Tetrafluoroethylene, from

The formation of tetrafluoroethylene from its elements is highly exothermic ... 

RELATIVE ENTHALPY OF POLY/TETRAFLUOROETHYLENE/ FROM 0 TO 440 DEGREES. 

A number of friction studies have been carried out on organic polymers in recent years. Coefficients of friction are for the most part in the normal range, with values about as expected from Eq. XII-5. The detailed results show some serious complications, however. First, n is very dependent on load, as illustrated in Fig. XlI-5, for a copolymer of hexafluoroethylene and hexafluoropropylene [31], and evidently the area of contact is determined more by elastic than by plastic deformation. The difference between static and kinetic coefficients of friction was attributed to transfer of an oriented film of polymer to the steel rider during sliding and to low adhesion between this film and the polymer surface. Tetrafluoroethylene (Telfon) has a low coefficient of friction, around 0.1, and in a detailed study, this lower coefficient and other differences were attributed to the rather smooth molecular profile of the Teflon molecule [32]. 

Poly(tetmfluoroethylene). Poly(tetrafluoroethylene) is prepared from tetrafluoroethy-lene and consists of repeating units in a predominantly linear chain ... 

TFE copolymers pLUORINE COMPOUNDS, ORGANIC - TETRAFLUOROETHYLENE-ETHYLENE COPOLYTffiRS] (Vol 11) -vinyl fluoride from pLUORINE COMPOUNDS, ORGANIC - POLY(VINYL FLUORIDE)] (Vol 11)... 

The Fe, Co, and Ni deposits are extremely fine grained at high current density and pH. Electroless nickel, cobalt, and nickel—cobalt alloy plating from fluoroborate-containing baths yields a deposit of superior corrosion resistance, low stress, and excellent hardenabiUty (114). Lead is plated alone or ia combination with tin, iadium, and antimony (115). Sound iasulators are made as lead—plastic laminates by electrolyticaHy coating Pb from a fluoroborate bath to 0.5 mm on a copper-coated nylon or polypropylene film (116) (see Insulation, acoustic). Steel plates can be simultaneously electrocoated with lead and poly(tetrafluoroethylene) (117). Solder is plated ia solutioas containing Pb(Bp4)2 and Sn(Bp4)2 thus the lustrous solder-plated object is coated with a Pb—Sn alloy (118). 

The reactions with IF are more amenable to control giving good yields of identifiable products and lower losses from oxidative fragmentation. The reaction of IF and iodine with tetrafluoroethylene produces the telomer perfluoroethyl iodide [354-64-3] ia yields that exceed 98% based on... 

The direct chlorination of hydrofluorocarbons and fluoroolefins has also been used commercially, eg, in the preparations of CH2CCIF2 from CH2CHF2 and CCIF2CCIF2 from tetrafluoroethylene. 

Fluorinated ether-containing dicarboxyhc acids have been prepared by direct fluorination of the corresponding hydrocarbon (17), photooxidation of tetrafluoroethylene, or by fluoride ion-cataly2ed reaction of a diacid fluoride such as oxalyl or tetrafluorosuccinyl fluorides with hexafluoropropylene oxide (46,47). Equation 8 shows the reaction of oxalyl fluoride with HEPO. A difunctional ether-containing acid fluoride derived from HEPO contains regular repeat units of perfluoroisopropoxy group and is terminated by two alpha-branched carboxylates. 

Tetrafluoroethylene was first synthesized in 1933 from tetrafluoromethane, CF, in an electric arc furnace (11). Since then, a number of routes have been developed (12—18). Depolymerization of PTFE by heating at ca 600°C is probably the preferred method for obtaining small amounts of 97% pure monomer on a laboratory scale (19,20). Depolymerization products contain highly toxic perfluoroisobutylene and should be handled with care. 

Transitions. Samples containing 50 mol % tetrafluoroethylene with ca 92% alternation were quenched in ice water or cooled slowly from the melt to minimise or maximize crystallinity, respectively (19). Internal motions were studied by dynamic mechanical and dielectric measurements, and by nuclear magnetic resonance. The dynamic mechanical behavior showed that the CC relaxation occurs at 110°C in the quenched sample in the slowly cooled sample it is shifted to 135°C. The P relaxation appears near —25°C. The y relaxation at — 120°C in the quenched sample is reduced in peak height in the slowly cooled sample and shifted to a slightly higher temperature. The CC and y relaxations reflect motions in the amorphous regions, whereas the P relaxation occurs in the crystalline regions. The y relaxation at — 120°C in dynamic mechanical measurements at 1 H2 appears at —35°C in dielectric measurements at 10 H2. The temperature of the CC relaxation varies from 145°C at 100 H2 to 170°C at 10 H2. In the mechanical measurement, it is 110°C. There is no evidence for relaxation in the dielectric data. 

