WO2024255789A1 - Copolymère à composants multiples, son procédé de préparation et son utilisation - Google Patents

Copolymère à composants multiples, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2024255789A1
WO2024255789A1 PCT/CN2024/098940 CN2024098940W WO2024255789A1 WO 2024255789 A1 WO2024255789 A1 WO 2024255789A1 CN 2024098940 W CN2024098940 W CN 2024098940W WO 2024255789 A1 WO2024255789 A1 WO 2024255789A1
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formula
hydrogen
structural unit
alkyl
independently selected
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Chinese (zh)
Inventor
王刚
李万军
王岩峰
孔祥吉
黎小刚
景宁
吉飞
刘纪童
仲昭
肖月
叶东庆
李甘璐
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China National Oil And Gas Exploration And Development Co Ltd
China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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China National Oil And Gas Exploration And Development Co Ltd
China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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Publication of WO2024255789A1 publication Critical patent/WO2024255789A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to the technical field of oil drilling, and in particular to a multi-component copolymer and a preparation method and application thereof.
  • Wellbore instability is one of the common underground complex situations encountered in drilling projects, which seriously affects the acquisition of geological data, drilling speed, drilling quality and cost.
  • the target layer cannot be drilled due to wellbore instability, which leads to delays in exploration and development speed and affects economic benefits.
  • the essence of wellbore instability is mechanical instability. When the stress on the wellbore rock exceeds its own strength, wellbore instability will occur.
  • the causes of wellbore instability are complex and can be mainly summarized into three aspects: mechanical factors, physical and chemical factors and engineering technical measures.
  • Wellbore instability is a common problem in the oil and gas industry. It exists in almost all oil and gas field developments, affecting safe drilling and causing significant economic losses. Therefore, improving wellbore stability technology is of great significance to achieving safe, efficient and low-cost drilling goals.
  • various technical measures to stabilize the wellbore have been summarized based on the wellbore instability phenomenon encountered in practice. Among them, optimizing the type and formula of drilling fluid is one of the important measures to improve wellbore instability, improve the inhibition of drilling fluid; use physical and chemical methods to seal the bedding and cracks of the formation to prevent the drilling fluid filtrate from entering the formation; improve the membrane efficiency of the drilling fluid on the formation, and minimize the amount of drilling fluid filtrate entering the formation.
  • Commonly used anti-collapse drilling fluid treatment agents at home and abroad include inorganic salts, asphalt, silicates, polymers, etc.
  • the mechanism of action of inorganic salts such as KCl and NH 4 Cl is mainly to inhibit clay hydration and expansion, but the intensity of action is limited.
  • Asphalt treatment agents are solid when the operating temperature is lower than their softening point, and become soft when approaching their softening point. Under the action of pressure difference, asphalt treatment agents are easily squeezed into the formation bedding cracks and pore throats, forming a plugging zone on the well wall, which can effectively prevent drilling fluid filtrate from entering the formation and prevent well wall collapse.
  • asphalt products usually have fluorescence, which affects geological logging, so their use is limited.
  • Polymer treatment agents mainly inhibit clay hydration and dispersion and prevent shale collapse through adsorption and coating, but polymer treatment agents usually have poor temperature resistance and high cost.
  • polymer treatment agents have their own advantages, they also have obvious shortcomings. Therefore, how to improve the effect of well wall stabilizers has always been a major technical difficulty in the field of drilling fluids.
  • the purpose of the present invention is to overcome the problem of wellbore instability in drilling operations in the prior art, and to provide a multi-polymer and its preparation method and application.
  • the multi-polymer can be used as a wellbore strengthening wellbore stabilizer to inhibit the hydration expansion of formation clay minerals, effectively seal cracks and rocks with developed stratification, and effectively strengthen the wellbore.
  • the first aspect of the present invention provides a multi-component copolymer, wherein the multi-component copolymer comprises a structural unit A, a structural unit B, a structural unit C and a structural unit D; wherein the structural unit A has a structure shown in formula (1); the structural unit B has a structure shown in formula (2); the structural unit C has a structure shown in formula (3); and the structural unit D has a structure shown in formula (4);
  • R1 and R2 are each independently selected from hydrogen or C1 - C6 alkyl; R3 is selected from C1 - C6 alkylene; M is selected from hydrogen or alkali metal;
  • R4 and R5 are each independently selected from hydrogen or C1 - C6 alkyl
  • R 6 and R 7 are each independently selected from hydrogen or a C 1 -C 6 alkyl group
  • R 8 and R 9 are each independently selected from hydrogen or C 1 -C 6 alkyl; and X is selected from halogen.
