A pore wall surface responsive coating oil-water selective selective plugging agent and its use method and application

Abstract

The present application relates to a kind of pore wall surface response coating oil-water selective plugging agent and its use method and application, it relates to oilfield chemical reagent technical field, the pore wall surface response coating oil-water selective plugging agent includes the wall surface anchoring agent and oil-water response brush agent with weight ratio ((0.05~0.2):(0.4~2.0)).The pore wall surface response coating oil-water selective plugging agent provided in the present application can form oil-water response coating on rock pore wall surface, when water phase flows, the coating expands, reduces pore effective percolation diameter and causes additional percolation resistance to hinder water phase, when oil phase flows, the coating shrinks, pore effective percolation diameter expands and reduces oil phase percolation resistance, to realize the selective plugging effect of "water blocking oil permeation", and the application prospect is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil field chemicals, in particular to a pore wall surface responsive coating oil-water selective profile control agent and a use method and application thereof. BACKGROUND

[0002] In the middle and later stages of oilfield development, the reservoirs generally enter the high water cut stage, and the heterogeneity of the formation leads to ineffective water circulation, which has become a key problem restricting the further improvement of recovery. Profile control operation is widely used in oilfield production as an effective way to control water channeling. In the process of profile control and water plugging, it is required that the plugging agent enters the high permeability layer as much as possible to effectively plug the water production layer, while the middle and low permeability layer area rich in remaining oil is damaged as little as possible. The commonly used pore wall surface responsive coating oil-water selective profile control agent is mainly polymer gel, polymer microsphere and pre-crosslinked body swelling particle, however, the conventional pore wall surface responsive coating oil-water selective profile control agent generally has poor oil-water selectivity, which often invades the oil-containing pore throat while plugging the high permeability water channeling channel, resulting in a sharp decrease in oil permeability, and even completely plugging the oil production layer, thereby causing the negative effect of controlling water without increasing oil. SUMMARY

[0003] To solve the above problems, the present application provides a pore wall surface responsive coating oil-water selective profile control agent and a use method and application thereof.

[0004] In a first aspect, the present application provides a pore wall surface responsive coating oil-water selective profile control agent, which comprises a wall anchoring agent and an oil-water response brush agent in a weight ratio of (0.05-0.2):(0.4-2.0).

[0005] The preparation of the wall anchoring agent comprises the following process:

[0006] The first reaction of ethylenediamine with citric acid gives an intermediate CD-N;

[0007] The intermediate CD-N is subjected to alternating reactions with methyl methacrylate and ethylenediamine in turn, and the alternating reactions are repeated at least 2 times to obtain the wall anchoring agent;

[0008] The oil-water response brush agent is obtained by the second reaction of a polyether compound and acryloyl chloride; wherein the chemical structure of the polyether compound is as follows:

[0009] ; m is 54-90, and n is 10-40.

[0010] Further, the weight ratio of the wall anchoring agent and the oil-water responsive brush agent is (0.08~0.15):(1.0~1.5).

[0011] Further, the step of reacting the ethylenediamine with the citric acid to obtain the intermediate CD-N includes the following process:

[0012] The ethylenediamine and the citric acid are mixed in a weight ratio of (1~2):1, and then the first reaction is carried out at a temperature of 175~185℃ for 5.5~6.5h to obtain the intermediate CD-N.

[0013] Further, the step of alternately reacting the intermediate CD-N with methyl methacrylate and ethylenediamine in turn and repeating the alternately reaction at least twice to obtain the wall anchoring agent includes the following process:

[0014] The intermediate CD-N and the methyl methacrylate are mixed in a weight ratio of 1:(3~4) in an alcohol solvent, and then the third reaction is carried out at room temperature for 22~26h to obtain the intermediate CD-MN-0.5;

[0015] The intermediate CD-MN-0.5 and the ethylenediamine are mixed in a weight ratio of 1:(2~3) in an alcohol solvent, and then the fourth reaction is carried out at room temperature for 22~26h to obtain the intermediate CD-MN-1.0;

[0016] The intermediate CD-MN-1.0 and the methyl methacrylate are mixed in a weight ratio of 1:(3~4) in an alcohol solvent, and then the fifth reaction is carried out at room temperature for 22~26h to obtain the intermediate CD-MN-1.5;

[0017] The intermediate CD-MN-1.5 and the ethylenediamine are mixed in a weight ratio of 1:(2~3) in an alcohol solvent, and then the sixth reaction is carried out at room temperature for 22~26h to obtain the intermediate CD-MN-2.0;

[0018] The intermediate CD-MN-2.0 and the methyl methacrylate are mixed in a weight ratio of 1:(3~4) in an alcohol solvent, and then the seventh reaction is carried out at room temperature for 22~26h to obtain the intermediate CD-MN-2.5;

[0019] The intermediate CD-MN-2.5 and the ethylenediamine are mixed in a weight ratio of 1:(2~3) in an alcohol solvent, and then the eighth reaction is carried out at room temperature for 22~26h to obtain the wall anchoring agent.

[0020] Further, the preparation of the oil-water responsive brush agent includes the following process:

[0021] dissolving the polyether compound and the basic catalyst in an organic solvent to obtain a mixture;

[0022] Under the condition of ice water bath, a solution of acryloyl chloride with a mass concentration of 2.5-4.0% is added dropwise into the mixture, and after the dropwise addition is completed, the second reaction is carried out at room temperature for 22-26 hours to obtain the oil-water response brush agent.

[0023] The molar ratio of the polyether compound, the basic catalyst and the acryloyl chloride is 1:(2.2-3):(1-1.05).

[0024] Further, the polyether compound is an amphiphilic block copolymer, the hydrophilic block in the amphiphilic block copolymer is a polyoxyethylene ether structure, and the hydrophobic block in the amphiphilic block copolymer is a polyoxypropylene ether structure; the basic catalyst includes triethylamine.

[0025] Further, the m is 60, and the n is 40.

