Chlorotrifluoroethylene

Poly(methyl methacrylate) (PMMA) Ethylene-chlorotrifluoroethylene copolymer... 

Poly(chlorotrifluoroethylene) (PCTFE) Butadiene-maleic acid copolymer (BMC)... 

Ethylene-Chlorotrifluoroethylene Copolymer. Ethylene-chlorotrilluoroethylene copolymer consists of linear chains in which the predominant 1 1 alternating copolymer is... 

Certain CFCs are used as raw materials to manufacture key fluorinated olefins to support polymer apphcations. Thermolysis of HCFC-22 affords tetrafluoroethylene and hexafluoropropylene [116-15 ] under separate processing conditions. Dechlorination of CFC-113 forms chlorotrifluoroethylene [79-38-9]. Vinyhdene fluoride [75-38-7] is produced by the thermal cracking of HCFC-142b. 

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). 

The synthesis of the high molecular weight polymer from chlorotrifluoroethylene [79-38-9] has been carried out in bulk (2 >—21 solution (28—30), suspension (31—36), and emulsion (37—41) polymerisation systems using free-radical initiators, uv, and gamma radiation. Emulsion and suspension polymers are more thermally stable than bulk-produced polymers. Polymerisations can be carried out in glass or stainless steel agitated reactors under conditions (pressure 0.34—1.03 MPa (50—150 psi) and temperature 21—53°C) that require no unique equipment. 

R. E. Mowers Cyogenic Properties ofPoly(Chlorotrifluoroethylene), Technical Document Report No. RTD-TDR-63-11, Air Eorce Contract No. AE04(611)-6354,1962. 

Alkylated aromatic lubricants, phosphate esters, polyglycols, chlorotrifluoroethylene, siUcones, and siUcates are among other synthetics that came into production during much that same period (28,29). Polyphenyl ethers and perfluoroalkyl polyethers have followed as fluids with distinctive high temperature stabiUty. Although a range of these synthetic fluids find appHcations which employ their unique individual characteristics, total production of synthetics represent only on the order of 2% of the lubricant market. Poly(a-olefin)s, esters, polyglycols, and polybutenes represent the types of primary commercial interest. 

Although synthetic lubrication oil production amounts to only about 2% of the total market, volume has been increasing rapidly (67). Growth rates of the order of 20% per year for poly( a-olefin)s, 10% for polybutenes, and 8% for esters (28) reflect increasing automotive use and these increases would accelerate if synthetics were adopted for factory fill of engines by automotive manufacturers. The estimated production of poly( a-olefin)s for lubricants appears to be approximately 100,000 m /yr, esters 75,000, poly(alkylene glycol)s 42,000, polybutenes 38,000, phosphates 20,000, and dialkyl benzene 18,000 (28,67). The higher costs reflected in Table 18 (18,28) have restricted the volume of siUcones, chlorotrifluoroethylene, perfluoroalkylpolyethers, and polyphenyl ethers. 

Pubhcations on curing polymers with TAIC include TEE—propylene copolymer (135), TEE—propylene—perfluoroaHyl ether (136), ethylene—chlorotrifluoroethylene copolymers (137), polyethylene (138), ethylene—vinyl acetate copolymers (139), polybutadienes (140), PVC (141), polyamide (142), polyester (143), poly(ethylene terephthalate) (144), sdoxane elastomers (145), maleimide polymers (146), and polyimide esters (147). 

Mihtary interest in the development of fuel and thermal resistant elastomers for low temperature service created a need for fluorinated elastomers. In the early 1950s, the M. W. Kellogg Co. in a joint project with the U.S. Army Quartermaster Corps, and 3M in a joint project with the U.S. Air Force, developed two commercial fluorocarbon elastomers. The copolymers of vinyUdene fluoride, CF2=CH2, and chlorotrifluoroethylene, CF2=CFC1, became available from Kellogg in 1955 under the trademark of Kel-F (1-3) (see Fluorine compounds, ORGANic-POLYcm.OROTRiFLUOROETHYLENE Poly(vinylidene) fluoride). In 1956, 3M introduced a polymer based on poly(l,l-dihydroperfluorobutyl acrylate) trademarked 3M Brand Fluorombber 1F4 (4). The poor balance of acid, steam, and heat resistance of the latter elastomer limited its commercial use. 

