Tetrafluoroethylene

Tetrafluoroethylene
Tetrafluoroethylene	Tetrafluoroethylene
Names
	Preferred IUPAC name Tetrafluoroethene
	Other names perfluoroethylene; TFE
Identifiers
CAS Number	116-14-3 ;
3D model (JSmol)	Interactive image;
ChEBI	CHEBI:38866 ;
ChEMBL	ChEMBL541730 ;
ChemSpider	8000 ;
ECHA InfoCard	100.003.752
KEGG	C19299 ;
PubChem CID	8301;
UNII	OMW63Z518S ;
CompTox Dashboard (EPA)	DTXSID6021325 ;
	InChI InChI=1S/C2F4/c3-1(4)2(5)6 Key: BFKJFAAPBSQJPD-UHFFFAOYSA-N ; InChI=1/C2F4/c3-1(4)2(5)6 Key: BFKJFAAPBSQJPD-UHFFFAOYAC;
	SMILES FC(F)=C(F)F;
Properties
Chemical formula	C2F4
Molar mass	100.02 g/mol
Appearance	Colorless gas
Odor	Odorless
Density	1.519 g/cm3 at −76 °C
Melting point	−142.5 °C (−224.5 °F; 130.7 K)
Boiling point	−76.3 °C (−105.3 °F; 196.8 K)
Hazards
NFPA 704 (fire diamond)	3 4 3 OX
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Tetrafluoroethylene (TFE) is a fluorocarbon with the chemical formula C₂F₄. It is the simplest perfluorinated alkene. This gaseous species is used primarily in the industrial preparation of fluoropolymers.

It was first reported as "dicarbon tetrafluoride" in 1890.^[2]

Properties

Tetrafluoroethylene is a synthetic colorless, odorless gas that is insoluble in water. Like all unsaturated fluorocarbons, it is susceptible to nucleophilic attack. It is unstable towards decomposition to carbon and carbon tetrafluoride (CF
₄) and prone to form explosive peroxides in contact with air.^[3]^[4]

Industrial use

Polymerization of tetrafluoroethylene produces polytetrafluoroethylene (PTFE) polymers such as Teflon and Fluon. PTFE is one of the two fluorocarbon resins composed wholly of fluorine and carbon. The other resin composed purely of carbon and fluorine is the copolymer of TFE with typically 6–9% hexafluoropropene (HFP), which is known as FEP (fluorinated ethylene propylene copolymer). TFE is also used in the preparation of numerous copolymers that also include hydrogen and/or oxygen, including both fluoroplastics and fluoroelastomers. Typical TFE-based fluoroplastics include ETFE, the alternating 1:1 copolymer with ethylene, and PFA, which is a random copolymer similar to FEP but with a minor amount of a perfluoroalkyl vinyl ether (PAVE) rather than HFP. DuPont uses primarily perfluoro(methylvinylether), whereas Daikin uses primarily perfluoro(propylvinylether) in manufacturing PFA. There are numerous other fluoropolymers that contain tetrafluoroethylene, but usually not at greater than 50% by weight.

Manufacture

TFE is manufactured from chloroform.^[5] Chloroform is fluorinated by reaction with hydrogen fluoride to produce chlorodifluoromethane (R-22). Pyrolysis of chlorodifluoromethane (at 550–750 °C) yields TFE, with difluorocarbene as an intermediate.

CHCl₃ + 2 HF → CHClF₂ + 2 HCl

2 CHClF₂ → C₂F₄ + 2 HCl

Alternatively, it can be prepared by pyrolysis of fluoroform (which is also produced from chloroform and HF):

2 CHF₃ → C₂F₄ + 2 HF

Laboratory methods

A convenient, safe method for generating TFE is the pyrolysis of the sodium salt of pentafluoropropionic acid:^[6]

C₂F₅CO₂Na → C₂F₄ + CO₂ + NaF

The depolymerization reaction – vacuum pyrolysis of PTFE at 650–700 °C (1,200–1,290 °F) in a quartz vessel – is a traditional laboratory synthesis of TFE. The process is however challenging because attention must be paid to pressure, as well as the avoidance of perfluoroisobutylene. PTFE polymer cracks, and at a pressure below 5 Torr (670 Pa) exclusively C₂F₄ is obtained. At higher pressures the product mixture contains hexafluoropropylene and octafluorocyclobutane.^[7]

