# US 11,306,159 B2 · Nanosheet polymer composite for water shutoff

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- Number: US 11,306,159 B2
- Document ID: US11306159B2
- Status: Granted
- Kind: B2
- Application number: 16/854,299
- Filed: 2020-04-21
- Published: 2021-10-21
- Granted: 2022-04-19
- Earliest claimed: 2020-04-21
- Assignees: Saudi Arabian Oil Company; Alfaisal University
- Applicants: Saudi Arabian Oil Company; Alfaisal University
- Inventors: Ayman Almohsin; Edreese Alsharaeh; Feven Mattews Michael
- Web page: https://patentgrep.com/patent/US11306159B2

## CPC

- C08F 2/22: Emulsion polymerisation
- C08F 2/32: Polymerisation in water-in-oil emulsions
- C08F 6/008: {Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes}
- C08F 6/02: Neutralisation of the polymerisation mass, e.g. killing the catalyst (short-stopping C08F2/42 ){also removal of catalyst residues}
- C08F 6/14: Treatment of polymer emulsions {(C08F6/001, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)}
- C08F 20/56: Acrylamide; Methacrylamide
- C08J 3/075: Macromolecular gels
- C08J 3/12: Powdering or granulating
- C08K 3/042: {Graphene or derivatives, e.g. graphene oxides}
- C08K 3/22: of metals
- C08K 3/30: Sulfur-, selenium- or tellurium-containing compounds
- C08K 3/38: Boron-containing compounds
- C08K 5/1535: Five-membered rings
- C09K 8/508: macromolecular compounds {(C09K8/512 takes precedence)}
- C09K 8/5083: {obtained by reactions only involving carbon-to-carbon unsaturated bonds}
- C09K 8/512: containing cross-linking agents
- C09K 8/516: characterised by their form or by the form of their components, e.g. encapsulated material
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C08J 2333/26: Homopolymers or copolymers of acrylamide or methacrylamide
- C08K 2003/2244: {of zirconium}
- C08K 2003/3054: {Ammonium sulfates}
- C08K 2003/385: {Binary compounds of nitrogen with boron}
- C08K 2201/011: Nanostructured additives
- C08L 33/26: Homopolymers or copolymers of acrylamide or methacrylamide
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A method of preparing a polymer composite includes dispersing a nanosheet filler within a polymer matrix by dissolving a monomer in water to form a first solution, dispersing the nanosheet filler in an organic solvent in the presence of an emulsifying agent to form a second solution, combining the first solution and the second solution, and adding a polymerization initiator to initiate a polymerization reaction of the monomer to form a polymer composite precursor comprising the nanosheet filler dispersed in the polymer matrix. The method further includes quenching the polymerization reaction and then filtering, washing, grinding, and drying the polymer composite precursor to form the polymer composite. A method of preparing a polymer composite hydrogel for water shutoff applications and the associated method of forming a barrier to shut off or reduce unwanted production of water in a subterranean formation utilizing the polymer composite hydrogel is also provided.

## Claims

### Claim 1

A method of preparing a polymer composite, the method comprising:
dispersing a nanosheet filler within a polymer matrix by:
dissolving a monomer in water to form a first solution,
dispersing the nanosheet filler in an organic solvent in the presence of an emulsifying agent to form a second solution,
combining the first solution and the second solution to form an emulsion having a weight ratio of nanosheet filler to monomer between 1:99 and 1:9, and
adding a polymerization initiator comprising a persulfate to the emulsion to initiate a polymerization reaction of the monomer to form a polymer composite precursor solution comprising a polymer composite precursor within an aqueous media, the polymer composite precursor comprising the nanosheet filler dispersed in a polymer matrix of the polymerized monomer;
quenching the polymerization reaction with the addition of a first alcohol to the polymer composite precursor solution;
filtering the polymer composite precursor from the aqueous media of the polymer composite precursor solution;
washing the polymer composite precursor with one or more of a second alcohol and acetone;
grinding the polymer composite precursor to an average particle size of 2 to 500 nm; and
drying the polymer composite precursor to form the polymer composite,
where the nanosheet filler comprises one or more of zirconium hydroxide, zirconium oxide, titanium oxide, graphene oxide, non-functionalized graphene, and hexagonal boron nitride.

### Claim 2 (depends on 1)

The method of claim 1, where the method further comprises adding a polymerization catalyst to the emulsion in combination with the polymerization initiator.

### Claim 3 (depends on 2)

The method of claim 2, where the polymerization initiator comprises ammonium persulfate.

### Claim 4 (depends on 2)

The method of claim 2, where the polymerization catalyst comprises tetramethylenediamine.

### Claim 5 (depends on 1)

The method of claim 1, where the monomer comprises one or more of acrylamide, acyrlonitrile, vinyl alcohol, ethylene terephthalic acid, butylene terephthalic acid, ethylene, isocyanates, polyols, and propylene.

### Claim 6 (depends on 5)

The method of claim 5, where the monomer comprises acrylamide.

### Claim 7 (depends on 1)

The method of claim 1, where the organic solvent is selected from the group consisting of hexane, cyclohexane, heptane, cycloheptane, toluene, and 1,2-Dichlorobenzene.

### Claim 8 (depends on 1)

The method of claim 1, where the emulsifying agent comprises polysorbate 60, polysorbate 80, sorbitane monostearate, sorbitane monooleate, or sodium dodecyl sulfate.

### Claim 9 (depends on 1)

The method of claim 1, where the first alcohol and the second alcohol are selected from the group consisting of methanol, ethanol, iso-propanol, and propanol.

### Claim 10 (depends on 1)

The method of claim 1, where the nanosheet filler comprises one or more of zirconium hydroxide, non-functionalized graphene, and hexagonal boron nitride.