Tetrafluoroethylene copolymer with

Commonly accepted practice restricts the term to plastics that serve engineering purposes and can be processed and reprocessed by injection and extrusion methods. This excludes the so-called specialty plastics, eg, fluorocarbon polymers and infusible film products such as Kapton and Upilex polyimide film, and thermosets including phenolics, epoxies, urea—formaldehydes, and silicones, some of which have been termed engineering plastics by other authors (4) (see Elastomers, synthetic-fluorocarbon elastomers Fluorine compounds, organic-tetrafluoroethylene copolymers with ethylene Phenolic resins Epoxy resins Amino resins and plastics). 

Hydrolysis of acyl fluoride end groups on hexa-fluoropropylene-tetrafluoroethylene copolymer with 1% water in a corrosion-resistant 28-mm intermeshing twin-screw extruder at 360°C. 

Xu, A., Zhao, J., Yuan, W. Z., Li, H., Zhang, H., Wang, L., Zhang, Y, Tetrafluoroethylene copolymers with sulfonyl fluoride pendants Syntheses in supercritical carbon dioxide, polymerization behaviors, and properties. Macromol. Chem. Phys. 2011, 212 (14), 1497-1509. 

The equimolar copolymer of ethylene and tetrafluoroethylene is isomeric with poly(vinyhdene fluoride) but has a higher melting point (16,17) and a lower dielectric loss (18,19) (see Fluorine compounds, organic-poly(VINYLIDENE fluoride)). A copolymer with the degree of alternation of about 0.88 was used to study the stmcture (20). Its unit cell was determined by x-ray diffraction. Despite irregularities in the chain stmcture and low crystallinity, a unit cell and stmcture was derived that gave a calculated crystalline density of 1.9 g/cm. The unit cell is befleved to be orthorhombic or monoclinic (a = 0.96 nm, b = 0.925 nm, c = 0.50 nm 7 = 96%. 

Ethylene—tetrafluoroethylene copolymers respond weU to melt bonding to untreated aluminum, steel, and copper with peel strengths above 3.5 kN/m (20 Ibf/in.). Eor melt bonding to itself, hot-plate welding is used. The material is heated to 271—276°C, and the parts are pressed together during cooling. 

Uses. Vinyhdene fluoride is used for the manufacture of PVDF and for copolymerization with many fluorinated monomers. One commercially significant use is the manufacture of high performance fluoroelastomers that include copolymers of VDF with hexafluoropropylene (HFP) (62) or chlorotrifluoroethylene (CTFE) (63) and terpolymers with HEP and tetrafluoroethylene (TEE) (64) (see Elastomers, synthetic-fluorocarbon elastomers). There is intense commercial interest in thermoplastic copolymers of VDE with HEP (65,66), CTEE (67), or TEE (68). Less common are copolymers with trifluoroethene (69), 3,3,3-trifluoro-2-trifluoromethylpropene (70), or hexafluoroacetone (71). Thermoplastic terpolymers of VDE, HEP, and TEE are also of interest as coatings and film. A thermoplastic elastomer that has an elastomeric VDE copolymer chain as backbone and a grafted PVDE side chain has been developed (72). 

Fig. 11. Effect of polyolefin primers on bond strength of ethyl cyanoacrylate to plastics. All assemblies tested in accordance with ASTM D 4501 (block shear method). ETFE = ethylene tetrafluoroethylene copolymer LDPE = low-density polyethylene PFA = polyper-fluoroalkoxycthylene PBT = polybutylene terephthalate, PMP = polymethylpentene PPS = polyphenylene sulfide PP = polypropylene PS = polystyrene PTFE = polytetrafluoroethylene PU = polyurethane. From ref. [73].

Silastic LS 420, possessing approximately Q.6%-0.9% pendant vinyl groups, was blended with Kynar 7201, a vinylidene fluoride copolymer with tetrafluoroethylene (Atochem), in the presence of triallylisocyanurate (TAIC) and DAP containing a small amount of benzoyl peroxide in the DAP fraction. 

Fluorinated polymers, especially polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and perfluorinated alkyl vinyl ethers (PFAVE) as well as other fluorine-containing polymers are well known as materials with unique inertness. However, fluorinated polymers with functional groups are of much more interest because they combine the merits of pefluorinated materials and functional polymers (the terms functional monomer/ polymer will be used in this chapter to mean monomer/polymer containing functional groups, respectively). Such materials can be used, e.g., as ion exchange membranes for chlorine-alkali and fuel cells, gas separation membranes, solid polymeric superacid catalysts and polymeric reagents for various organic reactions, and chemical sensors. Of course, fully fluorinated materials are exceptionally inert, but at the same time are the most complicated to produce. 

