Curable resin composition and use thereof, and honeycomb resin product and preparation method therefor and use thereof

Abstract

The present invention relates to the fields of high polymer materials and oil and gas exploitation, and disclosed are a curable resin composition and a use thereof, and a honeycomb resin product and a preparation method therefor and a use thereof. The curable resin composition comprises a component A and a component B; the component A and the component B are each independently present; the component A comprises an aqueous thermosetting resin, a solvent-type thermosetting resin, an emulsifier, and water; the component B comprises a curing agent, and the curing agent is selected from modified nanosilica represented by formula I and / or a bisphenol novolac resin; in the formula I, A is a structural unit from an anhydride-based compound, and B is a structural unit from a polyamino compound; the bisphenol novolac resin comprises a structural unit represented by formula II and a structural unit represented by formula III; and based on the total weight of the bisphenol novolac resin, the content of the structural unit represented by formula II is 0-100 wt%, and the content of the structural unit represented by formula III is 0-100 wt%.

Description

Curable resin composition and application, honeycomb resin product and preparation method and application thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application 202311773025.0 filed on December 21, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the fields of polymer materials and oil and gas extraction, and in particular to a curable resin composition and application thereof, a honeycomb resin product and a preparation method and application thereof. Background Art

[0004] The fracturing fluid system used in shale gas reservoir development is primarily water-based. Hydraulic fracturing technology primarily involves pumping fracturing fluid into the formation at high rates, creating fractures. A sand-carrying fluid containing proppants is then injected to propel the fractures and establish pathways for oil and gas transport. To address a range of issues with conventional hydraulic fracturing, including sand plugging, debris damage, equipment wear, and difficulty effectively supporting the distal ends of the fractures, researchers have conducted extensive research on proppants, primarily developing low-density proppants to enhance distal fracture conductivity. Maintaining the original structural morphology under high pressure is a fundamental requirement for proppants.

[0005] In existing proppant-fracturing fluid systems, high-viscosity fracturing fluids are typically required to suspend proppant particles to prevent them from settling. These fracturing fluids typically incorporate water-soluble polymers as thickeners to increase their viscosity. However, these fracturing operations require specialized fluid preparation and equipment. Furthermore, pumping the high-viscosity fracturing fluid to a designated location underground and for flowback consume significant pump power. Furthermore, the polymer compounds used in the fracturing fluid enter the formation along with the fracturing fluid. Any remaining polymer compounds can clog the formation's pores, reducing oil production and potentially contaminating the formation. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems that the proppants in the prior art cannot simultaneously meet high compressive strength and high conductivity, and are easily deformed under high temperature and high pressure conditions. A curable resin composition and its application, a honeycomb resin product and its preparation method and application are provided. Component A of the curable resin composition contains a water-based thermosetting resin and a solvent-based thermosetting resin, and is injected into the formation simultaneously with component B. Under high temperature and high pressure formation conditions, it can be rapidly cured to form a honeycomb proppant, which can have both high compressive strength and low deformation rate.

[0007] In order to achieve the above object, the first aspect of the present invention provides a curable resin composition, wherein the curable resin composition comprises a water-based thermosetting resin, a solvent-based thermosetting resin, an emulsifier, a curing agent and water;

[0008] Wherein, the curing agent is selected from modified nano-silica and / or bisphenol-formaldehyde resin shown in Formula I;

[0009] In formula I, M is a nano-silica particle, x is an integer of 1-4, and R1 is an alkyl group with 1-4 carbon atoms;

[0010] n is an integer from 0 to 3, m is an integer from 1 to 3, and n+m=3;

[0011] A is a structural unit derived from an acid anhydride compound, and B is a structural unit derived from a polyamino compound;

[0012] The bisphenol novolac resin comprises a structural unit shown in formula II and a structural unit shown in formula III;

[0013] Q wherein R2 and R3 are each independently H, CH3, CF3 or CH2CH3;

[0014] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit represented by formula II is 0-100 wt %, and the content of the structural unit represented by formula III is 0-100 wt %.

[0015] The second aspect of the present invention provides a honeycomb resin product, characterized in that it is made from the curable resin composition described in the first aspect of the present invention.

[0016] A third aspect of the present invention provides a method for preparing a honeycomb resin product, characterized in that the preparation method comprises:

[0017] The components of the curable resin composition described in the first aspect of the present invention are mixed and cured to obtain the honeycomb resin product.

[0018] The fourth aspect of the present invention provides a use of the curable resin composition according to the first aspect of the present invention or the honeycomb resin product according to the second aspect of the present invention in at least one of oil reservoir development, building floor tiles and adsorption materials.

[0019] Through the above technical solution, the curable resin composition and its application, honeycomb resin product, and its preparation method and application provided by the present invention achieve the following beneficial effects: Component A in the curable resin composition contains a water-based thermosetting resin, which exhibits excellent fluidity. When it and component B are simultaneously injected into a high-temperature, high-pressure formation environment, the water-based thermosetting resin in the composition and a specific curing agent rapidly cure to form a honeycomb product. The curing agent has a specific structure, and the product, after reacting with the water-based thermosetting resin, can serve as a proppant, exhibiting both high compressive strength and low deformation rate. DETAILED DESCRIPTION

[0020] 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.

