Phenolic resin inorganic fiber composition and applications, epoxy resin articles and methods of making

Abstract

The application relates to the fields of high polymer materials and oil and gas reservoir exploitation, and discloses a phenolic resin inorganic fiber composition and application, an epoxy resin product and a preparation method thereof. The composition comprises a curing agent, a reinforcing agent and water; the curing agent is a bisphenol phenolic resin, the bisphenol phenolic resin comprises structural unit A shown in formula I and structural unit B shown in formula II; the content of the structural unit A is 0-100 wt% and the content of the structural unit B is 0-100 wt% based on the total weight of the bisphenol phenolic resin; and the reinforcing agent is inorganic fiber. The composition comprises the bisphenol phenolic resin, the inorganic fiber with high strength and rigidity and water, the bisphenol phenolic resin and the inorganic fiber synergistically act, the bisphenol phenolic resin is used as the curing agent for curing the epoxy resin, and the cured epoxy resin has the excellent performances of not being easy to soften at high temperature and resisting deformation.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials and oil and gas reservoir exploitation, and particularly relates to a phenolic resin inorganic fiber composition and application, an epoxy resin product and a preparation method thereof. BACKGROUND

[0002] The chemical structure of epoxy resin is that the macromolecular chain contains epoxy groups. There are many types and varieties of epoxy resins, and the most important one is bisphenol A type epoxy resin. According to the requirements of proppant encapsulation, the epoxy resin used at room temperature should be solid, and the softening point should be above 80 DEG C, otherwise the proppant particles will be adhered during storage. The resin should have certain water emulsification to facilitate the mutual connection between the proppant particles. In order to make the epoxy resin have self-emulsifying property, strong hydrophilic groups must be introduced into the epoxy resin molecule. There are mainly two methods for water-based modification: one is to modify the epoxy resin into a resin containing acid-rich groups, and then neutralize it into a salt with alkali; the other is to modify the epoxy resin into a resin containing base-rich groups, and then neutralize it into a salt with acid.

[0003] Curing agent is an essential curing reaction aid for thermosetting resin. There are many types of epoxy resins, and more types of curing agents. According to the chemical reaction mechanism and chemical structure, the curing agent can be divided into addition polymerization type and catalytic polymerization type. The addition polymerization type curing agent includes polyamine, modified polyamine, acid anhydride, and high molecular pre-polymer (phenolic resin, polyester resin, amino resin, polysulfide rubber, polyamide); the catalytic polymerization type curing agent includes anion polymerization type such as tertiary amine and imidazole, and cation polymerization type such as BF3 complex. According to the curing temperature, the curing agent can be divided into low temperature, fast curing curing agent, normal temperature curing agent, medium temperature curing agent, high temperature curing agent and latent curing agent.

[0004] The epoxy resin has good bonding strength, good comprehensive performance, low shrinkage and other advantages, but has the disadvantages of low heat resistance and weak deformation resistance. Therefore, it is urgent to provide a curing agent which can prevent the softened epoxy resin after curing from softening at high temperature and has strong deformation resistance. SUMMARY

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

[0006] In order to achieve the above-mentioned purpose, the first aspect of the present application 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 phenolic resin, the bisphenol phenolic resin comprises structural unit A shown in formula I and structural unit B shown in formula II;

[0008]

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

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

[0011] The reinforcing agent is an inorganic fiber.

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

[0013] The third aspect of the present application provides a preparation method of an epoxy resin product, wherein the preparation method comprises:

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

[0015] The first component comprises an epoxy resin; and the curing agent is the above curing agent composition.

[0016] The fourth aspect of the present application provides an epoxy resin product prepared by the above preparation method.

