Resin composition and use thereof, resin product and use thereof

Abstract

The present application relates to the technical field of shale gas reservoir exploitation, and discloses a resin composition and application thereof, and a resin product and application thereof.The resin composition comprises: 30wt%-50wt% of a water-based thermosetting resin; 20wt%-30wt% of a solvent-based resin; 3wt%-8wt% of an emulsifier; and 12wt%-47wt% of water; wherein the emulsifier is a quaternary ammonium salt type emulsifier.The resin composition has excellent stability, and when used for preparing a resin product, the average pore size and hardness change rate of the obtained resin product are low.

Description

Technical Field

[0001] The present invention relates to the technical field of shale gas reservoir mining, and in particular to a resin composition and application thereof, a resin product and application thereof. Background Art

[0002] Shale oil refers to the petroleum resources contained in shale formations, primarily shale. This includes oil trapped in the pores and fractures of shale, as well as oil resources in adjacent layers and interlayers of dense carbonate or clastic rocks within shale formations. After years of theoretical research and practical exploration, effective development methods have emerged: multi-stage horizontal well fracturing and three-dimensional fracture network technology. These technologies, in addition to significantly improving the pumping capacity of fracturing pumps and improving downhole tubing and facilities, also play a crucial role in fracturing materials, particularly fracturing fluids.

[0003] Due to the characteristics of shale reservoirs, fracturing fluids require two key properties beyond general requirements: strong suspension capacity to ensure a wider and more even placement of proppants, and low cost. Shale oil fracturing typically uses tens to hundreds of thousands of cubic meters of fluid per well, necessitating a low cost. Overall, the pumping and cost-effective placement of proppants are key technical considerations for the entire shale oil fracturing process.

[0004] The above requirements for fracturing fluids also bring about some new contradictions and problems: (1) excessive consumption of fresh water resources; (2) the difficulty in handling large amounts of flowback fluid; and (3) the irreconcilable contradiction between high performance and low cost of fracturing fluids. In summary, there is an urgent need to provide a high-performance fracturing fluid to solve the above problems. Summary of the Invention

[0005] The present invention aims to overcome the problems of insufficient stability, easy stratification, and unstable IGP of fracturing fluid systems in the prior art, and to provide a resin composition and its application, a resin product, and its application. The resin composition has excellent storage stability and does not stratify during long-term storage. When the resin composition is used to prepare a resin product, the average pore size and hardness change rate of the obtained resin product are low.

[0006] In order to achieve the above object, the first aspect of the present invention provides a resin composition, wherein the resin composition comprises:

[0007] 30wt%-50wt% of water-based thermosetting resin;

[0008] 20wt%-30wt% of solvent-based resin;

[0009] 3 wt% to 8 wt% of an emulsifier;

[0010] 12 wt%-47 wt% water;

[0011] Wherein, the emulsifier is a quaternary ammonium salt emulsifier.

[0012] A second aspect of the present invention provides a resin product, wherein the resin product is prepared by mixing and curing the resin composition of the first aspect.

[0013] The third aspect of the present invention provides use of the resin composition of the first aspect or the resin product of the second aspect in reservoir exploration and development.

[0014] Through the above technical solution, the resin composition and its application, and the resin product and its application provided by the present invention achieve the following beneficial effects:

[0015] The resin composition provided by the present invention contains a water-based thermosetting resin and a solvent-based resin in a specific ratio, and is combined with a specific amount of a quaternary ammonium salt emulsifier. The compatibility between the water-based thermosetting resin and the solvent-based resin can be significantly improved, so that the resin composition has excellent storage stability and an apparent viscosity that meets the application requirements in the field of oil and gas exploration and production. The resin composition can be ensured not to delaminate during long-term storage.

[0016] Furthermore, by adopting a quaternary ammonium salt emulsifier having a specific structure and / or a specific molecular chain length, the storage stability of the resin composition can be further improved, and the resin product obtained after curing the resin composition can be ensured to be uniform. Specifically, the average pore size and hardness have a small deviation in each part of the entire resin product. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 These are photographs of the resin composition A1 of Example 1 (right) and the resin composition DA1 of Comparative Example 1 (left) after standing at 25° C. for 180 days. DETAILED DESCRIPTION

[0018] 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.

