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

Abstract

The present application relates to the technical field of oil and gas reservoir fracturing stimulation, discloses a phenolic resin biphenyl compound 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 reinforcing agent has a structure shown in formula III; 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.The composition comprises a crosslinked polymer and a reinforcing agent with a specific structure, which serves as a curing agent, and the prepared epoxy resin product has excellent high-temperature resistance and deformation resistance.

Description

TECHNICAL FIELD

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

[0002] With the continuous deepening of domestic and foreign oil and gas field exploration and development, the reservoirs characterized by deep layer, high temperature and low permeability have become the focus of oil and gas reservoir modification. For example, the Shunbei area in Xinjiang Uygur Autonomous Region has a well depth of more than 9000m, a formation pressure of more than 100MPa, a geothermal gradient of 3℃ / 100m, and a bottom hole temperature of more than 180℃; the Jiyang depression area of SINOPEC Shengli Oilfield has a burial depth of 5000-6000m, a temperature of 150℃, and a bottom hole extension pressure of more than 80MPa, which is a typical ultra-deep ultra-high temperature and high pressure oil and gas reservoir. At present, fracturing technology is generally used for effective development of shale oil and gas reservoirs, and the general temperature is greater than 140℃. Due to the large scale of fracturing modification of the three high and deep reservoirs and the long construction time, the fracturing fluid is subjected to excessive shearing in the high temperature environment of the reservoir for a long time, and if the good temperature resistance and deformation resistance cannot be maintained, the fracturing fluid will degrade prematurely and lose the ability of stable and continuous fracture creation and sand suspension, 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 thermosetting resins, epoxy resin has excellent bonding properties, chemical resistance and mechanical properties, and can be widely used as coatings, adhesives and molding materials in engineering technology, electronics and electrical appliances, optical machinery, rail transportation and other fields. However, traditional epoxy resins are flammable and have poor heat resistance, which has become a key factor restricting their further development. At the same time, the harsh environment of shale oil and gas reservoir exploitation requires higher high temperature and high pressure resistance of the fracturing fluid.

[0004] At present, water-based fracturing fluid is one of the widely used fracturing fluid systems, and the cross-linked fracturing fluid is often used in high temperature and deep well fracturing construction. The composition of the cross-linked fracturing fluid mainly includes water, cross-linking agent, thickening agent and other additives; due to the influence of monomer selection, synthesis process and other conditions, the temperature resistance of the cross-linked fracturing fluid formed by the monomers is still limited. Therefore, it is necessary to develop a temperature-resistant reinforcing agent to improve the high temperature resistance and deformation resistance of the epoxy resin.

[0005] In summary, it is urgent for the technical personnel in the field to develop a temperature-resistant reinforcing agent to improve the high temperature resistance and deformation resistance of the fracturing fluid system. SUMMARY

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

[0007] In order to achieve the above-mentioned purpose, the present application 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 phenolic resin, and the bisphenol phenolic resin comprises 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 reinforcing agent 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, and R5 is methylene or phenyl.

[0015] 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.

[0016] The present application provides the application of the above-mentioned curing agent composition as a curing agent in an epoxy resin.

[0017] The present application provides a preparation method of an epoxy resin product, wherein the epoxy resin product is prepared by mixing and curing component A and component B.

[0018] The component A comprises an epoxy resin.

[0019] The component B is the above-mentioned curing agent composition.

[0020] The present application provides an epoxy resin product prepared by the above-mentioned preparation method.

[0021] Through the above-mentioned technical solution, the curing agent composition and the application thereof, the epoxy resin composition and the epoxy resin product provided by the present application have the following beneficial effects:

[0022] The curing agent composition provided by the present application 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 an epoxy resin, and the two components act together to make the cured epoxy resin have excellent high-temperature resistance and deformation resistance.

