Phenolic resin inorganic fiber composition and application thereof, epoxy resin product and preparation method thereof

Abstract

The invention relates to the field of high polymer materials and oil and gas reservoir exploitation, and discloses a phenolic resin inorganic fiber composition and application thereof, an epoxy resin product and a preparation method thereof. The composition comprises a curing agent, a reinforcing agent and water, the curing agent is bisphenol phenolic resin, and the bisphenol phenolic resin comprises a structural unit A as shown in a formula I and a structural unit B as shown in a formula II; based on the total weight of the bisphenol phenolic resin, the content of the structural unit A of the # imgabs0 # is 0-100 wt%, and the content of the structural unit B of the # imgabs0 # is 0-100 wt%; the reinforcing agent is inorganic fiber. The composition comprises bisphenol phenolic resin, high-strength and high-rigidity inorganic fibers and water, and the bisphenol phenolic resin and the inorganic fibers have a synergistic effect and are used as a curing agent for curing epoxy resin, so that the cured epoxy resin has excellent properties of low probability of softening at high temperature and deformation resistance.

Description

Technical Field

[0001] The invention relates to the field of polymer materials and oil and gas reservoir exploitation, and in particular to a phenolic resin inorganic fiber composition and application thereof, an epoxy resin product and a preparation method thereof. Background Art

[0002] The chemical structure of epoxy resin is characterized by epoxy groups on the macromolecular chain. There are many types and varieties of epoxy resin, among which bisphenol A epoxy resin is the most important. According to the requirements of proppant encapsulation, the epoxy resin used should be solid at room temperature and the softening point should be above 80°C, otherwise the proppant particles will stick together during storage. The resin should have a certain water emulsification to facilitate the connection between proppant particles. In order to make the epoxy resin self-emulsifiable, strong hydrophilic groups must be introduced into the epoxy resin molecules. There are two main methods of water-based modification: one is to modify the epoxy resin into a resin containing acid-rich groups, and then neutralize it with alkali to form a salt; the other is to modify the epoxy resin into a resin containing alkaline groups, and then neutralize it with acid to form a salt.

[0003] Curing agent is an indispensable curing reaction aid for thermosetting resin. There are many varieties of epoxy resins, and there are even more varieties of curing agents. According to the chemical reaction mechanism and chemical structure, it can be divided into addition polymerization curing agent and catalytic polymerization curing agent. Addition polymerization curing agents include polyamines, modified polyamines, acid anhydrides, polymer prepolymers (phenolic resins, polyester resins, amino resins, polysulfide rubbers, polyamides); catalytic polymerization curing agents include anionic polymerization types such as tertiary amines, imidazoles, etc., and cationic polymerization types such as BF3 complexes. According to the curing temperature, it can be divided into low-temperature, fast-curing curing agents, room temperature curing machines, medium-temperature curing agents, high-temperature curing agents, and latent curing agents.

[0004] Epoxy resin has the advantages of good bonding strength, good comprehensive performance, low shrinkage, etc., but has the disadvantages of insufficient heat resistance and weak deformation resistance. Therefore, it is urgent to provide a curing agent that can prevent the cured epoxy resin from softening at high temperatures and has strong deformation resistance. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of epoxy resin being easy to soften at high temperature and having low deformation resistance in the prior art, and to provide a phenolic resin inorganic fiber composition and application, epoxy resin product and preparation method thereof. The composition can be used as a curing agent for curing epoxy resin, so that the cured epoxy resin product has excellent properties of not being easy to soften at high temperature and being resistant to deformation.

[0006] In order to achieve the above object, the first aspect of the present invention provides a curing agent composition, wherein the curing agent composition comprises a curing agent, a reinforcing agent and water;

[0007] The curing agent is a bisphenol-formaldehyde resin, and the bisphenol-formaldehyde resin includes a structural unit A shown in formula I and a structural unit B shown in formula II;

[0008]

[0009] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0010] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%;

[0011] The reinforcing agent is inorganic fiber.

[0012] The second aspect of the present invention provides use of the above curing agent composition as a curing agent in epoxy resin.

