Phenolic resin biphenyl compound composition and application thereof, epoxy resin product and preparation method thereof

Abstract

The invention relates to the technical field of fracturing yield increase of oil and gas reservoirs, and discloses a phenolic resin biphenyl compound 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; the reinforcing agent # imgabs0 is of a structure as shown in a formula III which is described in the specification; based on the total weight of the bisphenol phenolic resin, the content of the structural unit A in the # imgabs 1 # is 0-100 wt%, and the content of the structural unit B in the # imgabs 1 # is 0-100 wt%. The composition comprises a cross-linked polymer and a reinforcing agent with a specific structure, and the composition is used as a curing agent, so that the prepared epoxy resin product has excellent high temperature resistance and deformation resistance.

Description

Technical Field

[0001] The invention relates to the technical field of oil and gas reservoir fracturing and production increase, and in particular to a phenolic resin biphenyl compound composition and application thereof, an epoxy resin product and a preparation method thereof. Background Art

[0002] With the continuous deepening of oil and gas field exploration and development at home and abroad, reservoirs with deep layers, high temperatures and low permeability as the main characteristics have become the focus of oil and gas reservoir transformation. For example, in the Shunbei area of ​​Xinjiang Uygur Autonomous Region, when the well depth exceeds 9000m and the formation pressure exceeds 100MPa, the geothermal gradient reaches 3℃ / 100m and the bottom hole temperature exceeds 180℃; the Jiyang Depression area of ​​Sinopec Shengli Oilfield is buried at a depth of 5000-6000m, the temperature is as high as 150℃, and the bottom hole extension pressure reaches more than 80MPa, which is a typical ultra-deep ultra-high temperature and high pressure oil and gas reservoir. At present, fracturing technology is widely used to effectively develop shale oil and gas reservoirs, and the general temperature is greater than 140℃. Due to the large scale and long construction time of the three high and one deep reservoir fracturing transformation, the fracturing fluid is subjected to excessive shear for a long time in the high temperature environment of the reservoir. If it cannot maintain good temperature resistance and deformation resistance, it will be degraded prematurely and lose the stable and continuous fracture and sand suspension ability, resulting in construction failure. Therefore, the ultra-high temperature resistance of the fracturing fluid is one of the key factors to ensure the success of the construction.

[0003] As one of the three major thermosetting resins, epoxy resin has excellent bonding properties, chemical resistance and mechanical properties. It can be used as coatings, adhesives and molding materials in engineering technology, electronics and electrical, optical machinery, rail transportation and other fields. However, traditional epoxy resins are flammable and heat-resistant, which has become a key factor restricting their further development. At the same time, the harsh environment of shale oil and gas reservoir exploitation has higher requirements for the high temperature and high pressure resistance of fracturing fluids.

[0004] At present, water-based fracturing fluid is one of the most widely used fracturing fluid systems, among which cross-linked fracturing fluid is often used in high-temperature deep well fracturing construction. The composition of cross-linked fracturing fluid mainly includes water, cross-linking agent, thickener and other additives; due to the poor temperature resistance of the monomer selection, synthesis process and other conditions, the temperature resistance of the formed cross-linked fracturing fluid still has certain limitations. Therefore, it is necessary to develop a temperature resistance enhancer to improve the high temperature resistance and deformation resistance of epoxy resin.

[0005] In summary, developing a temperature resistance enhancer to improve the high temperature resistance and deformation resistance of the fracturing fluid system has become an urgent problem to be solved by those skilled in the art. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems of poor high temperature resistance and deformation resistance of the fracturing fluid system in the prior art, and to provide a phenolic resin biphenyl compound composition and application, an epoxy resin product and a preparation method thereof. The composition includes a cross-linked polymer and a reinforcing agent with a specific structure, which serves as a curing agent. The prepared epoxy resin product has excellent high temperature resistance and deformation resistance.

[0007] 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;

[0008] 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;

[0009]

[0010] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0011] The enhancer has a structure shown in Formula III;

[0012]

[0013] R3 and R4 are each independently selected from NH2, COOH or OH;

[0014] n is an integer of 0-10, R5 is methylene or phenyl;

[0015] 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%.

[0016] The second aspect of the present invention provides use of the above curing agent composition as a curing agent in epoxy resin.

