# US 2013/0280641 A1 · Method for creating multilayer high adsorptive covering for fluoropolymers

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- Number: US 2013/0280641 A1
- Document ID: US20130280641A1
- Status: Published application
- Kind: A1
- Application number: 13/497,093
- Filed: 2010-02-05
- Published: 2013-10-24
- Earliest claimed: 2009-02-05
- Assignees: Visitret Displays Ltd.
- Inventors: Jüri Liiv
- Web page: https://patentgrep.com/patent/US20130280641A1

## CPC

- C08J 7/16: with polymerisable compounds
- B01D 67/0006: {by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125)}
- B01D 67/00931: {by introduction of specific groups after membrane formation, e.g. by grafting}
- B01D 67/00933: {by addition of a layer chemically bonded to the membrane}
- B01D 69/141: {Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes}
- B01D 71/024: {Oxides}
- B01D 71/281: {Polystyrene}
- B01D 71/34: Polyvinylidene fluoride
- B01D 71/36: Polytetrafluoroethylene
- C08F 259/08: on to polymers containing fluorine
- C08J 5/2293: {After-treatment of fluorine-containing membranes}
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- H01M 8/0289: Means for holding the electrolyte (solid polymer electrolytes H01M8/1018)
- B01D 71/025: {Aluminium oxide}
- B01D 71/027: {Silicium oxide}
- B01D 2323/38: Graft polymerization
- B01D 2325/04: Characteristic thickness
- B01D 2325/10: Catalysts being present on the surface of the membrane or in the pores
- B01D 2325/26: Electrical properties
- C08F 2438/01: Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
- C08J 2327/02: not modified by chemical after-treatment
- Y02E 60/50: Fuel cells
- Y10T 428/261: In terms of molecular thickness or light wave length
- Y10T 428/3154: Of fluorinated addition polymer from unsaturated monomers
- 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)
- 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
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention relates to a method for coating fluoropolymers with a coating substance, by atom transfer radical polymerisation and subsequent processing whereas a fluoropolymer is contacted with a reaction mixture comprising at least one ligand selected from the group consisting of multichained and polycyclic amines, at least one metal salt wherein the metal is in a first oxidation state, at least one solvent, and the organic coating substance in monomer form.

## Claims

### Claim 1

A method for coating fluoropolymers with a coating substance, by atom transfer radical polymerisation, comprising contacting a fluoropolymer with a reaction mixture comprising
at least one ligand selected from the group consisting of multichained and polycyclic amines,
at least one metal salt wherein the metal is in a first oxidation state,
at least one solvent, and
the organic coating substance in monomer form.

### Claim 2 (depends on 1)

A method according to claim 1 wherein the reaction mixture further comprises an initiator.

### Claim 3 (depends on 1)

A method according to claim 1 wherein the initiation of a reaction using the reaction polymer is induced by the polymer crystal structure defects.

### Claim 4 (depends on 1)

A method according to claim 1, wherein the coating substance is selected from a group consisting of styrene, sulphonic acid, metacrylate, ethylene-imine a hydrophilic monomer and mixtures thereof.

### Claim 5 (depends on 1)

A method according to claim 1, wherein the reaction mixture comprises metal salts in more than one oxidation state.

### Claim 6 (depends on 1)

A method according to claim 1, wherein the ligand is selected from a group consisting of tris(2-aminoethyl)amine (TREN), tris[2-(dimethylamino)ethyl]amine (Me6 TREN), 2,2′-bipyridine (bpy), tetraazacyclotetradecane (CYCLAM) and mixtures thereof.

### Claim 7 (depends on 1)

A method according to claim 1, wherein the fluoropolymer is selected from a group consisting of polyvinylene, polytetrafluoroethylene, polyvinylfluoride and mixtures thereof.

### Claim 8 (depends on 1)

A method according to claim 1, wherein the solvent is selected from a group consisting of organic solvents, liquid salts and eutectic solvents reacting like liquid salts.

### Claim 9 (depends on 8)

A method according to claim 8, wherein the solvent is selected from a group consisting of mixture of tetrahydrofuran and acetonenitrile, choline chloride, glycerol and mixtures thereof.

### Claim 10 (depends on 1)

A method according to claim 1, wherein the metal salt is selected from a group consisting of CuBr, CuCI and FeCI2.

### Claim 11 (depends on 1)

A method according claim 1, wherein the initiator is selected from a group consisting of halides of organic acids such as isobutylic acid bromide or other organic halides.

### Claim 12 (depends on 1)

A method according to claim 1, further comprising a further step of coating the substance-coated fluoropolymer with an inorganic layer of A1203, Si02, or Ti02 by hydrolysis of metallorganic compound.

### Claim 13

(canceled)

### Claim 14 (depends on 1)

A method according to claim 1, further comprising a further step of coating the substance coated fluoropolymer or the monolayer and substance-coated fluoropolymer with a layer of microcrystallic or amorphous metallic oxide using hydrolysis or sol-gel process.

### Claim at position 15

15-18. (canceled)

### Claim 19 (depends on 1)

A method according to claim 1, wherein the reaction mixture further comprises at least one antioxidant such as ascorbic acid.

### Claim 20 (depends on 1)

A method according to claim 1, wherein the reaction mixture further comprises at least one liquid salt such as a mixture of choline chloride and glycerol.

### Claim at position 18

21-22. (canceled)

### Claim 23 (depends on 1)

A fluoropolymer coated with a coating substance obtainable by the method of claim 1.

### Claim 24

A fluoropolymer coated with a coating substance, where the chain of coating polymer is chemically bonded with the chain of base polymer according to schema (1).

### Claim 25 (depends on 23)

A coated fluoropolymer according to claim 23, wherein the coating substance is any hydrophilic polymer and in that the thickness of the any hydrophilic polymer coating is at least five styrene molecules.

### Claim 26 (depends on 23)

A coated fluoropolymer according to claim 23, wherein the fluoropolymer is further functionalised.

### Claim 27 (depends on 23)

Use of a coated fluoropolymer according to claim 23 for reaction column fillings, microfilters, electrical sensors, twist-ball or electrophoretic displays, membranes for biotechnology, fuel cell membranes, or biodepositors.

### Claim at position 24

28-32. (canceled)