Cold-resistant and impact-resistant epoxy resin composition, prepreg and laminated board

Abstract

The invention discloses a cold-resistant and impact-resistant epoxy resin composition, a prepreg and a laminated board. The cold-resistant and impact-resistant epoxy resin composition is prepared from the following components in parts by mass: 100 parts of weather-resistant epoxy resin, 20 to 40 parts of ethylene-glycidyl methacrylate copolymer, 10 to 30 parts of ethylene acrylate rubber, 5 to 30 parts of curing agent, 0.1 to 1 part of accelerant and 50 to 100 parts of solvent. Wherein the weather-resistant epoxy resin is selected from at least one of alicyclic epoxy resin and aliphatic epoxy resin. According to the scheme, the AEM rubber and the E-GMA copolymer which are low in brittleness temperature and excellent in impact strength are compounded with the weather-resistant epoxy resin, the weather-resistant epoxy resin composition which still has high impact strength under the low-temperature condition is prepared, and the reliability of a product prepared from the composition under the severe cold condition is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of epoxy resin composite materials, and specifically relates to a cold-resistant and impact-resistant epoxy resin composition, a prepreg and a laminate. Background Art

[0002] As a high-performance material, epoxy resin composites have shown extensive application potential in outdoor products such as automobile and aircraft parts shells, building materials, and outdoor equipment. These products are exposed to complex and changeable outdoor environments for a long time. They not only have to withstand the test of harsh conditions such as ultraviolet radiation, alternating high and low temperatures, salt spray corrosion, and physical scratches, but also face severe challenges from extreme natural factors such as extremely low temperatures, thin air, strong ultraviolet rays, and ozone in high latitudes and high altitudes. Epoxy resin has become one of the important choices for outdoor product materials due to its good adhesion, insulation, corrosion resistance, and molding processability. However, the rigid structure and symmetrical structural characteristics of epoxy resin lead to its greater brittleness, and there are obvious shortcomings in impact resistance and cold resistance, which limits its application effect in extreme environments.

[0003] In order to overcome these limitations of epoxy resin, researchers and engineers have been committed to improving the comprehensive performance of epoxy resin composites, especially in terms of impact resistance and cold resistance, through modification and reinforcement.

[0004] In terms of improving impact resistance, the strategies usually adopted by researchers include adding toughening agents such as elastomers, rubber particles, and thermoplastic resins, as well as introducing nanofillers such as nanoclay and nanosilica. These measures can effectively disperse the stress inside the epoxy resin and increase the toughness of the material. For example, by blending modification technology, epoxy resin is blended with thermoplastic polyurethane (TPU), which can significantly improve the impact strength of the composite material while maintaining good heat resistance and chemical corrosion resistance. In addition, using interpenetrating polymer network (IPN) technology to interpenetrate epoxy resin with another polymer network to form a three-dimensional network structure can also effectively improve the toughness of the material, so that it has better energy absorption and dispersion capabilities when facing external impacts.

[0005] In terms of cold resistance, improving the low-temperature brittleness of epoxy resin composites is another major challenge. Traditional epoxy resins tend to become brittle at low temperatures, resulting in a significant decrease in mechanical properties. In order to improve its cold resistance, researchers have developed a variety of strategies, such as introducing epoxy resin monomers containing flexible segments, using plasticizers that can still maintain flexibility at low temperatures, and adjusting the chemical cross-linking structure to reduce the glass transition temperature (Tg) of the material. Among them, the introduction of low-temperature active curing agents and cross-linking agents, such as amine or anhydride curing agents containing flexible aliphatic long chains, can effectively reduce the Tg of epoxy resin composites, so that they still maintain sufficient flexibility and mechanical strength in low temperature environments. In addition, the synthesis of epoxy resins with specific structures through molecular design, such as polyethers or polyesters containing epoxide functional groups, can also significantly improve the low-temperature performance of the material.

[0006] However, the above-mentioned existing technical means can often only improve a single property of epoxy resin composite materials, and fail to give epoxy resin composite materials excellent performance in both impact resistance and cold resistance, that is, to achieve a comprehensive improvement in both impact resistance and high cold resistance. Summary of the invention

[0007] The present invention aims to overcome at least one defect in the prior art and provide a cold-resistant and impact-resistant epoxy resin composition to solve the problem of insufficient impact resistance and cold resistance of epoxy resin and improve the reliability of epoxy resin composite materials under severe cold conditions.

