# US 2014/0194573 A1 · Hydrophobic coatings that provide renewable hydrophilic surface

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- Number: US 2014/0194573 A1
- Document ID: US20140194573A1
- Status: Published application
- Kind: A1
- Application number: 13/881,416
- Filed: 2012-11-21
- Published: 2014-07-10
- Earliest claimed: 2012-11-21
- Assignees: Empire Technology Development LLC
- Applicants: Empire Technology Development LLC
- Inventors: William Brenden Carlson; Gregory D. Phelan
- Web page: https://patentgrep.com/patent/US20140194573A1

## CPC

- C09D 143/00: Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- B01D 71/00: Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- C08F 130/06: containing boron
- C09D 5/00: Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes
- C09D 5/1681: {Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect}
- C09D 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Paints and coatings that change the coated surface from hydrophobic to a hydrophilic, self-cleaning surface when exposed to atmosphere are described. The compositions include a plurality of boronic acid functionalized polymers, and a blocking agent contacting at least one of the plurality of boronic acid, wherein the blocking agent is configured to be removed by a stimulus to provide a renewable hydrophilic, self-cleaning polymer coating.

## Claims

### Claim 1

A coating composition comprising:
a plurality of boronic acid functionalized polymers; and
a blocking agent contacting at least one of the plurality of boronic acid,
wherein the blocking agent is configured to be removed by a stimulus to provide a renewable hydrophilic, self-cleaning polymer coating.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the polymer is a vinyl polymer, an acrylic polymer, a styrenic polymer, or a combination thereof.

### Claim 3 (depends on 1)

The composition of claim 1, wherein the polymer is an alkyl methacrylate polymer, an allyl methacrylate polymer, acrylic acid polymer, methacrylic acid polymer, acrylamide polymer, 2-hydroxyethyl methacrylate polymer, 2-hydroxypropyl methacrylate polymer, thioethyl methacrylate polymer, vinyl methacrylate polymer, vinyl benzene polymer, 2-hydroxyethyl acrylate polymer, butyl acrylate polymer, 2-ethylhexyl acrylate polymer, vinyltrimethoxysilane polymer, vinyltriethoxysilane polymer, vinyltoluene polymer, α-methyl styrene polymer, chlorostyrene polymer, styrenesulfonic acid polymer, or a combination thereof.

### Claim 4

(canceled)

### Claim 5 (depends on 1)

The composition of claim 1, wherein the blocking agent is ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propandiol, 2,3-dimethyl-2,3-butanediol, 2-methyl-propane-1,2-diol, ethylene diamine, diethyl triamine, or any combination thereof.

### Claim 6 (depends on 1)

The composition of claim 1, wherein the polymer is a polymerization product of 2-methyl-acrylic acid 4-[1,3,2]dioxaborolan-2-yl-benzyl ester.

### Claim at position 7

7-9. (canceled)

### Claim 10 (depends on 1)

The composition of claim 1, wherein the stimulus is water, air, gas, light, sunlight, heat, or any combination thereof.

### Claim 11

A method for preparing a renewable hydrophilic coating composition, the method comprising:
contacting at least one boronic acid with at least one blocking agent to form a blocked boronic acid moiety;
contacting the blocked boronic acid moiety with an organic halide to form an ester; and
polymerizing the ester to form the coating composition.

### Claim 12 (depends on 11)

The method of claim 11, wherein the at least one boronic acid is 4-hydroxybenzyl boronic acid, vinyl boronic acid, alpha methyl vinyl boronic acid, 2-allyl boronic acid, 2-but-3-enyl-boronic acid, 2-hex-5-enyl-boronic acid, 1-boronic acid-2-yl-2-methyl-propenone, or any combination thereof.

### Claim 13 (depends on 11)

The method of claim 11, wherein the at least one blocking agent is ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propandiol, 2,3-dimethyl-2,3-butanediol, 2-methyl-propane-1,2-diol ethylene diamine, diethyl triamine, or any combination thereof.

### Claim 14 (depends on 11)

The method of claim 11, wherein the at least one organic halide is methyl methacrylic halide, ethyl methacrylic halide, vinyl methacrylic halide, thioethyl methacrylic halide, 2-hydroxyethyl acrylic halide, butyl acrylic halide, 2-ethylhexyl acrylic halide, p-styrenesulfonic acid halide, 4-vinylbenzyl halide, ethenesulfonyl halide, vinyl phosphonic acid halide, or a combination thereof.

### Claim 15 (depends on 11)

The method of claim 11, wherein the at least one blocking agent is dissolved in toluene.