[0019] A first aspect of the present invention provides a resin composition, wherein the resin composition comprises:

[0020] 30wt%-50wt% of water-based thermosetting resin;

[0021] 20wt%-30wt% of solvent-based resin;

[0022] 3 wt% to 8 wt% of an emulsifier;

[0023] 12 wt%-47 wt% water;

[0024] Wherein, the emulsifier is a quaternary ammonium salt emulsifier.

[0025] In the present invention, the resin composition contains a water-based thermosetting resin and a solvent-based resin in a specific ratio, and is combined with a specific amount of a quaternary ammonium salt emulsifier, which can significantly improve the compatibility between the water-based thermosetting resin and the solvent-based resin, so that the resin composition has excellent storage stability and an apparent viscosity that meets the application requirements in the field of oil and gas exploration and production, and can ensure that the resin composition does not delaminate during long-term storage.

[0026] Furthermore, in the present invention, in order to further improve the storage stability of the resin composition and enhance the uniformity of the performance of the cured resin product, preferably, the emulsifier is selected from the compound A represented by formula I and / or the compound B represented by formula II;

[0027]

[0028] wherein R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H or C1-C18 alkyl; n is an integer of 8-22, m is an integer of 2-4, and p1 and p2 are each independently an integer of 3-22;

[0029] X is Cl, Br or I.

[0030] Further, R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H or C1-C3 alkyl; n is an integer of 11-17, m is an integer of 2-3, and p1 and p2 are each independently an integer of 7-17;

[0031] X is Cl.

[0032] According to the present invention, the emulsifier is selected from at least one of compound A1 (structure as shown in Formula I, R1, R2, R3 are H; n is 12, X is Cl), compound A2 (structure as shown in Formula I, R1, R2, R3 are -CH3; n is 12, X is Cl), compound B1 (structure as shown in Formula II, R4, R5, R6 and R7 are H; m is 2, p1 is 8, p2 is 8; X is Cl) and compound B2 (structure as shown in Formula II, R4, R5, R6 and R7 are -CH3; m is 2, p1 is 8, p2 is 8; X is Cl).

[0033] According to the present invention, the emulsifier includes compound A and compound B.

[0034] According to the present invention, the mass ratio of the compound A to the compound B is 1:0.25-4.

[0035] In the present invention, two quaternary ammonium salt emulsifiers (Compound A and Compound B) with different structures are used together, and the storage stability of the resin composition and the uniformity of the performance of the cured resin product are more excellent. When the mass ratio of Compound A to Compound B meets the above range, the system has the characteristics of moderate viscosity, good storage stability and good fluidity, and the uniformity of the performance of the cured resin product is further improved.

[0036] Furthermore, the mass ratio of the compound A to the compound B is 1:0.5-2.

[0037] According to the present invention, the resin composition comprises:

[0038] 35wt%-45wt% water-based thermosetting resin;

[0039] 25wt%-28wt% of solvent-based resin;

[0040] 4-6 wt% of an emulsifier;

[0041] 21 wt% - 36 wt% water.

[0042] According to the present invention, the water-based thermosetting resin has a structure shown in Formula III;

[0043]

[0044] R8 is a C1-C4 alkylene group;

[0045] A is Among them, R9, R 10 Each independently is H, CH3, CF3 or CH2CH3;

[0046] 0 <m1+m2≤8;

[0047] M is K or Na.

[0048] In the present invention, the inventors have discovered that by using a water-based thermosetting resin having a structure represented by Formula III, since the water-based thermosetting resin contains sulfonic acid groups, it can form a high-concentration stable solution (60-80%) with water, thereby further improving the stability of the composition containing the water-based thermosetting resin.

[0049] In the present invention, in Formula III, the specific values ​​of m1 and m2 have no special meaning, but only indicate that the water-based thermosetting resin represented by Formula III contains SO3M groups. There is no special limitation on the specific values ​​of m1 and m2, as long as the water-based thermosetting resin contains SO3M groups.

