Aqueous thermosetting resin, method for producing the same, resin composition, honeycomb resin product, method for producing the same, and use thereof

Abstract

This invention relates to the field of polymer materials, and discloses an aqueous thermosetting resin and its preparation method, resin composition, honeycomb resin products and their preparation methods and applications. The aqueous thermosetting resin has the structure shown in Formula I; Formula (I); R1 is a C1-C4 alkylene group; A is of Formula (a) or Formula (b), wherein R2 and R3 are each independently H, CH3, CF3, or CH2CH3; 0 < m1 + m2 ≤ 8; M is K or Na. By introducing sulfonic acid groups into the molecular chain, this aqueous thermosetting resin can become hydrophilic, reducing the preparation cost of the support agent. Furthermore, products prepared from this aqueous thermosetting resin possess high compressive strength and are not easily deformed under certain temperature and pressure conditions.

Description

Water-based thermosetting resin and preparation method thereof, resin composition, honeycomb resin product and preparation method and application thereof Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to a water-based thermosetting resin and a preparation method thereof, a resin composition, a honeycomb resin product and a preparation method and application thereof. Background Art

[0002] Thermosetting resins are fluid at room or low temperatures and can be cured at high temperatures into products with high strength, good heat resistance, excellent electrical properties, corrosion resistance, aging resistance, and good dimensional stability. Therefore, they are widely used in high-tech fields such as electronics / electrical, energy, chemicals, machinery, automobiles, rail transportation, and construction.

[0003] Most water-based thermosetting resins are stable dispersions with water as the continuous phase and thermosetting resin particles or droplets as the dispersed phase. The presence of water makes them particularly useful in applications where organic solvents are inconvenient to use. For example, water-based epoxy resins, due to their environmentally friendly nature, have significant market and development potential in the coatings sector. Due to their strong cohesiveness and dense molecular structure, water-based thermosetting resins offer advantages such as high mechanical properties, low cure shrinkage, and heat resistance up to 200°C.

[0004] During oil and gas field development, fracturing formations with fracturing fluid is one of the measures used to increase production. Fracturing fluid primarily consists of two components: proppant and sand-carrying fluid. The proppant supports the fractures created by the fracturing and prevents them from closing. The sand-carrying fluid carries the proppant from the wellbore into the fractures at a high concentration. However, sand-adding fracturing technology presents challenges such as sand plugging, equipment wear, damage from fracturing fluid residue, limited conductivity of the propped fractures, and difficulty in forming effective support at the distal end of the fracture. To address these issues, research efforts, both domestically and internationally, have focused on fluid system and process innovations. While this has improved fracture conductivity and increased effective fracture length to a certain extent, it still remains unresolved, including low compressive strength, rapid conductivity loss due to easily damaged pore structures, difficulty adding sand, and difficulty in supporting the distal end of the fracture.

[0005] Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems of high preparation cost, low compressive strength and easy deformation of proppants in the prior art, which lead to rapid decrease in conductivity, difficulty in adding sand and difficulty in supporting the far end of the fracture. A water-based thermosetting resin and its preparation method, a resin composition, a honeycomb resin product and its preparation method and application are provided. The water-based thermosetting resin introduces sulfonic acid groups into the molecular chain to make the resin hydrophilic, which can reduce the preparation cost of the proppant. At the same time, the product prepared from the water-based thermosetting resin can present a honeycomb structure. When used as a proppant, it has high compressive strength and good heat resistance and is not easy to deform under certain temperature and pressure.

[0007] In order to achieve the above object, the first aspect of the present invention provides a water-based thermosetting resin, wherein the water-based thermosetting resin has a structure shown in Formula I;

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

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

[0010] 0 <m1+m2≤8;

[0011] M is K or Na.

[0012] A second aspect of the present invention provides a method for preparing a water-based thermosetting resin, wherein the preparation method comprises the following steps:

[0013] S1. In the presence of a first catalyst and water, contacting a bisphenol compound with a sulfonating agent to perform a sulfonation reaction to obtain a sulfonated bisphenol compound;

[0014] S2. In the presence of a second catalyst and water, contacting the sulfonated bisphenol compound with the monomer A represented by formula II to carry out a polycondensation reaction to obtain the water-soluble thermosetting resin;

[0015] wherein p is an integer of 1-4, and X is Cl or Br.

[0016] The third aspect of the present invention provides a water-based thermosetting resin prepared by the preparation method described in the second aspect of the present invention.

[0017] A fourth aspect of the present invention provides a resin composition, wherein the resin composition comprises a component A and a component B, wherein the component A and the component B exist independently;

[0018] The component A contains a water-based thermosetting resin, a solvent-based thermosetting resin, an emulsifier and water;

[0019] The B component contains a curing agent;

[0020] The content of the water-based thermosetting resin is 5wt%-40wt%, the content of the solvent-based thermosetting resin is 10wt%-76wt%, the content of the emulsifier is 0.5wt%-4wt%, and the content of water is 16wt%-50wt%;

[0021] The water-based thermosetting resin is the water-based thermosetting resin described in the first aspect and / or the second aspect of the present invention.

[0022] The fifth aspect of the present invention provides a honeycomb resin product, wherein the honeycomb resin product is made by mixing and curing the resin composition described in the fourth aspect of the present invention.

[0023] A sixth aspect of the present invention provides a method for preparing a honeycomb resin product, wherein the preparation method comprises:

[0024] The components of the resin composition described in the fourth aspect of the present invention are mixed and cured to obtain the honeycomb resin product.

[0025] The seventh aspect of the present invention provides an application of the water-based thermosetting resin described in the first aspect and / or the third aspect of the present invention, the resin composition described in the fourth aspect of the present invention, or the honeycomb resin product described in the fifth aspect of the present invention in at least one of oil reservoir development, building floor tiles, and adsorption materials.

[0026] Through the above technical solution, the water-based thermosetting resin and its preparation method, resin composition, honeycomb resin product and its preparation method and application provided by the present invention achieve the following technical effects:

[0027] (1) The water-based thermosetting resin can be made hydrophilic by introducing hydrophilic sulfonic acid groups into the molecular chain, and can be used as a phase change proppant system with high conductivity, and the preparation cost of the proppant can be reduced.

[0028] (2) The resin composition prepared from the water-based thermosetting resin can produce a product having high compressive strength after curing and is not easily deformed in high-temperature and high-pressure formation conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG1 is an infrared spectrum of the water-based thermosetting resin prepared in Preparation Example 1 of the present invention.

[0030] FIG2 is a photograph of an aqueous solution of a water-based thermosetting resin prepared in Preparation Example 1 of the present invention.

[0031] FIG3 is a 1H-NMR spectrum of water-based thermosetting resin A1. DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0033] A first aspect of the present invention provides a water-based thermosetting resin, wherein the water-based thermosetting resin has a structure shown in Formula I;

[0034] R1 is a C1-C4 alkylene group;

[0035] A is wherein R2 and R3 are each independently H, CH3, CF3 or CH2CH3;

[0036] 0 <m1+m2≤8;

[0037] M is K or Na.

[0038] In the present invention, the hydrophilic sulfonic acid group introduced into Formula I imparts hydrophilicity to the resin, forming a highly conductive phase-change proppant system and reducing proppant production costs. Furthermore, because the water-based resin is a liquid, it can fill cracks and microcracks of various sizes during pumping, fundamentally addressing the current problems of low conductivity, difficulty in adding sand, and difficulty supporting the distal ends of fractures during fracturing.

[0039] According to the present invention, R1 is a C1-C4 alkylene group.

[0040] According to the present invention, A is wherein R2 and R3 are each independently CH3 or H, CH3, CF3 or CH2CH3.

[0041] According to a preferred embodiment of the present invention, 1≤m1+m2≤5.

[0042] According to a preferred embodiment of the present invention, M is Na.

[0043] According to the present invention, the content of S element in the water-based thermosetting resin is 6-20 wt %.

[0044] In the present invention, the content of the S element in the water-based thermosetting resin satisfies the above range, so that the water-based thermosetting resin has excellent water solubility and is dispersed in water, and the aqueous solution formed is stable.

[0045] In the present invention, the content of S element in the water-based thermosetting resin can be any value in the range of 6-20wt%, for example, 6wt%, 6.2wt%, 6.5wt%, 7wt%, 7.2wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, 12wt%, 12.5wt%, 13wt%, 13.5wt%, 14wt%, 14.5wt%, 15wt%, 15.5wt%, 16wt%, 17wt%, 18.5wt%, 19wt%, 19.5wt%, 20wt% and combinations of the above individual point values ​​to obtain new numerical ranges.