Screening tests were conducted on potential construction materials. The candidate materials evaluated included the following polytetrafluoroethylene (PTFE, TFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy-alkanes (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (E-CTFE), poly vinylidene fluoride (PVDF), polypropylene (PP), and polyvinyl chloride (PVC). These materials were chosen based on cost, availability, and information from manufacturers on compatibility with acid solutions. 

Terpolymers made from two different olefins and CO are known. They were first described in Brubaker s initial patent and involved the free radical initiated terpolymerization of CO and C2H with another olefin such as propylene, isobutylene, butadiene, vinyl acetate, diethyl maleate or tetrafluoroethylene More recently, in another patent, Hammer has described the free radical initiated terpolymerization of CO and C2H with vinyl esters, vinyl ethers or methyl methacrylate 26Reaction temperatures of 180-200 °C and a combined pressure of 186 MPa were employed. Typically a CO QH4 olefin molar ratio of 10 65 25 was observed in the terpolymers. In other patents, Hammer 27,28) has described the formation of copolymers with pendant epoxy groups by the free radical initiated polymerization of CO, QH4, vinyl acetate and glycidyl methacrylate. Reaction conditions similar to those stated above were employed, and a typical CO C2H vinyl acetate glycidyl methacrylate molar ratio of 10 65 20 5 was observed in the product polymer. 

The need for highly fluorinated thermoplastic polymers that, unlike PTFE, could be fabricated by conventional melt-processing methods led to the development of a group of resins that are copolymers of tetrafluoroethylene (TFE) with other perflu-orinated monomers. Commercially, the copolymer of TFE and hexafluoropropylene (HFP) is commonly known as fluorinated ethylene propylene (FEP). Copolymerization of TFE with perfluoropropylvinyl ether (PPVE) leads to PFA resins, and copolymerization of TFE with perfluoromethylvinyl ether (PMVE) produces MFA resins. 

The compilation of such data constituted a firm basis that was used to study a specific and more complicated system the elucidation of the electronic structure of a copolymer of ethylene (48%) and tetrafluoroethylene (52%) whose synthesis was conducted in order to maximize the alternating sequences. The valence band spectrum of such a compound (Figure 8) was found very similar to the one measured e.g. for poly(vinylidene fluoride). But, by looking to the fine details of the spectrum, by simulating the valence band of a block copolymer (by addition of PE and PTFE spectra), and by comparison with model calculations, it was possible to show that the C-C band width and the distance F2s-top of the C-C band were characteristic of an ethylene-tetrafluoro-ethylene copolymer with dominant alternant structure (28). 

Perfluoroalkylvinyl ethers form an important class of monomers in that they are used as comonomers for the modihcation of the properties of homofluoropolymers in addition to their broad nse in copolymers with TFE and other monomers. They are capable of snppressing the crystallization of PTFE efficiently, which imparts usefnl mechanical properties to lower molecular weight of polytetrafluoroethylene polymers. Copolymers of PAVEs and tetrafluoroethylene are thermally stable as PTEE homopolymers. Commercially significant monomers are perfluoropropylvinyl ether and perflnoromethylvinyl ether (PMVE), used for the production of a variety of perflnoroalkoxy resins. 

Perfluoroalkoxy resin (PFA) Copolymer of tetrafluoroethylene (TFE) with perfluoro(propylvinyl ether), an engineering thermoplastic characterized by excellent thermal stability, release properties, low friction and toughness. Its performance is comparable to poiytetrafluoroethylene (PTFE) with the difference that it is melt processible. 

WAXD scans from unhydrolysed polymer, -SO F, reveal that the polymer is semicrystalline. (Figure 2) This result is similar to the behavior observed in copolymers of tetrafluoroethylene, (TFE) with hexafluoropropylene or perfluoropropylvinyl ether. As the EW increases, the molar ratio of TFE to comonomer increases and the amount of crystallinity also increases. The amount of crystallinity, deduced from the relative intensity of the amorphous halo and crystalline peak, ranges between 0 and 40%, however, these values represent qualitative estimates rather than quantitative results. 

Various copolymers of the fluorinated monomers have been prepared [243]. Copolymers of tetrafluoroethylene and hexafluoropropene have under vacuo a stability close to that of teflon (Fig. 66). Copolymers with trifluoronitroso me thane have a lower stability than PTFE (Figs. 66 and 67). The copolymer of vinylidenefluoride and hexafluoropropene is one of the most stable elastomers available at the present time (Fig. 66 and Table 12). For a typical copolymer containing 70% vinylidene fluoride, the rate of weight loss is 0.04% per min at 350°C and the activation energy is 57 to 46 kcal mole"1, according to Wright [243]. 

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