[0023] In the epoxy resin composition provided by the present application, the curing agent composition comprises a bisphenol phenolic resin and a reinforcing agent with a specific structure, which is used as a curing agent to make the epoxy resin product prepared after curing of the epoxy resin composition have high-temperature resistance and deformation resistance, and the high-temperature resistance is specifically manifested as not easy to soften at high temperature, and the deformation resistance is specifically manifested as low deformation rate. DETAILED DESCRIPTION

[0024] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges and values should be interpreted as approximations. The endpoints of the ranges and values are provided as a separate point for the convenience of the reader. The ranges and values are approximate values and are intended to be rounded off to the nearest value with the same force as if either the value was an exact number or the number of significant figures was limited to the number of significant figures in that number. Any numerical value, however, can inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0025] The present application 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 phenolic resin, and the bisphenol phenolic resin comprises structural unit A shown in formula I and 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 reinforcing agent 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, and R5 is methylene or phenyl;

[0033] 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.

[0034] In the present application, the curing agent composition comprises a bisphenol novolac resin, a reinforcing agent with a specific structure and water, wherein the reinforcing agent with a rigid benzene ring is added as a curing agent for curing the epoxy resin, and the two components jointly act to make the cured epoxy resin have excellent high-temperature resistance and deformation resistance.

[0035] In the present application, the content of the structural unit A and the structural unit B in the bisphenol novolac resin is not 0 at the same time, and the sum of the content of the structural unit A and the structural unit B is 100wt%.

[0036] Further, Q is wherein R1, R2 are each independently H or CH3, preferably CH3.

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

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

[0039] 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, and preferably, the bisphenol novolac resin described in the present application is prepared by the following method:

[0040] 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;

[0041] wherein the alkaline conditions make n(OH) - is 1.4mol / L-3mol / L;

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

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

[0044]

[0045] wherein Q is wherein R1, R2 are each independently H, CH3, CF3 or CH2CH3.

[0046] In the present application, the adjustment of n(OH) - in the system can be realized by the conventional method in the art, for example, adding alkaline substances such as NaOH.

[0047] In one embodiment of the present application, the first monomer is paraformaldehyde, which can slowly release formaldehyde in the system, so as to precisely control the polymerization rate and the polymerization degree.

[0048] Further, Q is wherein R1, R2 are each independently H or CH3, preferably CH3.

[0049] In one embodiment of the present application, the monomer A is bisphenol A, i.e. as shown in formula III, Q is and R1, R2 are CH3.

[0050] In one embodiment of the present application, the monomer A is bisphenol AF, i.e. as shown in formula III, Q is and R1, R2 are CF3.

[0051] In one embodiment of the present application, the monomer A is bisphenol B, i.e. as shown in formula III, Q is and R1 is CH3, R2 is CH2CH3.

[0052] 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.

[0053] In one embodiment of the present application, the monomer A is bisphenol S, i.e. as shown in formula III, Q is

[0054] 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.

[0055] 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.

[0056] 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.

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

[0058] In the present application, the monomer B can be commercially available, preferably, the monomer B is prepared according to the following method:

[0059] The bisphenol compound is contacted with a sulfonating agent in the presence of a first catalyst and water to perform a sulfonation reaction, so as to obtain the monomer B;

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

[0061] In the present application, by using the above method and controlling the mass ratio of the bisphenol compound to the sulfonating agent to meet the above range, the monomer B with formula IV, i.e. containing monosulfonated bisphenol compound, can be prepared.

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

[0063] 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.

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

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

[0066] 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.

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

[0068] 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.

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

[0070] 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.

[0071] According to the present application, the polymerization reaction conditions include: the polymerization temperature is 30-80℃, and the polymerization time is 1-6h.

[0072] In the present application, the polymerization reaction is carried out under the above polymerization reaction conditions, which can complete the polymerization reaction under relatively mild conditions, and substantially no byproduct is produced.

[0073] Further, the polymerization reaction conditions include: the polymerization temperature is 50-70℃, and the polymerization time is 2-4h.

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

[0075] According to the present application, n is an integer from 1 to 4, and R5 is methylene.

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

[0077] In the present application, the reinforcing agent selected from the above specific types is combined with the bisphenol phenolic resin, the active group NH2 in the reinforcing agent can be combined with the phenolic hydroxyl group in the bisphenol phenolic resin, which can further improve the crosslinking degree of the cured epoxy resin when the epoxy resin is cured, and finally make the epoxy resin product have excellent high temperature resistance and deformation resistance.