[0008] In order to solve the above technical problems, the following technical solutions are adopted:

[0009] In the first aspect, a cold-resistant and impact-resistant epoxy resin composition and a preparation method thereof are provided. The composition, by mass, comprises the following components: 100 parts of a weather-resistant epoxy resin, 20 to 40 parts of an ethylene-methacrylate glycidyl copolymer, 10 to 30 parts of an ethylene acrylate rubber, 5 to 30 parts of a curing agent, 0.1 to 1 part of an accelerator, and 50 to 100 parts of a solvent. Among them, the weather-resistant epoxy resin is selected from at least one of an alicyclic epoxy resin and an aliphatic epoxy resin.

[0010] The composition uses selected weather-resistant epoxy resin, ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) and ethylene acrylate rubber (AEM rubber) as the main materials, all of which do not contain unsaturated structures, thus giving the composition excellent weather resistance. This means that it can effectively resist the erosion of harsh environmental factors such as ultraviolet rays, ozone, extreme high and low temperatures, and salt spray, ensuring the long-term stability and service life of the material outdoors or in harsh conditions.

[0011] More importantly, the E-GMA copolymer can be co-cured with the weather-resistant epoxy resin and is well compatible with the AEM rubber, so that the AEM rubber that does not participate in the curing reaction can be evenly distributed in the epoxy resin and the E-GMA cured product during the curing process of the composition, forming a two-phase structure of a rubber dispersed phase and a thermosetting continuous phase. This structure enables the material to disperse and absorb the impact energy more effectively when it is impacted, ensuring that the material can still maintain good integrity and structural stability after being impacted. Specifically, when the cured product is impacted, the relatively brittle epoxy cured product cracks first, and the relatively flexible E-GMA segment has a certain buffer and dispersion of the cracks. When the cracks pass through the tougher rubber dispersed phase, the rubber dispersed phase absorbs the impact energy due to the stress concentration effect and stops the crack propagation. Moreover, thanks to the low brittle temperature of the rubber dispersed phase and E-GMA, the material can still maintain excellent toughness under low temperature conditions. This means that even in cold winter or extreme low temperature environments, it can still maintain sufficient strength and impact resistance, thereby avoiding performance degradation or damage caused by low temperature embrittlement.

[0012] In summary, the above-mentioned cold-resistant and impact-resistant epoxy resin composition achieves excellent weather resistance, impact resistance and low-temperature toughness through a carefully designed component ratio and a unique two-phase structure formed after curing, providing an ideal material choice for various application scenarios requiring high reliability and long-term stability.

[0013] Preferably, the weather-resistant epoxy resin is selected from at least one of bis((3,4-epoxycyclohexyl)methyl)adipate, the polymerization product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and caprolactone, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, hexahydrophthalic acid diglycidyl ester, and 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester.

[0014] Preferably, the ethylene-glycidyl methacrylate copolymer is selected from at least one of ethylene-glycidyl methacrylate binary copolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, and ethylene-glycidyl methacrylate-methyl acrylate terpolymer, such as Sumitomo BF-E, Sumitomo BF-7B, Sumitomo BF-7M, ARLANXEO Levapren NPG VP, etc.

[0015] Preferably, the above-mentioned ethylene acrylate rubber is selected from at least one of ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methoxyethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, and ethylene-methoxyethyl methacrylate copolymer, such as DuPont VAMAC VMX4017, DuPont VAMAC DP, DuPont VAMAC Ultra LT, etc.

[0016] Preferably, the curing agent is selected from at least one of aliphatic polyamine curing agents, aromatic amine curing agents, polyamide curing agents, and hydrazide curing agents. More preferably, the curing agent is selected from aliphatic polyamine curing agents or aromatic amine curing agents containing two or more amine groups in the molecular structure, such as 4,4'-diaminodiphenyl sulfone, p-aminodiphenylmethane, dicyandiamide, and the like.

[0017] Preferably, the accelerator is selected from at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0018] Preferably, the solvent is selected from at least one of acetone, butanone, N,N-dimethylformamide, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether and toluene.

[0019] If necessary, without damaging the original properties of the resin composition, the above composition may also be added with additives commonly used in the field, such as other thermosetting resins, thermoplastic resins, UV absorbers, antioxidants, flame retardants, coupling agents, fillers, surfactants, etc.

