Direct crosslinking process for preparing perfluoroalkyl-cross-linked fluoropolymer having perfluoroether pendant groups

Patent metadata

Field	Value
Publication number	US-9481769-B2
Application number	US-201314427867-A
Country	US
Kind code	B2
Filing date	Sep 26, 2013
Priority date	Sep 28, 2012
Publication date	Nov 1, 2016
Grant date	Nov 1, 2016

Abstract

This invention pertains to a novel thermal process for converting a fluoropolymer having cyano-functionalized perfluoroether pendant groups into a novel perfluoroalkyl-crosslinked fluoropolymer having perfluoroether pendant groups. The process comprises heating the fluoropolymer having cyano-functionalized perfluoroether pendant groups in the presence of Cl—F to a temperature in the range of 200 to 300° C. The fluoropolymer having cyano-functionalized perfluoroether pendant groups can first be formed into a shaped article, and the shaped article then subject to treatment in situ with Cl—F.

First claim

What is claimed is:

1. A process comprising forming a reaction mixture by combining, at a temperature in the range of room temperature to 100° C., Cl—F with a first cyano-functionalized polymer and a second cyano-functionalized polymer, each said cyano-functionalized polymer comprising a backbone chain, and wherein each said backbone chain comprises fluoroalkylene repeat units optionally substituted by ether oxygen, and a molar concentration in the range of a molar concentration of 0.5 to 50 mol-% of repeat units represented by Structure II

where x is an integer in the range of 0 to 3, y is an integer in the range of 0 to 6, and z is an integer in the range of 0 to 3; R 1 =(CF 2 ) a CFR 2 , where a is an integer in the range of 0 to 6, and R 2 is F or C 1-6 perfluoroalkyl optionally substituted by ether oxygen; and R 3 is F or C 1-6 perfluoroalkyl optionally substituted by ether oxygen; with the proviso that y and z cannot both be zero; and, with the further proviso that no monomeric species from which the repeat unit in the backbone chain of each said cyano-functionalized polymer has been formed, comprises more than two vinyl hydrogens attached thereto; and, heating said reaction mixture to a temperature in the range of 250 to 300° C.; with the proviso that said first and second cyano-functionalized polymers can be the same or different.

2. The process of claim 1 wherein said first cyano-functionalized polymer and a second cyano-functionalized polymer are the same.

3. The process of claim 2 wherein x=1, y=1, z=1, and a=1; R 2 =CF 3 ; and R 3 =F.

4. The process of claim 2 wherein the cyano-functionalized polymer further comprises perfluoroalkyl vinyl ether repeat units.

5. The process of claim 1 wherein said first cyano-functionalized polymer and a second cyano-functionalized polymer are different.

6. The process of claim 1 wherein the fluoroalkylene repeat units of at least one cyano-functionalized polymer comprise a combination of HFP and VF 2 repeat units.

7. The process of claim 1 wherein the fluoroalkylene repeat units of at least one cyano-functionalized polymer comprise a combination of TFE and PDD repeat units.

8. The process of claim 1 wherein at least one of said first or second polymers further comprises perfluoroalkyl vinyl ether repeat units.

9. The process of claim 1 wherein said first cyano-functionalized polymer and said second cyano-functionalized polymer each independently have no crystalline melting point above 180° C. that is associated with a latent heat of melting greater than 1 J/g.

10. The process of claim 1 further comprising the steps of removing residual Cl—F following the step of heating to 250 to 300° C., followed by further heating the polymer to a temperature in the range of >300 to 350° C. in an inert atmosphere.

11. A process comprising forming a reaction mixture by adding Cl—F, at a temperature in the range of room temperature to 100° C., to an evacuated vessel containing a cyano-functionalized polymer comprising a backbone chain comprising repeat units of tetrafluoroethylene, perfluoromethylvinyl ether, and a molar concentration in the range of 0.5 to 5 mol-% of repeat units represented by Structure VI

wherein said cyano-functionalized polymer has no crystalline melting point above 150° C. that is associated with a latent heat of melting greater than 1 J/g; subjecting said reaction mixture to heating to a temperature in the range of 250 to 300° C.; removing residual Cl—F following the step of heating in the range 250 to 300° C., followed by further heating the polymer to a temperature in the range of >300 to 350° C. in an inert atmosphere.

12. The process of claim 11 further comprising forming the reaction mixture into a shaped article prior to heating to a temperature in the range of 250 to 300° C.

Assignees

• Du Pont
• Du Pont

Inventors

• Bish Christopher J
• Wheland Robert Clayton

Classifications

• C08J2427/12

  containing fluorine atoms · CPC title

• C08J3/247 Primary

  Heating methods · CPC title

• C08J2327/18

  Homopolymers or copolymers of tetrafluoroethylene · CPC title

• C08J3/005

  Processes for mixing polymers · CPC title

• C08F214/26

  Tetrafluoroethene · CPC title