[0017] Through the above technical solution, the curing agent composition, the application thereof, the epoxy resin composition and the epoxy resin product provided by the present application have the following beneficial effects:

[0018] The curing agent composition provided by the present application comprises a bisphenol phenolic resin, a high-strength and high-rigidity inorganic fiber and water, and the bisphenol phenolic resin and the inorganic fiber synergistically act to be used as a curing agent for curing an epoxy resin, so that the cured epoxy resin has excellent high-temperature softening resistance and deformation resistance.

[0019] The epoxy resin product provided in the present application is prepared from a curing agent composition comprising a bisphenol phenolic resin and a high-strength and high-rigidity inorganic fiber and an epoxy resin, and the epoxy resin product has high-temperature softening resistance and excellent deformation resistance. DETAILED DESCRIPTION

[0020] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the properties. Any numerical range recited herein is intended to include all sub-ranges of the same numbers (i.e., every subset of numbers within the indicated range). For ranges containing one or more endpoints, the endpoints are included in the range. For ranges containing no endpoints, the range is intended to include all values and / or sub-ranges of the same numbers (i.e., every number falling within the range).

[0021] The first aspect of the present application 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 phenolic resin, the bisphenol phenolic resin comprises structural unit A shown in formula I and structural unit B shown in formula II;

[0023]

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

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

[0026] The reinforcing agent is inorganic fiber.

[0027] In the curing agent composition of the present application, the bisphenol phenolic resin and the inorganic fiber with high strength and high rigidity synergistically act, and are used as a curing agent for curing epoxy resin, so that the cured epoxy resin has excellent properties of not easily softening at high temperature and resisting deformation, wherein the inorganic fiber has the characteristics of high strength and containing a certain density of hydroxyl groups on the surface, so that it can significantly improve the softening temperature and deformation resistance of the cured epoxy resin at high temperature when applied to the curing of epoxy resin.

[0028] In the present application, the content of the structural unit A and the structural unit B is not zero at the same time, and the sum of the content of the structural unit A and the structural unit B is 100%.

[0029] Further, Q is wherein R1, R2 are each independently H or CH3, preferably CH3.

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

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

[0032] In the present application, the bisphenol novolac resin is not particularly limited, as long as it can obtain the bisphenol novolac resin described in the present application, preferably, the bisphenol novolac resin described in the present application is prepared by the method described below:

[0033] The first monomer, the second monomer and water are mixed under alkaline conditions, and then a polymerization reaction is carried out to obtain the bisphenol novolac resin;

[0034] The alkaline conditions make n(OH) - 1.4 mol / L-3 mol / L;

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

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

[0037]

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

[0039] In the present application, the adjustment of n(OH) - in the system can be realized by using conventional methods in the art, for example, adding alkaline substances such as NaOH.

[0040] In one specific embodiment of the present application, the first monomer is paraformaldehyde, which can slowly release formaldehyde in the system, realizing precise control of the polymerization rate and the degree of polymerization.

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

[0042] In one specific embodiment of the present application, monomer A is bisphenol A, i.e. as shown in formula III, Q is and R1, R2 are CH3.

[0043] In one specific embodiment of the present application, monomer A is bisphenol AF, i.e. as shown in formula III, Q is and R1, R2 are CF3.

[0044] In one specific embodiment of the present application, monomer A is bisphenol B, i.e. as shown in formula III, Q is and R1 is CH3, R2 is CH2CH3.

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

[0046] In one embodiment of the present application, the monomer A is bisphenol S, i.e. as shown in formula III, Q is

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

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

[0049] According to the present application, 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] Further, the mass ratio of the monomer A to the monomer B is 1:0.3-0.38.

[0051] In the present application, the monomer B can be commercially available, preferably, the monomer B is prepared according to the following method:

[0052] The bisphenol compound is contacted with a sulfonating agent in the presence of a first catalyst and water to perform a sulfonation reaction to obtain the monomer B;

[0053] The bisphenol compound and the sulfonating agent are in a molar ratio of 1:0.1-1.

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

[0055] Further, the bisphenol compound and the sulfonating agent are in a molar ratio of 1:0.7-1.