  • a second aspect of the present invention provides a method for preparing a multi-component copolymer, the preparation method comprising:
  • the polymerizable monomers are subjected to solution polymerization to obtain a multi-polymer; wherein the polymerizable monomers include: a monomer represented by formula (I), a monomer represented by formula (II), a monomer represented by formula (III) and a monomer represented by formula (IV);
  • R1 and R2 are each independently selected from hydrogen or C1 - C6 alkyl; R3 is selected from C1 - C6 alkylene; M1 is selected from hydrogen or alkali metal;
  • R 4 and R 5 are each independently selected from hydrogen or C 1 -C 6 alkyl
  • R 6 and R 7 are each independently selected from hydrogen or C 1 -C 6 alkyl
  • R 8 and R 9 are each independently selected from hydrogen or C 1 -C 6 alkyl; and M 2 is selected from halogen.
  • the third aspect of the present invention provides a multi-polymer obtained by the aforementioned preparation method.
  • a fourth aspect of the present invention provides the use of the aforementioned multi-polymer as a wellbore stabilizer in drilling; preferably, the multi-polymer is used as a wellbore stabilizer in a wellbore reinforcement type wellbore.
  • the fifth aspect of the present invention provides a water-based drilling fluid using the aforementioned multi-polymer as a wellbore stabilizer; preferably, the content of the multi-polymer is 1-6 wt % based on the total weight of the water-based drilling fluid.
  • the multi-component copolymer provided by the present invention has strong linear expansion ability, and can form multiple adsorption points on the well wall, thereby preventing clay from dispersing and playing a role in stabilizing the well wall, thereby reducing the occurrence of underground accidents.
  • the multi-polymer of the present invention can be used as a wellbore stabilizer, especially a wellbore strengthening wellbore stabilizer, which can inhibit the hydration expansion of formation clay minerals, effectively seal cracks and rocks with developed stratification, effectively strengthen the wellbore, maintain the stability of the wellbore, and at the same time has a certain filtration loss reduction effect, thereby improving the development and utilization efficiency of oil and gas resources and the economic benefits of oilfield companies.
  • FIG1 is an infrared spectrum of polymer W1 obtained in Example 1 of the present invention.
  • the first aspect of the present invention provides a multi-component copolymer, the multi-component copolymer comprising a structural unit A, a structural unit B, a structural unit C and a structural unit D; wherein the structural unit A has a structure shown in formula (1); the structural unit B has a structure shown in formula (2); the structural unit C has a structure shown in formula (3); the structural unit D has a structure shown in formula (4);
  • R1 and R2 are each independently selected from hydrogen or C1 - C6 alkyl; R3 is selected from C1 - C6 alkylene; M is selected from hydrogen or alkali metal;
  • R4 and R5 are each independently selected from hydrogen or C1 - C6 alkyl
  • R 6 and R 7 are each independently selected from hydrogen or a C 1 -C 6 alkyl group
  • R 8 and R 9 are each independently selected from hydrogen or C 1 -C 6 alkyl; and X is selected from halogen.
  • the alkyl group or alkylene group in the present invention includes a linear or branched substituted or unsubstituted alkyl group or alkylene group.
  • the multi-component copolymer of the present invention contains aromatic groups, which can enhance the electrostatic interaction of cationic groups so that the copolymer has better adhesion performance.
  • R1 and R2 are each independently selected from hydrogen or C1 - C3 alkyl, preferably hydrogen, methyl or ethyl; R3 is selected from C1 - C3 alkylene, preferably methylene or 1,2-ethylene; M is selected from hydrogen, sodium or potassium.
  • R4 and R5 are each independently selected from hydrogen or C1 - C3 alkyl, preferably hydrogen, methyl, ethyl or propyl.
  • R 6 and R 7 are each independently selected from hydrogen or C 1 -C 3 alkyl, preferably hydrogen, methyl, ethyl or propyl.
  • R8 and R9 are each independently selected from hydrogen or C1 - C3 alkyl, preferably hydrogen, methyl, ethyl or propyl; X is selected from Cl, Br or I.