[0050] In the present invention, the water-based thermosetting resin having the structure shown in Formula III is prepared according to the following method:

[0051] 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;

[0052] S2. In the presence of a second catalyst and water, contacting the sulfonated bisphenol compound with the monomer A represented by formula IA to carry out a polycondensation reaction to obtain the water-based thermosetting resin;

[0053] wherein p is an integer of 1-4, and X is Cl or Br.

[0054] 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 subjected to polycondensation with a monomer represented by Formula IA to produce a water-based thermosetting resin containing sulfonic acid groups. The thermosetting resin has excellent hydrophilicity, can be cured in an aqueous environment, and has interconnected pores while maintaining high strength.

[0055] In 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.

[0056] In the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0057] In the present invention, the first catalyst is Lewis acid.

[0058] 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.

[0059] In the present invention, the molar ratio of the bisphenol compound to the sulfonating agent is 1:1-5.

[0060] In the present invention, the molar ratio of the bisphenol compound to the sulfonating agent satisfies the above range, which can further meet the sulfonation degree requirement of the water-based thermosetting resin.

[0061] Furthermore, the molar ratio of the bisphenol compound to the sulfonating agent is 1:2-4.

[0062] According to the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001-0.0008.

[0063] 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.

[0064] Furthermore, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0003-1:0.0005.

[0065] In the present invention, in step S2, in formula IA, p is an integer of 1-3, and X is Cl.

[0066] In the present invention, the second catalyst is a base.

[0067] In the present invention, the base can be a conventional base in the art, for example, NaOH, KOH, Ca(OH)2, etc.

[0068] Furthermore, the second catalyst is more preferably NaOH.

[0069] In the present invention, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.25-0.65.

[0070] 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 solid phase proppant.

[0071] Furthermore, the mass ratio of the sulfonated bisphenol compound to the monomer A is 1:0.3-1:0.45.

[0072] In 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.

[0073] In the present invention, the conditions of the sulfonation reaction include: reaction temperature of 120-150° C., and reaction time of 2-6 h.

[0074] Furthermore, the conditions of the sulfonation reaction include: reaction temperature of 130-140° C., and reaction time of 2-4 h.

[0075] In the present invention, the conditions for the polycondensation reaction include: a reaction temperature of 40-80° C. and a reaction time of 2-4 h.

[0076] Furthermore, the conditions of the polycondensation reaction include: reaction temperature of 50-70° C., and reaction time of 2-3 h.

[0077] In the present invention, the preparation method further comprises:

[0078] In step S2, the mass concentration of NH3 in the reaction system is controlled to be lower than 100 mg / L.

[0079] In the present invention, the inventors found that by controlling the mass concentration of NH3 in the reaction system to be lower than 100 mg / L, it is possible to prevent the destruction of epoxy groups, which would result in the product being harder and unable to have good hydrophilicity, thereby affecting the subsequent curing process.

[0080] In the present invention, there is no particular limitation on the method for controlling the mass concentration of NH3 in the reaction system. NH3 can be controlled by vacuuming, heating to reduce the solubility of ammonia, or adding carbonate to absorb NH3.

[0081] Furthermore, the mass concentration of NH3 in the reaction system is controlled to be lower than 30 mg / L.

[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, a bisphenol compound selected from at least one of bisphenol A, bisphenol S, bisphenol B, bisphenol F, and bisphenol AF is contacted with a sulfonating agent selected from at least one of 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 1:0.0003-1:0.0005.

[0085] S2. Add alkali to deionized water and add a sulfonated bisphenol compound, while making the NH3 mass concentration in the system lower than 30 mg / L. Under the condition of not more than 60°C, add monomer A shown in formula IA dropwise for 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] According to the present invention, R8 is a C1-C3 alkylene group;

[0087] According to the present invention, A is Among them, R9, R 10 Each is independently H, CH3, CF3 or CH2CH3.

[0088] According to the present invention, M is Na.

[0089] According to the present invention, based on the total weight of the water-based thermosetting resin, the content of S element is 6-20 wt %.

[0090] Furthermore, based on the total mass of the water-based thermosetting resin, the content of S element is 10-15 wt %.

