Supramolecular polymer functional unit, supramolecular polymer as well as preparation method and application of supramolecular polymer

Abstract

The invention provides a supramolecular polymer functional unit, a supramolecular polymer as well as a preparation method and application of the supramolecular polymer. The supramolecular polymer functional unit comprises adamantane modified sodium carboxymethyl cellulose and cyclodextrin modified trimesic acid. The supramolecular polymer functional unit is designed according to characteristics and exploitation requirements of a low-permeability oil field, is small in molecular size and easy to inject, and is easy to self-assemble and form a supramolecular aggregate when the supramolecular polymer functional unit and the supramolecular polymer functional unit meet each other, so that the problem that a polymer is difficult to inject in low-permeability oil reservoir development can be possibly solved by utilizing the supramolecular polymer functional unit. The supramolecular polymer functional unit is green and renewable, and does not generate environmental pressure; and the cost is low.

Description

Technical Field

[0001] The invention belongs to the technical field of oil and gas field development, and relates to a supramolecular polymer functional unit, a supramolecular polymer, and a preparation method and application thereof. Background Art

[0002] CNPC has effectively improved crude oil recovery through polymer flooding, binary flooding, and ternary composite flooding technologies, and has achieved significant economic and social benefits. Among them, the results achieved by using polymer flooding technology are particularly significant. At present, how to promote the existing polymer flooding technology to newly developed low-permeability oil fields has become an important task we face.

[0003] As we all know, polymer molecules exist in the form of molecular coils in aqueous solution. There needs to be a certain match between the coil size and the reservoir pore throat. If the polymer molecular coil size does not match the reservoir pore throat, some pores in the reservoir will be inaccessible. At the same time, it will cause irreversible shear and tensile degradation of the polymer, thereby reducing the oil recovery effect. The rock pore size of low-permeability and ultra-low-permeability reservoirs in my country is mostly around a few hundred nanometers. The pore throat size is basically equivalent to the size of the polymer molecular coil currently used. This makes it difficult to directly promote the current mature chemical flooding technology in the exploitation of low-permeability and ultra-low-permeability reservoirs. Therefore, it is of great significance to develop a new polymer flooding technology suitable for the exploitation of low-permeability and ultra-low-permeability reservoirs.

[0004] Most of the polymers used in the current polymer flooding technology are polyacrylamide. In order to make the viscoelasticity of the displacement fluid meet the displacement requirements, the molecular weight of the polyacrylamide used is very large, mostly around 10 million or greater than 10 million. Therefore, the size of its molecular coil in water is basically equivalent to the rock pore size of low-permeability and ultra-low-permeability reservoirs. This makes it very difficult to inject the displacement fluid when these polyacrylamides are used in the exploitation of low-permeability and ultra-low-permeability reservoirs. And due to the shear and stretching effect of the pore size on the polymer molecules. The polymer molecules are degraded, resulting in a decrease in the oil recovery effect, or even a negative effect. At present, the above problems are mainly solved by changing the wettability of the rock and adjusting the molecular weight and molecular structure of the polymer. However, the effect is not good and no significant breakthrough has been achieved. Therefore, it is necessary to develop a new type of polymer to meet the development requirements of low-permeability reservoirs. Supramolecular polymers have the characteristics of environmental responsiveness, self-healing, and low modulus. Using it is likely to solve the problem of difficult polymer injection. This provides us with a new way to develop polymer materials. The research here is of great significance to the design and adjustment of low-permeability reservoir development methods.

[0005] At present, the designed and synthesized supramolecular functional units are mostly for the exploitation of medium and high permeability oil fields. The supramolecular functional units designed for the characteristics and exploitation requirements of low permeability oil fields are very rare. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a supramolecular polymer functional unit, a supramolecular polymer, and a preparation method and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a supramolecular polymer functional unit A, wherein the supramolecular polymer functional unit A is adamantane-modified sodium carboxymethyl cellulose.

[0009] In the present invention, the adamantane-modified sodium carboxymethyl cellulose can be represented by the following structure:

[0010]

[0011] Where x=250 and n=500.