Reactions

Tetrafluoroethylene is a reactive molecule that participates in myriad reactions. Owing to the presence of four fluorine substituents, its reactions differ strongly from the behavior of conventional alkenes such as ethylene. Tetrafluoroethylene dimerizes, giving octafluorocyclobutane. Even normal alkenes and dienes add tetrafluoroethylene in a [2+2] manner. 1,3-Butadiene gives 3-vinyl-1,1,2,2-tetrafluorocyclobutane.^[8]

Safety

The main hazard associated with TFE is that of explosion, especially if oxygen is present. TFE reacts with oxygen at low temperatures to form an explosive oxide,^[3] the detonation of which is usually sufficient to trigger explosive decomposition of TFE to C and CF₄.^[9] Explosions can also be caused by adiabatic compression if the TFE is handled under high pressure, which it typically is in an industrial setting. If pressurised TFE is allowed into a vessel or pipework at a lower pressure, then the atmosphere in the vessel will be compressed by the TFE, causing it to heat up, potentially to the point where it might detonate the TFE. This has been known to cause explosions.^[10] In industry, pipework is flushed with pressurized nitrogen, before the introduction of TFE, both to exclude oxygen and prevent adiabatic compression.

TFE is an alkylating agent, albeit a weak one, and as such is expected to be a carcinogen. LD₅₀(rat, inhalation) = 40000 ppm.^[11]

The International Agency for Research on Cancer classifies TFE as probably carcinogenic to humans based on animal studies.^[12]

References

^ "Hazard Rating Information for NFPA Fire Diamonds". Archived from the original on 2015-02-28. Retrieved 2015-03-15.
^ C. Chabrie "General Method for the Preparation of Carbon Fluorides" in Journal - Chemical Society, London. (1890). UK: Chemical Society.
^ ^a ^b Gozzo, F.; Camaggi, G. (January 1966). "Oxidation reactions of tetrafluoroethylene and their products—I". Tetrahedron. 22 (6): 1765–1770. doi:10.1016/S0040-4020(01)82248-1.
^ PubChem. "Tetrafluoroethylene". pubchem.ncbi.nlm.nih.gov. Retrieved 2023-09-25.
^ Siegemund, Günter; Schwertfeger, Werner; Feiring, Andrew; Smart, Bruce; Behr, Fred; Vogel, Herward; McKusick, Blaine; Kirschtitle=Fluorine Compounds, Organic, Peer (2016). Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_349.pub2. ISBN 978-3527306732.
^ Hercules, Daniel A.; Parrish, Cameron A.; Sayler, Todd S.; Tice, Kevin T.; Williams, Shane M.; Lowery, Lauren E.; Brady, Michael E.; Coward, Robert B.; Murphy, Justin A.; Hey, Trevyn A.; Scavuzzo, Anthony R.; Rummler, Lucy M.; Burns, Emory G.; Matsnev, Andrej V.; Fernandez, Richard E.; McMillen, Colin D.; Thrasher, Joseph S. (2017). "Preparation of tetrafluoroethylene from the pyrolysis of pentafluoropropionate salts". Journal of Fluorine Chemistry. 196: 107–116. doi:10.1016/j.jfluchem.2016.10.004.
^ R. J. Hunadi & K. Baum (1982). "Tetrafluoroethylene: A Convenient Laboratory Preparation". Synthesis. 39 (6): 454. doi:10.1055/s-1982-29830. S2CID 96276938.
^ Roberts, John D.; Sharts, Clay M. (2011). "Cyclobutane Derivatives from Thermal Cycloaddition Reactions". Organic Reactions. pp. 1–56. doi:10.1002/0471264180.or012.01. ISBN 978-0471264187.
^ Fabio, Ferrero; Robert, Zeps; Martin, Kluge; Volkmar, Schröde; Tom, Spoormaker (April 2013). "The explosive decomposition of tetrafluoroethylene: large scale tests and simulations". Chemical Engineering Transactions. 31: 817–822. doi:10.3303/CET1331137.
^ Reza, Ali; Christiansen, Erik (March 2007). "A case study of a TFE explosion in a PTFE manufacturing facility". Process Safety Progress. 26 (1): 77–82. doi:10.1002/prs.10174. S2CID 110305024.
^ NIH Substance Profile for TFE
^ "Terrafluoroethylene" (PDF). International Agency for Research on Cancer. Retrieved 20 May 2020.^{[permanent dead link]}