[0021] A first aspect of the present invention provides a curable resin composition, wherein the curable resin composition comprises component A and component B; wherein the component A and the component B are each present independently;

[0022] The component A comprises a water-based thermosetting resin, a solvent-based thermosetting resin, an emulsifier, a curing agent and water;

[0023] The component B includes a curing agent, and the curing agent is selected from the modified nano-silica and / or bisphenol-formaldehyde resin shown in Formula I;

[0024] In formula I, M is a nano-silica particle, x is an integer of 1-4, and R1 is an alkyl group with 1-4 carbon atoms;

[0025] n is an integer from 0 to 3, m is an integer from 1 to 3, and n+m=3;

[0026] A is a structural unit derived from an acid anhydride compound, and B is a structural unit derived from a polyamino compound;

[0027] The bisphenol novolac resin comprises a structural unit shown in formula II and a structural unit shown in formula III;

[0028] Q wherein R2 and R3 are each independently H, CH3, CF3 or CH2CH3;

[0029] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit represented by formula II is 0-100 wt %, and the content of the structural unit represented by formula III is 0-100 wt %.

[0030] In the present invention, the content of the structural unit represented by formula II and the content of the structural unit represented by formula III are each independently 0wt%, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 30wt%, 35wt%, 40wt%, 42wt%, 45wt%, 50wt%, 53wt%, 55wt%, 60wt%, 65wt%, 68wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 100wt% and the range consisting of any two of the above values.

[0031] In the present invention, the contents of the structural unit represented by formula II and the structural unit represented by formula III are not both 0, and the sum of the contents of the structural unit represented by formula II and the structural unit represented by formula III is 100%.

[0032] In the present invention, the water-based thermosetting resin can be completely dissolved in water.

[0033] In the present invention, the contents of the structural unit represented by formula II and the structural unit represented by formula III are measured by gel permeation chromatography (GPC).

[0034] In the present invention, the curing agent is selected from the modified nano-silica and / or bisphenol-formaldehyde resin of the above structure, which can enable the water-based thermosetting resin and the solvent-based thermosetting resin to be fully cured when the curable resin composition is injected into a high-temperature and high-pressure formation, thereby forming a honeycomb resin product with a specific structure, high compressive strength and low deformation rate.

[0035] In one specific embodiment of the present invention, the modified nano-silica shown in Formula I is used as a curing agent. Since the modified nano-silica has a small particle size and a large specific surface area, it has good dispersibility in the epoxy resin and a high amino content. A dendritic morphology is exhibited on the surface of the nano-silica particles M. When it is added to the epoxy resin, it can undergo a bonding reaction with the epoxy groups in the epoxy resin, giving full play to the advantages of both, so that the cured epoxy resin has a greater compressive strength.

[0036] In another specific embodiment of the present invention, using the bisphenol novolac resin as a curing agent, because the bisphenol novolac resin includes specific structural unit I and structural unit II, the molecular chain of the bisphenol novolac resin can be made to produce a micro-crosslinked structure, forming a phenolic resin with a micro-reticular shape, and finally making the bisphenol novolac resin have the special performance of ensuring that the resin product has a higher compressive strength after curing under the condition of good water solubility, when using it as a curing agent for curing epoxy resin, the high temperature resistance and the compressive strength of epoxy resin can be significantly improved. Especially, when the content of the structural unit shown in Formula II and the structural unit shown in Formula III in the bisphenol novolac resin meets the above-mentioned specific content, due to the reason of the sulfonic acid group, the bisphenol novolac resin is made to have good water solubility and storage-stable special performance, and then further improve the compressive strength under high temperature and high pressure conditions of the epoxy resin cured by it.

[0037] According to the present invention, in Formula I, the acid anhydride compound is selected from at least one of maleic anhydride, phthalic anhydride and succinic anhydride.

[0038] According to the present invention, the polyamino compound has a linear polyethylene polyamino compound or a nonlinear polyethyleneimine having a number average molecular weight of 300-3000, which is represented by formula IV:

[0039] Here, p is an integer from 1 to 6.

[0040] In the present invention, the polyamino compound is selected from the above compounds, so that the amino content in the modified nano-silica is high, further improving the curing effect of water-based thermosetting resin and solvent-based thermosetting resin.

[0041] According to the present invention, the average particle size of the nano-silicon dioxide particles M is 10-500 nm, and the specific surface area is 10-300 m 2 / g.

[0042] In the present invention, the average particle size of the nano-silica particles M is 10nm, 11nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 150nm, 200nm, 280nm, 300nm, 310nm, 330nm, 350nm, 400nm, 420nm, 430nm, 44nm, 450nm, 460nm, 470nm, 480nm, 490nm, 500nm and a range consisting of any two of the above values.

[0043] In the present invention, the specific surface area of ​​the nano-silicon dioxide particles M is 10m 2 / g, 20m2 / g、30m 2 / g, 40m 2 / g, 50m 2 / g, 60m 2 / g、70m 2 / g、80m 2 / g、90m 2 / g、100m 2 / g、110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 180m 2 / g, 200m 2 / g, 210m 2 / g, 220m 2 / g, 250m 2 / g, 260m 2 / g, 270m 2 / g, 280m 2 / g, 285m 2 / g, 290m 2 / g、300m 2 / g and the range consisting of any two of the above values.

