# US 9,517,952 B2 · Hydrophilic-oleophobic copolymer composition and uses thereof

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- Number: US 9,517,952 B2
- Document ID: US9517952B2
- Status: Granted
- Kind: B2
- Application number: 14/080,878
- Filed: 2013-11-15
- Published: 2015-05-21
- Granted: 2016-12-13
- Earliest claimed: 2013-11-15
- Assignees: General Electric Company
- Applicants: General Electric Company
- Inventors: Louisa Ruth Carr; James Manio Silva; Paul Michael Smigelski, Jr.; Jason Nichols
- Web page: https://patentgrep.com/patent/US9517952B2

## CPC

- B01D 71/76: Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 (rubbers in general B01D71/24)
- B01D 71/82: characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
- C02F 1/444: {by ultrafiltration or microfiltration}
- C02F 1/58: by removing specified dissolved compounds (using ion-exchange C02F1/42; softening water C02F5/00)
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/387: {and containing nitrogen and oxygen}
- C08J 7/0427: {with only one layer of a composition containing a polymer binder (with more layers C08J7/042)}
- C08J 7/056: Forming hydrophilic coatings
- C08J 9/365: {Coating}
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- B01D 61/145: {Ultrafiltration}
- B01D 61/147: {Microfiltration}
- B01D 2325/0283: Pore size
- B01D 2325/18: Membrane materials having mixed charged functional groups
- B01D 2325/36: Hydrophilic membranes
- C02F 2101/32: Hydrocarbons, e.g. oil
- C02F 2303/20: Prevention of biofouling
- C02F 2305/00: Use of specific compounds during water treatment
- C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene
- C08J 2433/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- 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)
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED 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)
- 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)

## Abstract

Provided herein are copolymers and copolymer compositions that are both hydrophilic and oleophobic. The copolymers include structural units derived from a fluoroalkyl monomer and a zwitterionic monomer. It further relates to membranes formed by coating a porous substrate with the copolymeric compositions. The copolymeric coating imparts hydrophilicity and oleophobicity/oil-tolerance to the membranes. The uses of such membranes as microfiltration membrane or ultrafiltration membrane are also provided.

## Claims

### Claim 1

A method of treating a contaminated water comprising:
providing the contaminated water comprising water and oil;
providing a membrane comprising a porous substrate and a coating attached to the porous substrate, wherein at least one of the porous substrate or the coating comprises a copolymer comprising 1 to 10 mole % of a structural unit of formula I; and 90 to 99 mole % of a structural unit of formula II,
wherein
R1 is a linear or branched C1-C30 fluoroalkyl group;
R2 and R3 are independently at each occurrence a hydrogen, or a linear or branched C1-C4 alkyl group;
either R4 and R5 are independently at each occurrence a linear or branched C1-C12 alkyl group, a C5-C12 carbocyclic group, or a C5-C12 heterocyclic group, and R6 and R7 are independently at each occurrence a linear or branched C1-C12 alkylene group, a linear or branched C2-C12 alkenylene group, a linear or branched C2-C12 alkynlene group, a C5-C12 carbocyclic group, or a C5-C12 heterocyclic group, or at least two of R4, R5, R6, or R7 together with the nitrogen atom to which they are attached form a heterocyclic ring containing 5 to 7 atoms;
X is independently at each occurrence an —O— or —NH—;
Y is a sulfite group or a carboxylate group; and
m and n are independently at each occurrence an integer ranging from 1 to 5; and
passing the contaminated water through the membrane to generate a treated water.

### Claim 2 (depends on 1)

The method of claim 1, wherein the contaminated water is a produced water.

### Claim 3 (depends on 1)

The method of claim 1, wherein the contaminated water comprises total organic components in a range between 1 and 1000 ppm.

### Claim 4 (depends on 3)

The method of claim 3, wherein the contaminated water comprises free un-dissolved oil in a range between 1 and 500 ppm, total dissolved solids in a range between 5000 and 200000 ppm, and total suspended solids in a range between 1 and 2000 ppm.

### Claim 5 (depends on 4)

The method of claim 4, wherein the concentration of the suspended solids in the treated water is lower than that of the contaminated water.

### Claim 6 (depends on 1)

The method of claim 1, wherein the copolymer comprises 1 to 10 mole % of a structural unit of formula VII, and 90 to 99 mole % of a structural unit of formula VIII, wherein R1 is a linear C5-C8 fluoroalkyl group; and

### Claim 7 (depends on 6)

The method of claim 6, wherein the porous substrate has a pore size ranging from about 0.01 micron to about 50 micron.

### Claim 8 (depends on 6)

The method of claim 6, wherein the porous substrate comprises a polymer selected from the group consisting of polytetrafluoroethylene, expanded polytetrafluoroethylene, polysulfone, polyethersulfone, polypropylene, polyvinylidine fluoride, polyamide, polystyrene, polyethylene, polyacrylonitrile, cellulose-based materials and combinations thereof.

### Claim 9 (depends on 6)

The method of claim 6, wherein the porous substrate is expanded polytetrafluoroethylene.

### Claim 10 (depends on 6)

The method of claim 6, wherein the copolymer comprises 10 mole % of the structural unit of formula VII, and 90 mole % of the structural unit of formula VIII.

### Claim 11 (depends on 10)

The method of claim 10, wherein R1 of the copolymer is —C6F13.