Amino group-containing modified silica, biphenyl compound curing agent composition, and use thereof, epoxy resin composition, and epoxy resin product

Abstract

The application relates to the field of organic polymers and discloses an amino-containing modified silica, a biphenyl compound curing agent composition and application, an epoxy resin composition and an epoxy resin product. The curing agent composition comprises a curing agent, a reinforcing agent and water; the curing agent is modified nano-silica shown in formula I; and the reinforcing agent has a structure shown in formula II. The curing agent composition contains the modified nano-silica with a specific structure and the reinforcing agent with a specific structure, so that, when the composition is added into the epoxy resin, the composition can occur bonding reaction with epoxy groups in the epoxy resin, the advantages between the two are fully exerted, meanwhile, due to the existence of the reinforcing agent with the specific structure, the epoxy resin product after curing has relatively large compressive strength, and the pore structure of the epoxy resin product is not easy to collapse at high temperature.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic polymers, in particular to a curing agent composition containing amino-modified silica and biphenyl compounds, application, epoxy resin composition and epoxy resin product. BACKGROUND

[0002] Epoxy resin has a wide range of applications in energy, machinery, chemical industry and other fields. At present, a curing agent is generally added for synthesizing epoxy resin to improve the performance of epoxy resin. Currently, ethylenediamine is commonly used as a curing agent. However, ethylenediamine has great toxicity when used for curing epoxy resin, and the application conditions are limited, which is not suitable for water systems.

[0003] In addition, the epoxy resin prepared by using the commonly used curing agent has low mechanical strength, and when used as a proppant in the petroleum field, it cannot fill various small cracks in the formation well, and cannot guarantee high permeability and adapt to special formation conditions and maintain a long working time.

[0004] Therefore, it is urgent to develop a product that can withstand high temperature and high pressure and does not affect the permeability. SUMMARY

[0005] The present application aims to overcome the problem that the existing epoxy resin product cannot be effectively used as a proppant in the field of oil fracturing, which is specifically manifested in that it cannot have high permeability and compressive strength at the same time, and at high temperatures, the pore structure of the epoxy product is easy to collapse, which causes the product to be easy to deform, affects the permeability, and cannot be used in formation operation for a long time. A curing agent composition containing amino-modified silica and biphenyl compounds, application, epoxy resin composition and epoxy resin product are provided. The curing agent composition contains modified nanosilica with a specific structure and a specific structure of the reinforcing agent, so that the composition added to the epoxy resin can bond with the epoxy groups in the epoxy resin, fully exerting the advantages between the two, and due to the presence of the specific structure of the reinforcing agent, the cured epoxy resin product has high compressive strength, and the pore structure of the epoxy resin product is not easy to collapse at high temperatures.

[0006] To achieve the above-mentioned purpose, the first aspect of the present application provides a curing agent composition, characterized in that the curing agent composition comprises a curing agent, a reinforcing agent and water;

[0007] The curing agent is a modified nanosilica shown in formula I;

[0008]

[0009] In formula I, M is a nanosilica particle, x is an integer of 1-4, and R is an alkyl group with a carbon atom number of 1-4;

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

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

[0012] The reinforcing agent has a structure shown in Formula II:

[0013] has a structure shown in Formula II;

[0014]

[0015] R3 and R4 are each independently selected from NH2, COOH or OH;

[0016] L is an integer from 0 to 10, and R5 is methylene or phenyl.

[0017] The second aspect of the present application provides the use of the curing agent composition of the first aspect of the present application as a curing agent in an epoxy resin.

[0018] The third aspect of the present application provides an epoxy resin composition, wherein the epoxy resin composition comprises an epoxy resin component and a curing agent component;

[0019] The curing agent component is the curing agent composition of the first aspect of the present application;

[0020] The epoxy resin component and the curing agent component are each independently present.

[0021] The fourth aspect of the present application provides an epoxy resin product, wherein the epoxy resin product is prepared by mixing and curing the epoxy resin composition of the third aspect.

