Polymer, preparation method and application thereof and profile control and displacement agent

Abstract

The application relates to the technical field of chemical oil displacement agents, and discloses a polymer, a preparation method and application thereof, and a profile control and displacement agent. The polymer comprises at least one structural unit A of formula 1, at least one structural unit B of formula 2 and at least one structural unit C of formula 3, Y is selected from a structure of formula I, a structure of formula II, a structure of formula III or a structure of formula IV, a is an integer of 0-22, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, X is halogen independently, and Z is a residue after dehydroxylation of a cyclodextrin. The polymer has strong salt resistance, temperature resistance and adsorption resistance.

Description

Technical Field

[0001] This invention relates to the field of chemical displacement agents, specifically to a polymer, its preparation method and application, and a displacement modifier. Background Technology

[0002] Polymer enhanced oil recovery (EOR) is currently one of the important methods for improving oil recovery in oilfields. Although partially hydrolyzed polyacrylamide (HPAM) exhibits excellent thickening, viscoelastic, and rheological properties, its viscosity decreases sharply with increasing temperature and salinity. In practical applications, it is necessary to increase the HPAM concentration, which leads to a sharp increase in production costs, thus limiting its promotion and application in high-temperature and high-salinity reservoirs. Therefore, the development of temperature- and salt-resistant polymers is crucial for improving oil recovery.

[0003] The paper "Improved viscoelasticity of xanthan gum through self-association with surfactant: β-cyclodextrin inclusion complexes for applications in enhanced oil recovery" (L Romero-Zerón, Rodrigue D. Polymer Engineering & Science, 2015, 55(3):523-532.) describes a self-assembled system with a host-guest network structure formed by mixing cyclodextrin with xanthan gum and ionic surfactants to improve oil recovery. However, the system exhibits only weak interactions and poor anti-adsorption properties.

[0004] Therefore, there is an urgent need to provide a supramolecular polymer with temperature resistance, salt resistance, and adsorption resistance. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor temperature resistance, salt resistance and anti-adsorption properties of polymers in the prior art, and to provide a polymer, its preparation method and application, as well as a modulator, wherein the polymer has strong salt resistance, temperature resistance and anti-adsorption properties.

[0006] To achieve the above objectives, a first aspect of the present invention provides a polymer, wherein the polymer comprises at least one structural unit A of formula (1), at least one structural unit B of formula (2), and at least one structural unit C of formula (3), wherein,

[0007]

[0008] Where R1 is H, C1-C 18Alkyl groups, -R2-SO3H, -R3-COOH or Wherein, R2 is a C3-C4 straight-chain or branched alkyl group, R3 is a C4-C8 straight-chain or branched alkyl group, n is an integer from 0 to 2, R4 is H or a C1-C4 straight-chain alkyl group, and R5 is H or methyl.

[0009] Y is selected from the structure shown in Formula I, the structure shown in Formula II, the structure shown in Formula III, or the structure shown in Formula IV.

[0010]

[0011]

[0012] Where a is an integer from 0 to 22, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, and X is a halogen independently;

[0013] Z represents the residue after the dehydroxylation of cyclodextrin.

[0014] The second aspect of the present invention provides a method for preparing a polymer, wherein the method includes: mixing at least one monomer A of formula (4), at least one monomer B of formula (5) and at least one monomer C of formula (6) with water to obtain a monomer mixed solution, adjusting the pH value of the monomer mixed solution, adding an initiator, carrying out a polymerization reaction under a nitrogen atmosphere, and obtaining a polymer after post-treatment;

[0015]

[0016] Where R1' represents H, C1-C 18 Alkyl groups, -R2'-SO3H, -R3'-COOH or Wherein, R2' is a C3-C4 straight-chain or branched alkyl group, R3' is a C4-C8 straight-chain or branched alkyl group, n' is an integer from 0 to 2, R4' is H or a C1-C4 straight-chain alkyl group, and R5' is H or methyl.

[0017] Y' is selected from the structure shown in Formula I', the structure shown in Formula II', the structure shown in Formula III', or the structure shown in Formula IV'.

[0018]

[0019]

[0020] Where a' is an integer from 0 to 22, b' is 2, c' is 1, d' is 2 or 3, R6' is -COO- or -CO-NH-, and X' is a halogen independently;

[0021] Z' represents the residue after the dehydroxylation of cyclodextrin.

[0022] A third aspect of the present invention provides a polymer prepared by the above-described preparation method.

[0023] A fourth aspect of the present invention provides an application of the above-mentioned polymer as a modulator / drive agent.

[0024] A fifth aspect of the present invention provides an application of the above-mentioned polymer as an oil stain detergent.

[0025] A sixth aspect of the present invention provides a modulating agent, wherein the modulating agent comprises the above-mentioned polymer and water.

[0026] The polymer, its preparation method, its application, and the modulator provided by the present invention, through the above technical solutions, have the following beneficial effects:

[0027] The polymer of the present invention contains structural unit A shown in formula (1), structural unit B shown in formula (2), and structural unit C shown in formula (3), which gives the polymer excellent temperature resistance, salt resistance, and anti-adsorption properties. Specifically, through structural unit C, cyclodextrin with a rigid structure is introduced into the polymer through covalent bonds, which gives it obvious temperature resistance, salt resistance, and shear resistance. The viscosity retention rate of the polymer is ≥90% at 85°C, which is characterized by high temperature resistance, reaching above 85°C. At a mineralization of 100,000 mg / L, the viscosity retention rate of the polymer is ≥80%, which is characterized by high salt resistance, reaching a mineralization of 100,000 mg / L or more. The introduction of structural unit B shown in formula (2) gives the polymer excellent anti-adsorption properties, and the static adsorption viscosity retention rate of the polymer is ≥85%.

