Use of amphiphilic surface modifying additives to improve performance of siloxane-polyurethane fouling-release coatings

• US 11,560,493 B2
• Filed: 04/05/2019
• Issued: 01/24/2023
• Est. Priority Date: 04/06/2018
• Status: Active Grant

• Current Assignee: United States Navy (U.S. Department Of Defense)
• Original Assignee: Ndsu-Research Foundation
• Inventors: Webster, Dean C., Benda, Jackson
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US16/376,144
• Publication Number:
  US 20190309187A1
• Time in Patent Office: 1,390 Days
• CPC Class Codes: C08G 18/289 containing silicon
• CPC Class Codes: C08G 18/4063 Mixtures of compounds of group C08G18/62 with other macromolecular compounds
• CPC Class Codes: C08G 18/42 Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/48 Polyethers
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/6229 Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/74 cyclic
• CPC Class Codes: C08G 18/757 containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
• CPC Class Codes: C08G 18/7692 containing at least one isocyanate or isothiocyanate group linked to an aromatic ring by means of an aliphatic group
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 77/045 containing less than 25 silicon atoms
• CPC Class Codes: C08G 77/458 containing polyurethane sequences
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/12 containing polyether sequences
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09D 175/06 from polyesters
• CPC Class Codes: C09D 183/10 Block or graft copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00
• CPC Class Codes: C09D 5/1637 Macromolecular compounds
• CPC Class Codes: C09D 5/1662 : Synthetic film-forming substance
• CPC Class Codes: C09D 5/1675 : Polyorganosiloxane-containing compositions

Abstract

The invention relates to curable coating compositions containing at least one surface modifying amphiphilic additive; and at least one siloxane-polyurethane coating composition. The invention also relates to methods of making and using the curable coating compositions of the invention. The invention also relates to objects coated with the curable coating composition of the invention. The invention also relates to methods for reducing or preventing biofouling of a surface exposed to an aqueous environment comprising the steps of coating the surface with the curable coating composition of the invention to form a coated surface, and curing the coating composition on the coated surface. The invention also relates to a marine fouling-release coating containing the curable coating composition of the invention.

Claims

1. A method for reducing or preventing biofouling of a surface exposed to an aqueous environment comprising the steps of:

coating the surface with a curable coating composition to form a coated surface, and

curing the coating composition on the coated surface,

wherein the curable coating composition comprises;

a) at least one surface modifying amphiphilic additive consisting of the reaction product of

a1) at least one Si—

H functional siloxane; and

a2) at least one allyl-functional poly(ethylene glycol) monomethyl ether; and

b) at least one siloxane-polyurethane coating composition comprising the reaction product of

b1) at least one aminopropyl terminated polydimethyl siloxane;

b2) at least one polyol; and

b3) at least one polyisocyanate crosslinker; and

c) optionally, at least one additive;

wherein the curable coating composition comprises 0.1-10 wt. % of the at least one surface modifying amphiphilic additive, based on the total weight of the curable coating composition,

wherein the Si—

H functional siloxane is a tetra functional Si—

H cyclosiloxane.

2. The method of claim 1, wherein the tetra functional Si—

H cyclosiloxane is selected from Si—

H functional 1,3,5,7-tetramethylcyclotetrasiloxane (D′

4).

3. The method of claim 1, wherein the allyl functional poly(ethylene glycol) monomethyl ether is selected from at least one allyl-terminated poly(ethylene glycol) monomethyl ether.

4. The method of claim 1, wherein the Si—

H functional siloxane and the allyl functional poly(ethylene glycol) monomethyl ether are present in a molar ratio of 1.0;

1.0.

5. The method of claim 1, wherein the polyol is an acrylic polyol, a polyester polyol, a polycarbonate polyol, a polyether polyol, or mixtures thereof.

6. The method of claim 1, wherein the polyol is a polyether polyol.

7. The method of claim 1, wherein the polyisocyanate crosslinker is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, and derivatives thereof.

8. The method of claim 1, wherein the polyisocyanate crosslinker is isophorone diisocyanate or a derivative thereof and the polyol is an acrylic polyol.

9. The method of claim 1, wherein the polyisocyanate crosslinker is methylene diphenyl diisocyanate or a derivative thereof and the polyol is a polyether polyol.

10. The method of claim 1, wherein the curable coating composition comprises 5-10 wt. % of the at least one surface modifying amphiphilic additive, based on the total weight of the curable coating composition.

11. The method of claim 1, wherein the surface modifying amphiphilic additive consists of poly(ethylene glycol) chains attached to the backbone of the Si—

H functional siloxane.

12. The method of claim 1, wherein the curable coating composition comprises 1-10 wt. % of the at least one surface modifying amphiphilic additive, based on the total weight of the curable coating composition.

13. The method of claim 3, wherein the at least one allyl-terminated poly(ethylene glycol) monomethyl ether has a molecular weight ranging from about 200 g/mol to about 1,500 g/mol.

14. The method of claim 1, wherein the surface is present on the hull of a marine vessel.

15. The method of claim 1, wherein the surface is present on a structure submerged in seawater.

16. The method of claim 1, wherein the additive is selected from the group consisting of pigments, curing catalysts, pot-life extenders, solvents, and mixtures thereof.

17. The method of claim 1, wherein the curable coating composition comprises 0.1-5 wt. % of the at least one surface modifying amphiphilic additive, based on the total weight of the curable coating composition.

18. The method of claim 1, wherein:

the tetra functional Si—

H cyclosiloxane is selected from Si—

H functional 1,3,5,7-tetramethylcyclotetrasiloxane (D′

4);

the allyl functional poly(ethylene glycol) monomethyl ether is selected from at least one allyl-terminated poly(ethylene glycol) monomethyl ether;

the Si—

H functional siloxane and the allyl functional poly(ethylene glycol) monomethyl ether are present in a molar ratio of 1.0;

1.0;

the polyol is an acrylic polyol, a polyester polyol, a polycarbonate polyol, a polyether polyol, or mixtures thereof; and

the polyisocyanate crosslinker is selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, and derivatives thereof.

19. The method of claim 18, wherein the at least one allyl-terminated poly(ethylene glycol) monomethyl ether has a molecular weight ranging from about 200 g/mol to about 1,500 g/mol.

20. The method of claim 18, wherein the polyisocyanate crosslinker is isophorone diisocyanate or a derivative thereof and the polyol is an acrylic polyol.

21. The method of claim 18, wherein the polyisocyanate crosslinker is methylene diphenyl diisocyanate or a derivative thereof and the polyol is a polyether polyol.

22. A curable coating composition comprising:

a) at least one surface modifying amphiphilic additive consisting of the reaction product of

a1) at least one Si—

H functional siloxane; and

a2) at least one allyl-functional poly(ethylene glycol) monomethyl ether; and

b) at least one siloxane-polyurethane coating composition comprising the reaction product of

b1) at least one aminopropyl terminated polydimethyl siloxane;

b2) at least one polyol; and

b3) at least one polyisocyanate crosslinker; and

c) optionally, at least one additive;

wherein the curable coating composition comprises 0.1-10 wt. % of the at least one surface modifying amphiphilic additive, based on the total weight of the curable coating composition,

wherein the Si—

H functional siloxane is a tetra functional Si—

H cyclosiloxane.