[0013] A third aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method comprises:

[0014] Mixing the first component with a curing agent and curing the mixture to obtain the epoxy resin product;

[0015] Wherein, the first component includes epoxy resin; the curing agent is the above-mentioned curing agent composition.

[0016] A fourth aspect of the present invention provides an epoxy resin product obtained by the above preparation method.

[0017] Through the above technical scheme, the curing agent composition and its application, epoxy resin composition and epoxy resin product provided by the present invention achieve the following beneficial effects:

[0018] The curing agent composition provided by the present invention comprises bisphenol phenolic resin, high-strength and high-rigidity inorganic fiber and water. The bisphenol phenolic resin and the inorganic fiber act synergistically and are used as a curing agent for curing epoxy resin, so that the cured epoxy resin has excellent properties of not being easily softened at high temperature and being resistant to deformation.

[0019] The epoxy resin product provided in the present invention is prepared from a curing agent composition containing bisphenol-formaldehyde resin and high-strength and high-rigidity inorganic fibers and epoxy resin. The epoxy resin product is not easily softened at high temperatures and has excellent anti-deformation ability. DETAILED DESCRIPTION

[0020] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0021] The first aspect of the present invention provides a curing agent composition, wherein the curing agent composition comprises a curing agent, a reinforcing agent and water;

[0022] The curing agent is a bisphenol-formaldehyde resin, and the bisphenol-formaldehyde resin includes a structural unit A shown in formula I and a structural unit B shown in formula II;

[0023]

[0024] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0025] Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%;

[0026] The reinforcing agent is inorganic fiber.

[0027] In the curing agent composition of the present invention, bisphenol-formaldehyde resin and high-strength and high-rigidity inorganic fibers work synergistically and are used as curing agents for curing epoxy resin, so that the cured epoxy resin has excellent properties of being difficult to soften at high temperatures and resisting deformation. The inorganic fibers have the characteristics of high strength and a certain density of hydroxyl groups on the surface, so that when applied to epoxy resin curing, the softening temperature and deformation resistance of the cured epoxy resin at high temperatures can be significantly improved.

[0028] In the present invention, the contents of the structural unit A and the structural unit B are not 0 at the same time, and the sum of the contents of the structural unit A and the structural unit B is 100%.

[0029] Furthermore, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0030] Furthermore, based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 70-90wt%, and the content of the structural unit B is 10-30wt%.

[0031] According to the present invention, the weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol, preferably 3000-5000 g / mol.

[0032] In the present invention, there is no particular limitation on the bisphenol novolac resin, as long as the bisphenol novolac resin of the present invention can be obtained. Preferably, the bisphenol novolac resin of the present invention is prepared by the following method:

[0033] Under alkaline conditions, the first monomer, the second monomer and water are mixed and polymerized to obtain the bisphenol novolac resin;

[0034] Wherein, the alkaline condition makes n(OH) - 1.4mol / L-3mol / L;

[0035] The first monomer is selected from formaldehyde and / or paraformaldehyde;

[0036] The second monomer includes a monomer A shown in formula III and / or a monomer B shown in formula IV:

[0037]

[0038] Among them, Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3.

[0039] In the present invention, conventional methods in the art can be used to achieve the n(OH) - Adjustments such as adding alkaline substances such as NaOH.

[0040] In a specific embodiment of the present invention, the first monomer is paraformaldehyde, which can slowly release formaldehyde in the system to achieve precise control of the polymerization reaction rate and polymerization degree.

[0041] Furthermore, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0042] In one embodiment of the present invention, monomer A is bisphenol A, that is, as shown in formula III, Q is And R1 and R2 are CH3.

[0043] In one embodiment of the present invention, monomer A is bisphenol AF, that is, as shown in formula III, Q is And R1 and R2 are CF3.

[0044] In one embodiment of the present invention, monomer A is bisphenol B, that is, as shown in formula III, Q is And R1 is CH3 and R2 is CH2CH3.

[0045] In one embodiment of the present invention, monomer A is bisphenol F, that is, as shown in formula III, Q is And R1 and R2 are H.

[0046] In one embodiment of the present invention, monomer A is bisphenol S, that is, as shown in formula III, Q is

[0047] According to the present invention, based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 10-40 wt %, and the amount of the second monomer is 60-90 wt %.