  • the structural unit A can be selected from, for example, the structure represented by formula (1-1), the structure represented by formula (1-2), the structure represented by formula (1-3), the structure represented by formula (1-4), the structure represented by formula (1-5), the structure represented by formula (1-6), the structure represented by formula (1-7), the structure represented by formula (1-8), the structure represented by formula (1-9), the structure represented by formula (1-10), the structure represented by formula (1-11), the structure represented by formula (1-12), the structure represented by formula (1-13), the structure represented by formula (1-14) , the structure shown in formula (1-15), the structure shown in formula (1-16), the structure shown in formula (1-17), the structure shown in formula (1-18), the structure shown in formula (1-19), the structure shown in formula (1-20), the structure shown in formula (1-21), the structure shown in formula (1-22), the structure shown in formula (1-23), the structure shown in formula (1-24), the structure shown in formula (1-25), the structure shown in formula (1-26) and the structure shown in formula (1-27) At least one of the structural units; wherein,
  • R 1 is H;
  • R 2 is H;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is H;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is H;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 2 CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 2 CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is H;
  • R 2 is -CH 2 CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is H;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is H;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is H;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is H;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is H;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is H;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is H;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is K;
  • R 3 is -CH 2 -;
  • R 1 is -CH 2 CH 3 ;
  • R 2 is -CH 2 CH 3 ;
  • M is Na;
  • R 3 is -CH 2 -.
  • the structural unit B can be selected from at least one of the structural units represented by formula (2-1), formula (2-2), formula (2-3), formula (2-4), formula (2-5), formula (2-6), formula (2-7), and formula (2-8); wherein,
  • R 4 is H;
  • R 5 is -CH 3 ;
  • R 4 is H;
  • R 5 is -CH 2 CH 3 ;
  • R 4 is -CH 3
  • R 5 is -CH 3 ;
  • R 4 is -CH 3 ;
  • R 5 is -CH 2 CH 3 ;
  • R 4 is -CH 2 CH 3 ;
  • R 5 is -CH 2 CH 3 ;
  • R 4 is -CH 2 CH 2 CH 3 ;
  • R 5 is -CH 2 CH 3 ;
  • R 4 is -CH 2 CH 2 CH 3 ;
  • R 5 is -CH 2 CH 2 CH 3 .
  • the structural unit C can be selected from at least one of the structural units represented by formula (3-1), formula (3-2), formula (3-3), formula (3-4), formula (3-5), formula (3-6), formula (3-7), and formula (3-8); wherein,
  • R 6 is H
  • R 7 is H
  • R 6 is H;
  • R 7 is -CH 3 ;
  • R 6 is H;
  • R 7 is -CH 2 CH 3 ;
  • R 6 is -CH 3
  • R 7 is -CH 3 ;
  • R 6 is -CH 3 ;
  • R 7 is -CH 2 CH 3 ;
  • R 6 is -CH 2 CH 3 ;
  • R 7 is -CH 2 CH 3 ;
  • R 6 is -CH 2 CH 2 CH 3 ;
  • R 8 is -CH 2 CH 3 ;
  • R 6 is -CH 2 CH 2 CH 3 ;
  • R 7 is -CH 2 CH 2 CH 3 .
  • the structural unit D can be, for example, selected from at least one of the structural units represented by formula (4-1), formula (4-2), formula (4-3), formula (4-4), formula (4-5), formula (4-6), formula (4-7), formula (4-8), formula (4-9), formula (4-10), formula (4-11), formula (4-12), formula (4-13), formula (4-14), formula (4-15), formula (4-16), formula (4-17), and formula (4-18); wherein,
  • R 8 is H; R 9 is -CH 3 ; X is Br;
  • R 8 is H; R 9 is -CH 3 ; X is Cl;
  • R 8 is H; R 9 is -CH 3 ; X is I;
  • R 8 is -CH 3 ;
  • R 9 is -CH 3 ;
  • X is Br;
  • R 8 is -CH 3 ;
  • R 9 is -CH 3 ;
  • X is Cl;
  • R 8 is -CH 3 ;
  • R 9 is -CH 3 ;
  • X is I;
  • R 8 is -CH 3 ;
  • R 9 is -CH 2 CH 3 ;
  • X is Br;
  • R 8 is -CH 3 ;
  • R 9 is -CH 2 CH 3 ;
  • X is Cl;
  • R 8 is -CH 3 ;
  • R 9 is -CH 2 CH 3 ;
  • X is I;
  • R 8 is -CH 3 ;
  • R 9 is -CH 2 CH 2 CH 3 ;
  • X is Br;
  • R 8 is -CH 3 ;
  • R 9 is -CH 2 CH 2 CH 3 ;
  • X is Cl;
  • R 8 is -CH 2 CH 3 ;
  • R 9 is -CH 2 CH 2 CH 3 ;
  • X is I;
  • R 8 is -CH 2 CH 3 ;
  • R 9 is -CH 2 CH 3 ;
  • X is Br;
  • R 8 is -CH 2 CH 3 ;
  • R 9 is -CH 2 CH 3 ;
  • X is Cl;
  • the structural unit represented by formula (1) is provided by 2-acrylamide-2-methylpropanesulfonic acid; the structural unit represented by formula (2) is provided by acrylamide; the structure represented by formula (3) is provided by 2-phenoxyethyl acrylate; and the structural unit represented by formula (4) is provided by 2-aminoethyl methacrylate hydrochloride.
