Anchored polysiloxane-modified polyurethane coatings and uses thereof

• US 8,299,200 B2
• Filed: 06/09/2008
• Issued: 10/30/2012
• Est. Priority Date: 06/11/2007
• Status: Active Grant

• Current Assignee: Ndsu-Research Foundation
• Original Assignee: Ndsu-Research Foundation
• Inventors: Webster, Dean C., Ekin, Abdullah, Sommer, Stacy
• Primary Examiner(s): Peng, Kuo-Liang
• Application Number:
  US12/663,334
• Publication Number:
  US 20100280148A1
• Time in Patent Office: 1,604 Days
• Field of Search: 528/38, 528/28
• US Class Current: 528/38
• CPC Class Codes: C08G 18/089 Reaction retarding agents
• CPC Class Codes: C08G 18/289 containing silicon
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/677 containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
• CPC Class Codes: C08G 18/725 Combination of polyisocyanates of C08G18/78 with other polyisocyanates
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 5/1675 Polyorganosiloxane-containing compositions

Abstract

A polymeric material, prepared by reacting a mixture comprising a polyorganosiloxane having one or more isocyanate-reactive functional groups, polyisocyanate, and polyol, is provided. The isocyanate-reactive functional groups, typically one or two, are attached to only a single end of the polyorganosiloxane chains. The polymeric material may be used to form coatings on a substrate and to inhibit fouling on surfaces exposed to aqueous conditions.

Claims

1. A polymeric material prepared by reacting a mixture comprising:

polyisocyanate;

polyol; and

a polysiloxane component having two or more polyorganosiloxane chains attached to a linker group, which has one or more functional groups capable of reacting with the polyisocyanate attached thereto.

2. The polymeric material of claim 1, wherein the linker molecule has one or more amino groups attached thereto;

the polyisocyanate comprises hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, or a mixture thereof; and

the polyol comprises hydroxy-functional poly(meth)acrylate, polycaprolactone polyol, or a mixture thereof.

3. The polymeric material of claim 1, wherein the polysiloxane component is a reaction product of reaction of a silane-terminated polydimethylsiloxane with pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether or a mixture thereof.

4. A polymeric material prepared by reacting a mixture comprising:

polyisocyanate;

polyorganosiloxane having one or more reactive functional groups attached to only a single end of the polyorganosiloxane; and

polyol which comprises hydroxyl-functional poly(meth)acrylate, polycaprolactone polyol, or a mixture thereof;

wherein the reactive functional groups are hydroxyl alkyl carbamate groups or amino groups.

5. The polymeric material of claim 4 wherein the polysiloxane component has a formula I:

6. The polymeric material of claim 5, wherein the LINK is an alkylene group, which may have one or more oxygen, nitrogen or sulfur atoms substituted for a carbon atom of its backbone;

the LINK has no more than about 10 atoms in its backbone; and

R′

Si—

is a trialkylsilyl group.

7. The polymeric material of claim 4, wherein the polyorganosiloxane includes poly(dialkylsiloxane) having one or more amino groups attached to only a single end.

8. The polymeric material of claim 7, wherein the polyorganosiloxane has (a) two or more amino groups attached to only a single end of the polyorganosiloxane.

9. A substrate having a surface capable of being exposed to aqueous conditions;

wherein the surface has a fouling release coating thereon;

the fouling release coating comprises the polymeric material of claim 7;

the fouling release coating has an initial water contact angle of at least about 100°

; and

the water contact angle of the fouling release coating changes by no more than about 10°

after immersion in deionized water for 30 days.

10. The substrate of claim 9, wherein the fouling release coating has an initial pseudobarnacle pull off adhesion release force of no more than about 80 N.

11. The polymeric material of claim 4, wherein the mixture has a ratio of (isocyanate groups)/(amine+alcohol groups) of about 1.0 to 1.2.

12. The polymeric material of claim 4, wherein the polyisocyanate comprises hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, or a mixture thereof.

13. A coating composition comprising the mixture according to claim 4.

14. A method of inhibiting fouling on a surface exposed to aqueous conditions comprising applying the coating composition of claim 13 to the surface.

15. A method of inhibiting fouling on a surface exposed to aqueous conditions comprising applying the coating composition of claim 13 to the surface;

wherein the coating composition comprises;

about 2 to 20 wt. % (on a solids basis) of an amino functional polyorganosiloxane, wherein the amino functional polyorganosiloxane has one or more amino groups attached to only a single end of the polyorganosiloxane;

from about 30 wt. % to 85 wt. % (on a solids basis) of polyisocyanate; and

the polyol.

16. The method of claim 15, wherein the polyorganosiloxane has a number average molecular weight of about 1,000 to 20,000;

the polyisocyanate comprises hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, or a mixture thereof; and

the coating composition has a ratio of (isocyanate groups)/(amine+alcohol groups) of about 1.05 to 1.15.

17. A substrate having a surface capable of being exposed to aqueous conditions;

wherein the surface has a coating thereon; and

the coating comprises the polymeric material of claim 4.

18. The substrate of claim 17, wherein the coating has an initial water contact angle of at least about 100°

.

19. The substrate of claim 18, wherein the water contact angle of the coating changes by no more than about 10°

after immersion in deionized water for 30 days.

20. The substrate of claim 17, wherein the coating has an initial pseudobarnacle pull off adhesion release force of no more than about 80 N.

21. A polymeric material formed from reactants which comprise:

polyisocyanate;

polydialkylsiloxane having one or more amino groups attached to only a single end of the polyorganosiloxane; and

polyol, which includes a polyester polyol, acrylic polyol or a mixture thereof.

22. The polymeric material of claim 21, wherein the polyol comprises polyester polyol.

23. The polymeric material of claim 22, wherein the polyester polyol comprises polycaprolactone polyol, poly(hexamethylene adipate) or a mixture thereof.

24. The polymeric material of claim 21, wherein the polyol comprises acrylic polyol.

25. The polymeric material of claim 24, wherein the acrylic polyol comprises hydroxy-functional poly(meth)acrylate.

26. The polymeric material of claim 24, wherein the acrylic polyol is formed from monomers which include hydroxyalkyl acrylate, alkyl acrylate, alkyl methacrylate or a mixture thereof.

27. The polymeric material of claim 24, wherein the acrylic polyol is formed from monomers, which include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate or a mixture thereof.

28. The polymeric material of claim 21, wherein the polysiloxane component has a formula I:

29. The polymeric material of claim 28, wherein the polyol comprises acrylic polyol;

and the polyisocyanate comprises isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, oligomers thereof or a mixture thereof.

30. The polymeric material of claim 28, wherein the amino functional polyorganosiloxane has a number average molecular weight of about 500 to 30,000.

31. A substrate having a surface capable of being exposed to aqueous conditions;

wherein the surface has a coating comprising the polymeric material of claim 30 thereon; and

the coating has an initial water contact angle of at least about 100°

.