Perfluorooctanesulfonyl fluoride

Last updated
Perfluorooctanesulfonyl fluoride
Perfluorooctane sulfonyl fluoride.svg
Perfluorooctanesulfonyl-fluoride-3D-spacefill.png
Names
Preferred IUPAC name
1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-Heptadecafluorooctane-1-sulfonyl fluoride
Identifiers
3D model (JSmol)
AbbreviationsPOSF, PFOSF
ChemSpider
ECHA InfoCard 100.005.638 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 206-200-6
PubChem CID
UNII
  • InChI=1S/C8F18O2S/c9-1(10,3(13,14)5(17,18)7(21,22)23)2(11,12)4(15,16)6(19,20)8(24,25)29(26,27)28 X mark.svgN
    Key: BHFJBHMTEDLICO-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C8F18O2S/c9-1(10,3(13,14)5(17,18)7(21,22)23)2(11,12)4(15,16)6(19,20)8(24,25)29(26,27)28
    Key: BHFJBHMTEDLICO-UHFFFAOYAY
  • C(C(C(C(C(F)(F)S(=O)(=O)F)(F)F)(F)F)(F)F)(C(C(C(F)(F)F)(F)F)(F)F)(F)F
Properties
C8F18O2S
Molar mass 502.12 g/mol
Boiling point 154 °C (309 °F; 427 K) [1]
Related compounds
Related compounds
 Perfluorooctanesulfonic acid (PFOS), Perfluorooctanesulfonamide (PFOSA), Perfluorooctanoic acid (PFOA), Perfluorobutanesulfonic acid (PFBS)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Perfluorooctanesulfonyl fluoride (POSF) is a synthetic perfluorinated compound with a sulfonyl fluoride functional group. It is used to make perfluorooctanesulfonic acid (PFOS) and PFOS-based compounds. These compounds have a variety of industrial and consumer uses, but POSF-derived substances ultimately degrade to form PFOS.

Contents

Because of environmental concerns over PFOS, 3M ceased POSF use in 2002 and global production plummeted. However, Chinese production grew after 3M's phaseout. As of May 2009, POSF and PFOS are listed as persistent organic pollutants (POPs) included in Annex B of the Stockholm Convention.

Synthesis

POSF is synthesized by electrochemical fluorination of octanesulfonyl fluoride in anhydrous hydrogen fluoride by the equation: [2]

C8H17SO2F + 17 F− → C8F17SO2F + 17 H+ + 34 e−.

This reaction results in a 25% yield for POSF, less than that for shorter perfluorosulfonyl fluorides. [2] The POSF obtained is impure as it is a mixture of linear and branched isomers, with ~70% linear. [2] POSF can also be obtained by ECF of the sulfonyl halide octanesulfonyl chloride. [2]

Production

In 1949, 3M began producing POSF by electrochemical fluorination (ECF). [3] From 1966 to the 1990s, 3M production increased to meet demand for POSF-based compounds. [3] In 1999, 3M reported POSF was its most highly produced fluorochemical. [4] Before 2000, 3M was the largest global producer of POSF (mainly at their Decatur, AL and Antwerp facilities) and global production peaked at ~4500 tonnes per year. [3]

In 1999, the U.S. Environmental Protection Agency began investigating perfluorinated compounds after receiving data on the global distribution and toxicity of PFOS, the key ingredient in Scotchgard. [5] For these reasons, and USEPA pressure, [6] the primary American producer of PFOS, 3M, announced, in May 2000, the phaseout of the production of PFOS, PFOA, and PFOS-related products. [7] 3M stated that they would have made the same decision regardless of USEPA pressure. [8]

Immediately after the 2000–2002 3M phaseout, production plummeted, but dominant and growing production shifted to China. [9] In 2004 Chinese production of PFOS-based compounds was estimated to be <50 tonnes. [9] In 2005 global production was estimated to be between 73 and 162 tonnes, [10] and by 2006 Chinese production was estimated at >200 tonnes. [9] Total historical global production was estimated at ~120,000 tonnes in 2009. [3]

Most, if not all industrially synthesized perfluorooctanesulfonyl derivatives, such as PFOS, have POSF as their precursor. [2]

Reactivity

POSF and POSF-based polymers degrade to form PFOS [11] which is not known to degrade by any environmental processes. [6] POSF hydrolysis in water, however, occurs slowly. [2]

POSF reacts with bases such as potassium hydroxide to form PFOS salts: [2]

C8F17SO2F + KOH → C8F17O2SO3−K+ + HF.

