# US 10,119,035 B2 · Abhesive coatings

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- Number: US 10,119,035 B2
- Document ID: US10119035B2
- Status: Granted
- Kind: B2
- Application number: 14/235,447
- Filed: 2012-07-26
- Published: 2014-10-09
- Granted: 2018-11-06
- Earliest claimed: 2011-07-26
- Assignees: Virginia Commonwealth University
- Applicants: Kenneth J. Wynne; Wei Zhang; Chenyu Wang; Souvik Chakrabarty
- Inventors: Kenneth J. Wynne; Wei Zhang; Chenyu Wang; Souvik Chakrabarty
- Web page: https://patentgrep.com/patent/US10119035B2

## CPC

- C09D 5/1662: {Synthetic film-forming substance}
- C08G 18/5015: {having fluorine atoms}
- C08G 18/6674: {with compounds of group C08G18/3203}
- C08G 18/718: {containing silicon}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 65/18: Oxetanes
- C08G 65/226: {containing fluorine}
- C09D 175/04: Polyurethanes
- Y10T 428/1393: Multilayer [continuous layer]
- Y10T 428/31551: Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A monolithic, self-stratifying polymer coating, comprising: inner and outer-most surfaces on opposite sides of the coating, the inner surface being in contact with and adhered to an article; a surface region, extending from the outermost surface to a depth of about 2 nm from the outermost surface; a middle region, extending from a depth of about 2 nm from the outermost surface to a depth of less than about 2000 nm from the outermost surface; and a bulk region, extending from a depth of less than about 2000 nm from the outermost surface to the inner surface; wherein the surface region comprises a fluorous polyoxetane having the formula: (I) wherein n is an integer of 0-1 1, and m is an integer>0, in a greater concentration relative to the middle and bulk regions; wherein the middle region comprises 3F-SiO1.5 groups in a greater concentration relative to the surface and bulk regions; and wherein the bulk region comprises a polyurethane in a greater concentration relative to the surface and middle regions.

## Claims

### Claim 1

A composition, comprising a polymerization product of:
(A) one or more of (A-1), (A-2), or a combination of (A-1) and (A-2),
wherein (A-1) is a mixture, comprising:
a fluorous oxetane having the formula:
wherein n is an integer of 0-11 and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%,
wherein (A-2) is a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
and
(B) an isocyanate having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3;
and p is an integer of 1-10;
and
(C) optionally, a diol or diamine chain extender.

### Claim 2 (depends on 1)

The composition of claim 1, wherein (A) is the mixture.

### Claim 3 (depends on 1)

The composition of claim 1, wherein (A) is the copolyoxetane.

### Claim 4 (depends on 1)

A method for making the composition of claim 1, comprising contacting (A), (B), and optionally (C), and polymerizing, to produce the composition of claim 1.

### Claim 5

A composition, comprising a polymerization product of:
(A) one or more of (A-1), (A-2), or a combination of (A-1) and (A-2),
wherein (A-1) is a mixture, comprising:
a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%,
wherein (A-2) is a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
and
(B) a diisocyanate and one or more amines having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3;
and q is an integer of 1-10; and
(C) optionally, a diol or diamine chain extender.

### Claim 6 (depends on 5)

The composition of claim 5, wherein the diisocyanate is methylene dicyclohexyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, phenylene diisocyanate, or a combination of two or more thereof.

### Claim 7 (depends on 5)

A coated surface, comprising the cured polymerization product of claim 5 in contact with a surface.

### Claim 8 (depends on 5)

A method for making the composition of claim 5, comprising:
contacting:
(a1) a mixture comprising a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%;
(a2) a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
or
(a3) a combination of (a1) and (a2); and
(b1) one or more diisocyanate; and
(c1) optionally, a diol or diamine chain extender;
and polymerizing, to produce a first polymerization product;
contacting the first polymerization product with one or more amines having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3; and
wherein q is an integer of 1-10;
and reacting,
to produce the composition of claim 5.

