Partially fluorinated polysulfinic acids and their salts

Patent metadata

Field	Value
Publication number	US-9580526-B2
Application number	US-201113885185-A
Country	US
Kind code	B2
Filing date	Dec 9, 2011
Priority date	Dec 17, 2010
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

Described herein is a composition comprising a fluorinated polysulfinic acid or a salt thereof having the following formula (I):

wherein X 1 , X 2 , and X 3 are independently selected from H, F, Cl, Br, I, CF 3 , and CH 3 and wherein at least one of X 1 , X 2 , or X 3 is H; R 1 is a linking group; Z 1 and Z 2 are independently selected from Br, Cl, I, F, CF 3 , and a perfluorinated alkyl group; M is a cation; p is 0 or 1; and n is at least 2. Also described is a method of making the partially fluorinated polysulfinic acid or salt thereof.

First claim

What is claimed is:

1. A composition comprising the following formula (I):

wherein X 1 , X 2 , and X 3 are all H; R 1 is a perfluorinated alkylene optionally comprising O atoms; Z 1 and Z 2 are independently selected from Br, Cl, I, and F, CF 3 , and a perfluorinated alkyl group; M is a cation; p is 0 or 1; and n is at least 2.

2. The composition according to claim 1 , further comprising:

wherein X 4 , X 5 , and X 6 are independently selected from H, F, Cl, Br, I, CF 3 , and CH 3 ; R 2 is linking group; Z 3 and Z 4 are independently selected from Br, Cl, F, CF 3 , and a perfluorinated alkyl group; Y is selected from —H, —Br, —I, —COOM, —SO 3 M, and —[CX 1 X 3 —CX 2 (R 1 CZ 1 Z 2 Y 1 )]q, where Y 1 is selected from —H, —Br, —COOM, —SO 3 M, —SO 2 M, and —[CX 1 X 3 —CX 2 (R 1 CZ 1 Z 2 Y 1 )]q; M is a cation; p is 0 or 1; and m is at least 1 and q is at least 1.

3. The composition according to claim 1 , further comprising:

wherein Q is derived from a monomer and p is at least 1.

4. The composition according to claim 3 , wherein the monomer is selected from the following formula: CX 2 ═CX(Z), wherein each X is independently selected from H or F; and Z is selected from I, Br, and R f —U wherein U=I or Br, and R f is a perfluorinated or partially perfluorinated alkylene group optionally containing O atoms.

5. The composition according to claim 3 , wherein the monomer is selected from: ethylene, tetrafluoroethylene, propylene, hexafluoropropylene, vinyl chloride, vinyl fluoride, a fluoroalkyl substituted ethylene, vinylidene fluoride, allyl iodide, fluorinated alkyl vinyl ethers, fluorinated alkoxy vinyl ethers, bromotrifluoroethylene, chlorotrifluoroehtylene, CF 3 CH═CH 2 , C 4 F 9 CH═CH 2 , CH 2 ═CHCF 2 CFOCF 2 CF 2 SO 2 F, CF 3 OCF═CF 2 , C 3 F 7 OCF═CF 2 , CF 2 ═CFO(CF 2 ) 4 SO 2 F, CF 2 ═CFOCF 2 CFOCF 2 CF 2 SO 2 F, CF 2 ═CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 F, CF 2 ═CFOCF 2 CF(CF 3 )OCF 2 CF 2 CO 2 CH 3 , and CF 2 ═CFOCF 2 CF 2 CF 2 OCF 3 .

6. The composition according to claim 1 , wherein R 1 is selected from: —(CF 2 ) a —, —(CF 2 ) a —O—(CF 2 ) b —, and —(CF 2 ) a —[O—(CF 2 ) b ] c —, —[(CF 2 ) a —O—] b —[(CF 2 ) c —O—] d , and combinations thereof, wherein a, b, c, and d are independently at least 1.

7. An article comprising the composition according to claim 1 .

8. The article of according to claim 7 , wherein the article is at least one of: a surfactant, a dispersion stabilizer, or an initiator.

9. The composition according to claim 1 , wherein the composition has a number average molecular weight of no more than 20,000 grams/mole.

10. A method for making a composition comprising:
oligomerizing a halofluoroalkene monomer, CX 7 X 9 ═CX 8 —(R 3 ) p —CZ 5 Z 6 —Y, with a sulfinating agent to produce the composition of formula (I),

wherein X 7 , X 8 , and X 9 are independently selected from H, F, Cl, Br, I, CF 3 , and CH 3 , and wherein at least one of X 7 , X 8 , and X 9 is H; and R 3 is a linking group; Z 5 and Z 6 are independently selected from Br, Cl, I, F, CF 3 , and a perfluoroalkyl group; p is 0 or 1; and Y is selected from I, Br, and Cl.

11. The method according to claim 10 , wherein the halofluoroalkene monomer is selected from BrCF 2 CH═CH 2 , ICF 2 CH═CH 2 , BrCF 2 CF 2 CH═CH 2 , ICF 2 CF 2 CH═CH 2 , CBr 3 CF 2 CF 2 CH═CH 2 , CCl 3 CF 2 CF 2 CH═CH 2 , ICF 2 CF 2 CH 2 CH═CH 2 , BrCF 2 CF 2 CH 2 CH═CH 2 , ICF 2 CF 2 CF 2 CF 2 CH═CH 2 , BrCF 2 CF 2 CF 2 CF 2 CH═CH 2 , ICF 2 CF 2 CF 2 CF 2 CH 2 CH═CH 2 , and BrCF 2 CF 2 CF 2 CF 2 CH 2 CH═CH 2 .

12. The method according to claim 10 , wherein no oxidizing agent is added during the oligomerization.

13. The method according to claim 10 , further comprising a second monomer, and the second monomer is selected from non-fluorinated olefin, a partially fluorinated olefin, and a perfluorinated olefin.

14. The method according to claim 10 , further comprising a solvent, wherein the solvent is water.

15. The method according to claim 10 , further comprising a buffer system.

16. The method according to claim 15 , wherein the buffer system is buffered at a pH greater than 2.

17. The method according to claim 10 , wherein the sulfinating agent system is selected from: Na 2 S 2 O 4 , NaHSO 3 /(NH 4 ) 2 Ce(NO 3 ) 6 , NaHSO 3 /FeCl 3 , NaHSO 3 /K 3 [Fe(CN) 6 ], HOCH 2 SO 2 Na, (NH 2 ) 2 CSO 2 , Na 2 S 2 O 5 , and combinations thereof.

18. The method according to claim 10 , wherein the oligomerizing is conducted at a temperature of between 20 to 100° C.

19. The method according to claim 10 , wherein the oligomerizing is conducted under an oxygen-free atmosphere.

Assignees

• Qiu Zai-Ming
• Dahlke Gregg D
• Fukushi Tatsuo
• Grootaert Werner M
• Guerra Miguel A
• 3M Innovative Properties Co

Inventors

• Qiu Zai-Ming
• Dahlke Gregg D
• Fukushi Tatsuo
• Grootaert Werner M
• Guerra Miguel A

Classifications

• C08F8/44 Primary

  Preparation of metal salts or ammonium salts · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F28/02

  by a bond to sulfur · CPC title

• C08F14/16

  Monomers containing bromine or iodine · CPC title

• C08F114/16 Primary

  Monomers containing bromine or iodine · CPC title