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. 

Chlorotrifluoroethylene [79-38-9] M 116.5, b -26 to -24 . Scrubbed witb 10% KOH soln, then 10% H2SO4 soln to remove inhibitors, and dried. Passed through silica gel. 

Copolymers of chlorotrifluoroethylene and ethylene were introduced by Allied Chemicals under the trade name Halar in the early 1970s. This is essentially a 1 1 alternating copolymer compounded with stabilising additives. The polymer has mechanical properties more like those of nylon than of typical fluoroplastic, with low creep and very good impact strength. Furthermore the polymers have very good chemical resistance and electrical insulation properties and are resistant to burning. They may be injection moulded or formed into fibres. 

As will be seen from Table 13.4 elastomers are also available which are copolymers of vinylidene fluoride and chlorotrifluoroethylene. These materials... 

The chlorotrifluoroethylene cylinder is fitted with a pressure-reduction valve which is set at a maximum pressure of 40 lb. (2.7 atm.). 

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. 

Chemical Designations - Synonyms Chlorotrifluoroethylene Kel F monomer Plascon monomer Trifluoromonochloroethylene Trifluoroevinil chloride Chemical Formula F2C=CFC1. 

A mixture of either bromine or iodine and sulfur trioxide reacts with either tetrafluoroethylene or chlorotrifluoroethylene to produce an intermediate, which, when treated with fuming sulfuric acid, yields a difluorohaloacetyl fluoride [2] (equation 2) 1,1,2-Trichlorotrifluoroethane can be used as a solvent. 

A -Halogenated compounds such as iV-chlorotnfluoroacetamide, A -chloro-imidosulfuryl fluonde and N N dichlorotnfluoromethylamine add across C=C bonds to form saturated amides [14] tmidosulfury I fluorides [15] and amines [16], respectively Allylic halogenation also occurs with the use of A-bromo- or A-chIo roperfluoroamides The primary amine A,A-dichlorotrifluororaethylamine selectively affords 11 or 2 1 adducts with either tetrafluoroethylene or chlorotrifluoroethylene [16] (equation 7) The reaction mechanism is believed to involve thermal free radicals, with control achieved principally by reaction temperature The 1 1 adduct is formed even in the presence of a large excess of olefin... 

Fluorinated cyclobutanes and cyclobutenes are relatively easy to prepare because of the propensity of many gem-difluoroolefins to thermally cyclodimerize and cycloadd to alkenes and alkynes. Even with dienes, fluoroolefins commonly prefer to form cyclobutane rather than six-membered-ring Diels-Alder adducts. Tetrafluoroethylene, chlorotrifluoroethylene, and l,l-dichloro-2,2-difluoroethyl-ene are especially reactive in this context. Most evidence favors a stepwise diradical or, less often, a dipolar mechanism for [2+2] cycloadditions of fluoroalkenes [S5, (5], although arguments for a symmetry-allowed, concerted [2j-t-2J process persist [87], The scope, characteristic features, and mechanistic studies of fluoroolefin... 

Perfluoroisobutylene undergoes cycloadditions with azides only at elevated temperatures, the reaction can lead to subsequent loss of nitrogen [6] (equation 4) In another high-temperature reaction, chlorotrifluoroethylene undergoes cy cloaddition with the azomethineylide generated from the thermal electrocyclic nng opening of an azindine, a reaction that contributes to a good overall synthesis of 3,4-difluoropyrroles [7] (equation 5)... 

The high thermal and chemical stability of fluorocarbons, combined with their very weak intermolecular interactions, makes them ideal stationary phases for the separation of a wide variety of organic compounds, including both hydrocarbons and fluorine-containing molecules Fluonnated stationary phases include per-fluoroalkanes, fluorocarbon surfactants, poly(chlorotrifluoroethylene), polyfper-fluoroalkyl) ethers, and other functionalized perfluoro compounds The applications of fluonnated compounds as stationary phases in gas-liquid chroma... 

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