[0028] The polymer prepared by the present invention using monomers shown in formulas (4) to (6) as raw materials has excellent temperature resistance, salt resistance and anti-adsorption properties; and using maleic acid cyclodextrin esters as raw materials is environmentally friendly. At the same time, the synthesis conditions of the polymer are easy to control, the reaction process is stable, and it is easy to industrialize.

[0029] The oil displacement agent made from the polymer of the present invention has excellent oil displacement effect, with a static oil removal rate of ≥90%. When the polymer of the present invention is applied to oil stain detergent, due to the introduction of an internally hydrophilic and externally hydrophobic cyclodextrin structure into the polymer, it has the properties of a surfactant, thus it can exert a washing effect without phase separation, and the oil stain cleaning rate reaches more than 80%. Detailed Implementation

[0030] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0031] A first aspect of the present invention provides a polymer, wherein the polymer comprises at least one structural unit A of formula (1), at least one structural unit B of formula (2), and at least one structural unit C of formula (3), wherein,

[0032]

[0033] Where R1 is H, C1-C 18 Alkyl groups, -R2-SO3H, -R3-COOH or Wherein, R2 is a C3-C4 straight-chain or branched alkyl group, R3 is a C4-C8 straight-chain or branched alkyl group, n is an integer from 0 to 2, R4 is H or a C1-C4 straight-chain alkyl group, and R5 is H or methyl.

[0034] Y is selected from the structure shown in Formula I, the structure shown in Formula II, the structure shown in Formula III, or the structure shown in Formula IV.

[0035]

[0036] Where a is an integer from 0 to 22, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, and X is a halogen independently;

[0037] Z represents the residue after the dehydroxylation of cyclodextrin.

[0038] In this invention, the polymer contains structural unit A as shown in formula (1), structural unit B as shown in formula (2), and structural unit C as shown in formula (3), which gives the polymer excellent temperature resistance, salt resistance, and anti-adsorption properties. Specifically, through structural unit C, cyclodextrin with a rigid structure is introduced into the polymer through covalent bonds, giving it significant temperature resistance, salt resistance, and shear resistance. At 85°C, the polymer's viscosity retention rate is ≥90%, exhibiting high temperature resistance, with a temperature resistance of over 85°C. At a mineralization of 100,000 mg / L, the polymer's viscosity retention rate is ≥80%, exhibiting high salt resistance, with a salt resistance capacity of over 100,000 mg / L. The introduction of structural unit B as shown in formula (2) gives the polymer excellent anti-adsorption properties, with a static adsorption viscosity retention rate of ≥85%.

[0039] In this invention, the carbon atom in R6 is connected to the carbon atom in formula (2).

[0040] Furthermore, R1 is H, C3-C 12 Alkyl groups, -R2-SO3H, -R3-COOH or In this configuration, R2 is isobutyl; R3 is isobutyl, n is 0 or 1, R4 is H or a C1-C2 alkyl group, and R5 is H.

[0041] Furthermore, a is an integer from 0 to 18, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, and X is chloride ion.

[0042] Furthermore, the cyclodextrin is selected from at least one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, and 2-hydroxypropyl-γ-cyclodextrin.

[0043] According to the present invention, based on the total mass of the polymer, the content of structural unit A is 40-65 wt%, the content of structural unit B is 5-30 wt%, and the content of structural unit C is 15-40 wt%.

[0044] In this invention, when the contents of structural unit A, structural unit B and structural unit C in the copolymer meet the above-mentioned limits, the polymer has better temperature resistance, salt resistance and anti-adsorption properties.

[0045] In this invention, the sum of the contents of structural unit A, structural unit B and structural unit C is 100 wt%.

[0046] Furthermore, based on the total mass of the polymer, the content of structural unit A is 45-63 wt%, the content of structural unit B is 7-29 wt%, and the content of structural unit C is 18-35 wt%.

[0047] According to the present invention, the structural unit B includes the structure shown in formula (2-1) and the structure shown in formula (2-2);

[0048]

[0049] In this invention, when both the structure shown in formula (2-1) and the structure shown in formula (2-2) are used as structural unit B, the two structures can produce a synergistic effect, further improving the polymer's temperature resistance, salt resistance and anti-adsorption properties.

[0050] According to the present invention, in the structural unit B, the weight ratio of the structure shown in formula (2-1) to the structure shown in formula (2-2) is 1-4:1.

[0051] Furthermore, in the structural unit B, the weight ratio of the structure shown in equation (2-1) to the structure shown in equation (2-2) is 1-3.5:1.

[0052] According to the present invention, the polymer has a viscosity-average relative molecular weight of 1,000,000-8,000,000 g / mol.

[0053] Furthermore, the polymer has a viscosity-average relative molecular weight of 1,000,000-6,000,000 g / mol.

[0054] The second aspect of the present invention provides a method for preparing a polymer, wherein the method includes: mixing at least one monomer A of formula (4), at least one monomer B of formula (5) and at least one monomer C of formula (6) with water to obtain a monomer mixed solution, adjusting the pH value of the monomer mixed solution, adding an initiator, carrying out a polymerization reaction under a nitrogen atmosphere, and obtaining a polymer after post-treatment;

[0055]

[0056] Where R1' represents H, C1-C 18 Alkyl groups, -R2'-SO3H, -R3'-COOH or Wherein, R2' is a C3-C4 straight-chain or branched alkyl group, R3' is a C4-C8 straight-chain or branched alkyl group, n' is an integer from 0 to 2, R4' is H or a C1-C4 straight-chain alkyl group, and R5' is H or methyl.

[0057] Y' is selected from the structure shown in Formula I', the structure shown in Formula II', the structure shown in Formula III', or the structure shown in Formula IV'.

[0058]

[0059]

[0060] Where a' is an integer from 0 to 22, b' is 2, c' is 1, d' is 2 or 3, R6' is -COO- or -CO-NH-, and X' is a halogen independently;

[0061] Z' represents the residue after the dehydroxylation of cyclodextrin.