### Claim 9

A composition for coating, comprising a compound having the formula:
and optionally a solvent;
wherein —O—RA—O— is derived from a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
or a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
wherein —(C═O)NH—RB—NH(C═O)— is derived from methylene dicyclohexyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, phenylene diisocyanate, or a combination of two or more thereof;
wherein Rc is a C1-10 alkylene; and
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3.

### Claim 10 (depends on 9)

A method, comprising applying the composition of claim 9 to a surface, and allowing to cure, to produce a coated surface.

### Claim 11

A coating, comprising a compound having the formula:
in contact with a surface;
wherein —O—RA—O— is derived from a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
or a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
wherein —(C═O)NH—RB—NH(C═O)— is derived from methylene dicyclohexyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, phenylene diisocyanate, or a combination of two or more thereof;
wherein Rc is a C1-10 alkylene; and
wherein each Z is independently SiO1.5 or H.

### Claim 12 (depends on 11)

An article selected from the group consisting of an airfoil, wing, propeller, hull, superstructure, railing, intake, hatch, keel, rudder, deck, antenna, medical device, kitchen device, counter, pipe, wind turbine, aircraft, ship, rotor blade, transmission tower, transmission line, cable, cooling coil, refrigerator, freezer, and combination thereof, comprising the coating of claim 11.

### Claim 13

A composition, comprising a polymerization product of:
first and second compositions, wherein the first composition comprises a polymerization product of:
(A) one or more of (A-1), (A-2), or a combination of (A-1) and (A-2),
wherein (A-1) is a mixture, comprising:
a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%,
wherein (A-2) is a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
(B) one or more of an isocyanate, diisocyanate, or combination thereof; and
(C) optionally, a diol or diamine chain extender;
and wherein the second composition comprises
one or more bis(trialkoxysilyl)alkanes having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3; and
wherein r is an integer of 1-10.

### Claim 14 (depends on 13)

A composition, comprising a polymerization product of:
the composition of claim 13; and
a composition comprising a polymerization product of:
(A1) a mixture, comprising:
a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%;
(A2) a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
or
(A3) a combination of the mixture (A1) and copolyoxetane (A2); and
(B) one or more of an isocyanate, diisocyanate, or combination thereof; and
(C) optionally, a diol or diamine chain extender.

### Claim 15 (depends on 13)

A method for making the composition of claim 13, comprising:
contacting:
(a1) a mixture comprising a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%;
(a2) a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
or
(a3) a combination of (a1) and (a2); and
(b1) one or more of an isocyanate, diisocyanate, or combination thereof; and
(c1) optionally, a diol or diamine chain extender;
and polymerizing, to produce a first polymerization product;
contacting the first polymerization product with one or more bis(trialkoxysilyl)alkanes having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3; and
wherein r is an integer of 1-10;
and reacting,
to produce the composition of claim 13.

### Claim 16 (depends on 14)

A method for making the composition of claim 14, comprising:
contacting:
(a1) a mixture comprising a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%;
(a2) a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
or
(a3) a combination of (a1) and (a2); and
(b1) one or more of an isocyanate, diisocyanate, or combination thereof; and
(c1) optionally, a diol or diamine chain extender;
and polymerizing, to produce a first polymerization product;
contacting the first polymerization product with one or more bis(trialkoxysilyl)alkanes having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3; and
wherein r is an integer of 1-10;
and reacting,
to produce a second polymerization product;
contacting the second polymerization product with:
(a1) a mixture comprising a fluorous oxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0;
a polydispersity index, PDIO Mw/Mn, of 1.0-2.0; and
a percent purity of 90%-100%;
(a2) a copolyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0; and
wherein y is an integer of 0-11, and x is an integer>0;
or
(a3) a combination of (a1) and (a2); and
(b1) one or more of an isocyanate, diisocyanate, or combination thereof; and
(c1) optionally, a diol or diamine chain extender;
and polymerizing, to produce the composition of claim 14.