  • the structural units contained in the multi-component copolymer are formed by addition polymerization of carbon-carbon double bonds contained in monomers corresponding to the structural units.
  • the molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 0.5-2:1.4-1.8:1.5-4.2:0.3-0.8, preferably 1-1.5:1.6-1.7:2-3:0.5-0.7.
  • the average molecular weight of the multi-polymer is 20,000-150,000 g/mol, preferably 30,000-100,000 g/mol, and more preferably 80,000-90,000 g/mol.
  • the intrinsic viscosity of the multi-polymer is 200-500 mL/g, preferably 240-460 mL/g.
  • composition and structure of the multi-polymer can be obtained by infrared analysis or inferred by monomer feeding and reaction.
  • a second aspect of the present invention provides a method for preparing a multi-component copolymer, the preparation method comprising:
  • the polymerizable monomers are subjected to solution polymerization to obtain a multi-polymer; wherein the polymerizable monomers include: a monomer represented by formula (I), a monomer represented by formula (II), a monomer represented by formula (III) and a monomer represented by formula (IV);
  • R1 and R2 are each independently selected from hydrogen or C1 - C6 alkyl; R3 is selected from C1 - C6 alkylene; M1 is selected from hydrogen or alkali metal;
  • R 4 and R 5 are each independently selected from hydrogen or C 1 -C 6 alkyl
  • R 6 and R 7 are each independently selected from hydrogen or C 1 -C 6 alkyl
  • R 8 and R 9 are each independently selected from hydrogen or C 1 -C 6 alkyl; and M 2 is selected from halogen.
  • the present invention prepares a multi-polymer by a free radical polymerization method, adopts solution polymerization, dissolves a polymerization monomer and an initiator (i.e., a free radical initiator) in a suitable solvent, and performs a polymerization reaction in a solution state.
  • the present invention can prepare polymers of different molecular weights by controlling the selection of solvents and initiators, the order and amount of polymerization monomers added, etc.
  • the order of adding the polymerizable monomers can be to add them together and perform solution polymerization in a one-step method. It can also be added in two steps and perform solution polymerization in a two-step method. That is, the monomers represented by formula (III), the monomers represented by formula (IV) and the initiator are first reacted in a solvent in a first step, and then the product of the first step reaction is reacted with the monomers represented by formula (I), the monomers represented by formula (II) and the initiator in a solvent in a second step.
  • the solution polymerization method of the present invention has the advantages of easy diffusion of polymerization heat, easy control of reaction temperature, low system viscosity, less branching or cross-linking products generated by chain transfer to polymers, easy control of product molecular weight, narrow molecular weight distribution, and direct product preparation in solution. It can be used to prepare polymers that can be used as wellbore strengthening well wall stabilizers and has broad application prospects in wellbore strengthening technology.
  • R1 and R2 are each independently selected from hydrogen or C1- C3 alkyl, preferably hydrogen, methyl or ethyl; R3 is selected from C1 - C3 alkylene, preferably methylene or 1,2 -ethylene; M1 is selected from hydrogen, sodium or potassium.
  • R 4 and R 5 are each independently selected from hydrogen or C 1 -C 3 alkyl, preferably hydrogen, methyl, ethyl or propyl.
  • R 6 and R 7 are each independently selected from hydrogen or C 1 -C 3 alkyl, preferably hydrogen, methyl, ethyl or propyl.
  • R 8 and R 9 are each independently selected from hydrogen or C 1 -C 3 alkyl, preferably hydrogen, methyl, ethyl or propyl; M 2 is selected from Cl, Br or I.
  • the polymerizable monomers in the present invention correspond one-to-one to the structural units in the first aspect, and each substituent is also the same as in the first aspect.
  • each substituent is also the same as in the first aspect.
  • reference may be made to the description of the first aspect, which will not be repeated here.
  • the monomer represented by formula (I) can be selected from 2-acrylamide-2-methylpropanesulfonic acid; the monomer represented by formula (II) can be selected from acrylamide; the monomer represented by formula (III) can be selected from 2-phenoxyethyl acrylate; the monomer represented by formula (IV) can be selected from 2-aminoethyl methacrylate hydrochloride.
  • the molar ratio of the monomer represented by formula (I), the monomer represented by formula (II), the monomer represented by formula (III) and the monomer represented by formula (IV) is 0.5-2:1.4-1.8:1.5-4.2:0.3-0.8, preferably 1-1.5:1.6-1.7:2-3:0.5-0.7.