[0026] In a second aspect, based on the same inventive concept, the present application provides a use method of the pore wall surface responsive coating oil-water selective profile control agent according to any one of the first aspect, which includes the following steps:

[0027] The wall surface anchoring agent is dissolved in a solvent to obtain a wall surface anchoring agent dispersion;

[0028] The oil-water response brush agent is dissolved in a solvent to obtain an oil-water response brush agent dispersion;

[0029] The wall surface anchoring agent dispersion is injected into the oil reservoir, then pure water is continuously injected into the oil reservoir, and finally the oil-water response brush agent dispersion is continuously injected into the oil reservoir.

[0030] Further, the solvent includes at least one of water and a sodium chloride aqueous solution, the mass percentage of the wall surface anchoring agent in the wall surface anchoring agent dispersion is 0.05-0.2%, the mass percentage of the oil-water response brush agent in the oil-water response brush agent dispersion is 0.4-2.0%, and the weight ratio of the wall surface anchoring agent dispersion, the oil-water response brush agent dispersion and the pure water is 1:1:(2.5-3.5).

[0031] In a third aspect, based on the same inventive concept, the present application provides an application of the pore wall surface responsive coating oil-water selective profile control agent according to any one of the first aspect in oil field exploitation.

[0032] Compared with the prior art, the above technical solution provided by the embodiments of the present application has at least the following advantages:

[0033] The embodiment of the present application provides a pore wall surface responsive coating oil-water selective plugging agent and a use method and application thereof. The pore wall surface responsive coating oil-water selective plugging agent provided by the present application can form an oil-water responsive coating on the pore wall surface of rock. When water phase flows through, the coating expands, the effective seepage diameter of the pore is reduced, and additional seepage resistance is caused to hinder the water phase from passing through. When oil phase flows through, the coating shrinks, the effective seepage diameter of the pore is expanded, and the oil phase seepage resistance is reduced, thereby realizing the selective plugging effect of "water blocking and oil permeating". The application prospect is wide. Specifically,

[0034] 1) The pore wall surface responsive coating oil-water selective plugging agent provided by the present application has a wall surface anchoring agent with a very small particle size (<10 nm) and a surface hyperbranched structure, and a large number of amine groups exist on the surface. After being injected into the formation, the surface energy and surface amine groups generated by the small particle size of the wall surface anchoring agent are gradually adsorbed and retained on the surface of the formation rock. When the oil-water response brush agent is injected into the formation in the subsequent slug, the wall surface anchoring agent adsorbed on the surface of the rock is contacted in the formation. The oil-water response brush agent is grafted to the surface of the wall surface anchoring agent adsorbed on the rock through Michael addition reaction. With the continuous enrichment of the oil-water response brush agent on the surface of the wall surface anchoring agent, hydrophobic physical crosslinking points are gradually formed between the brush agents and gelation occurs. Then, the wall surface anchoring agent forms a physical hydrogel layer on the rock wall surface through hydrophobic crosslinking, that is, an oil-water responsive coating. When the subsequent liquid flow is water phase, the oil-water responsive coating can absorb water and expand and maintain a three-dimensional network structure, reducing or plugging the pore to hinder the water phase from passing through. When the subsequent liquid flow is oil phase, the hydrophobic physical crosslinking points in the oil-water responsive coating are destroyed, and the hydrophilic block of the oil-water response brush agent shrinks at the same time. The three-dimensional network structure of the oil-water responsive coating is destroyed and the volume shrinks at the same time. The effective seepage diameter of the pore is expanded and the oil phase seepage resistance is reduced, thereby realizing the selective plugging of oil and water.

[0035] 2) The pore wall surface responsive coating oil-water selective plugging agent provided by the present application has a small particle size / molecular size of components, good injection property of oil reservoir, and large applicable range of oil reservoir properties.

[0036] 3) The pore wall surface responsive coating oil-water selective plugging agent provided by the present application has sensitive oil-water identification performance, and has stronger oil-water selective plugging capacity compared with conventional pore wall surface responsive coating oil-water selective plugging agents.

[0037] 4) The pore wall surface responsive coating oil-water selective plugging agent provided by the present application has good washability and long effective period after construction operation. BRIEF DESCRIPTION OF DRAWINGS

[0038] The drawings herein are incorporated into the description and constitute a part of the description, show embodiments consistent with the present application, and are used together with the description to explain the principles of the present application.

[0039] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, for those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0040] Figure 1 The preparation flow chart of the wall anchoring agent in the pore wall responsive coating oil-water selective profile control agent provided by the embodiments of the present application.

[0041] Figure 2 The micro-morphology diagram of the wall anchoring agent in the pore wall responsive coating oil-water selective profile control agent provided by the embodiments of the present application.

[0042] Figure 3 The infrared characterization diagram of the wall anchoring agent in the pore wall responsive coating oil-water selective profile control agent provided by the embodiments of the present application. DETAILED DESCRIPTION

[0043] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without any creative effort fall within the protection scope of the present application.

[0044] Unless otherwise specifically indicated, all the various raw materials, reagents, instruments and equipment and the like used in the present application can be purchased from the market or can be prepared by the existing methods.

[0045] The present application will be further described below in combination with specific examples. It should be understood that these examples are only used to illustrate the present application and not used to limit the scope of the present application. The experimental methods in the following examples without specific conditions are generally determined according to the national standards. If there is no corresponding national standard, the international standard, the conventional condition or the condition suggested by the manufacturer is used.

[0046] The main information of the polyether compounds involved in the following examples and comparative examples is as follows:

[0047] PPO 60 -PEO 40 -PPO 60 The chemical structure characteristics of the above are as follows:

[0048] ; m is 60 and n is 40, which is purchased from BASF with product type Pluronic ®L-44, CAS No. 9003-11-6, molecular weight 2200 Da.

[0049] PPO 54 -PEO 10 -PPO 54 The chemical structure of PEO-PPO-PEO is shown below:

[0050] ; m is 54, n is 10, available from BASF under the trade designation Pluronic L-62® ® L-61, CAS No. 9003-11-6, molecular weight 2000 Da.

[0051] PPO 90 -PEO 10 -PPO 90 The chemical structure of PEO-PPO-PEO is shown below:

[0052] ; m is 90, n is 10, available from BASF under the trade designation Pluronic L-92® ® L-121, CAS No. 9003-11-6, molecular weight 4400 Da.

