Water-soluble thermosetting resins and their preparation methods, curable resin compositions, epoxy resin products and their preparation methods

Abstract

The present invention relates to the fields of synthesis of polymer materials and exploitation of oil and gas reservoirs, and discloses a water-soluble thermosetting resin, a preparation method thereof, a curable resin composition, an epoxy resin product and a preparation method thereof. The water-soluble thermosetting resin has a structure shown in Formula I: wherein, R1 is an alkylene group with 1 to 4 carbon atoms; A is wherein, R2 and R3 are each independently H, CH3, CF3 or CH2CH3; M1 and M2 are each independently H, K or Na, and at least one of M1 and M2 is H; 0 < m1 + m2 ≤ 8. This water-soluble thermosetting resin has a specific structure, and the epoxy resin product prepared therefrom has a low swelling rate in water and hydrocarbon solvents and a high pressure-bearing strength after a long time at high temperature.

Description

Technical Field

[0001] This invention relates to the fields of polymer material synthesis and oil and gas reservoir development, specifically to a water-soluble thermosetting resin and its preparation method, a curable resin composition, and an epoxy resin product and its preparation method. Background Technology

[0002] Waterborne thermosetting resins, especially waterborne epoxy resins, have excellent application prospects in coatings and special working conditions due to their environmental friendliness and the good mechanical properties, processability, temperature resistance and bonding properties of cured products.

[0003] There are currently two methods for preparing waterborne epoxy resins: one is external emulsification, which involves dispersing epoxy resin particles in water by adding an emulsifier; the other is self-emulsification, which involves introducing hydrophilic groups such as polyoxyethylene segments onto the epoxy resin chain, allowing it to disperse in water through its own emulsifying properties. External emulsification is achieved through mechanical methods, i.e., pre-grinding solid epoxy resin into micron-sized epoxy resin powder using a ball mill, colloid mill, or homogenizer, then adding an aqueous emulsifier solution, and finally dispersing the particles in water through mechanical stirring; or mixing epoxy resin and emulsifier, heating to a suitable temperature, and gradually adding water under vigorous stirring to form an emulsion. The advantages of mechanical methods for preparing waterborne epoxy resin emulsions are simple process and low emulsifier dosage. However, the dispersed epoxy resin particles in the emulsion are relatively large, with irregular shapes and wide size distribution, resulting in poor emulsion stability and easy particle collision and coagulation. Self-emulsification, a chemical modification method, involves the hydrophobic polymer chains agglomerating into particles when the modified polymer is emulsified with water. Ionic or polar groups are distributed on the surface of these particles, repelling each other due to their like charge. Under certain kinetic conditions, a stable waterborne epoxy resin emulsion can be formed. This is the basic principle of chemical modification for preparing waterborne epoxy resins. Based on the different properties of the introduced surface-active hydrophilic groups, waterborne epoxy resin emulsions prepared by chemical modification can be classified into three types: anionic, cationic, and nonionic.

[0004] Neither external emulsification nor self-emulsification methods yield cured products with interconnected pores. To function as a formation support material in fracturing operations during oilfield development, a water-soluble, aqueous epoxy resin is necessary, where homogeneous curing allows water to occupy spaces that form interconnected pores. To achieve this, this patented technology provides a water-soluble thermosetting resin and its preparation method, a curable resin composition, and epoxy resin products and their preparation methods, enabling the long-term maintenance of the morphological structure under the complex and harsh environment of oil wells, providing high-speed and high-efficiency oil and gas channels. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of epoxy resin swelling and structural damage when exposed to water at high temperatures in the prior art. This invention provides a water-soluble thermosetting resin and its preparation method, a curable resin composition, epoxy resin products and their preparation method. The water-soluble thermosetting resin has a specific structure, and the epoxy resin products made from it have high compressive strength. Furthermore, the epoxy resin products have a low swelling rate and can still maintain their shape and structure after being exposed to a high-temperature water environment for a long time.