[0044] Furthermore, the average particle size of the modified nano-silica is 10-500nm, and the specific surface area is 50-500m 2 / g.

[0045] According to the present invention, the particle size dispersion coefficient of the modified nano-silica is 0.09-0.15.

[0046] In the present invention, the particle size dispersion coefficient of the modified nano-silica is 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, and a range consisting of any two of the above values.

[0047] In the present invention, the particle size dispersion coefficient of the modified nano-silica satisfies the above range, which can improve the dispersibility of the modified nano-silica in water-based thermosetting resins and solvent-based thermosetting resins, and further improve the curing performance of the curable resin composition using the modified nano-silica as a curing agent.

[0048] According to the present invention, the amino content in the modified nano-silica is 0.1-5 mmol / g.

[0049] In the present invention, the amino content in the modified nano-silica is 0.1mmol / g, 0.2mmol / g, 0.3mmol / g, 0.4mmol / g, 0.5mmol / g, 0.6mmol / g, 0.7mmol / g, 0.8mmol / g, 0.9mmol / g, 1mmol / g, 1.1mmol / g, 1.2mmol / g, 1.3mmol / g, 1.4mmol / g, 1.5mmol / g and a range consisting of any two of the above values.

[0050] According to the present invention, in the bisphenol-formaldehyde resin, Q is wherein R2 and R3 are each independently H or CH3.

[0051] Furthermore, R2 and R3 are each independently CH3.

[0052] According to the present invention, based on the total weight of the bisphenol novolac resin, the content of the structural unit represented by formula II is 60-80 wt %, and the content of the structural unit represented by formula III is 20-40 wt %.

[0053] In the present invention, the content of the structural unit shown in Formula II is 60wt%, 65wt%, 68wt%, 70wt%, 75wt%, 80wt% and the range consisting of any two of the above values; the content of the structural unit shown in Formula III is 20wt%, 23wt%, 25wt%, 26wt%, 27wt%, 28wt%, 30wt%, 32wt%, 35wt%, 36wt%, 37wt%, 38wt%, 40wt% and the range consisting of any two of the above values.

[0054] According to the present invention, the weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol.

[0055] In the present invention, the weight average molecular weight of the bisphenol novolac resin is 2000g / mol, 2100g / mol, 2200g / mol, 2300g / mol, 2500g / mol, 3000g / mol, 3300g / mol, 3500g / mol, 4000g / mol, 4500g / mol, 4800g / mol, 5000g / mol, 5300g / mol, 5400g / mol, 5500g / mol, 5600g / mol, 6000g / mol, 6100g / mol, 6200g / mol, 6500g / mol, 6800g / mol, 7000g / mol, 8000g / mol, 8500g / mol, 9000g / mol, 9500g / mol, 10000g / mol and a range consisting of any two of the above numerical values.

[0056] Furthermore, the weight average molecular weight of the bisphenol novolac resin is 3000-5000 g / mol.

[0057] According to the present invention, in the curable resin composition, the content of the aqueous thermosetting resin is 5-40 parts by weight, the content of the solvent-based thermosetting resin is 10-76 parts by weight, the content of the emulsifier is 0.5-4 parts by weight, and the content of water is 16-50 parts by weight.

[0058] In the present invention, in the curable resin composition, the content of the aqueous thermosetting resin is 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, and a range consisting of any two of the above values.

[0059] In the present invention, the content of the solvent-based thermosetting resin is 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 45 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 55 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, and a range consisting of any two of the above values.

[0060] In the present invention, the content of the emulsifier is 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 3 parts by weight, 3.1 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight and a range consisting of any two of the above values.

[0061] In the present invention, the content of water is 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight and a range consisting of any two of the above values.

[0062] In the present invention, the components of the curable resin composition meet the above ranges, so that the composition can be rapidly cured in a high-temperature and high-pressure formation environment to form a honeycomb-shaped product.

[0063] Furthermore, in the curable resin composition, the content of the aqueous thermosetting resin is 30-40 parts by weight, the content of the solvent-based thermosetting resin is 20-40 parts by weight, the content of the emulsifier is 2-3 parts by weight, and the content of water is 17-48 parts by weight.

[0064] According to the present invention, relative to the total amount of component A, the amount of component B is 40-80 parts by weight, preferably 60-80 parts by weight.

[0065] In the present invention, relative to the total amount of component A, the amount of component B is 40 parts by weight, 45 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 55 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight and the range consisting of any two of the above values, preferably 60-80 parts by weight.

[0066] According to the present invention, the water-based thermosetting resin has a structure shown in Formula V;

[0067] R4 is a C1-C3 alkylene group;

[0068] Ar is wherein R5 and R6 are each independently H, CH3, CF3 or CH2CH3;

[0069] 0 <y1+y2≤8;

[0070] M is K or Na.

