Fluoropolymers tetrafluoroethylene

Keywords Supercritical carbon dioxide Fluoropolymers Tetrafluoroethylene Vinylidene fluoride... 

In 1972 Du Pont introduced Teflon PFA, a copolymer of tetrafluoroethylene and perfluorofpropyl vinyl ether) (CF2 = CFOCF2CF2CF3). Similar materials are now also produeed by Asahi Glass, Daikin, Hoechst and Monteflos and are commonly referred to as PFA fluoropolymers. In 1994 Hoechst introduced Hostaflon PFA-N, claimed to have significantly lower melt viscosities than earlier grades of material. 

Temperature dependence (related to the temperature dependence of the conformational structure and the morphology of polymers) of the radiation effect on various fluoropolymers e.g., poly (tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluoroalkylvinylether), and poly(tetrafluoroethylene-co-ethylene) copolymers has been reported by Tabata [419]. Hill et al. [420] have investigated the effect of environment and temperature on the radiolysis of FEP. While the irradiation is carried out at temperatures above the glass transition temperature of FEP, cross-linking reactions predominate over chain scission or degradation. Forsythe et al. [421]... 

The first reactions of fluorinated olefins in C02 reported by DeSimone et al. involved the free-radical telomerization of 1,1 -difluoroethylene29 and tetrafluor-oethylene.30 This work demonstrated the feasibility of carrying out free-radical reactions of highly electrophilic species in solvents other than expensive fluorocarbons and environmentally detrimental chlorofluorocarbons. The work has since been more broadly applied to the synthesis of tetrafluoroethylene-based, nonaqueous grades of fluoropolymers,31,32 such as poly(tetrafluoroethylene-co-peduoropropylvinyl ether) (Scheme 2). These reactions were typically carried out at between 20 and 40% solids in C02 at initial pressures of between 100 and 150 bars, and 30-35°C (Table 10.1). 

CF20—)m (—CF2CF20—) . This fluoropolymer has better low-temperature properties than Krytox, but is more expensive. Fomblin Z is made by photochemical polymerization of a mixture of oxygen and tetrafluoroethylene to prepare the random copolymer. The methylene oxide unit (—CF20—) imparts even more extraordinary low-temperature properties than those derived from vibration and free rotation of other perfluoroether linkages. 

PVC, another widely used polymer for wire and cable insulation, crosslinks under irradiation in an inert atmosphere. When irradiated in air, scission predominates.To make cross-linking dominant, multifunctional monomers, such as trifunctional acrylates and methacrylates, must be added. Fluoropolymers, such as copol5miers of ethylene and tetrafluoroethylene (ETFE), or polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), are widely used in wire and cable insulations. They are relatively easy to process and have excellent chemical and thermal resistance, but tend to creep, crack, and possess low mechanical stress at temperatures near their melting points. Radiation has been found to improve their mechanical properties and crack resistance. Ethylene propylene rubber (EPR) has also been used for wire and cable insulation. When blended with thermoplastic polyefins, such as low density polyethylene (LDPE), its processibility improves significantly. The typical addition of LDPE is 10%. Ethylene propylene copolymers and terpolymers with high PE content can be cross-linked by irradiation. ... 

Terpolymer blends containing poly(tetrafluoroethylene-co-perfluoro-a-olefins) and platinum nanoparticles imbedded in Nation 1100 fluoropolymer resin were previously prepared by the authors (1) and used as electrodes in fuel cells. 

Fluoropolymers, such as copolymer of ethylene and tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), are widely used in wire and cable insulations. They are relatively easy to process and have excellent chemical and thermal resistance, but tend to creep, crack and possess low mechanical stress at temperatures near their melting points. Radiation has been found to improve their mechanical properties and crack resistance.36... 

Firstly from a comparison of the integrated area ratios for the F ls and Cls levels and secondly from the individual components of the Cis levels. This readily establishes that the materials are copolymers of ethylene and tetrafluoroethylene which are largely alternating in character and that the outermost surface sampled by ESCA is identical in composition to the bulk. This is shown in Table 4 where a comparison is drawn with compositions determined by standard microanalysis (carbon by combustion, fluorine by potassium fusion). ESCA is highly competitive as a routine means of establishing compositions for fluoropolymers in particular, in terms of accuracy, nondestructive nature and speed. 

