Water- and oil-repellent fluoroacrylates

• US 20050143541A1
• Filed: 12/28/2004
• Published: 06/30/2005
• Est. Priority Date: 12/31/2003
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Kinning, David J., Klun, Thomas P., Qiu, Zai-Ming, Moore, George G.I., Ross, Richard B., Kumar, Ramesh C., Mader, Roger A., Clark, John C., Kirk, Alan R., Caldwell, Gregg A.
• Granted Patent: US 7,199,197 B2
• Time in Patent Office: Days
• US Class Current: 526/242
• CPC Class Codes: C07C 271/20 to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
• CPC Class Codes: C07C 271/28 to a carbon atom of a non-condensed six-membered aromatic ring
• CPC Class Codes: C07C 311/09 the carbon skeleton being further substituted by at least two halogen atoms
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen
• CPC Class Codes: Y10T 442/2287 Fluorocarbon containing

Abstract

Fluoroacrylates comprise the reaction product of: (a) at least one fluorochemical alcohol represented by the formula:
C_nF_2n+1—X—OH
wherein:  R=hydrogen or an alkyl group of 1 to 4 carbon atoms,  m=2 to 8,

• •  R_f═C_nF_2n+1,  y=0 to 6, and  q=1 to 8; (b) at least one unbranched symmetric diisocyanate; and (c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoro acrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

Claims

1. A fluoroacrylate comprising the reaction product of:

(a) at least one fluorochemical alcohol represented by the formula;

C_nF_2n+1—

X—

OH

wherein;

 

R=hydrogen or an alkyl group of 1 to 4 carbon atoms,

 

m=2 to 8,

 

R_f═

C_nF_2n+1,

 

y=0 to 6, and

 

q=1 to 8;

(b) at least one unbranched symmetric diisocyanate; and

(c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

2. The fluoroacrylate of claim 1 wherein said X is

3. The fluoroacrylate of claim 2 wherein said R is a methyl group.

4. The fluoroacrylate of claim 3 wherein said m is 2 to 4.

5. The fluoroacrylate of claim 1 wherein said n is 1 to 4.

6. The fluoroacrylate of claim 5 wherein n is 4.

7. The fluoroacrylate of claim 6 wherein said fluorochemical alcohol is selected from the group consisting of C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, and C₄F₉(CH₂)₂OH.

8. The fluoroacrylate of claim 7 wherein said fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

9. The fluoroacrylate of claim 1 wherein said unbranched symmetric diisocyanate is selected from the group consisting of 4,4′

-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and 1,4-phenylene diisocyanate.

10. The fluoroacrylate of claim 9 wherein said unbranched symmetric diisocyanate is 4,4′

-diphenylmethane diisocyanate.

11. The fluoroacrylate of claim 1 wherein said hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer has between about 2 and about 12 carbon atoms in its alkylene portion.

12. The fluoroacrylate of claim 1 wherein said hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer is a hydroxy-terminated acrylate monomer.

13. The fluoroacrylate of claim 12 wherein said hydroxy-terminated alkyl acrylate monomer is selected from the group consisting of hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, and hydroxy dodecyl acrylate.

28. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate of claim 1.

29. The fluorinated acrylic polymer of claim 28 further comprising repeating units derived from one or more nonfunctional comonomers.

30. The fluorinated acrylic polymer of claim 28 further comprising repeating units derived from one or more functional comonomers.

31. A coating composition comprising a solvent and the fluorinated acrylic polymer of claim 28.

36. An article comprising a substrate having one or more surfaces coated with the coating composition of claim 31.

37. The article of claim 36 wherein said substrate is a hard substrate or a fibrous substrate.

40. A release coating composition comprising a solvent and the fluorinated acrylic polymer of claim 28.

42. An article comprising a substrate having one or more surfaces coated with the release coating composition of claim 40.

14. A fluoroacrylate comprising the reaction product of:

(a) C₄F₉SO₂NCH₃(CH₂)₂OH,

(b) 4,4′

-diphenylmethane diisocyanate, and

(c) hydroxy butyl acrylate or hydroxy ethyl acrylate.

15. A fluoroacrylate represented by the following general formula:

C_nF_2n+1—

X—

OC(O)NH-A-HNC(O)O—

(C_pH_2p)(O)COC(R′

)═

CH₂

wherein;

16. The fluoroacrylate of claim 15 wherein said n is 1 to 4.

17. The fluoroacrylate of claim 16 wherein n is 4.

18. The fluoroacrylate of claim 15 wherein said X is

19. The fluoroacrylate of claim 18 wherein said R is CH₃.

20. The fluoroacrylate of claim 19 wherein said m is 2 to 4.

21. The fluoroacrylate of claim 15 wherein said A is selected from the group consisting of

22. The fluoroacrylate of claim 21 wherein said A is

23. The fluoroacrylate of claim 15 wherein said p is 2 to 12.

24. The fluoroacrylate of claim 23 wherein said p is selected from the group consisting of 2, 4, 6, 10, and 12.

25. The fluoroacrylate of claim 24 wherein said p is 2.

26. The fluoroacrylate of claim 15 wherein said R′

is H.

32. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate of claim 15.

33. The fluorinated acrylic polymer of claim 32 further comprising repeating units derived from one or more nonfunctional comonomers.

34. The fluorinated acrylic polymer of claim 32 further comprising repeating units derived from one or more functional comonomers.

35. A coating composition comprising a solvent and the fluorinated acrylic polymer of claim 32.

38. An article comprising a substrate having one or more surfaces coated with the coating composition of claim 35.

39. The article of claim 38 wherein said substrate is a hard substrate or a fibrous substrate.

41. A release coating composition comprising a solvent and the fluorinated acrylic polymer of claim 32.

43. An article comprising a substrate having one or more surfaces coated with the release coating composition of claim 41.

27. A fluorinated isocyanate represented by the following general formula:

C_nF_2n+1—

X—

OC(O)NH-A-NCO

wherein;