### Claim 17 (depends on 14)

A coated surface, comprising the cured polymerization product of claim 14 in contact with a surface.

### Claim 18 (depends on 14)

A composition for coating, comprising the composition of claim 14 and a solvent.

### Claim 19 (depends on 18)

A method, comprising applying the composition of claim 18 to a surface, and allowing to cure, to produce a coated surface.

### Claim 20 (depends on 14)

An article selected from the group consisting of an airfoil, wing, propeller, hull, superstructure, railing, intake, hatch, keel, rudder, deck, antenna, medical device, kitchen device, counter, pipe, wind turbine, aircraft, ship, rotor blade, transmission tower, transmission line, cable, cooling coil, refrigerator, freezer, and combination thereof, comprising the cured polymerization product of claim 14 on a surface thereof.

### Claim 21 (depends on 13)

The composition of claim 13, wherein the diisocyanate is methylene dicyclohexyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, cyclohexane diisocyanate, tetramethyl xylylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, phenylene diisocyanate, or a combination of two or more thereof.

### Claim 22 (depends on 13)

The composition of claim 13, wherein (B) is a diisocyanate and further comprises one or more amines having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3;
and q is an integer of 1-10.

### Claim 23 (depends on 13)

The composition of claim 13, wherein (B) is an isocyanate having the formula:
wherein RD is —CH3, —CH2CH3, —CH2CH2CH3, —CH2CH2CH2CH3;
and p is an integer of 1-10.

### Claim 24 (depends on 13)

The composition of claim 13, wherein diol or diamine chain extender (C) is present and is selected from the group consisting of C1-10 alkylene diol, C1-10 alkenylene diol, C1-20 aralkylene diol, 1,4-butanediol, C1-10 alkylene diamine, C1-10 alkenylene diamine, and C1-20 aralkylene diamine.

### Claim 25 (depends on 13)

The composition of claim 13, further comprising a linear polyurethane.

### Claim 26 (depends on 25)

A composition for coating, comprising the composition of claim 25 and a solvent.

### Claim 27 (depends on 25)

A coating, comprising the composition of claim 25.

### Claim 28 (depends on 27)

An article selected from the group consisting of an airfoil, wing, propeller, hull, superstructure, railing, intake, hatch, keel, rudder, deck, antenna, medical device, kitchen device, counter, pipe, wind turbine, aircraft, ship, rotor blade, transmission tower, transmission line, cable, cooling coil, refrigerator, freezer, and combination thereof, comprising the coating of claim 27 on a surface thereof.

### Claim 29

A monolithic, self-stratifying polymer coating, comprising:
inner and outermost surfaces on opposite sides of the coating, the inner surface being in contact with and adhered to an article;
a surface region, extending from the outermost surface to a depth of about 2 nm from the outermost surface;
a middle region, extending from a depth of about 2 nm from the outermost surface to a depth of less than about 2000 nm from the outermost surface; and
a bulk region, extending from a depth of less than about 2000 nm from the outermost surface to the inner surface;
wherein the surface region comprises a fluorous polyoxetane having the formula:
wherein n is an integer of 0-11, and m is an integer>0, in a greater concentration relative to the middle and bulk regions;
wherein the middle region comprises —SiO1.5 in a greater concentration relative to the surface and bulk regions;
and wherein the bulk region comprises a polyurethane in a greater concentration relative to the surface and middle regions.

### Claim 30 (depends on 29)

The coating of claim 29, wherein the article is selected from the group consisting of an airfoil, wing, propeller, hull, superstructure, railing, intake, hatch, keel, rudder, deck, antenna, medical device, kitchen device, counter, pipe, wind turbine, aircraft, ship, rotor blade, transmission tower, transmission line, cable, cooling coil, refrigerator, freezer, and combination thereof.