Curable polysiloxane compositions and slippery materials and coatings and articles made therefrom
The present teachings generally provide curable polysiloxane compositions including a base resin including a surface active polymer. Articles of manufacture including the curable polysiloxane compositions and slippery coatings and materials also are provided. The compositions may be used to provide slippery, lubricious, or repellent materials and coatings and may provide anti-fouling function. The compositions can provide anti-fouling or foul-release function on open surfaces, internal surfaces, membranes; to provide pinning free or low contact angle hysteresis surfaces; to provide homogeneous interface to suppress nucleation; to provide a barrier layer such as anti-corrosion; to provide anti-stain, anti-smudge, anti-fingerprint, anti-soil function.
1. A curable polysiloxane composition comprising:
A base resin composition capable of a condensation reaction for curing, the base resin composition comprising:
(i) a compound comprising hydrolyzable alkoxy, enoxy, oxime, amine, ethoxy, methoxy, or acetoxy silane groups;
(ii) a polysiloxane comprising one or more silanol groups capable of undergoing a condensation reaction with the hydrolysable groups of the compounds of (i); and
(iii) a surface active polymer having a structure according to Formula I or Formula II,
where m 1 is an integer 1 to 50, n 1 is an integer 0 to 250, p 1 is an integer 1 to 16, n 2 is an integer 0 to 250, each occurrence of p 2 is independently an integer 1 to 16, each occurrence of X is independently an integer 3 to 20, and each occurrence of R 1 is independently an ester or silyl ether group so long as at least one occurrence of R 1 is a silyl ether group linked through a carbamate group.
2. The curable polysiloxane composition according to claim 1 , wherein the surface active polymer has a structure according to Formula I; and
wherein at least one occurrence of R 1 has a structure according to the following formula
where each occurrence of Z is independently —CH 3 , —CH 2 CH 3 , or CH 2 CH 2 CH 3 , and Y is an integer from 3 to 20.
3. The curable polysiloxane composition according to claim 2 , wherein X is 3, n 1 is 0 or 1, and p 1 is 6 to 16.
4. The curable polysiloxane composition according to claim 2 , wherein m 1 is 1.
5. The curable polysiloxane composition according to claim 1 , wherein the surface active polymer has a structure according to Formula II; and
wherein at least one occurrence of R 1 has a structure according to the following formula
where each occurrence of Z is independently —CH 3 , —CH 2 CH 3 , or CH 2 CH 2 CH 3 , and Y is an integer from 3 to 20.
6. The curable polysiloxane composition according to claim 5 , wherein X is 3, p 2 is 6 to 12, and n 2 is 30 to 45.
7. The curable polysiloxane composition according to claim 1 , wherein the surface active polymer has a structure according to Formula I; and
m 1 is 1.
8. The curable polysiloxane composition according to claim 1 , wherein the surface active polymer has a structure according to Formula I; and
n 1 is 0 or 1.
9. The curable polysiloxane composition according to claim 1 , wherein the surface active polymer has a structure according to Formula II; and
n 2 is 30 to 45.
10. The curable polysiloxane composition according to claim 1 , wherein X is 3.
11. The curable polysiloxane composition according to claim 1 , wherein the polysiloxane composition does not exhibit micro-scale phase separation.
12. The curable polysiloxane composition according to claim 1 , wherein the composition is capable of curing to form a slippery coating; and
wherein the polysiloxane composition further comprises (b) a lubricating liquid, wherein the lubricating liquid is chemically and physically matched with the base resin in such a way that, when cured therewith to form a cured polysiloxane composition, the lubricating liquid spontaneously provides an overlayer of the lubricating liquid at an exposed surface of the cured polysiloxane composition to form the slippery surface.
13. The curable polysiloxane composition according to claim 12 , wherein the lubricating liquid comprises at least one of a fluorosiloxane and a partially fluorinated polysiloxane.
14. The curable polysiloxane composition according to claim 12 , wherein the lubricating liquid comprises at least one of a polyethyleneglycol-modified silicone, a polypropyleneglycol-modified silicone, and a hydrocarbon oil.
15. The curable polysiloxane composition according to claim 12 , wherein the lubricating liquid is present in the composition at a weight percent greater than about 30% of the total weight of the polysiloxane composition.
16. A coating made by a process comprising:
applying a curable polysiloxane composition according to claim 1 to a substrate; and
curing the polysiloxane composition to form the coating.
17. The coating according to claim 16 , further comprising a lubricating liquid, wherein the lubricating liquid is chemically and physically matched with the base resin in such a way that the lubricating liquid spontaneously wets the coating to provide an overlayer of the lubricating liquid at an exposed surface of the cured polysiloxane composition to form a slippery coating.
18. The coating according to claim 17 , wherein the surface active polymer is reactive with the silanol groups in the polysiloxane so that they are incorporated into the cured polysiloxane composition upon curing and extend into the overlayer of the lubricating liquid at the exposed surface of the cured polysiloxane composition to form the slippery coating.
19. The coating according to claim 16 , wherein the substrate is on an article selected from the group consisting of a marine vessel and other marine structures, an optical lens, a camera, a pipe, a cable, a building, and an adhesive film;
wherein the curable polysiloxane composition is combined with fillers and pigments to form a paint applied to the substrate; and
wherein the slippery coating prevents or delays accumulation of a marine organism on the substrate.
20. The coating according to claim 16 , wherein the surface active polymer has a structure according to Formula I; and
wherein at least one occurrence of R 1 has a structure according to the following formula
where each occurrence of Z is independently —CH 3 , —CH 2 CH 3 , or CH 2 CH 2 CH 3 , and Y is an integer from 3 to 20.
21. The coating according to claim 20 , wherein X is 3, n 1 is 0 or 1, and p 1 is 6 to 16.
22. The coating according to claim 21 , wherein m 1 is 1.
23. The coating according to claim 16 , wherein the surface active polymer has a structure according to Formula II; and
wherein at least one occurrence of R 1 has a structure according to the following formula
where each occurrence of Z is independently —CH 3 , —CH 2 CH 3 , or CH 2 CH 2 CH 3 , and Y is an integer from 3 to 20.
24. The coating according to claim 23 , wherein X is 3, p 2 is 6 to 12, and n 2 is 30 to 45.
25. The coating according to claim 16 , wherein the coating is transparent.
26. The coating according to claim 17 , wherein the lubricating liquid comprises at least one of a fluorosiloxane, a partially fluorinated polysiloxane, and a fluorinated and polyethyleneglycol-modified silicone.
27. The coating according to claim 17 , wherein the lubricating liquid comprises at least one of a polyethyleneglycol-modified silicone, a polypropyleneglycol-modified silicone, and a hydrocarbon oil.
28. The coating according to claim 17 , wherein the lubricating liquid is present in the composition at a weight percent greater than about 30% of the total weight of the polysiloxane composition.
29. The coating according to claim 16 , wherein the coating exhibits little or no leachate toxicity when measured according to ISO 10993-5 cytotoxicity test.
30. The coating according to claim 16 , wherein the surface has foul-release and/or foul impeding (“anti-fouling”) properties.