Water- and oil-repellent fluorourethanes and fluoroureas

• US 7,268,197 B2
• Filed: 12/12/2005
• Issued: 09/11/2007
• Est. Priority Date: 12/28/2004
• Status: Active Grant

• 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, Jariwala, Chetan P., Kumar, Ramesh C., Clark, John C.
• Primary Examiner(s): Wu; David W.
• Assistant Examiner(s): BERNSHTEYN, MICHAEL
• Application Number:
  US11/275,114
• Publication Number:
  US 20060142474A1
• Time in Patent Office: 638 Days
• Field of Search: 526/242, 526/286, 526/319, 528/70, 524/544, 560/167
• US Class Current: 526/242
• CPC Class Codes: C08G 18/2845 Monohydroxy epoxy compounds
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/3228 acyclic
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/6212 Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
• CPC Class Codes: C08G 18/6705 Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
• CPC Class Codes: C08G 18/71 Monoisocyanates or monoisothiocyanates
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

A fluorochemical compound comprises the reaction product of:

• • (a) the reaction product of:
    • (i) at least one fluorochemical alcohol represented by the formula:
      C_nF_2n+1—X—OH
  • wherein:
  • n=1 to 6,

• • 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,
  • q=1 to 8; and
    • (ii) at least one unbranched symmetric diisocyanate, and
  • (b) at least one co-reactant comprising two or more functional groups that are capable of reacting with an isocyanate group.

Claims

1. A fluorochemical compound comprising the reaction product of:

(a) the reaction product of;

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

C_nF_2n+1—

X—

OH

wherein;

n=1 to 6,

2. The fluorochemical compound of claim 1 wherein n=1 to 5.

3. The fluorochemical compound of claim 2 wherein n=4.

4. The fluorochemical compound of claim 1 wherein X is

5. The fluorochemical compound of claim 1 wherein the fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

6. The fluorochemical compound of claim 1 wherein the unbranched symmetric diisocyanate is 4,4′

-diphenylmethane diisocyanate.

7. The fluorochemical compound of claim 1 wherein at least one co-reactant is a polythiol.

8. A coating composition comprising a solvent and the fluorochemical compound of claim 1.

9. The coating composition of claim 8 wherein the coating composition is a release coating.

11. The fluorochemical compound of claim 1 wherein at least one co-reactant comprises an acrylate polymer or copolymer comprising hydroxyl-containing (meth)acrylate monomers;

a polyester diol;

a dimer diol;

a fatty acid ester diol;

a polysiloxane dicarbinols;

an alkane diol;

an alkane tetraols;

a polyvinyl alcohol;

a polyepoxides;

a polystyrene;

a polyester;

or a polyurethane.

12. The fluorochemical compound of claim 11 wherein at least one co-reactant comprises an acrylate polymer or copolymer comprising hydroxyl-containing (meth)acrylate monomers.

13. The fluorochemical compound of claim 12 wherein at least one co-reactant comprises an acrylate copolymer comprising hydroxyethyl acrylate in combination with butyl acrylate, isooctyl acrylate, or octadecyl acrylate;

poly co{hydroxyethyl acrylate/mercaptopropylmethylsiloxane-co-dimethylsiloxane};

or poly(2-hydroxyethyl methacrylate).

14. The fluorochemical compound of claim 1 wherein at least one co-reactant comprises H₂N(CH₂CH₂NH)₂H;

H₂N(CH₂CH₂NH)₃H;

H₂N(CH₂CH₂NH)₄H;

H₂N(CH₂CH₂NH)₅H;

H₂N(CH₂CH₂CH₂NH)₂H;

H₂N(CH₂CH₂CH₂NH)₃H;

H₂N(CH₂CH₂CH₂CH₂NH)₂H;

H₂N(CH₂CH₂CH₂CH₂CH₂CH₂NH) ₂H;

H₂N(CH₂)₃NHCH₂CH═

CHCH₂NH(CH₂)₃NH₂;

H₂N(CH₂)₄NH(CH₂)₃NH₂;

H₂N(CH₂)₃NH(CH₂)₄NH(CH₂)₃NH₂;

H₂N(CH₂)₃NH(CH₂)₂NH (CH₂)₃NH₂;

H₂N(CH₂)₂NH(CH₂)₃NH(CH₂)₂NH₂;

H₂N(CH₂)₃NH(CH₂)₂NH ₂;

C₆H₅NH(CH₂)₂NH(CH₂)₂NH₂;

1,10-diaminodecane;

1,12-diaminododecane;

9,9-bis(3-aminopropyl)fluorene;

bis(3-aminopropyl)phenylphosphine;

2-(4-aminophenyl)ethylamine;

1,4-butanediol bis(3-aminopropyl)ether;

N(CH₂CH₂NH₂)₃;

1,8-diamino-p-menthane;

4,4′

-diaminodicyclohexylmethane;

1,3-bis(3-aminopropyl) tetramethyldisiloxane;

1,8-diamino-3,6-dioxaoctane;

1,3-bis(aminomethyl)cyclohexane;

1,4-bis(3-aminopropyl)piperazine;

a homopolymer or copolymer of ethyleneimine;

aminopropylmethylsiloxane-co-dimethylsiloxane;

or bis-aminopropyldimethylsiloxane.