[0071] In the present invention, the water-based thermosetting resin contains hydrophilic sulfonate groups, which can significantly improve the hydrophilicity of the water-based thermosetting resin. When it is combined with a solvent-based thermosetting resin and a specific curing agent is added, a phase change reaction can occur under formation conditions to form a honeycomb solid phase proppant.

[0072] According to the present invention, R4 is a C1-C3 alkylene group.

[0073] According to the present invention, Ar is Wherein, R5 and R6 are each independently H, CH3, CF3 or CH2CH3.

[0074] According to the present invention, M is Na.

[0075] According to the present invention, the content of S element in the water-based thermosetting resin is 6-20 wt %.

[0076] In the present invention, the content of S element in the water-based thermosetting resin is 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt% and a range consisting of any two of the above values.

[0077] In the present invention, when the content of the S element in the waterborne thermosetting resin satisfies the above range, the sulfonic acid group content in the waterborne thermosetting resin meets the requirements, and the waterborne thermosetting resin has excellent water solubility and can be stably dispersed in an aqueous solution.

[0078] Furthermore, the content of S element in the water-based thermosetting resin is 10-15 wt %.

[0079] According to the present invention, the epoxy equivalent of the water-based thermosetting resin is 100-300 mol / 100g.

[0080] In the present invention, the epoxy equivalent of the water-based thermosetting resin is 100 mol / 100 g, 120 mol / 100 g, 150 mol / 100 g, 160 mol / 100 g, 170 mol / 100 g, 180 mol / 100 g, 200 mol / 100 g, 250 mol / 100 g, 280 mol / 100 g, 300 mol / 100 g, and a range consisting of any two of the above values.

[0081] In the present invention, the epoxy equivalent of the water-based thermosetting resin satisfies the above-mentioned range, which can improve its reactivity, so that the water-based thermosetting resin reacts more thoroughly during the curing reaction, further improving the compressive strength of the product prepared from the resin when used as a proppant, while being less prone to deformation and improving the permeability.

[0082] Furthermore, the epoxy equivalent of the water-based thermosetting resin is 150-200 mol / 100g.

[0083] According to the present invention, the emulsifier is selected from cationic emulsifiers and / or anionic emulsifiers.

[0084] Furthermore, the cationic emulsifier is selected from at least one of dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, N,N-ethylenedioctadecyldimethylammonium chloride, dodecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride and octadecyldimethylbenzylammonium chloride.

[0085] Furthermore, the anionic emulsifier is selected from at least one of sodium stearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium laurate, sodium rosinate, sodium didodecylphenyl ether disulfonate, and sodium dibutylnaphthyl sulfonate.

[0086] According to the present invention, the solvent-based thermosetting resin is at least one selected from epoxy resin (EP), polyimide (PI) and unsaturated resin.

[0087] According to the present invention, at 25° C., the apparent viscosity of the curable resin composition is 100-400 mPa·s, preferably 200-300 mPa·s.

[0088] In the present invention, at 25°C, the apparent viscosity of the curable resin composition is 100mPa·s, 110mPa·s, 120mPa·s, 150mPa·s, 160mPa·s, 170mPa·s, 180mPa·s, 190mPa·s, 200mPa·s, 220mPa·s, 250mPa·s, 280mPa·s, 300mPa·s, 330mPa·s, 350mPa·s, 380mPa·s, 400mPa·s and a range consisting of any two of the above values, preferably 200-300mPa·s.

[0089] 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.

[0090] The second aspect of the present invention provides a honeycomb resin product, characterized in that it is made from the curable resin composition described in the first aspect of the present invention.

[0091] According to the present invention, the honeycomb resin product has interconnected channels.

[0092] In the present invention, the honeycomb resin product has interconnected channels, which can support cracks and microcracks while giving the cracks excellent flow conductivity. When used in oil reservoirs, the oil and gas recovery rate can be improved.

[0093] According to the present invention, the porosity of the honeycomb resin product is 1-40%.

[0094] In the present invention, the porosity of the honeycomb resin product is 1%, 2%, 3%, 4%, 5%, 10%, 20%, 25%, 26%, 28%, 30%, 31%, 35%, 38%, 40% and a range consisting of any two of the above values.

[0095] According to the present invention, the pore size of the honeycomb resin product is 0.1-0.7 nm.

[0096] In the present invention, the pore diameter of the honeycomb resin product is 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, or a range consisting of any two of the above values.

[0097] According to the present invention, the cell density of the honeycomb resin product is 200-10,000.

[0098] In the present invention, the cell density of the honeycomb resin product is 200, 210, 300, 350, 400, 500, 600, 700, 800, 900, 1000, 1200, 1500, 2000, 2200, 3000, 3500, 4000, 4500, 5000, 5500, 5800, 6000, 6600, 7000, 7800, 8000, 9000, 9200, 9500, 9800, 10000, and a range consisting of any two of the above values.

[0099] According to the present invention, the density of the honeycomb resin product is 0.85-0.95 g / cm3 .