  • the conditions for solution polymerization include: temperature of 30-100° C., preferably 40-70° C.; time of 4-8 h, preferably 6-7 h.
  • the reaction time in the present invention refers to the total time required for the reaction of four monomers.
  • the total time of the first step reaction and the second step reaction is 4-8 hours, preferably 6-7 hours; the reaction time of the first step reaction and the second step reaction is independently selected from 2-6 hours, preferably 3-3.5 hours.
  • the air in the reaction system may be replaced by ventilation, and the introduced gas may be a gas selected from nitrogen, helium, neon and other substantially reaction inert gases.
  • the initiator is selected from one of alkyl halides, azobisisobutyronitrile (AIBN), 2-ketoglutaric acid, potassium persulfate, cerium ammonium nitrate and azobisisobutyramidine hydrochloride (V50); preferably potassium persulfate.
  • AIBN azobisisobutyronitrile
  • 2-ketoglutaric acid 2-ketoglutaric acid
  • potassium persulfate potassium persulfate
  • cerium ammonium nitrate and azobisisobutyramidine hydrochloride (V50); preferably potassium persulfate.
  • the amount of the initiator (by mass) is preferably 0.5-5 wt %, more preferably 1-2 wt % of the total weight of the polymerized monomers.
  • the amount of the initiator used for the four monomers is based on the total weight of the polymerized monomers.
  • the amount of the initiator used in each step of the reaction is 0.25-2.5wt% of the total weight of the polymerized monomers, preferably 0.5-1wt%.
  • the solution polymerization is carried out in a solvent.
  • the solvent is selected from one of deionized water, ethanol, methanol and dimethyl sulfoxide; preferably deionized water.
  • the amount of the solvent used is such that the total concentration of the polymerizable monomers in the solvent is 0.01-5 mol/L, preferably 0.1-1 mol/L.
  • the present invention when a one-step method is adopted, four monomers are added to a solvent together.
  • the present invention does not specifically limit the concentration of the monomers shown in formula (III) and the monomers shown in formula (IV) in the solvent in the first step reaction, and the conventional operation in the art can be carried out.
  • the total concentration of the polymerized monomers in the solvent refers to the total concentration of the monomers shown in formula (I), the monomers shown in formula (II), the monomers shown in formula (III) and the monomers shown in formula (IV) in the second step solvent in the second step reaction, based on the amount of feed, of 0.01-5 mol/L, preferably 0.1-1 mol/L.
  • the synthesis steps of the multi-polymer using a two-step solution polymerization method are as follows:
  • the third aspect of the present invention provides a multi-polymer obtained by the aforementioned preparation method.
  • the multi-polymer can achieve excellent well wall stability at a relatively low dosage.
  • the fifth aspect of the present invention provides a water-based drilling fluid using the aforementioned multi-polymer as a wellbore stabilizer.
  • the content of the multi-polymer is 1-6 wt %.
  • the water-based drilling fluid may also contain other additives conventionally used in the art, such as bentonite, thickeners, anti-collapse agents, lubricants, weighting agents, alkaline regulators, etc.
  • additives conventionally used in the art, such as bentonite, thickeners, anti-collapse agents, lubricants, weighting agents, alkaline regulators, etc.
  • the types and contents of these additives may be the types and contents conventionally used in the art, and the present invention has no particular limitation on this.
  • the multi-polymer of the present invention can be used as a wellbore stabilizer for drilling fluid, can inhibit the hydration expansion of formation clay minerals, effectively seal cracks and rocks with developed stratification, effectively strengthen the wellbore, maintain the stability of the wellbore, and at the same time has a certain filtration loss reduction effect, thereby improving the development and utilization efficiency of oil and gas resources and the economic benefits of oilfield companies.
  • the drilling fluid is a water-based drilling fluid
  • the synthesis of the polymer in the drilling fluid is studied and evaluated from multiple angles such as different additives, polymer structure and polymer action mechanism.
  • the aforementioned additives may be commercially available products, or may be prepared according to methods known in the art, which will not be described in detail in the present invention.
  • the preparation method of the drilling fluid polymer adopts a free radical solution polymerization preparation method well known to those skilled in the art, which will not be described in detail herein.
  • the present invention lists specific operations in the following text, which should not be understood by those skilled in the art as limiting the present invention.
  • the monomer represented by formula (I) (2-acrylamide-2-methylpropanesulfonic acid): Anaiji Chemical Technology (Shanghai) Co., Ltd.;
  • ME104/02 constant temperature magnetic stirrer (T09-1S), digital display constant temperature water bath (XMTD203), electric stirrer (HD2004W), variable frequency high-speed stirrer (GJSS-B12K), 1103 six-speed rotation viscometer (MK-03), variable frequency high-temperature roller heating furnace (GW300) were all purchased from Qingdao Tongchun Petroleum Instrument Co., Ltd.