[0078] In the present application, 4,4'- methylenedianiline has the following structure:

[0079]

[0080] In the present application, 3,3',5,5'- tetramethylbenzidine has the following structure:

[0081]

[0082] 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 water is 30-55 parts by weight.

[0083] In the present application, when the components in the curing agent composition meet the above specific weight parts, as a curing agent, the softening temperature of the epoxy resin product obtained after curing is increased at high temperature, and the deformation resistance is further improved.

[0084] Further, 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 application, 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 application, the accelerator is selected from a polycarboxylic acid and / or a small molecule polyamine.

[0087] 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.

[0088] 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.

[0089] According to the present application, the promoter is a mixture of polycarboxylic acid and small molecule polyamine, wherein the mass ratio of the polycarboxylic acid and the small molecule polyamine is 1:0.1-0.8.

[0090] In the present application, the mixture of polycarboxylic acid and small molecule polyamine as a promoter, has the beneficial effects of polycarboxylic acid and small molecule polyamine, specifically, can ensure that the curing agent composition has a suitable viscosity to ensure good injectability while further improving the high temperature resistance of the epoxy resin product under a small amount of promoter addition.

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

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

[0093] In the present application, adding a certain amount of co-curing agent in the curing agent composition can cooperate with each component 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] Further, the curing agent composition further comprises 0.1-1 parts by weight of a co-curing agent.

[0095] According to the present application, the co-curing agent is selected from at least one of zirconium oxychloride, aluminum trichloride, titanium tetrachloride, and iron trichloride.

[0096] According to the present application, the apparent viscosity of the curing agent composition is 100-500 mPa·s, preferably 200-300 mPa·s at 25°C.

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

[0098] In the present application, when the curing agent composition satisfies the above apparent viscosity, the curing agent composition exhibits more excellent injectability, and when it is injected into the formation, it can better mix with the epoxy resin and realize the curing of the epoxy resin.

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

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

[0101] The component A comprises an epoxy resin.

[0102] The component B is the curing agent composition.

[0103] In the present application, the component A can further comprise conventional auxiliaries in the art, such as emulsifiers, etc. 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.

[0104] In the present application, the equipment for mixing the epoxy resin composition is not particularly limited, and the component A and the component B in the epoxy resin composition can be mixed by using conventional equipment in the art, such as a double-screw extruder or a stirrer, etc., as long as the component A and the component B can be fully mixed.

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

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

[0107] In the present application, the curing conditions include a curing temperature of 30-80℃, a curing time of 1-6h, and a curing pressure of 20-40MPa.

[0108] The fourth aspect of the present application provides an epoxy resin product prepared by the above preparation method.

[0109] In the present application, the curing agent composition comprises a bisphenol phenolic resin and a specific structure of a reinforcing agent, which acts as a curing agent, so that the epoxy resin product prepared after the curing of the epoxy resin composition has excellent temperature resistance, deformation resistance and compression 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 application, the deformation rate of the epoxy resin product is less than or equal to 5% at 120℃ and 30MPa, and preferably less than or equal to 1%.

[0111] According to the present application, the softening point of the epoxy resin product is 90-120℃, and preferably 110-120℃.

[0112] The present application will be described in detail by the following examples. In the following examples and comparative examples,

[0113] The content of each structural unit in the bisphenol novolac resin is measured by using the feeding ratio method.

[0114] The weight average molecular weight of the bisphenol novolac resin is measured by GPC.

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

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

[0117] Reinforcing agent E1: 4,4'-methylene dianiline;

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

[0119] Reinforcing agent E3: 4,4'-biphenyl dicarboxylic acid;

[0120] Reinforcing agent E4: 4,4'-biphenyl diol;

[0121] Reinforcing agent DE: melamine.

[0122] Promoter

[0123] Promoter C1: terephthalic acid;

[0124] Promoter C2: citric acid;

[0125] Promoter C3: polyethylene polyamine;

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

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

[0128] Co-curing agent Z2: aluminum trichloride.