[0091] In the present invention, the S element in the water-based thermosetting resin is measured using an element analyzer.

[0092] In the present invention, by controlling the content of the S element in the water-based thermosetting resin to meet the above range, it is indicated that the water-based thermosetting resin contains an appropriate content of SO3M, which can make the water-based thermosetting resin have excellent water properties, the state of the aqueous solution formed by dispersion in water is stable, and the resin composition containing the water-based thermosetting resin has appropriate viscosity and excellent fluidity.

[0093] According to the present invention, the epoxy equivalent of the water-based thermosetting resin is 100-300 g / eq.

[0094] In the present invention, when the epoxy equivalent of the waterborne thermosetting resin is controlled to meet the above range, it can ensure that there are sufficient reactive groups in the waterborne thermosetting resin, so that the resin product after the resin composition is cured has properties such as strength that meet actual needs.

[0095] Furthermore, the epoxy equivalent of the water-based thermosetting resin is 150-200 g / eq.

[0096] According to the present invention, the weight average molecular weight of the waterborne thermosetting resin is 2000-10000 g / mol, preferably 3000-5000 g / mol.

[0097] In the present invention, in order to further improve the stability of the resin composition, preferably, a thickener is added to the resin composition. Specifically, the resin composition further includes 0.01 wt% to 2 wt% of the thickener.

[0098] Furthermore, the resin composition further comprises 0.1 wt% to 0.3 wt% of a thickener.

[0099] According to the present invention, the thickener is selected from at least one of polyacrylamide (PAM), poly(2-methyl-2-acrylamidopropanesulfonic acid) (PAMPS), polydimethyldiallyl ammonium chloride (PDADMAC), polyacryloyloxyethyltrimethylammonium chloride (PDAC), polymethacryloyloxyethyltrimethylammonium chloride (PDMC), acrylamide-2-methyl-2-acrylamidopropanesulfonic acid copolymer (P(AM-AMPS)), acrylamide-dimethyldiallyl ammonium chloride copolymer, acrylamide-acryloyloxyethyltrimethylammonium chloride copolymer, and acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer.

[0100] According to the present invention, the solvent-based resin is selected from at least one of epoxy resin, polyimide and unsaturated thermosetting resin.

[0101] According to the present invention, at 25° C., the apparent viscosity of the resin composition is 100-350 mPa·s, preferably 150-230 mPa·s.

[0102] A second aspect of the present invention provides a resin product, wherein the resin product is prepared by mixing and curing the resin composition of the first aspect.

[0103] In the present invention, conventional equipment in the art may be used to mix the components in the epoxy resin composition, such as a twin-screw extruder or a stirrer.

[0104] In the present invention, there is no particular limitation on the mixing conditions, as long as the components in the resin composition can be fully and uniformly mixed.

[0105] In the present invention, the curing conditions include: curing temperature of 90-150° C., curing time of 10 min-6 h, and curing pressure of 20-50 MPa.

[0106] In the present invention, the resin product obtained after curing the resin composition provided by the present invention has high uniformity. Specifically, the average pore diameter and hardness of the resin product have small deviations in various parts of the entire resin product.

[0107] According to the present invention, the pore size P of the resin product at any position i is i The following relationship is satisfied:

[0108]

[0109] In the present invention, the pore size P of the resin product at any position i is iThe pore size of the honeycomb solid phase proppant was measured by using a stereo microscope. Specifically, the resin product was observed under a stereo microscope and the pore size of the resin product was tested within a field of view of 1 cm × 1 cm. The pore size of 20 pores was tested and the average value was taken as the pore size P of the honeycomb solid phase proppant. i , test the aperture P at i different positions respectively i , i is an integer greater than 3, i apertures P i The average value of i apertures P i The maximum value in P max , the minimum value is P min .

[0110] Furthermore, the pore size P at any position i of the resin product i The following relationship is satisfied:

[0111]

[0112] According to the present invention, the hardness A at any position j of the resin product j The following relationship is satisfied:

[0113]

[0114] In the present invention, the hardness P of the resin product at any position j is i Measured using a hardness tester, specifically: Test the hardness A at j different positions of the resin product j , j is an integer greater than 3, j A j The average value of j hardness A j The maximum value in A is max , the minimum value is A min .