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

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

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

[0059] In the present application, the Lewis acid can be a Lewis acid commonly used in the art, such as titanium tetrachloride, ferric trichloride, diiron trioxide, zirconium oxychloride, aluminum trioxide, aluminum trichloride, hydrated tin tetrachloride, etc.

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

[0061] In the present application, the mass ratio of the bisphenol compound to the first catalyst meets the above range, which can reduce the reaction temperature by 20-30℃, and make the reaction condition more mild.

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

[0063] According to the present application, the basic condition is such that n(OH) - is 1.6-2.5 mol / L, preferably 1.8-2 mol / L.

[0064] According to the present application, the polymerization reaction condition includes that the polymerization temperature is 30-80℃, and the polymerization time is 1-6h.

[0065] In the present application, the polymerization reaction is carried out under the above polymerization reaction condition, which can complete the polymerization reaction under a relatively mild condition, and substantially no byproduct is generated.

[0066] Further, the polymerization reaction condition includes that the polymerization temperature is 50-70℃, and the polymerization time is 2-4h.

[0067] According to the present application, 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 the water is 30-55 parts by weight.

[0068] Further, 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 the water is 36-50 parts by weight.

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

[0070] In the present application, when the size of the inorganic fiber meets the above range, it can be ensured that the inorganic fiber can be fully mixed and uniform with other components in the curing agent composition, and it can be ensured that the inorganic fiber has better anisotropy, and it can be ensured that the epoxy resin product obtained by curing the curing agent composition has a high softening point and a low deformation rate at high temperature.

[0071] Further, the inorganic fiber has a diameter of 500-600 nm and an aspect ratio of 1:0.05-0.0625.

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

[0073] In the present application, the inorganic fiber of the above-mentioned specific type has more excellent resin reinforcing performance, and when it is added to the curing agent composition, the deformation resistance of the epoxy resin product cured by the curing agent composition as a curing agent at high temperature can be further improved.

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

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

[0076] In the present application, 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 injection performance, preferably, the accelerator is selected from polycarboxylic acid and / or small molecule polyamine.

[0077] According to the present application, 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.

[0078] According to the present application, the small molecule polyamine is selected from at least one of polyethylene polyamine, ethylenediamine, 1,6-hexanediamine, isophorone diamine, 2-methyl-1,5 pentanediamine, 3-methyl-1,5 pentanediamine, hydrazine and bis-hydrazide.

[0079] In one specific embodiment of the present application, 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 application, by compounding polycarboxylic acid and small molecule polyamine in the above-mentioned specific mass ratio, the injection performance of the curing agent composition can be further improved, and at the same time, the high temperature resistance of the cured epoxy resin product is improved, specifically, the deformation rate at high temperature is reduced and the softening point is improved.

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

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

[0083] In the present application, 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 application provides the use of the above curing agent composition as a curing agent in an epoxy resin.

[0085] The third aspect of the present application provides a preparation method of an epoxy resin product, wherein the preparation method comprises:

[0086] mixing the first component with the curing agent, and curing to obtain the epoxy resin product;

[0087] wherein the first component comprises an epoxy resin; and the curing agent is the above curing agent composition.

[0088] In the present application, the curing agent composition comprises bisphenol phenolic resin and high-strength and high-rigidity inorganic fibers, which, as a curing agent, makes the epoxy resin product prepared after curing of the epoxy resin composition have excellent temperature resistance and anti-deformation ability, 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 application, the first component can further comprise conventional auxiliaries in the art, such as emulsifiers, etc., and there is no particular requirement for the specific type and amount of emulsifiers, and conventional types of emulsifiers in the art can be used and added according to the conventional amount in the art.

[0090] In the present application, the equipment for mixing the epoxy resin composition is not particularly limited, and 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 double-screw extruder or a stirrer, etc., as long as sufficient mixing of the first component and the second component can be achieved.

