Extrudable fluoropolymer blends

• US 6,790,912 B2
• Filed: 12/11/2001
• Issued: 09/14/2004
• Est. Priority Date: 12/11/2001
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Blong, Thomas J.
• Primary Examiner(s): RAYFORD, SANDRA M
• Application Number:
  US10/015,154
• Publication Number:
  US 20030138580A1
• Time in Patent Office: 1,008 Days
• Field of Search: 428/35.7, 525/197, 525/199, 264/211
• US Class Current: 525/197
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 27/18 Homopolymers or copolymers or tetrafluoroethene
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/139 Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 428/31891 Where addition polymer is an ester or halide

Abstract

Provided is a melt processable fluorothermoplastic composition comprising a major amount of a first semi-crystalline fluorinated copolymer and a minor amount of a second fluoropolymer effective to reduce melt defects in the composition. Each fluoropolymer is selected from four classes. The first class, (a), includes a semi-crystalline perfluorinated copolymer. The second class, (b), includes a fluoropolymer derived from interpolymerized units of at least one essentially perfluorinated monomer and at least one non-fluorinated hydrogen-containing monomer. The third class, (c), includes a fluoropolymer derived from interpolymerized units of at least one partially-fluorinated monomer, and optionally at least one essentially perfluorinated monomer. The second fluoropolymer is selected from a category other than the category in which the first fluoropolymer is selected. The minor component also can include interpolymerized units of a PAVE, and/or a PAOVE. A method of improving surface properties in a fluoropolymer extrudate is also provided.

Claims

1. A melt processable fluorothermoplastic composition comprising a major amount of a first fluoropolymer, wherein the first fluoropolymer comprises a semi-crystalline fluorinated copolymer, and a minor amount of a second fluoropolymer effective to reduce melt defects in the composition, each fluoropolymer being selected from:

(a) a semi-crystalline perfluorinated copolymer,

(b) a fluoropolymer derived from interpolymerized units of at least one essentially perfluorinated monomer, at least one non-fluorinated hydrogen-containing monomer, and optionally, perfluorobutyl-ethylene and/or no more than about 1% by weight of other partially fluorinated monomers;

(c) a fluoropolymer derived from interpolymerized units of at least one partially-fluorinated monomer, and optionally at least one essentially perfluorinated monomer, and

(d) an amorphous copolymer of tetrafluoroethylene and hexafluoropropylene;

wherein when the first fluoropolymer is selected from (a), the second fluoropolymer is a semi-crystalline fluoropolymer selected from (b) and/or (c);

when the first fluoropolymer is selected from (b), the second fluoropolymer is selected from (a), (c), and/or (d); and

when the first fluoropolymer is a copolymer selected from (c), the second fluoropolymer is selected from (a), (b), and/or (d);

with the proviso that, when the melt processable fluorothermoplastic composition comprises one or more copolymers selected from (c), the melt processable fluorothermoplastic composition comprises either;

at least about 80% by weight of copolymers selected from (c) or no more than about 5% by weight of copolymers selected from (c).

2. The composition of claim 1 wherein the first fluoropolymer comprises a semi-crystalline perfluorinated copolymer.

3. The composition of claim 2 wherein the first fluoropolymer comprises a copolymer of TFE with HFP and/or a PAVE.

4. The composition of claim 3 wherein the level of HFP is from about 10 to about 20% by weight.

5. The composition of claim 3 wherein the level of PAVE is from about 2 to about 10% by weight.

6. The composition of claim 2 wherein the second fluoropolymer comprises:

(i) a fluoropolymer derived from interpolymerized units of at least one essentially perfluorinated monomer and at least one non-fluorinated hydrogen-containing monomer, and/or (ii) a fluoropolymer derived from interpolymerized units of at least one partially-fluorinated monomer, and optionally at least one essentially perfluorinated monomer.

7. The composition of claim 6 wherein the essentially perfluorinated monomer comprises TFE and/or HFP and the non-fluorinated hydrogen-containing monomer comprises ethylene and/or propylene.

8. The composition of claim 7 wherein the level of non-fluorinated hydrogen-containing monomer is about 10% by weight or greater.

9. The composition of claim 6 wherein the second fluoropolymer is derived from interpolymerized units of TFE and ethylene, and optionally HFP, a PAVE, and/or PFBE.

