Fluoropolymer synthesis in supercritical carbon dioxide

Du, Libin; Kelly, Jennifer Y.; Roberts, George W.; DeSimone, Joseph M.

doi:10.1016/j.supflu.2008.11.011

Cited by 110 publications

(53 citation statements)

References 56 publications

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“…13(A)]. All the spectra exhibit a diffraction feature at 2y ¼ [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] . Similar to other TFE-based copolymers, such characteristic profile can be deconvoluted into two peaks at 2y ¼ 18.06 and 16.8 , 41,42 which are assignable to the crystalline and amorphous scatterings of the polymer chains.…”

Section: Effect Of Reaction Timementioning

confidence: 99%

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Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

Yuan

Zhao

et al. 2011

J of Applied Polymer Sci

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Tetrafluoroethylene (TFE) and perfluoropropylvinyl ether (PPVE) were copolymerized in supercritical carbon dioxide (sc-CO 2 ) with a perfluorodiacyl initiator bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP). The resultant copolymers with stable perfluoroalkyl end groups were obtained, avoiding the decomposition during processing and applications. Reactivity ratios of TFE and PPVE were first reported. The r TFE and r PPVE values are about 8 and 0.08, respectively. Such parameters are significant for the modification of PTFE through copolymerization of TFE and PPVE. It is found that through increasing the reaction pressure from 8.5 to 25 MPa, while r TFE increases by 12.0%, r PPVE decreases by 9.0%, which should be ascribed to the enhancement of the polarity of CO 2 under high pressures.Because the reactivity of TFE is by two orders of magnitude higher than that of PPVE; on one hand, the copolymerization rate falls rapidly with the decrease of TFE feed ratio; on the other hand, TFE content in the copolymer decreases with the reaction time. All copolymers containing different fractions of PPVE enjoy outstanding thermal stability. The DSC result indicates that there exist two forms of crystals with highly regular molecular arrangement or less ordered chain packing which is disturbed by perfluoropropyl pendants.

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Section: Effect Of Reaction Timementioning

confidence: 99%

“…8,9 Particularly, supercritical carbon dioxide (sc-CO 2 ) is of tremendous interest in the syntheses of polymers as it is cheap, facile to obtain, inflammable, and environment friendly. What's more, polymers can be isolated from the reaction mixture via simple depressurization, resulting in clean and dry polymer products.…”

Section: Introductionmentioning

confidence: 99%

Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

Yuan

Zhao

et al. 2011

J of Applied Polymer Sci

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“…CO 2 has been exploited as a solvent for polymerisations [7,8], as a foaming agent [1,[9][10][11][12][13], for precipitation/separation [14], particle formation [15,16] and encapsulation [17].…”

Section: Introductionmentioning

confidence: 99%

High-pressure rheological analysis of CO2-induced melting point depression and viscosity reduction of poly(ε-caprolactone)

Curia

Focatiis

Howdle

2015

Polymer

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(2015) High-pressure rheological analysis of CO2-induced melting point depression and viscosity reduction of poly(ε-caprolactone). Polymer, Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/45413/1/curia_polymer2015_preprint.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the Creative Commons Attribution Non-commercial No Derivatives licence and may be reused according to the conditions of the licence. For more details see: http://creativecommons.org/licenses/by-nc-nd/2.5/ A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. Furthermore, a significant decrease in the viscosity of two PCL grades with different molecular weight (M n~1 0 kDa and 80 kDa) was also detected upon increasing the CO 2 pressure to 300 bar.Experimental viscosity data were fitted to the Carreau model to quantify the extent of the plasticising effects on the zero-shear viscosity and relaxation time under different conditions. Similar analyses were conducted under high-pressure nitrogen, to compare the effects obtained in the presence of a non-plasticising gas.

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“…In recent years interest in the use of compressed CO2 as a reaction medium or plasticiser for polymer synthesis and processing has increased steeply (32)(33)(34)(35). CO2 has been exploited as a solvent for polymerisations (36,37), as a foaming agent (32,38), for precipitation/separation (39), particle formation (40,41) and encapsulation (42). High-pressure CO2 is a good solvent for many small molecules and it is very effective at plasticising and effectively liquefying many polymers at temperatures below their glass transition temperature (Tg) and melting point (Tm) (33,41,(43)(44)(45)(46)(47)(48)(49)(50)(51)(52), therefore opening up new opportunities for polymer synthesis and modification.…”

Section: Introductionmentioning

confidence: 99%

Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO ₂

Curia

Barclay

Torrón

et al. 2015

Phil. Trans. R. Soc. A.

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SummaryWe present a novel near ambient temperature approach to telechelic renewable polyesters by exploiting the unique properties of supercritical CO2 (scCO2). Bio-based commercially available monomers have been polymerised and functional telechelic materials with targeted molecular weight were prepared by end-capping the chains with molecules containing reactive moieties in a one-pot reaction. The use of scCO2 as a reaction medium facilitates the effective use of Candida Antarctica Lipase B (CaLB) as a catalyst at a temperature as low as 35°C, hence avoiding side reactions, maintaining the end-capper functionality and preserving the enzyme activity. The functionalised polymer products have been characterised by 1 H-NMR, MALDI-TOF, GPC and DSC in order to carefully assess their structural and thermal properties. We demonstrate that telechelic materials can be produced enzymatically at mild temperatures, in a solvent-free system and using renewably sourced monomers without pre-modification, by exploiting the unique properties of scCO2. The macromolecules we prepare are ideal green precursors that can be further reacted to prepare useful bio-derived films and coatings.

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Fluoropolymer synthesis in supercritical carbon dioxide

Cited by 110 publications

References 56 publications

Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

High-pressure rheological analysis of CO2-induced melting point depression and viscosity reduction of poly(ε-caprolactone)

Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO ₂

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Fluoropolymer synthesis in supercritical carbon dioxide

Cited by 110 publications

References 56 publications

Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

Copolymerizations of tetrafluoroethylene and perfluoropropylvinyl ether in supercritical carbon dioxide: Polymer synthesis, characterization, and thermal properties

High-pressure rheological analysis of CO2-induced melting point depression and viscosity reduction of poly(ε-caprolactone)

Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO 2

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Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO ₂