[0046] Furthermore, the content of S element in the water-based thermosetting resin is 10-15 wt %.

[0047] According to the present invention, the epoxy equivalent of the water-based thermosetting resin is 100 g / eq-300 g / eq.

[0048] In the present invention, the epoxy equivalent of the waterborne thermosetting resin satisfies the above range, which can improve its reactivity, so that the waterborne thermosetting resin reacts more thoroughly during the curing reaction, further improves the compressive strength of the product prepared from the resin when used as a proppant, and is not easily deformed.

[0049] In the present invention, the epoxy equivalent of the water-based thermosetting resin can be any value in the range of 100g / eq-300g / eq, for example, 100g / eq, 120g / eq, 125g / eq, 130g / eq, 135g / eq, 140g / eq, 150g / eq, 165g / eq, 170g / eq, 180g / eq, 185g / eq, 190g / eq, 195g / eq, 2 00g / eq, 210g / eq, 220g / eq, 225g / eq, 230g / eq, 240g / eq, 245g / eq, 250g / eq, 260g / eq, 265g / eq, 270g / eq, 280g / eq, 285g / eq, 290g / eq, 295g / eq, 300g / eq and the above individual point values ​​are combined with each other to obtain a new numerical range.

[0050] Furthermore, the epoxy equivalent of the water-based thermosetting resin is 150 g / eq-200 g / eq.

[0051] In the present invention, the weight average molecular weight of the water-based thermosetting resin is 2000 g / mol-10000 g / mol, preferably 3000 g / mol-5000 g / mol.

[0052] In the present invention, the weight average molecular weight of the water-based thermosetting resin is any value in the range of 2000 g / mol-10000 g / mol, for example, 2000 g / mol, 2200 g / mol, 2300 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 3600 g / mol, 4000 g / mol, 4200 g / mol, 4500 g / mol, 4800 g / mol, 5000 g / mol, 5300 g / mol, 5500 g / mol, 5600 g / mol. g / mol, 8500 g / mol, 8700 g / mol, 9000 g / mol, 9200 g / mol, 9500 g / mol, 9800 g / mol, 10000 g / mol and combinations thereof and the like.

[0053] A second aspect of the present invention provides a method for preparing a water-based thermosetting resin, wherein the preparation method comprises the following steps:

[0054] S1. In the presence of a first catalyst and water, contacting a bisphenol compound with a sulfonating agent to perform a sulfonation reaction to obtain a sulfonated bisphenol compound;

[0055] S2. In the presence of a second catalyst and water, contacting the sulfonated bisphenol compound with the monomer A represented by formula II to carry out a polycondensation reaction to obtain the water-based thermosetting resin;

[0056] wherein p is an integer of 1-4, and X is Cl or Br.

[0057] In the present invention, a sulfonating agent is brought into contact with a bisphenol compound to achieve sulfonation of the bisphenol compound, and the sulfonated bisphenol compound is polycondensed with a monomer represented by Formula II to prepare a water-based thermosetting resin containing a sulfonic acid group. The thermosetting resin has excellent hydrophilicity, can be cured in an aqueous environment, and has interconnected pores while maintaining high strength.

[0058] 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.

[0059] According to the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0060] According to the present invention, the first catalyst is Lewis acid.

[0061] In the present invention, the Lewis acid can be a Lewis acid commonly used in the art, such as titanium tetrachloride, ferric chloride, ferric oxide, zirconium oxychloride, aluminum oxide, aluminum chloride, hydrated tin tetrachloride, and the like.

[0062] According to the present invention, the molar ratio of the bisphenol compound to the sulfonating agent is 1:1-5, preferably 1:2-4.

[0063] In the present invention, the molar ratio of the bisphenol compound to the sulfonating agent is any value in the range of 1:1-5, for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.8, 1:2, 1:2.3, 1:2.5, 1:2.8, 1:3, 1:3.3, 1:3.5, 1:3.8, 1:4, 1:4.1, 1:4.2, 1:4.5, 1:4.8, 1:4.9, 1:5, and new numerical ranges obtained by combining the above individual point values.

[0064] According to the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001-0.0008.

[0065] In the present invention, the mass ratio of the bisphenol compound to the first catalyst satisfies the above range, which can reduce the reaction temperature by 20° C.-30° C. and make the reaction conditions milder.

[0066] Furthermore, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0003-0.0005.

[0067] In the present invention, the molar ratio of the bisphenol compound to the sulfonating agent is any value in the range of 1:1-5, for example, 1:0.0001, 1:0.0002, 1:0.0003, 1:0.0004, 1:0.0005, 1:0.0006, 1:0.0007, 1:0.0008, and new numerical ranges obtained by combining the above individual point values.

[0068] According to the present invention, in step S2, in formula II, p is an integer of 1-3, and X is Cl.

[0069] According to the present invention, the second catalyst is a base.

[0070] In the present invention, the base can be a conventional base in the art, for example, NaOH, KOH, Ca(OH)2, etc.

[0071] Furthermore, the second catalyst is more preferably NaOH.

[0072] According to the present invention, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.25-0.65.

[0073] In the present invention, the mass ratio of the sulfonated bisphenol compound to the monomer A satisfies the above range, so that the prepared water-based thermosetting resin has a specific epoxy equivalent that meets the requirements, thereby being able to undergo a phase change reaction with the curing agent under formation conditions to form a honeycomb proppant with a suitable pore structure.

[0074] Furthermore, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.3-1:0.45.

[0075] In the present invention, the mass ratio of the sulfonated bisphenol compound to the monomer A is any value in the range of 1:0.25-0.65, for example, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.3, 1:0.32, 1:0.33, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, and new numerical ranges obtained by combining the above individual point values.

[0076] According to the present invention, the mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.1-0.5, preferably 1:0.15-0.38.

[0077] In the present invention, the mass ratio of the sulfonated bisphenol compound to the second catalyst is any value in the range of 1:0.1-0.5, for example, 1:0.1, 1:0.15, 1:0.18, 1:0.2, 1:0.24, 1:0.26, 1:0.27, 1:0.28, 1:0.3, 1:0.32, 1:0.33, 1:0.35, 1:0.38, and new numerical ranges obtained by combining the above individual point values.

[0078] According to the present invention, the conditions of the sulfonation reaction include: a reaction temperature of 120-150° C. and a reaction time of 2-6 hours.

[0079] Furthermore, the conditions of the sulfonation reaction include: reaction temperature of 130-140° C., and reaction time of 2-4 h.

[0080] According to the present invention, the conditions of the polycondensation reaction include: reaction temperature of 40-80° C., and reaction time of 2-4 h.

[0081] Furthermore, the conditions of the polycondensation reaction include: reaction temperature of 50-70° C., and reaction time of 2-3 h.

[0082] In the present invention, the inventors have found that in the process of preparing water-based thermosetting resin, controlling the oxygen concentration in the system to no more than 3.1 mg / L is conducive to the smooth progress of the reaction and the efficient preparation of water-based thermosetting resin with a specific structure.

[0083] Exemplarily, according to a preferred embodiment of the present invention, the preparation method of the water-based thermosetting resin is as follows:

[0084] S1. In the presence of Lewis acid and water, contacting at least one bisphenol compound selected from bisphenol A, bisphenol S, bisphenol B, bisphenol F, and bisphenol AF with at least one sulfonating agent selected from concentrated sulfuric acid, chlorosulfonic acid, and aminosulfonic acid to carry out a sulfonation reaction, the reaction temperature being 130-140° C. and the reaction time being 2-4 hours to obtain a sulfonated bisphenol compound; wherein the molar ratio of the bisphenol compound to the sulfonating agent is 1:2-3, and the mass ratio of the bisphenol compound to the Lewis acid is 1:0.0003-0.0005.

[0085] S2. Add alkali to deionized water, add a sulfonated bisphenol compound, and dropwise add monomer A shown in formula II at a temperature not exceeding 60° C. to carry out a polycondensation reaction. The reaction temperature is 50-70° C. and the reaction time is 2-3 hours to obtain a water-based thermosetting resin, wherein the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.3-0.45, and the mass ratio of the sulfonated bisphenol compound to the alkali is 1:0.15-0.3.

[0086] The third aspect of the present invention provides a water-based thermosetting resin prepared by the preparation method provided by the second aspect of the present invention.