[0062] In this invention, the polymer prepared by using the monomers shown in formulas (4) to (6) as raw materials has excellent temperature resistance, salt resistance and anti-adsorption properties; and the use of maleic acid cyclodextrin esters as raw materials is environmentally friendly. At the same time, the synthesis conditions of the polymer are easy to control, the reaction process is stable, and it is easy to industrialize.

[0063] In this invention, maleic acid-cyclodextrin esters can be prepared according to existing technical methods. Preferably, the preparation method of maleic acid-cyclodextrin esters includes: weighing cyclodextrin (α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin or 2-hydroxypropyl-γ-cyclodextrin) and maleic anhydride at a mass ratio of 1:0.5-1.5, mixing with N,N-dimethylformamide, and heating the mixture solution at 70-90°C for 8-12 hours. After the reaction is complete, the solution is cooled, chloroform is added, and then washed with acetone and dried.

[0064] In this invention, the carbon atom in R6' is connected to the carbon atom in formula (6).

[0065] Furthermore, R1' is H, C3-C 12 Alkyl groups, -R2'-SO3H, -R3'-COOH or Wherein, R2' is isobutyl; R3' is isobutyl, n' is 0 or 1, R4' is H or a C1-C2 alkyl group, and R5' is H.

[0066] Furthermore, a' is an integer from 0 to 18, b' is 2, c' is 1, d' is 2 or 3, R6' is -COO- or -CO-NH-, and X' is chloride ion.

[0067] Furthermore, the cyclodextrin is selected from at least one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, and 2-hydroxypropyl-γ-cyclodextrin.

[0068] According to the present invention, based on the total mass of monomers A, B, and C, the amount of monomer A is 40-65 wt%, the amount of monomer B is 5-30 wt%, and the amount of monomer C is 15-40 wt%.

[0069] In this invention, when the amounts of monomer A, monomer B, and monomer C are within the above-mentioned range, the temperature resistance, salt resistance, and anti-adsorption properties of the polymer can be improved.

[0070] Furthermore, based on the total mass of monomers A, B, and C, the amount of monomer A is 45-63 wt%, the amount of monomer B is 7-29 wt%, and the amount of monomer C is 18-35 wt%.

[0071] According to the present invention, the monomer B includes the structure shown in (5-1) and the structure shown in formula (5-2);

[0072]

[0073] In this invention, when monomer B adopts the above combination, the obtained polymer has high temperature resistance, high salt resistance and high anti-adsorption properties.

[0074] According to the present invention, the ratio of the amount of monomer B in the structure shown in formula (5-1) to the amount of monomer B in the structure shown in formula (5-2) is 1-4:1 relative to the total amount of monomer B.

[0075] According to the present invention, the initiator is selected from at least one of sodium bisulfite, sodium thiosulfate, sodium metabisulfite, potassium persulfate, sodium persulfate, hydrogen peroxide, 2,2'-azo[2-(2-imidazolin-2-yl)propane] dihydrochloride, azobis(2,5-dimethyl-6-carboxy)hexanonitrile, and 4,4'-azobis(4-cyanopentanoic acid).

[0076] In this invention, when the above-mentioned initiator is used, it is more conducive to the polymerization reaction between monomers, so that the polymer has the characteristic of low homopolymer content, and the obtained polymer has excellent temperature resistance, salt resistance and anti-adsorption properties.

[0077] Furthermore, the initiator is an initiator composition of potassium persulfate and sodium bisulfite, or an initiator composition of ammonium persulfate and sodium bisulfite.

[0078] In a preferred embodiment of the present invention, the sodium bisulfite is 20-35 parts by weight relative to 100 parts by weight of the initiator composition.

[0079] According to the present invention, the amount of initiator added is 0.1-0.6 wt%, based on the total mass of monomers A, B and C.

[0080] Furthermore, based on the total mass of monomers A, B, and C, the amount of initiator added is 0.3-0.6 wt%.

[0081] According to the present invention, the pH value of the monomer mixture solution is adjusted to 6-8.

[0082] In this invention, the monomer mixture solution is generally acidic. Those skilled in the art can adjust the pH of the monomer mixture solution using an alkaline solution according to the actual situation. Preferably, the alkaline solution can be a sodium hydroxide solution or a potassium hydroxide solution.

[0083] According to the present invention, the polymerization reaction is carried out at a temperature of 5-50°C for 6-9 hours.

[0084] In this invention, when the polymerization reaction meets the above conditions, it is more conducive to the polymerization between monomers, and the reaction process is stable.

[0085] Furthermore, the polymerization reaction is carried out at a temperature of 10-40°C for 7-8 hours.

[0086] In this invention, the post-processing includes: precipitation with an organic solvent, filtration, drying, and pulverization. The organic solvent may be selected from acetone, ethanol, or methanol.

[0087] A third aspect of the present invention provides a polymer prepared by the above-described preparation method.

[0088] According to the present invention, the polymer has a viscosity-average relative molecular weight of 1,000,000-8,000,000 g / mol.

[0089] Furthermore, the polymer has a viscosity-average relative molecular weight of 1,000,000-6,000,000 g / mol.

[0090] A fourth aspect of the present invention provides an application of the above-mentioned polymer as a modulator / drive agent.

[0091] The polymers used in this invention have excellent temperature resistance, salt resistance, and anti-adsorption properties, making them suitable for oil displacement operations. Furthermore, the resulting modifiers have excellent oil displacement effects, with a static deoiling rate of ≥90%, which can meet the oil displacement needs of oil fields.

[0092] A fifth aspect of the present invention provides an application of the above-mentioned polymer as an oil stain detergent.

[0093] When the polymer of the present invention is applied to an oil stain detergent, it has the properties of a surfactant due to the introduction of a cyclodextrin structure with an inner hydrophilic and an outer hydrophobic structure. Therefore, it can exert a washing effect without phase separation, and the oil stain cleaning rate reaches more than 80%.