[0115] Furthermore, the hardness A of the resin product at any position j is j The following relationship is satisfied:

[0116]

[0117] The third aspect of the present invention provides use of the resin composition of the first aspect or the resin product of the second aspect in reservoir exploration and development.

[0118] The present invention will be described in detail below by way of examples.

[0119] The content of S element in water-based thermosetting resin was measured by elemental analysis method.

[0120] The epoxy equivalent of waterborne thermosetting resin was measured by the hydrochloric acid-pyridine method.

[0121] The weight average molecular weight of the waterborne thermosetting resin was measured by GPC.

[0122] The apparent viscosity of the resin composition is measured by a six-speed rotation viscometer method.

[0123] The stability of the resin composition is measured by the following method: the resin composition is allowed to stand at 25° C., and the time when the resin composition begins to delaminate is observed. The longer the time when delaminate begins to appear, the better the stability of the resin composition.

[0124] The pore size of the resin product was measured using a stereo microscope.

[0125] The hardness of resin products is measured using a hardness tester.

[0126] Emulsifier:

[0127] Emulsifier EA1: Compound A1: The structure is as shown in Formula I, R1, R2, and R3 are H; n is 12, and X is Cl.

[0128] Emulsifier EA2: The structure is as shown in Formula I, R1, R2, and R3 are -CH3; n is 12, and X is Cl;

[0129] Emulsifier EB1: The structure is shown in Formula II, R4, R5, R6 and R7 are H; m is 2, p1 is 8, p2 is 8; and X is Cl.

[0130] Emulsifier EB2: The structure is shown in Formula II, R4, R5, R6 and R7 are -CH3; m is 2, p1 is 8, p2 is 8; X is Cl.

[0131] Emulsifier E3: decyltrimethylammonium chloride, wherein R1, R2, and R3 are -CH3, n is 9, and X is Cl.

[0132] Emulsifier E4: octyltrimethylammonium chloride, wherein R1, R2, and R3 are -CH3, n is 7, and X is Cl.

[0133] Emulsifier E5: hexyltrimethylammonium chloride, wherein R1, R2, and R3 are -CH3, n is 5, and X is Cl.

[0134] Emulsifier E6: sodium dodecylbenzenesulfonate.

[0135] Water-based acrylic modified epoxy resin: WX-609.

[0136] Unsaturated thermosetting resin: 901.

[0137] Epoxy resin: E51.

[0138] Other raw materials used in the examples and comparative examples are all commercially available.

[0139] Preparation Example - Water-based Thermosetting Resin

[0140] Preparation Example 1

[0141] (a) 68.4 g of bisphenol A, 0.03 g of ferric chloride, and 60 g of concentrated sulfuric acid (98%) were contacted for a sulfonation reaction at a temperature of 130° C. for 3 hours to obtain a sulfonated bisphenol compound BPAS-1; wherein the molar ratio of bisphenol A to concentrated sulfuric acid was 1:2, and the mass ratio of bisphenol A to ferric chloride was 1:0.00044.

[0142] (b) 10 g of NaOH was dissolved in deionized water, 48 g of BPAS-1 was added, and 18 g of epichlorohydrin was added dropwise at 50°C for 3 h to carry out a polycondensation reaction, thereby obtaining a water-based thermosetting resin C1. The mass ratio of BPAS-1 to NaOH was 1:0.21, and the mass ratio of BPAS-1 to epichlorohydrin was 1:0.375.

[0143] The content of S element in the waterborne thermosetting resin C1 is 10.9 wt %, the epoxy equivalent is 193 g / eq, and the weight average molecular weight is 3946 g / mol.

[0144] Preparation Example 2

[0145] A water-based thermosetting resin C2 was prepared according to the method of Preparation Example 1, except that the mass of concentrated sulfuric acid was changed to 90 g, and the molar ratio of bisphenol A to concentrated sulfuric acid was 1:3. The content of S element in the water-based thermosetting resin C2 was 13.3 wt %, the epoxy equivalent was 185 g / eq, and the weight-average molecular weight was 4238 g / mol.