[0100] In the present invention, the density of the honeycomb resin product is 0.85g / cm 3 , 0.86g / cm 3 , 0.87g / cm 3 、0.88g / cm 3 , 0.89g / cm 3 , 0.9g / cm 3 , 0.93g / cm 3 、0.94g / cm 3 , 0.95g / cm 3 and the range consisting of any two of the above values.

[0101] In the present invention, the honeycomb resin product has the above-mentioned specific porosity, pore size, pore density and density, which enables the solid phase proppant to have high conductivity while still maintaining high compressive strength, low deformation degree and high permeability.

[0102] In the present invention, the permeability of the epoxy resin product at 40 MPa is used to characterize the flow conductivity of the epoxy resin product. That is, the higher the permeability of the epoxy resin product at 40 MPa, the higher the flow conductivity of the epoxy resin product.

[0103] 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.

[0104] Furthermore, the porosity of the honeycomb resin product is 20-30%.

[0105] Furthermore, the pore size of the honeycomb resin product is 0.3-0.5 nm.

[0106] Furthermore, the cell density of the honeycomb resin product is 1000-1500 cells / cm 2 .

[0107] Furthermore, the density of the honeycomb resin product is 0.88-0.91 g / cm 3 .

[0108] According to the present invention, the compressive strength of the honeycomb resin product is 20-40 MPa, preferably 30-40 MPa.

[0109] In the present invention, the compressive strength of the honeycomb resin product is 20 MPa, 22 MPa, 23 MPa, 25 MPa, 28 MPa, 30 MPa, 35 MPa, 40 MPa, or a range consisting of any two of the above values, preferably 30-40 MPa.

[0110] According to the present invention, at 40 MPa and 90° C., the deformation rate of the honeycomb resin product is less than or equal to 8%, preferably less than or equal to 4%.

[0111] In the present invention, at 40 MPa and 90°C, the deformation rate of the honeycomb resin product is 0.1%, 0.5%, 0.8%, 0.9%, 1%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 6%, 7%, 8% and a range consisting of any two of the above values, preferably 0.1-4%.

[0112] A third aspect of the present invention provides a method for preparing a honeycomb resin product, characterized in that the preparation method comprises:

[0113] The honeycomb resin product is obtained by mixing the components of component A in the curable resin composition described in the first aspect of the present invention, and then mixing and curing the components with component B.

[0114] 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.

[0115] Furthermore, the curing conditions include: curing temperature of 120-150° C., and curing time of 30 min-4 h.

[0116] In the present invention, there is no particular limitation on the mixing conditions of the components in component A and the mixing conditions of component A and component B, as long as the components can be fully mixed and uniform.

[0117] The fourth aspect of the present invention provides a use of the curable resin composition according to the first aspect of the present invention or the honeycomb resin product according to the second aspect of the present invention in at least one of oil reservoir development, building floor tiles and adsorption materials.

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

[0119] The permeability of honeycomb resin products is measured according to the petroleum and natural gas industry standard SY / T5345-2007. The specific test method is as follows: a sample with dimensions of 24 mm in diameter and 40 mm in length is cured. The cured sample is placed in a core flooding device, ensuring there is no leakage between the sample column and the rubber sleeve on the inner wall of the core flooding device's holder. After assembly, a certain pressure differential is applied, and the volume and time of the fluid flowing through are recorded. Finally, the permeability is calculated.

[0120] The calculation formula is:

[0121] Among them, K gis the measured permeability, mD; Q2 is the fluid flow rate at the core outlet, cm 3 / s; L is the core length, cm; A is the core cross-sectional area, cm 2 ; P0 is atmospheric pressure, MPa; P1 is the absolute pressure at the core inlet, MPa; P2 is the absolute pressure at the core outlet, MPa; μ is the fluid viscosity, mPa·s.

[0122] The porosity of honeycomb resin products is measured using the saturated liquid volume. Specifically, the cured sample column is placed in a 10°C forced air oven and dried to constant weight. The radius r (mm) and length L (mm) of the sample column are measured, and the volume of the sample column is calculated for later use. 200 mL of deionized water is measured in a graduated cylinder, and the sample column is fully immersed in the deionized water. After 24 hours, the water in the graduated cylinder is removed and the volume V1 (mL) is measured. The porosity is calculated according to the following formula: Porosity = (200 - V1) / (3.14 × r 2 ×L)

[0123] The pore size of honeycomb resin products is measured by stereo microscope observation. Specifically:

[0124] 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.

[0125] The cell density of the honeycomb product is measured by a statistical method using a stereo microscope. Specifically:

[0126] 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 .

[0127] The compressive strength of honeycomb resin products is measured using a universal weight loading machine.

[0128] The deformation rate of honeycomb resin products is measured according to the following method:

[0129] At normal pressure and 25°C, the diameter of the tested honeycomb resin product is D0, mm. 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%.

[0130] The density of honeycomb resin products is measured by determining the mass and calculating the volume.

[0131] The apparent viscosity of the curable resin composition was measured using a six-speed rotational viscometer. Specifically, 300 ml of the curable resin composition was placed in a 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.

[0132] The weight average molecular weight of the water-based thermosetting resin and the bisphenol-formaldehyde resin is measured by gel permeation chromatography (GPC). Specifically, a certain amount of water-based thermosetting resin (or bisphenol-formaldehyde 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 (or bisphenol-formaldehyde resin) is measured.