[0017] The third aspect of the present invention provides a method for preparing an epoxy resin product, wherein the epoxy resin product is prepared by mixing component A and component B and curing them;

[0018] Wherein, the component A comprises epoxy resin;

[0019] Wherein, the component B is the curing agent composition described above.

[0020] A fourth aspect of the present invention provides an epoxy resin product obtained by the above preparation method.

[0021] 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:

[0022] The curing agent composition provided by the present invention comprises a bisphenol phenolic resin, a reinforcing agent with a specific structure and water, wherein the reinforcing agent with a specific structure has a certain rigidity and is used as a curing agent for curing epoxy resin. The above two components act together so that the cured epoxy resin has excellent high temperature resistance and deformation resistance.

[0023] In the epoxy resin composition provided in the present invention, the curing agent composition comprises a bisphenol phenolic resin and a reinforcing agent of a specific structure, which acts as a curing agent so that the epoxy resin product obtained after the epoxy resin composition is cured has high temperature resistance and deformation resistance. The high temperature resistance is specifically manifested in that it is not easy to soften at high temperature, and the deformation resistance is specifically manifested in that the deformation rate is low. DETAILED DESCRIPTION

[0024] 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.

[0025] 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;

[0026] 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;

[0027]

[0028] Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3;

[0029] The enhancer has a structure shown in Formula III;

[0030]

[0031] R3 and R4 are each independently selected from NH2, COOH or OH;

[0032] n is an integer of 0-10, R5 is methylene or phenyl;

[0033] 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%.

[0034] In the present invention, the curing agent composition includes bisphenol phenolic resin, a reinforcing agent with a specific structure and water, wherein a reinforcing agent with a rigid benzene ring is added and used as a curing agent for curing epoxy resin. The above two components work together to make the cured epoxy resin have excellent high temperature resistance and deformation resistance.

[0035] In the present invention, in the bisphenol-formaldehyde resin, the amounts of the structural unit A and the structural unit B are not both 0, and the sum of the contents of the structural unit A and the structural unit B is 100 wt %.

[0036] Furthermore, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0037] According to the present invention, based on the total weight of the bisphenol-formaldehyde resin, the content of the structural unit A is 60-80wt%, and the content of the structural unit B is 20-40wt%.

[0038] According to the present invention, the weight average molecular weight of the bisphenol novolac resin is 2000-10000 g / mol, preferably 3000 g / mol-5000 g / mol.

[0039] 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:

[0040] Under alkaline conditions, the first monomer, the second monomer and water are mixed and polymerized to obtain the bisphenol novolac resin;

[0041] Wherein, the alkaline condition makes n(OH) - 1.4mol / L-3mol / L;

[0042] The first monomer is selected from formaldehyde and / or paraformaldehyde;

[0043] The second monomer includes a monomer A shown in formula III and / or a monomer B shown in formula IV:

[0044]

[0045] Among them, Q is Wherein, R1 and R2 are each independently H, CH3, CF3 or CH2CH3.

[0046] 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.

[0047] 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.

[0048] Furthermore, Q is Wherein, R1 and R2 are each independently H or CH3, preferably CH3.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] In one embodiment of the present invention, monomer A is bisphenol S, that is, as shown in formula III, Q is

[0054] 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 %.

[0055] 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%.

[0056] 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.

[0057] Furthermore, the mass ratio of monomer A to monomer B is 1:0.3-0.38.

[0058] In the present invention, the monomer B can be purchased commercially. Preferably, the monomer B is prepared according to the following method:

[0059] 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;

[0060] The molar ratio of the bisphenol compound to the sulfonating agent is 1:0.1-1.

[0061] 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.

[0062] Furthermore, the molar ratio of the bisphenol compound to the sulfonating agent is 1:0.7-1.

[0063] In the present invention, the bisphenol compound is at least one selected from bisphenol A, bisphenol S, bisphenol B, bisphenol F and bisphenol AF.

[0064] In the present invention, the sulfonating agent is selected from at least one of concentrated sulfuric acid, chlorosulfonic acid and aminosulfonic acid.

[0065] In the present invention, the first catalyst is Lewis acid.

[0066] 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.