[0006] To achieve the above objectives, a first aspect of the present invention provides a water-soluble thermosetting resin, wherein the water-soluble thermosetting resin has the structure shown in Formula I:

[0007]

[0008] Wherein, R1 is a C1-C4 alkylene group;

[0009] A is Among them, R2 and R3 are each independently H, CH3, CF3 or CH2CH3;

[0010] M1 and M2 are each uniquely H, K or Na, and at least one of M1 and M2 is H;

[0011] 0 <m1+m2≤8。

[0012] A second aspect of the present invention provides a method for preparing a water-soluble thermosetting resin, wherein the preparation method includes:

[0013] S1. In the presence of a first catalyst and water, bisphenol compounds are contacted with a sulfonating agent to carry out a sulfonation reaction, thereby obtaining sulfonated bisphenol compounds;

[0014] S2. In the presence of a second catalyst and water, sulfonated bisphenol compounds are contacted with monomer A shown in Formula II to carry out a polycondensation reaction to obtain the water-soluble thermosetting resin.

[0015] Where p is an integer from 1 to 4, and X is Cl or Br;

[0016] The mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.025-0.3.

[0017] A third aspect of the present invention provides a water-soluble thermosetting resin prepared by the above-described preparation method.

[0018] A fourth aspect of the present invention provides a curable resin composition, wherein the curable resin composition comprises a first component and a second component, wherein the first component and the second component exist independently of each other;

[0019] The first component includes the above-mentioned water-soluble thermosetting resin;

[0020] The second component includes a curing agent.

[0021] The fifth aspect of the present invention provides an epoxy resin article, wherein the epoxy resin article is obtained by mixing and curing the above-mentioned curable resin composition.

[0022] A sixth aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method includes:

[0023] The first component, which contains the above-mentioned water-soluble thermosetting resin, and the second component, which contains a curing agent, are mixed and cured to obtain the epoxy resin product.

[0024] Through the above technical solutions, the water-soluble thermosetting resin and its preparation method, the curable resin composition, the epoxy resin product and its preparation method provided by the present invention achieve the following beneficial effects:

[0025] The water-soluble thermosetting resin provided by this invention has a specific structure. The benzene ring provides a rigid structure, and the epoxy group has the property of forming a network structure by undergoing ring-opening reaction with hydroxyl, carboxyl, amide, and amine groups. The appropriate content of sulfonic acid groups makes the formed epoxy resin have a certain degree of hydrophilicity. The epoxy resin products made from it have high compressive strength. Furthermore, after the epoxy resin products are exposed to a high-temperature water environment for a long time, the swelling rate is low and they can still maintain their morphological structure.

[0026] The epoxy resin product provided in this invention is made from a water-soluble thermosetting resin containing a specific structure and a curing agent. The epoxy resin product has high compressive strength. Furthermore, after being exposed to a high-temperature water environment for a long time, the epoxy resin product has a low swelling rate and can still maintain its shape and structure, making it suitable for oil and gas reservoir exploitation under harsh conditions. Detailed Implementation

[0027] 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.

[0028] A first aspect of the present invention provides a water-soluble thermosetting resin, wherein the water-soluble thermosetting resin has the structure shown in Formula I:

[0029]

[0030] Wherein, R1 is a C1-C4 alkylene group;

[0031] A is Among them, R2 and R3 are each independently H, CH3, CF3 or CH2CH3;

[0032] M1 and M2 are each uniquely H, K or Na, and at least one of M1 and M2 is H;

[0033] 0 <m1+m2≤8。

[0034] In this invention, the water-soluble thermosetting resin, while having good hydrophilicity, also maintains a high epoxy equivalent (100-400 g / eq), and can form a cured product with a honeycomb-like interconnected pore structure and a relatively dense cross-linked structure with the curing agent, which has a fairly high compressive strength in terms of engineering mechanics and bulk structure.