[0022] By the above technical solution, the amino-containing modified silica, the biphenyl compound curing agent composition and application, the epoxy resin composition and the epoxy resin product provided by the present application have the following beneficial effects: the polyamino groups in the modified silica present a dendritic morphology on the surface of the nanosilica, when the modified nanosilica is added to the epoxy resin, the polyamino groups on the surface thereof can bond with the epoxy groups in the epoxy resin, the advantages between the two are fully played, and the modified nanosilica is used in cooperation with the reinforcing agent with a specific structure, so that the cured epoxy resin has a large compressive strength when used as a proppant, and the pore structure thereof is not easy to collapse at high temperature, thereby improving the application stability. DETAILED DESCRIPTION

[0023] 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 invention. Any numeric range recited is intended to include all values from the lower value to the upper value, inclusive of both values, and to also include any value approximately or about the value. For ranges including upper and lower limits, the range includes all values between the upper and lower limits that can be equally measured with the same degree of accuracy or precision as the upper and lower limits. For ranges excluding the endpoints, the range includes all values between the upper and lower limits, not including the endpoints. All individual values of the range and subranges are included herein.

[0024] The first aspect of the present application provides a curing agent composition, characterized in that the curing agent composition comprises a curing agent, a reinforcing agent and water;

[0025] The curing agent is a modified nanosilica shown in formula I;

[0026]

[0027] In formula I, M is a nanosilica particle, x is an integer of 1-4, and R is an alkyl group with a carbon atom number of 1-4;

[0028] n is an integer of 0-3, m is an integer of 1-3, and n+m=3;

[0029] A is a structural unit from an acid anhydride compound, and B is a structural unit from a polyamino compound;

[0030] The reinforcing agent has a structure shown in formula II:

[0031] has a structure shown in formula II;

[0032]

[0033] R3 and R4 are each independently selected from NH2, COOH or OH;

[0034] L is an integer of 0-10, and R5 is a methylene group or a phenyl group.

[0035] In the present application, the polyamino groups on the surface of the modified nanosilica exhibit a dendritic morphology, can occur bonding reaction with the epoxy groups in the epoxy resin when applied to the epoxy resin, fully play the advantages between the two, and cooperate with the reinforcing agent with a specific structure, so that the cured epoxy resin has a large compressive strength when used as a proppant, and its pore structure is not easy to collapse at high temperature.

[0036] According to the present application, in formula I, the acid anhydride compound is selected from at least one of maleic anhydride, phthalic anhydride and succinic anhydride.

[0037] According to the present application, the polyamino compound is a linear polyethylene polyamino compound with a structure shown in formula III or a non-linear polyethylene imine with a number average molecular weight of 300-3000:

[0038]

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

[0040] In the present application, the polyamino compound is selected from the above-mentioned compounds, so that the amino content in the modified nanosilica is high, further improving the curing performance on the epoxy resin.

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

[0042] According to the present application, the particle size of the modified nanosilica is 10-500 nm, and the specific surface area is 50-500 m 2 / g.

[0043] According to the present application, the particle size dispersion coefficient of the modified nanosilica is 0.09-0.15.

[0044] According to the present application, the amino content of the modified nanosilica is 0.1-5 mmol / g.

[0045] In the present application, the modified nanosilica can be prepared according to the following steps:

[0046] S1, dispersing the nanosilica particles M in a first solvent in the presence of a protective gas, adding an amino silane to perform a first reaction, to obtain an amino-functionalized nanosilica shown in formula IV;

[0047]

[0048] S2, in the presence of a second solvent, the amino-functionalized nanosilica is reacted with an acid anhydride compound to obtain a carboxyl-functionalized nanosilica shown in formula V;

[0049]

[0050] S3, in the presence of a basic catalyst, the carboxyl-functionalized nanosilica is mixed with a condensing agent, activated, and then a polyamino compound is added to perform a third reaction to obtain a modified nanosilica.

[0051] In the present application, the protective gas is nitrogen and / or inert gas.

[0052] In the present application, the steps S1, S2 and S3 each independently comprise a separation, washing, and drying step.

[0053] Further, the separation method is not particularly limited, and can be at least one of filtration, rotary evaporation, or centrifugal separation, for example.

[0054] Further, the conditions for the washing are not particularly limited, and the washing can be performed 3 to 4 times using a solvent conventionally used in the art, wherein the solvent can be at least one of methanol, ethanol, or acetone, and preferably, acetone and dichloromethane are used in the step S1.

[0055] According to the present application, the mass ratio of the nanosilica particles M to the aminosilane in the step S1 is 5 to 100:1.

[0056] Further, the mass ratio of the nanosilica particles M to the aminosilane is 10 to 50:1.

[0057] According to the present application, the aminosilane is at least one selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, and aminopropylmethyldiethoxysilane.