[0053] PPO 54 -PEO 24 -PPO 54 The chemical structure of PEO-PPO-PEO is shown below: ; m is 54, n is 24, available from BASF under the trade designation Pluronic L-62® ® 10R5, CAS No. 9003-11-6, molecular weight 4000 Da.

[0054] PPO 20 -PEO 80 -PPO 20 The chemical structure of PEO-PPO-PEO is shown below:

[0055] ; m is 20, n is 80, available from BASF under the trade designation Pluronic L-80® ® F-108, CAS No. 9003-11-6, molecular weight 14600 Da.

[0056] Example 1

[0057] This example provides a pore wall responsive coating oil-water selective profile control agent, the pore wall responsive coating oil-water selective profile control agent comprising a wall anchoring agent and an oil-water responsive brush agent in a weight ratio of 0.1:1.2;

[0058] The preparation process of the wall anchoring agent is as shown in the following: Figure 1 The preparation process of the wall anchoring agent is as shown in the following:

[0059] (1) 6 g of ethylenediamine and 4 g of citric acid were mixed in a 250 mL three-necked flask, then heated to 180°C under stirring at 200 r / min for 6 h, and then cooled to room temperature. The reaction product was dissolved in 150 mL of excess anhydrous ethanol and centrifuged at 12000 rpm for 10 min. The supernatant after centrifugation was distilled under reduced pressure to remove ethanol to obtain a crude product. The crude product was dissolved in 50 mL of deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, and then freeze-dried to obtain an intermediate CD-N;

[0060] (2) 5 g of the intermediate CD-N was dispersed in 50 mL of methanol, then 17.5 g of methyl methacrylate was added, and the reaction was carried out at room temperature under stirring at 200 r / min for 24 h. After centrifugation for 10 min, filtration and drying, an intermediate CD-MN-0.5 was obtained;

[0061] (3) 10 g of the intermediate CD-MN-0.5 was dispersed in 50 mL of methanol, then 25 g of ethylenediamine was added, and the reaction was carried out at room temperature under stirring at 200 r / min for 24 h. After centrifugation for 10 min, filtration and drying, an intermediate CD-MN-1.0 was obtained;

[0062] (4) Steps (2) and (3) were repeated twice to obtain a wall anchoring agent product CD-MN-3.0 (i.e., a wall anchoring agent);

[0063] The preparation of the oil-water responsive brush agent includes the following process:

[0064] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 60 -PEO 40 -PPO 60 ) was dissolved in 55 g of dichloromethane and 0.575 g of triethylamine was added, then 6.56 g of acryloyl chloride dissolved in dichloromethane (mass concentration of acryloyl chloride was 3.2%) was slowly added dropwise under ice water bath condition. After the addition was completed, the temperature of the reaction system was allowed to rise to room temperature, and then the reaction was continued for 24 hours;

[0065] (2) The triethylamine hydrochloride was removed by filtration from the mixture after the reaction of step (1), and the obtained filtrate was precipitated in 400 mL of diethyl ether. The white solid obtained by precipitation was dried under vacuum at 30°C for 48 h to obtain an oil-water responsive brush agent.

[0066] The above pore wall responsive coating oil-water selective plugging agent includes the following process when in use:

[0067] The wall anchoring agent is dissolved in water to obtain a wall anchoring agent dispersion with a mass percentage of 0.1%;

[0068] The oil-water responsive brush agent is dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 1.5%;

[0069] The wall anchoring agent dispersion is injected into the oil reservoir, then pure water (i.e. an injection water slug is used as an isolation slug) is continuously injected into the oil reservoir, and finally the oil-water responsive brush agent dispersion is continuously injected into the oil reservoir; the weight ratio of the wall anchoring agent dispersion, the oil-water responsive brush agent dispersion, and the pure water is 1:1:3.

[0070] Example 2

[0071] This example provides a pore wall responsive coating oil-water selective profile control agent, which comprises a wall anchoring agent and an oil-water responsive brush agent in a weight ratio of 0.1:1.2;

[0072] The preparation of the wall anchoring agent comprises the following process:

[0073] (1) 6 g of ethylenediamine and 3 g of citric acid are added to a 250 mL three-necked flask for mixing, then the temperature is raised to 180°C under stirring at 200 r / min for 6 h, then cooled to room temperature, the reaction product is dissolved in 150 mL of excess anhydrous ethanol and centrifuged at 12000 rpm for 10 min, the upper liquid after centrifugation is distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product is dissolved in 50 mL of deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, then freeze-dried to obtain an intermediate CD-N;

[0074] (2) 5 g of the intermediate CD-N is dispersed in 50 mL of methanol, then 20 g of methyl methacrylate is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain an intermediate CD-MN-0.5;

[0075] (3) 10 g of the intermediate CD-MN-0.5 is dispersed in 50 mL of methanol, then 30 g of ethylenediamine is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain an intermediate CD-MN-1.0;

[0076] (4) Steps (2) and (3) are repeated twice to obtain a wall anchoring agent product CD-MN-3.0 (i.e. a wall anchoring agent);

[0077] The preparation of the oil-water responsive brush agent comprises the following process:

[0078] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 60 - PEO 40 - PPO 60 ) is dissolved in 55 g of dichloromethane and 0.575 g of triethylamine is added, then 6.56 g of an acryloyl chloride solution in dichloromethane (mass concentration of acryloyl chloride is 3.2%) is slowly added dropwise under the condition of an ice water bath, after the dropwise addition is completed, the temperature of the reaction system is allowed to rise to room temperature, then the reaction is continued for 24 hours;

[0079] (2) The mixture after the reaction in step (1) is filtered to remove triethylamine hydrochloride, the obtained filtrate is precipitated in 400 mL of ether, the white solid obtained by precipitation is vacuum dried at 30°C for 48 h to obtain an oil-water responsive brush agent.