[0048] Furthermore, based on the total weight of the first monomer and the second monomer, the amount of the first monomer is 20-35wt%, and the amount of the second monomer is 65-80wt%.

[0049] According to the present invention, the second monomer A and the monomer B, wherein the mass ratio of the monomer A to the monomer B is 1:0.25-0.43.

[0050] Furthermore, the mass ratio of monomer A to monomer B is 1:0.3-0.38.

[0051] In the present invention, the monomer B can be purchased commercially. Preferably, the monomer B is prepared according to the following method:

[0052] In the presence of a first catalyst and water, a bisphenol compound is contacted with a sulfonating agent to carry out a sulfonation reaction to obtain a monomer B;

[0053] The molar ratio of the bisphenol compound to the sulfonating agent is 1:0.1-1.

[0054] In the present invention, by adopting the above method and controlling the molar ratio of the bisphenol compound to the sulfonating agent to satisfy the above range, the monomer B having formula IV of the present invention, i.e., containing a monosulfonated bisphenol compound, can be obtained.

[0055] Furthermore, the molar ratio of the bisphenol compound to the sulfonating agent is 1:0.7-1.

[0056] In the present invention, the bisphenol compound is at least one selected from bisphenol A, bisphenol S, bisphenol B, bisphenol F and bisphenol AF.

[0057] In the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0058] In the present invention, the first catalyst is Lewis acid.

[0059] 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.

[0060] In the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001-0.0006.

[0061] 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.

[0062] Furthermore, the mass ratio of the bisphenol compound to the first catalyst is 1:0.00015-0.00045.

[0063] According to the present invention, the alkaline conditions make n(OH) - It is 1.6-2.5 mol / L, preferably 1.8-2 mol / L.

[0064] According to the present invention, the conditions of the polymerization reaction include: a polymerization temperature of 30-80° C. and a polymerization time of 1-6 h.

[0065] In the present invention, the polymerization reaction is carried out under the above-mentioned polymerization reaction conditions, and the polymerization reaction can be completed under relatively mild conditions, and substantially no side reaction products are generated.

[0066] Furthermore, the conditions of the polymerization reaction include: a polymerization temperature of 50-70° C. and a polymerization time of 2-4 h.

[0067] According to the present invention, in the curing agent composition, the content of the curing agent is 40-60 parts by weight, the content of the reinforcing agent is 5-10 parts by weight, and the content of water is 30-55 parts by weight.

[0068] Furthermore, in the curing agent composition, the content of the curing agent is 42-56 parts by weight, the content of the reinforcing agent is 6-8 parts by weight, and the content of water is 36-50 parts by weight.

[0069] According to the present invention, the diameter of the inorganic fiber is 500-900 nm, and the aspect ratio is 1:0.05-0.1.

[0070] In the present invention, by controlling the size of the inorganic fiber to meet the above-mentioned range, it can be ensured that the inorganic fiber can be fully and evenly mixed with other components in the curing agent composition, and that the inorganic fiber has better anisotropy, and that the epoxy resin product cured by the curing agent composition has a high softening point and a low deformation rate at high temperature.

[0071] Furthermore, the diameter of the inorganic fiber is 500-600 nm, and the aspect ratio is 1:0.05-0.0625.

[0072] According to the present invention, the inorganic fiber is selected from at least one of carbon fiber, SiC fiber, ceramic fiber and nano glass fiber.

[0073] In the present invention, the above-mentioned specific type of inorganic fiber has more excellent resin reinforcement performance. When added to the curing agent composition, it can further improve the deformation resistance of the epoxy resin product obtained by curing the curing agent composition as a curing agent at high temperature.

[0074] Furthermore, the inorganic fiber is nano glass fiber.

[0075] According to the present invention, the curing agent composition further comprises 2-6 parts by weight, preferably 3-5 parts by weight of an accelerator.

[0076] In the present invention, in order to further improve the high temperature resistance of the cured epoxy resin product while ensuring that the curing agent composition has a suitable viscosity and good injectability, preferably, the accelerator is selected from polycarboxylic acids and / or small molecule polyamines.

