Azo-crosslinked fluoropolymer with perfluoroether pendant groups, process for preparing, and method for forming imaged article therewith

1. An azo-crosslinked polymer represented by Structure III

wherein each of Π α and Π β is a polymeric radical having a backbone chain comprising fluoroalkylene repeat units optionally substituted by ether oxygen, and azo-crosslinked repeat units at a molar concentration in the range of a molar concentration of 0.5 to 50 mol-%; where x 1 and x 2 each independently is an integer in the range of 0 to 3; y 1 and y 2 each independently is an integer in the range of 0 to 6, and z 1 and z 2 each independently 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; 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 and R 3 ′ are each independently F or C 1-6 perfluoroalkyl optionally substituted by ether oxygen; with the proviso that y 1 and z 1 cannot both be zero; with the further proviso that y 2 and z 2 cannot both be zero; with the further proviso that no repeat unit in the backbone chain of said Π α and Π β polymeric radicals has more than two vinyl hydrogens attached thereto; and, with the further proviso that Π α and Π β can be the same or different.

2. The azo-crosslinked polymer of claim 1 wherein Π α and Π β are the same.

3. The azo-crosslinked polymer of claim 2 wherein x 1 , x 2 , y 1 , y 2 , z 1 , z 2 , a and a′=1; R 2 and R 2 ′=CF 3 ; and R 3 and R 3 ′=F.

4. The azo-crosslinked polymer of claim 1 wherein Π α and Π β are different.

5. The azo-crosslinked polymer of claim 1 wherein the fluoroalkylene repeat units comprise a combination of TFE and PDD repeat units.

6. The azo-crosslinked polymer of claim 1 wherein at least one of Π α and Π β further comprises perfluoroalkyl vinyl ether repeat units.

7. An azo formation process for preparing the azo-crosslinked polymer of claim 1 comprising combining a first dichloroamino-functionalized polymer having a first backbone chain and a second dichloroamino-functionalized polymer having a second backbone chain to form a reaction mixture, and subjecting said thus formed reaction mixture to exposure to ultra-violet irradiation, at least a portion of which lies in the wavelength range from 200 to 425 nm for a period of time sufficient to convert at least a portion of said first and second polymers into a crosslinked product, each said first and second backbone chains comprising 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 dichloroamino-functionalized repeat units represented by Structure I

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; R1=(CF2)aCFR2, where a is an integer in the range of 0 to 6, and R2 is F or C1-6 perfluoroalkyl optionally substituted by ether oxygen; R3 is F or C1-6 perfluoroalkyl optionally substituted by ether oxygen; with the proviso that y and z cannot both be zero; and, with the further proviso that no repeat unit in the backbone chain of said dichloroamino-functionalized polymer has more than two vinyl hydrogens attached thereto; and, wherein said dichloroamino-functionalized polymer has no crystalline melting point above 180° C. that is associated with a latent heat of melting greater than 1 J/g; and, wherein said first polymer and said second polymer can be the same or different.

8. The azo formation process of claim 7 wherein said first dichloroamino-functionalized polymer and second dichloroamino-functionalized polymer are the same.

9. The azo formation process of claim 8 wherein x=1, y=1, z=1, and a=1; R2=CF3; and R3=F.

10. The azo formation process of claim 7 wherein said first dichloroamino-functionalized polymer and second dichloroamino-functionalized polymer are different.

11. The azo formation process of claim 7 wherein the fluoroalkylene repeat units comprise a combination of TFE and PDD repeat units.

12. The azo formation process of claim 7 wherein at least one of said first dichloroamino-functionalized polymer and second dichloroamino-functionalized polymer further comprises perfluoroalkyl vinyl ether repeat units.

13. The azo formation of process of claim 7 further comprising filmwise disposing the dichloroamino-functionalized polymers upon a substrate.

14. The azo formation process of claim 13 further comprising imagewise exposure of the filmwise disposed dichloroamino-functionalized polymers to the ultra-violet radiation.

15. An azo formation process for preparing the azo-crosslinked polymer of claim 1 comprising subjecting to ultra-violet irradiation in the wave-length range from 250-370 nm, a dichloroamino-functionalized polymer having a backbone chain for a period of time sufficient to convert at least a portion of said dichloroamino-functionalized polymer into a crosslinked product; said backbone chain comprising repeat units of tetrafluoroethylene, perfluoromethylvinyl ether, and a molar concentration in the range of 0.5 to 5 mol-% of dichloroamino-functionalized repeat units represented by Structure V

wherein said dichloroamino-functionalized polymer has no crystalline melting point above 150° C. that is associated with a latent heat of melting greater than 1 J/g.

16. The azo formation of process of claim 15 further comprising filmwise disposing the dichloroamino-functionalized polymer upon a substrate.

17. The azo formation process of claim 16 further comprising imagewise exposure of the filmwise disposed dichloroamino-functionalized polymer to the ultra-violet radiation.

18. azo-crosslinked polymer represented by Structure VII:

wherein π is a polymeric radical having a backbone chain comprising repeat units of tetrafluoroethylene, perfluoromethyvinyl ether, and azo-crosslinked repeat units at a molar concentration of 0.5 to 5 mol-%.