[0067] In the present invention, the mass ratio of the bisphenol compound to the first catalyst is 1:0.0001-0.0006.

[0068] 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.

[0069] Furthermore, the mass ratio of the bisphenol compound to the first catalyst is 1:0.00015-0.00045.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] Furthermore, the conditions of the polymerization reaction include: a polymerization temperature of 50-70° C. and a polymerization time of 2-4 h.

[0074] According to the present invention, R3 and R4 are each independently selected from NH2 or COOH.

[0075] According to the present invention, n is an integer of 1-4, and R5 is a methylene group.

[0076] According to the present invention, the enhancer is selected from 4,4'-methylenedianiline and / or 3,3',5,5'-tetramethylbenzidine.

[0077] In the present invention, the reinforcing agent selected from the above-mentioned specific types is matched with the bisphenol novolac resin. The active group NH2 in the reinforcing agent can cooperate with the phenolic hydroxyl group in the bisphenol novolac resin. When used to cure the epoxy resin, it can further improve the crosslinking degree of the cured epoxy resin, etc., and ultimately make the epoxy resin products have excellent high temperature resistance and deformation resistance.

[0078] In the present invention, 4,4'-methylenedianiline has the structure shown below:

[0079]

[0080] In the present invention, 3,3',5,5'-tetramethylbenzidine has the structure shown below:

[0081]

[0082] 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.

[0083] In the present invention, when the components in the curing agent composition meet the above-mentioned specific weight parts, the epoxy resin product obtained after curing has a higher softening temperature at high temperature and further improved anti-deformation performance.

[0084] Furthermore, in the curing agent composition, the content of the curing agent is 45-55 parts by weight, the content of the reinforcing agent is 7-9 parts by weight, and the content of water is 36-48 parts by weight.

[0085] According to the present invention, the curing agent composition further comprises 3-7 parts by weight, preferably 4-5 parts by weight of an accelerator.

[0086] According to the present invention, the accelerator is selected from polycarboxylic acids and / or small molecule polyamines.

[0087] 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.

[0088] According to the present invention, 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.

[0089] According to 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.

[0090] In the present invention, the mixture of polycarboxylic acid and small molecule polyamine is used as an accelerator, which has the beneficial effects of polycarboxylic acid and small molecule polyamine. Specifically, when the amount of accelerator added is small, it can ensure that the curing agent composition has a suitable viscosity and thus ensure good injectability, while further improving the high temperature resistance of the epoxy resin product.

[0091] Furthermore, the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.4-0.6.

[0092] According to the present invention, the curing agent composition further comprises 0.1-1 parts by weight of a co-curing agent.

[0093] In the present invention, a certain amount of co-curing agent is added to the curing agent composition, which can cooperate with the components in the curing agent composition to promote the curing of the epoxy resin, so that the high temperature resistance and deformation resistance of the epoxy resin product prepared from the curing agent composition are further improved.

[0094] Furthermore, the curing agent composition further comprises 0.1-1 parts by weight of a co-curing agent.

[0095] According to the present invention, the auxiliary curing agent is selected from at least one of zirconium oxychloride, aluminum trichloride, titanium tetrachloride and ferric chloride.

[0096] 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.

[0097] In the present invention, the apparent viscosity of the curing agent composition is measured at room temperature using a six-speed rotational viscometer.

[0098] In the present invention, when the curing agent composition meets the above apparent viscosity, the curing agent composition exhibits more excellent injectability. When injected into a formation, it can be better mixed with the epoxy resin and cure the epoxy resin.

[0099] The second aspect of the present invention provides use of the above curing agent composition as a curing agent in epoxy resin.

[0100] The third aspect of the present invention provides a method for preparing an epoxy resin product, wherein the epoxy resin product is prepared by mixing component A and component B and curing them;

[0101] Wherein, the component A comprises epoxy resin;

[0102] Wherein, the component B is the above-mentioned curing agent composition.

[0103] In the present invention, the component A 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.

[0104] 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 component A and component B in the epoxy resin composition, such as a twin-screw extruder or a stirrer, as long as component A and component B can be fully mixed.

[0105] According to the present invention, relative to 100 parts by weight of component A, the amount of component B is 40-80 parts by weight.

