A clay stabilizer composition and preparation method thereof

Abstract

The invention relates to a clay stabilizer composition and a preparation method thereof. The main components of the clay stabilizer composition are a modified cationic polymer stabilizer and an auxiliary clay stabilizer. Since the modified cationic polymer stabilizer is synthesized with a hyperbranched polymer as a matrix, and the auxiliary clay stabilizer contains a benzene ring and a triazole structure, both of which have good thermal stability, the clay stabilizer composition has good high temperature resistance. Since the modified cationic polymer stabilizer is also grafted with a silane segment, it has good water washing resistance. Since the auxiliary clay stabilizer has a small molecular weight, the auxiliary clay stabilizer can enter into pores that the modified cationic polymer stabilizer cannot enter, so that the modified cationic polymer stabilizer and the auxiliary clay stabilizer play a good composite anti-swelling effect.

Description

Technical Field

[0001] The invention relates to the field of clay stabilizers, and in particular to a clay stabilizer composition and a preparation method thereof. Background Art

[0002] In order to reduce extraction costs and stabilize oil field production during the oil production process, water injection development is often used. However, the oil reservoir contains a large amount of clay minerals. When encountering injected water, the clay minerals expand in volume and then disperse, and even migrate with the injected water, thereby blocking the reservoir pores and rock pore throats, causing the water injection pressure to increase and reduce oil field production.

[0003] To solve this problem, clay stabilizers are usually added to stabilize the oil reservoir and increase oil field production. However, as the degree of oil exploitation deepens, the temperature of the formation increases and the permeability decreases, which puts higher requirements on the temperature resistance of the clay stabilizer. The commonly used clay stabilizers on the market are cationic organic polymers, which have the characteristics of small usage, high anti-swelling rate and less restrictions on the formation environment. However, their anti-swelling performance is insufficient under high temperature conditions. At the same time, cationic organic polymers generally have a large molecular weight and a curled molecular form, which cannot enter some smaller pores and cannot exert their good anti-swelling performance. Summary of the invention

[0004] The object of the present invention is to provide a clay stabilizer composition and a preparation method thereof, which solves the problem of poor high temperature resistance and water wash resistance of the existing clay stabilizer, and by compounding the stabilizer, the clay stabilizer composition has better anti-swelling performance.

[0005] The objective of the present invention can be achieved by the following technical scheme: a clay stabilizer composition is prepared by the following steps: weighing the following raw materials in weight percentage: 2.4-3% of a modified cationic polymer stabilizer and 1-1.6% of an auxiliary clay stabilizer, the remainder being water, the modified cationic polymer stabilizer and the auxiliary clay stabilizer accounting for 4% of the total mass fraction of the raw materials, mixing the modified cationic polymer stabilizer, the auxiliary clay stabilizer and water to prepare a clay stabilizer composition.

[0006] The modified cationic polymer stabilizer is prepared by the following steps:

[0007] Step A1: maleic anhydride and diethanolamine are mixed, and the mixture is reacted for 0.5 h under nitrogen protection, at a stirring rate of 100-120 rpm and a temperature of 75° C., and the mixture is heated to 140° C. and trimethylolpropane and p-toluenesulfonic acid are added with stirring, and the mixture is reacted for 3 h to obtain a hyperbranched polymer. The hyperbranched polymer is mixed with methanol, and epichlorohydrin and a sodium hydroxide solution are added with stirring at a stirring rate of 100-120 rpm and a temperature of 70° C., and the mixture is reacted for 6-8 h to obtain a modified hyperbranched polymer.

[0008] The dosage ratio of maleic anhydride, diethanolamine, trimethylolpropane and p-toluenesulfonic acid is 0.2-0.3 mol: 0.2-0.3 mol: 0.3-0.4 g: 0.5 g, the mass fraction of sodium hydroxide solution is 10%, and the dosage ratio of hyperbranched polymer, epichlorohydrin and sodium hydroxide solution is 45-50 g: 25-35 mL: 30 mL;

[0009] During the reaction, maleic anhydride reacts with the secondary amine group in diethanolamine to form an amide group and a carboxyl group, and the carboxyl group can further undergo an esterification reaction with the hydroxyl group in diethanolamine. Then, under the action of p-toluenesulfonic acid, with trimethylolpropane as the core molecule, the hydroxyl group in the trimethylolpropane and the carboxyl group generated after the maleic anhydride ring-opening undergo an esterification reaction to obtain a hyperbranched polymer containing an unsaturated double bond and an amide group and a hydroxyl group at the chain end. The hydroxyl group at the chain end of the hyperbranched polymer further reacts with the epoxy group in epichlorohydrin to form an ether bond and generate a new hydroxyl group and introduce a chlorine group to obtain a modified hyperbranched polymer.

