# US 2019/0169464 A1 · Interpenetrating polymer networks

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- Number: US 2019/0169464 A1
- Document ID: US20190169464A1
- Status: Published application
- Kind: A1
- Application number: 16/300,175
- Filed: 2017-05-10
- Published: 2019-06-06
- Earliest claimed: 2016-05-10
- Assignees: The Australian National University
- Applicants: The Australian National University
- Inventors: William Sai Yau Wong; Antonio Tricoli; David Russell Nisbet; Zbigniew Stachurski
- Web page: https://patentgrep.com/patent/US20190169464A1

## CPC

- C09D 175/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- C03C 17/007: {containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase}
- C03C 17/30: with silicon-containing compounds
- C03C 17/322: {Polyurethanes or polyisocyanates}
- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/3206: {aliphatic}
- C08G 18/4063: {Mixtures of compounds of group C08G18/62 with other macromolecular compounds}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/6229: {Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols}
- C08G 18/65: Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen {(C08G18/2805 takes precedence)}
- C08G 18/6677: {having at least three hydroxy groups}
- C08G 18/673: {containing two or more acrylate or alkylacrylate ester groups}
- C08G 18/7614: {containing only one aromatic ring}
- C08G 18/7621: {being toluene diisocyanate including isomer mixtures}
- C08J 3/246: {Intercrosslinking of at least two polymers}
- 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 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D 175/08: from polyethers
- C03C 2217/445: Organic continuous phases
- C03C 2217/47: consisting of a specific material
- C03C 2217/48: having a specific function
- C03C 2217/76: Hydrophobic and oleophobic coatings
- C03C 2218/112: by spraying
- C08G 2270/00: Compositions for creating interpenetrating networks
- C08J 2333/12: Homopolymers or copolymers of methyl methacrylate
- C08J 2375/04: Polyurethanes
- C08K 3/36: Silica
- 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)
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The invention relates to a film comprising an interpenetrating network, its uses and processes for making the same. The film produced displays good durability, chemical resistance and transparency. The film is produced from an interpenetrating network formed as a colloidal suspension in an organic solvent and a particulate solid.

## Claims

### Claim 1

A process for making a coating comprising an interpenetrating polymer network, said process comprising the steps of:
a) applying a colloidal suspension to a surface to produce a coated surface, wherein the colloidal suspension comprises colloidal particles suspended in an organic solvent, and wherein the colloidal particles comprise an interpenetrating polymer network, and;
b) applying a particulate solid to the coated surface, wherein substantially the entire surface of the particulate solid is hydrophobic.

### Claim 2 (depends on 1)

The process of claim 1 wherein the colloidal suspension is applied to the surface by dipcoating, spincoating, dropcasting, or electrospinning.

### Claim 3 (depends on 1)

The process according to claim 1 wherein the colloidal suspension is applied to the surface by spraying.

### Claim 4 (depends on 1, 2, 3)

The process according to any one of claims 1 to 3 wherein the colloidal suspension has a viscosity of less than about 1000 cP.

### Claim 5 (depends on 1, 2, 3, 4)

The process according to any one of claims 1 to 4 wherein the colloidal suspension has a solids content of from about 5 to about 25% w/v.

### Claim 6 (depends on 1, 2, 3, 4, 5)

The process according to any one of claims 1 to 5 wherein the particulate solid has a mean particle size of between about 5 and about 20 nm.

### Claim 7 (depends on 1, 2, 3, 4, 5, 6)

The process according to any one of claims 1 to 6, further comprising a step wherein the particulate solid is functionalised across substantially the entire surface of the particulate solid with hydrophobic organic groups prior to step b), so as to produce a hydrophobic particulate solid for use in step b).

### Claim 8 (depends on 1, 2, 3, 4, 5, 6, 7)

The process of any one of claims 1 to 7 wherein the particulate solid is a hydrophobic fumed silica.

### Claim 9 (depends on 1, 2, 3, 4, 5, 6, 7, 8)

The process of any one of claims 1 to 8 wherein the particulate solid is perfluoroalkyl-functionalised particles.

### Claim 10 (depends on 8)

The process of claim 8 comprising reacting the fumed silica with a hydrophobing agent prior to step b) so as to produce a hydrophobic particulate solid.

### Claim 11 (depends on 10)

The process of claim 10 wherein the hydrophobing agent is a perfluoroalkylsilane.

### Claim 12 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11)

The process according to any one of claims 1 to 11 wherein the particulate solid prior to step b) is in suspension in an organic solvent.

### Claim 13 (depends on 12)

The process according to claim 12 wherein the applying in step b) is by spraying.

### Claim 14 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13)

The process of any one of claims 1 to 13 comprising the step of waiting following the application of the colloidal suspension and before application of the particulate solid, said waiting being for a period of from about 10 to about 40 minutes.

### Claim 15 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14)

The process of any one of any one of claims 1 to 14 wherein the particulate solid is at least partially wetted by the colloidal suspension after application to the coated surface.

### Claim 16 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15)

A process for making the colloidal suspension of any one of claims 1 to 15, said process comprising preparing a polymerisation mixture comprising:
i. a non-crosslinking acrylic monomer
ii. a cross-linking acrylic monomer
iii. a free radical initiator
iv. a polyol
v. an oligomeric or polymeric diol
vi. an isocyanate having at least two isocyanate groups per molecule
vii. an organic solvent;
adding a polyurethane polymerisation catalyst to the polymerisation mixture; and
heating the polymerisation mixture to at least a 10 hour half-life temperature of the free radical initiator.