  • the molecular weight and molecular weight distribution of the polymer were determined by gel permeation chromatography (three-detector gel permeation chromatography, Wyatt Company, USA). Tetrahydrofuran was used as the mobile phase, the flow rate was 1.0 mL/min, narrow distribution polystyrene was used as the standard sample, the differential refractive index detector was used as the basic detector, and the column temperature and detection temperature were 35°C.
  • the purified sample was prepared into a solution of a certain concentration by adding an appropriate amount of tetrahydrofuran, and the insoluble impurities were filtered out with a filter head before being sent for inspection.
  • the intrinsic viscosity of the polymer was measured using an Ubbelohde viscometer (1836-A, Tianjin Hongyang Machinery Equipment Co., Ltd.). Anhydrous methanol was used as the solvent to prepare a 2 g/mL polymer solution, which was then diluted to 2/3, 1/2, 1/3, and 1/2 of the original concentration. 1/4, the test temperature is 35°C, the elution time of solvent methanol and polymer solutions of different concentrations are measured, and the intrinsic viscosity of the polymer is obtained by extrapolating the elution time against the concentration.
  • the reference data of rheological properties of drilling fluid include apparent viscosity, plastic viscosity and dynamic shear force. After the water-based drilling fluid is stirred at a high-frequency speed of 12000rpm for 20min, the values of ⁇ 600 and ⁇ 300 are measured by a six-speed rotary viscometer according to the standard GB/T 16782-1997, and the apparent viscosity (AV), plastic viscosity (PV) and dynamic shear force (YP) of the water-based drilling fluid are calculated by the following formula.
  • AV apparent viscosity
  • PV plastic viscosity
  • YP dynamic shear force
  • the inhibitory performance of the treatment agent is evaluated through a linear expansion test. Using a dual-channel shale expansion meter, the difference in swelling height of bentonite in different treatment agent solutions and deionized water is measured to intuitively measure the effect and ability of the treatment solution in inhibiting clay hydration expansion.
  • the specific process is as follows:
  • the inhibition performance of the treatment agent was evaluated by core immersion experiments.
  • the appearance and morphological integrity of the cores were measured after being immersed in different wellbore stabilizer solutions for 24 hours.
  • a method for preparing a multi-component copolymer comprises the following steps:
  • Step 1 dissolving 2-phenoxyethyl acrylate and 2-aminoethyl methacrylate hydrochloride in deionized water at a molar ratio of 2:0.5, pouring the solution into a three-necked flask, stirring at 300-400 rpm, and passing nitrogen for 10-20 minutes to remove oxygen in the container, uniformly adding 1 wt% (i.e., 1% of the total mass of the polymerizable monomer) of the initiator potassium persulfate, heating to 70°C, and reacting for 3 hours;
  • 1 wt% i.e., 1% of the total mass of the polymerizable monomer
  • Step 2 Pour the product and the solution into a rotary evaporator to remove the solvent, and place the remaining product in an oven to dry;
  • Step 3 Heat and dissolve the dried product with deionized water, then add 2-acrylamide-2-methylpropanesulfonic acid and acrylamide in a molar ratio of 1:1.6, pour the solution into a three-necked flask, stir at a speed of 300-400 rpm, pass nitrogen for 10-20 min, remove oxygen in the container, uniformly add 1 wt% potassium persulfate initiator (i.e., 1% of the total mass of the polymerized monomers), heat to 70°C, and react for 3 hours;
  • Step 4 The entire reaction process was carried out in a constant temperature water bath to ensure a stable nitrogen environment and temperature.
  • step 3 the total concentration of the polymerized monomers in the three-necked flask was 0.1 mol/L.
  • the synthesized product was polymer W 1 .
  • Table 1 The test results are shown in Table 1.
  • the obtained polymer W 1 was subjected to rotary evaporation drying treatment, and the polymer W 1 was detected by infrared spectrum analysis method, and an infrared spectrum as shown in FIG1 was obtained. As can be seen from FIG1 , a block copolymer containing NH, C ⁇ O, and sulfonic acid structural units was obtained.