[0058] According to the present application, the conditions for the first reaction include a reaction temperature of 120 to 160°C and a reaction time of 2 to 24 hours.

[0059] Further, the conditions for the first reaction include a reaction temperature of 120 to 140°C and a reaction time of 8 to 16 hours.

[0060] According to the present application, the mass ratio of the aminofunctionalized nanosilica to the acid anhydride compound in the step S2 is 5 to 100:1.

[0061] Further, the mass ratio of the aminofunctionalized nanosilica to the acid anhydride compound is 10 to 50:1.

[0062] According to the present application, the acid anhydride compound is at least one selected from the group consisting of maleic anhydride, phthalic anhydride, and succinic anhydride.

[0063] According to the present application, the conditions for the second reaction include a reaction temperature of 90 to 160°C and a reaction time of 2 to 12 hours.

[0064] Further, the conditions for the second reaction include a reaction temperature of 90 to 120°C and a reaction time of 6 to 12 hours.

[0065] According to the present application, the first solvent and the second solvent are each independently at least one selected from the group consisting of toluene, xylene, benzene, and N,N-dimethylformamide.

[0066] According to the present application, in step S3, the mass ratio of the carboxyl-functionalized nanosilica, the condensing agent, the basic catalyst and the polyamino compound is 1:0.05-0.5:0.01-0.1:0.1-5.

[0067] In the present application, when the mass ratio of the carboxyl-functionalized nanosilica, the condensing agent, the basic catalyst and the polyamino compound meets the above-mentioned preferred range, the obtained modified nanosilica has the best comprehensive performance, and further improves the curing performance on the epoxy resin.

[0068] Further, the mass ratio of the carboxyl-functionalized nanosilica, the condensing agent, the basic catalyst and the polyamino compound is 1:0.05-0.3:0.01-0.05:0.1-4.

[0069] According to the present application, the condensing agent is selected from one of dicyclohexyl carbodiimide, diisopropyl carbodiimide and 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide.

[0070] According to the present application, the basic catalyst is selected from at least one of 4-dimethylaminopyridine, 1,8-diazabicycloundec-7-ene and triethylamine.

[0071] According to the present application, the conditions of the third reaction include: the reaction temperature is 0-40℃, and the reaction time is 2-48h.

[0072] Further, the conditions of the third reaction include: the reaction temperature is 10-25℃, and the reaction time is 8-16h.

[0073] According to the present application, in step S3, the activation conditions include: the activation temperature is 10-25℃, and the activation time is 8-24h.

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

[0075] According to the present application, L is an integer of 0-4, and R5 is methylene.

[0076] According to the present application, the reinforcing agent is selected from at least one of 4,4'-methylene dianiline and / or 3,3',5,5'-tetramethylbenzidine. In the present application, the inventors have found that the reinforcing agent selected from the above-mentioned types can further improve the high-temperature resistance of the cured epoxy resin product.

[0077] According to the present application, the content of the curing agent is 40-60wt% based on the total weight of the curing agent composition, the content of the reinforcing agent is 5-10wt%, and the content of the water is 30-55wt%.

[0078] In the present application, the components in the curing agent composition meet the above-mentioned ranges, and the components synergize with each other, so that when the composition is applied to an epoxy resin, the compressive strength of the cured epoxy resin is further improved, and the cured epoxy resin product is not easy to deform at high temperature.

[0079] Further, the content of the curing agent is 50-60wt%, the content of the reinforcing agent is 6-8wt%, and the content of the water is 32-44wt% based on the total weight of the curing agent composition.

[0080] According to the present application, the curing agent composition further comprises 2-5 parts by weight, preferably 3-4 parts by weight of an accelerator.

[0081] According to the present application, the accelerator is selected from at least one of polycarboxylic acid and / or small molecule polyamine.

[0082] 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, ascorbic acid.

[0083] 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.

[0084] According to the present application, the accelerator is a mixture of polycarboxylic acid and small molecule polyamine, and the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.1-0.8.

[0085] In the present application, the accelerator is a mixture of polycarboxylic acid and small molecule polyamine, which can ensure the fluidity of the curing agent composition while improving its high temperature resistance. Further, when the mass ratio of the polycarboxylic acid to the small molecule polyamine meets the above-mentioned range, the high temperature resistance of the curing composition can be significantly improved, and it is not easy to deform at high temperature.

