Citation: Qian Geng, Xin Xiao, Guang-Rui He, Su-Mei Yao, Guang-Xin Liang. One stone two birds: Degradation of persistent organic pollutants to a valuable industrial chemical production of pentafluoropropionyl fluoride from HFPO oligomers catalyzed by cesium fluoride in tetraglyme[J]. Chinese Chemical Letters, ;2016, 27(7): 1009-1012. doi: 10.1016/j.cclet.2016.04.026 shu

One stone two birds: Degradation of persistent organic pollutants to a valuable industrial chemical production of pentafluoropropionyl fluoride from HFPO oligomers catalyzed by cesium fluoride in tetraglyme

Qian Geng ^a,c ,
Xin Xiao ^c ,
Guang-Rui He ^c ,
Su-Mei Yao ^c ,
Guang-Xin Liang ^a,b,,

a.
State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, China
b.
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University , Tianjin 300071, China
c.
Changlu Engineering Research Center of New Chemical Materials, Tianjin 300160, China

Corresponding author: Guang-Xin Liang, lianggx@nankai.edu.cn
Received Date: 31 March 2016
Revised Date: 22 April 2016
Accepted Date: 28 April 2016
Available Online: 17 July 2016

Figures(6)

Hexafluoropropylene oxide (HFPO) oligomers are toxic, bioaccumulative, and persistent organic pollutants (POPs). Consuming the harmful chemicals to prevent them from releasing to nature is of serious significance as far as both natural environments and human health are concerned. In this study, investigation on degradation of HFPO oligomers to pentafluoropropionyl fluoride (PPF), a valuable industrial chemical, is reported. Different combinations of alkali metal fluoride in either diglyme or tetraglyme under both flask and batch autoclave conditions were examined. Under the optimal reaction conditions, HFPO oligomers (n = 2-10) were completely degraded to PPF in over 90% yield. Reactions on 200 g scale were tested and no deduction of efficiency was observed, which indicates the potential for practical industrial application of this chemistry.
- Hexafluoropropylene oxide (HFPO) oligomers,
- Persistent organic pollutants,
- Degradation,
- Cleavage of ether bond,
- Pentafluoropropionyl fluoride (PPF)
1. [1]
  EPA Data of HFPO Trimer, see: http://yosemite.epa.gov/oppts/epatscat8.nsf/by+Service/E91FE2961720F6DC85256930004F2372/$File/88940000083.pdf
2. [2]
  HFPO Trimer Toxicology Study data see: http://www.siri.org/msds/tox/tf/q112/q689.html.
3. [3]
  C. Lu, Y.L. Shi, Z. Zhou. Perfluorinated compounds in blood of textile workers and barbers[J]. Chin. Chem. Lett., 2014,25:1145-1148.
4. [4]
  T. Oberg, M.S. Iqbal. The chemical and environmental property space of REACH chemicals[J]. Chemosphere, 2012,87:975-981.
5. [5]
  M. Scheringer, S. Strempel, S. Hukari. How many persistent organic pollutants should we expect?[J]. Atmos. Pollut. Res., 2012,3:383-391.
6. [6]
  M. Sha, P. Xing, B. Jiang. Strategies for synthesizing non-bioaccumulable alternatives to PFOA and PFOS[J]. Chin. Chem. Lett., 2015,46:491-498.
7. [7]
  UNEP, Stockholm Convention on Persistent Organic Pollutants. http://www.pops. int/documents/convtext/convtext_en.pdf
8. [8]
  FluoroCouncil. Global regulatory activity on long chain perfluorochemicals and fluoropolymers, in: Spring Fluoropolymers Division Conference, Miami Beach, FL. 2012.
9. [9]
  O. Kysilka, M. Rybá čková, M. Skalický, M. Kvíčalová, J. Cvačka. Fluorous imidazolium room-temperature ionic liquids based on HFPO trimer[J]. J. Fluor. Chem., 2009,130:629-639.
10. [10]
  J. Lapčík, O. Gimello, V. Ladmiral, C.M. Friesen, B. Ameduri. A new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide) diblock surfactant obtained by radical reactions[J]. Polym. Chem., 2015,6:79-96.
11. [11]
  S. Jr, C. E. Tamborski. Fluorinated aliphatic polyalkylether lubricant with an additive composed of an aromatic phosphine substituted with perfluoroalkylether groups. US, 4, 443, 349, 1984.
12. [12]
  F. Richard. Dielectric liquids, US, 5, 159, 527 A. 1991.
13. [13]
  P.D. Brothers, S.V. Gangal. Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant[J]. US, 2010,B27705074.
14. [14]
  L. Robert, Burwell Jr.. The cleavage of ethers[J]. Chem. Rev., 1954,54:615-685.
15. [15]
  M.V. Bhatt, S.U. Kulkarni. Cleavage of ethers[J]. Synthesis, 1983,4:249-282.
16. [16]
  G. Drivera, K.E. Johnsona. 3-Methylimidazolium bromohydrogenates(I): a roomtemperature ionic liquid for ether cleavage[J]. Green Chem., 2003,5:163-169.
17. [17]
  M. Yamashita, A. Tani, F. Kawai. Cloning and expression of an ether-bond-cleaving enzyme involved in the metabolism of polyethylene glycol[J]. J. Biosci. Bioeng., 2004,98:313-315.
18. [18]
  A. Atesin, N. Ray, P. Stair, T. Marks. Etheric C-O bond hydrogenolysis using a tandem lanthanide triflate/supported palladium nanoparticle catalyst system[J]. J. Am. Chem. Soc., 2012,134:14682-14685.
19. [19]
  A.K. Kim, G.P. Crampton. Performance of Novec1230 in electronic facility fire protection, fire suppression and detection-A technical working conference (Proceedings of SUPDET, 2010): 16 February 2010, Orlando. Florida.
20. [20]
  B.M. Dwight, F.R. Victor, M.R. Alan. Process for treating melt-processible tetrafluoroethylene/perfluoro(alkyl vinyl)-ether copolymers. EP, 0226668 B1, 1992.
21. [21]
  DuPontTM GenX processing aid for making f luoropolymer resins; DuPont, 2010 http://www2.dupont.com/Industrial_Bakery_Solutions/en_GB/assets/downloads/DuPont_GenX_Brochure_Final_07July2010.pdf.
22. [22]
  R.M. Flynn, M.G. Costello, D.R. Vitcak. Hydrofluoroether compounds and processes for their preparation and use. WO:, 2008070606, 2008.
23. [23]
  G. Siegemun, R. Franz. Process for the preparation of perfluoropropionyl fluoride,US[J]. , 19975684193.
24. [24]
  S.V. Kostjuk, E. Ortega, F. Ganachaud, B. Amé duri, B. Boutevin. Anionic ringopening polymerization of hexafluoropropylene oxide using alkali metal fluorides as catalysts: a mechanistic study[J]. Macromolecules, 2009,42:612-619.
25. [25]
  Paul H. Kasai. Perfluoropolyethers: intramolecular disproportionation[J]. Macromolecules, 1992,25:6791-6799.
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