  • Step 1 dissolving 2-phenoxyethyl acrylate and 2-aminoethyl methacrylate hydrochloride in deionized water at a molar ratio of 2:0.5, pouring the solution into a three-necked flask, stirring at 300-400 rpm, and passing nitrogen for 10-20 minutes to remove oxygen in the container, uniformly adding 1 wt% (i.e., 1% of the total mass of the polymerizable monomer) of the initiator potassium persulfate, heating to 70°C, and reacting for 3 hours;
  • 1 wt% i.e., 1% of the total mass of the polymerizable monomer
  • Step 2 Pour the product and the solution into a rotary evaporator to remove the solvent, and place the remaining product in an oven to dry;
  • Step 3 Heat and dissolve the dried product with deionized water, then add 2-acrylamide-2-methylpropanesulfonic acid and acrylamide in a molar ratio of 1:1.6, pour the solution into a three-necked flask, stir at a speed of 300-400 rpm, pass nitrogen for 10-20 min, remove oxygen in the container, uniformly add 1 wt% potassium persulfate initiator (i.e., 1% of the total mass of the polymerized monomers), heat to 70°C, and react for 3 hours;
  • Step 4 The entire reaction process was carried out in a constant temperature water bath to ensure a stable nitrogen environment and temperature.
  • step 3 the total concentration of the polymerized monomers in the three-necked flask was 0.5 mol/L.
  • the synthesized product was polymer W 2 .
  • Table 1 The test results are shown in Table 1.
  • Step 1 dissolving 2-phenoxyethyl acrylate methacrylate 2-aminoethyl ester hydrochloride in deionized water at a molar ratio of 2:0.5, pouring the solution into a three-necked flask, stirring at 300-400 rpm, and passing nitrogen for 10-20 minutes to remove oxygen in the container, uniformly adding 1wt% (i.e., 1% of the total mass of the polymerized monomer) of the initiator potassium persulfate, heating to 70°C, and reacting for 3 hours;
  • 1wt% i.e., 1% of the total mass of the polymerized monomer
  • Step 2 Pour the product and the solution into a rotary evaporator to remove the solvent, and place the remaining product in an oven to dry;
  • Step 3 Heat and dissolve the dried product with deionized water, then add 2-acrylamide-2-methylpropanesulfonic acid and acrylamide in a molar ratio of 1:1.6, pour the solution into a three-necked flask, stir at a speed of 300-400 rpm, pass nitrogen for 10-20 min, remove oxygen in the container, uniformly add 1 wt% potassium persulfate initiator (i.e., 1% of the total mass of the polymerized monomers), heat to 70°C, and react for 3 hours;
  • Step 4 The entire reaction process was carried out in a constant temperature water bath to ensure a stable nitrogen environment and temperature.
  • the total concentration of the polymerized monomers in the three-necked flask was 1.0 mol/L.
  • the synthesized product was polymer W 3 .
  • the test results are shown in Table 1.
  • Example 1 The method described in Example 1 is different in that the amounts of the four monomers are based on 2-acrylamide-2-methylpropanesulfonic acid: The molar ratio of acrylamide:2-phenoxyethyl acrylate:2-aminoethyl methacrylate hydrochloride is 1.2:1.65:2.5:0.6, and the total monomer concentration is kept unchanged. After the whole process, polymer W 7 is finally obtained. The test results are shown in Table 1.
  • Example 1 The method described in Example 1 is different in that an equal amount (ie, equal volume) of ethanol is used as a solvent instead of deionized water. After the whole process, polymer W 10 is finally obtained. The test results are shown in Table 1.
  • Example 1 The method described in Example 1 is different in that an equal amount of ammonium cerium nitrate is used as an initiator instead of potassium persulfate, and the polymer W 11 is finally obtained after the whole process.
  • the test results are shown in Table 1.
  • Example 1 The method described in Example 1 is different in that an equal molar amount of sodium styrene sulfonate is used instead of 2-acrylamide-2-methylpropane sulfonic acid, and the polymer D 1 is finally obtained through the whole process.
  • the test results are shown in Table 1.
  • Example 1 The method described in Example 1 is different in that ammonium persulfate is used as the initiator, and the polymer D 2 is finally obtained after the whole process.
  • the test results are shown in Table 1.
  • the prepared well wall stabilizer polymers W1 , W2 , W3 , W4 , W5 , W6 , W7 , W8 , W9 , W10 , W11 , D1 , and D2 were respectively prepared into aqueous solutions with a mass fraction concentration of 1%, and the single-dose performance of the well wall stabilizer was tested.
  • the bentonite block was pressed into a linear expansion instrument, and deionized water and the polymer well wall stabilizer prepared in Examples 1-6 were added respectively. After soaking for 16 hours, the final expansion height on the linear expansion instrument was read. The test results of the linear expansion experiment are shown in Table 2.