[0129] Preparation example - preparation of bisphenol novolac resin

[0130] Preparation of monosulfonated bisphenol A

[0131] 57 g of bisphenol A, 0.03 g of ferric trichloride, and 25 g of concentrated sulfuric acid are contacted to perform a sulfonation reaction, the reaction temperature is 130°C, and the reaction time is 4 h, 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 trichloride is 1:0.00052.

[0132] Preparation of trisulfonated bisphenol A

[0133] Sulfonate 57 g of bisphenol A with 0.03 g of ferric chloride and 75 g of concentrated sulfuric acid, the reaction temperature is 130°C, the reaction time is 4 h, to obtain tri-sulfonated bisphenol A; wherein, the molar ratio of bisphenol A to concentrated sulfuric acid is 1:3, and the mass ratio of bisphenol A to ferric chloride is 1:0.00052.

[0134] Preparation Example 1

[0135] Under stirring, 32 parts by weight of mono-sulfonated bisphenol A, 48 parts by weight of bisphenol A, 33.01 parts by weight of paraformaldehyde and deionized water are mixed, 5.95 parts by weight of NaOH is added, so that n(OH) - is 1.44 mol / L, and the polymerization is carried out at 50°C for 4 h to obtain bisphenol phenolic resin A1, in the structure unit A, Q is R1, R2 are CH3, the structure unit A is 60wt%, in the structure unit B, Q is R1, R2 are CH3, the structure unit B is 40wt%, and the weight average molecular weight is 3986 g / mol.

[0136] Preparation Example 2

[0137] Under stirring, 40 parts by weight of mono-sulfonated bisphenol A, 40 parts by weight of bisphenol A, 31.58 parts by weight of paraformaldehyde and deionized water are mixed, 5.95 parts by weight of NaOH is added, so that n(OH) - is 1.44 mol / L, and the polymerization is carried out at 50°C for 4 h to obtain bisphenol phenolic resin A2, in the structure unit A, Q is R1, R2 are CH3, wherein the structure unit A is 50wt%, in the structure unit B, Q is R1, R2 are CH3, the structure unit B is 50wt%, and the weight average molecular weight is 4085 g / mol.

[0138] Comparative Preparation Example

[0139] Under stirring, 32 parts by weight of mono-sulfonated bisphenol A, 48 parts by weight of bisphenol A, 33.01 parts by weight of paraformaldehyde and deionized water are mixed, 5.95 parts by weight of NaOH is added, so that n(OH) - is 1.44 mol / L, and the polymerization is carried out at 50°C for 4 h to obtain bisphenol phenolic resin A1, in the structure unit A, Q is

[0140] Example and Comparative Example - Curing Agent Composition

[0141] The bisphenol phenolic resin, the reinforcing agent, the accelerator, the co-curing agent and water are mixed according to the amount shown in Table 1 to obtain curing agent compositions B1-B15 and comparative examples DB1-DB2. The apparent viscosity of the curing agent composition is 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] From the results in Table 2, it can be seen that the curing agent compositions B1-B15 provided by the present application have a specific apparent viscosity, compared with comparative examples DB1-DB2, which meets 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 the epoxy resin is mixed with 80 parts by weight of the curing agent composition of the examples, and placed in a high-temperature reaction kettle at 40 MPa and 80°C for 6 hours. After removal, the curing is complete, and epoxy resin products P1-P15 and DP1-DP2 are obtained. The performance of the epoxy resin products is tested, and the results are shown in Table 3.

[0149] 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".

[0150] At normal pressure and 25°C, the diameter of the epoxy resin product is D0. After the epoxy resin product is extruded at 30 MPa and 120°C using a high-low temperature universal material testing machine, the diameter of the extruded epoxy resin product is D1, and the deformation rate is (D0-D1)D0x100%.