### Claim 17 (depends on 16)

The process of claim 16 comprising preparing a first mixture comprising i to iii and a second mixture comprising iv to vi and combining the first and second mixtures to form the polymerisation mixture, wherein either
the first mixture or the second mixture comprises the solvent vii or
the first mixture comprises a first solvent and the second mixture comprises a second solvent and the solvent vii comprises both the first solvent and the second solvent.

### Claim 18 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17)

The process according to any one of claims 1 to 17 wherein the colloidal suspension is stable for at least about 6 months when stored in the dark without agitation.

### Claim 19 (depends on 16, 17, 18)

The process of any one of claims 16 to 18 wherein the non-crosslinking acrylic monomer is an acrylate ester or a methacrylate ester.

### Claim 20 (depends on 16, 17, 18, 19)

The process of any one of claims 16 to 19 wherein the crosslinking acrylic monomer is a diol di(meth)acrylate, a triol tri(meth)acrylate, a tetraol tetra(meth)acrylate or a pentaol penta(meth)acrylate.

### Claim 21 (depends on 16, 17, 18, 19, 20)

The process of any one of claims 16 to 20 wherein the free radical initiator has a 10 hour half-life temperature of from about 50 to about 70° C.

### Claim 22 (depends on 16, 17, 18, 19, 20, 21)

The process of any one of claims 16 to 21 wherein the free radical initiator is an azo initiator.

### Claim 23 (depends on 16, 17, 18, 19, 20, 21, 22)

The process of any one of claims 16 to 22 wherein the polyol is a triol, a tetraol or a pentaol.

### Claim 24 (depends on 16, 17, 18, 19, 20, 21, 22, 23)

The process of any one of claims 16 to 23 wherein the oligomeric or polymeric diol is a polyether diol.

### Claim 25 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24)

The process of any one of claims 16 to 24 wherein the isocyanate is a bisisocyanate.

### Claim 26 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24, 25)

The process of any one of claims 16 to 25 wherein the organic solvent dissolves each of i to vi.

### Claim 27 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26)

The process of any one of claims 16 to 26 wherein the polyurethane polymerisation catalyst is a diorganotin (IV) salt.

### Claim 28 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27)

The process of any one of claims 16 to 27 comprising preparing a first mixture comprising i to iii in a first solvent and a second mixture comprising iv to vi in a second solvent and combining the first and second mixtures to form the polymerisation mixture, wherein the solvent vii comprises both the first solvent and the second solvent.

### Claim 29 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28)

The process of any one of claims 16 to 28 wherein the step of heating is conducted in the dark.

### Claim 30 (depends on 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29)

A colloidal suspension produced by conducting the process of any one of claims 16 to 29.

### Claim 31 (depends on 30)

The colloidal suspension of claim 30 which is stable for at least about 6 months when stored in the dark without agitation.

### Claim 32 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15)

A film produced by conducting the process of any one of claims 1 to 15 and allowing the resulting film to dry and/or cure.

### Claim 33 (depends on 32)

The film of claim 32 comprising an interpenetrating polymer network of polyurethane and a polyacrylate, said film having a microroughness of at least about 2500 nm.

### Claim 34 (depends on 32, 33)

The film of claim 32 or 33 wherein the particulate solid is at least partially wetted by the colloidal suspension when applied to the coated surface.

### Claim 35 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 32, 33, 34)

The film of any one of claims 32 to 34 which is produced by conducting the process of any one of claims 1 to 15 and allowing the resulting film to dry and/or cure, and which has a surface layer comprising a hydrophobic particulate solid.

### Claim 36 (depends on 34, 35)

The film of claim 34 or claim 35 wherein the hydrophobic particulate solid is at least partially embedded in the film.

### Claim 37 (depends on 32, 33, 34, 35, 36)

The film of any one of claims 32 to 36 having a static water contact angle of at least about 150°.

### Claim 38 (depends on 32, 33, 34, 35, 36, 37)

The film of any one of claims 32 to 37 having a water sliding angle of less than about 10°.

### Claim 39 (depends on 37, 38)

The film of claim 37 or claim 38 wherein the water contact angle and/or water sliding angle are reduced by no more than 5% after at least 100 abrasion cycles performed according to ASTM D4060-14.

### Claim 40

A film comprising:
a base layer comprising a polyurethane and a polyacrylate in an interpenetrating polymer network, and;
a hydrophobic particulate solid at least partially embedded in the upper surface of the base layer, wherein the hydrophobic particulate solid comprises a surface which is substantially entirely hydrophobic.

### Claim 41 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40)

The film according to any one of claims 32 to 40, wherein the hydrophobic particulate solid provides the film with a surface roughness of at least 2500 nm.

### Claim 42 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41)

The film according to any one of claims 32 to 41 wherein the film is substantially transparent.

### Claim 43 (depends on 42)

The film according to claim 42 wherein the transmittance of the film is at least 70% when measured at a light wavelength of 600 nm and wherein the film thickness is less than 50 microns.

### Claim 44 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43)

The film according to any one of claims 32 to 43 wherein the water contact angle of the film is greater than 150° following immersion in a 1M mineral acid for at least 24 hours.

### Claim 45 (depends on 44)

The film according to claim 44 wherein the mineral acid is HCl.

### Claim 46 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45)

The film according to any one of claims 32 to 45 wherein the water contact angle of the film is greater than 150° following immersion in tetradecane or another suitable oil analogue for at least 24 hours.

### Claim 47 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46)

A method of rendering a surface superhydrophobic comprising forming a film according to any one of claims 32 to 46 thereon.

### Claim 48 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46)

Use of a film according to any one of claims 32 to 46 as a protective coating on a surface.

### Claim 49 (depends on 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46)

Use of a film according to any one of claims 32 to 46 to render a surface superhydrophobic.