Water- and oil-repellent fluoroacrylates

• US 7,199,197 B2
• Filed: 12/28/2004
• Issued: 04/03/2007
• Est. Priority Date: 12/31/2003
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Moore, George G. I., Klun, Thomas P., Qiu, Zai-Ming, Ross, Richard B., Kinning, David J., Kumar, Ramesh C., Mader, Roger A., Clark, John C., Kirk, Alan R., Caldwell, Gregg A.
• Primary Examiner(s): Wu; David W.
• Assistant Examiner(s): Bernshteyn; M.
• Application Number:
  US11/027,604
• Publication Number:
  US 20050143541A1
• Time in Patent Office: 826 Days
• Field of Search: 526/242, 526/286, 526/319, 528/28, 528/70, 524/544, 560/167
• 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 monomer consisting of the reaction product of:

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

C_nF_2n+1—

X—

OH

wherein;

2. The fluoroacrylate monomer of claim 1 wherein X is

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

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

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

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

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

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

-diphenylmethane diisocyanate.

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

13. The fluoroacrylate monomer 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.

14. The fluoroacrylate monomer of claim 1 wherein the fluoroacrylate monomer is the reaction product of:

(a) C₄F₉SO₂NCH₃(CH₂)₂OH,

(b) 4,4′

-diphenylmethane diisocyanate, and

(c) hydroxy butyl acrylate or hydroxy ethyl acrylate.

15. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate monomer of claim 1 and repeating units derived from one or more nonfunctional comonomers.

16. A coating composition comprising a solvent and the fluorinated acrylic polymer of claim 15.

17. An article comprising a substrate having one or more surfaces coated with the coating composition of claim 16.

18. The article of claim 17 wherein said substrate is a hard substrate or a fibrous substrate.

19. A release coating composition comprising a solvent and the fluorinated acrylic polymer of claim 15.

20. An article comprising a substrate having one or more surfaces coated with the release coating composition of claim 19.

21. The fluoroacrylate monomer of claim 1 wherein the alkylene portion of the hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer is represented by the following general formula:

—

(C_pH_2p)—

wherein p=2 to 30.

22. The fluoroacrylate monomer of claim 21 wherein said hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer is a hydroxy-terminated alkyl acrylate monomer.

23. The fluoroacrylate monomer of claim 22 wherein said at least one unbranched symmetric diisocyanate comprises an aromatic diisocyanate, and p=2.

24. The fluoroacrylate monomer of claim 1 wherein the fluoroacrylate monomer is 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;

A=an unbranched symmetric alkylene group, arylene group, or aralkylene group,

p=2 to 30, and

R′

=H, CH₃, or F.

25. The fluoroacrylate monomer of claim 24 wherein A is an aromatic group, p=2, and R′

=H.

26. The fluoroacrylate monomer of claim 25 wherein said n is 1 to 4.

27. The fluoroacrylate monomer of claim 25 wherein X is

28. The fluoroacrylate monomer of claim 27 wherein R is CH₃ and m is from 2 to 4.

29. The fluoroacrylate monomer of claim 27 wherein A is selected from the group consisting of

30. The fluoroacrylate monomer of claim 29 wherein A is

31. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate monomer of claim 25.

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

33. An article comprising a substrate having one or more surfaces coated with the coating composition of claim 32.

34. The fluoroacrylate monomer of claim 14 wherein the fluoroacrylate monomer is 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;

n is 4,

35. A fluoroacrylate monomer consisting of the reaction product of:

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

C_nF_2n+1—

X—

OH

wherein;

36. The fluoroacrylate monomer of claim 35 wherein the fluoroacrylate monomer is 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;

A=an unbranched symmetric alkylene group, arylene group, or aralkylene group,

p=2 to 30, and

R′

=H or F.

37. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate monomer of claim 35.

38. A fluoroacrylate monomer comprising of the reaction product of:

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

C_nF_2n+1—

X—

OH

wherein;

39. The fluoroacrylate monomer of claim 38 wherein the fluoroacrylate monomer is 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;

A=an unbranched symmetric alkylene group, arylene group, or aralkylene group,

p=2 to 30, and

R′

=H or F.

40. A fluorinated acrylic polymer comprising repeating units of the fluoroacrylate monomer of claim 39.

41. A fluoroacrylate monomer comprising of the reaction product of:

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

C_nF_2n+1—

X—

OH

wherein;

42. The fluoroacrylate monomer of claim 41 wherein the fluoroacrylate monomer is 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;

A=an unbranched symmetric alkylene group, arylene group, or aralkylene group,

p=2 to 30, and

R′

=H or F.

43. The fluoroacrylate monomer of claim 42 wherein R′

=H.