[0080] The above pore wall surface responsive coating oil-water selective profile control agent includes the following processes when used:

[0081] The wall surface anchoring agent is dissolved in water to obtain a wall surface anchoring agent dispersion with a mass percentage of 0.1%;

[0082] The oil-water responsive brush agent is dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 1.5%;

[0083] The wall surface anchoring agent dispersion is injected into the oil reservoir, then pure water (i.e. an injection water slug is used as an isolation slug) is continuously injected into the oil reservoir, and finally the oil-water responsive brush agent dispersion is continuously injected into the oil reservoir; wherein the weight ratio of the wall surface anchoring agent dispersion, the oil-water responsive brush agent dispersion and the pure water is 1:1:3.

[0084] Example 3

[0085] This example provides a pore wall surface responsive coating oil-water selective profile control agent, which includes a wall surface anchoring agent and an oil-water responsive brush agent with a weight ratio of 0.1:1.2;

[0086] The preparation of the wall surface anchoring agent includes the following processes:

[0087] (1) 6 g of ethylenediamine and 4 g of citric acid are added to a 250 mL three-necked flask and mixed, then the temperature is raised to 180°C under the condition of stirring at 200 r / min for 6 h, then cooled to room temperature, the reaction product is dissolved in 150 mL of excess anhydrous ethanol and centrifuged at 12000 rpm for 10 minutes, the upper liquid after centrifugation is distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product is dissolved in 50 mL of deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, then freeze-dried to obtain an intermediate CD-N;

[0088] (2) 5 g of intermediate CD-N was dispersed in 50 mL of methanol, then 17.5 g of methyl methacrylate was added, and the reaction was carried out at room temperature under the condition of stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain intermediate CD-MN-0.5;

[0089] (3) 10 g of intermediate CD-MN-0.5 was dispersed in 50 mL of methanol, then 25 g of ethylenediamine was added, and the reaction was carried out at room temperature under the condition of stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain intermediate CD-MN-1.0;

[0090] (4) Steps (2) and (3) were repeated twice to obtain a wall anchoring agent product CD-MN-3.0 (i.e. a wall anchoring agent);

[0091] The preparation of the oil-water responsive brush agent includes the following processes:

[0092] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 90 -PEO 10 -PPO 90 ) was dissolved in 55 g of dichloromethane and 0.288 g of triethylamine was added, then 3.28 g of acryloyl chloride dissolved in dichloromethane (the mass concentration of acryloyl chloride was 3.2%) was slowly added dropwise under the condition of ice water bath, and after the addition was completed, the temperature of the reaction system was allowed to rise to room temperature, and then the reaction was continued for 24 hours;

[0093] (2) The reaction mixture after step (1) was filtered to remove triethylamine hydrochloride, and the obtained filtrate was precipitated in 400 mL of ethyl ether, and the white solid obtained by precipitation was vacuum dried at 30°C for 48 h to obtain an oil-water responsive brush agent.

[0094] The above pore wall responsive coating oil-water selective profile control agent includes the following processes when used:

[0095] The wall anchoring agent was dissolved in water to obtain a wall anchoring agent dispersion with a mass percentage of 0.1%;

[0096] The oil-water responsive brush agent was dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 1.5%;

[0097] The wall anchoring agent dispersion was injected into the oil reservoir, then pure water (i.e. an injection water slug was used as an isolation slug) was continuously injected into the oil reservoir, and finally the oil-water responsive brush agent dispersion was continuously injected into the oil reservoir; wherein the weight ratio of the wall anchoring agent dispersion, the oil-water responsive brush agent dispersion and the pure water was 1:1:3.

[0098] Example 4

[0099] The example provides a pore wall surface responsive coating oil-water selective plugging agent, the pore wall surface responsive coating oil-water selective plugging agent comprising a wall surface anchoring agent and an oil-water responsive brush agent in a weight ratio of 0.1:1.2;

[0100] The preparation of the wall surface anchoring agent comprises the following process:

[0101] (1) 6g ethylenediamine and 4g citric acid were mixed in a 250mL three-necked flask, then heated to 180℃ under stirring at 200r / min for 6h, then cooled to room temperature, the reaction product was dissolved in 150mL excess anhydrous ethanol and centrifuged at 12000rpm for 10min, the supernatant after centrifugation was distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product was dissolved in 50mL deionized water and dialyzed for 24h using a 1kDa dialysis membrane, then freeze-dried to obtain an intermediate CD-N;

[0102] (2) 5g of the intermediate CD-N was dispersed in 50mL methanol, then 17.5g of methyl methacrylate was added, and the reaction was carried out at room temperature under stirring at 200r / min for 24h, centrifuged for 10min, filtered and dried to obtain an intermediate CD-MN-0.5;

[0103] (3) 10g of the intermediate CD-MN-0.5 was dispersed in 50mL methanol, then 25g of ethylenediamine was added, and the reaction was carried out at room temperature under stirring at 200r / min for 24h, centrifuged for 10min, filtered and dried to obtain an intermediate CD-MN-1.0;

[0104] (4) Steps (2) and (3) were repeated twice to obtain a wall surface anchoring agent product CD-MN-3.0 (i.e. wall surface anchoring agent);

[0105] The preparation of the oil-water responsive brush agent comprises the following process:

[0106] (1) 5g of polyether (BAB type amphiphilic block copolymer, PPO 60 -PEO 40 -PPO 60 ) was dissolved in 55g of dichloromethane and 0.575g of triethylamine was added, then 6.45g of acryloyl chloride dissolved in dichloromethane (mass concentration of acryloyl chloride was 3.1%) was slowly added dropwise under ice water bath condition, after the dropwise addition was completed, the reaction system was allowed to warm up to room temperature, then the reaction was continued for 24h;

[0107] (2) The mixture after the reaction of step (1) was filtered to remove triethylamine hydrochloride, the obtained filtrate was precipitated in 400mL of diethyl ether, and the white solid obtained by precipitation was vacuum dried at 30℃ for 48h to obtain an oil-water responsive brush agent.