[0094] In this invention, water and polymer can be mixed according to actual needs to prepare an oil stain detergent. For example, the polymer can be formulated into a 1-3 wt% aqueous solution for use as an oil stain detergent, and the cleaning time can be 10-25 minutes.

[0095] A sixth aspect of the present invention provides a modulating agent, wherein the modulating agent comprises the above-mentioned polymer and water.

[0096] In this invention, the modulator has excellent temperature resistance, salt resistance and anti-adsorption properties, can adapt to the environment of oil displacement operation, and the prepared modulator has excellent oil displacement effect with a static oil removal rate ≥90%.

[0097] According to the present invention, the polymer is 0.1-5 parts by weight, preferably 0.1-2.5 parts by weight, relative to 100 parts by weight of water.

[0098] According to the present invention, the modulator further comprises a surfactant.

[0099] In this invention, the type and amount of surfactant can be conventionally selected in the art, and are not limited herein. For example, the surfactant is 0.1-10 parts by weight relative to 100 parts by weight of water.

[0100] The present invention will be described in detail below through embodiments.

[0101] The content of each structural unit in the polymer was obtained by estimating the proportion of raw materials.

[0102] The viscosity-average relative molecular weight of the polymer was determined by the calculation method of intrinsic viscosity and viscosity-average relative molecular mass in SY / T 5862-2020.

[0103] Oil removal rate: The oil removal test was conducted under normal pressure. Specifically: (1) Prepared oil sand: Mix the quartz sand and crude oil at a mass ratio of 8:2, and then put them into an oven to age for 24 hours at a formation temperature of 45℃; (2) Put 15g of oil sand into an oil removal bottle, compact it, and then inject polymer solution to the 1mL mark. Then put it into a constant temperature box and record the volume of oil produced at regular intervals. The oil removal rate was calculated by dividing the volume of oil produced by the volume of crude oil by 100%.

[0104] Oil stain cleaning rate: The ratio of the mass of oil stains removed by cleaning to the total mass of oil stains on the test panel; specifically, cleaning is carried out by immersion at 25°C for 15 minutes.

[0105] The salt resistance of the polymer was evaluated: 0.01 wt% aqueous solutions of the polymer were prepared using both clean water and 100,000 mg / L saline solution. The apparent viscosity (in cP) of each solution was measured using a Brookfield viscometer at 25°C and a rotation speed of 6 r / min. The viscosity retention rate in the 100,000 mg / L saline solution was calculated as: (apparent viscosity of the polymer in the 100,000 mg / L saline solution to apparent viscosity of the polymer in clean water) × 100%.

[0106] The temperature resistance of the polymer was evaluated: a 0.01 wt% aqueous solution of the polymer was prepared with water. Using a Brookfield viscometer at a rotation speed of 6 r / min, the apparent viscosity (in cP) of each solution was measured at 25℃, 45℃, 65℃, and 85℃. The viscosity retention rate at 85℃ was calculated as 100% of the ratio of the apparent viscosity of the polymer at 85℃ to the apparent viscosity of the polymer at 25℃.

[0107] The anti-adsorption property of the polymer was evaluated by the static adsorption viscosity retention rate. The method included: (1) washing quartz sand with a particle size range of 30-40 mesh with deionized water and drying it at 105°C, repeating twice. The polymer was prepared into a polymer aqueous solution with a mass concentration of 0.01wt% with water. The apparent viscosity (in cP) of the polymer aqueous solution was tested at 75°C and a rotation speed of 6r / min using a Brookfield viscometer, and recorded as η0. (2) 25g of quartz sand was placed in a 250mL stoppered bottle, 75g of polymer aqueous solution was added, and the mixture was shaken well and placed in a constant temperature water bath shaker. The shaking frequency was 120 times / min, and the mixture was shaken repeatedly at 30°C for 24h. The sample was taken out, centrifuged, and the supernatant was collected. The solution was preheated in a constant temperature water bath and the apparent viscosity (in cP) of the solution was tested again at 75°C and a rotation speed of 6r / min, and recorded as η1. The static adsorption viscosity retention rate is η1 / η0×100%.

[0108] Maleic anhydride, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, and 2-hydroxypropyl-γ-cyclodextrin are all commercially available products of Shanghai Aladdin Biochemical Technology Co., Ltd.

[0109] Initiator composition A: The mass ratio of ammonium persulfate to sodium bisulfite is 1:0.5;

[0110] Initiator composition B: The mass ratio of potassium persulfate to sodium bisulfite is 1:0.4;

[0111] All other raw materials used in the examples and comparative examples are commercially available products.

[0112] The room temperature described in the preparation example is 25°C.

[0113] Preparation Example 1

[0114] Preparation of maleic acid-α-cyclodextrin esterified product: 9 g of α-cyclodextrin, 9 g of maleic anhydride, and 8 mL of N,N-dimethylformamide were stirred and mixed. The mixture was heated at 80 °C for 10 hours. After the reaction was complete, the solution was cooled to room temperature. A white precipitate was obtained after adding 60 mL of chloroform, and then washed with a large amount of acetone. Finally, it was dried in a vacuum oven at 80 °C to obtain the maleic acid-α-cyclodextrin esterified product.

[0115] Preparation Example 2

[0116] Preparation of maleic acid-β-cyclodextrin esterified product: 11 g of β-cyclodextrin, 10 g of maleic anhydride, and 10 mL of N,N-dimethylformamide were stirred and mixed. The mixture was heated at 80 °C for 10 hours. After the reaction was complete, the solution was cooled to room temperature. A white precipitate was obtained after adding 60 mL of chloroform, and then washed with a large amount of acetone. Finally, it was dried in a vacuum oven at 80 °C to obtain the maleic acid-β-cyclodextrin esterified product.

