# US 10,865,267 B2 · Compositions for fabricating durable, low-ice-adhesion coatings

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,865,267 B2
- Document ID: US10865267B2
- Status: Granted
- Kind: B2
- Application number: 16/144,123
- Filed: 2018-09-27
- Published: 2019-01-24
- Granted: 2020-12-15
- Earliest claimed: 2014-08-19
- Assignees: HRL Laboratories, LLC
- Applicants: HRL Laboratories, LLC
- Inventors: Andrew P. Nowak; April R. Rodriguez; Elena Sherman; Adam F. Gross
- Web page: https://patentgrep.com/patent/US10865267B2

## CPC

- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/4833: {Polyethers containing oxyethylene units}
- C08G 18/5015: {having fluorine atoms}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 81/00: Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42})
- C08G 81/025: {containing polyether sequences}
- C09D 7/61: inorganic
- C09D 127/14: Homopolymers or copolymers of vinyl fluoride
- C09D 127/16: Homopolymers or copolymers of vinylidene fluoride
- C09D 175/08: from polyethers
- C09D 187/005: {Block or graft polymers not provided for in groups C09D101/00 - C09D185/04}
- B64D 15/00: De-icing or preventing icing on exterior surfaces of aircraft
- C09D 7/65: macromolecular (C09D7/41-C09D7/48 take precedence)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- B64D: EQUIPMENT FOR FITTING IN OR TO AIRCRAFT; FLIGHT SUITS; PARACHUTES; ARRANGEMENT OR MOUNTING OF POWER PLANTS OR PROPULSION TRANSMISSIONS IN AIRCRAFT

## Abstract

This invention provides durable, low-ice-adhesion coatings with excellent ice-adhesion reduction. Some variations provide a low-ice-adhesion composition comprising a composite material containing at least a first-material phase and a second-material phase that are nanophase-separated on a length scale from 10 nanometers to less than 100 nanometers, wherein the first-material phase and the second-material phase further are microphase-separated on a length scale from 0.1 microns to 100 microns. The larger length scale of separation is driven by an emulsion process, which provides microphase separation that is in addition to classic molecular-level phase separation. The composite material has a glass-transition temperature above −80° C. The coatings may be characterized by an AMIL Centrifuge Ice Adhesion Reduction Factor up to 100 or more. These coatings are useful for aerospace surfaces and many other applications.

## Claims

### Claim 1

A low-ice-adhesion composition comprising a composite polymer material containing at least a first-material phase and a second-material phase that is chemically distinct from said first-material phase, wherein said first-material phase and said second-material phase are nanophase-separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers, wherein said first-material phase and said second-material phase further are microphase-separated on an average microphase-separation length scale that is greater than 0.2 microns to about 100 microns and is hierarchically distinct from said nanophase-separation length scale, wherein said first-material phase and said second-material phase are connected by polymer chain extension and/or polymer crosslinking, wherein said first-material phase and said second-material phase are covalently connected in a segmented block copolymer, and wherein said composite polymer material has a glass-transition temperature above −80° C.

### Claim 2 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein said average microphase-separation length scale is from about 0.5 microns to about 75 microns.

### Claim 3 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein said composite polymer material has a glass-transition temperature above 60° C.

### Claim 4 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein one of said first-material phase and said second-material phase is hydrophobic, and the other is hydrophilic.

### Claim 5 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein one of said first-material phase and said second-material phase is omniphobic, and the other is hydrophilic.

### Claim 6 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein one of said first-material phase and said second-material phase is hydrophobic, and the other is hygroscopic.

### Claim 7 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein one of said first-material phase and said second-material phase is hygroscopic, and the other comprises a low-surface-energy polymer having a surface energy between about 5 mJ/m2 to about 50 mJ/m2.

### Claim 8 (depends on 7)

The low-ice-adhesion composition of claim 7, wherein said low-surface-energy polymer is a fluoropolymer.

### Claim 9 (depends on 8)

The low-ice-adhesion composition of claim 8, wherein said fluoropolymer is selected from the group consisting of polyfluoroethers, perfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes, polytetrafluoroethylene, polyvinylidene difluoride, polyvinylfluoride, polychlorotrifluoroethylene, copolymers of ethylene and trifluoroethylene, copolymers of ethylene and chlorotrifluoroethylene, and combinations thereof.

