Graphene enhanced polymer composites and methods thereof

Patent metadata

Field	Value
Publication number	US-10036239-B2
Application number	US-201514720342-A
Country	US
Kind code	B2
Filing date	May 22, 2015
Priority date	May 22, 2015
Publication date	Jul 31, 2018
Grant date	Jul 31, 2018

Abstract

It has been discovered that blending nano-graphene materials into cross-linked polymer compositions increases the thermal degradation resistance and compressive strength of the graphene enhanced polymer composites formed. Graphene enhanced polymer composites and their methods of use provide improved relative permeability modifiers for conformance applications.

First claim

What is claimed is:

1. A graphene-enhanced polymer composite comprising:
from about 0.01% w/v to about 10% w/v of a nano-graphene material; and
a cross-linked polymer, wherein the cross-linked polymer is:
a reaction product of (1) a hydrophilic reactive polymer and (2) (a) a hydrophobic compound or (b) a hydrophilic compound, wherein the hydrophilic reactive polymer comprises a reactive amino group, or
a copolymerization product of (1) a hydrophilic monomer and (2) a hydrophobically modified hydrophilic monomer.

2. The graphene-enhanced polymer composite of claim 1 , wherein the hydrophilic reactive polymer is selected from polyethyleneimine, polyvinylamine, polyamine, poly(vinylamine/vinyl alcohol), chitosan, polylysine, and an alkyl acrylate polymer.

3. The graphene-enhanced polymer composite of claim 1 , wherein the hydrophobic compound comprises at least one of an alkyl halide having from about 4 to about 30 carbons and a bisphenol epoxide.

4. The graphene-enhanced polymer composite of claim 1 , wherein the hydrophilic compound comprises an acrylamide-co-acrylate ester copolymer, or
a halogen containing polyether, wherein the polyether is selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and mixtures thereof.

5. The graphene-enhanced polymer composite of claim 1 , wherein the hydrophilic monomer is selected from acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, vinyl pyrrolidone, dimethylaminoethyl methacrylate, acrylic acid, dimethylaminopropylmethacrylamide, vinyl amine, trimethylammoniumethyl methacrylate chloride, methacrylamide, and hydroxyethyl acrylate.

6. The graphene-enhanced polymer composite of claim 1 , wherein the hydrophobically modified hydrophilic monomer is selected from alkyl acrylates, alkyl methacrylates, alkyl acrylamides, alkyl methacrylamides, alkyl dimethylammoniumethyl methacrylate bromide, alkyl dimethylammoniumethyl methacrylate chloride, alkyl dimethylammoniumethyl methacrylate iodide, alkyl dimethylammoniumpropyl methacrylamide bromide, alkyl dimethylammoniumpropyl methacrylamide chloride, and alkyl dimethylammoniumpropyl methacrylamide iodide, wherein the alkyl groups have from about 4 to about 22 carbon atoms.

7. The graphene-enhanced polymer composite of claim 1 , wherein the nano-graphene material comprises a nano-graphene plate powder, a nano-graphene ribbon, a functionalized graphene, a graphene oxide, and combinations thereof.

8. The graphene-enhanced polymer composite of claim 7 , wherein the functionalized graphene has at least one functional group selected from a sulfonate, a sulfate, a sulfosuccinate, a thiosulfate, a succinate, a carboxylate, a hydroxyl, a glucoside, an ethoxylate, a propoxylate, a phosphate, an ether, an amine, an amide, and combinations thereof.

9. The graphene-enhanced polymer composite of claim 1 , wherein the nano-graphene materials comprise a nano-graphene plate powder having a particle size of from about 30 nm to about 300 nm and a particle thickness of from about 1 nm to about 100 nm.

10. The graphene-enhanced polymer composite of claim 9 , wherein the nano-graphene plate powder has a ratio of the particle size to the particle thickness of about 10:1 to about 30:1.

