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).
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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] [ better source needed ] 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

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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 carboxylic acid "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 it is a perfluorosulfonic acid and a perfluoroalkyl substance (PFAS). 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

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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.

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<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.

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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.
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