[0108] The pore wall surface responsive coating oil-water selective adjusting and plugging agent in use comprises the following processes:

[0109] The wall surface anchoring agent is dissolved in water to obtain a wall surface anchoring agent dispersion liquid with a mass percentage of 0.1%;

[0110] The oil-water responsive brush agent is dissolved in water to obtain an oil-water responsive brush agent dispersion liquid with a mass percentage of 1.5%;

[0111] The wall surface anchoring agent dispersion liquid is injected into the oil reservoir, then pure water is continuously injected into the oil reservoir (namely, an injection water slug is used as an isolation slug), and finally the oil-water responsive brush agent dispersion liquid is continuously injected into the oil reservoir; wherein the weight ratio of the wall surface anchoring agent dispersion liquid, the oil-water responsive brush agent dispersion liquid and the pure water is 1:1:3.

[0112] Example 5

[0113] This example provides a pore wall surface responsive coating oil-water selective adjusting and plugging agent, which comprises a wall surface anchoring agent and an oil-water responsive brush agent with a weight ratio of 0.05:2;

[0114] The preparation of the wall surface anchoring agent comprises the following processes:

[0115] (1) 6 g of ethylenediamine and 4 g of citric acid are added into a 250 mL three-necked flask for mixing, then the temperature is raised to 180℃ under stirring at 200 r / min for 6 h, then cooled to room temperature, the reaction product is dissolved in 150 mL of excess anhydrous ethanol and centrifuged at 12000 rpm for 10 min, the upper liquid after centrifugation is distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product is dissolved in 50 mL of deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, then freeze-dried to obtain an intermediate CD-N;

[0116] (2) 5 g of the intermediate CD-N is dispersed in 50 mL of methanol, then 17.5 g of methyl methacrylate is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain an intermediate CD-MN-0.5;

[0117] (3) 10 g of the intermediate CD-MN-0.5 is dispersed in 50 mL of methanol, then 25 g of ethylenediamine is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 24 h, centrifuged for 10 min, filtered and dried to obtain an intermediate CD-MN-1.0;

[0118] (4) Steps (2) and (3) are repeated twice to obtain a wall surface anchoring agent product CD-MN-3.0 (namely, a wall surface anchoring agent);

[0119] The preparation of the oil-water responsive brush agent includes the following process:

[0120] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 60 -PEO 40 -PPO 60 ) is dissolved in 55 g of dichloromethane and 0.575 g of triethylamine is added, then 6.56 g of acryloyl chloride dissolved in dichloromethane (mass concentration of acryloyl chloride is 3.2%) is slowly added dropwise under ice water bath conditions, after the dropwise addition is completed, the temperature of the reaction system is allowed to rise to room temperature, and then the reaction is continued for 24 hours;

[0121] (2) The mixture after the reaction of step (1) is filtered to remove triethylamine hydrochloride, the obtained filtrate is precipitated in 400 mL of ether, and the white solid obtained by precipitation is vacuum dried at 30°C for 48 h to obtain an oil-water responsive brush agent.

[0122] The above pore wall surface responsive coating oil-water selective plugging agent includes the following process when used:

[0123] The wall surface anchoring agent is dissolved in water to obtain a wall surface anchoring agent dispersion with a mass percentage of 0.05%;

[0124] The oil-water responsive brush agent is dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 2%;

[0125] The wall surface anchoring agent dispersion is injected into the oil reservoir, then pure water (i.e. an injection water slug is used as an isolation slug) is continuously injected into the oil reservoir, and finally the oil-water responsive brush agent dispersion is continuously injected into the oil reservoir; wherein the weight ratio of the wall surface anchoring agent dispersion, the oil-water responsive brush agent dispersion, and the pure water is 1:1:3.

[0126] Example 6

[0127] This example provides a pore wall surface responsive coating oil-water selective plugging agent, which includes a wall surface anchoring agent and an oil-water responsive brush agent in a weight ratio of 0.2:1.5;

[0128] The preparation of the wall surface anchoring agent includes the following process:

[0129] (1) 6 g ethylenediamine and 6 g citric acid were mixed in a 250 mL three-necked flask, then heated to 175 °C under stirring at 200 r / min for 6.5 h, then cooled to room temperature, the reaction product was dissolved in 150 mL excess anhydrous ethanol and centrifuged at 12000 rpm for 10 min, the supernatant after centrifugation was distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product was dissolved in 50 mL deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, then freeze-dried to obtain the intermediate CD-N;

[0130] (2) 5 g of the intermediate CD-N was dispersed in 50 mL of methanol, then 15 g of methyl methacrylate was added, and the reaction was carried out at room temperature under stirring at 200 r / min for 22 h, centrifuged for 10 min, filtered and dried to obtain the intermediate CD-MN-0.5;

[0131] (3) 10 g of the intermediate CD-MN-0.5 was dispersed in 50 mL of methanol, then 20 g of ethylenediamine was added, and the reaction was carried out at room temperature under stirring at 200 r / min for 22 h, centrifuged for 10 min, filtered and dried to obtain the intermediate CD-MN-1.0;

[0132] (4) Steps (2) and (3) were repeated twice to obtain the wall anchoring agent product CD-MN-3.0 (i.e. the wall anchoring agent);

[0133] The preparation of the oil-water responsive brush agent includes the following processes:

[0134] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 54 -PEO 10 -PPO 54 ) was dissolved in 55 g of dichloromethane and 0.557 g of triethylamine was added, then 5.94 g of acryloyl chloride dissolved in dichloromethane (mass concentration of acryloyl chloride was 4.0%) was slowly added dropwise under ice water bath, after the dropwise addition was completed, the reaction system was allowed to warm to room temperature, then the reaction was continued for 22 h;

[0135] (2) The mixture after the reaction of step (1) was filtered to remove triethylamine hydrochloride, the obtained filtrate was precipitated in 400 mL of diethyl ether, and the white solid obtained by precipitation was vacuum dried at 30 °C for 48 h to obtain the oil-water responsive brush agent.

[0136] The above pore wall responsive coating oil-water selective plugging agent includes the following processes when in use:

[0137] The wall anchoring agent was dissolved in water to obtain a wall anchoring agent dispersion with a mass percentage of 0.2%;

[0138] The oil-water responsive brush agent is dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 1.5%;

[0139] The wall anchoring agent dispersion is injected into the oil reservoir, and then pure water is continuously injected into the oil reservoir (namely, an injection water slug is used as an isolation slug), and finally the oil-water responsive brush agent dispersion is continuously injected into the oil reservoir; wherein the weight ratio of the wall anchoring agent dispersion, the oil-water responsive brush agent dispersion and the pure water is 1:1:2.5.