[0012] On the other hand, the present invention provides a method for preparing the supramolecular polymer functional unit A as described above, the preparation method comprising the following steps:

[0013] The sodium carboxymethyl cellulose solution and the adamantane alcohol solution are mixed and reacted to obtain the adamantane-modified sodium carboxymethyl cellulose, which is the supramolecular polymer functional unit A.

[0014] The reaction formula of the reaction is as follows:

[0015]

[0016] In the present invention, the sodium carboxymethyl cellulose solution is an aqueous solution of sodium carboxymethyl cellulose.

[0017] Preferably, the concentration of the sodium carboxymethylcellulose solution is 10-100 mg / mL, for example 10 mg / mL, 15 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL or 100 mg / mL.

[0018] Preferably, the adamantane alcohol solution is an ethanol solution of adamantane alcohol.

[0019] Preferably, the concentration of the adamantane alcohol solution is 10-80 mg / mL, for example 10 mg / mL, 15 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL or 80 mg / mL.

[0020] Preferably, the mass ratio of sodium carboxymethyl cellulose to adamantane alcohol is 1:0.73-1.72, for example, 1:0.73, 1:0.75, 1:0.8, 1:1, 1:1.1, 1:1.3, 1:1.5, 1:1.7 or 1:1.72, etc.

[0021] Preferably, after the mixing, 1-hydroxybenzotriazole (HOBT) and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl) are added to the system.

[0022] Preferably, the concentration of 1-hydroxybenzotriazole in the reaction system is 0-40 mg / mL, for example 0 mg / mL, 1 mg / mL, 3 mg / mL, 5 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL or 40 mg / mL.

[0023] Preferably, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in the reaction system is 10-40 mg / mL, for example 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL or 40 mg / mL.

[0024] Preferably, the reaction is carried out at room temperature.

[0025] Preferably, the reaction time is 12-72 h, for example 12 h, 14 h, 18 h, 20 h, 24 h, 28 h, 30 h, 32 h, 36 h, 40 h, 42 h, 48 h, 50 h, 55 h, 60 h, 65 h, 70 h or 72 h.

[0026] Preferably, dialysis is performed after the reaction is completed.

[0027] Preferably, the dialysis uses a dialysis bag with a molecular weight cut-off of 2000.

[0028] Preferably, the dialysis time is 24-48 h, for example 24 h, 28 h, 30 h, 32 h, 36 h, 40 h, 42 h or 48 h.

[0029] After the dialysis is completed, the solution in the dialysis bag is placed in a freeze dryer for freeze drying, and the obtained solid is the supramolecular polymer functional unit A.

[0030] In another aspect, the present invention provides a supramolecular polymer functional unit B, wherein the supramolecular polymer functional unit B is cyclodextrin-modified trimesic acid.

[0031] In the present invention, the cyclodextrin-modified trimesic acid has the following structure:

[0032]

[0033] Where -CD means The wavy lines represent the attachment sites of the groups.

[0034] On the other hand, the present invention provides a method for preparing the supramolecular polymer functional unit B as described above, the preparation method comprising the following steps:

[0035] Amino-β-cyclodextrin reacts with trimesic acid to obtain cyclodextrin-modified trimesic acid, namely, the supramolecular polymer functional unit B.

[0036] Preferably, the molar ratio of amino-β-cyclodextrin to trimesic acid is 1.9-2.3:1, such as 1.9:1, 2.0:1, 2.1:1, 2.2:1 or 2.3:1.

[0037] Preferably, the solvent for the reaction is water.

[0038] Preferably, the concentration of amino-β-cyclodextrin in the reaction system is 20-120 mg / mL, for example 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, 100 mg / mL, 110 mg / mL or 120 mg / mL.

[0039] Preferably, the concentration of trimesic acid in the reaction system is 2-10 mg / mL, for example 2 mg / mL, 3 mg / mL, 4 mg / mL, 5 mg / mL, 6 mg / mL, 7 mg / mL, 8 mg / mL, 9 mg / mL or 10 mg / mL.