[0010] Step A2: 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dichloromethane are mixed, stirred at a stirring rate of 150-180 rpm and room temperature, and dodecyl primary amine is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, modified hyperbranched polymer and toluene are mixed, stirred at a rate of 150-180 rpm and a temperature of 110° C., and the reaction is carried out for 24 hours, and then the temperature is reduced to 60° C. and γ-mercaptopropyltriethoxysilane is added, and the reaction is carried out for 12 hours to obtain a modified cationic polymer stabilizer;

[0011] The amount ratio of 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dodecyl primary amine is 0.1-0.12 mol: 5 g: 6 g: 0.1-0.12 mol, and the amount ratio of intermediate 1, modified hyperbranched polymer and γ-mercaptopropyltriethoxysilane is 0.2-0.3 mol: 45-50 g: 0.2-0.3 mol;

[0012] During the reaction, under the action of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 1-hydroxybenzotriazole, the carboxyl group in 1-methylpiperidine-4-carboxylic acid reacts with the amino group in dodecyl primary amine to form an amide group to obtain an intermediate 1, and the piperidine tertiary amine group in the intermediate 1 reacts with the chlorine group of the modified hyperbranched polymer chain segment to form a quaternary ammonium group, and then γ-mercaptopropyltriethoxysilane is added, and a siloxane structure is introduced through a click reaction between the mercapto group and the double bond in the modified hyperbranched polymer to obtain a modified cationic polymer stabilizer;

[0013] The auxiliary clay stabilizer is prepared by the following steps:

[0014] Step B1: 4-octyloxybenzyl chloride, sodium azide and N,N-dimethylformamide were mixed, and the mixture was reacted for 24 hours under nitrogen protection at a stirring rate of 100-120 rpm and a temperature of 80° C. to obtain intermediate a;

[0015] The ratio of 4-octyloxybenzyl chloride to sodium azide is 2-3g:0.15-0.2g;

[0016] During the reaction, the chlorine group in 4-octyloxybenzyl chloride undergoes a substitution reaction with sodium azide to introduce an azide group to prepare intermediate a;

[0017] Step B2: Mix intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N,N-dimethylformamide, stir under nitrogen protection, at a stirring rate of 200-240 rpm and a temperature of 90° C., add N-tert-butoxycarbonylaminopropyne, and react for 24 hours to obtain intermediate b; mix intermediate b with ethyl acetate solution of hydrogen chloride, and react for 2 hours at a stirring rate of 200-240 rpm and room temperature to obtain intermediate c;

[0018] The amount ratio of intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N-tert-butyloxycarbonylaminopropyne is 0.02 mol: 0.2-0.25 g: 0.15-0.2 g: 0.02-0.025 mol, the molar concentration of hydrogen chloride ethyl acetate solution is 4 mol / L, and the amount ratio of intermediate b and hydrogen chloride ethyl acetate solution is 0.02 mol: 10 mL;

[0019] During the reaction, under the action of copper sulfate pentahydrate and sodium L-ascorbate, the azide group in intermediate a reacts with the alkynyl group in N-tert-butyloxycarbonylaminopropyne to form a triazole structure to obtain intermediate b, and intermediate b is then subjected to Boc deprotection in a hydrogen chloride ethyl acetate solution to obtain intermediate c containing a primary amino group and a triazole structure;

[0020] Step B3: Mix the intermediate c, hexamethylene diisocyanate and toluene, and react for 4-6 hours at a stirring rate of 200-240 rpm and a temperature of 60° C. to obtain an auxiliary clay stabilizer;

[0021] The ratio of intermediate c to hexamethylene diisocyanate is 0.02-0.024 mol:0.01 mol;

[0022] During the reaction, the amino group in the intermediate c reacts with the isocyanate group in hexamethylene diisocyanate to form a urea group, thereby obtaining an auxiliary clay stabilizer;