[0117] Preparation Example 3

[0118] Preparation of maleic acid-γ-cyclodextrin esterified product: 12 g of γ-cyclodextrin, 11 g of maleic anhydride, and 11 mL of N,N-dimethylformamide were stirred and mixed. The mixture was heated at 80 °C for 10 hours. After the reaction was complete, the solution was cooled to room temperature. A white precipitate was obtained after adding 60 mL of chloroform, and then washed with a large amount of acetone. Finally, it was dried in a vacuum oven at 80 °C to obtain the maleic acid-γ-cyclodextrin esterified product.

[0119] Preparation Example 4

[0120] Preparation of maleic acid-2-hydroxypropyl-β-cyclodextrin ester: 14 g of 2-hydroxypropyl-propylcyclodextrin, 13 g of maleic anhydride, and 15 mL of N,N-dimethylformamide were stirred and mixed. The mixture was heated at 80 °C for 10 hours. After the reaction was complete, the solution was cooled to room temperature. A white precipitate was obtained after adding 60 mL of chloroform, and then washed with a large amount of acetone. Finally, it was dried in a vacuum oven at 80 °C to obtain maleic acid-2-hydroxypropyl-β-cyclodextrin ester.

[0121] Preparation Example 5

[0122] Preparation of maleic acid-2-hydroxypropyl-γ-cyclodextrin esterified product: 16 g of 2-hydroxypropyl-propylcyclodextrin, 15 g of maleic anhydride, and 18 mL of N,N-dimethylformamide were stirred and mixed. The mixture was heated at 80 °C for 10 hours. After the reaction was complete, the solution was cooled to room temperature. A white precipitate was obtained after adding 60 mL of chloroform, and then washed with a large amount of acetone. Finally, it was dried in a vacuum oven at 80 °C to obtain maleic acid-2-hydroxypropyl-γ-cyclodextrin esterified product.

[0123] Example 1

[0124] 0.54 g of N-vinylpyrrolidone, 0.16 g of allyltrimethylammonium chloride, 5.3 g of 2-acrylamide-2-methylpropanesulfonic acid, and 3 g of maleic acid-β-cyclodextrin ester were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0125] The prepared polymer contains:

[0126] Structural unit A ( Where R1 is R4 is H);

[0127] Structural Unit B ( Equation (2-1) and The combination of formula (2-2), where R5 is H and X is chloride ion;

[0128] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0129] Based on the total mass of the polymer, the content of structural unit A is 58.9 wt%, the content of structural unit B is 7.8 wt% (6 wt% in formula (2-1) and 1.8 wt% in formula (2-2), with a weight ratio of 3.3:1), and the content of structural unit C is 33.3 wt%.

[0130] Example 2

[0131] 5.3 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.7 g of allyltrimethylammonium chloride, and 3 g of maleic acid-β-cyclodextrin ester were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0132] The prepared polymer contains:

[0133] Structural unit A ( Where R1 is R4 is H);

[0134] Structural Unit B ( Where R5 is H and X is chloride ion;

[0135] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0136] Based on the total mass of the polymer, the content of structural unit A is 58.9 wt%, the content of structural unit B is 7.8 wt%, and the content of structural unit C is 33.3 wt%.

[0137] Example 3

[0138] 5.3 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.7 g of N-vinylpyrrolidone, and 3 g of maleic acid-β-cyclodextrin ester were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0139] The prepared polymer contains:

[0140] Structural unit A ( Where R1 is R4 is H);

[0141] Structural Unit B ( Where R5 is H);

[0142] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0143] Based on the total mass of the polymer, the content of structural unit A is 58.9 wt%, the content of structural unit B is 7.8 wt%, and the content of structural unit C is 33.3 wt%.

[0144] Example 4

[0145] 1.4 g of N-vinylpyrrolidone, 3.6 g of acrylamide, and 2.5 g of maleic acid-α-cyclodextrin ester were dissolved in 42.5 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.03 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 6 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0146] The prepared polymer contains:

[0147] Structural unit A ( Where R1 and R4 are both H);

[0148] Structural Unit B ( Where R5 is H, and Y is );

[0149] Structural unit C ( Where Z represents the residue after dehydroxylation of α-cyclodextrin;

[0150] Based on the total mass of the polymer, the content of structural unit A is 48 wt%, the content of structural unit B is 18.7 wt%, and the content of structural unit C is 33.3 wt%.

[0151] Example 5

[0152] 2.6 g of acryloyloxyethyltrimethylammonium chloride, 4.9 g of N-dodecylacrylamide, and 2.5 g of maleic acid-γ-cyclodextrin ester were dissolved in 40 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 8 with NaOH solution. 0.03 g of initiator composition B (potassium persulfate and sodium bisulfite) was added, and the reaction was carried out at 40 °C for 8 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0153] The prepared polymer contains:

[0154] Structural unit A ( Where R1 is C 12 Alkyl group, where R4 is H);

[0155] Structural Unit B ( Where R5 is H, and Y is

[0156] Structural unit C ( Where Z represents the residue after the dehydroxylation of γ-cyclodextrin;

[0157] Based on the total mass of the polymer, the content of structural unit A is 49 wt%, the content of structural unit B is 26 wt%, and the content of structural unit C is 25 wt%.

[0158] Example 6

[0159] 3.1 g of methacryloyloxyethyl dimethyl benzyl ammonium chloride, 5.9 g of N-isopropylacrylamide, and 2 g of maleic-2-hydroxypropyl-β-cyclodextrin ester were dissolved in 39 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 8 with NaOH solution. Then, 0.05 g of initiator composition B (potassium persulfate and sodium bisulfite) was added, and the reaction was carried out at 45 °C for 8 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0160] The prepared polymer contains:

[0161] Structural unit A ( Wherein, R1 is isopropyl and R4 is H);

[0162] Structural Unit B ( Where R5 is H, and Y is

[0163] Structural unit C ( Where Z represents the residue after dehydroxylation of 2-hydroxypropyl-β-cyclodextrin;

[0164] Based on the total mass of the polymer, the content of structural unit A is 53.6 wt%, the content of structural unit B is 28.2 wt%, and the content of structural unit C is 18.2 wt%.