Upon treatment with sulfuric acid the sulfonic acid PFOS tetrahydrate is obtained. [2]

POSF also reacts with ammonia to form perfluorooctanesulfonamide: [2]

C8F17SO2F + NH3 → C8F17O2SNH2.

Sulfonamides and sulfonamidoethanols synthesized from POSF can in turn react to form a variety of different functional groups for different applications and products. [12]

Uses

Because of multiple carbon–fluorine bonds, POSF-derivatives have chemical properties that are hydrophobic ("water-afraid"), lipophobic ("fat-afraid"), and surface tension lowering (as fluorosurfactants). [4] The main uses of chemical substances derived from POSF have been: [3]

The Stockholm Convention lists a variety of acceptable purposes and specific exemptions for POSF and PFOS (and it salts) including

International status

At the Fourth Conference of Parties, decision SC-4/17 put POSF, along with PFOS, in the Stockholm Convention on Persistent Organic Pollutants (Annex B) in May 2009. [14] [15] As such, POSF is not "banned" but has approved uses and exemptions—along with a program (SC-4/19) in Annex B that encourages reduced production. [16] [17]

Environmental concern

The POSF degradation product, PFOS, is the dominant perfluorinated compound detected in biomonitoring studies, [18] where concentrations that have been detected are considered sufficient to "alter health parameters". [19] [20]

See also

Related Research Articles

<span class="mw-page-title-main">Perfluorooctanoic acid</span> Perfluorinated carboxylic acid

Perfluorooctanoic acid is a perfluorinated carboxylic acid produced and used worldwide as an industrial surfactant in chemical processes and as a material feedstock. PFOA is considered a surfactant, or fluorosurfactant, due to its chemical structure, which consists of a perfluorinated, n-heptyl "tail group" and a carboxylate "head group". The head group can be described as hydrophilic while the fluorocarbon tail is both hydrophobic and lipophobic.

<span class="mw-page-title-main">Perfluorooctanesulfonic acid</span> Fluorosurfactant and persistent organic pollutant

Perfluorooctanesulfonic acid (PFOS) is a chemical compound having an eight-carbon fluorocarbon chain and a sulfonic acid functional group and thus a perfluorosulfonic acid. It is an anthropogenic (man-made) fluorosurfactant, now regarded as a global pollutant. PFOS was the key ingredient in Scotchgard, a fabric protector made by 3M, and related stain repellents. The acronym "PFOS" refers to the parent sulfonic acid and to various salts of perfluorooctanesulfonate. These are all colorless or white, water-soluble solids. Although of low acute toxicity, PFOS has attracted much attention for its pervasiveness and environmental impact. It was added to Annex B of the Stockholm Convention on Persistent Organic Pollutants in May 2009.

<span class="mw-page-title-main">Stockholm Convention on Persistent Organic Pollutants</span> International environmental treaty

Stockholm Convention on Persistent Organic Pollutants is an international environmental treaty, signed on 22 May 2001 in Stockholm and effective from 17 May 2004, that aims to eliminate or restrict the production and use of persistent organic pollutants (POPs).

<span class="mw-page-title-main">Persistent organic pollutant</span> Organic compounds that are resistant to environmental degradation

Persistent organic pollutants (POPs) are organic compounds that are resistant to degradation through chemical, biological, and photolytic processes. They are toxic and adversely affect human health and the environment around the world. Because they can be transported by wind and water, most POPs generated in one country can and do affect people and wildlife far from where they are used and released.

