Tetrafluoroethylene and perfluorinated allyl ether copolymers

Patent metadata

Field	Value
Publication number	US-10844152-B2
Application number	US-201615550308-A
Country	US
Kind code	B2
Filing date	Feb 12, 2016
Priority date	Feb 12, 2015
Publication date	Nov 24, 2020
Grant date	Nov 24, 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 —0— groups, n is independently from 1 to 6, 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. 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 derived from at least one perfluorinated terminal olefin independently having from 3 to 8 carbon atoms, 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 n is independently from 1 to 6, 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.

2. The copolymer of claim 1 , wherein the copolymer has up 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.

3. The copolymer of claim 2 , wherein the —SO 2 X groups comprise —SO 2 X end groups.

4. The copolymer of claim 2 , further comprising 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, and 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.

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

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

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

8. The copolymer of claim 1 , wherein the units derived from the at least one perfluorinated terminal olefin are hexafluoropropylene units.

9. The copolymer of claim 8 , wherein at least one of the following limitations is met:
the hexafluoropropylene units are present in the copolymer at 10 percent to 17 percent by weight, based on the total weight of the copolymer, or
the copolymer has a melting point in a range from 220° C. to 285° C.

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

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

12. The extruded article of claim 11 , wherein the extruded article comprises at least one of a film, tube, pipe, or hose.

13. The extruded article of claim 11 , wherein the extruded article is a conductor having the copolymer extruded thereon.

14. A method of making the copolymer of claim 1 , the method comprising copolymerizing components comprising tetrafluoroethylene, at least one perfluorinated terminal olefin independently having from 3 to 8 carbon atoms, and at least one compound independently represented by formula CF 2 ═CFCF 2 (OC n F 2n ) z ORf, wherein n is independently from 1 to 6, 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.

15. The extruded article of claim 11 , wherein the extruded article is not foamed.

16. The extruded article of claim 11 , wherein the extruded article is foamed.

17. The copolymer of claim 1 , wherein the copolymer comprises less than 50 ppm alkali-metal cations.

18. The copolymer of claim 1 , wherein the copolymer comprises at least 50 ppm alkali-metal cations.

19. The copolymer of claim 1 , wherein z is 0.

20. 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 n is independently from 1 to 6, 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.

Assignees

• 3M Innovative Properties Co

Inventors

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

Classifications

• H01B3/445

  from vinylfluorides or other fluoroethylenic compounds · CPC title

• C08J2327/18

  Homopolymers or copolymers of tetrafluoroethylene · CPC title

• C08F214/26 Primary

  Tetrafluoroethene · CPC title

• C08F214/262 Primary

  with fluorinated vinyl ethers · CPC title

• C08J2201/03

  Extrusion of the foamable blend · CPC title