[0165] Example 7

[0166] 2.2 g of (3-acrylamidopropyl)trimethylammonium chloride, 7.8 g of N-hydroxypropylacrylamide, and 2.5 g of maleic-2-hydroxypropyl-γ-cyclodextrin ester were dissolved in 37.5 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 8 with NaOH solution. Then, 0.05 g of initiator composition B (potassium persulfate and sodium bisulfite) was added, and the reaction was carried out at 40 °C for 9 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0167] The prepared polymer contains:

[0168] Structural unit A ( Where R1 is a hydroxyl group and R4 is an H group;

[0169] Structural Unit B ( Where R5 is H, and Y is

[0170] Structural unit C ( Where Z represents the residue after the dehydroxylation of 2-hydroxypropyl-γ-cyclodextrin;

[0171] Based on the total mass of the polymer, the content of structural unit A is 62.4 wt%, the content of structural unit B is 17.6 wt%, and the content of structural unit C is 20 wt%.

[0172] Example 8

[0173] 0.4 g of N-vinylpyrrolidone, 0.2 g of allyltrimethylammonium chloride, 4.4 g of 2-acrylamide-2-methylpropanesulfonic acid, and 5 g of maleic acid-β-cyclodextrin ester were dissolved in 40 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0174] The prepared polymer contains:

[0175] Structural unit A ( Where R1 is R4 is H);

[0176] Structural Unit B ( Equation (2-1) and The combination of formula (2-2), where R5 is H and X is chloride ion;

[0177] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0178] Based on the total mass of the polymer, the content of structural unit A is 44 wt%, the content of structural unit B is 6 wt% (4 wt% in formula (2-1) and 2 wt% in formula (2-2), with a weight ratio of 2:1), and the content of structural unit C is 50 wt%.

[0179] Example 9

[0180] 0.6 g of N-vinylpyrrolidone, 0.1 g of allyltrimethylammonium chloride, 5.3 g of 2-acrylamide-2-methylpropanesulfonic acid, and 3 g of maleic acid-β-cyclodextrin ester were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0181] The prepared polymer contains:

[0182] Structural unit A ( Where R1 is R4 is H);

[0183] Structural Unit B ( Equation (2-1) and The combination of formula (2-2), where R5 is H and X is chloride ion;

[0184] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0185] Based on the total mass of the polymer, the content of structural unit A is 58.9 wt%, the content of structural unit B is 7.8 wt% (6.7 wt% in formula (2-1) and 1.1 wt% in formula (2-2), with a weight ratio of 6.1:1), and the content of structural unit C is 33.3 wt%.

[0186] Comparative Example 1

[0187] 6 g of 2-acrylamide-2-methylpropanesulfonic acid and 3 g of maleic-maleic acid cyclodextrin ester were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0188] Structural unit A ( Where R1 is R4 is H);

[0189] Structural unit C ( Where Z represents the residue after the dehydroxylation of β-cyclodextrin;

[0190] Based on the total mass of the polymer, the content of structural unit A is 66.7 wt%, and the content of structural unit C is 33.3 wt%.

[0191] Comparative Example 2

[0192] 8.3 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.54 g of N-vinylpyrrolidone, and 0.16 g of allyltrimethylammonium chloride were dissolved in 41 g of deionized water. Nitrogen gas was introduced, and the pH of the system was adjusted to 6 with NaOH solution. 0.04 g of initiator composition A (ammonium persulfate and sodium bisulfite) was added, and the reaction was carried out at 10 °C for 7 hours. The system was cooled to room temperature, precipitated with acetone, filtered, dried, and pulverized to obtain the polymer. The polymer test results are shown in Table 1.

[0193] Structural unit A ( Where R1 is R4 is H);

[0194] Structural Unit B ( B-1 and Combination B-2, where R5' is H and X is chloride ion;

[0195] Based on the total mass of the polymer, the content of structural unit A is 92.2 wt%, and the content of structural unit B is 7.8 wt% (6 wt% in formula (2-1), 1.8 wt% in formula (2-2), with a weight ratio of 3.3:1).

[0196] Table 1

[0197]

[0198]

[0199] Test Example 1

[0200] The salt resistance of the polymers in Examples 1-9 and Comparative Examples 1-2 was evaluated. The results are shown in Table 2.

[0201] Table 2

[0202]

[0203] Test Example 2

[0204] The temperature resistance properties of the polymers in Examples 1-9 and Comparative Examples 1-2 were evaluated, and the results are shown in Table 3.

[0205] Table 3

[0206]

[0207] Test Example 3

[0208] The anti-adsorption properties of the polymers in Examples 1-9 and Comparative Examples 1-2 were evaluated, and the results are shown in Table 4.

[0209] Table 4

[0210] <![CDATA[η0 / cP]]> <![CDATA[η1 / cP]]> Static adsorption viscosity retention rate / % Example 1 14.8 13.2 89 Example 2 13.9 12.2 88 Example 3 13.5 11.7 87 Example 4 12.4 10.7 86 Example 5 12. 10.3 86 Example 6 11.6 9.9 85 Example 7 11 9.4 85 Example 8 14.4 12.4 86 Example 9 14.7 12.8 87 Comparative Example 1 7.5 4.8 64 Comparative Example 2 5.9 3 51

[0211] The results show that the polymer of the present invention contains structural unit A as shown in formula (1), structural unit B as shown in formula (2), and structural unit C as shown in formula (3). The obtained polymer has the following characteristics: (1) high temperature resistance, with a viscosity retention rate ≥90% at 85°C; (2) excellent salt resistance, with a viscosity retention rate ≥80% at a mineralization of 100,000 mg / L; and (3) excellent anti-adsorption properties, with a static adsorption viscosity retention rate ≥85%. Furthermore, when structural unit B of the present invention contains specific structures shown in formula (2-1) and formula (2-2), a synergistic effect can be generated, further improving the polymer's temperature resistance, salt resistance, and anti-adsorption properties.

