Switchable antifouling coatings and uses thereof

Patent metadata

Field	Value
Publication number	US-10435568-B2
Application number	US-201715407164-A
Country	US
Kind code	B2
Filing date	Jan 16, 2017
Priority date	Aug 8, 2014
Publication date	Oct 8, 2019
Grant date	Oct 8, 2019

Abstract

The present invention relates to antifouling coatings capable of being switched by using heat or ultraviolet light. Prior to switching, the coating includes an onium cation component having antimicrobial and antibacterial properties. Upon switching, the coating is converted to a conjugated polymer state, and the cationic component is released with any adsorbed biofilm layer. Thus, the coatings herein have switchable and releasable properties. Methods of making and using such coatings are also described.

First claim

The invention claimed is:

1. A method of treating a marine surface, the method comprising:
applying a first antifouling coating having releasable and switchable properties on the marine surface, or a portion thereof, wherein the coating comprises an onium cation covalently attached to an alpha carbon of a switchable polymer;
treating the first coating with heat or ultraviolet light to release the cation, thereby maintaining a polymerized layer on the marine surface, wherein the polymerized layer comprises a conjugated form of the switchable polymer; and
treating the polymerized layer with one or more onium cation precursors to generate a second antifouling coating on the marine surface.

2. The method of claim 1 , further comprising:
performing an anion exchange reaction with the polymerized layer and an oxidizing agent or a ZA agent, in which Z is an alkali cation or an alkaline cation and A is an anion.

3. The method of claim 1 , further comprising, before applying the first antifouling coating:
applying a primer layer between the marine surface and the first antifouling coating.

4. The method of claim 3 , wherein the primer layer comprises a primer or a siloxane polymer.

5. The method of claim 4 , wherein the primer is selected from the group consisting of an epoxy-based primer, a polyamide epoxy-based primer, a vinyl-based primer, and a zinc-based primer.

6. The method of claim 4 , wherein the siloxane polymer is a trialkoxy siloxane or a trihalide siloxane.

7. The method of claim 1 , wherein the switchable polymer comprises one or more hydrogens covalently attached to a beta carbon that is adjacent to the alpha carbon.

8. The method of claim 1 , wherein the onium cation is a sulfonium cation, an ammonium cation, an oxonium cation, a diazonium cation, a halonium cation, or a phosphonium cation.

9. The method of claim 1 , wherein the switchable polymer comprises a polyphenylene backbone or a polysiloxane backbone.

10. The method of claim 9 , wherein the switchable polymer comprises a conjugated form of the polyphenylene backbone or the polysiloxane backbone.

11. The method of claim 1 , wherein the switchable polymer has a structure of:

wherein:
each of X 1′ , X 1″ , X 2′ , X 2″ , X 3′ , X 3″ , and X 4 is, independently, selected from the group consisting of H, optionally substituted C 1-6 alkyl, optionally substituted C 2-6 alkenyl, and halo;
B is an onium cation;
A is an anion;
m is an integer of from 0 to 1000; and
n is an integer of from 1 to 1000.

12. The method of claim 11 , wherein at least one of X 3′ and X 3 is H.

13. The method of claim 11 , wherein m is not 0.

14. The method of claim 1 , wherein the switchable polymer has a structure of:

wherein
each of R 1b , R 2b , and R 3b is, independently, selected from the group consisting of H, hydroxyl, optionally substituted C 1-6 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 1-6 alkoxy, and halo;
each of R B1 and R B2 is, independently, H, optionally substituted C 1-24 alkyl, or optionally substituted C 2-6 alkenyl; or wherein R B1 and R B2 , taken together with the sulfur atom to which each are attached, form an optionally substituted heterocycle; or wherein R B1 and R B2 , taken together, comprises an optionally substituted C 2-12 alkylene or an optionally substituted C 2-12 heteroalkylene;
X L is optionally substituted C 1-16 alkylene or optionally substituted C 1-12 heteroalkylene;
A is an anion;
m is an integer of from 0 to 1000; and
n is an integer of from 1 to 1000.

15. The method of claim 1 , wherein the switchable polymer has a structure of:

wherein
each of R 1b , R 2b , and R 3b is, independently, selected from the group consisting of H, hydroxyl, optionally substituted C 1-6 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 1-6 alkoxy, and halo;
each of R B1 , R B2 , and R B3 is, independently, H, optionally substituted C 1-24 alkyl, or optionally substituted C 2-6 alkenyl; or wherein two or more of R B1 , R B2 , and R B3 , taken together with the nitrogen atom to which each are attached, form an optionally substituted heterocycle; or wherein R B1 and R B2 , taken together, comprises an optionally substituted C 2-12 alkylene or an optionally substituted C 2-12 heteroalkylene;
X L is optionally substituted C 1-16 alkylene or optionally substituted C 1-12 heteroalkylene;
A is an anion; and
m is an integer of from 0 to 1000; and
n is an integer of from 1 to 1000.

16. The method of claim 1 , wherein the switchable polymer has a structure of:

wherein:
each of X 1′ , X 1″ , X 2′ , X 2″ , X 3′ , X 3″ , and X 4 is, independently, selected from the group consisting of H, optionally substituted C 1-6 alkyl, optionally substituted C 2-6 alkenyl, and halo;
A is an anion;
each of R 1a , R 2a , and R 3a , if present, is, independently, H, optionally substituted C 1-24 alkyl, or optionally substituted C 2-24 alkenyl; or wherein two of R 1a , R 2a , and R 3a , taken together with the heteroatom to which each are attached, form an optionally substituted heterocycle; or wherein R 1a and R 2a , taken together, includes an optionally substituted C 2-12 alkylene or an optionally substituted C 2-12 heteroalkylene,
m is an integer of from 0 to 1000; and
n is an integer of from 1 to 1000.

17. A method of treating a marine surface, the method comprising:
applying a first antifouling coating having releasable and switchable properties on the marine surface, or a portion thereof, wherein the coating comprises an onium cation covalently attached to an alpha carbon of a switchable polymer; and
treating the first coating with heat or ultraviolet light to release the cation, thereby maintaining a polymerized layer on the marine surface, wherein the polymerized layer comprises a conjugated form of the switchable polymer, wherein the switchable polymer has a structure of:

and wherein n is an integer of from 1 to 1000.

18. The method of claim 1 , wherein the switchable polymer has a structure of:

19. A method of treating a marine surface, the method comprising:
applying a primer layer to the marine surface;
applying a first antifouling coating having releasable and switchable properties on the primer layer, or a portion thereof, wherein the coating comprises an onium cation covalently attached to an alpha carbon of a polymer;
treating the first coating with heat or ultraviolet light to release the cation, thereby maintaining a polymerized layer on the marine surface, wherein the polymerized layer comprises a conjugated form of the polymer; and
treating the polymerized layer with one or more onium cation precursors to generate a second antifouling coating on the marine surface.

20. The method of claim 19 , further comprising:
performing an anion exchange reaction with the polymerized layer and an oxidizin

Assignees

• Sandia Corp
• Nat Tech & Eng Solutions Sandia Llc

Inventors

• Denton Michele L Baca
• Dirk Shawn M
• Johnson Ross Stefan

Classifications

• C09D165/02

  Polyphenylenes · CPC title

• A01N31/04

  Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system · CPC title

• C09D5/1637 Primary

  Macromolecular compounds · CPC title

• B05D3/065

  After-treatment · CPC title

• C09D5/1693

  as part of a multilayer system · CPC title