[0146] Preparation Example 3

[0147] A water-based thermosetting resin C3 was prepared according to the method of Preparation Example 1, except that ferric chloride was replaced with tin tetrachloride of the same mass, concentrated sulfuric acid was replaced with aminosulfonic acid of the same molar number, and when aminosulfonic acid was added to S2, a vacuum pump was simultaneously turned on to extract the generated NH3 for 50 minutes, so that the mass concentration of NH3 in the system was 20 mg / L, and then epichlorohydrin was added dropwise.

[0148] The content of S element in the waterborne thermosetting resin C3 is 13.4 wt %, the epoxy equivalent is 198 g / eq, and the weight average molecular weight is 4036 g / mol.

[0149] Preparation Example 4

[0150] A water-based thermosetting resin C4 was prepared according to the method of Preparation Example 1, except that the mass of NaOH was changed to 12 g, so that the mass ratio of BPAS-1 to NaOH was 1:0.25.

[0151] The content of S element in the waterborne thermosetting resin C4 is 10.7 wt %, the epoxy equivalent is 186 g / eq, and the weight average molecular weight is 4185 g / mol.

[0152] Example 1

[0153] 40 parts by weight of C1 (a water-based thermosetting resin), 27 parts by weight of epoxy resin E51 (a solvent-based resin), 2 parts by weight of A1 (emulsifier), 4 parts by weight of B1 (emulsifier), and 0.1 parts by weight of PDAC (thickener) were added to 26.8 parts by weight of water and mixed to obtain resin composition A1. The types and amounts of each component are detailed in Table 1. The apparent viscosity and time to onset of delamination (T) of resin composition A1 were tested, and the results are shown in Table 2.

[0154] Examples 2-10, Comparative Examples 1-2

[0155] Resin compositions A2-A10 and DA1-DA2 were prepared according to the method of Example 1, except that the types and amounts of water-based thermosetting resin, solvent-based resin, emulsifier, thickener, and the amount of water were different from those in Example 1, as shown in Table 1.

[0156] The apparent viscosity and the time (T) of the resin compositions A2-A10 and DA1-DA2 were tested. The results are shown in Table 2.

[0157] Table 1

[0158]

[0159]

[0160] Table 2

[0161]

[0162] From the results in Table 2, it can be seen that Examples A1-A10 using the resin composition of the present invention have suitable viscosity and excellent storage stability. When used in oil and gas development, it can ensure that the resin composition has excellent injectability and prolong the operability time.

[0163] Figure 1 The following are photos of the resin compositions of Example 1 and Comparative Example 1 after standing at 25°C for 180 days. Figure 1 It can be seen that Figure 1(Left) is the resin composition DA1 of comparative example 1, which showed obvious delamination after standing at 25°C for 180 days. Figure 1 (Right) is the resin composition A1 of Example 1. After standing at 25°C for 180 days, there is no delamination phenomenon, which meets the requirements of oil and gas fracturing.

[0164] Application Examples

[0165] The resin compositions obtained in Examples A2-A10 and Comparative Examples DA1-DA2 were mixed, 60 parts by weight of a curing agent were added, and the mixture was cured at 140° C. and 40 MPa for 6 h to obtain resin products B1-B10 and DB1-DB2.

[0166] The pore size P at any position on the transverse cross section of the resin product i Test and calculate P max and P min ; Hardness A at the radial section of the resin product j Test and calculate A max and A min , the results are shown in Table 3.

[0167] Table 3

[0168]

[0169] The results in Table 3 indicate that the resin products obtained by curing the resin compositions provided herein, Example B1-B10, exhibit superior uniformity compared to Comparative Example DB1-DB2. Specifically, the average pore diameter and strength of the cured resin products exhibit minimal deviations across various components. This indicates that the resin products as a whole possess superior compressive and shear resistance.