[0212] Test Example 4

[0213] Polymers from Examples 1-9 and Comparative Examples 1-2 were used to prepare polymer aqueous solutions with a mass concentration of 0.01 wt% using water. Sodium dodecyl sulfonate was added to 100 parts by weight of water to prepare the degreasing agent. The deoiling rate of each agent was tested, and the results are shown in Table 5.

[0214] Test Example 5

[0215] The polymers from Examples 1-9 and Comparative Examples 1-2 were mixed with water to prepare 2.5 wt% aqueous solutions, i.e., oil stain detergents. Their oil stain removal efficiency was tested, and the results are shown in Figure 5.

[0216] Table 5

[0217] Oil removal rate / vol% Oil stain removal rate / wt% Example 1 98 87 Example 2 97 85 Example 3 96 84 Example 4 94 83 Example 5 92 82 Example 6 91 82 Example 7 90 81 Example 8 95 82 Example 9 97 86 Comparative Example 1 76 67 Comparative Example 2 41 55

[0218] As shown in Table 5, compared with Comparative Examples 1-2, the oil displacement agent made from the polymer of the present invention has a superior oil displacement effect, with a static oil removal rate ≥90%. Furthermore, when the preferred method is adopted, the oil displacement effect of the oil displacement agent of the present invention is even better. In the oil stain detergent made from the polymer of the present invention, due to the introduction of an internally hydrophilic and externally hydrophobic cyclodextrin structure into the polymer, it possesses surfactant properties, thus exhibiting a washing effect without phase separation, and achieving an oil stain removal rate of over 80%. When the preferred embodiment of the present invention is adopted, the washing performance of the oil stain detergent is even stronger.

[0219] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polymer, characterized in that, The polymer comprises at least one structural unit A of formula (1), at least one structural unit B of formula (2), and at least one structural unit C of formula (3), wherein, Equation (1), Equation (2), Equation (3), Where R1 is H, C1-C 18 Alkyl groups, -R2-SO3H, -R3-COOH or Wherein, R2 is a C3-C4 straight-chain or branched alkyl group, R3 is a C4-C8 straight-chain or branched alkyl group, n is an integer from 0 to 2, R4 is H or a C1-C4 straight-chain alkyl group, and R5 is H or methyl. Y is selected from the structure shown in Formula I, the structure shown in Formula II, the structure shown in Formula III, or the structure shown in Formula IV. Formula I; Formula II; Formula III; Formula IV; Where a is an integer from 0 to 22, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, and X is a halogen independently; Z represents the residue after the dehydroxylation of cyclodextrin; Based on the total mass of the polymer, the content of structural unit A is 40-65 wt%; the content of structural unit B is 5-30 wt%; and the content of structural unit C is 15-40 wt%.

2. The polymer according to claim 1, wherein, R1 is H, C3-C 12 Alkyl groups, -R2-SO3H, -R3-COOH or Wherein, R2 is isobutyl; R3 is isobutyl, n is 0 or 1, R4 is H or a C1-C2 alkyl group, and R5 is H; And / or, a is an integer from 0 to 18, b is 2, c is 1, d is 2 or 3, R6 is -COO- or -CO-NH-, and X is chloride ion; And / or, the cyclodextrin is selected from at least one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin and 2-hydroxypropyl-γ-cyclodextrin.

3. The polymer according to claim 1, wherein, Based on the total mass of the polymer, the content of structural unit A is 45-63 wt%; the content of structural unit B is 7-29 wt%; and the content of structural unit C is 18-35 wt%.

4. The polymer according to any one of claims 1-3, wherein, The structural unit B includes the structure shown in equation (2-1) and the structure shown in equation (2-2); Equation (2-1); Equation (2-2).

5. The polymer according to claim 4, wherein, In the structural unit B, the weight ratio of the structure shown in formula (2-1) to the structure shown in formula (2-2) is 1-4:

1.

6. The polymer according to any one of claims 1-3 and 5, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-8,000,000 g / mol.

7. The polymer according to claim 6, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-6,000,000 g / mol.

8. The polymer according to claim 4, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-8,000,000 g / mol.

9. The polymer according to claim 8, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-6,000,000 g / mol.

10. A method for preparing a polymer, characterized in that, The method includes: mixing at least one monomer A of formula (4), at least one monomer B of formula (5) and at least one monomer C of formula (6) with water to obtain a monomer mixed solution, adjusting the pH value of the monomer mixed solution, adding an initiator, carrying out a polymerization reaction under a nitrogen atmosphere, and obtaining a polymer after post-treatment; Equation (4); Equation (5); Equation (6); Where R1' represents H, C1-C 18 Alkyl groups, -R2'-SO3H, -R3'-COOH or Wherein, R2' is a C3-C4 straight-chain or branched alkyl group, R3' is a C4-C8 straight-chain or branched alkyl group, n' is an integer from 0 to 2, R4' is H or a C1-C4 straight-chain alkyl group, and R5' is H or methyl. Y' is selected from the structure shown in Formula I', the structure shown in Formula II', the structure shown in Formula III', or the structure shown in Formula IV'. Formula I'; Formula II'; Formula III'; Formula IV'; Where a' is an integer from 0 to 22, b' is 2, c' is 1, d' is 2 or 3, R6' is -COO- or -CO-NH-, and X' is a halogen independently; Z' represents the residue after the dehydroxylation of cyclodextrin; Specifically, based on the total mass of monomers A, B, and C, the amount of monomer A is 40-65 wt%; the amount of monomer B is 5-30 wt%; and the amount of monomer C is 15-40 wt%.

