The first fluorous biphase hydrogenation catalyst incorporating a perfluoropolyalkylether: [RhCl(PPh2(C6H4C(O)OCH2CF(CF3)(OCF2CF(CF3))nF))3] with n=4–9

Friesen, Chadron M.; Montgomery, Craig D.; Temple, Sebastian A.J.U.

doi:10.1016/j.jfluchem.2012.09.001

Cited by 18 publications

(6 citation statements)

References 42 publications

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“…But this observation was not noted in any of the MALDI-TOF-MS spectra. 59 However, this macroradical could trap a radical initiator fragment or add onto an aromatic decomposition product. The product corresponding to the latter hypothesis was detected by 19 F NMR spectroscopy (Fig.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

confidence: 99%

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

et al. 2015

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“…Further, the chain length of the oligomeric poly(HFPO) can be adjusted to allow preferential solubility in organic or in fluorinated materials depending on the applications. It was also known that poly(HFPO) based aromatics readily formed emulsion in toluene:hexanes:Krytox (K6) [39]. The PFPAE derivatives have shown to be non-bioaccumulative and non-persistent compared to their perfluoroalkyl counterparts [40,41] and hence preferred candidates for stabilizing nanoemulsions for biomedical applications.…”

Section: Resultsmentioning

confidence: 99%

Design and formulation of nanoemulsions using 2-(poly(hexafluoropropylene oxide)) perfluoropropyl benzene in combination with linear perfluoro(polyethylene glycol dimethyl ether)

Mountain

Jelier

Bagia

et al. 2014

Journal of Fluorine Chemistry

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This is the first report where PFPAE aromatic conjugates and perfluoro(polyethylene glycol dimethyl ether) are combined and formulated as nanoemulsions with droplet size below 100 nm. A perfluoropolyalkylether (PFPAE) aromatic conjugate, 2-(poly(hexafluoropropylene oxide)) perfluoropropyl benzene, was used as fluorophilic-hydrophilic diblock (FLD) aimed at stabilizing perfluoro(polyethylene glycol dimethyl ether) nanoemulsions. Its effects on colloidal behaviors in triphasic (organic/fluorous/aqueous) nanoemulsions were studied. The addition of FLD construct to fluorous phase led to decrease in PFPAE nanoemulsion droplet size to as low as 85 nm. Prepared nanoemulsions showed high colloidal stability. Our results suggest that these materials represent viable novel approach to fluorous colloid systems design with potential for biomedical and synthetic applications.

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“…This resulting catalyst was used as a hydrogenation catalyst tested on 2-cyclohexen-1-one and could then be recycled. 67 However, no significant improvement was brought in comparison to the literature on this type of catalyst. Further investigation could be performed to increase the number of fluorinated chain per phosphine or to vary the molecular weights to modulate the properties of the catalyst.…”

Section: Condensation Reactionsmentioning

confidence: 92%

Diversity of Synthetic Approaches to Functionalized Perfluoropolyalkylether Polymers

et al. 2021

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Perfluoropolyalkylethers (PFPAEs) are a class of fluorinated polymers having −OCF2–, −OCF2CF2–, and −OCF2CF(CF3)– as common chain units. The ether linkages distinguish them from other famous fluorinated polymers such as poly(tetrafluoroethylene). Their higher mobility highlighted by below zero glass transition temperatures permit them to be noncrystalline, which makes them easy to use for many applications. They possess interesting tribological properties, combined with an excellent thermal and chemical stability, make them very useful as lubricants. However, after chemical modifications, they also demonstrated to be very useful in numerous applications as surfactants, electrolytes, high performance coatings, vitrimers, or microfluidic devices, to give a few examples. This Perspective aims to summarize all the chemical modifications reported on these PFPAEs to provide a new insight into their potential utility in emerging fields. Indeed, the end group can modulate the properties of PFPAE-based materials such as lubricity, superhydrophobicity, biofouling, antibacterial activity, amphiphilicity, and the ability to react further with comonomers under photochemical and thermal processes. It can also modulate their intrinsic properties such as viscosity and solubility in common organic solvents. The chemical modifications are sorted in five main parts: the condensation reactions, the nucleophilic reactions, the click chemistry reactions, the radical reactions, and finally reactions going through other mechanisms or requiring a multistep process. They can be employed as such or for further polymerization processes depending on the targeted application. Examples of applications are thoroughly described to demonstrate their current usefulness and to help provide direction for their future use.

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The first fluorous biphase hydrogenation catalyst incorporating a perfluoropolyalkylether: [RhCl(PPh2(C6H4C(O)OCH2CF(CF3)(OCF2CF(CF3))nF))3] with n=4–9

Cited by 18 publications

References 42 publications

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

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

Design and formulation of nanoemulsions using 2-(poly(hexafluoropropylene oxide)) perfluoropropyl benzene in combination with linear perfluoro(polyethylene glycol dimethyl ether)

Diversity of Synthetic Approaches to Functionalized Perfluoropolyalkylether Polymers

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