Romack, T. J. DeSimone, J. M. Synthesis of Tetrafluoroethylene-Based, Non-aqueous Fluoropolymers in Supercritical Carbon Dioxide. Macromolecules 1995, 28, 8429-8431. 

TFE — Tetrafluoroethylene, a perfluorinated monomer used as a feedstock for the production of PTFE and as a comonomer for the production of a variety of other fluoropolymers. 

Chloroform is used to produce chlorodiflu-oromethane (HCFC-22), which is used as a refrigerant (70%) and to synthesize the monomer tetrafluoroethylene (30%). Fluoropolymers that use HCFC-22 as a feedstock are strong. But the uses for refrigerant will be phased out beginning 2010. The major uses for carbon tetrachloride were to make aerosol propellants such as dichlorodifluo-romethane (CFC-12) and trichlorofluo-romethane (CFC-11). The volume of carbon tetrachloride decreases to almost zero as CFC-11 and 12 will be phased out. 

The major commercial fluoropolymers are made by homopolymerization of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE),vinyhdene fluoride (VF2), and vinyl fluoride (VF), or by co-polymerization of these monomers with hexafluoropropylene (HFP), perfluoro(propyl vinyl ether) (PPVE), per-fluoro(methyl vinyl ether) (PMVE), or ethylene. The polymers are formed by free-radical polymerization in water or fluorinated solvents. 

Currently, there is concern about the use of ammonium perfluorooctanoate (APFO), also known as C8 , which is necessary for the manufacture of fluorinated plastics and elastomers in water. C8 is a perfluorinated anionic surfactant used as a dispersing agent in the polymerization and copolymerization of many fluoropolymers, including poly(tetrafluoroethylene) (PTFE), poly(vinylidene... 

Fluoro-substituted Polymers. The fluoropolymers were between the first to be studied by the XPS technique because the substitution of F atom(s) in the -CH.-CH - unit induced very large modifications in the XPS core level spectra (shifts up to 8eV) that were easy to detect and interpret. The XPS valence band spectra of similar compounds, namely poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVF2), poly(trifluoroethylene) (PVF3), and poly(tetrafluoroethylene) (PTFE) (26, 27, 28) are also expected to reflect the induction of such strong electronic effects at the valence molecular level. 

In this entry, fluoropolymer means a polymer that consists of partially or fully fluorinated olefinic monomers, such as vinylidene fluoride (CH2=CF2) and tetrafluor-oethylene (CF2=CF2). Commercial fluoropolymers include homopolymers and copolymers. Homopolymers contain 99wt.% or more one monomer and lwt.% or less of another monomer according to the convention by American Society for Testing Materials. Copolymers contain 1 wt.% or more of one or more comonomers. The major commercial fluoropolymers are based on tetrafluoroethylene, vinylidene fluoride, and to a lesser extent chlorotrifluoroethylene. Examples of comonomers include perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoro-propyl vinyl ether (PPVE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), and perfluorobutyl ethylene (PFBE). 

Fluoropolymers discussed include polytetrafluoro-ethylene (PTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene polymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF). 

Polytetrafluoroethylene (PTFE Teflon) was discovered accidently by PlunkettCZ nd commercialized by DuPont in the 1940 s. This polymer has a solubility parameter of about 6H and a high melting point of 327°C and is not readily moldable. Poly-chlorotrifluoroethylene (CTFE, Kel-F), the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), polyvinylidene fluoride (PVDF, Kynar), the copolymer of tetrafluoroethylene and ethylene (ETFE), the copolymer of vinylidene fluoride and hexafluoroisobutylene (CM-1), perfluoroalkoxyethylene (PFA) and polyvinyl fluoride (PVF, Tedlar) are all more readily processed than PTFE. However, the lubricity and chemical resistance of these fluoropolymers is less than that of PTFE. 

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