[0020] The cold-resistant and impact-resistant epoxy resin composition can be prepared by the following method: 50 to 100 parts of solvent, 100 parts of weather-resistant epoxy resin, 20 to 40 parts of ethylene-methacrylate glycidyl copolymer, 10 to 30 parts of ethylene acrylate rubber, 5 to 30 parts of curing agent, and 0.1 to 1 part of accelerator are sequentially added into a container and stirred evenly.

[0021] In a second aspect, a cold-resistant and impact-resistant epoxy resin prepreg and a preparation method thereof are provided. The prepreg comprises a reinforcement and a resin matrix attached to the reinforcement, and the resin matrix is ​​prepared by using the cold-resistant and impact-resistant epoxy resin composition.

[0022] The cold-resistant and impact-resistant epoxy resin composition used in the prepreg is a combination of weather-resistant epoxy resin, ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) and ethylene acrylate rubber (AEM rubber), so that the prepared prepreg has excellent weather resistance, impact resistance and low-temperature toughness, providing an ideal material choice for various application scenarios requiring high reliability and long-term stability.

[0023] The material of the reinforcement is not limited, and can be made of at least one of plant fiber, animal fiber, mineral fiber and synthetic fiber. Preferably, the reinforcement is selected from at least one of glass fiber cloth, glass fiber mat, glass fiber paper, unidirectional glass fiber, basalt fiber cloth, unidirectional basalt fiber, carbon fiber cloth, unidirectional carbon fiber, aramid cloth and aramid paper.

[0024] The cold-resistant and impact-resistant epoxy resin prepreg can be prepared by the following method: impregnating the reinforcement with the cold-resistant and impact-resistant epoxy resin composition, and drying in an oven at 150±5°C for 3±1min.

[0025] In a third aspect, a cold-resistant and impact-resistant epoxy resin laminate and a preparation method thereof are provided. The laminate comprises at least one of the cold-resistant and impact-resistant epoxy resin prepregs.

[0026] The cold-resistant and impact-resistant epoxy resin prepreg used in the laminate has excellent weather resistance, impact resistance and low-temperature toughness. The laminate made therefrom can be used in various application scenarios requiring high reliability and long-term stability.

[0027] The above-mentioned cold-resistant and impact-resistant epoxy resin laminate can be prepared by the following method: combine the cold-resistant and impact-resistant epoxy resin prepreg with other prepregs, or combine multiple cold-resistant and impact-resistant epoxy resin prepregs into a laminate, cover both sides of the laminate with a PET release film, send it into a fast press at 130℃~180℃, increase the pressure to 100psi~400psi, keep the temperature and pressure constant for 10min~30min, take out the material, cool it to room temperature, and then tear off the PET release films on both sides.

[0028] Compared with the prior art, this solution has the following beneficial effects: this solution uses selected weather-resistant epoxy resin, ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) and ethylene acrylate rubber (AEM rubber) as the main materials, all of which do not contain unsaturated structures, thereby giving the composition excellent weather resistance. This means that it can effectively resist the erosion of harsh environmental factors such as ultraviolet rays, ozone, extreme high and low temperatures, and salt spray, ensuring the long-term stability and service life of the material outdoors or in harsh conditions.

[0029] More importantly, the E-GMA copolymer can be co-cured with the weather-resistant epoxy resin and is well compatible with the AEM rubber, so that the AEM rubber that does not participate in the curing reaction can be evenly distributed in the epoxy resin and the E-GMA cured product during the curing process of the composition, forming a two-phase structure of a rubber dispersed phase and a thermosetting continuous phase. This structure enables the material to disperse and absorb the impact energy more effectively when it is impacted, ensuring that the material can still maintain good integrity and structural stability after being impacted. Specifically, when the cured product is impacted, the relatively brittle epoxy cured product cracks first, and the relatively flexible E-GMA segment has a certain buffer and dispersion of the cracks. When the cracks pass through the tougher rubber dispersed phase, the rubber dispersed phase absorbs the impact energy due to the stress concentration effect and stops the crack propagation. Moreover, thanks to the low brittle temperature of the rubber dispersed phase and E-GMA, the material can still maintain excellent toughness under low temperature conditions. This means that even in cold winter or extreme low temperature environments, it can still maintain sufficient strength and impact resistance, thereby avoiding performance degradation or damage caused by low temperature embrittlement. DETAILED DESCRIPTION

[0030] This scheme proposes a cold-resistant and impact-resistant epoxy resin composition, prepreg and laminate. The cold-resistant and impact-resistant epoxy resin composition, in parts by mass, includes the following components: 100 parts of weather-resistant epoxy resin, 20 to 40 parts of ethylene-methacrylate glycidyl ester copolymer, 10 to 30 parts of ethylene acrylate rubber, 5 to 30 parts of curing agent, 0.1 to 1 part of accelerator, and 50 to 100 parts of solvent. Among them, the weather-resistant epoxy resin is selected from at least one of alicyclic epoxy resin and aliphatic epoxy resin.

