Polymer-liquid composites for improved anti-fouling performance

Patent metadata

Field	Value
Publication number	US-11034846-B2
Application number	US-201815960149-A
Country	US
Kind code	B2
Filing date	Apr 23, 2018
Priority date	Mar 14, 2014
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

This disclosure describes incorporation of a liquid additive within one or more phases of a multiphase polymer coating. The structure of the microphase-separated network provides reservoirs for liquid in discrete and/or continuous phases. Some variations provide an anti-fouling segmented copolymer composition comprising: (a) one or more first soft segments selected from fluoropolymers; (b) one or more second soft segments selected from polyesters or polyethers; (c) one or more isocyanate species; (d) one or more polyol or polyamine chain extenders or crosslinkers; and (e) a liquid additive disposed in the first soft segments and/or the second soft segments. The first soft segments and the second soft segments are microphase-separated on a microphase-separation length scale from 0.1 microns to 500 microns. These solid/liquid hybrid materials improve physical properties associated with the coating in applications such as anti-fouling (e.g., anti-ice or anti-bug) surfaces, ion conduction, and corrosion resistance.

First claim

What is claimed is:

1. An anti-fouling segmented copolymer composition comprising:
(a) one or more first soft segments selected from fluoropolymers having an average molecular weight from about 500 g/mol to about 20,000 g/mol, wherein said fluoropolymers are (α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;
(b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;
(c) one or more isocyanate species possessing an isocyanate functionality of 2 or greater, or a reacted form thereof;
(d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof; and
(e) a liquid additive at least 60% selectively disposed in one of said first soft segments or said second soft segments,
wherein said first soft segments and said second soft segments are microphase-separated on a microphase-separation length scale from about 0.5 microns to about 500 microns.

2. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive is a freezing-point depressant for water.

3. The anti-fouling segmented copolymer composition of claim 2 , wherein said freezing-point depressant for water is selected from the group consisting of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, poly(ethylene glycol), and combinations, isomers, or homologous species thereof.

4. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive is a lubricant.

5. The anti-fouling segmented copolymer composition of claim 4 , wherein said lubricant is selected from the group consisting of fluorinated oils, fluorocarbon ether polymers of polyhexafluoropropylene, siloxanes, silicone-based oils, polydimethylsiloxanepoly(ethylene glycol) copolymers, polydimethylsiloxane-fluoropolymer copolymers, petroleum-derived oils, mineral oil, plant-derived oils, canola oil, soybean oil, and combinations thereof.

6. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive is an electrolyte for use in battery or other energy-device applications.

7. The anti-fouling segmented copolymer composition of claim 6 , wherein said electrolyte is selected from the group consisting of poly(ethylene glycol), dimethyl carbonate, diethyl carbonate, methyl ethyl dicarbonate, ionic liquids, and combinations thereof.

8. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive includes alcohol groups, amine groups, thiol groups, or a combination thereof.

9. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive includes water.

10. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive is at least partially in gel form.

11. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive further contains a solid lubricant suspended or dissolved in said liquid.

12. The anti-fouling segmented copolymer composition of claim 1 , wherein said fluoropolymers are present in the triblock structure:

wherein:
X, Y═CH 2 —(O—CH 2 —CH 2 ) p -T, and X and Y are independently selected;
p=1 to 50;
T is a hydroxyl, amine, or thiol terminal group;
m=1 to 100; and
n=0 to 100.

13. The anti-fouling segmented copolymer composition of claim 12 , wherein n=1 to 100.

14. The anti-fouling segmented copolymer composition of claim 1 , wherein the molar ratio of said second soft segments to said first soft segments is less than 2.0.

15. The anti-fouling segmented copolymer composition of claim 1 , wherein said first soft segments and said second soft segments further are nanophase-separated on a nanophase-separation length scale from about 10 nanometers to about 100 nanometers, and wherein said nanophase-separation length scale is hierarchically distinct from said microphase-separation length scale.

16. The anti-fouling segmented copolymer composition of claim 1 , wherein said liquid additive is present in said composition at a concentration from about 1 wt % to about 75 wt %.

17. The anti-fouling segmented copolymer composition of claim 1 , wherein said composition is present in a coating.

18. An anti-fouling segmented copolymer precursor composition comprising:
(a) one or more first soft segments selected from fluoropolymers having an average molecular weight from about 500 g/mol to about 20,000 g/mol, wherein said fluoropolymers are (α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;
(b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated, (α,ω)-amine-terminated, and/or (α,ω)-thiol-terminated;
(c) one or more isocyanate species possessing an isocyanate functionality of 2 or greater, or a reacted form thereof;
(d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof; and
(e) a liquid additive precursor at least 60% selectively disposed in one of said first soft segments or said second soft segments, wherein said liquid additive precursor includes a protecting group,
wherein said first soft segments and said second soft segments are microphase-separated on a microphase-separation length scale from about 0.5 microns to about 500 microns.

19. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said liquid additive precursor includes alcohol groups and at least one protecting group that protects said alcohol groups from reacting with said anti-fouling segmented copolymer precursor composition.

20. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said liquid additive precursor includes amine groups and at least one protecting group that protects said amine groups from reacting with said anti-fouling segmented copolymer precursor composition.

21. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said liquid additive precursor includes thiol groups and at least one protecting group that protects said thiol groups from reacting with said anti-fouling segmented copolymer precursor composition.

22. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said liquid additive precursor includes a protecting group that is capable of deprotecting said liquid additive precursor in the presence of atmospheric moisture.

23. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said liquid additive precursor is capable of condensation curing to increase its molecular weight.

24. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein said fluoropolymers are present in the triblock structure:

wherein:
X, Y═CH 2 —(O—CH 2 —CH 2 ) p -T, and X and Y are independently selected;
p=1 to 50;
T is a hydroxyl, amine, or thiol terminal group;
m=1 to 100; and
n=0 to 100.

25. The anti-fouling segmented copolymer precursor composition of claim 18 , wherein the molar ratio of said se

Assignees

• Hrl Lab Llc

Inventors

• Nowak Andrew P
• Rodriguez April R
• Graetz Jason A
• Gross Adam F

Classifications

• C08G18/5015

  having fluorine atoms · CPC title

• C08G18/4833

  Polyethers containing oxyethylene units · CPC title

• C09D175/08

  from polyethers · CPC title

• C09D5/1656

  characterised by the film-forming substance (C09D5/1637 takes precedence) · CPC title

• C08G18/758

  containing two or more cycloaliphatic rings · CPC title