[0140] Example 7

[0141] The present example provides a pore wall surface responsive coating oil-water selective profile control agent, which comprises a wall anchoring agent and an oil-water responsive brush agent with a weight ratio of 0.08:0.4;

[0142] The preparation of the wall anchoring agent comprises the following process:

[0143] (1) 6 g of ethylenediamine and 3 g of citric acid are added to a 250 mL three-necked flask for mixing, then heated to 185°C under stirring at 200 r / min for 5.5 h, then cooled to room temperature, the reaction product is dissolved in 150 mL of excess anhydrous ethanol and centrifuged at 12000 rpm for 10 minutes, the upper liquid after centrifugation is distilled under reduced pressure to remove ethanol to obtain a crude product, the crude product is dissolved in 50 mL of deionized water and dialyzed for 24 h using a 1 kDa dialysis membrane, then freeze-dried to obtain an intermediate CD-N;

[0144] (2) 5 g of intermediate CD-N is dispersed in 50 mL of methanol, then 20 g of methyl methacrylate is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 26 h, centrifuged for 10 minutes, filtered and dried to obtain an intermediate CD-MN-0.5;

[0145] (3) 10 g of intermediate CD-MN-0.5 is dispersed in 50 mL of methanol, then 30 g of ethylenediamine is added, and the reaction is carried out at room temperature under stirring at 200 r / min for 26 h, centrifuged for 10 minutes, filtered and dried to obtain an intermediate CD-MN-1.0;

[0146] (4) Steps (2) and (3) are repeated twice to obtain a wall anchoring agent product CD-MN-3.0 (i.e. wall anchoring agent);

[0147] The preparation of the oil-water responsive brush agent comprises the following process:

[0148] (1) 5 g of polyether (BAB type amphiphilic block copolymer, PPO 54 -PEO 24 -PPO 54) was dissolved in 55 g of dichloromethane and 0.379 g of triethylamine was added, then 4.52 g of acryloyl chloride dissolved in dichloromethane (mass concentration of acryloyl chloride was 2.5%) was slowly added dropwise under the condition of ice water bath, after the dropwise addition was completed, the temperature of the reaction system was allowed to rise to room temperature, then the reaction was continued for 26 hours;

[0149] (2) The mixture after the reaction of step (1) was filtered to remove triethylamine hydrochloride, the obtained filtrate was precipitated in 400 mL of ether, and the white solid obtained by precipitation was vacuum dried at 30°C for 48 h to obtain the oil-water responsive brush agent.

[0150] The above-mentioned pore wall surface responsive coating oil-water selective profile control agent, when used, includes the following processes:

[0151] The wall surface anchoring agent was dissolved in water to obtain a wall surface anchoring agent dispersion with a mass percentage of 0.08%;

[0152] The oil-water responsive brush agent was dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 0.4%;

[0153] The wall surface anchoring agent dispersion was injected into the oil reservoir, then pure water (i.e. an injection water slug was used as an isolation slug) was continuously injected into the oil reservoir, and finally the oil-water responsive brush agent dispersion was continuously injected into the oil reservoir; wherein the weight ratio of the wall surface anchoring agent dispersion, the oil-water responsive brush agent dispersion and the pure water was 1:1:3.5.

[0154] Comparative Example 1

[0155] This example provides a profile control agent, which is different from Example 1 only in that:

[0156] (1) No wall surface anchoring agent was added (i.e. the profile control agent was only composed of the oil-water responsive brush agent in Example 1).

[0157] The above-mentioned profile control agent, when used, includes the following processes:

[0158] The oil-water responsive brush agent was dissolved in water to obtain an oil-water responsive brush agent dispersion with a mass percentage of 1.2%.

[0159] Comparative Example 2

[0160] This example provides a profile control agent, which is different from Example 1 only in that:

[0161] (1) The oil-water responsive brush agent was selected to be unmodified polyether (i.e. the oil-water responsive brush agent was PPO 60 -PEO 40 -PPO 60 in Example 1).

[0162] The above blocking agent is used in the same way as in Example 1.

[0163] Comparative Example 3

[0164] This example provides a blocking agent, which is only different from Example 1 in that:

[0165] (1) PPO in the oil-water responsive brush agent is replaced by PPO 60 -PEO 40 -PPO 60 -PEO 20 -PEO 80 -PPO 20 .

[0166] The above blocking agent is used in the same way as in Example 1.

[0167] Comparative Example 4

[0168] This example provides a blocking agent, which is only different from Example 1 in that:

[0169] (1) The intermediate CD-MN-1.0 in Example 1 is used as a wall anchoring agent.

[0170] The above blocking agent is used in the same way as in Example 1.

[0171] Test Example 1

[0172] This example characterizes the wall anchoring agent obtained in the above Example 1, and the test results are as follows:

[0173] (1) Micro-morphology of the wall anchoring agent:

[0174] The micro-morphology of the sample is observed by Talos F200X G2 transmission electron microscope, and the test results are shown in Figure 2 , the wall anchoring agent is spherical particle, uniformly distributed.

[0175] (2) Fourier infrared characterization of the wall anchoring agent

[0176] Based on Tensor II Fourier infrared spectrometer (Bruker, Germany), ATR is used to test the infrared spectrum of the sample, and the wave number range is 4000~700cm -1 .

[0177] The test results are shown in Figure 3 , the relatively wide absorption peak at a wave number of 3429cm -1 is the stretching vibration absorption peak of N-H bond on amide group, the absorption peaks at 2927cm -1 and 2852cm -1 belong to the stretching vibration of -CH2 and -CH3 respectively, and the absorption peak at 1694cm-1 The absorption peak at 1406 cm⁻¹ is due to the stretching vibration of the C=O bond. -1 The absorption peak at 1229 cm⁻¹ belongs to the stretching vibration absorption peak of the CH bond. -1 The absorption peak at 1076 cm⁻¹ is the absorption peak of the stretching vibration of the CN bond. -1 The absorption peak at that point is the absorption peak of the stretching vibration of the CO bond.