[0023] Beneficial effects of the invention: The invention relates to a clay stabilizer composition and a preparation method thereof. The main components of the clay stabilizer composition are a modified cationic polymer stabilizer and an auxiliary clay stabilizer. Since the modified cationic polymer stabilizer is synthesized with a hyperbranched polymer as a matrix, and the auxiliary clay stabilizer contains a benzene ring and a triazole structure, both of which have good thermal stability, the clay stabilizer composition has good high temperature resistance. In addition, a siloxane chain is introduced into the modified cationic polymer stabilizer by a thiol double bond click reaction. During the use of the clay stabilizer composition, the ethoxy group of the siloxane chain is hydrolyzed, and after the hydrolysis, the ethoxy group of the siloxane chain reacts with the hydroxyl group on the surface of the clay to form a Si-O-Si bond. Since there is a quaternary ammonium structure in the modified cationic polymer stabilizer, it dissociates in water to generate an organic cation with a high positive charge, which is adsorbed on the clay through electrostatic action and intermolecular force, and plays a synergistic role with the formed Si-O-Si bond, so that the modified cationic polymer stabilizer is fixed on the clay surface, thereby ensuring that it is not It is easy to fall off, and because the modified cationic polymer stabilizer contains multiple siloxane chains, these siloxane chains can "bridge" between clay crystal layers. At the same time, because the modified cationic polymer stabilizer is adsorbed on the clay surface, the clay particles are protected, and the siloxane chains it contains can also form a layer with a hydrophobic effect, thereby preventing the hydration expansion and dispersion transfer of the clay particles. The auxiliary clay stabilizer contains a triazole structure and a urea structure, which is positively charged and can be adsorbed with clay, which can effectively balance the negative charge of the clay surface, increase the clay interlayer spacing, and can effectively and permanently control the hydration expansion and particle migration of the clay. Moreover, because the molecular weight of the auxiliary clay stabilizer is much smaller than that of the modified cationic polymer stabilizer, it can enter the pores that the modified cationic polymer stabilizer cannot enter, thereby exerting a good compounding effect. At the same time, because it also contains a long alkane chain, it can also form a hydrophobic layer on the clay surface, thereby exerting a water-resistant expansion and dispersion transfer effect, thereby exerting a good anti-swelling performance of the clay stabilizer composition. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] Example 1

[0026] A clay stabilizer composition is prepared by the following steps: a modified cationic polymer stabilizer, an auxiliary clay stabilizer and water are mixed to prepare a clay stabilizer composition, wherein the mass fraction of the modified cationic polymer stabilizer is 2.4%, the mass fraction of the auxiliary clay stabilizer is 1.6%, and the total mass fraction of the modified cationic polymer stabilizer and the auxiliary clay stabilizer is 4%;

[0027] The modified cationic polymer stabilizer is prepared by the following steps:

[0028] Step A1: maleic anhydride and diethanolamine are mixed, and the mixture is reacted for 0.5 h under nitrogen protection, at a stirring rate of 100 rpm and a temperature of 75° C., and the mixture is heated to 140° C. and stirred and added with trimethylolpropane and p-toluenesulfonic acid, and the mixture is reacted for 3 h to obtain a hyperbranched polymer. The hyperbranched polymer is mixed with methanol, and epichlorohydrin and a sodium hydroxide solution are added under stirring at a stirring rate of 100 rpm and a temperature of 70° C., and the mixture is reacted for 8 h to obtain a modified hyperbranched polymer.

[0029] The amount ratio of maleic anhydride, diethanolamine, trimethylolpropane and p-toluenesulfonic acid is 0.2 mol: 0.2 mol: 0.3 g: 0.5 g, the mass fraction of sodium hydroxide solution is 10%, and the amount ratio of hyperbranched polymer, epichlorohydrin and sodium hydroxide solution is 45 g: 25 mL: 30 mL;

[0030] Step A2: 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dichloromethane are mixed, stirred at a stirring rate of 150 rpm and room temperature, and dodecyl primary amine is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, modified hyperbranched polymer and toluene are mixed, stirred at a stirring rate of 150 rpm and a temperature of 110° C., and the reaction is carried out for 24 hours, and then the temperature is reduced to 60° C. and γ-mercaptopropyltriethoxysilane is added, and the reaction is carried out for 12 hours to obtain a modified cationic polymer stabilizer;