  • the wellbore strengthening wellbore stabilizer polymer provided by the present invention has a certain inhibitory effect on the hydration expansion of bentonite, and the prepared polymer can significantly reduce the expansion height of the bentonite block and effectively enhance the wellbore stability of the formation.
  • the cores were placed in 1% concentration of wellbore stabilizer polymer W1 , W2 , W3 , W4 , W5 , W6 , W7 , W8 , W9 , W10 , W11 , D1 , and D2 solutions, respectively, and immersed for 24 hours. The integrity of the cores was observed. The test results are shown in Table 3.
  • the wellbore strengthening wellbore stabilizer provided by the present invention has a certain degree of cementing effect on clay particles, thereby playing a role in stabilizing the wellbore and strengthening the wellbore.
  • the wellbore stabilizer prepared by the present invention is formulated into a water-based drilling fluid system, wherein the polymer addition amount is 1%, and the basic properties such as filtration loss and rheology of each water-based drilling fluid containing the synthesized wellbore stabilizer are tested.
  • the results of the apparent viscosity (AV/mPa ⁇ s), plastic viscosity (PV/mPa ⁇ s), dynamic shear force (YP/Pa), dynamic plastic ratio (YP/PV (Pa/mPa ⁇ s)), and medium pressure filtration loss (API/mL) of the above-mentioned drilling fluid are shown in Table 4.
  • the wellbore strengthening wellbore stabilizer provided by the present invention can improve the viscosity of the drilling fluid, effectively reduce the filtration loss, reduce the loss of drilling fluid during drilling work, and play a role in stabilizing the wellbore wall.
  • the polymer synthesized by the solution polymerization method provided by the present invention is applied to water-based drilling fluid, and the preparation of wellbore strengthening wellbore stabilizer has a very obvious effect, which can greatly improve the rheological properties and filtration loss of the drilling fluid, and the preparation method is simple and the cost is low. Therefore, the present invention has a very broad application prospect, can effectively solve the wellbore instability problem existing in drilling work, improve the inhibition performance of drilling fluid on the hydration expansion of formation clay, reduce the occurrence of complex accidents underground, and bring about the improvement of economic benefits.

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Abstract

La présente invention se rapporte au domaine technique du forage pétrolier. L'invention concerne spécifiquement un copolymère à composants multiples et son procédé de préparation et son utilisation. Le copolymère à composants multiples comprend un motif structural A, un motif structural B, un motif structural C et un motif structural D, le motif structural A ayant une structure telle que représentée par la formule (1), le motif structural B ayant une structure telle que représentée par la formule (2), et le motif structural C ayant une structure telle que représentée par la formule (3). Le copolymère à composants multiples de la présente invention peut être utilisé en tant que stabilisant de paroi de puits, en particulier en tant que stabilisant de paroi de puits de type renforcement de trou de forage, peut inhiber l'hydratation et le gonflement de minéraux argileux de strates, bouche efficacement des roches présentant des fractures et une stratification développées, renforce efficacement un trou de forage, maintient une stabilité de paroi de puits, a un certain effet de réduction de perte de filtrat, et améliore l'efficacité de développement et d'utilisation de ressources pétrolières et gazières et les avantages économiques des sociétés pétrolières.
PCT/CN2024/098940 2023-06-13 2024-06-13 Copolymère à composants multiples, son procédé de préparation et son utilisation Pending WO2024255789A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119842372A (zh) * 2025-03-21 2025-04-18 陕西合信油服科技股份有限公司 一种复合井壁稳定剂及其制备方法

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WO2013162902A1 (fr) * 2012-04-25 2013-10-31 Isp Investments Inc Combinaison synergique d'un additif de perte de circulation et d'un modificateur de rhéologie
CN107964399A (zh) * 2017-11-23 2018-04-27 北京捷贝通石油技术股份有限公司 一种页岩气压裂用多功能纳米乳液减阻剂及其制备方法
CN113698534A (zh) * 2020-08-26 2021-11-26 中国石油大学(北京) 高性能环保水基钻井液用井壁稳定剂用聚合物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013162902A1 (fr) * 2012-04-25 2013-10-31 Isp Investments Inc Combinaison synergique d'un additif de perte de circulation et d'un modificateur de rhéologie
CN107964399A (zh) * 2017-11-23 2018-04-27 北京捷贝通石油技术股份有限公司 一种页岩气压裂用多功能纳米乳液减阻剂及其制备方法
CN113698534A (zh) * 2020-08-26 2021-11-26 中国石油大学(北京) 高性能环保水基钻井液用井壁稳定剂用聚合物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119842372A (zh) * 2025-03-21 2025-04-18 陕西合信油服科技股份有限公司 一种复合井壁稳定剂及其制备方法

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