[0086] Further, the mass ratio of the polycarboxylic acid to the small molecule polyamine is 1:0.4-0.6.

[0087] According to the present application, the curing agent composition further comprises 0.01-0.06 parts by weight of a co-curing agent.

[0088] Further, the co-curing agent is selected from at least one of zirconium oxychloride, aluminum chloride, titanium tetrachloride and ferric chloride.

[0089] 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.

[0090] The second aspect of the present application provides a use of the curing agent composition of the first aspect of the present application as a curing agent in an epoxy resin.

[0091] The third aspect of the present application provides an epoxy resin composition, wherein the epoxy resin composition comprises an epoxy resin component and a curing agent component;

[0092] The curing agent component is the curing agent composition of the first aspect of the present application;

[0093] The epoxy resin component and the curing agent component are each independently present.

[0094] In the present application, the epoxy resin and the curing agent in the epoxy resin composition are each independently stored separately, which can avoid the premature curing of the epoxy resin affecting the subsequent normal use. When used in the subsequent process, the epoxy resin and the curing agent are respectively injected into the stratum at the same time, so that they perform a curing reaction in the stratum, thereby preparing a honeycomb product for use as a proppant, which can have a high permeability rate while having a high compressive strength.

[0095] In the present application, the curing agent component can further comprise an auxiliary agent in the art, such as an emulsifier, etc. There is no particular requirement for the specific type and amount of the emulsifier, and a conventional type of emulsifier in the art can be used and added according to the conventional amount in the art.

[0096] According to the present application, the amount of the curing agent component is 30-80 parts by weight relative to 100 parts by weight of the epoxy resin component.

[0097] In the present application, the amount of the curing agent satisfies the above range, which can enable the cured epoxy resin to have a high compressive strength while not being easily deformed at high temperatures.

[0098] Further, the amount of the curing agent component is 40-60 parts by weight relative to 100 parts by weight of the epoxy resin.

[0099] The fourth aspect of the present application provides an epoxy resin product, which is prepared by mixing and curing the epoxy resin composition of the third aspect of the present application.

[0100] According to the present application, the deformation rate of the epoxy resin product is less than or equal to 5% at 90℃ and 40MPa, preferably less than or equal to 3%, and more preferably less than or equal to 1%.

[0101] According to the present application, the softening point of the epoxy resin product is 90-120℃, preferably 110-120℃.

[0102] The present application will be described in detail below through examples. In the following examples,

[0103] The particle size of the modified nanosilica is measured by transmission electron microscopy (TEM) and scanning electron microscopy (SEM);

[0104] The specific surface area of the modified nanosilica is measured by the BET adsorption method;

[0105] The particle size dispersion index PDI of the modified nanosilica is measured by the laser particle size analyzer (DLS) method;

[0106] The amino content in the modified nanosilica is measured by the acid-base neutralization titration method;

[0107] The apparent viscosity of the curing agent composition is measured by the six-speed rotary viscometer method;

[0108] The deformation rate of the epoxy resin product is measured according to the following method:

[0109] At normal pressure and 25°C, the diameter of the honeycomb resin product is D0, after the honeycomb resin product is extruded by a high-low temperature universal material testing machine at 40 MPa and 90°C, the diameter of the extruded honeycomb resin product is D1, and the deformation rate = (D0-D1) / D0x100%.

[0110] Preparation of nanosilica M1

[0111] S1, Preparation of amino-propyl functionalized nanosilica:

[0112] 2g of nanosilica particles with an average particle size of 30 nm and a specific surface area of 200 m 2 / g were weighed into 100 mL of anhydrous toluene, then 0.2 g of aminopropyl triethoxysilane was added, and the reaction was stirred under reflux at 150°C for 24 hours under nitrogen protection. After the reaction was completed, the solid product was obtained by centrifugation, the obtained solid product was repeatedly washed with acetone and dichloromethane for 3 times, and vacuum dried at 40°C for 12h to obtain the amino-propyl functionalized nanosilica.

[0113] S2, Preparation of carboxyl functionalized nanosilica:

[0114] 2g of the above prepared amino-propyl functionalized nanosilica was weighed into 50 mL of dimethylbenzene, 0.2 g of maleic anhydride was added, and the reaction was stirred under reflux at 160°C for 6 hours under nitrogen protection. After the reaction was completed, it was repeatedly washed with methanol for 3 times, and vacuum dried at 40°C for 12h to obtain the carboxyl functionalized nanosilica.