[0040] Preferably, the reaction is carried out in the presence of 1-hydroxybenzotriazole (HOBT) and 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC).

[0041] Preferably, the concentration of 1-hydroxybenzotriazole in the reaction system is 5-20 mg / mL, for example 5 mg / mL, 8 mg / mL, 10 mg / mL, 12 mg / mL, 15 mg / mL, 18 mg / mL or 20 mg / mL.

[0042] Preferably, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide in the reaction system is 0-40 mg / mL, for example, 0 mg / mL, 1 mg / mL, 3 mg / mL, 5 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL or 40 mg / mL.

[0043] Preferably, the reaction is carried out at room temperature, and the reaction time is 24-96 h, for example 24 h, 28 h, 30 h, 32 h, 36 h, 40 h, 42 h, 48 h, 50 h, 55 h, 60 h, 65 h, 70 h, 72 h, 78 h, 80 h, 84 h, 88 h, 90 h, 93 h, 95 h or 96 h.

[0044] Preferably, dialysis is performed after the reaction is completed.

[0045] Preferably, the dialysis uses a dialysis bag with a molecular weight cut-off of 2000.

[0046] Preferably, the dialysis time is 24-96h, for example 24h, 28h, 30h, 32h, 36h, 40h, 42h, 48h, 50h, 55h, 60h, 65h, 70h, 72h, 78h, 80h, 84h, 88h, 90h, 93h, 95h or 96h.

[0047] Preferably, after the dialysis is completed, the solution in the dialysis bag is placed in a freeze dryer for freeze drying, and the obtained solid is the supramolecular polymer functional unit B.

[0048] In the present invention, adamantane-modified sodium carboxymethyl cellulose and cyclodextrin-modified trimesic acid are prepared. For adamantane-modified sodium carboxymethyl cellulose, 1-2 adamantane groups are modified on every 3 carboxymethyl cellulose basic units, and the yield is 32%-65%. For cyclodextrin-modified trimesic acid, the ratio of the number of cyclodextrin to benzene rings is about 2:1, and the yield is 48%-88%.

[0049] In another aspect, the present invention provides a supramolecular aggregate, wherein the supramolecular aggregate is obtained by self-assembly of supramolecular polymer functional units A and B.

[0050] In the present invention, the self-assembly is achieved by mixing a supramolecular polymer functional unit A solution and a supramolecular polymer functional unit B solution with each other, so that the two are spontaneously assembled into a target supramolecular polymer in an aqueous solution.

[0051] When 500ppm of supramolecular polymer functional unit A and 500ppm of supramolecular polymer functional unit B are used for assembly, the viscosity of the solution can be increased by about 5% compared with the solution of 1000ppm supramolecular polymer functional unit A. When 750ppm of supramolecular polymer functional unit A and 750ppm of supramolecular polymer functional unit B are used for assembly, the viscosity of the solution can be increased by about 12% compared with the solution of 1500ppm supramolecular polymer functional unit A. These experimental results show that when the two meet, they can self-assemble to form supramolecular aggregates, thereby increasing the viscosity of the solution.

[0052] Preferably, the mass ratio of the supramolecular polymer functional unit A to the supramolecular polymer functional unit B is 1:1.

[0053] On the other hand, the present invention provides the use of the supramolecular polymer functional unit A, supramolecular polymer functional unit B or supramolecular aggregate as described above in the exploitation of low permeability oil fields.

[0054] Compared with the prior art, the present invention has the following beneficial effects:

[0055] The supramolecular polymer functional unit of the present invention is designed for the characteristics of low-permeability oil fields and the requirements of exploitation. They are small in molecular size and easy to inject. When the two meet, they are easy to self-assemble to form supramolecular aggregates. Using them may solve the problem of difficult injection of polymers in the development of low-permeability oil reservoirs. The supramolecular polymer functional unit is green and renewable, does not generate environmental pressure, and has low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is the H NMR spectrum of sodium carboxymethyl cellulose modified with adamantane.