[0087] A fourth aspect of the present invention provides a resin composition, wherein the resin composition comprises a component A and a component B, wherein the component A and the component B exist independently;

[0088] The component A contains a water-based thermosetting resin, a solvent-based thermosetting resin, an emulsifier and water;

[0089] The B component contains a curing agent;

[0090] The content of the water-based thermosetting resin is 5wt%-40wt%, the content of the solvent-based thermosetting resin is 10wt%-76wt%, the content of the emulsifier is 0.5wt%-4wt%, and the content of water is 16wt%-50wt%;

[0091] The water-based thermosetting resin is the water-based thermosetting resin described in the first aspect and / or the second aspect of the present invention.

[0092] In the present invention, the water-based thermosetting resin in the composition is the water-based thermosetting resin described in the first aspect and / or the third aspect of the present invention, and the content of each component satisfies the above-mentioned range, so that the resin product prepared from the composition can have good compressive strength and is not easy to deform when used as a proppant.

[0093] Furthermore, the content of the water-soluble thermosetting resin is 30wt%-40wt%, the content of the solvent-based thermosetting resin is 20wt%-40wt%, the content of the emulsifier is 2wt%-3wt%, and the content of water is 17wt%-48wt%.

[0094] In the present invention, the content of the water-soluble thermosetting resin is any value in the range of 30wt%-40wt%, for example, 30wt%, 31wt%, 31.5wt%, 32wt%, 33.5wt%, 35wt%, 35.5wt%, 36wt%, 36.5wt%, 37wt%, 38.5wt%, 39wt%, 39.5wt%, 40wt% and the above-mentioned individual point values ​​are combined with each other to obtain a new numerical range.

[0095] In the present invention, the content of the solvent-based thermosetting resin is any value in the range of 20wt%-40wt%, for example, 20wt%, 21wt%, 21.5wt%, 23wt%, 23.5wt%, 24wt%, 25wt%, 26.5wt%, 27wt%, 28wt%, 29wt%, 30wt%, 31wt%, 31.5wt%, 32wt%, 33.5wt%, 35wt%, 35.5wt%, 36wt%, 36.5wt%, 37wt%, 38.5wt%, 39wt%, 39.5wt%, 40wt% and combinations of the above-mentioned individual point values ​​to obtain a new numerical range.

[0096] In the present invention, the content of the emulsifier is any value in the range of 2wt%-3wt%, for example, 2wt%, 2.1wt%, 2.2wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt% and combinations of the above individual point values ​​to obtain a new numerical range.

[0097] According to the present invention, based on 100 parts by weight of component A, the amount of the curing agent is 50-80 parts, preferably 60-80 parts.

[0098] In the present invention, based on 100 parts by weight of component A, the amount of the curing agent is any value in the range of 50-80 parts, for example, 50 parts, 51 parts, 53 parts, 55 parts, 56 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, 67 parts, 69 parts, 70 parts, 71 parts, 73 parts, 75 parts, 78 parts, 80 parts, and combinations of the above individual points to obtain new numerical ranges.

[0099] According to the present invention, the emulsifier is selected from cationic emulsifiers and / or anionic emulsifiers.

[0100] According to the present invention, the cationic emulsifier is at least one selected from the group consisting of dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, N,N-ethylenedioctadecyldimethylammonium chloride (18-2-18), dodecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride and octadecyldimethylbenzylammonium chloride.

[0101] According to the present invention, the anionic emulsifier is at least one selected from sodium stearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium laurate, sodium rosinate, sodium didodecylphenyl ether disulfonate and sodium dibutylnaphthylsulfonate.

[0102] According to the present invention, the emulsifier is a cationic emulsifier and an anionic emulsifier.

[0103] According to the present invention, the mass ratio of the cationic emulsifier to the anionic emulsifier is 1:0.25-1.

[0104] In the present invention, the mass ratio of the cationic emulsifier to the anionic emulsifier satisfies the above range, which can further efficiently prepare the water-based thermosetting resin and make the water-based thermosetting resin have better comprehensive properties.

[0105] Furthermore, the mass ratio of the cationic emulsifier to the anionic emulsifier is 1:0.3-0.65.

[0106] In the present invention, the mass ratio of the cationic emulsifier to the anionic emulsifier is any value in the range of 1:0.25-0.65, for example, 1:0.25, 1:0.26, 1:0.27, 1:0.28, 1:0.3, 1:0.32, 1:0.33, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, 1:0.5, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, and new numerical ranges obtained by combining the above individual point values ​​with each other.

[0107] According to the present invention, the solvent-based thermosetting resin is at least one selected from epoxy resin, polyimide and unsaturated resin.

[0108] In the present invention, the solvent-based thermosetting resin is selected from the above types, which can further make the resin product prepared from the composition have higher compressive strength.

[0109] According to the present invention, the curing agent is selected from waterborne phenolic resin and / or unsaturated amide polymer.

[0110] In the present invention, the unsaturated amide polymer is selected from unsaturated amide polymer A and / or unsaturated amide polymer B.

[0111] According to one embodiment of the present invention, the unsaturated amide polymer A comprises structural unit Ia, structural unit IIa and structural unit IIIa;

[0112] The structural unit Ia has a structure shown in Formula 1a, the structural unit IIa has a structure shown in Formula 2a, and the structural unit IIIa has a structure shown in at least one of Formula 3a, Formula 4a, and Formula 5a;

[0113] In formula 1a, R 1a is -H or -CH3, R 2a and R 3a Each independently represents -H or a C1-C18 alkyl group; R 4a -H, A, C1-C20 alkyl or -(CH2) n -OR 21a ; R 21a is -H or a C1-C18 alkyl group, and n is an integer from 0 to 12;

[0114] A has the structure shown in Formula 6a;

[0115] In formula 6a, R 22a and R 23aEach is independently -H or a C1-C18 alkyl group, and m is an integer from 0 to 18;

[0116] In formula 2a, R 5a 、R 6a and R 7a Each is independently -H, C1-C12 alkyl or -(CH2) r -OH, r is an integer from 1 to 12; X is -(CH2) z -, z is an integer from 0 to 5;

[0117] In formula 3a, R 8a is -H or -CH3;

[0118] In formula 4a, R 9a is -H or -CH3;

[0119] In formula 5a, R 10a 、R 11a and R 12a Each is independently -H or -NH2, and at least one is -NH2; R 13a It is -H or -CH3.

[0120] In the present invention, the unsaturated amide copolymer A comprises the structural unit Ia, structural unit IIa and structural unit IIIa having the above-mentioned specific structure. In particular, due to the introduction of structural unit IIIa, the side groups of the unsaturated amide copolymer A have a large number of amino groups. When the curing agent composition containing the copolymer is used to cure the epoxy resin, the epoxy resin can be cured at 90°C-150°C.

[0121] Specifically, the unsaturated amide polymer A of the present invention contains the structural unit IIa represented by formula 2a, which can not only adjust the intrinsic viscosity of the unsaturated amide polymer A to meet the requirements of the curing agent for epoxy resin, but also, because the structural unit IIIa contains a rigid group, it can improve the strength of the product after curing of the curing agent composed of the unsaturated amide polymer A, especially the strength of the epoxy resin.

[0122] Furthermore, in one embodiment of the present invention, in Formula 1a, R 1a is -H or -CH3, R 2a and R 3a Each independently represents -H or a C1-C12 alkyl group; R 4a -H, A, C8-C12 alkyl or -(CH2) n -OR 21a ; R 21a is a C1-C12 alkyl group, and n is an integer from 0 to 12. Preferably, R 1a is -H or -CH3, R2a and R 3a Each independently represents -H, R 4a is -H, C2 alkyl or C12 alkyl; more preferably, R 1a 、R 2a 、R 3a and R 4a All are -H.

[0123] In one embodiment of the present invention, A has the structure shown in Formula 6a;

[0124] In formula 6a, R 22a and R 23a Each independently represents -H or a C1-C12 alkyl group, m is an integer from 1 to 12, preferably, R 22a and R 23a Each is independently -H or C1-C6 alkyl, m is an integer of 1-6, more preferably, R 22a and R 23a Each is independently -H or a C1-C3 alkyl group, and m is an integer of 1-3.

[0125] In the present invention, R 22a and R 23a Each is independently -H or a C1-C12 alkyl group, for example, -H, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, a C10 alkyl group, a C11 alkyl group, or a C12 alkyl group.

[0126] In the present invention, m is an integer of 1-12, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0127] In one embodiment of the present invention, in Formula 2a, R 5a -(CH2) r -OH or -H, r is an integer of 1-3; R 6a and R 7a Each is independently -H; X is -(CH2) z -, z is an integer from 0 to 2; more preferably, R 5a 、R 6a and R 7a Each is independently -H.