[0133] The S content in the waterborne thermosetting resin is measured by elemental analysis, specifically, by an oxygen bottle combustion method.

[0134] The epoxy equivalent of waterborne thermosetting resins is measured using the hydrochloric acid-pyridine method. Specifically, 0.5 g of sample is added to 25 mL of hydrochloric acid-acetone solution and reacted at 45°C for 3.5 hours. Pipette 25 mL of hydrochloric acid-acetone solution, add 3 drops of mixed indicator, and perform a blank titration (titration must be completed within 30 seconds). The endpoint is the volume of NaOH standard solution consumed if it does not fade for 5 seconds. Pipette the mixed solution, add three drops of mixed indicator (30 seconds), and titrate with sodium hydroxide if it does not fade for 5 seconds. Record the amount of 0.5 mol / L NaOH consumed, recorded as V, mL. Calculate according to the following formula:

[0135] 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.

[0136] The particle size dispersion coefficient of modified nano-silica M was measured by laser particle size analyzer (DLS).

[0137] The average particle size of the modified nano-silica M was measured by SEM. Specifically, a certain number Z of particles were selected in the SEM image, and the particle size (nm) of each particle was measured respectively. The particle size values ​​were added up and recorded as S (nm). The average value was calculated as the average particle size according to the following formula: Average particle size = S / Z, nm.

[0138] The amino content in the modified nano-silica M is determined by elemental analysis. Specifically, a certain mass m of nano-silica particles is weighed and analyzed to obtain the N content, recorded as M1. The same mass m of modified nano-silica M is then weighed and analyzed to obtain the N content, recorded as M2. The molar number of N in the measured sample, n, is then calculated as (M2 - M1) × M / 14. The amino content in the measured sample is calculated using the following formula: Amino Content = (n / m) × 1000, mmol / g.

[0139] The specific surface area of ​​the modified nano-silica M was measured by a specific surface area tester (model BSD-660A6S|B6S).

[0140] Other raw materials used in the examples and comparative examples are all commercially available.

[0141] According to the formulations in Table 1, curable compositions A1-A10, D1-D2 were prepared.

[0142] Wherein, the water-based thermosetting resin is prepared by the following method:

[0143] 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.

[0144] 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 a polycondensation reaction. The reaction temperature is 50°C and the reaction time is 3 h to obtain a water-based thermosetting resin, wherein the mass ratio of BPAS-1 to NaOH is 1:0.17.

[0145] Among them, in the water-based thermosetting resin, the content of S element is 13.4wt%, the epoxy equivalent is 182mol / 100g, the weight average molecular weight is 3891g / mol, R1 is C1 alkylene, R2 is 1, R3 is 1, and M is Na.

[0146] The modified nano-silica M1-M2 is prepared according to the following method:

[0147] Preparation of modified nano-silica M1

[0148] S1. Preparation of aminopropyl functionalized nano-silica:

[0149] Weigh 2g of the average particle size of 30nm and the specific surface area of ​​200m 2 / g of nano-silica particles were dispersed in 100mL of anhydrous toluene, and then 0.2g of aminopropyltriethoxysilane was added. The mixture was refluxed and stirred at 150°C under nitrogen protection for 24 hours. After the reaction, the solid product was centrifuged to obtain the solid product. The solid product was repeatedly washed with acetone and dichloromethane three times and vacuum dried at 40°C for 12 hours to obtain aminopropyl-functionalized nano-silica.

[0150] S2. Preparation of carboxyl functionalized nano-silica:

[0151] Weigh 2 g of the aminopropyl-functionalized nano-silica prepared above, disperse it in 50 mL of xylene, add 0.2 g of maleic anhydride, and reflux and stir at 160°C under nitrogen protection for 6 hours. After the reaction, wash it repeatedly with methanol three times and vacuum dry it at 40°C for 12 hours to obtain carboxyl-functionalized nano-silica.

[0152] S3. Preparation of modified nano-silica:

[0153] Weigh 1 g of the carboxyl-functionalized nano-silica prepared above, disperse it in 50 mL of toluene, then add 0.25 g of diisopropylcarbodiimide (DIC) and 0.06 g of 1,8-diazabicycloundec-7-ene (DBU), stir and activate at room temperature (25°C) for 1 hour, then add 4 g of polyethyleneimine (number average molecular weight of 1500), continue to react at room temperature for 12 hours, and after the reaction is completed, wash it repeatedly with methanol three times, and vacuum dry it at 40°C for 12 hours to obtain modified nano-silica M1 with the structure of formula I, wherein n is 0, m is 3, and x is 3.

[0154] The particle size of the modified nano-silica M1 is 30 nm and the specific surface area is 300 m 2 / g, the amino content is 2mmol / g, and the dispersion coefficient PDI is 0.11.

[0155] Preparation of modified nano-silica M2

[0156] The preparation method of M1 was followed, except that the specific surface area of ​​the nano-silica particles was 100 m 2 / g, and in step S3, the amount of polyethyleneimine used is 0.4g; the particle size of the modified nano-silica M2 is 30nm, and the specific surface area is 230m 2 / g, the amino content is 0.1mmol / g, and the dispersion index PDI is 0.13.