[0035] In this invention, the water-soluble thermosetting resin has a specific structure as shown in Formula I. Specifically, the water-soluble thermosetting resin contains some sulfonic acid groups (SO3H). Under the action of the sulfonic acid groups, the thermosetting resin has a certain hydrophilic property, which makes the epoxy resin product obtained after curing the curable resin composition containing the water-soluble thermosetting resin have high compressive strength. Furthermore, after the epoxy resin product is exposed to a high-temperature water environment for a long time, the swelling rate is low and it can still maintain its shape and structure.

[0036] According to the present invention, R1 is a C1-C2 alkylene group.

[0037] According to the present invention, A is Among them, R2 and R3 are independently H, CH3, CH2CH3 or CF3.

[0038] According to the present invention, M1 is H and M2 is Na.

[0039] According to the present invention, the pH value of the water-soluble thermosetting resin is 1-6.

[0040] According to the present invention, the sulfur content of the water-soluble thermosetting resin is 6-20 wt%.

[0041] In this invention, when the pH value and S content of the water-soluble thermosetting resin meet the above-mentioned range, the thermosetting resin has a certain hydrophilic property, which makes the epoxy resin product obtained after curing the curable resin composition containing the water-soluble thermosetting resin have high compressive strength. Furthermore, after the epoxy resin product is exposed to a high-temperature water environment for a long time, the swelling rate is low and it can still maintain its morphological structure.

[0042] Furthermore, the pH value of the water-soluble thermosetting resin is 2-4.

[0043] Furthermore, the sulfur content of the water-soluble thermosetting resin is 10-15 wt%.

[0044] According to the present invention, the epoxy equivalent of the waterborne thermosetting resin is 100-400 g / eq, preferably 150-250 g / eq.

[0045] According to the present invention, the weight-average molecular weight of the water-soluble thermosetting resin is 2000-10000 g / mol, preferably 3000-5000 g / mol.

[0046] A second aspect of the present invention provides a method for preparing a water-soluble thermosetting resin, wherein the preparation method includes:

[0047] S1. In the presence of a first catalyst and water, bisphenol compounds are contacted with a sulfonating agent to carry out a sulfonation reaction, thereby obtaining sulfonated bisphenol compounds;

[0048] S2. In the presence of a second catalyst and water, sulfonated bisphenol compounds are contacted with monomer A shown in Formula II to carry out a polycondensation reaction to obtain the water-soluble thermosetting resin.

[0049] Where p is an integer from 1 to 4, and X is Cl or Br;

[0050] The mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.025-0.3.

[0051] In this invention, under a specific amount of catalyst, a sulfonated bisphenol compound obtained from a bisphenol compound is condensed with a monomer A of a specific structure to obtain a water-soluble thermosetting resin. The water-soluble thermosetting resin contains some sulfonic acid groups (SO3H), which makes the epoxy resin product obtained after curing the curable resin composition containing the water-soluble thermosetting resin have high compressive strength. Furthermore, the epoxy resin product has a low swelling rate after being exposed to a high-temperature water environment for a long time and can still maintain its morphological structure.

[0052] According to the present invention, the mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.05-0.18.

[0053] In this invention, when the mass ratio of the sulfonated bisphenol compound to the second catalyst meets the above-mentioned limit, the sulfonation temperature is reduced by about 20°C, making the reaction conditions more mild. The resulting water-soluble thermosetting resin has certain hydrophilic properties, and the epoxy resin products made from it have higher compressive strength. Furthermore, after the epoxy resin products are exposed to a high-temperature water environment for a long time, the swelling rate is lower, and they can still maintain their morphological structure.

[0054] According to the present invention, in step S1, the bisphenol compound is selected from at least one of bisphenol A, bisphenol S, bisphenol B, bisphenol F and bisphenol AF.

[0055] According to the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0056] According to the present invention, the first catalyst is a Lewis acid.

[0057] In this invention, there are no special requirements for the specific type of Lewis acid. Any Lewis acid of conventional type in the art that can catalyze the sulfonation reaction between bisphenol compounds and sulfonating agents can be used, such as titanium tetrachloride, ferric chloride, ferric oxide, zirconium oxychloride, aluminum oxide, aluminum trichloride, hydrated tin tetrachloride, etc.

