Tetrafluoroethylene/hexafluoropropylene copolymers having pendant sulfonyl groups

Patent metadata

Field	Value
Publication number	US-10717795-B2
Application number	US-201615550314-A
Country	US
Kind code	B2
Filing date	Feb 12, 2016
Priority date	Feb 12, 2015
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

A copolymer having tetrafluoroethylene units, hexafluoropropylene units, and units independently represented by formula in a range from 0.001 to 2 mole percent, based on the total amount of the copolymer. In these units, a is 0 or 1, each b is independently from 1 to 4, c is 0 to 4, d is 0 or 1, and e is 1 to 6. In the —SO 2 X groups, X is independently —F, —NH 2 , —OH, or —OZ, wherein Z is independently a metallic cation or a quaternary ammonium cation. The copolymer has a melt flow index in a range from 20 grams per 10 minutes to 40 grams per 10 minutes. The copolymer can be extruded to make articles, such as insulated cables. A method of making the copolymer is also disclosed.

First claim

What is claimed is:

1. A copolymer comprising tetrafluoroethylene units, hexafluoropropylene units, and units independently represented by formula

in a range from 0.001 to 2 mole percent, based on the total amount of the copolymer, wherein a is 0 or 1, each b is independently from 1 to 4, c is 0 to 4, d is 0 or 1, e is 1 to 6, and X is independently F, —NH 2 , —OH, or —OZ, wherein Z is independently a metallic cation or a quaternary ammonium cation, and wherein the copolymer has a melt flow index in a range from 20 grams per 10 minutes to 40 grams per 10 minutes measured at a temperature of 372° C. and at a support weight of 5.0 kg.

2. The copolymer of claim 1 , wherein c is 0, d is 1, and e is 1 to 4.

3. The copolymer of claim 1 , wherein a is 0, OC b F 2b is OCF 2 CF(CF 3 ), c is 1 or 2, d is 1, and e is 1 to 4.

4. The copolymer of claim 1 , wherein a is 1, b is 1, c is 0 to 4, d is 1, and e is 1 to 4.

5. The copolymer of claim 1 , wherein the copolymer has a polydispersity of less than or equal to 2.5.

6. The copolymer of claim 1 , wherein the copolymer has up to 100 unstable end groups per 10 6 carbon atoms, wherein the unstable end groups are selected from —COOM, —CH 2 OH, —COF, and —CONH 2 , and wherein M is independently an alkyl group, a hydrogen atom, a metallic cation, or a quaternary ammonium cation.

7. The copolymer of claim 1 , wherein the units independently represented by formula

are present in a range from 0.001 to 0.5 mole percent, based on the total amount of the copolymer.

8. The copolymer of claim 1 , wherein the hexafluoropropylene units are present in the copolymer at 10 percent to 17 percent by weight, based on the total weight of the copolymer.

9. The copolymer of claim 1 , wherein the copolymer has a melting point in a range from 220° C. to 285° C.

10. The copolymer of claim 1 , wherein the copolymer further comprises units independently represented by formula

wherein each n is independently from 1 to 6, m is 0 or 1, z is 0, 1, or 2, and Rf is a linear or branched perfluoroalkyl group having from 1 to 8 carbon atoms and optionally interrupted by one or more —O— groups.

11. The copolymer of claim 10 , wherein the copolymerized units independently represented by formula

and the copolymerized units independently represented by formula

are present in the copolymer in a combined amount from 0.02 mole percent to 2 mole percent, based on the total amount of the copolymer.

12. A method of making an extruded article, the method comprising extruding a melted composition comprising the copolymer of claim 1 .

13. An extruded article comprising the copolymer of claim 1 .

14. A method of making the copolymer of claim 1 , the method comprising copolymerizing components comprising tetrafluoroethylene, hexafluoropropylene, and at least one compound independently represented by formula CF 2 ═CF(CF 2 ) a —(OC b F 2b ) c —(O) d —(C e F 2e )—SO 2 X, wherein a is 0 or 1, each b is independently from 1 to 4, c is 0 to 4, d is 0 or 1, e is 1 to 6, and X is independently F, —NH 2 , —OH, or —OZ, and wherein Z is independently a metallic cation or a quaternary ammonium cation.

15. The method of claim 14 , wherein copolymerizing is carried out in the presence of a bisulfite or sulfite salt to generate —SO 2 X end groups, wherein X is independently —F, —NH 2 , —OH, or —OZ, and wherein Z is independently a metallic cation or a quaternary ammonium cation.

16. The extruded article of claim 13 , wherein the extruded article comprises at least one of a film, tube, pipe, or hose.

17. The extruded article of claim 13 , wherein the extruded article is a conductor having the copolymer extruded thereon.

18. The extruded article of claim 13 , wherein the extruded article is a cable or wire having the copolymer extruded thereon.

19. The copolymer of claim 10 , wherein z is 1 or 2.

20. The copolymer claim 1 , further comprising —SO 2 X end groups.

Assignees

• 3M Innovative Properties Co

Inventors

• Duchesne Denis
• Hintzer Klaus
• Kaspar Harald
• Lochhaas Kai H
• Schrooten Jens
• Zipplies Tilman C

Classifications

• C08J9/00

  Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C) · CPC title

• H01B3/445

  from vinylfluorides or other fluoroethylenic compounds · CPC title

• C08J2201/03

  Extrusion of the foamable blend · CPC title

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C08F214/262 Primary

  with fluorinated vinyl ethers · CPC title