### Claim 16 (depends on 11)

The method of claim 11, wherein contacting the at least one boronic acid with the at least one blocking agent comprises mixing the blocking agent and the boronic acid in a molar ratio of about 1:0.5 to about 1:1.5.

### Claim 17 (depends on 11)

The method of claim 11, wherein contacting the at least one boronic acid with the at least one blocking agent comprises mixing the boronic acid and the blocking agent under a reflux.

### Claim at position 16

18-19. (canceled)

### Claim 20 (depends on 11)

The method of claim 11, wherein contacting the blocked boronic acid moiety with the halide comprises mixing the blocked boronic acid moiety and the halide in the presence of triethyl amine to form the ester.

### Claim 21 (depends on 11)

The method of claim 11, wherein polymerizing the ester comprises heating a mixture of water, an initiator, and a surfactant to a temperature of about 50° C. to about 95° C., and adding a solution of ester to the mixture.

### Claim 22 (depends on 21)

The method of claim 21, wherein polymerizing the ester comprises mixing the mixture and the ester solution for a period of about 1 hour to about 12 hours.

### Claim 23 (depends on 21)

The method of claim 21, wherein the surfactant is dodecyl sulfate, alkyl phenol ethoxylate, sodium lauryl sulfate, dodecylbenzene sulfonate, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl allyl ether, an acetylene glycol, polyoxyethylene, polyoxypropylene, or any combination thereof.

### Claim 24 (depends on 21)

The method of claim 21, wherein the initiator is benzoyl peroxide, a persulfate, a water soluble azo initiator, a water soluble peroxide, a persulfate redox system, or any combination thereof.

### Claim 25

A method of coating a substrate, the method comprising:
applying a coating composition to the substrate, wherein the coating composition comprises a plurality of boronic acid functionalized polymers, and
a blocking agent contacting at least one of the plurality of boronic acid,
wherein the blocking agent is configured to be removed by a stimulus to provide a renewable hydrophilic, self-cleaning polymer coating.

### Claim 26 (depends on 25)

The method of claim 25, wherein the polymer is an alkyl methacrylate polymer, an allyl methacrylate polymer, acrylic acid polymer, methacrylic acid polymer, acrylamide polymer, 2-hydroxyethyl methacrylate polymer, 2-hydroxypropyl methacrylate polymer, thioethyl methacrylate polymer, vinyl methacrylate polymer, vinyl benzene polymer, 2-hydroxyethyl acrylate polymer, butyl acrylate polymer, 2-ethylhexyl acrylate polymer, vinyltrimethoxysilane polymer, vinyltriethoxysilane polymer, vinyltoluene polymer, α-methyl styrene polymer, chlorostyrene polymer, styrenesulfonic acid polymer, or a combination thereof.

### Claim 27 (depends on 25)

The method of claim 25, wherein the blocking agent is ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propandiol, 2,3-dimethyl-2,3-butanediol, 2-methyl-propane-1,2-diol ethylene diamine, diethyl triamine, or any combination thereof.

### Claim 28 (depends on 25)

The method of claim 25, wherein the polymer is a polymerization product of 2-methyl-acrylic acid 4-[1,3,2]dioxaborolan-2-yl-benzyl ester.

### Claim at position 26

29-32. (canceled)

### Claim 33 (depends on 25)

The method of claim 25, wherein removing the blocking agent from contacting at least one of the plurality of boronic acid is performed by exposing the blocking agent to the stimulus.

### Claim 34 (depends on 33)

The method of claim 33, wherein the stimulus is water, air, gas, light, sunlight, heat, or any combination thereof.

### Claim 35

(canceled)

### Claim 36

An article of manufacture comprising:
a coating covering at least a portion of the article, wherein the coating comprises a plurality of boronic acid functionalized polymers; and
a blocking agent contacting at least one of the plurality of boronic acid;
wherein the blocking agent is configured to be removed by a stimulus to provide a renewable hydrophilic, self- cleaning polymer coating.

### Claim 37

(canceled)

### Claim 38 (depends on 36)

The article of claim 36, wherein the blocking agent is ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propandiol, 2,3-dimethyl-2,3-butanediol, 2-methyl-propane-1,2-diol ethylene diamine, diethyl triamine, or any combination thereof.

### Claim 39 (depends on 36)

The article of claim 36, wherein the polymer is a polymerization product of 2-methyl-acrylic acid 4-[1,3,2]dioxaborolan-2-yl-benzyl ester.

### Claim at position 34

40-41. (canceled)