[0077] According to the present invention, the polycarboxylic acid is at least one selected from terephthalic acid, citric acid, tartaric acid, oxalic acid, malic acid, citric acid and ascorbic acid.

[0078] According to the present invention, the small molecule polyamine is at least one selected from polyethylene polyamine, ethylenediamine, 1,6-hexanediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, hydrazine and dihydrazide.

[0079] In a specific embodiment of the present invention, the accelerator is a mixture of polycarboxylic acid and small molecule polyamine, wherein the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.1-0.8.

[0080] In the present invention, by compounding the polycarboxylic acid and the small molecule polyamine in the above-mentioned specific mass ratio, the injectability of the curing agent composition can be further improved, and at the same time, the high temperature resistance of the cured epoxy resin product can be made, specifically, the deformation rate at high temperature is reduced and the softening point is increased.

[0081] Furthermore, the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.4-0.6.

[0082] According to the present invention, at 25° C., the apparent viscosity of the curing agent composition is 100-500 mPa·s, preferably 200-300 mPa·s.

[0083] In the present invention, the apparent viscosity of the curing agent composition is measured at room temperature using a six-speed rotational viscometer.

[0084] The second aspect of the present invention provides use of the above curing agent composition as a curing agent in epoxy resin.

[0085] A third aspect of the present invention provides a method for preparing an epoxy resin product, wherein the preparation method comprises:

[0086] Mixing the first component with a curing agent and curing the mixture to obtain the epoxy resin product;

[0087] Wherein, the first component includes epoxy resin; the curing agent is the above-mentioned curing agent composition.

[0088] In the present invention, the curing agent composition comprises bisphenol phenolic resin and high-strength and high-rigidity inorganic fiber, which serves as a curing agent, so that the epoxy resin product obtained after the epoxy resin composition is cured has excellent temperature resistance and deformation resistance. Specifically, the epoxy resin product has a low deformation rate and a high softening point under high temperature and high pressure.

[0089] In the present invention, the first component may also include conventional auxiliary agents in the art, such as emulsifiers, etc. There are no special requirements for the specific type and amount of the emulsifier. Conventional emulsifiers in the art can be used and added according to conventional amounts in the art.

[0090] In the present invention, there is no particular limitation on the equipment for mixing the epoxy resin composition. Conventional equipment in the art can be used to mix the first component and the second component in the epoxy resin composition, such as a twin-screw extruder or a stirrer, as long as the first component and the second component can be fully mixed.

[0091] In the present invention, the curing conditions include: a curing temperature of 130-150° C., a curing time of 2-6 hours, and a curing pressure of 20-40 MPa.

[0092] According to the present invention, the amount of the curing agent is 40-80 parts by weight relative to 100 parts by weight of the first component.

[0093] Further, relative to 100 parts by weight of the first component, the amount of the second component is 60-80 parts by weight.

[0094] A fourth aspect of the present invention provides an epoxy resin product obtained by the above preparation method.

[0095] According to the present invention, at 150° C. and 40 MPa, the deformation rate of the epoxy resin product is less than or equal to 3%, preferably less than or equal to 1%.

[0096] According to the present invention, the softening point of the epoxy resin product is 140-160°C, preferably 145-160°C.

[0097] The present invention will be described in detail below by way of examples. In the following examples and comparative examples,

[0098] The content of each structural unit in bisphenol-formaldehyde resin was measured by feed ratio method.

[0099] The weight average molecular weight of the bisphenol-formaldehyde resin was measured by GPC.

[0100] The diameter and length of inorganic fibers were measured by scanning electron microscopy.

[0101] The apparent viscosity of the curing agent composition is measured by a six-speed rotation viscometer.

[0102] The raw materials used in the preparation examples, embodiments, application examples and their respective comparative examples are all commercially available products.

[0103] Enhancer

[0104] Reinforcement Z1: nano glass fiber;

[0105] Reinforcement Z2: carbon fiber;

[0106] Reinforcement Z3: SiC fiber;

[0107] Reinforcement Z4: ceramic fiber;

[0108] Reinforcement agent DZ: polyurethane.

[0109] Accelerator

[0110] Accelerator C1: tartaric acid;

[0111] Accelerator C2: oxalic acid;

[0112] Accelerator C3: ethylenediamine;

[0113] Accelerator C4: isophorone diamine.