[0170] 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. A resin composition, characterized in that The resin composition comprises: 30wt%-50wt% water-based thermosetting resin; 20wt%-30wt% solvent-based resin; 3wt%-8wt% emulsifier; 12wt%-47wt% water; Wherein, the emulsifier is a quaternary ammonium salt emulsifier; The water-based thermosetting resin has a structure shown in Formula III; Formula III; R8 is a C1-C4 alkylene group; A is or , among which R9, R 10 Each independently is H, CH3, CF3 or CH2CH3; 0 <m1+m2≤8; M is K or Na; Wherein, the solvent-based resin is selected from at least one of epoxy resin, polyimide and unsaturated thermosetting resin; The emulsifier is compound A represented by formula I and compound B represented by formula II; Formula I; Formula II; wherein R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H or C1-C18 alkyl; n is an integer of 8-22, m is an integer of 2-4, and p1 and p2 are each independently an integer of 3-22; X is Cl, Br or I.

2. The resin composition according to claim 1, wherein R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H or C1-C4 alkyl; n is an integer from 11 to 17, m is an integer from 2 to 3, and p1 and p2 are each independently an integer from 7 to 17; X is Cl.

3. The resin composition according to claim 1 or 2, wherein The mass ratio of the compound A to the compound B is 1:0.25-4.

4. The resin composition according to claim 3, wherein The mass ratio of the compound A to the compound B is 1:0.5-2.

5. The resin composition according to claim 1 or 2, wherein The resin composition comprises: 35wt%-45wt% water-based thermosetting resin; 25wt%-28wt% solvent-based resin; 4wt%-6wt% emulsifier; 21wt%-36wt% water.

6. The resin composition according to claim 1 or 2, wherein R8 is a C1-C3 alkylene group; and / or, A is , among which R9, R 10 Each independently is H, CH3, CF3 or CH2CH3; M is Na.

7. The resin composition according to claim 1 or 2, wherein Based on the total weight of the water-based thermosetting resin, the content of the S element is 6-20 wt %.

8. The resin composition according to claim 7, wherein Based on the total weight of the water-based thermosetting resin, the content of the S element is 10-15 wt %.

9. The resin composition according to claim 1 or 2, wherein The epoxy equivalent of the water-based thermosetting resin is 100-300 g / eq.

10. The resin composition according to claim 9, wherein The epoxy equivalent of the water-based thermosetting resin is 150-200 g / eq.

11. The resin composition according to claim 1 or 2, wherein The weight average molecular weight of the water-based thermosetting resin is 2000-10000 g / mol.

12. The resin composition according to claim 11, wherein The weight average molecular weight of the water-based thermosetting resin is 3000-5000 g / mol.

13. The resin composition according to claim 1 or 2, wherein The resin composition further comprises 0.01 wt % to 2 wt % of a thickener.

14. The resin composition according to claim 13, wherein The resin composition includes 0.1 wt % to 0.3 wt % of a thickener.

15. The resin composition according to claim 13, wherein The thickener is selected from at least one of polyacrylamide, poly(2-methyl-2-acrylamidopropanesulfonic acid), polydimethyldiallylammonium chloride, polyacryloyloxyethyltrimethylammonium chloride, polymethacryloyloxyethyltrimethylammonium chloride, acrylamide-2-methyl-2-acrylamidopropanesulfonic acid copolymer, acrylamide-dimethyldiallylammonium chloride copolymer, acrylamide-acryloyloxyethyltrimethylammonium chloride copolymer and acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer.

16. The resin composition according to claim 1 or 2, wherein At 25° C., the resin composition has an apparent viscosity of 100-350 mPa·s.

17. The resin composition according to claim 16, wherein At 25° C., the resin composition has an apparent viscosity of 150-230 mPa·s.

18. A resin product, characterized in that: The resin product is prepared by mixing and curing the resin composition according to any one of claims 1 to 17.

19. The resin product according to claim 18, wherein The pore size P of the resin product at any position i i The following relationship is satisfied: |P max - | / ×100%≤2%;|P min - | / ×100%≤2%。 20. The resin product according to claim 18, wherein The hardness A of the resin product at any position j j The following relationship is satisfied: |A max - / ×100%≤2%;|A min - / ×100%≤2%。 21. Use of the resin composition according to any one of claims 1 to 17 or the resin product according to any one of claims 18 to 20 in reservoir exploration and development.

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