Chlorotrifluoroethylene synthesis

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. 

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 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. 

The commercial process for the synthesis of chlorotrifluoroethylene has two steps. The first step is hydrofluorination of perchloroethane ... 

The stoichiometric reaction of CFC-113 with metallic zinc to produce chlorotrifluoroethylene is a well-known process. Catalytic approaches to this synthesis are also available. Charcoal (47) as well as supported nickel, iron, cobalt, and chromium operating at elevated temperature (48) give chlorotrifluoroethylene yields in excess of 90%. The selective replacement of the vinylic chlorine by hydrogen while still maintaining the olefinic linkage provides still another entry into trifluoroethylene. 

Bulk polymerization of vinylene carbonate (VCA) initiated by 60Co y-rays was studied at 30°-110°C at a constant dose rate of 1 - 105 rad/hr. An overall activation energy of 5.0 kcal/mole and a maximum reaction rate of 1 10 3 mole/l-sec were obtained. As has been reported, purification of the monomer is a crucial point because inhibiting impurities are formed during the synthesis. From experiments with chlorine-substituted ethylene and vinylene carbonates, we tentatively conclude that, in addition to mono- and dichloroethylene carbonate, dichloro-vinylene carbonate is mainly responsible for the inhibition. The copolymerization behavior of VC A with some chlorine-substituted olefins was studied. Chlorotrifluoroethylene (CTFE) is an especially suitable comonomer the reactivity ratios found were rVCA = 0.42 and rCXFE = 0.48. 

Generally, 1,2-disubstituted ethylene derivatives have only a small tendency for radical homopolymerization. An exception is vinylene carbonate (VCA) which can be easily polymerized by chemical as well as radiation initiation. However, the reaction is strongly affected by traces of impurities formed during the synthesis. Inhibition experiments are discussed with regard to the nature of the inhibiting impurities. The copolymerization behavior of VCA with some halo-substituted olefins was studied with chlorotrifluoroethylene (CTFE), a statistical copolymer with a slight tendency for alternation was obtained. 

The original reports on synthesis of fluorinated p-sultones appeared from three different groups at approximately the same time in late 1950s.Addition of freshly distilled sulfur trioxide to TFE, chlorotrifluoroethylene, hexafluoropropylene, and... 

It should be pointed out that this reaction is of general nature and it can be used for the synthesis of different types heteroarenes, including derivatives 94-95 obtained in the reaction of quinoline oxide with chlorotrifluoroethylene and 2-7/-pentafluoro-propene, respectively (Fig. 7.31). ... 

Hazardous Decomp. Prods. Heated to decomp., emits toxic fumes of F and CF Uses Intermediate monomer for chlorotrifluoroethylene resins Manuf./Distrib. Lancaster Synthesis... 

Cellulose acetate butyrate Glass lonomer resin Phenoxy resin Polycarbonate Polyethylene, low-density Polyvinyl chloride Vinylidene chloride monomer piping, chemical Chlorotrifluoroethylene polymer piping, chemical processing Polyvinylidene chloride piping/equip., chemical-resistant Polyvinylidene fluoride resin piracetam synthesis... 

Watkins, J. J. and McCarthy, T. J. (1995) Polymerization of Styrene in Supercritical CQ-Swollen Poly(Chlorotrifluoroethylene), Macromolecules 28,4067-4074. Watkins, J. J. and McCarthy, T. J. (1995) Polymer/Metal Nanocomposite Synthesis in Supercritical CQ, Chem. Mater, 7,1991-1994. 

More reports concerned with the replacement of hydroxy-functions by fluorine through the agency of the chlorotrifluoroethylene-diethylamine adduct EtaN-CFa CHFCl (see Vol. 1, p. 101) have become available, and the area has also been reviewed. The efn-diamine (CF5)3C(NH,), has seen service in the synthesis of the heterocyclic nitramines (37)—(40) via... 

Certain polymers, such as poly(vinyl chloride), poly(acrylonitrile), poly-(chlorotrifluoroethylene), and poly(vinyl alcohol), are crystalline as usually prepared, despite the strong possibility of the occurrence of significant stereochemical irregularities. In many instances x-ray diffraction patterns, when used as a criterion, did not definitely support the contention of crystallinity. However, particularly in the cases of poly(vinyl chloride)(54,55) and poly(acrylonitrile),(56) solution and mechanical properties gave substantial evidence of the existence of crystallinity. Subsequent synthesis of these polymers by methods designed to impart a greater amount of chain regularity has confirmed those conclusions.(42,57)... 

This monomer is fairly simple to manufacture compared to the perfluorinated monomers.[" lf" l The com-mereial process for the synthesis of chlorotrifluoroethylene (CTFE) begins with 1,1,2-trichloro-1,2,2-trifluoroethane (TCTFE). It is deehlorinated by pyrolysis at 500-600°C in vapor phase. An alternative method for preparation of TCTFE is catalytic dechlorination ... 

Valade, D., Boschet, F., Amdduri, B. (2009) Synthesis and modification of alternating copolymers based on vinyl ethers, chlorotrifluoroethylene, and hexafiuoropropylene. Macromolecules, 42, 7689-7700. 

N-(2-Chloro-l,l,2-trifluoroethyl)diethylamine, which is readily prepared from chlorotrifluoroethylene (EtjNH + CFa CFCI- EtjN-CF -CHFCI), has seen more use in the conversion of steroidal alcohols into the corresponding monofluorides with the synthesis of 11 j8-fluoro-counterparts of 1 loi-hydroxy-19-nor-steroids. Furthermore, the ll)3-chloro- and -bromo-analogues have been obtained by treatment of the 1 la-hydroxy-steroids with the a-fluoroamine reagent in the presence of lithium chloride and bromide, respectively, e.g. 

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