[0157] The bisphenol novolac resins F1-F2 were prepared according to the following method.

[0158] Preparation of Bisphenol-formaldehyde Resin F1

[0159] S1. 57 g of bisphenol A, 0.03 g of ferric chloride, and 25 g of concentrated sulfuric acid (98 wt%) were contacted for sulfonation at 130°C for 4 hours. The molar ratio of bisphenol A to concentrated sulfuric acid was 1:1, and the mass ratio of bisphenol A to ferric chloride was 1:0.0005. After purification, monosulfonated bisphenol A monomer B1 was obtained.

[0160] S2, under stirring conditions, 60g of the second monomer monomer A (bisphenol A) and 21 parts by weight of monomer B1 (monosulfonated bisphenol compound S1) were mixed with 30g of the first monomer (paraformaldehyde) in deionized water, and NaOH was added to make n(OH) - The first monomer was 27 wt % and the second monomer was 73 wt % based on the total weight of the monomers, and the weight average molecular weight was 3657 g / mol.

[0161] Preparation of Bisphenol-formaldehyde Resin F2

[0162] Bisphenol-formaldehyde resin F2 was prepared according to the method for preparing F1, except that paraformaldehyde was replaced with an equal mass of formaldehyde. The first monomer was used in an amount of 27 wt % and the second monomer was used in an amount of 73 wt % based on the total weight of the monomers, with a weight-average molecular weight of 4089 g / mol.

[0163] Preparation of Bisphenol-formaldehyde Resin DF1

[0164] Bisphenol-formaldehyde resin was prepared according to the method of F1, except that NaOH was added to make n(OH) - The molecular weight is 4 mol / L and the weight average molecular weight is 1203 g / mol.

[0165] Table 1

[0166] Table 1 (continued)

[0167] Examples 1-10

[0168] According to the formulas in Table 1 and Table 1 (Continued), the components of component A in the curable resin compositions A1-A10 were mixed, and then mixed with component B and cured. The curing conditions were: a curing temperature of 130° C. and a curing time of 30 minutes to obtain the honeycomb resin products L1-L10.

[0169] Comparative Example 1-2

[0170] The method of Example 1 was followed, except that A1 was replaced by D1-D2, to prepare honeycomb resin products DL1-DL2.

[0171] Test Case

[0172] The properties of the honeycomb resin products prepared in the examples and comparative examples were tested, and the results are shown in Table 2.

[0173] Table 2

[0174] The permeabilities of the honeycomb resin products, quartz sand, and ceramsite sand prepared in the examples and comparative examples were tested, respectively. A high-pressure displacement device was used in accordance with the Sinopec Shengli Oilfield Administration Enterprise Standard Q / SH1020 "Method for Determining the Permeability of High Permeability Consolidated Cores." The results are shown in Table 3.

[0175] Table 3

[0176] *In the present invention, 5000 mD in the test example does not represent the upper limit of permeability, but only the upper limit of the high-pressure displacement device test instrument.

[0177] 1- The particle size of quartz sand is 400-800μm.

[0178] 2- The particle size of ceramsite sand is 400-800μm.

[0179] From the above results, it can be seen that Examples 1-10 achieve good technical effects and have suitable pore structures.

[0180] Among them, preferred embodiments 1-4 achieve significantly better technical effects, wherein the compressive strength is not less than 40 MPa and the deformation rate is not higher than 1.5%.

[0181] Compared with quartz sand and ceramsite sand, the honeycomb resin product provided by the present invention, which is made from the curable composition, has excellent permeability. In particular, under high-pressure conditions, the honeycomb resin product provided by the present invention has better permeability than quartz sand and ceramsite sand. During the fracturing process, there is no need to add additional quartz sand and ceramsite sand as proppants.

[0182] 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 curable resin composition, characterized in that The curable resin composition comprises component A and component B; wherein the component A and the component B exist independently of each other; The component A comprises a water-based thermosetting resin, a solvent-based thermosetting resin, an emulsifier and water; The component B comprises a curing agent, and the curing agent is selected from the modified nano-silicon dioxide and / or bisphenol-formaldehyde resin shown in formula I; In Formula I, M is a nano-silicon dioxide particle, x is an integer of 1-4, and R1 is an alkyl group having 1-4 carbon atoms; n is an integer from 0 to 3, m is an integer from 1 to 3, n+m=3; A is a structural unit derived from anhydride compounds, and B is a structural unit derived from polyamino compounds; The bisphenol novolac resin comprises a structural unit shown in formula II and a structural unit shown in formula III; Q Wherein, R2 and R3 are each independently H, CH3, CF3 or CH2CH3; Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit represented by formula II is 0-100wt%, and the content of the structural unit represented by formula III is 0-100wt%.

2. The curable resin composition according to claim 1, wherein In Formula I, the acid anhydride compound is selected from at least one of maleic anhydride, phthalic anhydride and succinic anhydride; Preferably, the polyamino compound has a linear polyethylene polyamino compound having a structure shown in Formula IV or a nonlinear polyethyleneimine having a number average molecular weight of 300-3000: Here, p is an integer from 1 to 6.