[0058] According to the present invention, the molar ratio of the bisphenol compound to the sulfonating agent is 1:1-5, preferably 1:2-3.

[0059] According to the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0003-0.0005, preferably 1:0.00035-0.00045.

[0060] According to the present invention, in step S2, in formula II, p is an integer from 1 to 2, and X is Cl.

[0061] In this invention, when p is the value mentioned above, the strength of the water-soluble thermosetting resin is further improved.

[0062] According to the present invention, the second catalyst is a base.

[0063] According to a preferred embodiment of the present invention, the alkali is NaOH.

[0064] According to the present invention, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.25-0.625, preferably 1:0.25-0.5.

[0065] In this invention, the mass ratio of the sulfonated bisphenol compound to monomer A affects the curing and pressure resistance of the product. When the above-mentioned limitations are met, the epoxy resin product obtained after curing the curable resin composition containing the product has high pressure resistance. Furthermore, the epoxy resin product has a low swelling rate and can still maintain its morphological structure after being exposed to a high-temperature water environment for a long time.

[0066] According to the present invention, the conditions for the sulfonation reaction include: a reaction temperature of 120-150°C and a reaction time of 1-6 hours.

[0067] Furthermore, the sulfonation reaction conditions include: a reaction temperature of 120-130℃ and a reaction time of 2-4 hours.

[0068] According to the present invention, the conditions for the polycondensation reaction include: a reaction temperature of 50-80°C and a reaction time of 2-3 hours.

[0069] Furthermore, the conditions for the polycondensation reaction include: a reaction temperature of 50-70°C and a reaction time of 2.5-3 hours.

[0070] A third aspect of the present invention provides a water-soluble thermosetting resin prepared by the above-described preparation method.

[0071] A fourth aspect of the present invention provides a curable resin composition, wherein the curable resin composition comprises a first component and a second component, wherein the first component and the second component exist independently of each other;

[0072] The first component includes the above-mentioned water-soluble thermosetting resin;

[0073] The second component includes a curing agent.

[0074] In this invention, the first component may also include conventional additives in the art, such as emulsifiers. There are no special requirements for the specific type and amount of emulsifier. Conventional types of emulsifiers in the art can be used and added in accordance with conventional amounts in the art.

[0075] In this invention, there are no special requirements for the specific type and amount of curing agent. Conventional curing agents in the art can be used, as long as the curable resin composition is cured.

[0076] According to a preferred embodiment of the present invention, the curing agent is a bisphenol phenolic resin.

[0077] According to the present invention, the amount of the second component is 40-80 parts by weight relative to 100 parts by weight of the first component.

[0078] The fifth aspect of the present invention provides an epoxy resin article, wherein the epoxy resin article is obtained by mixing and curing the above-mentioned curable resin composition.

[0079] A sixth aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method includes:

[0080] The first component, which contains the above-mentioned water-soluble thermosetting resin, and the second component, which contains a curing agent, are mixed and cured to obtain the epoxy resin product.

[0081] In this invention, there are no particular limitations on the equipment used for mixing epoxy resin products. Conventional equipment in the art can be used to mix the first and second components in the epoxy resin products, such as a twin-screw extruder or a mixer, as long as it can achieve sufficient mixing of the first and second components.

[0082] According to the present invention, the curing conditions include: a curing temperature of 70-150°C and a curing time of 2-6 hours.

[0083] According to the present invention, the curing conditions include: a curing temperature of 90-150°C and a curing time of 4-6 hours.

[0084] The present invention will be described in detail below through embodiments. In the following embodiments and comparative examples,

[0085] The structure of the water-soluble thermosetting resin was determined by 1H NMR spectroscopy.

[0086] The pH value of water-soluble thermosetting resins is measured using a pH meter.

[0087] The epoxy equivalent of water-soluble thermosetting resins was determined by hydrochloric acid-pyridine.

[0088] The weight-average molecular weight of the water-soluble thermosetting resin was determined by gel permeation chromatography (GPC).

[0089] The sulfur (S) content in water-soluble thermosetting resins was determined by elemental analysis.