Hexachloroethane has been suggested as a degasifter in the manufacture of aluminum and magnesium metals. Hexachloroethane has been used as a chain-transfer agent in the radiochemical emulsion preparation of propylene tetrafluoroethylene copolymer (152). It has also been used as a chlorinating agent in the production of methyl chloride from methane (153). 

Roughly 65% of the substituents are trifluoroethoxy, and 35% are telomer alcohols prepared from tetrafluoroethylene and methanol. About 0.5 mol % of an aHyhc substituent is used as a cross-link site. The substituent pattern is beUeved to be stricdy statistical. 

The most chemical-resistant plastic commercially available today is tetrafluoroethylene or TFE (Teflon). This thermoplastic is practically unaffected by all alkahes and acids except fluorine and chlorine gas at elevated temperatures and molten metals. It retains its properties up to 260°C (500°F). Chlorotrifluoroethylene or CTFE (Kel-F, Plaskon) also possesses excellent corrosion resistance to almost all acids and alkalies up to 180°C (350°F). A Teflon derivative has been developed from the copolymerization of tetrafluoroethylene and hexafluoropropylene. This resin, FEP, has similar properties to TFE except that it is not recommended for continuous exposures at temperatures above 200°C (400°F). Also, FEP can be extruded on conventional extrusion equipment, while TFE parts must be made by comphcated powder-metallurgy techniques. Another version is poly-vinylidene fluoride, or PVF2 (Kynar), which has excellent resistance to alkahes and acids to 150°C (300°F). It can be extruded. A more recent development is a copolymer of CTFE and ethylene (Halar). This material has excellent resistance to strong inorganic acids, bases, and salts up to 150°C. It also can be extruded. 

In attempts to further improve the stability of fluorine-containing elastomers Du Pont developed a polymer with no C—H groups. This material is a terpolymer of tetrafluoroethylene, perfluoro(methyl vinyl ether) and, in small amounts, a cure site monomer of undisclosed composition. Marketed as Kalrez in 1975 the polymer withstands air oxidation up to 290-315°C and has an extremely low volume swell in a wide range of solvents, properties unmatched by any other commercial fluoroelastomer. This rubber is, however, very expensive, about 20 times the cost of the FKM rubbers and quoted at 1500/kg in 1990, and production is only of the order of 1 t.p.a. In 1992 Du Pont offered a material costing about 75% as much as Kalrez and marketed as Zalak. Structurally, it differs mainly from Kalrez in the choice of cure-site monomer. 

In 1991 MMM announced Fluorel II, a terpolymer of tetrafluoroethylene, vinylidene fluoride and propylene. As might be expected from the structure, this is intermediate between FKM and Aflas, having better resistance to many newer automotive oils, lubricants and transmission fluids than the former but better heat resistance than the latter. 

Chloro-2,2,3-trifluoropropionic acid has been prepared by permanganate oxidation of 3-chloro-2,2,3-trifluoropropanol which is one of the telomerization products of chlorotrifluoroethylene with methanol. The present procedure is a modification of one reported earlier and is undoubtedly the method of choice for making propionic acids containing 2 fluorine atoms, i.e., 2,2,3,3-tetrafluoropropionic acid, 3,3-dichloro-2,2-difluoropropionic acid, and 3-bromo-2,2,3-trifluoropropionic acid. When preparing 2,2,3,3-tetrafluoropropionic acid from tetrafluoroethylene, it is desirable to use an additional 50 ml. of acetonitrile and externally applied heat to initiate the reaction. 

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].

These types of reactions have been used extensively to pTspaicJluorotelomers For example, Zonyl products, manufactured by E I du Pont de Nemours Co, Inc, are based on materials prepared from perfluoroethyl iodide and tetrafluoroethylene [2] (equation 1)... 

Similarly, difunctional materials can be made from tetrafluoroethylene and 1,2-diiodotetrafIuoroethane in a thermal process [i] (equation 2)... 

Consider Teflon, the polymer made from tetrafluoroethylene. 

The synthesis of 2-chloro-2,3,3-trifluorocyclobutyl acetate illustrates a general method of preparing cyclobutanes by heating chlorotrifluoroethylene, tetrafluoroethylene, and other highly fluorinated ethylenes with alkenes. The reaction has recently been reviewed.11 Chlorotrifluoroethylene has been shown to form cyclobutanes in this way with acrylonitrile,6 vinylidene chloride,3 phenylacetylene,7 and methyl propiolate.3 A far greater number of cyclobutanes have been prepared from tetrafluoroethylene and alkenes 4,11 when tetrafluoroethylene is used, care must be exercised because of the danger of explosion. The fluorinated cyclobutanes can be converted to a variety of cyclobutanes, cyclobutenes, and butadienes. 

---