11. The preparation method according to claim 10, wherein, R1' represents H, C3-C 12 Alkyl groups, -R2'-SO3H, -R3'-COOH or Wherein, R2' is isobutyl; R3' is isobutyl, n' is 0 or 1, R4' is H or a C1-C2 alkyl group, and R5' is H; And / or, a' is an integer from 0 to 18, b' is 2, c' is 1, d' is 2 or 3, R6' is -COO- or -CO-NH-, and X' is chloride ion; And / or, the cyclodextrin is selected from at least one of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin and 2-hydroxypropyl-γ-cyclodextrin.

12. The preparation method according to claim 10 or 11, wherein, Based on the total mass of monomers A, B, and C, the amount of monomer A is 45-63 wt%; the amount of monomer B is 7-29 wt%; and the amount of monomer C is 18-35 wt%.

13. The preparation method according to claim 10 or 11, wherein, The monomer B includes the structure shown in (5-1) and the structure shown in formula (5-2); Equation (5-1); Equation (5-2).

14. The preparation method according to claim 13, wherein, The ratio of monomer B used in the structure shown in Equation (5-1) to that used in the structure shown in Equation (5-2) is 1-4:1, relative to the total amount of monomer B used.

15. The preparation method according to claim 12, wherein, The monomer B includes the structure shown in (5-1) and the structure shown in formula (5-2); Equation (5-1); Equation (5-2).

16. The preparation method according to claim 15, wherein, The ratio of monomer B used in the structure shown in Equation (5-1) to that used in the structure shown in Equation (5-2) is 1-4:1, relative to the total amount of monomer B used.

17. The preparation method according to any one of claims 10-11 and 14-16, wherein, The initiator is selected from at least one of sodium bisulfite, sodium thiosulfate, sodium metabisulfite, potassium persulfate, sodium persulfate, hydrogen peroxide, 2,2'-azo[2-(2-imidazolin-2-yl)propane] dihydrochloride, azobis(2,5-dimethyl-6-carboxy)hexanonitrile, and 4,4'-azobis(4-cyanopentanoic acid); And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.1-0.6 wt%.

18. The preparation method according to claim 17, wherein, The initiator is an initiator composition of potassium persulfate and sodium bisulfite, or an initiator composition of ammonium persulfate and sodium bisulfite; And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.3-0.6 wt%.

19. The preparation method according to claim 12, wherein, The initiator is selected from at least one of sodium bisulfite, sodium thiosulfate, sodium metabisulfite, potassium persulfate, sodium persulfate, hydrogen peroxide, 2,2'-azo[2-(2-imidazolin-2-yl)propane] dihydrochloride, azobis(2,5-dimethyl-6-carboxy)hexanonitrile, and 4,4'-azobis(4-cyanopentanoic acid); And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.1-0.6 wt%.

20. The preparation method according to claim 19, wherein, The initiator is an initiator composition of potassium persulfate and sodium bisulfite, or an initiator composition of ammonium persulfate and sodium bisulfite; And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.3-0.6 wt%.

21. The preparation method according to claim 13, wherein, The initiator is selected from at least one of sodium bisulfite, sodium thiosulfate, sodium metabisulfite, potassium persulfate, sodium persulfate, hydrogen peroxide, 2,2'-azo[2-(2-imidazolin-2-yl)propane] dihydrochloride, azobis(2,5-dimethyl-6-carboxy)hexanonitrile, and 4,4'-azobis(4-cyanopentanoic acid); And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.1-0.6 wt%.

22. The preparation method according to claim 21, wherein, The initiator is an initiator composition of potassium persulfate and sodium bisulfite, or an initiator composition of ammonium persulfate and sodium bisulfite; And / or, based on the total mass of said monomers A, B and C, the amount of said initiator added is 0.3-0.6 wt%.

23. The preparation method according to any one of claims 10-11, 14-16, and 18-20, wherein, Adjust the pH of the monomer mixture solution to 6-8; And / or, the polymerization reaction temperature is 5-50°C; the polymerization reaction time is 7-8 hours.

24. The preparation method according to claim 23, wherein, The polymerization reaction is carried out at a temperature of 10-40℃.

25. The preparation method according to claim 12, wherein, Adjust the pH of the monomer mixture solution to 6-8; And / or, the polymerization reaction temperature is 5-50°C; the polymerization reaction time is 7-8 hours.

26. The preparation method according to claim 25, wherein, The polymerization reaction is carried out at a temperature of 10-40℃.

27. The preparation method according to claim 13, wherein, Adjust the pH of the monomer mixture solution to 6-8; And / or, the polymerization reaction temperature is 5-50°C; the polymerization reaction time is 7-8 hours.

28. The preparation method according to claim 27, wherein, The polymerization reaction is carried out at a temperature of 10-40℃.

29. The preparation method according to claim 17, wherein, Adjust the pH of the monomer mixture solution to 6-8; And / or, the polymerization reaction temperature is 5-50°C; the polymerization reaction time is 7-8 hours.

30. The preparation method according to claim 29, wherein, The polymerization reaction is carried out at a temperature of 10-40℃.

31. A polymer prepared by the method according to any one of claims 10-30.

32. The polymer according to claim 31, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-8,000,000 g / mol.

33. The polymer according to claim 32, wherein, The polymer has a viscosity-average relative molecular weight of 1,000,000-6,000,000 g / mol.

34. The use of the polymer according to any one of claims 1-9, 31-33 as a modulator / demodulator.

35. The use of the polymer according to any one of claims 1-9, 31-33 as an oil stain detergent.

36. A modulator, characterized in that, The modulator comprises the polymer and water as described in any one of claims 1-9 and 31-33.

37. The modulator according to claim 36, wherein, The polymer is 0.1-5 parts by weight relative to 100 parts by weight of water; And / or, the modulator may further comprise a surfactant.

38. The modulator according to claim 37, wherein, The polymer is 0.1-2.5 parts by weight relative to 100 parts by weight of water.

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