[0114] Preparation Example - Preparation of Bisphenol Novolac Resin

[0115] Preparation Example 1

[0116] S1: 57g of bisphenol A, 0.03g of ferric chloride and 25g of concentrated sulfuric acid (98wt%) were contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4h, wherein 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 was obtained.

[0117] S2: Under stirring conditions, 38.6 parts by weight of bisphenol A and 9.2 parts by weight of monosulfonated bisphenol A were mixed with 24.35 parts by weight of paraformaldehyde in deionized water, and NaOH was added to make n(OH) - 2 mol / L, polymerized at 50°C for 4 h to obtain bisphenol novolac resin A1. In structural unit A, Q is R1 and R2 are CH3, structural unit A is 80 wt%, and in structural unit B, Q is R1 and R2 are CH3, the structural unit B is 20wt%, and the weight average molecular weight is 3987g / mol.

[0118] Preparation Example 2 (the content of structural units is different, please modify the amount of S2 monomer)

[0119] S1: 57g of bisphenol A, 0.03g of ferric chloride and 25g of concentrated sulfuric acid (98wt%) were contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4h, wherein 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 was obtained.

[0120] S2: Under stirring conditions, 28.8 parts by weight of bisphenol A and 19.2 parts by weight of monosulfonated bisphenol A were mixed with 21.11 parts by weight of paraformaldehyde in deionized water, and NaOH was added to make n(OH) - The bisphenol-formaldehyde resin A2 was obtained by polymerization at 50°C for 4 hours. In the structural unit A, Q is R1 and R2 are CH3, structural unit A is 60wt%, and in structural unit B, Q is R1 and R2 are CH3, the structural unit B is 40wt%, and the weight average molecular weight is 4296g / mol.

[0121] Comparative Preparation Example

[0122] S1: 57g of bisphenol A, 0.03g of ferric chloride and 75g of concentrated sulfuric acid (98wt%) were contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4h, wherein the molar ratio of bisphenol A to concentrated sulfuric acid was 1:3, and the mass ratio of bisphenol A to ferric chloride was 1:0.0005. After purification, trisulfonated bisphenol A was obtained.

[0123] S2: Under stirring conditions, 38.6 parts by weight of bisphenol A and 9.2 parts by weight of trisulfonated bisphenol A were mixed with 25.3 parts by weight of paraformaldehyde in deionized water, and NaOH was added to make n(OH) - 2 mol / L, polymerized at 50°C for 4 h to obtain bisphenol-formaldehyde resin DA. In structural unit A, Q is R1 and R2 are CH3, structural unit A is 80 wt%, and in structural unit B, Q is R1 and R2 are CH3, the structural unit B is 20wt%, and the weight average molecular weight cannot be measured.

[0124] Examples and Comparative Examples - Curing Agent Compositions

[0125] Bisphenol-formaldehyde resin, reinforcing agent, accelerator and water were mixed in the amounts shown in Table 1 to obtain curing agent compositions B1-B16 and comparative examples DB1-DB2. The apparent viscosity of the curing agent compositions was tested, and the results are shown in Table 2.

[0126] Table 1

[0127]

[0128]

[0129] Table 2

[0130] Curing agent composition Apparent viscosity mPa·s B1 267 B2 270 B3 222 B4 375 B5 174 B6 363 B7 171 B8 192 B9 198 B10 384 B11 213 B12 201 B13 291 B14 231 B15 243 B16 429 DB1 549 DB2 570

[0131] It can be seen from the results in Table 2 that the curing agent composition embodiments B1-B16 provided by the present invention have a specific apparent viscosity compared to comparative examples DB1-DB2, and meet the requirements for use as a curing agent, especially as an epoxy resin curing agent.

[0132] Application example-epoxy resin products

[0133] 100 parts by weight of epoxy resin and 80 parts by weight of the curing agent composition of the embodiment were mixed evenly, placed in a high temperature reactor, kept at 40 MPa, 150°C for 6 hours, and completely cured after being taken out to obtain epoxy resin products P1-P16 and DP1-DP2. The properties of the epoxy resin products were tested, and the results are shown in Table 3.