10. The composition of claim 6 wherein the second fluoropolymer is derived from interpolymerized units of TFE and propylene.

11. The composition of claim 3 wherein the second copolymer is derived from interpolymerized units of TFE and ethylene, and optionally HFP, a PAVE, and/or PFBE.

12. The composition of claim 1 wherein the first fluoropolymer comprises a fluoropolymer derived from interpolymerized units of at least one essentially perfluorinated monomer and at least one non-fluorinated hydrogen-containing monomer.

13. The composition of claim 12 wherein the first fluoropolymer is derived from interpolymerized units of TFE and ethylene, and optionally HFP, PPVE-1, and/or PFBE.

14. The composition of claim 12 wherein the second fluoropolymer comprises a semi-crystalline perfluorinated copolymer;

and/or a fluoropolymer derived from interpolymerized units of at least one partially-fluorinated monomer, and optionally at least one essentially perfluorinated monomer.

15. The composition of claim 14 wherein the second fluorinated copolymer comprises a copolymer of TFE with HFP and/or a PAVE.

16. The composition of claim 1 wherein the first fluoropolymer comprises a fluoropolymer derived from interpolymerized units of at least one partially-fluorinated monomer, and at least one essentially perfluorinated monomer.

17. The composition of claim 16 wherein the partially fluorinated monomer comprises VF2 and the essentially perfluorinated monomer comprises TFE, HFP, and/or a PAVE.

18. The composition of claim 16 wherein the first fluoropolymer comprises interpolymerized units of VF2, TFE, and HFP, and optionally a PAVE.

19. The composition of claim 17 wherein the amount of VF2 comprises from about 5 to about 40% by weight.

20. The composition of claim 17 wherein the amount of VF2 comprises from about 5 to about 20% by weight.

21. The composition of claim 16 wherein the second fluoropolymer comprises a semi-crystalline perfluorinated copolymer;

and/or a fluoropolymer derived from interpolymerized units of at least one essentially perfluorinated monomer and at least one non-fluorinated hydrogen-containing monomer.

22. The composition of claim 1 wherein the first fluoropolymer comprises interpolymerized units of TFE, HFP, and from about 5 to about 20% by weight of VF2, and the second copolymer comprises interpolymerized units of ethylene and/or propylene, and TFE and/or HFP.

23. The composition of claim 1 wherein the second fluoropolymer further comprises an amorphous fluorinated copolymer derived from interpolymerized units of a perfluoro (alkoxy vinyl) ether and a comonomer which may be partially or fully fluorinated;

and/or an amorphous fluorinated copolymer derived from interpolymerized units of at least 3 mole percent (mol %) of an hydrogen containing comonomer, and a perfluoro (alkoxy vinyl) ether and/or a perfluoro (alkyl vinyl) ether.

29. An article comprising the composition of claim 1.

30. The composition of claim 1 in the form of a container, film, hose, tubing, or wire coating.

24. A melt processable fluorothermoplastic composition comprising a major amount of a first fluoropolymer, wherein the first fluoropolymer comprises semi-crystalline fluorinated copolymer, and a minor amount of a second fluoropolymer effective to reduce melt defects in the composition, the second fluoropolymer being selected from:

(a) an amorphous fluorinated copolymer derived from interpolymerized units of a perfluoro (alkoxy vinyl) ether and a comonomer which may be partially or fully fluorinated; and

/or

(b) up to about 5% by weight of an amorphous fluorinated copolymer derived from interpolymerized units of at least 3 mole percent (mol %) of an hydrogen containing comonomer, and a perfluoro (alkoxy vinyl) ether.

25. The composition of claim 24 wherein the second fluoropolymer comprises at least about 5 mol % of an hydrogen containing comonomer.

26. The composition of claim 24 wherein the second fluoropolymer comprises a perfluoro (alkoxy vinyl) ether wherein the alkoxy group contains 2 to 6 carbon atoms.

27. The composition of claim 24 wherein the second fluoropolymer comprises a perfluoro (alkyl vinyl) ether wherein the alkyl group contains 1 to 5 carbon atoms.

28. The composition of claim 24 wherein the second fluoropolymer comprises a hydrogen containing comonomer selected from vinylidene fluoride, trifluoroethylene, ethylene, propylene, and combinations thereof.