[0178] Test Example 2

[0179] In this example, the plugging agents obtained in Examples 1-6 and Comparative Examples 1-4 were subjected to erosion resistance core displacement experiments to examine their respective erosion resistance performance.

[0180] The testing method is as follows:

[0181] 1. Using 5 g / L sodium chloride brine as the preparation solvent, the wall anchoring agent or oil-water responsive brush agent contained in the plugging agents obtained in Examples 1-6 and Comparative Examples 1-4 were respectively prepared into a 0.1 wt% wall anchoring agent dispersion and a 0.1 wt% oil-water responsive brush agent dispersion.

[0182] 2. The erosion resistance of the plugging agent was evaluated using a sand-filled pipe (2.5cm in diameter, 20cm in length, and sand permeability of 350mD). The basic experimental steps are as follows:

[0183] (1) Water drive was performed at a displacement rate of 0.2 mL / min until the pressure stabilized;

[0184] (2) Inject 0.1 times the pore volume (PV) of wall anchoring agent into the sand-filled pipe at a displacement rate of 0.2 mL / min (the same volume of 5 g / L sodium chloride saline was used in Comparative Example 1), and then inject 0.1 times the pore volume (PV) of oil-water responsive brushing agent.

[0185] (3) Remove the core tube and place it in a 75℃ constant temperature chamber for 48 hours;

[0186] (4) Inject formation water of 30 times the pore volume (PV) into the sand-filled pipe at a displacement rate of 0.2 mL / min.

[0187] The permeability change during the displacement process was calculated based on the experimental pressure data, and the plugging rate was calculated. The plugging rate was recalculated when 30 PV was injected to evaluate the erosion resistance of the plugging agent. The experimental results are shown in Table 1.

[0188] Table 1

[0189] Test sample Plugging rate (%) 30 PV plugging rate (%) Example 1 94% 91% Example 2 92% 86% Example 3 65% 30% Example 4 86% 82% Example 5 64% 23% Example 6 73% 57% Example 7 68% 31% Comparative Example 1 3% 0% Comparative Example 2 12% 5% Comparative Example 3 5% 0% Comparative Example 4 43% 15%

[0190] From Table 1, compared with Comparative Examples 1-4, the anti-washout performance of the blocking agent provided by the embodiments of the present application is better. Specifically, Comparative Example 1 has no anchoring agent, and the brush agent cannot be fixed to achieve plugging. Comparative Example 2 is not modified polyether and can only rely on van der Waals adsorption, which will desorb under low shear force. The PEO chain of Comparative Example 3 is too hydrophilic and quickly dissolves in water, which cannot achieve water plugging. Comparative Example 4 is only iterated once, the branching degree of CD-MN-1.0 is low, the cross-linked network has defects, resulting in low entanglement degree and fragmentation of the coating, which is difficult to achieve effective plugging.

[0191] Test Example 3

[0192] In this example, the oil-water selective core flow experiments of the blocking agents obtained in Examples 1-6 and Comparative Examples 1-4 were carried out to investigate the plugging performance of each.

[0193] The test method is as follows:

[0194] 1. The wall anchoring agent or the oil-water responsive brush agent contained in the blocking agents obtained in Examples 1-6 and Comparative Examples 1-4 were respectively prepared into 0.1wt% wall anchoring agent dispersion and 0.1wt% oil-water responsive brush agent dispersion using 5g / L sodium chloride brine as the preparation solvent.

[0195] 2. Artificial sandstone cores were used, the core size was φ2.5cm×10cm, the porosity was about 26%, and the permeability was about 100mD; the basic steps of the experiment were as follows:

[0196] (1) Water flooding was carried out at a displacement speed of 0.1mL / min until the pressure was stable;

[0197] (2) 5 times of pore volume (PV) of formation water was injected into the core at a displacement speed of 1mL / min;

[0198] (3) 5 times of pore volume (PV) of kerosene was injected into the core at a displacement speed of 1mL / min;

[0199] (4) 0.1 times of pore volume (PV) of wall anchoring agent (5g / L sodium chloride brine of the same volume was used instead in Comparative Example 1) was injected into the core at a displacement speed of 1mL / min, and then 0.1 times of pore volume (PV) of oil-water responsive brush agent was injected;

[0200] (5) The core tube was removed and placed in a 75℃ constant temperature box for 7d;

[0201] (6) The core was reversed water flooded and then reversed oil flooded at a displacement speed of 1mL / min.

[0202] According to the pressure data of each stage experiment, the permeability change in the displacement process was calculated, and the water plugging rate and the oil plugging rate were calculated, and the experimental results are shown in Table 2.

[0203] Table 2

[0204] Test sample Water-flooding plugging rate (%) Oil-flooding plugging rate (%) Example 1 85% 8% Example 2 90% 12% Example 3 65% 94% Example 4 80% 16% Example 5 55% 19% Example 6 75% 28% Example 7 58% 38% Comparative Example 1 2% 5% Comparative Example 2 15% 20% Comparative Example 3 12% 5% Comparative Example 4 40% 45%

[0205] From Table 2, it can be seen that, compared with Comparative Examples 1-4, the oil-water selectivity of the profile control agent provided by the embodiment of the application is more significant, and the selective profile control effect of "water isolation and oil permeation" can be effectively achieved. Specifically, Comparative Example 1 lacks an anchoring agent and cannot block water or oil. Comparative Example 2 is not modified with a brush agent and can only block part of the small pores and form loose micelles in the oil phase, slightly increasing the seepage resistance. The PEO chain of Comparative Example 3 is too hydrophilic and quickly dissolves in water, and cannot block water, and the dissolved brush agent is also washed out by oil, and cannot block oil. Comparative Example 4 has a small number of iterations, a low branching degree of CD-MN-1.0, and a small number of crosslinking sites, and the water blocking effect is insufficient, and the weakly crosslinked coating is easily detached, resulting in oil absorption and blockage in the oil phase.