[0128] In one embodiment of the present invention, in Formula 3a, R 8a is -H.

[0129] In one embodiment of the present invention, in Formula 4a, R 9a is -H.

[0130] In one embodiment of the present invention, in Formula 5a, R 10a 、R 11a and R 12a Each is independently -H or -NH2, and at least one is -NH2; R 13a is -H.

[0131] According to the present invention, based on the total weight of the unsaturated amide copolymer A, the content of the structural unit Ia is 65wt%-85wt%, the content of the structural unit IIa is 5wt%-7wt%, and the content of the structural unit IIIa is 12wt%-27wt%.

[0132] Furthermore, based on the total weight of the unsaturated amide polymer, the content of the structural unit Ia is 70 wt%-82 wt%, the content of the structural unit IIa is 5 wt%-6 wt%, and the content of the structural unit IIIa is 12.5 wt%-20 wt%.

[0133] In the present invention, based on the total weight of the unsaturated amide copolymer A, the content of the structural unit Ia is any value in the range of 65 wt% to 85 wt%, for example, 65 wt%, 66 wt%, 66.5 wt%, 67 wt%, 68 wt%, 68.5 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73.5 wt%, 74 wt%, 75.5 wt%, 76 wt%, 77.5 wt%, 78 wt%, 79 wt%, 80 wt%, 81.5 wt%, 82 wt%, 82.5 wt%, 83 wt%, 84 wt%, 84.5 wt%, 85 wt%, and new numerical ranges obtained by combining the above individual point values ​​with each other.

[0134] In the present invention, based on the total weight of the unsaturated amide polymer, the content of the structural unit IIa is any value in the range of 5wt%-6wt%, for example, 5wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.8wt%, 6wt%, 6.5wt%, 7wt% and combinations of the above-mentioned individual point values ​​to obtain a new numerical range.

[0135] In the present invention, based on the total weight of the unsaturated amide polymer, the content of the structural unit IIIa is any value in the range of 12.5 wt% to 20 wt%, for example, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 13.8 wt%, 14 wt%, 14.4 wt%, 14.6 wt%, 14.8 wt%, 15 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt%, 18 wt%, 18.5 wt%, 19 wt%, 19.5 wt%, 20 wt%, 21 wt%, 22 wt%, 23.5 wt%, 24 wt%, 25 wt%, 25.5 wt%, 26 wt%, 27 wt%, and combinations thereof to obtain new numerical ranges.

[0136] In the present invention, the total content of the structural unit Ia, the structural unit IIa and the structural unit IIIa is 100 wt %.

[0137] In the present invention, the content of each structural unit in the copolymer is calculated based on the feed amount.

[0138] According to the present invention, at 25° C., the intrinsic viscosity of the copolymer is 200 mL / g-1200 mL / g, preferably 900 mL / g-1200 mL / g.

[0139] According to one embodiment of the present invention, the unsaturated amide polymer B includes structural unit Ib, structural unit IIb, structural unit IIIb and structural unit IVb.

[0140] The structural unit Ib has the structure shown in Formula 1b, the structural unit IIb has the structure shown in Formula 2b and / or Formula 3b, the structural unit IIIb has the structure shown in Formula 4b and / or Formula 5b, and the structural unit IVb has the structure shown in at least one of Formula 6b, Formula 7b and Formula 8b.

[0141] Based on the total weight of the unsaturated amide polymer B, the content of the structural unit Ib is 30 wt%-50 wt%, the content of the structural unit IIb is 30 wt%-50 wt%, the content of the structural unit IIIb is 4 wt%-10 wt%, and the content of the structural unit IVb is 10 wt%-16 wt%;

[0142] In formula 1b, R 1b is H or CH3, R 2b and R 3b Each independently represents H or a C1-C18 alkyl group; R 4b is H, A or -(CH2)n -OR 21b ; R 21b is a C1-C18 alkyl group, and n is an integer from 0 to 12;

[0143] A has the structure shown in Formula 9b;

[0144] In formula 9b, R 22b and R 23b Each independently represents H, a C1-C18 alkyl group, and m is an integer from 0 to 18;

[0145] In formula 3b, R 5b and R 6b Each is independently H or a C2-C16 alkyl group;

[0146] In formula 4b, R 7b 、R 8b and R 9b are independently H, C1-C11 alkyl, -(CH2) r -OH or -(CH2) q SO3Q, Q is H, Na or K, r is an integer from 0 to 12, q is an integer from 0 to 10; X is -(CH2) z -, z is an integer from 0 to 5;

[0147] In formula 5b, R 10b is H or CH3, M is H, Na or K;

[0148] In formula 6b, R 11b is H or CH3;

[0149] In formula 7b, R 12b is H or CH3;

[0150] In formula 8b, R 13b 、R 14b and R 15b are each independently H, NH2, F or Br; R 16b is H or CH3.

[0151] In the present invention, in Formula 9b, R 22b and R 23b Each independently represents any value of H or C1-C18 alkyl, for example, it can be H, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl.

[0152] In the present invention, in formula 9b, m is an integer of 0-18, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and combinations of the above individual point values ​​to obtain a new numerical range.

[0153] In the present invention, in Formula 3b, R 5b and R 6b Each independently represents H or any value of C2-C16 alkyl, for example, it can be H, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C11 alkyl, C12, C13 alkyl, C14 alkyl, C15 alkyl, C16 alkyl.

[0154] In the present invention, in Formula 4b, R 7b 、R 8b and R 9b Each independently represents any value among H and C1-C11 alkyl, for example, it can be H, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, and C11 alkyl.

[0155] In the present invention, the unsaturated amide polymer B contains the structural unit Ib, structural unit IIb, structural unit IIIb and structural unit IVb having the above-mentioned specific structure. In particular, due to the introduction of structural unit IIb and structural unit IVb, the side groups of the unsaturated amide polymer B have a large number of carboxyl groups and amino groups. When the polymer is used as a curing agent for epoxy resin, the epoxy resin can be cured at a relatively low temperature (50°C-90°C) or a high temperature (90°C-150°C).

[0156] Specifically, the structural unit IIIb containing the structure represented by Formula 4b and / or Formula 5b in the unsaturated amide polymer B of the present invention can not only adjust the molecular weight of the unsaturated amide polymer to meet the requirements of the epoxy resin curing agent, but also, because the structural unit IIIb contains a rigid group, it can reduce the toughness of the product after curing of the unsaturated amide polymer B and improve the hardness of the cured product.

[0157] Furthermore, the structural unit IIb comprising the structure represented by Formula 2b and / or Formula 3b in the unsaturated amide polymer B of the present invention, due to the introduction of the anhydride structure, avoids the loss of carboxylic acid and amine groups due to the easy reaction of carboxylic acid and amine groups to form an intramolecular ring structure, resulting in a decrease in the curing activity of the unsaturated amide polymer B when used as a curing agent.

[0158] In the present invention, when the content of each structural unit in the unsaturated amide polymer B is controlled to meet the above range, not only can the unsaturated amide polymer have a suitable molecular weight, but the obtained unsaturated amide polymer can also contain suitable rigid groups and active groups. This ensures that when the unsaturated amide polymer B is used as a curing agent for curing epoxy resin, it has active groups that meet actual needs, and can ensure that the epoxy resin product obtained after curing has high compressive strength, etc.

[0159] Furthermore, based on the total weight of the unsaturated amide polymer B, the content of the structural unit Ib is 30wt%-45wt%, the content of the structural unit IIb is 35wt%-45wt%, the content of the structural unit IIIb is 6wt%-10wt%, and the content of the structural unit IVb is 12wt%-15wt%.

[0160] In the present invention, based on the total weight of the unsaturated amide polymer B, the content of the structural unit Ib is any value in the range of 30 wt% to 50 wt%, for example, 30 wt%, 31 wt%, 31.5 wt%, 32 wt%, 33.5 wt%, 35 wt%, 35.5 wt%, 36 wt%, 36.5 wt%, 37 wt%, 38.5 wt%, 39 wt%, 39.5 wt%, 40 wt%, 41 wt%, 41.5 wt%, 42 wt%, 43.5 wt%, 45 wt%, 45.5 wt%, 46 wt%, 46.5 wt%, 47 wt%, 48 wt%, 49 wt%, 49.5 wt%, 50 wt%, and new numerical ranges obtained by combining the above individual points.