### Claim 10 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein said segmented block copolymer comprises:
(a) one or more first soft segments selected from fluoropolymers having an average molecular weight from about 500 g/mol to about 10,000 g/mol, wherein said fluoropolymers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated;
(b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated;
(c) one or more isocyanate species, or a reacted form thereof, possessing an isocyanate functionality of 2 or greater; and
(d) one or more polyol or polyamine chain extenders or crosslinkers, or a reacted form thereof.

### Claim 11 (depends on 10)

The low-ice-adhesion composition of claim 10, wherein said fluoropolymers include a fluoropolymer having the structure:
wherein:
X, Y═CH2—(O—CH2—CH2)p—OH wherein p=0 to 50 and wherein X and Y are independently selected;
m=1 to 100; and
n=0 to 100.

### Claim 12 (depends on 10)

The low-ice-adhesion composition of claim 10, wherein said polyesters or polyethers are selected from the group consisting of poly(oxymethylene), poly(ethylene glycol), poly(propylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), and combinations thereof.

### Claim 13 (depends on 1)

The low-ice-adhesion composition of claim 1, wherein said composition is present in a coating.

### Claim 14

A 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 10,000 g/mol, wherein said fluoropolymers contain an oxygen atom connected to two alkyl or aryl groups, wherein at least one hydrogen atom of said alkyl or aryl group is replaced by a fluorine atom, and wherein said fluoropolymers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated;
(b) one or more second soft segments selected from polyesters or polyethers, wherein said polyesters or polyethers are selected from the group consisting of poly(oxymethylene), poly(ethylene glycol), poly(propylene glycol), poly(glycolic acid), poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), and combinations thereof, and wherein said polyesters or polyethers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated;
(c) one or more hard segments containing a reacted form of one or more isocyanate species possessing an isocyanate functionality of 2 or greater; and
(d) in said hard segments, a reacted form of one or more polyol or polyamine chain extenders or crosslinkers,
wherein said first soft segments and said second soft segments are covalently connected with each other,
wherein said first soft segments and said second soft segments are microphase-separated on an average microphase-separation length scale that is greater than 0.2 microns to about 100 microns, and
wherein said segmented copolymer composition has a glass-transition temperature above −80° C.

### Claim 15 (depends on 14)

The segmented copolymer composition of claim 14, wherein said first soft segments and said hard segments are nanophase-separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers.

### Claim 16 (depends on 14)

The segmented copolymer composition of claim 14, wherein said second soft segments and said hard segments are nanophase-separated on an average nanophase-separation length scale from about 10 nanometers to less than 100 nanometers.

### Claim 17 (depends on 14)

The segmented copolymer composition of claim 14, wherein said fluoropolymers are selected from the group consisting of perfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes, and combinations thereof.

### Claim 18 (depends on 14)

The segmented copolymer composition of claim 14, wherein said fluoropolymers include a fluoropolymer having the structure:
wherein:
X, Y═CH2—(O—CH2—CH2)p—OH wherein p=0 to 50 and wherein X and Y are independently selected;
m=1 to 100; and
n=0 to 100.

### Claim 19 (depends on 14)

The segmented copolymer composition of claim 14, wherein said isocyanate species is selected from the group consisting of 4,4′-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate, 4,4′-methylenebis(phenyl isocyanate), isophorone diisocyanate, and combinations or derivatives thereof.

### Claim 20 (depends on 14)

The segmented copolymer composition of claim 14, wherein at least one of said one or more polyol or polyamine chain extenders or crosslinkers possesses a functionality of 2 or greater.

### Claim 21 (depends on 14)

The segmented copolymer composition of claim 14, wherein at least one of said one or more polyol or polyamine chain extenders or crosslinkers is selected from the group consisting of 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, 1,2-ethanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, ethanol amine, diethanol amine, methyldiethanolamine, phenyldiethanolamine, glycerol, trimethylolpropane, 1,2,6-hexanetriol, triethanolamine, pentaerythritol, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, diethyltoluenediamine, dimethylthiotoluenediamine, isophoronediamine, diaminocyclohexane, N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and homologues, derivatives, or combinations thereof.

### Claim 22 (depends on 14)

The segmented copolymer composition of claim 14, wherein said composition is present in a coating.