoperfluorohexane (C 6 F 13 I) onto allyl alcohol and allyl-O-PEG-OCH 3 were optimized in terms of the choice of the initiator (azobisisobutyronitrile [AIBN], tert-butylperoxypivalate [TBBPi], and benzoyl peroxide [BPO]) and of the solvent, temperature, and time. Allyl-O-PEG-OCH 3 was obtained from the etherification of ω-hydroxy-PEG with allyl bromide. End-capping of oligo(HFPO) with PEG was successfully achieved by the radical addition of 1-iodoperfluoropropyl-2-oligo(hexafluoropropylene oxide) [oligo(HFPO)-CF(CF 3 )CF 2 I] onto allyl-O-PEG-OCH 3 using the best conditions of the model reactions. Although TBPPi failed and led to oligo(HFPO)-isobutyl iodide, AIBN and BPO yielded oligo (HFPO)-CH 2 CHICH 2 -oligo(PEG). The selective reduction of the latter compound led to oligo(HFPO)-boligo(PEG) in 77% yield, the surface tension properties of which were compared to those of commercially available ammonium perfluorooctanoate (APFO) and perfluorooctanoic acid (PFOA). Its critical micelle concentration was 0.04 g mol −1 . All models, intermediates, and diblock co-oligomers were characterized by 1 H, 19 F, and 13 C NMR spectroscopy as well as matrix assisted laser desorption ionization (MALDI) and atmospheric pressure solids analysis probe (ASAP) time-of-flight mass spectrometry (TOF-MS). † Electronic supplementary information (ESI) available. See Scheme 1 Synthesis of oligo(hexafluoropropylene oxide)-b-polyethylene glycol, oligo(HFPO)-b-PEG diblock surfactant by radical addition of [oligo(HFPO)] primary iodide onto allyl PEG followed by a selective reduction of the iodine atom. Paper Polymer Chemistry 80 | Polym. Chem., 2015, 6, 79-96This journal is

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Synthesis of 3,3,3-trifluoropropene telomers and their modification into fluorosurfactants

Abstract: Original fluorinated surfactants based on 3,3,3-trifluoropropene as alternatives to perfluorooctanoic acid (PFOA) were prepared and characterized.

Cited by 21 publications

References 32 publications

Per- and polyfluorinated substances (PFASs): Environmental challenges

Per- and polyfluorinated substances (PFASs): Environmental challenges

Fluoropolymer Nanoparticles Prepared Using Trifluoropropene Telomer Based Fluorosurfactants

A new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide) diblock surfactant obtained by radical reactions

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