Re-crosslinkable hyper-branched polymer gels based on a transamidation reaction

Patent metadata

Field	Value
Publication number	US-12534663-B2
Application number	US-202118251859-A
Country	US
Kind code	B2
Filing date	Sep 20, 2021
Priority date	Nov 4, 2020
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The present invention generally relates to the field of conformance control in oil fields, particularly to a re-crosslinkable preformed particle gel system, and composition thereof. The composition of the re-crosslinkable preformed particle gel system contains monomers, crosslinkers, a polymer matrix, and additives. Components in the composition for re-crosslinkable preformed particle gel in the present invention have excellent compatibility with each other, and the obtained gel has excellent long term high-temperature resistance property. Different from prior products, in the re-crosslinkable preformed particle gel compositions according to embodiments of the present invention, the components that are used to re-crosslink the particle gels may be grafted on the polymer chain and will act as initiator or secondary crosslinker in different conditions. During particle injection process, all compositions would move together, thereby avoiding chromatographic problems typical of prior products.

First claim

The invention claimed is:

1 . A composition for controlling fluid flow, said composition comprising a plurality of swellable particles, said particles comprising a re-crosslinking agent embedded within a polymer matrix, and wherein upon swelling, said particles exhibit less than about 50 percent decrease in volume after being exposed to a temperature of at least about 100° C. for at least about 1 hour,
wherein said re-crosslinking agent is selected from the group consisting of tetraethylenepentamine, ceric ammonium nitrate, and

2 . The composition of claim 1 , wherein said particles further comprise a re-associating agent comprising a clay or a salt of a multivalent metal ion.

3 . The composition of claim 1 , wherein said particles further comprise a crosslinking agent selected from the group consisting of methylene bisacrylamide, diallylamide, divinyl sulfone, divinyl-benzene, poly (ethylene glycol) diacrylate, diacrylyl tertiary amide, diacrylylpiperazine, diallyltartardiamide, dihydroxyethylene-bis-acrylamide, bis-acrylylcystamine, trimethylolpropane trimethacrylate, propyleneglycol triacrylate, tripropyleneglycol diacrylate, allyl methacrylate, triethyleneglycol dimethacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,5 pentane diol dimethacrylate, pentaerythritol triallylether, and combinations thereof.

4 . The composition of claim 1 , wherein the crosslinking agent comprises divinyl-benzene.

5 . The composition of claim 1 , wherein said polymer matrix comprises:
one of more monomers selected from the group consisting of acrylamide, 2-acrylamide-2-aethylpropanesulfonic acid, 4-acryloylmorpholine, N,N-dimthylacrylamide, N-methylolacrylamide, acryloyloxyethyltrimethyl ammonium chloride, methacryloxyethyltrimethyl ammonium chloride sodium, 4-ethenylbenzene-1-sulfonate, acrylic acid, vinyl acetate, N-vinyl formamide, N-viny pyrrolidone, 4-vinylpyridine, tolylene-2,4-diisocyanate, octacosyl acrylate, vinylimidazole, dodecyl acrylate, hexadecyl acrylate, and octacosyl acrylate; one or more monomers selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-tert-butylacrylamide, N-ethylacrylamide, N-hydroxyethyl acrylamide, N-isopropylacrylamide, N,N-diethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, acrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, and N-vinyl formamide; one or more monomers selected from the group consisting of sulfonates, sulfates, and phosphates; 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt; one or more monomers selected from the group consisting of diallyldimethylammonium chloride, (3-(methacryloylamino) propyl) trimethyl ammonium chloride, (2-(methacryloyloxy) ethyl) trimethyl ammonium chloride, and vinylbenzyl trimethyl ammonium chloride, dimethylaminoethylacrylate methyl chloride quaternary salt, dimethylaminoethylacrylate benzyl chloride quaternary salt, and dimethylaminoethylmethacrylate methyl chloride quaternary salt; one or more monomers selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethylacrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEM), alkyl esters, α-olefins, vinyl alkylates, vinyl alkyl ethers, N-vinyl amides, and alkyl aromatics; and/or one or more polymers selected from the group consisting of poly (vinyl alcohol), sodium alginate, and poly (vinyl pyrrolidone).

6 . The composition of claim 1 , wherein said polymer matrix comprises one or monomers comprising a re-crosslinkable moiety.

7 . The composition of claim 6 , wherein said one or more monomers comprise one or more amide groups and/or isocyanate groups.

8 . The compositions of claim 1 , wherein the particles have an average particle size of 10 nm to 10 mm.

9 . A method of forming the composition of claim 1 , said method comprising:
(a) polymerizing said polymer matrix in the presence of said re-crosslinking agent to form said polymer matrix and embed said re-crosslinking agent within said polymer matrix; (b) drying said polymer matrix to form a dried polymer matrix; and (c) grinding said dried polymer matrix to form said composition.

10 . The method of claim 9 , wherein said polymerizing of step (a) occurs at a temperature of at least 20° C. and/or less than 200° C.

11 . The method of claim 9 , wherein said polymerizing of step (a) comprises ultrasonication.

12 . The method of claim 11 , wherein said ultrasonication occurs for at least 10 minutes and/or less than 6 hours.

13 . The method of claim 9 , wherein said polymerizing of step (a) occurs for at least 1 hour and/or less than 18 hours.

14 . A method of forming a gel formation in a target zone of a subterranean environment, said method comprising:
(a) dispersing the composition of claim 1 into a carrier fluid, thereby causing said swellable particles to swell; and (b) introducing said carrier fluid comprising said composition into said target zone having a temperature of at least 50° C., thereby causing said re-crosslinking agent to react with a monomer within said polymer matrix and form said gel formation.

15 . The method of claim 14 , wherein said carrier fluid is selected from the group consisting of fresh water, produced water, sea water, brine, and drilling fluid.

16 . The method of claim 14 , wherein said subterranean environment is selected from the group consisting of wells and pipelines.

17 . The method of claim 14 , wherein said target zone is selected from the group consisting of fractures, conduits, lost-circulation zones, cavernous formations, high-permeability zones, wellbores, and perforations.

18 . The method of claim 14 , wherein said particles have an initial average particle size prior to said contact and wherein upon contact with said fluid, said particles swell to a second average particle size that is at least about 5 times greater than that of the initial average particle size.

19 . A synthetic crosslinking and/or re-crosslinking compound having the chemical formula:

20 . The composition of claim 1 , wherein the polymer matrix is free of CO 2 -philic moieties.

Assignees

• Univ Missouri

Inventors

• Song Tao
• Bai Baojun
• Schuman Thomas P

Classifications

• C09K2208/10

  Nanoparticle-containing well treatment fluids · CPC title

• C08J2333/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• C08J2300/202

  Dendritic macromolecules, e.g. dendrimers or hyperbranched polymers · CPC title

• C08K3/346

  Clay · CPC title

• C08J3/075 Primary

  Macromolecular gels · CPC title