[0115] S3, Preparation of modified nanosilica:

[0116] ​Take 1 g of the carboxyl functionalized nano-silica prepared above, disperse in 50 mL of toluene, then add 0.25 g of diisopropyl carbodiimide (DIC) and 0.06 g of 1,8-diazabicycloundec-7-ene (DBU), stir at room temperature (25 °C) for 1 hour, then add 4 g of polyethyleneimine (number average molecular weight of 1500), continue to react at room temperature for 12 hours, after the reaction is completed, wash repeatedly with methanol for 3 times, and vacuum dry at 40 °C for 12 h to obtain the modified nano-silica M1 of formula I, wherein n is 0, m is 3, and x is 3.

[0117] The particle size of the modified nano-silica M1 is 30 nm, the specific surface area is 300 m 2 / g, the amino content is 2 mmol / g, and the dispersion coefficient PDI is 0.11.

[0118] Preparation of nano-silica M2

[0119] According to the preparation method of M1, except that the specific surface area of the nano-silica particles is 100 m 2 / g, and in step S3, the amount of polyethyleneimine used is 0.4 g; the particle size of the modified nano-silica M2 prepared is 30 nm, the specific surface area is 230 m 2 / g, the amino content is 0.1 mmol / g, and the dispersion coefficient PDI is 0.13.

[0120] The following preparation examples and comparative preparation examples are used to illustrate the preparation of the cured resin composition

[0121] Preparation Example 1

[0122] Mix 55 g of modified nano-silica M1, 8 g of 4,4'-methylene dianiline (DDM1), 2.2 g of terephthalic acid, 0.9 g of polyethylene polyamine, 0.04 g of zirconium oxychloride, and 49.8 g of water, and stir uniformly to obtain a curing agent composition A1, and the apparent viscosity thereof is 198 mPa·s.

[0123] Preparation Examples 2-10

[0124] The curing agent compositions A2-A10 are prepared according to the method of Preparation Example 1, except that the types and amounts of the curing agent, accelerator, and reinforcing agent are different from those of Preparation Example 1, and the specific details are shown in Table 1 and Table 1 (continued). The apparent viscosities of the curing agent compositions A2-A10 are shown in Table 1 and Table 1 (continued).

[0125] Table 1

[0126]

[0127] * refers to the mass ratio of the amount of accelerator 1 to the amount of accelerator 2

[0128] Table 1 (continued)

[0129]

[0130]

[0131] Comparative Preparation Examples D1-D3

[0132] The curing agent compositions D1-D3 were prepared according to the method of Preparation Example 1, except that the types and amounts of the curing agent, accelerator, and enhancer were different from those of Preparation Example 1, as shown in Table 2. The apparent viscosities of the curing agent compositions D1-D3 are shown in Table 2.

[0133] Table 2

[0134]

[0135] The following examples are used to illustrate the preparation of the epoxy resin products

[0136] Examples 1-10

[0137] The curing agent compositions 65 g prepared in Examples 1-10 were mixed with 100 g of the epoxy resin E44, and cured at a curing temperature of 120 °C for 4 h to obtain the epoxy resin products P1-P10. The distortion rate and softening point of the products P1-P10 at 90 °C and 40 MPa were tested, and the results are shown in Table 3.

[0138] Comparative Examples 1-3

[0139] The curing agent compositions 65 g prepared in Comparative Preparation Examples 1-3 were mixed with 100 g of the epoxy resin E44, and cured at a curing temperature of 120 °C for 4 h to obtain the epoxy resin products DP1-DP3. The distortion rate and softening point of the products DP1-DP3 at 90 °C and 40 MPa were tested, and the results are shown in Table 3.

[0140] Table 3

[0141]

[0142]

[0143] From the results in Table 1, it can be seen that the Examples 1-10 of the present application achieved good technical effects, in which the distortion rate at 90 °C and 40 MPa was not higher than 4%, and the softening point was not lower than 90 °C.

[0144] Further, the preferred Examples 1-3 achieved significantly better effects, in which the distortion rate at 90 °C and 40 MPa was not higher than 2.6%, and the softening point was not lower than 110 °C.