[0134] The softening point of epoxy resin products is measured by the ring and ball method in accordance with GB12007.6 "Epoxy resin softening point determination method - ring and ball method".

[0135] At normal pressure and 25°C, the diameter of the tested epoxy resin product is D0. At 150°C and 40MPa, the epoxy resin product is extruded using a high and low temperature universal material testing machine. The diameter of the tested epoxy resin product after extrusion is D1. The deformation rate = (D0-D1)D0×100%.

[0136] Table 3

[0137]

[0138]

[0139] It can be seen from the results in Table 3 that the epoxy resin products of Examples P1-P16 of the present invention have excellent high temperature resistance compared to DP1-DP2. Specifically, the epoxy resin products have a high softening point, and under high temperature and high pressure conditions, the epoxy resin products have a low deformation rate.

[0140] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A curing agent composition, characterized in that The curing agent composition comprises a curing agent, a reinforcing agent and water; The curing agent is a bisphenol-formaldehyde resin, and the bisphenol-formaldehyde resin includes a structural unit A shown in formula I and a structural unit B shown in formula II; Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3; Based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 0-100wt%, and the content of the structural unit B is 0-100wt%; The reinforcing agent is inorganic fiber.

2. The curing agent composition according to claim 1, wherein In the curing agent composition, the content of the curing agent is 40-60 parts by weight, the content of the reinforcing agent is 5-10 parts by weight, and the content of water is 30-55 parts by weight.

3. The curing agent composition according to claim 1 or 2, wherein Q is Wherein, R1 and R2 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 A is 70-90 wt %, and the content of the structural unit B is 10-30 wt %.

4. The curing agent composition according to any one of claims 1 to 3, wherein The weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol, preferably 3000-5000 g / mol.

5. The curing agent composition according to any one of claims 1 to 4, wherein The inorganic fiber has a diameter of 500-900 nm and an aspect ratio of 1:0.05-0.1; Preferably, the inorganic fiber has a diameter of 500-600 nm and an aspect ratio of 1:0.05-0.0625.

6. The curing agent composition according to any one of claims 1 to 5, wherein The inorganic fiber is selected from at least one of carbon fiber, SiC fiber, ceramic fiber and nano glass fiber, preferably nano glass fiber.

7. The curing agent composition according to any one of claims 1 to 6, wherein The curing agent composition further comprises 2-6 parts by weight, preferably 3-5 parts by weight of an accelerator; Preferably, the accelerator is selected from polycarboxylic acids and / or small molecule polyamines; Preferably, the polycarboxylic acid is selected from at least one of terephthalic acid, citric acid, tartaric acid, oxalic acid, malic acid, citric acid and ascorbic acid; Preferably, the small molecule polyamine is selected from at least one of polyethylene polyamine, ethylenediamine, 1,6-hexanediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, hydrazine and bishydrazide.

8. The curing agent composition according to claim 7, wherein The accelerator is a mixture of polycarboxylic acid and small molecule polyamine, wherein the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.1-0.8, preferably 1:0.4-0.

6.

9. The curing agent composition according to any one of claims 1 to 8, wherein At 25° C., the apparent viscosity of the curing agent composition is 100-500 mPa·s, preferably 200-300 mPa·s.

10. Use of the curing agent composition according to any one of claims 1 to 9 as a curing agent in epoxy resin.

11. A method for preparing an epoxy resin product, characterized in that: The preparation method comprises: Mixing the first component with a curing agent and curing the mixture to obtain the epoxy resin product; Wherein, the first component comprises epoxy resin; and the curing agent is the curing agent composition according to any one of claims 1 to 9.

12. The preparation method according to claim 11, wherein Relative to 100 parts by weight of the first component, the amount of the curing agent is 40-80 parts by weight, preferably 60-80 parts by weight.

13. An epoxy resin product obtained by the preparation method according to claim 11 or 12.

14. The epoxy resin product according to claim 13, wherein: At 150°C and 40MPa, the deformation rate of the epoxy resin product is less than or equal to 3%, preferably less than or equal to 1%; Preferably, the softening point of the epoxy resin product is 140-160°C, preferably 145-160°C.

Images