[0031] The ratio of 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dodecyl primary amine is 0.1 mol: 5 g: 6 g: 0.1 mol, and the ratio of intermediate 1, modified hyperbranched polymer and γ-mercaptopropyltriethoxysilane is 0.2 mol: 45 g: 0.2 mol;

[0032] The auxiliary clay stabilizer is prepared by the following steps:

[0033] Step B1: 4-octyloxybenzyl chloride, sodium azide and N,N-dimethylformamide were mixed, and the mixture was reacted for 24 hours under nitrogen protection at a stirring rate of 100 rpm and a temperature of 80° C. to obtain intermediate a;

[0034] The ratio of 4-octyloxybenzyl chloride and sodium azide is 2g:0.15g;

[0035] Step B2: Mix intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N,N-dimethylformamide, stir under nitrogen protection, at a stirring rate of 200 rpm and a temperature of 90°C, add N-tert-butyloxycarbonylaminopropyne, and react for 24 hours to obtain intermediate b; mix intermediate b with hydrogen chloride ethyl acetate solution, and react for 2 hours at a stirring rate of 200 rpm and room temperature to obtain intermediate c;

[0036] The amount ratio of intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N-tert-butyloxycarbonylaminopropyne is 0.02 mol: 0.2 g: 0.15 g: 0.02-0.025 mol, the molar concentration of hydrogen chloride ethyl acetate solution is 4 mol / L, and the amount ratio of intermediate b and hydrogen chloride ethyl acetate solution is 0.02 mol: 10 mL;

[0037] Step B3: Mix the intermediate c, hexamethylene diisocyanate and toluene, and react for 4-6 hours at a stirring rate of 200 rpm and a temperature of 60° C. to obtain an auxiliary clay stabilizer;

[0038] The ratio of intermediate c to hexamethylene diisocyanate is 0.02 mol:0.01 mol;

[0039] Example 2

[0040] A clay stabilizer composition is prepared by the following steps: mixing a modified cationic polymer stabilizer, an auxiliary clay stabilizer and water to prepare a clay stabilizer composition, wherein the mass fraction of the modified cationic polymer stabilizer is 2.4-3%, the mass fraction of the auxiliary clay stabilizer is 1-1.6%, and the total mass fraction of the modified cationic polymer stabilizer and the auxiliary clay stabilizer is 4%;

[0041] The modified cationic polymer stabilizer is prepared by the following steps:

[0042] Step A1: maleic anhydride and diethanolamine are mixed, and the mixture is reacted for 0.5 h under nitrogen protection, at a stirring rate of 100-120 rpm and a temperature of 75° C., and the mixture is heated to 140° C. and stirred to add trimethylolpropane and p-toluenesulfonic acid, and the mixture is reacted for 3 h to obtain a hyperbranched polymer. The hyperbranched polymer is mixed with methanol, and epichlorohydrin and a sodium hydroxide solution are added under stirring at a stirring rate of 120 rpm and a temperature of 70° C., and the mixture is reacted for 8 h to obtain a modified hyperbranched polymer.

[0043] The dosage ratio of maleic anhydride, diethanolamine, trimethylolpropane and p-toluenesulfonic acid is 0.3 mol: 0.3 mol: 0.4 g: 0.5 g, the mass fraction of sodium hydroxide solution is 10%, and the dosage ratio of hyperbranched polymer, epichlorohydrin and sodium hydroxide solution is 45-50 g: 25-35 mL: 30 mL;

[0044] Step A2: 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dichloromethane are mixed, stirred at a stirring rate of 180 rpm and room temperature, and dodecyl primary amine is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, modified hyperbranched polymer and toluene are mixed, stirred at a rate of 180 rpm and a temperature of 110° C., and the reaction is carried out for 24 hours, and then the temperature is reduced to 60° C. and γ-mercaptopropyltriethoxysilane is added, and the reaction is carried out for 12 hours to obtain a modified cationic polymer stabilizer;

[0045] The ratio of 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dodecyl primary amine is 0.12 mol: 5 g: 6 g: 0.1 mol, and the ratio of intermediate 1, modified hyperbranched polymer and γ-mercaptopropyltriethoxysilane is 0.3 mol: 50 g: 0.3 mol;

[0046] The auxiliary clay stabilizer is prepared by the following steps:

[0047] Step B1: 4-octyloxybenzyl chloride, sodium azide and N,N-dimethylformamide were mixed, and the mixture was reacted for 24 hours under nitrogen protection at a stirring rate of 120 rpm and a temperature of 80° C. to obtain intermediate a;

[0048] The ratio of 4-octyloxybenzyl chloride and sodium azide is 3g:0.2g;

[0049] Step B2: Mix intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N,N-dimethylformamide, stir under nitrogen protection, at a stirring rate of 240 rpm and a temperature of 90°C, add N-tert-butyloxycarbonylaminopropyne, and react for 24 hours to obtain intermediate b; mix intermediate b with hydrogen chloride ethyl acetate solution, and react for 2 hours at a stirring rate of 240 rpm and room temperature to obtain intermediate c;

[0050] The amount ratio of intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N-tert-butyloxycarbonylaminopropyne is 0.02 mol: 0.2 g: 0.15 g: 0.02 mol, the molar concentration of hydrogen chloride ethyl acetate solution is 4 mol / L, and the amount ratio of intermediate b and hydrogen chloride ethyl acetate solution is 0.02 mol: 10 mL;

[0051] Step B3: Mix the intermediate c, hexamethylene diisocyanate and toluene, and react for 6 hours at a stirring rate of 200 rpm and a temperature of 60° C. to obtain an auxiliary clay stabilizer;

[0052] The ratio of intermediate c to hexamethylene diisocyanate is 0.02 mol:0.01 mol;

[0053] Example 3

[0054] A clay stabilizer composition is prepared by the following steps: mixing a modified cationic polymer stabilizer, an auxiliary clay stabilizer and water to prepare a clay stabilizer composition, wherein the mass fraction of the modified cationic polymer stabilizer is 3%, the mass fraction of the auxiliary clay stabilizer is 1%, and the total mass fraction of the modified cationic polymer stabilizer and the auxiliary clay stabilizer is 4%;

[0055] The modified cationic polymer stabilizer is prepared by the following steps:

[0056] Step A1: maleic anhydride and diethanolamine are mixed, and the mixture is reacted for 0.5 h under nitrogen protection, at a stirring rate of 120 rpm and a temperature of 75° C., and the mixture is heated to 140° C. and trimethylolpropane and p-toluenesulfonic acid are added with stirring, and the mixture is reacted for 3 h to obtain a hyperbranched polymer. The hyperbranched polymer is mixed with methanol, and epichlorohydrin and a sodium hydroxide solution are added with stirring at a stirring rate of 120 rpm and a temperature of 70° C., and the mixture is reacted for 6 h to obtain a modified hyperbranched polymer.

[0057] The amount ratio of maleic anhydride, diethanolamine, trimethylolpropane and p-toluenesulfonic acid is 0.3 mol: 0.2 mol: 0.4 g: 0.5 g, the mass fraction of sodium hydroxide solution is 10%, and the amount ratio of hyperbranched polymer, epichlorohydrin and sodium hydroxide solution is 45 g: 35 mL: 30 mL;

[0058] Step A2: 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dichloromethane are mixed, stirred at a stirring rate of 180 rpm and room temperature, and dodecyl primary amine is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, modified hyperbranched polymer and toluene are mixed, stirred at a rate of 180 rpm and a temperature of 110° C., and the reaction is carried out for 24 hours, and then the temperature is reduced to 60° C. and γ-mercaptopropyltriethoxysilane is added, and the reaction is carried out for 12 hours to obtain a modified cationic polymer stabilizer;

[0059] The ratio of 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dodecyl primary amine is 0.12 mol: 5 g: 6 g: 0.12 mol, and the ratio of intermediate 1, modified hyperbranched polymer and γ-mercaptopropyltriethoxysilane is 0.3 mol: 50 g: 0.3 mol;

[0060] The auxiliary clay stabilizer is prepared by the following steps:

[0061] Step B1: 4-octyloxybenzyl chloride, sodium azide and N,N-dimethylformamide were mixed, and the mixture was reacted for 24 hours under nitrogen protection at a stirring rate of 120 rpm and a temperature of 80° C. to obtain intermediate a;

[0062] The ratio of 4-octyloxybenzyl chloride and sodium azide is 3g:0.15g;