[0145] The preferred embodiments of the present application are described in detail above, 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 that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within 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 modified nanosilica represented by Formula I; Formula I; In Formula I, M is a nanosilica particle, x is an integer of 1-4, and R is an alkyl group having 1-4 carbon atoms; n is an integer of 0-3, m is an integer of 1-3, and n+m = 3; A is a structural unit from an anhydride compound, and B is a structural unit from a polyamino compound; The reinforcing agent has a structure represented by Formula II: has a structure represented by Formula II; Formula II; R3 and R4 are each independently selected from NH2, COOH, or OH; L is an integer of 0-10, and R5 is a methylene group or a phenyl group; wherein, based on the total weight of 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.

2. The curative composition of claim 1, wherein, In Formula I, the anhydride compound is selected from at least one of maleic anhydride, phthalic anhydride, and succinic anhydride; and / or, the polyamino compound is a linear polyethylene polyamino compound having a structure represented by Formula III or a non-linear polyethylene imine having a number average molecular weight of 300-3000: Formula III; wherein, p is an integer of 1-6.

3. The curative composition of claim 1 or 2, wherein, The nano-silica particles M have a particle size of 10-500 nm and a specific surface area of 10-300 m 2 / g; And / or, the modified nanosilica has a particle size of 10-500 nm, a specific surface area of 50-500 m 2 / g; and / or, the particle size dispersion coefficient of the modified nanosilica is 0.09-0.15; and / or, the content of the secondary amino group of the modified nanosilica is 0.1-5 mmol / g.

4. The curative composition of claim 1 or 2, wherein, In Formula II, R3 and R4 are each independently selected from NH2 or COOH; and / or, L is an integer of 0-4, and R5 is a methylene group.

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

6. The curative composition of claim 1 or 2, wherein, Based on the total weight of the curing agent composition, the content of the curing agent is 50-60 parts by weight, the content of the reinforcing agent is 6-8 parts by weight, and the content of the water is 32-44 parts by weight.

7. The curative composition of claim 1 or 2, wherein, The curing agent composition further comprises 2-5 parts by weight of an accelerator.

8. The curative composition of claim 7, wherein, The curing agent composition further comprises 3-4 parts by weight of an accelerator.

9. The curative composition of claim 8, wherein, The accelerator is selected from a polycarboxylic acid and / or a small molecule polyamine.

10. The curative composition of claim 9, 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; and / or, the small molecule polyamine is selected from at least one of a polyethylene polyamine, ethylenediamine, 1,6-hexanediamine, isophorone diamine, 2-methyl-1,5 pentanediamine, 3-methyl-1,5 pentanediamine, hydrazine, and bis-hydrazide.

11. The curative composition of claim 9, 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.

12. The curative composition of claim 11, 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 1:0.4-0.

6.

13. The curative composition of claim 1 or 2, wherein, The curing agent composition further comprises 0.01-0.06 parts by weight of a co-curing agent.

14. The curative composition of claim 13, wherein, The co-curing agent is selected from at least one of zirconium oxychloride, aluminum trichloride, titanium tetrachloride, and iron trichloride.

15. 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.

16. The curative composition of claim 15, wherein, The apparent viscosity of the curing agent composition is 200-300 mPa·s at 25°C.

17. Use of the curing agent composition according to any one of claims 1 to 16 as a curing agent in an epoxy resin.

18. An epoxy resin composition, characterized by comprising: The epoxy resin composition comprises a resin component and a curing agent component; The curing agent component is the curing agent composition according to any one of claims 1 to 16; wherein the epoxy resin component and the curing agent component are each independently present.

19. The epoxy resin composition according to claim 18, wherein, The amount of the curing agent component is 30 to 80 parts by weight relative to 100 parts by weight of the epoxy resin.

20. The epoxy resin composition according to claim 19, wherein, The amount of the curing agent component is 40 to 60 parts by weight relative to 100 parts by weight of the epoxy resin.

21. An epoxy resin article, characterized by, The epoxy resin product is prepared by mixing and curing the epoxy resin composition according to any one of claims 18 to 20.

22. The epoxy resin article of claim 21, wherein, The epoxy resin product has a deformation rate of less than or equal to 5% at 90°C and 40 MPa; and / or the epoxy resin product has a softening point of 90 to 120°C.

23. The epoxy resin article of claim 22, wherein, The epoxy resin product has a deformation rate of less than or equal to 3% at 90°C and 40 MPa; and / or the epoxy resin product has a softening point of 110 to 120°C.

24. The epoxy resin article of claim 23, wherein, The epoxy resin product has a deformation rate of less than or equal to 2% at 90°C and 40 MPa.

Images