[0106] Furthermore, relative to 100 parts by weight of component A, the amount of component B is 60-80 parts by weight.

[0107] In the present invention, the curing conditions include: a curing temperature of 30-80° C., a curing time of 1-6 hours, and a curing pressure of 20-40 MPa.

[0108] A fourth aspect of the present invention provides an epoxy resin product obtained by the above preparation method.

[0109] In the present invention, the curing agent composition comprises a bisphenol-formaldehyde resin and a reinforcing agent of a specific structure, which acts as a curing agent, so that the epoxy resin product obtained after the epoxy resin composition is cured has excellent temperature resistance, deformation resistance and pressure resistance. Specifically, the epoxy resin product has a low deformation rate and a high softening point under high temperature and high pressure.

[0110] In the present invention, at 120° C. and 30 MPa, the deformation rate of the epoxy resin product is less than or equal to 5%, preferably less than or equal to 1%.

[0111] According to the present invention, the softening point of the epoxy resin product is 90-120°C, preferably 110-120°C.

[0112] The present invention will be described in detail below by way of examples. In the following examples and comparative examples,

[0113] The content of each structural unit in bisphenol-formaldehyde resin was measured by feed ratio method.

[0114] The weight average molecular weight of the bisphenol-formaldehyde resin was measured by GPC.

[0115] The apparent viscosity of the curing agent composition is measured by a six-speed rotation viscometer.

[0116] The raw materials used in the preparation examples, embodiments, application examples and their respective comparative examples are all commercially available products.

[0117] Enhancer E1: 4,4'-methylenedianiline;

[0118] Enhancer E2: 3,3',5,5'-tetramethylbenzidine;

[0119] Enhancer E3: 4,4'-biphenyldicarboxylic acid;

[0120] Enhancer E4: 4,4'-biphenylene glycol;

[0121] Enhancer DE: melamine.

[0122] Accelerator

[0123] Accelerator C1: terephthalic acid;

[0124] Accelerator C2: citric acid;

[0125] Accelerator C3: polyethylene polyamine;

[0126] Accelerator C4: 1,6-hexanediamine.

[0127] Co-curing agent Z1: zirconium oxychloride;

[0128] Auxiliary curing agent Z2: aluminum chloride.

[0129] Preparation Example - Preparation of Bisphenol Novolac Resin

[0130] Preparation of Monosulfonated Bisphenol A

[0131] 57g of bisphenol A, 0.03g of ferric chloride and 25g of concentrated sulfuric acid are contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4 hours to obtain monosulfonated bisphenol A; wherein the molar ratio of bisphenol A to concentrated sulfuric acid is 1:1, and the mass ratio of bisphenol A to ferric chloride is 1:0.00052.

[0132] Preparation of trisulfonated bisphenol A

[0133] 57g of bisphenol A, 0.03g of ferric chloride and 75g of concentrated sulfuric acid were contacted for sulfonation reaction at a reaction temperature of 130°C for a reaction time of 4h to obtain trisulfonated bisphenol A; 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 1:0.00052.

[0134] Preparation Example 1

[0135] Under stirring conditions, 32 parts by weight of monosulfonated bisphenol A, 48 parts by weight of bisphenol A, 33.01 parts by weight of paraformaldehyde and deionized water were mixed, and 5.95 parts by weight of NaOH was added to make n(OH) in the system - The bisphenol-formaldehyde resin A1 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 3986g / mol.

[0136] Preparation Example 2

[0137] Under stirring conditions, 40 parts by weight of monosulfonated bisphenol A, 40 parts by weight of bisphenol A, 31.58 parts by weight of paraformaldehyde and deionized water were mixed, and 5.95 parts by weight of NaOH was added to make n(OH) in the system - The bisphenol-formaldehyde resin A2 was obtained by polymerization at 50°C for 4 hours. The Q in the structural unit A is R1 and R2 are CH3, wherein the structural unit A is 50 wt%, and in the structural unit B, Q is R1 and R2 are CH3, the structural unit B is 50wt%, and the weight average molecular weight is 4085g / mol.