[0091] In the present application, the curing conditions include a curing temperature of 130-150℃, a curing time of 2-6h, and a curing pressure of 20-40MPa.

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

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

[0094] The fourth aspect of the present application provides an epoxy resin product prepared by the above preparation method.

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

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

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

[0098] The content of each structural unit in the bisphenol novolac resin was measured by the feeding ratio method.

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

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

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

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

[0103] Reinforcing agent

[0104] Reinforcing agent Z1: nano glass fiber;

[0105] Reinforcing agent Z2: carbon fiber;

[0106] Reinforcing agent Z3: SiC fiber;

[0107] Reinforcing agent Z4: ceramic fiber;

[0108] Reinforcing agent DZ: polyurethane.

[0109] Promoter

[0110] Promoter C1: tartaric acid;

[0111] Promoter C2: oxalic acid;

[0112] Promoter C3: ethylenediamine;

[0113] Promoter C4: isophorone diamine.

[0114] Preparation example - preparation of bisphenol novolac resin

[0115] Preparation example 1

[0116] 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 reaction, the reaction temperature was 130°C, and the reaction time was 4 h, 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, mono-sulfonated bisphenol A was obtained.

[0117] S2: 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 under stirring, and NaOH was added to make n(OH) - 2 mol / L, and polymerized at 50°C for 4h to obtain bisphenol novolac resin A1. In structural unit A, Q is R1, R2 are CH3, structural unit A is 80wt%, in structural unit B, Q is R1, R2 are CH3, structural unit B is 20wt%, and the weight average molecular weight is 3987g / mol.

[0118] Preparation Example 2 (different structural unit contents, please modify the monomer amount in S2)

[0119] S1: 57g of bisphenol A, 0.03g of ferric chloride and 25g of concentrated sulfuric acid (98wt%) were contacted for sulfonation reaction, the reaction temperature was 130°C, and the reaction time was 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: 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 under stirring, and NaOH was added to make n(OH) - 2 mol / L, and polymerized at 50°C for 4h to obtain bisphenol novolac resin A2. In structural unit A, Q is R1, R2 are CH3, structural unit A is 60wt%, in structural unit B, Q is R1, R2 are CH3, 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, the reaction temperature was 130°C, and the reaction time was 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: 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 under stirring, and NaOH was added to make n(OH) - 2 mol / L, and polymerized at 50°C for 4h to obtain bisphenol novolac resin DA. In structural unit A, Q is R1, R2 are CH3, the structural unit A is 80 wt%, in the structural unit B, Q is R1, R2 are CH3, the structural unit B is 20 wt%, the weight average molecular weight cannot be measured.

[0124] Examples and comparative examples - curing agent composition

[0125] The bisphenol phenolic resin, the reinforcing agent, the accelerator and water are mixed according to the amount shown in Table 1 to obtain the curing agent compositions B1-B16 and the comparative examples DB1-DB2, the apparent viscosity of the curing agent composition is 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] From the results in Table 2, it can be seen that the curing agent composition examples B1-B16 provided by the present application have a specific apparent viscosity compared to the comparative examples DB1-DB2, which meets the requirements for use as a curing agent, especially as an epoxy resin curing agent.

[0132] Application example - epoxy resin product

[0133] 100 parts by weight of the epoxy resin is mixed with 80 parts by weight of the curing agent composition of the examples to obtain the epoxy resin products P1-P16 and DP1-DP2. The performance of the epoxy resin product is tested, and the results are shown in Table 3.

[0134] The softening point of the epoxy resin product is measured by the globe method according to GB12007.6 "Epoxy Resin Softening Point Test Method Globe Method".

[0135] At normal pressure and 25°C, the diameter of the epoxy resin product is D0, after the epoxy resin product is extruded at 150°C and 40MPa using a high-low temperature universal material testing machine, the diameter of the extruded epoxy resin product is D1, and the deformation rate = (D0-D1)D0x100%.