[0161] In the present invention, based on the total weight of the unsaturated amide polymer B, the content of the structural unit IIb is any value in the range of 30 wt% to 50 wt%, for example, 30 wt%, 31 wt%, 31.5 wt%, 32 wt%, 33.5 wt%, 35 wt%, 35.5 wt%, 36 wt%, 36.5 wt%, 37 wt%, 38.5 wt%, 39 wt%, 39.5 wt%, 40 wt%, 41 wt%, 41.5 wt%, 42 wt%, 43.5 wt%, 45 wt%, 45.5 wt%, 46 wt%, 46.5 wt%, 47 wt%, 48 wt%, 49 wt%, 49.5 wt%, 50 wt%, and new numerical ranges obtained by combining the above individual point values ​​with each other.

[0162] In the present invention, based on the total weight of the unsaturated amide polymer B, the content of the structural unit IIIb is any value in the range of 4wt%-10wt%, for example, 4wt%, 4.2wt%, 4.5wt%, 5wt%, 5.5wt%, 5.6wt%, 6wt%, 6.2wt%, 6.5wt%, 7wt%, 7.2wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt% and combinations of the above-mentioned individual point values ​​to obtain a new numerical range.

[0163] In the present invention, based on the total weight of the unsaturated amide polymer B, the content of the structural unit IVb is any value in the range of 10 wt% to 16 wt%, for example, 10 wt%, 11 wt%, 12.5 wt%, 13 wt%, 13.3 wt%, 14 wt%, 14.2 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, and new numerical ranges obtained by combining the above individual point values.

[0164] In the present invention, the total content of the structural unit Ib, the structural unit IIb, the structural unit IIIb and the structural unit IVb is 100 wt %.

[0165] In the present invention, the content of each structural unit in the polymer is calculated based on the feeding amount of the monomer.

[0166] In a preferred embodiment of the present invention, the structural unit Ib has the structure shown in Formula 1b, the structural unit IIb has the structure shown in Formula 2b, the structural unit IIIb has the structure shown in Formula 4b, and the structural unit IVb has the structure shown in Formula 6b or Formula 8b, preferably having the structure shown in Formula 8b.

[0167] In one embodiment of the present invention, in Formula 1b, R 1b is H or CH3, R 2b and R 3b Each independently represents H or a C1-C12 alkyl group; R 4b is H, A or -(CH2) n -OR 21b ; R 21b is a C1-C12 alkyl group, and n is an integer from 1 to 10. Preferably, R 1b is H or CH3, R 2b 、R 3b and R 4b are each independently H; more preferably, R 1b 、R 2b 、R 3b and R 4b Both are H.

[0168] In the present invention, A has the structure shown in Formula 9b;

[0169] In formula 9b, R 22b and R 23b Each independently represents H or a C1-C12 alkyl group, m represents an integer from 0 to 13, preferably, R 22b and R 23b Each is independently H or a C1-C4 alkyl group, and m is an integer of 0-3.

[0170] In one embodiment of the present invention, in Formula 3, R 5b and R 6b Each independently is H or a C2-C14 alkyl group, preferably, R 5b H, R 6b is C2H5.

[0171] In one embodiment of the present invention, in Formula 4b, R 7b 、R 8b and R 9b Each independently represents H or C1-C8 alkyl, -(CH2) r -OH or -(CH2) q SO3Q, Q is H, Na or K, r is an integer from 0 to 10, q is an integer from 0 to 8; X is -(CH2) z -, z is an integer from 0 to 3, preferably, R 7b -(CH2) q SO3Q, Q is H or Na, q is an integer from 0 to 2; R 8b and R 9b Each independently represents H; X b -(CH2) z -, z is 0; preferably, R 7b -(CH2) q SO3Q, Q is Na, q is 0.

[0172] In one embodiment of the present invention, in Formula 5b, R 10b is H, M is Na.

[0173] In one embodiment of the present invention, in Formula 6b, R 11b For H.

[0174] In one embodiment of the present invention, in Formula 7b, R 12b For H.

[0175] In one embodiment of the present invention, in Formula 8b, R 13b 、R 14band R 15b are each independently H or NH2; R 16b is H or NH, R 17b For H.

[0176] According to the present invention, at 25° C., the intrinsic viscosity of the unsaturated amide polymer B is 100 mL / g-1200 mL / g, preferably 800 mL / g-1200 mL / g.

[0177] In the present invention, the intrinsic viscosity of the unsaturated amide polymer B is any value in the range of 100 mL / g to 1200 mL / g, for example, 100 mL / g, 150 mL / g, 200 mL / g, 250 mL / g, 300 mL / g, 350 mL / g, 400 mL / g, 450 mL / g, 460 mL / g, 500 mL / g, 550 mL / g, 560 mL / g, 600 mL / g, 630mL / g, 650mL / g, 670mL / g, 700mL / g, 760mL / g, 800mL / g, 850mL / g, 870mL / g, 890mL / g, 900mL / g, 920mL / g, 950mL / g, 980mL / g, 1000mL / g, 1100mL / g, 1200mL / g and combinations of the above individual point values ​​give new numerical ranges.

[0178] According to the present invention, at 25° C., the apparent viscosity of the resin composition is 100-400 mPa·s, preferably 200-300 mPa·s.

[0179] In the present invention, the apparent viscosity of the resin composition is any value in the range of 100-400 mPa·s, for example, it can be 100 mPa·s, 110 mPa·s, 150 mPa·s, 160 mPa·s, 180 mPa·s, 190 mPa·s, 200 mPa·s, 210 mPa·s, 250 mPa·s, 260 mPa·s, 300 mPa·s, 330 mPa·s, 350 mPa·s, 380 mPa·s, 400 mPa·s, and new numerical ranges obtained by combining the above-mentioned individual point values ​​with each other.

[0180] In the present invention, the apparent viscosity is the apparent viscosity within 30 minutes of mixing component A and component B in the resin composition. This is because after 30 minutes, component A will be cured due to the presence of the curing agent in the resin composition, and the apparent viscosity at this time will be meaningless.

[0181] A fifth aspect of the present invention provides a honeycomb resin product, wherein the honeycomb resin product is obtained by mixing and curing the above resin composition.

[0182] According to the present invention, the honeycomb resin product has interconnected channels.

[0183] According to the present invention, the porosity of the honeycomb resin product is 1%-40%.

[0184] In the present invention, the porosity of the honeycomb resin product can be any value in the range of 1% to 40%, for example, it can be 1%, 2%, 3%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 8%, 9%, 10%, 12%, 12.5%, 13%, 15%, 16%, 17%, 18.5%, 19%, 19.5%, 20%, 21%, 23%, 26%, 28%, 30%, 31%, 32%, 33%, 35%, 36%, 37%, 38%, 39%, 40%, and new numerical ranges obtained by combining the above individual point values.

[0185] According to the present invention, the pore size of the honeycomb resin product is 0.1 nm-0.7 nm.

[0186] In the present invention, the pore size of the honeycomb resin product can be any value in the range of 0.1nm-0.7nm, for example, 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, and a new numerical range obtained by combining the above individual point values.

[0187] According to the present invention, the cell density of the honeycomb resin product is 20-500.

[0188] In the present invention, the cell density of the honeycomb resin product can be any value in the range of 20-500, for example, 20, 22, 25, 30, 35, 36, 38, 40, 45, 50, 60, 65, 70, 78, 80, 90, 100, 110, 120150, 180, 200, 210, 225, 230, 250, 300, 325, 330, 350, 400, 450, 465, 470, 480, 500, and new numerical ranges obtained by combining the above individual point values.

[0189] In the present invention, the porosity, pore size and pore density of the honeycomb resin product satisfy the above ranges, so that the resin product has high compressive strength and is not easily deformed.

[0190] In the present invention, the cell density refers to the number of cells within a certain size (1 cm×1 cm) of the honeycomb resin product.

[0191] Furthermore, the porosity of the honeycomb resin product is 20%-30%.

[0192] Furthermore, the pore size of the honeycomb resin product is 0.3nm-0.5nm.

[0193] Furthermore, the cell density of the honeycomb resin product is 50-400.

[0194] According to the present invention, the density of the honeycomb resin product is 0.85 g / cm 3 -0.95g / cm 3 , preferably 0.88 g / cm 3 -0.91g / cm 3 .

[0195] According to the present invention, within the temperature range of 60-150° C., the compressive strength of the honeycomb resin product is greater than or equal to 20 MPa, preferably greater than or equal to 37 MPa.