[0063] Step B2: Mix intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N,N-dimethylformamide, stir under nitrogen protection, at a stirring rate of 240 rpm and a temperature of 90°C, add N-tert-butyloxycarbonylaminopropyne, and react for 24 hours to obtain intermediate b; mix intermediate b with hydrogen chloride ethyl acetate solution, and react for 2 hours at a stirring rate of 240 rpm and room temperature to obtain intermediate c;

[0064] The amount ratio of intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N-tert-butyloxycarbonylaminopropyne is 0.02 mol: 0.25 g: 0.2 g: 0.025 mol, the molar concentration of hydrogen chloride ethyl acetate solution is 4 mol / L, and the amount ratio of intermediate b and hydrogen chloride ethyl acetate solution is 0.02 mol: 10 mL;

[0065] Step B3: Mix the intermediate c, hexamethylene diisocyanate and toluene, and react for 4 hours at a stirring rate of 240 rpm and a temperature of 60° C. to obtain an auxiliary clay stabilizer;

[0066] The ratio of intermediate c to hexamethylene diisocyanate is 0.024 mol:0.01 mol;

[0067] Comparative Example 1

[0068] Compared with Example 9, this comparative example removes the intermediate 1 in the preparation process of the modified cationic polymer stabilizer in Example 3, and the other steps are the same.

[0069] Comparative Example 2

[0070] Compared with Example 9, this comparative example removes the γ-mercaptopropyltriethoxysilane in the preparation process of the modified cationic polymer stabilizer in Example 3, and the other steps are the same.

[0071] Comparative Example 3

[0072] Compared with Example 9, this comparative example is different in that the 4-octyloxybenzyl chloride in the preparation process of the auxiliary clay stabilizer in Example 3 is replaced by 4-methoxybenzyl chloride, and the other steps are the same.

[0073] Comparative Example 4

[0074] Compared with Example 9, this comparative example is different in that the auxiliary clay stabilizer in Example 3 is replaced by 4-octyloxybenzyl chloride, and the other steps are the same.

[0075] The clay stabilizer compositions prepared in Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were measured for their anti-swelling rate and water washing resistance at room temperature with reference to Q / SH10201966-2013, and their anti-swelling rate and water washing resistance at 300°C for 24 hours were measured. The test results are as follows:

[0076]

[0077]

[0078] It can be seen from the test results in the table shown that when Example 1, Example 2 and Example 3 are compared with Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, in Comparative Example 1, the intermediate 1 is removed during the preparation of the modified cationic polymer stabilizer in Example 3. Since the modified cationic polymer lacks a quaternary ammonium group, its anti-swelling performance and water washing resistance at room temperature and high temperature conditions are significantly reduced, indicating that the quaternary ammonium group can effectively improve the anti-swelling performance and water washing resistance of the clay stabilizer composition. In Comparative Example 2, the γ-mercaptopropyltriethoxysilane is removed during the preparation of the modified cationic polymer stabilizer in Example 3. Due to the lack of a siloxane chain, its anti-swelling performance and water washing resistance at high temperature conditions are significantly reduced, indicating that the silane The presence of the oxyalkyl chain can effectively improve the high temperature performance of the clay stabilizer composition. In Comparative Example 3, the 4-octyloxybenzyl chloride in the preparation process of the auxiliary clay stabilizer in Example 3 is replaced by 4-methoxybenzyl chloride. Due to the lack of hydrophobic long alkane chain segments in the auxiliary clay stabilizer, its anti-swelling performance and water washing resistance decrease to a certain extent, indicating that the presence of long alkane chain segments can improve the anti-swelling performance of the clay stabilizer. In Comparative Example 4, the auxiliary clay stabilizer in Example 3 is replaced by 4-octyloxybenzyl chloride, and its anti-swelling performance and water washing resistance at room temperature and high temperature conditions are significantly reduced, indicating that the compounding of modified cationic polymers and auxiliary clay stabilizers can effectively improve the anti-swelling performance and water washing resistance of the clay stabilizer composition.