Organofluorine chemistry describes the chemistry of organofluorine compounds, organic compounds that contain a carbon–fluorine bond. Organofluorine compounds find diverse applications ranging from oil and water repellents to pharmaceuticals, refrigerants, and reagents in catalysis. In addition to these applications, some organofluorine compounds are pollutants because of their contributions to ozone depletion, global warming, bioaccumulation, and toxicity. The area of organofluorine chemistry often requires special techniques associated with the handling of fluorinating agents.

Pentabromodiphenyl ether is a brominated flame retardant which belongs to the group of polybrominated diphenyl ethers (PBDEs). Because of their toxicity and persistence, their industrial production is to be eliminated under the Stockholm Convention, a treaty to control and phase out major persistent organic pollutants (POP).

Scotchgard is a 3M brand of products, a stain and durable water repellent applied to fabric, furniture, and carpets to protect them from stains. Scotchgard products typically rely on organofluorine chemicals as the main active ingredient along with petroleum distillate solvents.

Perfluorononanoic acid, or PFNA, is a synthetic perfluorinated carboxylic acid and fluorosurfactant that is also an environmental contaminant found in people and wildlife along with PFOS and PFOA.

<span class="mw-page-title-main">Per- and polyfluoroalkyl substances</span> Class of perfluorinated chemical compounds

Per- and polyfluoroalkyl substances are a group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain. The PubChem database lists more than 6 million unique compounds in this group. PFASs started being used in the mid-20th century to make fluoropolymer coatings and products that resist heat, oil, stains, grease, and water. They are used in a variety of products including waterproof clothing, furniture, adhesives, food packaging, heat-resistant non-stick cooking surfaces, and the insulation of electrical wire. They have played a key economic role for companies such as DuPont, 3M, and W. L. Gore & Associates that use them to produce widely known materials such as Teflon or Gore-Tex.

Fluorotelomer alcohols, or FTOHs, are fluorotelomers with an alcohol functional group. They are volatile precursors to perfluorinated carboxylic acids, such as PFOA and PFNA, and other compounds.

<span class="mw-page-title-main">Perfluorobutanesulfonic acid</span> Chemical compound

Perfluorobutanesulfonic acid (PFBS) is a PFAS chemical compound having a four-carbon fluorocarbon chain and a sulfonic acid functional group. It is stable and unreactive because of the strength of carbon–fluorine bonds. It can occur in the form of a colorless liquid or a corrosive solid. Its conjugate base is perfluorobutanesulfonate which functions as the hydrophobe in fluorosurfactants.

Fluorotelomers are fluorocarbon-based oligomers, or telomers, synthesized by telomerization. Some fluorotelomers and fluorotelomer-based compounds are a source of environmentally persistent perfluorinated carboxylic acids such as PFOA and PFNA, while others are under extended investigation.

<span class="mw-page-title-main">Perfluorinated compound</span>

A perfluorinated compound (PFC) or perfluoro compound is an organofluorine compound lacking C-H bonds. Many perfluorinated compounds have properties that are quite different from their C-H containing analogues. Common functional groups in PFCs are OH, CO2H, chlorine, O, and SO3H. Electrofluorination is the predominant method for PFC production. Due to their chemical stability, some of these perfluorinated compounds bioaccumulate.

<span class="mw-page-title-main">Perfluorooctanesulfonamide</span> Chemical compound

Perfluorooctanesulfonamide (PFOSA) is a synthetic organofluorine compound. It is a fluorocarbon derivative and a perfluorinated compound, having an eight-carbon chain and a terminal sulfonamide functional group. PFOSA, a persistent organic pollutant, was an ingredient in 3M's former Scotchgard formulation from 1956 until 2003, and the compound was used to repel grease and water in food packaging along with other consumer applications. It breaks down to form perfluorooctane sulfonate (PFOS). The perfluorooctanesulfonyl fluoride-based chemistry that was used to make sulfonamides like PFOSA was phased out by 3M in the United States (US) during 2000–2002 but it has grown in China by other producers.