15. The fluorochemical compound of claim 7 wherein at least one co-reactant comprises a homopolymer of mercaptopropylmethylsiloxane;

a copolymer of mercaptopropylmethylsiloxane and dimethylsiloxane;

1,1,1-trimethylolpropane tris-(3-mercaptopropionate);

pentaerythritol tetra(3-mercaptopropionate);

trimethylolpropane tris(3-mercaptopropionate);

tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate;

2,2′

-oxydiethanethiol;

1,2-ethanethiol;

3,7-dithia-1,9-nonanedithiol;

1,4-butanedithiol;

1,6-hexanedithiol;

1,7-heptanedithiol;

1,8-octanedithiol;

1,9- nonanedithiol;

3,6-dioxa-1,8-octanedithiol;

1,10-decanedithiol;

1,12-dimercaptododecane;

ethylene glycol bis(3-mercaptopropionate);

or 1,4-butanediol bis(3-mercaptopropionate).

21. An article comprising a substrate coated with the coating composition of claim 1.

22. The article of claim 21 wherein the substrate is a hard substrate or a fibrous substrate.

23. The article of claim 22 wherein the substrate is a fibrous substrate.

10. A method for making a fluorochemical compound comprising:

(a) reacting at least one fluorochemical alcohol with at least one unbranched symmetric diisocyanate to form a fluorinated isocyanate, the fluorochemical alcohol being represented by the formula;

C_nF_2n+1—

X—

OH

wherein;

n=1 to 6,

16. The method of claim 10 wherein the fluorochemical compound comprises unreacted functional groups thereon.

17. The method of claim 10 wherein at least one compound comprises an acrylate polymer or copolymer comprising hydroxyl-containing (meth)acrylate monomers;

a polyester diol;

a dimer diol;

a fatty acid ester diol;

a polysiloxane dicarbinols;

an alkane diol;

an alkane tetraols;

a polyvinyl alcohol;

a polyepoxides;

a polystyrene;

a polyester;

or a polyurethane.

18. The method of claim 17 wherein at least one compound comprises an acrylate copolymer comprising hydroxyethyl acrylate in combination with butyl acrylate, isooctyl acrylate, or octadecyl acrylate;

poly co{hydroxyethyl acrylate/mercaptopropylmethylsiloxane-co-dimethylsiloxane};

or poly(2-hydroxyethyl methacrylate).

19. The method of claim 10 wherein at least one compound comprises H₂N(CH₂CH₂NH)₂H;

H₂N(CH₂CH₂NH)₃H;

H₂N(CH₂CH₂NH)₄H;

H₂N(CH₂CH₂NH)₅H;

H₂N(CH₂CH₂CH₂NH)₂H;

H₂N(CH₂CH₂CH₂NH)₃H;

H₂N(CH₂CH₂CH₂CH₂NH)₂H;

H₂N(CH₂CH₂CH₂CH₂CH₂CH₂NH)₂H;

H₂N(CH₂)₃NHCH₂CH═

CHCH₂NH(CH₂)3NH₂;

H₂N(CH₂)₄NH(CH₂)₃NH₂;

H₂N(CH₂)₃NH(CH₂)₄NH(CH₂)₃NH<sub>2;

H2</sub>N(CH₂)₃NH(CH₂)₂NH(CH₂)₃NH₂;

H₂N(CH₂)₂NH(CH₂) ₃NH(CH₂)₂NH₂;

H₂N(CH₂)₃NH(CH₂)₂NH₂;

C₆H₅NH(CH₂)₂NH(CH₂)₂NH₂;

1,10-diaminodecane;

1,12-diaminododecane;

9,9-bis(3-aminopropyl)fluorene;

bis(3 -aminopropyl)phenylphosphine;

2-(4-aminophenyl)ethylamine;

1,4-butanediol bis(3-aminopropyl)ether;

N(CH₂CH₂NH₂)₃;

1,8-diamino-p-menthane;

4,4′

-diaminodicyclohexylmethane;

1,3-bis(3-aminopropyl) tetramethyldisiloxane;

1,8-diamino-3,6-dioxaoctane;

1,3-bis(aminomethyl) cyclohexane;

1,4-bis(3-aminopropyl)piperazine;

a homopolymer or copolymer of ethyleneimine;

aminopropylmethylsiloxane-co-dimethylsiloxane;

or bis-aminopropyldimethylsiloxane.

20. The method of claim 10 wherein at least one compound comprises a polyvinyl butyral.

24. A fluorochemical compound comprising the reaction product of:

(a) the reaction product of;

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

C_nF_2n+1—

X—

OH

wherein;

n=1 to 6,

25. The fluorochemical compound of claim 24 wherein the coating composition is a release coating.

26. An article comprising a substrate coated with a coating composition comprising the fluorochemical compound of claim 24.

27. The article of claim 26 wherein the substrate is a hard substrate or a fibrous substrate.