[0196] In the present invention, the compressive strength is uniaxial compressive strength. Specifically, the test method is: measuring using a high and low temperature universal material testing machine, and the test sample is cylindrical, with a diameter of 2.4 cm and a height of 4 cm.

[0197] In a specific embodiment of the present invention, at 150° C., the compressive strength of the honeycomb resin product is 20 MPa-40 MPa, preferably 37 MPa-40 MPa.

[0198] In the present invention, at 150°C, the compressive strength of the honeycomb resin product is any value within the range of 20MPa-40MPa, for example, it can be 20MPa, 21MPa, 22MPa, 25MPa, 26MPa, 28MPa, 30MPa, 32MPa, 35MPa, 37MPa, 38MPa, 39MPa, 40MPa, and a new numerical range obtained by combining the above-mentioned individual point values.

[0199] According to the present invention, within the range of 40 MPa and 60-150° C., the deformation rate of the honeycomb resin product is less than or equal to 8%, preferably less than or equal to 4%, and more preferably less than or equal to 1.5%.

[0200] In the present invention, within the range of 40 MPa and 60-150°C, the deformation rate of the honeycomb resin product is less than or equal to 8%, for example, it can be 1%, 2%, 3%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 8%, and a new numerical range obtained by combining the above-mentioned individual point values.

[0201] A sixth aspect of the present invention provides a method for preparing a honeycomb resin product, wherein the method comprises:

[0202] The components of the resin composition described in the fourth aspect of the present invention are mixed and cured to obtain the honeycomb resin product.

[0203] According to the present invention, the curing conditions include: a curing temperature of 90-150° C. and a curing time of 10 min-6 h.

[0204] Furthermore, the curing conditions include: curing temperature of 120-150° C., and curing time of 30 min-4 h.

[0205] The seventh aspect of the present invention provides an application of the water-based thermosetting resin described in the first aspect and / or the third aspect of the present invention, the resin composition described in the fourth aspect of the present invention, or the honeycomb resin product described in the fifth aspect of the present invention in at least one of oil reservoir development, building floor tiles, and adsorption materials.

[0206] The present invention will be described in detail below by way of examples.

[0207] The content of S element in the waterborne thermosetting resin is measured by an elemental analysis method, specifically, by an oxygen bottle combustion method.

[0208] The epoxy equivalent of the waterborne thermosetting resin is measured by the hydrochloric acid-pyridine method. The specific method is:

[0209] Take 0.5g of sample and add it to 25mL of hydrochloric acid-acetone solution. React at 45℃ for 3.5h. Pipette 25mL of hydrochloric acid-acetone solution, add 3 drops of mixed indicator, and perform blank titration (titration must be completed within 30s). The endpoint is when it does not fade for 5s. The volume of NaOH standard solution consumed is V0, mL. Pipette the mixed solution and add 3 drops of mixed indicator (30s). If it does not fade for 5s, titrate with sodium hydroxide. Record the amount of 0.5mol / LNaOH consumed, recorded as V, mL. Calculate according to the following formula:

[0210] Where EV = epoxy equivalent, mol / 100g; V0 = volume of sodium hydroxide standard solution consumed in the blank experiment, mL; V = volume of sodium hydroxide standard solution consumed in the test sample, mL; C = concentration of NaOH standard solution, mol / L; m = test mass, g.

[0211] The apparent viscosity of the resin composition was measured using a six-speed rotational viscometer. Specifically, 300 ml of the phase change material liquid was placed in the sample chamber, the temperature was set at 25° C., the rotation speed was set at 100 rad / min, and the apparent viscosity value was read after 1 minute.

[0212] The weight average molecular weight of the resin composition is measured by gel permeation chromatography (GPC). Specifically, a certain amount of resin is dissolved in chromatographically pure tetrahydrofuran (THF) to prepare a test solution, the mobile phase is THF, and the reference substance is polystyrene. The weight average molecular weight of the water-soluble thermosetting resin is measured.

[0213] The porosity of honeycomb resin products is measured by the saturated liquid volume method, the specific method is:

[0214] The sample was cured to a size of 24 mm in diameter and 40 mm in length. The cured sample was placed in the permeameter, ensuring there was no leakage between the sample column and the permeameter. After assembly, a pressure differential was applied, and the volume and time of fluid flow were recorded. The permeability was then calculated.

[0215] The calculation formula is: K g =2Q2LμP0 / A(P1 2 -P2 2 )

[0216] Among them, K g To measure the permeability, μm 2 Q2 is the fluid flow rate at the core outlet, ml / s; L is the core length, cm; A is the core cross-sectional area, cm2; P0 is the atmospheric pressure in MPa; P1 is the absolute pressure at the core inlet, MPa; P2 is the absolute pressure at the outlet, MPa; μ is the fluid viscosity in mPa﹒s.

[0217] The pore size of honeycomb resin products is measured by stereo microscope observation. Specifically:

[0218] The honeycomb resin product is observed under a stereo microscope, and the pore diameter of the honeycomb resin product is tested within a field of view of 1 cm×1 cm. The pore diameters of 20 holes are tested, and the average value is the pore diameter of the honeycomb resin product.

[0219] The cell density of the honeycomb product is measured by a statistical method using a stereo microscope. Specifically:

[0220] The honeycomb resin product was observed under a stereo microscope, and the pore diameter of the honeycomb resin product was measured within a 1 cm × 1 cm field of view. The pore diameters of 20 pores were tested, and the average value was taken as the pore diameter D (mm) of the honeycomb resin product. The pore density was calculated using the following formula: pore density = (1 cm × 1 cm) × porosity / pore area, where the pore area is calculated as a circular pore, i.e., pore area = π × (D / 2) 2 , mm 2 .

[0221] The density of honeycomb resin products is measured by determining the mass and volume calculation method;

[0222] The compressive strength of the honeycomb resin product is measured by a universal weight loading machine, wherein the test sample is cylindrical with a diameter of 2.4 cm and a height of 4 cm.

[0223] The deformation rate of the honeycomb resin product is obtained according to the following method:

[0224] At normal pressure and 25°C, the diameter of the tested honeycomb resin product is D0. At 40 MPa and 90°C, the honeycomb resin product is extruded using a high and low temperature universal material testing machine. The diameter of the honeycomb resin product after extrusion is D1, and the deformation rate = (D0-D1) / D0×100%.

[0225] The following are the reagents involved in the examples and comparative examples:

[0226] Bisphenol compounds: bisphenol A, Sinopharm Group;

[0227] Sulfonating agents: 98 wt% concentrated sulfuric acid and aminosulfonic acid, purchased from Sinopharm Group;

[0228] The first catalyst: ferric chloride, aluminum chloride, water and tin tetrachloride, all purchased from Sinopharm Group;

[0229] The second catalyst: sodium hydroxide, purchased from Sinopharm Group;

[0230] Monomer A: epichlorohydrin (p is an integer of 1), purchased from Sinopharm Group;

[0231] Epibromohydrin (p is an integer of 1) was purchased from Sinopharm Group;

[0232] Epoxy resin: brand, E44, purchased from Baling Petrochemical.

[0233] The following preparation example illustrates the preparation of water-based thermosetting resin

[0234] Preparation Example 1

[0235] S1. Contact 57 g of bisphenol A, 0.02 g of ferric chloride, and 75 g of concentrated sulfuric acid for sulfonation reaction at a reaction temperature of 130° C. for a reaction time of 3 h to obtain a sulfonated bisphenol compound BPAS-1; wherein the molar ratio of bisphenol A to concentrated sulfuric acid is 1:3, and the mass ratio of bisphenol A to ferric chloride is 1:0.00035.

[0236] S2. Dissolve 8 g of NaOH in deionized water, add 48 g of BPAS-1, and dropwise add 18 g of epichlorohydrin at 50°C for 3 h to carry out polycondensation reaction to obtain a water-based thermosetting resin A1, wherein the mass ratio of BPAS-1 to NaOH is 1:0.17.

[0237] Among them, in the water-based thermosetting resin A1, the content of S element is 13.4 wt %, the epoxy equivalent is 182 g / mol, the weight-average molecular weight is 3891, R1 is a C1 alkylene group, R2 is 1, R3 is 1, and M is Na. The yield of the water-based thermosetting resin A1 is shown in Table 1.