[0090] All raw materials used in the preparation examples, examples, application examples and their respective comparative examples are commercially available products.

[0091] Example A - Preparation of water-soluble thermosetting resin

[0092] Example A1

[0093] S1: 57g bisphenol A, 50g concentrated sulfuric acid (98wt%) and 0.0257g ferric chloride were reacted at a constant temperature of 130℃ for 4h to obtain 101.75g ​​sulfonated bisphenol compound H1; the molar ratio of bisphenol A to concentrated sulfuric acid was 1:2 and the mass ratio of bisphenol A to ferric chloride was 1:0.00045.

[0094] S2: Add 48g of sulfonated bisphenol compound H1, 2.4g of NaOH, and 12g of epichlorohydrin (monomer A, p = 1, X = Cl) to water, and react at a constant temperature of 50℃ for 3h to obtain water-soluble thermosetting resin A1 (A = 1). Wherein, R2 and R3 are CH3; M1 is H and M2 is Na; the mass ratio of sulfonated bisphenol compound H1 to NaOH is 1:0.05, the mass ratio of sulfonated bisphenol compound H1 to epichlorohydrin is 1:0.25, the S element content of water-soluble epoxy resin A1 is 14.66wt%, the pH value is 3.5, the epoxy equivalent is 195g / mol, and the weight-average molecular weight is 4285g / mol, as detailed in Table 1.

[0095] Example A2

[0096] S1: Add 57g of bisphenol A, 75g of concentrated sulfuric acid (98wt%) and 0.02g of aluminum trichloride to water, and react at a constant temperature of 120℃ for 4h to obtain 118.5g of sulfonated bisphenol compound H2; the molar ratio of bisphenol A to concentrated sulfuric acid is 1:3, and the mass ratio of bisphenol A to aluminum trichloride is 1:0.00035.

[0097] S2: Add 48g of sulfonated bisphenol compound H2, 8.64g of NaOH, and 24g of epichlorohydrin (monomer A, p = 1, X = Br) to water, and react at a constant temperature of 50℃ for 2.5h to obtain water-soluble thermosetting resin A2 (A = Br). Wherein, R2 and R3 are CH3; M1 is H and M2 is Na; the mass ratio of sulfonated bisphenol compound H2 to NaOH is 1:0.18, the mass ratio of sulfonated bisphenol compound H2 to epichlorohydrin is 1:0.5, the S element content of water-soluble epoxy resin A2 is 12.64wt%, the pH value is 4, the epoxy equivalent is 186g / mol, and the weight-average molecular weight is 4662g / mol, as detailed in Table 1.

[0098] Example A3

[0099] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that bisphenol A was replaced with 60.5g of bisphenol B, concentrated sulfuric acid was replaced with an equal amount of chlorosulfonic acid, and the mass of NaOH was 6.05g, so that the mass ratio of sulfonated bisphenol compounds to NaOH was 1:0.1, and water-soluble thermosetting resin A3 was obtained. The content of S element, pH value, epoxy equivalent and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0100] Examples A4-A6

[0101] Example A4

[0102] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 7.2g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.15, and water-soluble thermosetting resin A4 was obtained. The content of S element, pH value, epoxy equivalent and weight-average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0103] Example A5

[0104] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 1.2g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.025, and water-soluble thermosetting resin A5 was obtained. The content of S element, pH value, epoxy equivalent and weight-average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0105] Example A6

[0106] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 14.4 g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.3, and water-soluble thermosetting resin A6 was obtained. The content of S element, pH value, epoxy equivalent and weight average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0107] Examples A7-A8

[0108] Example A7

[0109] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of concentrated sulfuric acid was 25g, so that the molar ratio of bisphenol A to concentrated sulfuric acid was 1:1, and water-soluble thermosetting resin A7 was obtained. The content of sulfur element, pH value, epoxy equivalent and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0110] Example A8