[0138] Comparative Preparation Example

[0139] Under stirring conditions, 32 parts by weight of trisulfonyl bisphenol A, 48 parts by weight of bisphenol A, 33.64 parts by weight of paraformaldehyde and deionized water were mixed, and 6.5 parts by weight of NaOH was added to make n(OH) in the system - The molecular weight of the bisphenol-formaldehyde resin was 1.44 mol / L and polymerized at 50 °C for 4 h to obtain bisphenol-formaldehyde resin DA with a weight-average molecular weight of 1983 g / mol.

[0140] Examples and Comparative Examples - Curing Agent Compositions

[0141] Bisphenol-formaldehyde resin, reinforcing agent, accelerator, co-curing agent and water were mixed in the amounts shown in Table 1 to obtain curing agent compositions B1-B15 and comparative examples DB1-DB2. The apparent viscosity of the curing agent compositions was tested, and the results are shown in Table 2.

[0142] Table 1

[0143]

[0144] Table 2

[0145] Curing agent composition Apparent viscosity mPa·s B1 252 B2 243 B3 228 B4 213 B5 219 B6 114 B7 471 B8 312 B9 132 B10 102 B11 236 B12 216 B13 201 B14 114 B15 492 DB1 573 DB2 63

[0146] It can be seen from the results in Table 2 that the curing agent composition embodiments B1-B15 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.

[0147] Application example-epoxy resin products

[0148] 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, 80°C for 6 hours, and completely cured after being taken out to obtain epoxy resin products P1-P15 and DP1-DP2. The performance of the epoxy resin products was tested, and the results are shown in Table 3.

[0149] 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".

[0150] At normal pressure and 25°C, the diameter of the epoxy resin product tested is D0. At 30MPa and 120°C, the epoxy resin product is extruded using a high and low temperature universal material testing machine. The diameter of the epoxy resin product after extrusion is D1. The deformation rate = (D0-D1)D0×100%.

[0151] Table 3

[0152]

[0153]

[0154] It can be seen from the results of Table 2 and Table 3 that when the curing agent composition containing a reinforcing agent of a specific structure and a bisphenol-formaldehyde resin in the embodiment of the present invention is used as a curing agent composition, not only can the curing agent composition have a suitable apparent viscosity to ensure that the curing agent composition has excellent injectability, but also when used as a curing agent for curing epoxy resin, the high temperature resistance of the epoxy resin product can be significantly improved. Specifically, the epoxy resin product has a high softening point, and under high temperature (120° C.) and high pressure (30 MPa) conditions, the epoxy resin product has a low deformation rate.

[0155] 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; The enhancer has a structure shown in Formula III; R3 and R4 are each independently selected from NH2, COOH or OH; n is an integer of 0-10, R5 is methylene or phenyl; 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%.

2. The curing agent composition according to claim 1, wherein R3 and R4 are each independently selected from NH2 or COOH; Preferably, n is an integer of 1-4, and R5 is a methylene group.

3. The curing agent composition according to claim 1 or 2, wherein The enhancer is selected from 4,4'-methylenedianiline and / or 3,3',5,5'-tetramethylbenzidine.

4. The curing agent composition according to any one of claims 1 to 3, 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.

5. The curing agent composition according to any one of claims 1 to 4, 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 60-80 wt %, and the content of the structural unit B is 20-40 wt %.

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

7. The curing agent composition according to any one of claims 1 to 6, wherein The curing agent composition further comprises 3-7 parts by weight, preferably 4-5 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 The curing agent composition further comprises 0.1-1 parts by weight of a co-curing agent; Preferably, the auxiliary curing agent is selected from at least one of zirconium oxychloride, aluminum trichloride, titanium tetrachloride and ferric chloride.

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

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

12. A method for preparing an epoxy resin product, characterized in that: The epoxy resin product is prepared by mixing component A and component B and curing them; Wherein, the component A comprises epoxy resin; Wherein, the component B is the curing agent composition according to any one of claims 1 to 10.

13. The preparation method according to claim 12, wherein: Relative to 100 parts by weight of component A, the amount of component B is 40-80 parts by weight, preferably 60-80 parts by weight.

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

15. The epoxy resin product according to claim 14, wherein: At 120°C and 30MPa, the deformation rate of the epoxy resin product is less than or equal to 5%, preferably less than or equal to 1%; Preferably, the softening point of the epoxy resin product is 90-120°C, preferably 110-120°C.

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