[0238] As can be seen from Figure 1, the characteristic peak positions of the epoxy group in Figure 1 are located at 1121 cm -1 、937cm -1 、829cm -1 The ether bond and benzene ring are the dominant components of the product, and their characteristic peaks are large, with a peak area of ​​1000-900 cm in the fingerprint region. -1 There is no corresponding absorption peak in the range, so 937cm -1 The presence of epoxy groups can be the most important basis for the presence of epoxy groups. The presence of epoxy groups can make the water-based thermosetting resin have good curing properties. As shown in Figure 2, the water-based thermosetting resin prepared in Preparation Example 1 has excellent water solubility, the solution is clear and transparent brown, and it is stably dispersed in water. Figure 3 shows the water-based thermosetting resin A1. 1 The H-NMR spectrum showed the following characteristic peaks: d6DMSO: 1.5 (s, 12H, 4-CH3), 3.53-3.71 (m, 14H, -CH2—CO-), 5.01 (d, 1H, 2-CH-O), 6.65-6.71 (m, 4H, 4-CH-(ph)), 6.94-7.1 (m, 1H, -CH2), 7.35-7.41 (m, 4H, 4-CH-(ph)), 9.12 (s, 2H, 2-OH). A clear water peak appeared at a chemical shift of 3.3 ppm, indicating that the water-based thermosetting resin A1 obtained in step S2 was pure without further purification.

[0239] Preparation Example 2

[0240] 57 g of bisphenol A, 0.03 g of hydrated tin tetrachloride and 100 g of concentrated sulfuric acid were contacted for a sulfonation reaction at a reaction temperature of 140° C. for a reaction time of 2 h to obtain a sulfonated bisphenol compound BPAS-2; wherein the molar ratio of bisphenol A to concentrated sulfuric acid was 1:4, and the mass ratio of bisphenol A to hydrated tin tetrachloride was 1:0.0005.

[0241] S2, 13g NaOH, make n(OH) - The aqueous thermosetting resin A2 was obtained by adding 36 g of BPAS-2 to 16.2 g of epibromohydrin at 70 ° C for 2.5 h to obtain the aqueous thermosetting resin A2, wherein the mass ratio of BPAS-2 to NaOH was 1:0.36.

[0242] Among them, the content of S element in the water-based thermosetting resin A2 is 14.6 wt %, the epoxy equivalent is 165 g / mol, the weight-average molecular weight is 4386, R1 is a C1 alkylene group, R2 is 1, R3 is 1, and M is Na. The yield of the water-based thermosetting resin A2 is shown in Table 1.

[0243] Preparation Example 3

[0244] The method of Preparation Example 1 was followed, except that bisphenol A was replaced with 60.5 g of bisphenol B, and concentrated sulfuric acid was replaced with an equal molar amount of aminosulfonic acid. The S content, epoxy equivalent, weight-average molecular weight, and yield of water-based thermosetting resin A3 were obtained and are shown in Table 1.

[0245] Preparation Example 4

[0246] The method of Example 1 was followed, except that the amount of concentrated sulfuric acid used was 125 g, resulting in a molar ratio of bisphenol A to concentrated sulfuric acid of 1:5. The S content, epoxy equivalent, weight-average molecular weight, and yield of water-based thermosetting resin A4 were obtained and are shown in Table 1.

[0247] Preparation Example 5

[0248] The method of Preparation Example 1 was followed, except that in step S2, 36 g of BPAS-1 was used, resulting in a mass ratio of BPAS-1 to epichlorohydrin of 1:0.5. The S content, epoxy equivalent weight, weight-average molecular weight, and yield of water-based thermosetting resin A5 were obtained and are shown in Table 1.

[0249] Preparation Example 6

[0250] The method of Preparation Example 1 was followed, except that 0.04 g of ferric chloride was used, resulting in a mass ratio of bisphenol A to ferric chloride of 1:0.0007. The S content, epoxy equivalent, weight-average molecular weight, and yield of water-based thermosetting resin A6 were obtained and are shown in Table 1.

[0251] Preparation Example 7

[0252] The method of Preparation Example 1 was followed, except that 4.8 g of sodium hydroxide was used, resulting in a mass ratio of BPAS-1 to sodium hydroxide of 1:0.1. The S content, epoxy equivalent, weight-average molecular weight, and yield of water-based thermosetting resin A7 were obtained and are shown in Table 1.

[0253] Preparation Example 8

[0254] The method of Preparation Example 1 was followed, except that in step S2, 9.6 g of epichlorohydrin was used, resulting in a mass ratio of BPAS-1 to epichlorohydrin of 1:0.2. The S content, epoxy equivalent weight, weight-average molecular weight, and yield of water-based thermosetting resin A8 were obtained and are shown in Table 1.

[0255] Preparation Example 9

[0256] The method of Example 1 was followed, except that the amount of concentrated sulfuric acid used was 12.5 g, resulting in a molar ratio of bisphenol A to concentrated sulfuric acid of 1:0.5. The S content, epoxy equivalent, weight-average molecular weight, and yield of the water-based thermosetting resin A9 were obtained and are shown in Table 1.

[0257] Comparative Preparation Example 1

[0258] The method of Preparation Example 1 was followed, except that bisphenol A was not sulfonated. The S content, epoxy equivalent, weight average molecular weight, and yield of the obtained waterborne thermosetting resin D1 are shown in Table 1.

[0259] Table 1 ps: cat1 refers to the first catalyst, cat2 refers to the second catalyst

[0260] Table 1 (continued)

[0261] The curing agent NA was prepared according to the following method:

[0262] S1. In the presence of nitrogen, a four-necked round-bottom flask containing 55 parts by weight of deionized water, 30 parts by weight of acrylamide (monomer A1), 3 parts by weight of sodium maleic anhydride monohexadecyl carboxylate (HEC16) (emulsifier), and 2 parts by weight of nonylphenol polyoxyethylene ether (OP-10) (emulsifier) ​​was placed in a constant temperature water bath at 30°C, stirred at 1000 r / min, and mixed for 10 minutes to obtain a first mixture.

[0263] S2. Add 8 parts by weight of 4-vinylaniline (monomer C1) and 2 parts by weight of styrene (monomer B1) to the first mixture, stir at 1000 r / min, and mix for 15 minutes to obtain a second mixture.

[0264] S3. Add 0.01 parts by weight of azobisisobutyronitrile and 0.02 parts by weight of azobisisobutylimidazoline hydrochloride (VA044) to the second mixture, stir and mix, reduce the speed to 300 rpm, and polymerize at 30°C for 4 hours. Discharge and purify to obtain an unsaturated amide copolymer NA. The amount of initiator used is 0.075 wt% based on the total amount of the monomer mixture.

[0265] Based on the total weight of the monomer mixture, the amount of the monomer A1 is 75 wt %, the amount of the monomer B1 is 5 wt %, and the amount of the monomer C1 is 20 wt %.

[0266] Based on the total weight of the unsaturated amide copolymer NA, the content of the structural unit I is 75 wt %, the content of the structural unit II is 5 wt %, and the content of the structural unit III is 20 wt %.

[0267] The curing agent NB was prepared according to the following method:

[0268] S1. In the presence of nitrogen, a four-necked round-bottom flask containing 30 parts by weight of deionized water, 24 parts by weight of acrylamide (monomer A1), 27 parts by weight of maleic anhydride (monomer B1), 1.5 parts by weight of sodium maleic anhydride monohexadecyl carboxylate (HEC16) (emulsifier), 1 part by weight of nonylphenol polyoxyethylene ether (OP-10), and 0.5 parts by weight of sodium maleic anhydride monohydroxyethyl methacrylate carboxylate (MAME) (emulsifier) ​​was placed in a thermostatic water bath at 30° C., stirred at a speed of 300 r / min, and mixed for 10 minutes to obtain a first mixture;

[0269] S2, adding 10 parts by weight of 4-vinylaniline (monomer D1) and 6 parts by weight of styrene (monomer C1) to the first mixture and mixing for 15 minutes to obtain a second mixture;

[0270] S3. Add 0.006 parts by weight of azobisisobutyronitrile (I1) and 0.024 parts by weight of azobisisobutylimidazoline hydrochloride (VA044) (I2) to the second mixture, stir and mix, and polymerize at 40° C. for 4 hours to obtain an unsaturated amide polymer NB after purification.

[0271] Based on the total weight of the monomer mixture, the amount of monomer A is 35.8wt%, the amount of monomer B is 40.3wt%, the amount of monomer C is 9wt%, and the amount of monomer D is 14.9wt%; the amount of emulsifier is 4.4wt%, the total amount of initiator is 0.045wt%, the amount of initiator azobisisobutyronitrile is 0.009wt%, and the amount of initiator azobisisobutylimidazoline hydrochloride (VA044) is 0.036wt%.