[0206] Various embodiments of the application can exist in a range of forms; it should be understood that the description in the form of a range is merely for the convenience and brevity, and should not be understood as a rigid limitation on the scope of the application; therefore, it should be considered that the described range has specifically disclosed all possible sub-ranges and single values within the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the described range, such as 1, 2, 3, 4, 5 and 6, regardless of the range. In addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) within the indicated range.

[0207] The above description is merely specific embodiments of the application, enabling those skilled in the art to understand or implement the application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the application. Therefore, the application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features applied herein.

Claims

1. A pore wall surface responsive coating water-oil selectivity regulator, characterized in that, The pore wall surface responsive coating oil-water selective plugging agent comprises a wall surface anchoring agent and an oil-water responsive brush agent in a weight ratio of (0.05-0.2):(0.4-2.0); The preparation of the wall surface anchoring agent comprises the following process: ethylenediamine is subjected to a first reaction with citric acid to obtain an intermediate CD-N; the intermediate CD-N is subjected to alternating reactions with methyl methacrylate and ethylenediamine in sequence, and the alternating reactions are repeated at least twice to obtain the wall surface anchoring agent; the oil-water responsive brush agent is obtained by subjecting a polyether compound to a second reaction with acryloyl chloride; wherein the chemical structure of the polyether compound is as shown below: m has a value of 54 to 90 and n has a value of 10 to 40.

2. The pore wall responsive coating water-oil selective profile control agent of claim 1, wherein, the weight ratio of the wall surface anchoring agent to the oil-water responsive brush agent is (0.08-0.15):(1.0-1.5).

3. The pore wall responsive coating water-oil selective profile control agent of claim 1, wherein, The step of subjecting ethylenediamine to a first reaction with citric acid to obtain an intermediate CD-N comprises the following process: The ethylenediamine and the citric acid are mixed in a weight ratio of (1-2):1, and then the first reaction is carried out at a temperature of 175-185°C for 5.5-6.5h to obtain the intermediate CD-N.

4. The pore wall responsive coating water-oil selective profile control agent of claim 1, wherein, The step of subjecting the intermediate CD-N to alternating reactions with methyl methacrylate and ethylenediamine in sequence, and repeating the alternating reactions at least twice to obtain the wall surface anchoring agent comprises the following process: The intermediate CD-N and the methyl methacrylate are mixed in an alcohol solvent in a weight ratio of 1:(3-4), and then the third reaction is carried out at room temperature for 22-26h to obtain an intermediate CD-MN-0.5; The intermediate CD-MN-0.5 and the ethylenediamine are mixed in an alcohol solvent in a weight ratio of 1:(2-3), and then the fourth reaction is carried out at room temperature for 22-26h to obtain an intermediate CD-MN-1.0; The intermediate CD-MN-1.0 and the methyl methacrylate are mixed in an alcohol solvent in a weight ratio of 1:(3-4), and then the fifth reaction is carried out at room temperature for 22-26h to obtain an intermediate CD-MN-1.5; The intermediate CD-MN-1.5 and the ethylenediamine are mixed in an alcohol solvent in a weight ratio of 1:(2-3), and then the sixth reaction is carried out at room temperature for 22-26h to obtain an intermediate CD-MN-2.0; The intermediate CD-MN-2.0 and the methyl methacrylate are mixed in an alcohol solvent in a weight ratio of 1:(3-4), and then the seventh reaction is carried out at room temperature for 22-26h to obtain an intermediate CD-MN-2.5; The intermediate CD-MN-2.5 and the ethylenediamine are mixed in an alcohol solvent in a weight ratio of 1:(2-3), and then the eighth reaction is carried out at room temperature for 22-26h to obtain the wall surface anchoring agent.

5. The pore wall responsive coating water-oil selective shutoff agent of claim 1, wherein, The preparation of the oil-water responsive brush agent comprises the following process: a polyether compound and a basic catalyst are dissolved in an organic solvent to obtain a mixture; Under the condition of ice water bath, acryloyl chloride solution with mass concentration of 2.5-4.0% is added dropwise into the mixture, and after the dropwise addition is completed, the second reaction is carried out at room temperature for 22-26 hours to obtain the oil-water response brush agent. The molar ratio of the polyether compound, the basic catalyst and the acryloyl chloride is 1:(2.2-3):(1-1.05).

6. The pore wall responsive coating water-oil selective shutoff agent of claim 5, wherein, The polyether compound is an amphiphilic block copolymer, the hydrophilic block of the amphiphilic block copolymer is a polyoxyethylene ether structure, and the hydrophobic block of the amphiphilic block copolymer is a polyoxypropylene ether structure; the basic catalyst includes triethylamine.

7. The pore-walled surface-responsive coating water-oil selective profile control agent of claim 1, wherein, The m takes the value of 60, and the n takes the value of 40.

8. A method for using the pore wall surface-responsive coating water-oil selectivity adjustment blocking agent according to any one of claims 1 to 7, characterized in that, The use method of the pore wall surface responsive coating oil-water selective adjusting and plugging agent includes the following steps: The wall surface anchoring agent is dissolved in a solvent to obtain a wall surface anchoring agent dispersion liquid; The oil-water response brush agent is dissolved in a solvent to obtain an oil-water response brush agent dispersion liquid; The wall surface anchoring agent dispersion liquid is injected into the oil reservoir, then pure water is continuously injected into the oil reservoir, and finally the oil-water response brush agent dispersion liquid is continuously injected into the oil reservoir.

9. The method of using a pore wall responsive coating water selective shutoff agent of claim 8, wherein, The solvent includes at least one of water and a sodium chloride aqueous solution, the mass percentage of the wall surface anchoring agent in the wall surface anchoring agent dispersion liquid is 0.05-0.2%, the mass percentage of the oil-water response brush agent in the oil-water response brush agent dispersion liquid is 0.4-2.0%, and the weight ratio of the wall surface anchoring agent dispersion liquid, the oil-water response brush agent dispersion liquid and the pure water is 1:1:(2.5-3.5).

10. Application of the pore wall surface responsive coating oil-water selective adjusting and plugging agent in any one of claims 1-7 in oil field exploitation.

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