[0079] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0080] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a clay stabilizer composition, characterized in that: The method is prepared by the following steps: mixing a modified cationic polymer stabilizer, an auxiliary clay stabilizer and water to prepare a clay stabilizer composition, wherein the mass fraction of the modified cationic polymer stabilizer is 2.4-3%, the mass fraction of the auxiliary clay stabilizer is 1-1.6%, and the total mass fraction of the modified cationic polymer stabilizer and the auxiliary clay stabilizer is 4%; The modified cationic polymer stabilizer is prepared by the following steps: Step A1: maleic anhydride and diethanolamine are mixed, and the mixture is reacted for 0.5 h under nitrogen protection, at a stirring rate of 100-120 rpm and a temperature of 75° C., and the mixture is heated to 140° C. and trimethylolpropane and p-toluenesulfonic acid are added with stirring, and the mixture is reacted for 3 h to obtain a hyperbranched polymer. The hyperbranched polymer is mixed with methanol, and epichlorohydrin and a sodium hydroxide solution are added with stirring at a stirring rate of 100-120 rpm and a temperature of 70° C., and the mixture is reacted for 6-8 h to obtain a modified hyperbranched polymer. Step A2: 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dichloromethane are mixed, stirred at a stirring rate of 150-180 rpm and room temperature, and dodecyl primary amine is added, and the reaction is carried out for 12 hours to obtain intermediate 1; intermediate 1, modified hyperbranched polymer and toluene are mixed, stirred at a rate of 150-180 rpm and a temperature of 110° C., and the reaction is carried out for 24 hours, and then the temperature is reduced to 60° C. and γ-mercaptopropyltriethoxysilane is added, and the reaction is carried out for 12 hours to obtain a modified cationic polymer stabilizer; The auxiliary clay stabilizer is prepared by the following steps: Step B1: 4-octyloxybenzyl chloride, sodium azide and N,N-dimethylformamide were mixed, and the mixture was reacted for 24 hours under nitrogen protection at a stirring rate of 100-120 rpm and a temperature of 80° C. to obtain intermediate a; Step B2: Mix intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N,N-dimethylformamide, stir under nitrogen protection, at a stirring rate of 200-240 rpm and a temperature of 90° C., add N-tert-butoxycarbonylaminopropyne, and react for 24 hours to obtain intermediate b; mix intermediate b with ethyl acetate solution of hydrogen chloride, and react for 2 hours at a stirring rate of 200-240 rpm and room temperature to obtain intermediate c; Step B3: Mix the intermediate c, hexamethylene diisocyanate and toluene, and react for 4-6 hours at a stirring rate of 200-240 rpm and a temperature of 60° C. to obtain an auxiliary clay stabilizer.

2. The method for preparing a clay stabilizer composition according to claim 1, characterized in that: In step A1, the amount ratio of maleic anhydride, diethanolamine, trimethylolpropane and p-toluenesulfonic acid is 0.2-0.3 mol: 0.2-0.3 mol: 0.3-0.4 g: 0.5 g, the mass fraction of the sodium hydroxide solution is 10%, and the amount ratio of the hyperbranched polymer, epichlorohydrin and sodium hydroxide solution is 45-50 g: 25-35 mL: 30 mL.

3. The method for preparing a clay stabilizer composition according to claim 2, characterized in that: In step A2: the amount ratio of 1-methylpiperidine-4-carboxylic acid, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 1-hydroxybenzotriazole and dodecyl primary amine is 0.1-0.12 mol: 5 g: 6 g: 0.1-0.12 mol, and the amount ratio of intermediate 1, modified hyperbranched polymer and γ-mercaptopropyltriethoxysilane is 0.2-0.3 mol: 45-50 g: 0.2-0.3 mol.

4. The method for preparing a clay stabilizer composition according to claim 3, characterized in that: In step B1, the ratio of 4-octyloxybenzyl chloride to sodium azide is 2-3 g: 0.15-0.2 g.

5. The method for preparing a clay stabilizer composition according to claim 4, characterized in that: In step B2, the amount ratio of intermediate a, copper sulfate pentahydrate, sodium L-ascorbate and N-tert-butyloxycarbonylaminopropyne is 0.02 mol: 0.2-25 g: 0.15-0.2 g: 0.02-0.025 mol, the molar concentration of hydrogen chloride ethyl acetate solution is 4 mol / L, and the amount ratio of intermediate b and hydrogen chloride ethyl acetate solution is 0.02 mol: 10 mL.

6. The method for preparing a clay stabilizer composition according to claim 5, characterized in that: In step B3: the ratio of the intermediate c to hexamethylene diisocyanate is 0.02-0.024 mol:0.01 mol.

7. A clay stabilizer composition, characterized in that: Prepared according to any one of claims 1 to 6.

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