[0272] The following examples illustrate the preparation of honeycomb resin products

[0273] Examples 1-11, Comparative Example 1

[0274] According to the formulations in Table 2 and Table 2 (Continued), the resin compositions were mixed and cured to prepare honeycomb products L1-L11 and DL1.

[0275] Among them, the curing time is 2 hours at a temperature of 120°C; the apparent viscosity of the resin composition is shown in Table 2, and the porosity, pore size, pore density, density, compressive strength and deformation rate of the honeycomb epoxy resin products L1-L11 and DL1 are shown in Table 3.

[0276] Table 2 ps: 1:0.25 a Refers to the mass ratio of cationic emulsifier 18-2-18 and anionic emulsifier sodium stearate is 1:0.25

[0277] Table 2 (continued) ps: 1:0.5 b Refers to the mass ratio of cationic emulsifier 18-2-18 and anionic emulsifier sodium stearate is 1:0.5

[0278] Table 3

[0279] It can be seen from the above results that the water-based thermosetting resin prepared by Preparation Examples 1-11 of the present invention has a good effect. The honeycomb resin products obtained after curing have a suitable pore structure and porosity, and also have strong compressive strength, specifically not less than 25 MPa, and a small deformation rate, which can be no more than 4% at 40 MPa and 150°C.

[0280] Furthermore, preferred embodiments 1-2, 5, and 7-9 of the present invention achieve better effects, with a compressive strength of not less than 38 MPa, and a deformation rate of not more than 1.2% at 40 MPa and 150°C.

[0281] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. An aqueous thermosetting resin, characterized in that, The aqueous thermosetting resin has the structure shown in Formula I; R1 is an alkylene group of C1-C4; A is wherein, R2 and R3 are each independently H, CH3, CF3 or CH2CH3; 0 < m1 + m2 ≤ 8; M is K or Na.

2. The aqueous thermosetting resin according to claim 1, wherein R1 is an alkylene group of C1-C3; Preferably, A is wherein, R2 and R3 are each independently H, CH3, CF3 or CH2CH3; M is Na.

3. The aqueous thermosetting resin according to claim 1 or 2, wherein, The content of S element in the aqueous thermosetting resin is 6-20 wt%, preferably 10-15 wt%; Preferably, the epoxy equivalent of the aqueous thermosetting resin is 100 g / eq - 300 g / eq, preferably 150 g / eq - 200 g / eq; Preferably, the weight-average molecular weight of the aqueous thermosetting resin is 2000 g / mol - 10000 g / mol, preferably 3000 g / mol - 5000 g / mol.

4. A preparation method of an aqueous thermosetting resin, characterized in that, The preparation method includes the following steps: S1. In the presence of a first catalyst and water, contact a bisphenol compound with a sulfonating agent to carry out a sulfonation reaction to obtain a sulfonated bisphenol compound; S2. In the presence of a second catalyst and water, contact the sulfonated bisphenol compound with monomer A shown in Formula II to carry out a polycondensation reaction to obtain the water-soluble thermosetting resin; wherein, p is an integer from 1 to 4, and X is Cl or Br.

5. The preparation method according to claim 4, wherein, In step S1, the bisphenol compound is selected from at least one of bisphenol A, bisphenol S, bisphenol B, bisphenol F and bisphenol AF; Preferably, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and sulfamic acid; Preferably, the first catalyst is a Lewis acid; Preferably, the molar ratio of the bisphenol compound to the sulfonating agent is 1:1 - 5, preferably 1:2 - 4; Preferably, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001 - 0.0008, preferably 1:0.0003 - 0.0005.

6. The preparation method according to claim 4 or 5, wherein, In step S2, in Formula II, p is an integer from 1 to 3, and X is Cl; Preferably, the second catalyst is a base; Preferably, the mass ratio of the sulfonated bisphenol compound to monomer A is 1:0.25 - 0.65, preferably 1:0.3 - 0.5; Preferably, the mass ratio of the sulfonated bisphenol compound to the second catalyst is 1:0.1 - 0.5, preferably 1:0.15 - 0.

38.

7. The preparation method according to any one of claims 4-6, wherein, The conditions of the sulfonation reaction include: the reaction temperature is 120 - 150 °C, and the reaction time is 2 - 6 h; Preferably, the conditions of the polycondensation reaction include: the reaction temperature is 40 - 80 °C, and the reaction time is 2 - 4 h.

8. An aqueous thermosetting resin prepared by the preparation method according to any one of claims 4 - 7.

9. A resin composition, characterized in that, The resin composition includes component A and component B, wherein component A and component B exist independently; Component A contains an aqueous thermosetting resin, a solvent-based thermosetting resin, an emulsifier and water; Component B contains a curing agent; The content of the aqueous thermosetting resin is 5wt%-40wt%, the content of the solvent-based thermosetting resin is 10wt%-76wt%, the content of the emulsifier is 0.5wt%-4wt%, and the content of water is 16wt%-50wt%. The aqueous thermosetting resin is the aqueous thermosetting resin described in any one of claims 1-3 and 8.

10. The resin composition according to claim 9, wherein, The content of the water-soluble thermosetting resin is 30wt%-40wt%, the content of the solvent-based thermosetting resin is 20wt%-40wt%, the content of the emulsifier is 2wt%-3wt%, and the content of water is 17wt%-48wt%. Preferably, based on 100 parts by weight of the component A, the dosage of the curing agent is 50-80 parts, preferably 60-80 parts.

11. The resin composition according to claim 9 or 10, wherein The emulsifier is selected from cationic emulsifiers and / or anionic emulsifiers. Preferably, the cationic emulsifier is selected from at least one of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, docosyl trimethyl ammonium chloride, N,N-ethylene bis octadecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl benzyl ammonium chloride. Preferably, the anionic emulsifier is selected from at least one of sodium stearate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium oleate, sodium laurate, sodium rosinate, disodium dodecyl phenyl ether disulfonate, and sodium dibutylnaphthalene sulfonate.

12. The resin composition according to claim 11, wherein, The emulsifier is a cationic emulsifier and an anionic emulsifier. Wherein, the mass ratio of the cationic emulsifier to the anionic emulsifier is 1:0.25-1, preferably 1:0.3-0.

65.

13. The resin composition according to any one of claims 9 to 12, wherein, The solvent-based thermosetting resin is selected from at least one of epoxy resins, polyimides, and unsaturated resins. The curing agent is selected from aqueous phenolic resins and / or unsaturated amide polymers.

14. The resin composition according to any one of claims 9 to 13, wherein, At 25°C, the apparent viscosity of the resin composition is 100mPa·s-400mPa·s, preferably 200mPa·s-300mPa·s.

15. A honeycomb resin product, characterized in that, The honeycomb resin product is prepared by mixing and curing the resin composition described in any one of claims 9-14.

16. The honeycomb resin product according to claim 15, wherein there are connected channels in the honeycomb resin product.

17. The honeycomb resin product according to claim 15 or 16, wherein, The porosity of the honeycomb resin product is 1%-40%, preferably 20%-30%. Preferably, the pore diameter of the honeycomb resin product is 0.1mm-0.7mm; preferably 0.3mm-0.5mm. Preferably, the pore density of the honeycomb resin product is 20-500, preferably 50-400.

18. The honeycomb resin product according to any one of claims 15-17, wherein, The density of the honeycomb resin product is 0.85 g / cm 3 - 0.95 g / cm 3 , preferably 0.88 g / cm 3 - 0.91 g / cm 3 .

19. The honeycomb resin product according to any one of claims 15-18, wherein, In the range of 60-150°C, the compressive strength of the honeycomb resin product is greater than or equal to 20MPa; preferably greater than or equal to 37MPa. Preferably, in the range of 40MPa and 60-150°C, the deformation rate of the honeycomb resin product is less than or equal to 8%, preferably less than or equal to 4%, more preferably less than or equal to 1.5%.

20. A method for preparing a honeycomb resin product, characterized in that, The preparation method includes: Mixing and curing each component in the resin composition according to any one of claims 9-14 to obtain the honeycomb resin product.

21. The preparation method according to claim 20, wherein The conditions for curing include: the curing temperature is 90°C - 150°C, and the curing time is 10 min - 6 h; Preferably, the conditions for curing include: the curing temperature is 120°C - 150°C, and the curing time is 30 min - 4 h.

22. Application of the aqueous thermosetting resin according to any one of claims 1-3 and 8, the resin composition according to any one of claims 9-14, or the honeycomb resin product according to any one of claims 15-19 in at least one of reservoir development, building floor tiles, and adsorption materials.

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