[0111] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of concentrated sulfuric acid was 125g, so that the molar ratio of bisphenol A to concentrated sulfuric acid was 1:5, and water-soluble thermosetting resin A8 was obtained. The content of sulfur element, pH value, epoxy equivalent and weight-average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0112] Examples A9-A10

[0113] Example A9

[0114] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of ferric chloride was 0.0171 g, so that the molar ratio of bisphenol A to ferric chloride was 1:0.0003, and water-soluble thermosetting resin A9 was obtained. The content of sulfur element, pH value, epoxy equivalent and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0115] Example A10

[0116] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of ferric chloride was 0.0285 g, so that the molar ratio of bisphenol A to ferric chloride was 1:0.0005, and water-soluble thermosetting resin A10 was obtained. The content of sulfur element, pH value, epoxy equivalent and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0117] Example A11

[0118] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of epibromopropane was 30g, so that the mass ratio of sulfonated bisphenol compound to epibromopropane was 1:0.625, and water-soluble thermosetting resin A11 was obtained. The content of S element, pH value, epoxy equivalent and weight-average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0119] Example A12

[0120] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 1.2 g, the mass of concentrated sulfuric acid was 150 g, the mass of ferric chloride was 0.0114 g, and the mass of epibromopropane was 11.52 g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.025, the molar ratio of bisphenol A to concentrated sulfuric acid was 1:6, the molar ratio of bisphenol A to ferric chloride was 1:0.0002, and the mass ratio of sulfonated bisphenol compound to epibromopropane was 1:0.24, resulting in water-soluble thermosetting resin A12. The sulfur content, pH value, epoxy equivalent, and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0121] Example A13

[0122] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 14.4 g, the mass of concentrated sulfuric acid was 20.83 g, the mass of ferric chloride was 0.0342 g, and the mass of epibromopropane was 31.2 g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.3, the molar ratio of bisphenol A to concentrated sulfuric acid was 1.2:1, the molar ratio of bisphenol A to ferric chloride was 1:0.0006, and the mass ratio of sulfonated bisphenol compound to epibromopropane was 1:0.65, resulting in water-soluble thermosetting resin A13. The sulfur content, pH value, epoxy equivalent, and weight-average molecular weight of the water-soluble thermosetting resin are shown in Table 1.

[0123] Comparative Examples

[0124] Comparative Example 1

[0125] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 0.48 g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.01, and water-soluble thermosetting resin DA1 was obtained. The content of S element, pH value, epoxy equivalent and weight-average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0126] Comparative Example 2

[0127] A water-soluble thermosetting resin was prepared according to the preparation method of Example A1, except that the mass of NaOH was 24g, so that the mass ratio of sulfonated bisphenol compound to NaOH was 1:0.5, and water-soluble thermosetting resin DA2 was obtained. The content of S element, pH value, epoxy equivalent and weight average molecular weight of water-soluble thermosetting resin are shown in Table 1.

[0128] Table 1

[0129]

[0130]

[0131] Example B - Preparation of Curable Resin Composition

[0132] Take 100 parts by weight of the water-soluble thermosetting resin (first component) of Example A and 60 parts by weight of the curing agent polyethylene polyamine to obtain curable resin composition B.

[0133] Application Example - Epoxy Resin Products

[0134] The curable resin composition of Example B was mixed and cured at 150°C for 6 hours to obtain an epoxy resin product. The properties of the epoxy resin product were tested, and the results are shown in Table 3.

[0135] The compressive strength of epoxy resin products at 120℃ was measured using a universal testing machine.

[0136] The test method for the swelling rate of epoxy resin products is as follows:

[0137] The length and diameter of the epoxy resin product were precisely measured with vernier calipers (three measurements at different positions were taken and the average value was taken), and recorded as L0 and d0. Then, the product was completely immersed in water and heated at 90°C for 12 hours. After taking it out, the length and diameter were measured with vernier calipers (three measurements at different positions were taken and the average value was taken), and recorded as L1 and d1.

[0138] The length swelling ratio is calculated as (L0-L1) / L0×100%.

[0139] The diameter swelling ratio is calculated as (d0-d1) / d0×100%.

