Tetrafluoroethylene copolymers having sulfonyl groups

Patent metadata

Field	Value
Publication number	US-10676555-B2
Application number	US-201615550295-A
Country	US
Kind code	B2
Filing date	Feb 12, 2016
Priority date	Feb 12, 2015
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

A copolymer having tetrafluoroethylene units and units independently represented by formula (I) in a range from 0.02 to 2 mole percent, based on the total amount of the copolymer. Rf is a linear or branched perfluoroalkyl group having from 1 to 8 carbon atoms and optionally interrupted by one or more —O— groups, each n is independently from 1 to 6, m is 0 or 1, and z is 0, 1, or 2. The copolymer has a melt flow index in a range from 20 grams per 10 minutes to 40 grams per 10 minutes and has in a range from 2 to 200 —SO 2 X groups per 10 6 carbon atoms and up to 100 unstable end groups per 10 6 carbon atoms. 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, units independently represented by formula

in a range from 0.02 to 2 mole percent, based on the total amount of the copolymer, 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, and units represented by formula

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,
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, and wherein the copolymer has in a range from 2 to 200 SO 2 X groups per 10 6 carbon atoms and up to 100 unstable end groups per 10 6 carbon atoms, wherein X is independently —F, —NH 2 , —OH, or —OZ, wherein Z is independently a metallic cation or a quaternary ammonium cation, 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.

2. The copolymer of claim 1 , wherein m is 0.

3. The copolymer of claim 1 , wherein Rf is —CF 3 , and wherein n is 1 or 3.

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

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 c is 0, d is 1, and e is 1 to 4; or wherein a is 1, b is 1, c is 0 to 4, d is 1, e is 1 to 4.

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

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

9. The extruded article of claim 8 , wherein the extruded article comprises at least one of a film, tube, pipe, or hose.

10. The extruded article of claim 8 , wherein the extruded article is a conductor having the copolymer extruded thereon.

11. The extruded article of claim 8 , wherein the extruded article is a cable or wire having the copolymer extruded thereon.

12. A method of making the copolymer of claim 1 , the method comprising copolymerizing components comprising tetrafluoroethylene and at least one compound independently represented by formula CF 2 ═CF(CF 2 ) m (OC n F 2n ) z ORf, 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.

13. The method of claim 12 , wherein copolymerizing is carried out in the presence of a bisulfite or sulfite salt.

14. 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.

15. A copolymer comprising tetrafluoroethylene units and units independently represented by formula

in a range from 0.02 to 2 mole percent, based on the total amount of the copolymer, 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, 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, and wherein the copolymer has in a range from 2 to 200 —SO 2 X end groups per 10 6 carbon atoms and up to 100 unstable end groups per 10 6 carbon atoms, wherein X is independently —F, —NH 2 , —OH, or —OZ, wherein Z is independently a metallic cation or a quaternary ammonium cation, 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.

16. The copolymer of claim 15 , further comprising units derived from at least one perfluorinated terminal olefin independently having from 3 to 8 carbon atoms.

17. The copolymer of claim 16 , wherein the units derived from the at least one perfluorinated terminal olefin are hexafluoropropylene units.

18. The copolymer of claim 17 , 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.

19. The copolymer of claim 17 , wherein the copolymer has a melting point in a range from 220° C. to 285° C.

20. The copolymer of claim 15 , wherein the copolymer further comprises units represented by formula

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.

Assignees

• 3M Innovative Properties Co

Inventors

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

Classifications

• H01B3/445

  from vinylfluorides or other fluoroethylenic compounds · CPC title

• C08F2800/10

  as molar percentages · CPC title

• C08F214/26 Primary

  Tetrafluoroethene · CPC title

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title

• C08J2327/18

  Homopolymers or copolymers of tetrafluoroethylene · CPC title