3. The curable resin composition according to claim 1 or 2, wherein The average particle size of the nano-silicon dioxide particles M is 10-500nm, and the specific surface area is 10-300m 2 / g; Preferably, the modified nano-silicon dioxide has an average particle size of 10-500 nm and a specific surface area of ​​50-500 m 2 / g; Preferably, the particle size dispersion coefficient of the modified nano-silicon dioxide is 0.09-0.15; Preferably, the amino content of the modified nano-silica is 0.1-5 mmol / g.

4. The curable resin composition according to any one of claims 1 to 3, wherein Q is Wherein, R2 and R3 are each independently H or CH3, preferably CH3; Preferably, based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit represented by formula II is 60-80 wt %, and the content of the structural unit represented by formula III is 20-40 wt %.

5. The curable resin composition according to any one of claims 1 to 4, wherein The weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol, preferably 3000-5000 g / mol.

6. The curable resin composition according to any one of claims 1 to 5, wherein In the component A, the content of the aqueous thermosetting resin is 5-40 parts by weight, preferably 30-40 parts by weight, the content of the solvent-based thermosetting resin is 10-76 parts by weight, preferably 20-40 parts by weight, the content of the emulsifier is 0.5-4 parts by weight, preferably 2-3 parts by weight, and the content of water is 16-50 parts by weight, preferably 17-48 parts by weight; Preferably, the mass ratio of the modified nano-silicon dioxide to the bisphenol-formaldehyde resin is 1:10-20, preferably 1:12-15; Preferably, relative to the total amount of component A, the amount of component B is 40-80 parts by weight, preferably 60-80 parts by weight.

7. The curable resin composition according to any one of claims 1 to 6, wherein The water-based thermosetting resin has a structure shown in Formula V; R4 is a C1-C3 alkylene group; Ar Wherein, R5 and R6 are each independently H, CH3, CF3 or CH2CH3; 0 <y1+y2≤8; M is K or Na.

8. The curable resin composition according to claim 7, wherein R4 is a C1-C2 alkylene group; Preferably, Ar is Wherein, R5 and R6 are each independently H, CH3, CF3 or CH2CH3; M is Na.

9. The curable resin composition according to any one of claims 1 to 8, wherein The content of S element in the water-based thermosetting resin is 6-20wt%, preferably 10-15wt%; Preferably, the epoxy equivalent of the waterborne thermosetting resin is 100-300 mol / 100g, preferably 150-200 mol / 100g.

10. The curable resin composition according to any one of claims 1 to 9, wherein The emulsifier is selected from cationic emulsifiers and / or anionic emulsifiers; Preferably, 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, dodecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium chloride and octadecyldimethylbenzylammonium chloride; Preferably, the anionic emulsifier is selected from at least one of sodium stearate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, sodium laurate, sodium rosin acid, sodium didodecylphenyl ether disulfonate, and sodium dibutylnaphthyl sulfonate.

11. The curable resin composition according to any one of claims 1 to 10, wherein The solvent-based thermosetting resin is selected from at least one of epoxy resin, polyimide and unsaturated resin.

12. The curable resin composition according to any one of claims 1 to 11, wherein At 25° C., the apparent viscosity of the curable resin composition is 100-400 mPa·s, preferably 200-300 mPa·s.

13. A honeycomb resin product, characterized in that: Prepared from the curable resin composition according to any one of claims 1 to 12.

14. The honeycomb resin product according to claim 13, wherein interconnected channels exist in the honeycomb resin product.

15. The honeycomb resin product according to claim 13 or 14, wherein: The porosity of the honeycomb resin product is 1-40%, preferably 20-30%; Preferably, the pore size of the honeycomb resin product is 0.1-0.7 mm; preferably 0.3-0.5 mm; Preferably, the cell density of the honeycomb resin product is 20-450 cells / cm 2 , preferably 100-400 pcs / cm 2 .

16. The honeycomb resin product according to any one of claims 13 to 15, wherein: The density of the honeycomb resin product is 0.85-0.95 g / cm 3 , preferably 0.88-0.91 g / cm 3 .

17. The honeycomb resin product according to any one of claims 13 to 16, wherein: The compressive strength of the honeycomb resin product is 20-40 MPa; preferably 30-40 MPa; Preferably, at 40 MPa and 90° C., the deformation rate of the honeycomb resin product is less than or equal to 8%, preferably less than or equal to 4%.

18. A method for preparing a honeycomb resin product, characterized in that: The preparation method comprises: The honeycomb resin product is obtained by mixing the components in component A of the curable resin composition according to any one of claims 1 to 12, and then mixing and curing with component B.

19. The preparation method according to claim 18, wherein: The curing conditions include: curing temperature of 90-150°C and curing time of 10min-6h; Preferably, the curing conditions include: curing temperature of 120-150° C., and curing time of 30 min-4 h.

20. Use of the curable resin composition according to any one of claims 1 to 12 or the honeycomb resin product according to any one of claims 13 to 16 in at least one of oil reservoir development, building floor tiles and adsorbent materials.

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