[0136] Table 3

[0137]

[0138]

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

[0140] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A curing agent composition, characterized in that, The curing agent composition includes a curing agent, a reinforcing agent, and water; The curing agent is bisphenol phenolic resin, which includes structural unit A shown in Formula I and structural unit B shown in Formula II. Formula I; Formula II; Q is or In this context, R1 and R2 are each independently H, CH3, CF3, or CH2CH3; Based on the total weight of the bisphenol A resin, the content of structural unit A is 60-90 wt%, and the content of structural unit B is 10-40 wt%. The reinforcing agent is an 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 In this context, R1 and R2 are each independently H or CH3; And / or, based on the total weight of the bisphenol phenolic resin, the content of structural unit A is 70-90 wt%, and the content of structural unit B is 10-30 wt%.

4. The curing agent composition according to claim 3, wherein, R1 and R2 are each independently CH3.

5. The curing agent composition according to claim 1 or 2, wherein, The weight-average molecular weight of the bisphenol phenolic resin is 2000-10000 g / mol.

6. The curing agent composition according to claim 5, wherein, The weight-average molecular weight of the bisphenol phenolic resin is 3000-5000 g / mol.

7. The curing agent composition according to claim 1 or 2, wherein, The inorganic fiber has a diameter of 500-900 nm and an aspect ratio of 1:0.05-0.

1.

8. The curing agent composition according to claim 7, wherein, The inorganic fiber has a diameter of 500-600 nm and an aspect ratio of 1:0.05-0.0625.

9. The curing agent composition according to claim 1 or 2, wherein, The inorganic fiber is selected from at least one of carbon fiber, SiC fiber, ceramic fiber and nanofiber.

10. The curing agent composition according to claim 9, wherein, The inorganic fiber is a nanofiber.

11. The curing agent composition according to claim 1 or 2, wherein, The curing agent composition also includes 2-6 parts by weight of an accelerator.

12. The curing agent composition according to claim 11, wherein, The curing agent composition also includes 3-5 parts by weight of an accelerator.

13. The curing agent composition according to claim 11, wherein, The accelerator is selected from polycarboxylic acids and / or small molecule polyamines.

14. The curing agent composition according to claim 13, wherein, 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.

15. The curing agent composition according to claim 13, wherein, 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 dihydrazide.

16. The curing agent composition according to claim 11, wherein, The accelerator is a mixture of polycarboxylic acids and small molecule polyamines, wherein the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.1-0.

8.

17. The curing agent composition according to claim 16, wherein, The mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.4-0.

6.

18. The curing agent composition according to claim 1 or 2, wherein, At 25°C, the apparent viscosity of the curing agent composition is 100-500 mPa·s.

19. The curing agent composition according to claim 18, wherein, At 25°C, the apparent viscosity of the curing agent composition is 200-300 mPa·s.

20. The use of the curing agent composition according to any one of claims 1-19 as a curing agent in epoxy resin.

21. A method for preparing an epoxy resin product, characterized in that, The preparation method includes: The first component is mixed with a curing agent and cured to obtain the epoxy resin product. Wherein, the first component includes epoxy resin; the curing agent is the curing agent composition according to any one of claims 1-19.

22. The preparation method according to claim 21, wherein, The amount of the curing agent is 40-80 parts by weight relative to 100 parts by weight of the first component.

23. The preparation method according to claim 22, wherein, The amount of the curing agent is 60-80 parts by weight relative to 100 parts by weight of the first component.

24. An epoxy resin article prepared by any one of claims 21-23.

25. The epoxy resin product according to claim 24, wherein, At 150°C and 40 MPa, the deformation rate of the epoxy resin product is less than or equal to 3%. And / or, the softening point of the epoxy resin product is 140-160℃.

26. The epoxy resin product according to claim 25, wherein, At 150°C and 40 MPa, the deformation rate of the epoxy resin product is less than or equal to 1%. And / or, the softening point of the epoxy resin product is 145-160℃.

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