[0057] Figure 2 This is the H NMR spectrum of cyclodextrin modified trimesic acid. DETAILED DESCRIPTION

[0058] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0059] Example 1

[0060] In this embodiment, a diamond-modified sodium carboxymethyl cellulose is provided, and the preparation method thereof comprises the following steps:

[0061] (1) Dissolve 0.25 g of sodium carboxymethyl cellulose in 25 mL of deionized water to prepare a 10 mg / mL sodium carboxymethyl cellulose solution, which is labeled as solution A; (2) Dissolve 0.43 g of adamantane alcohol in 43 mL of ethanol to prepare a 10 mg / mL adamantane alcohol ethanol solution, which is labeled as solution B; (3) After thoroughly mixing solution A and solution B, add 0.68 g of EDC, and then stir at room temperature for 12 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 24 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid is adamantane-modified sodium carboxymethyl cellulose. The yield is 32%.

[0062] The product was characterized by H NMR spectroscopy. Figure 1 As shown, 1 H NMR (400MHz, D2O) δ = 4.4-3.0 (m, 9119H), 2.16 (s, 1500H), 1.96 (m, 742H), 1.39 (s, 1517H).

[0063] Example 2

[0064] In this embodiment, a diamond-modified sodium carboxymethyl cellulose is provided, and the preparation method thereof comprises the following steps:

[0065] (1) Dissolve 1 g of sodium carboxymethyl cellulose in 25 mL of deionized water to prepare a 40 mg / mL sodium carboxymethyl cellulose solution, which is labeled as solution A; (2) Dissolve 1.4549 g of adamantane alcohol in 43 mL of ethanol to prepare a 34 mg / mL adamantane alcohol ethanol solution, which is labeled as solution B; (3) After thoroughly mixing solution A and solution B, add 1.3583 g of HOBT and 1.9179 g of EDC, and then stir at room temperature for 48 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 48 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid is adamantane-modified sodium carboxymethyl cellulose. The yield is 51%.

[0066] Example 3

[0067] In this embodiment, a diamond-modified sodium carboxymethyl cellulose is provided, and the preparation method thereof comprises the following steps:

[0068] (1) Dissolve 2.5 g of sodium carboxymethyl cellulose in 25 mL of deionized water to prepare a 100 mg / mL sodium carboxymethyl cellulose solution, which is labeled as solution A; (2) Dissolve 3.44 g of adamantane alcohol in 43 mL of ethanol to prepare an 80 mg / mL adamantane alcohol ethanol solution, which is labeled as solution B; (3) After thoroughly mixing solution A and solution B, add 2.72 g of HOBT and 2.72 g of EDC, and stir at room temperature for 72 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 48 h; (5) placing the solution in the dialysis bag in a freeze dryer for freeze drying, and the resulting solid is adamantane-modified sodium carboxymethyl cellulose. The yield is 45%.

[0069] Example 4

[0070] In this embodiment, a diamond-modified sodium carboxymethyl cellulose is provided, and the preparation method thereof comprises the following steps:

[0071] (1) Dissolve 1 g of sodium carboxymethyl cellulose in 25 mL of deionized water to prepare a 40 mg / mL sodium carboxymethyl cellulose solution, which is labeled as solution A; (2) Dissolve 0.73 g of adamantane alcohol in 43 mL of ethanol to prepare a 17 mg / mL adamantane alcohol ethanol solution, which is labeled as solution B; (3) After thoroughly mixing solution A and solution B, add 1.3583 g of HOBT and 1.3583 g of EDC, and then stir at room temperature for 24 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 36 h; (5) placing the solution in the dialysis bag in a freeze dryer for freeze drying, and the resulting solid is adamantane-modified sodium carboxymethyl cellulose. The yield is 65%.

[0072] Example 5

[0073] In this embodiment, a cyclodextrin-modified trimesic acid is provided, and a preparation method thereof comprises the following steps:

[0074] (1) Dissolve 0.4 g of amino-β-cyclodextrin in 20 mL of deionized water to prepare a 20 mg / mL cyclodextrin aqueous solution; (2) Add 0.04 g of trimesic acid to the above cyclodextrin aqueous solution; (3) Add 0.10 g of HOBT and stir at room temperature for 24 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 24 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid is cyclodextrin-modified trimesic acid with a yield of 48%.