The Global Monitoring Plan (GMP) under the Stockholm Convention on Persistent Organic Pollutants is a programme that enables collection of comparable monitoring data from all regions of the world to assess the effectiveness of the Stockholm Convention in minimizing human and environmental exposure to persistent organic pollutants (POPs). To know whether the levels of POPs are increasing or decreasing over time, information on environmental and human exposure levels of these chemicals should enable detection of trends. GMP looks at background levels of POPs at locations not influenced by local sources, such as ‘hot spots’. For human sampling, the focus is on the general population rather than on individuals who may have suffered high exposure to POPs.

<span class="mw-page-title-main">Water contamination in Lawrence and Morgan Counties, Alabama</span>

Water contamination in Lawrence and Morgan Counties, Alabama, revolves around the presence of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in the water supply. After the US Environmental Protection Agency (EPA) released new health advisories in March 2016, there was concern over health risks of the levels of PFOA and PFOS present. The responses of different government officials, agencies, and companies raise questions as to whether or not there was any environmental injustice involved.

This timeline of events related to per- and polyfluoroalkyl substances (PFASs) includes events related to the discovery, development, manufacture, marketing, uses, concerns, litigation, regulation, and legislation, involving the human-made PFASs. The timeline focuses on some perfluorinated compounds, particularly perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and on the companies that manufactured and marketed them, mainly DuPont and 3M. An example of PFAS is the fluorinated polymer polytetrafluoroethylene (PTFE), which has been produced and marketed by DuPont under its trademark Teflon. GenX chemicals and perfluorobutanesulfonic acid (PFBS) are organofluorine chemicals used as a replacement for PFOA and PFOS.

<span class="mw-page-title-main">Perfluorosulfonic acids</span>

Perfluorosulfonic acids (PFSAs) are chemical compounds of the formula CnF(2n+1)SO3H and thus belong to the family of perfluorinated and polyfluorinated alkyl compounds (PFASs). The simplest example of a perfluorosulfonic acid is the trifluoromethanesulfonic acid. Perfluorosulfonic acids with six or more perfluorinated carbon atoms, i.e. from perfluorohexanesulfonic acid onwards, are referred to as long-chain.

<span class="mw-page-title-main">Perfluorohexanesulfonic acid</span> Chemical compound

Perfluorohexanesulfonic acid (PFHxS) is a synthetic chemical compound. It is one of many compounds collectively known as per- and polyfluoroalkyl substances (PFASs). It is an anionic fluorosurfactant and a persistent organic pollutant with bioaccumulative properties. Although the use of products containing PFHxS and other PFASs have been banned or are being phased out in many jurisdictions, it remains ubiquitous in many environments and within the general population, and is one of the most commonly detected PFASs.

Sulfluramid (N-EtFOSA) is a chemical compound from the group of sulfonic acid amides and per- and polyfluoroalkyl substances (PFASs) that is effective as an insecticide.