11. A method of reducing water permeability of a wellbore in a subterranean formation, comprising:
introducing a relative permeability modifier comprising a graphene-enhanced polymer composite into the wellbore;
the graphene-enhanced polymer composite comprising:
from about 0.01% w/v to about 10% w/v of a nano-graphene material; and
a cross-linked polymer, wherein the cross-linked polymer is:
a reaction product of (1) a hydrophilic reactive polymer and (2) (a) a hydrophobic compound or (b) a hydrophilic compound, wherein the hydrophilic reactive polymer comprises a reactive amino group, or
a copolymerization product of (1) a hydrophilic monomer and (2) a hydrophobically modified hydrophilic monomer.

12. The method of claim 11 , wherein the hydrophilic reactive polymer is selected from polyethyleneimine, polyvinylamine, polyamine, poly(vinylamine/vinyl alcohol), chitosan, polylysine, and an alkyl acrylate polymer.

13. The method of claim 11 , wherein the hydrophobic compound comprises at least one of an alkyl halide having from about 4 to about 30 carbons and a bisphenol epoxide, or
wherein the hydrophilic compound comprises an acrylamide-co-acrylate ester copolymer, or a halogen containing polyether, wherein the polyether is selected from the group consisting of polyethylene oxide, polypropylene oxide, polybutylene oxide, and mixtures thereof.

14. The method of claim 11 , wherein the hydrophilic monomer is selected from acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, vinyl pyrrolidone, dimethylaminoethyl methacrylate, acrylic acid, dimethylaminopropylmethacrylamide, vinyl amine, trimethylammoniumethyl methacrylate chloride, methacrylamide, and hydroxyethyl acrylate.

15. The method of claim 11 , wherein the hydrophobically modified hydrophilic monomer is selected from alkyl acrylates, alkyl methacrylates, alkyl acrylamides, alkyl methacrylamides, alkyl dimethylammoniumethyl methacrylate bromide, alkyl dimethylammoniumethyl methacrylate chloride, alkyl dimethylammoniumethyl methacrylate iodide, alkyl dimethylammoniumpropyl methacrylamide bromide, alkyl dimethylammoniumpropyl methacrylamide chloride, and alkyl dimethylammoniumpropyl methacrylamide iodide, wherein the alkyl groups have from about 4 to about 22 carbon atoms.

16. The method of claim 11 , wherein the nano-graphene material comprises a nano-graphene plate powder, a nano-graphene ribbon, a functionalized graphene, a graphene oxide, and combinations thereof.

17. The method of claim 16 , wherein the functionalized graphene has at least one functional group selected from a sulfonate, a sulfate, a sulfosuccinate, a thiosulfate, a succinate, a carboxylate, a hydroxyl, a glucoside, an ethoxylate, a propoxylate, a phosphate, an ether, an amine, an amide, and combinations thereof.

18. The method of claim 11 , wherein the nano-graphene materials comprise a nano-graphene plate powder having a particle size of from about 30 nm to about 300 nm and a particle thickness of from about 1 nm to about 100 nm.

19. The method of claim 18 , wherein the nano-graphene materials comprise a nano-graphene plate powder having a ratio of the particle size to the particle thickness of about 10:1 to about 30:1.

20. The method of claim 11 , further comprising, before introducing the relative permeability modifier,
locating a lost circulation zone in the wellbore by applying a detection method to the wellbore,
wherein the detection method is at least one selected from the group consisting of magnetic resonance imaging, resistivity imaging, gamma ray imaging, neutron density imaging, sonic imaging, and caliper imaging.

21. The method of claim 11 , wherein the relative permeability modifier is introduced during or after completion of the wellbore, and before production of the wellbore.

22. The method of claim 11 , further comprising,
detecting degradation of the graphene-enhanced polymer composite during production by applying at least one of UV spectroscopy, IR spectroscopy, and Raman spectroscopy to a production fluid.

Assignees

• Halliburton Energy Services Inc

Inventors

• Salla Rajender
• Raysoni Neelam Deepak

Classifications

• E21B47/00 Primary

  Survey of boreholes or wells (monitoring pressure or flow of drilling fluid E21B21/08) · CPC title

• C09K2208/10

  Nanoparticle-containing well treatment fluids · CPC title

• C09K8/03

  Specific additives for general use in well-drilling compositions · CPC title

• C09K8/516 Primary

  characterised by their form or by the form of their components, e.g. encapsulated material · CPC title