[0075] The product was characterized by H NMR spectroscopy. Figure 2 As shown, 1 H NMR (400MHz, D2O) δ = 8.5-8.32 (m, 2.26H), 5.02 (s, 14H), 3.9-3.14 (m, 84H).

[0076] Example 6

[0077] In this embodiment, a cyclodextrin-modified trimesic acid is provided, and a preparation method thereof comprises the following steps:

[0078] (1) Dissolve 1.134 g of amino-β-cyclodextrin in 20 mL of deionized water to prepare a 56.7 mg / mL cyclodextrin aqueous solution; (2) Add 0.06368 g of trimesic acid to the above cyclodextrin aqueous solution; (3) Add 0.163 g of HOBT and 0.23 g of EDC, and stir at room temperature for 72 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 72 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid was cyclodextrin-modified trimesic acid with a yield of 67%.

[0079] Example 7

[0080] In this embodiment, a cyclodextrin-modified trimesic acid is provided, and a preparation method thereof comprises the following steps:

[0081] (1) Dissolve 2.4 g of amino-β-cyclodextrin in 20 mL of deionized water to prepare a 120 mg / mL cyclodextrin aqueous solution; (2) Add 0.2 g of trimesic acid to the above cyclodextrin aqueous solution; (3) Add 0.4 g of HOBT and 0.8 g of EDC, and stir at room temperature for 96 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 96 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid is cyclodextrin-modified trimesic acid with a yield of 56%.

[0082] Example 8

[0083] In this embodiment, a cyclodextrin-modified trimesic acid is provided, and a preparation method thereof comprises the following steps:

[0084] (1) Dissolve 2.26 g of amino-β-cyclodextrin in 20 mL of deionized water to prepare a 113 mg / mL cyclodextrin aqueous solution; (2) Add 0.06368 g of trimesic acid to the above cyclodextrin aqueous solution; (3) Add 0.163 g of HOBT and 0.23 g of EDC, and stir at room temperature for 72 h; (4) After the reaction is completed, transfer the reaction solution to a dialysis bag (M w =2000), followed by dialysis in deionized water for 48 h; (5) placing the solution in the dialysis bag into a freeze dryer for freeze drying, and the resulting solid is cyclodextrin-modified trimesic acid with a yield of 88%.

[0085] Example 9

[0086] 1000mg supramolecular polymer functional unit A was dissolved in 1000mL water to obtain 1000ppm supramolecular polymer functional unit A solution. At the same time, 1000mg supramolecular polymer functional unit B was dissolved in 1000mL water to obtain 1000ppm supramolecular polymer functional unit B solution. 200mL of each of the above solutions was taken, and the two were mixed to obtain 1000ppm supramolecular solution. The viscosity of the solution was 5.6mPa s. The viscosity of 1000ppm supramolecular polymer functional unit A solution was 5.34mPa s. Comparing the two, the viscosity of the supramolecular solution was about 5% higher than that of the supramolecular polymer functional unit A solution.

[0087] Example 10

[0088] 1500mg supramolecular polymer functional unit A was dissolved in 1000mL water to obtain 1500ppm supramolecular polymer functional unit A solution. At the same time, 1550mg supramolecular polymer functional unit B was dissolved in 1000mL water to obtain 1500ppm supramolecular polymer functional unit B solution. 200mL of each of the above solutions was taken, and the two were mixed to obtain 1500ppm supramolecular solution. The viscosity of the solution was 9.5mPa s. The viscosity of 1500ppm supramolecular polymer functional unit A solution was 8mPa s. Comparing the two, the viscosity of the supramolecular solution was about 12% higher than that of the supramolecular polymer functional unit A solution.

[0089] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the supramolecular polymer functional unit, supramolecular polymer and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A supramolecular polymer functional unit A, characterized in that: The supramolecular polymer functional unit A is adamantane-modified sodium carboxymethyl cellulose.