References

  1. ↑ "Perfluoro-1-octanesulfonyl fluoride". National Institute of Standards and Technology. 1990. p. 1. Retrieved 10 July 2009.
  2. 1 2 3 4 5 6 7 8 9 Lehmler, HJ (2005). "Synthesis of Environmentally Relevant Fluorinated Surfactants – A Review". Chemosphere . 58 (11): 1471–96. Bibcode:2005Chmsp..58.1471L. doi:10.1016/j.chemosphere.2004.11.078. PMID   15694468.
  3. 1 2 3 4 5 Paul AG, Jones KC, Sweetman AJ (2009). "A first global production, emission, and environmental inventory for perfluorooctane sulfonate". Environ. Sci. Technol. 43 (2): 386–92. Bibcode:2009EnST...43..386P. doi:10.1021/es802216n. PMID   19238969.
  4. 1 2 (1999) 3M. 1999. The science of organic fluorochemistry. 3M Company, February 5, 1999. (PDF readily accessible via a Google search for the article title.)
  5. ↑ Aziz Ullah. "The Fluorochemical Dilemma: What the PFOS/PFOA fuss is all about" Cleaning & Restoration. www.ascr.org, (October, 2006). Accessed October 25, 2008.
  6. 1 2 Lee, Jennifer 8. (15 April 2003). "E.P.A. Orders Companies to Examine Effects of Chemicals". The New York Times . Retrieved 15 May 2009.{{cite news}}: CS1 maint: numeric names: authors list (link)
  7. ↑ 3M: "PFOS-PFOA Information: What is 3M Doing?" Archived 2008-09-22 at the Wayback Machine Accessed October 25, 2008.
  8. ↑ Weber, Joseph (5 June 2000). "3M's Big Cleanup – Why it decided to pull the plug on its best-selling stain repellant". Business Week (3684): 96.
  9. 1 2 3 Wang T, Wang Y, Liao C, Cai Y, Jiang G (2009). "Perspectives on the Inclusion of Perfluorooctane Sulfonate into the Stockholm Convention on Persistent Organic Pollutants". Environ. Sci. Technol. 43 (14): 5171–5. Bibcode:2009EnST...43.5171W. doi: 10.1021/es900464a . PMID   19708337.
  10. ↑ (December 2006). "Results of the 2006 OECD Survey on Production and Use Of PFOS, PFAS, PFOA, PFCA, Their Related Substances and Products/Mixtures Containing These Substances" (PDF). Organisation for Economic Co-operation and Development. p. 10. Retrieved 30 August 2009.
  11. ↑ Giesy JP, Kannan K (2002). "Perfluorochemical Surfactants in the Environment". Environ. Sci. Technol. 36 (7): 146A–152A. Bibcode:2002EnST...36..146G. doi: 10.1021/es022253t . PMID   11999053.
  12. ↑ "Hazard Assessment of Perfluorooctane sulfonate (PFOS) and its Salts" (PDF). Organisation for Economic Co-operation and Development. 21 November 2002. p. 14.
  13. ↑ "Report of the Conference of the Parties of the Stockholm Convention on Persistent Organic Pollutants on the work of its fourth meeting" (PDF). p. 67.
  14. ↑ "Governments unite to step-up reduction on global DDT reliance and add nine new chemicals under international treaty". Geneva: Stockholm Convention Secretariat. 8 May 2008.
  15. ↑ "Report of the Conference of the Parties of the Stockholm Convention on Persistent Organic Pollutants on the work of its fourth meeting" (PDF). Geneva. 8 May 2009. p. 66.
  16. ↑ "Report of the Conference of the Parties of the Stockholm Convention on Persistent Organic Pollutants on the work of its fourth meeting" (PDF). pp. 67–69.
  17. ↑ "U.N. treaty expanded by 9 more chemicals: Participating nations get one year to decide on next steps". NBC News. Associated Press. 11 May 2009. Retrieved 5 September 2009.
  18. ↑ Houde M, Martin JW, Letcher RJ, Solomon KR, Muir DC (June 2006). "Biological monitoring of polyfluoroalkyl substances: A review". Environ. Sci. Technol. 40 (11): 3463–73. Bibcode:2006EnST...40.3463H. doi:10.1021/es052580b. PMID   16786681. Supporting Information (PDF).
  19. ↑ Peden-Adams, M. M.; Keil, D. E.; Romano, T.; Mollenhauer, M. A. M.; Fort, D. J.; Guiney, P. D.; Houde, M.; Kannan, K.; Muir, D. C.; Rice, C. D.; Stuckey, J.; Segars, A. L.; Scott, T.; Talent, L.; Bossart, G. D.; Fair, P. A.; Keller, J. M. (2009). "Health effects of perfluorinated compounds—What are the wildlife telling us?". Reproductive Toxicology. 27 (3–4): 414. doi:10.1016/j.reprotox.2008.11.016.
  20. ↑ Peden-Adams et al. (June 2008). In PFAA Days II Archived 2011-07-26 at the Wayback Machine (PDF). p. 28.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.