[0140] Table 3

[0141]

[0142]

[0143] As can be seen from the results in Table 3, the epoxy resin products prepared by curing the water-soluble thermosetting resin of the present invention not only have excellent compressive strength, but also have a low swelling rate after being immersed in water at high temperature for a long time. This indicates that the epoxy resin products can still maintain their original structure under high pressure. Furthermore, the epoxy resin products can still maintain their morphological structure after being in a high-temperature water environment for a long time, which meets the requirements of oil and gas reservoir exploitation.

[0144] 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 method for producing a water-soluble thermosetting resin, characterized by, The preparation method comprises: S1, in the presence of a first catalyst and water, a bisphenol compound is contacted with a sulfonating agent to perform a sulfonation reaction, to obtain a sulfonated bisphenol compound; S2, in the presence of a second catalyst and water, the sulfonated bisphenol compound is contacted with a monomer A shown in formula II to perform a polycondensation reaction, to obtain the water-soluble thermosetting resin; Formula II; wherein p is an integer from 1 to 4 and X is CI or Br; The mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.025-0.3; The bisphenol compound is bisphenol A; The molar ratio of the bisphenol compound to the sulfonating agent is 1:1-5; The second catalyst is NaOH.

2. The production method according to claim 1, wherein, The mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.05-0.

18.

3. The production method according to claim 1 or 2, wherein The sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and sulfamic acid; And / or, the first catalyst is a Lewis acid; And / or, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0003-0.0005.

4. The production method according to claim 1 or 2, wherein The molar ratio of the bisphenol compound to the sulfonating agent is 1:2-3; And / or, the mass ratio of the bisphenol compound to the first catalyst is 1:0.00035-1:0.00045.

5. The production method according to claim 1 or 2, wherein In step S2, in formula II, p is an integer of 1-2, and X is Cl; And / or, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.25-1:0.

625.

6. The production method according to claim 1 or 2, wherein The conditions of the sulfonation reaction include: the reaction temperature is 120-150℃, and the reaction time is 1-6h.

7. The production method according to claim 1 or 2, wherein The conditions of the polycondensation reaction include: the reaction temperature is 50-80℃, and the reaction time is 2-3h.

8. The water-soluble thermosetting resin prepared by the preparation method in any one of claims 1-7.

9. The water-soluble thermosetting resin according to claim 8, wherein, The weight average molecular weight of the water-soluble thermosetting resin is 2000-10000g / mol.

10. The water-soluble thermosetting resin according to claim 8 or 9, wherein, The pH value of the water-soluble thermosetting resin is 1-6; And / or, the content of S element in the water-soluble thermosetting resin is 6-20wt%; And / or, the epoxy equivalent weight of the water-soluble thermosetting resin is 100-400g / eq; And / or, the weight average molecular weight of the water-soluble thermosetting resin is 3000-5000g / mol.

11. The water-soluble thermosetting resin according to claim 10, wherein, The pH value of the water-soluble thermosetting resin is 2-4; And / or, the content of S element in the water-soluble thermosetting resin is 10-15wt%; And / or, the epoxy equivalent weight of the water-soluble thermosetting resin is 150-250g / eq.

12. A curable resin composition characterized by comprising: The curable resin composition comprises a first component and a second component, wherein the first component and the second component are each independently present; The first component comprises the water-soluble thermosetting resin in any one of claims 8-11; The second component comprises a curing agent.

13. The curable resin composition of claim 12, wherein, The amount of the second component is 40-80 parts by weight relative to 100 parts by weight of the first component.

14. An epoxy resin article, characterized by, The epoxy resin product is prepared by mixing and curing the curable resin composition in claim 12 or 13.

15. A method of producing an epoxy resin product, characterized by, The preparation method comprises: Mixing the first component containing the water-soluble thermosetting resin according to any one of claims 8-11 and the second component containing the curing agent, and curing to obtain the epoxy resin product.

16. The method of manufacturing according to claim 15, wherein, The curing conditions include a curing temperature of 70-150℃ and a curing time of 2-6h.

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