2. The method for preparing the supramolecular polymer functional unit A according to claim 1, characterized in that: The preparation method comprises the following steps: The sodium carboxymethyl cellulose solution and the adamantane alcohol solution are mixed and reacted to obtain the adamantane-modified sodium carboxymethyl cellulose, which is the supramolecular polymer functional unit A.

3. The preparation method according to claim 2, characterized in that: The sodium carboxymethyl cellulose solution is an aqueous solution of sodium carboxymethyl cellulose; Preferably, the concentration of the sodium carboxymethyl cellulose solution is 10-100 mg / mL; Preferably, the adamantane alcohol solution is an ethanol solution of adamantane alcohol; Preferably, the concentration of the adamantane alcohol solution is 10-80 mg / mL.

4. The preparation method according to claim 2 or 3, characterized in that: The mass ratio of the sodium carboxymethyl cellulose to adamantane alcohol is 1:0.73-1.

72.

5. The preparation method according to any one of claims 2 to 4, characterized in that: After the mixing, 1-hydroxybenzotriazole and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added to the system; Preferably, the concentration of 1-hydroxybenzotriazole in the reaction system is 0-40 mg / mL; Preferably, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride in the reaction system is 10-40 mg / mL; Preferably, the reaction is carried out at room temperature; Preferably, the reaction time is 12-72h; Preferably, dialysis is performed after the reaction is completed; Preferably, the dialysis uses a dialysis bag with a molecular weight cut-off of 2000; Preferably, the dialysis time is 24-48h; Preferably, after the dialysis is completed, the solution in the dialysis bag is placed in a freeze dryer for freeze drying, and the obtained solid is the supramolecular polymer functional unit A.

6. A supramolecular polymer functional unit B, characterized in that: The supramolecular polymer functional unit B is cyclodextrin-modified trimesic acid.

7. The supramolecular polymer functional unit B according to claim 6, characterized in that: The cyclodextrin-modified trimesic acid has the following structure: Where -CD means The wavy lines represent the attachment sites of the groups.

8. A method for preparing the supramolecular polymer functional unit B, comprising the following steps: Amino-β-cyclodextrin reacts with trimesic acid to obtain cyclodextrin-modified trimesic acid, namely, the supramolecular polymer functional unit B; Preferably, the molar ratio of amino-β-cyclodextrin to trimesic acid is 1.9-2.3:1; Preferably, the solvent of the reaction is water; Preferably, the concentration of amino-β-cyclodextrin in the reaction system is 20-120 mg / mL; Preferably, the concentration of trimesic acid in the reaction system is 2-10 mg / mL; Preferably, the reaction is carried out in the presence of 1-hydroxybenzotriazole and 1-ethyl-(3-dimethylaminopropyl)carbodiimide; Preferably, the concentration of 1-hydroxybenzotriazole in the reaction system is 5-20 mg / mL; Preferably, the concentration of 1-ethyl-(3-dimethylaminopropyl)carbodiimide in the reaction system is 0-40 mg / mL; Preferably, the reaction is carried out at room temperature and the reaction time is 24-96h; Preferably, dialysis is performed after the reaction is completed; Preferably, the dialysis uses a dialysis bag with a molecular weight cut-off of 2000Da; Preferably, the dialysis time is 24-96h; Preferably, after the dialysis is completed, the solution in the dialysis bag is placed in a freeze dryer for freeze drying, and the obtained solid is the supramolecular polymer functional unit B.

9. A supramolecular aggregate, characterized in that: The supramolecular aggregate is obtained by self-assembly of supramolecular polymer functional unit A and supramolecular polymer functional unit B; Preferably, the mass ratio of the supramolecular polymer functional unit A to the supramolecular polymer functional unit B for self-assembly is 1:

1.

10. Use of the supramolecular polymer functional unit A according to claim 1 or 2, the supramolecular polymer functional unit B according to claim 6 or 7, or the supramolecular aggregate according to claim 9 in exploitation of low permeability oil fields.

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