[0151] Table 3

[0152]

[0153]

[0154] As can be seen from the results of Table 2 and Table 3, when the curing agent composition of the present application embodiment containing the reinforcing agent having a specific structure and the curing agent of the bisphenol novolac resin is used as the curing agent composition, not only can the curing agent composition have a suitable apparent viscosity to ensure that the curing agent composition has excellent injection property, but also when it is used as a curing agent for curing the 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 the condition of high temperature (120°C) and high pressure (30 MPa), the epoxy resin product has a low deformation rate.

[0155] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept scope 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 belong to the protection scope of the present application.

Claims

1. A curing agent composition characterized by comprising: The curing agent composition comprises a curing agent, a reinforcing agent and water; The curing agent is a bisphenol phenol resin comprising structural unit A shown in Formula I and structural unit B shown in Formula II; Formula I; Formula II; Q is or wherein R1, R2are each independently H, CH3, CF3, or CH2CH3; The reinforcing agent has a structure shown in Formula III; Formula III; R3 and R4 are each independently selected from NH2, COOH or OH; n is an integer of 0-10, and R5 is methylene or phenylene; The content of the structural unit A is 60-80 wt% and the content of the structural unit B is 20-40 wt% based on the total weight of the bisphenol phenol resin.

2. The curative composition of claim 1, wherein, R3 and R4 are each independently selected from NH2 or COOH.

3. The curative composition of claim 1 or 2, wherein, n is an integer of 1-4, and R5 is methylene.

4. The curative composition of claim 1 or 2, wherein, The reinforcing agent is selected from 4,4'-methylene dianiline.

5. The curative composition of claim 1 or 2, 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 the water is 30-55 parts by weight.

6. The curative composition of claim 1 or 2, wherein, Q is wherein R1, R2are each independently H or CH3.

7. The curative composition of claim 1 or 2, wherein, R1 and R2 are each independently CH3.

8. The curative composition of claim 1 or 2, wherein, The weight average molecular weight of the bisphenol phenol resin is 2000-10000 g / mol.

9. The curative composition of claim 8, wherein, The weight average molecular weight of the bisphenol phenol resin is 3000-5000 g / mol.

10. The curative composition of claim 1 or 2, wherein, The curing agent composition further comprises 3-7 parts by weight of an accelerator.

11. The curative composition of claim 10, wherein, The curing agent composition further comprises 4-5 parts by weight of an accelerator.

12. The curative composition of claim 10, wherein, The accelerator is selected from a polycarboxylic acid and / or a small molecule polyamine; 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.

13. The curative composition of claim 12, wherein, The polycarboxylic acid is selected from at least one of terephthalic acid, citric acid, tartaric acid, oxalic acid, malic acid and citric acid.

14. The curative composition of claim 12, wherein, The accelerator is a mixture of a polycarboxylic acid and a small molecule polyamine, wherein the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.1-0.

8.

15. The curative composition of claim 14, wherein, The mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.4-0.

6.

16. The curative composition of claim 1 or 2, wherein, The curing agent composition further comprises 0.1-1 parts by weight of a co-curing agent.

17. The curative composition of claim 16, wherein, The co-curing agent is selected from at least one of zirconium oxychloride, aluminum trichloride, titanium tetrachloride and ferric trichloride.

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

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

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

21. A method of making an epoxy resin article, characterized by, The epoxy resin product is prepared by mixing and curing component A and component B; The component A comprises an epoxy resin. The component B is the curing agent composition according to any one of claims 1-10.

22. The method of making according to claim 21, wherein, The amount of the component B is 40-80 parts by weight relative to 100 parts by weight of the component A.

23. The method of making according to claim 22, wherein, The amount of the component B is 60-80 parts by weight relative to 100 parts by weight of the component A.

24. An epoxy resin product prepared by the preparation method according to any one of claims 21-23.

25. The epoxy resin article of claim 24, wherein, a deformation rate of the epoxy resin product is less than or equal to 5% at 120°C and 30 MPa; and / or, a softening point of the epoxy resin product is 90-120°C.

26. The epoxy resin article of claim 25, wherein, a deformation rate of the epoxy resin product is less than or equal to 1% at 120°C and 30 MPa; and / or, a softening point of the epoxy resin product is 110-120°C.

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