[0031] The weather-resistant epoxy resin is preferably at least one of bis((3,4-epoxycyclohexyl)methyl)adipate, a polymerization product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and caprolactone, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, hexahydrophthalic acid diglycidyl ester, and 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester.

[0032] The ethylene-glycidyl methacrylate copolymer (E-GMA copolymer) is preferably at least one of ethylene-glycidyl methacrylate binary copolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, and ethylene-glycidyl methacrylate-methyl acrylate terpolymer, such as Sumitomo BF-E, Sumitomo BF-7B, Sumitomo BF-7M, ARLANXEO Levapren NPG VP, etc.

[0033] The ethylene acrylate rubber (AEM rubber) is preferably at least one of ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methoxyethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, and ethylene-methoxyethyl methacrylate copolymer, such as DuPont VAMAC VMX4017, DuPont VAMAC DP, DuPont VAMAC Ultra LT, etc.

[0034] The curing agent is preferably at least one of an aliphatic polyamine curing agent, an aromatic amine curing agent, a polyamide curing agent, and a hydrazide curing agent. More preferably, the curing agent is selected from an aliphatic polyamine curing agent or an aromatic amine curing agent containing two or more amine groups in the molecular structure, such as 4,4'-diaminodiphenyl sulfone, p-aminodiphenylmethane, dicyandiamide, and the like.

[0035] The accelerator is preferably at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0036] The solvent is preferably at least one of acetone, butanone, N,N-dimethylformamide, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether and toluene.

[0037] If necessary, without damaging the original properties of the resin composition, the above composition may also be added with additives commonly used in the field, such as other thermosetting resins, thermoplastic resins, UV absorbers, antioxidants, flame retardants, coupling agents, fillers, surfactants, etc.

[0038] The cold-resistant and impact-resistant epoxy resin prepreg comprises a reinforcement and a resin matrix attached to the reinforcement, and the resin matrix is ​​prepared by adopting the cold-resistant and impact-resistant epoxy resin composition.

[0039] The cold-resistant and impact-resistant epoxy resin laminate comprises at least one of the cold-resistant and impact-resistant epoxy resin prepregs.

[0040] In order to allow those skilled in the art to better understand this solution, the solution is further described in detail below in conjunction with specific examples. The process methods used in the examples are all conventional methods unless otherwise specified; the materials used are all commercially available unless otherwise specified.

[0041] Among them, the weather-resistant epoxy resin used is: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (Huntsman CY179), bis((3,4-epoxycyclohexyl)methyl)adipate (Daicel Celloxide 2081), polymerization product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and caprolactone (Hunan Binghang New Materials CF108128), 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (Synasia S-186), 4-vinyl-1-cyclohexene diepoxide (Jiangsu Taitel TTA 22), hexahydrophthalic acid diglycidyl ester (Tokyo Chemical Industry C1434), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester (Jiangsu Taitel TTA 60). E-GMA copolymers used: Japan Sumitomo BF-7B; Japan Sumitomo BF-7B; Japan Sumitomo BF-7M; ARLANXEO Levapren NPG VP. AEM rubbers used: DuPont VAMAC VMX4017; DuPont VAMAC DP; DuPont VAMAC Ultra LT. Curing agents used: 4,4'-diaminodiphenyl sulfone (CAS#: 80-08-0), p-aminodiphenylmethane (CAS#: 101-77-9), dicyandiamide (CAS#: 461-58-5). Accelerators used: 2-methylimidazole (CAS#: 693-98-1), 2-ethyl-4-methylimidazole (CAS#: 931-36-2). Solvents used: butanone (CAS#: 78-93-3), acetone (CAS#: 67-64-1), N,N-dimethylformamide (CAS#: 68-12-2), cyclohexanone (CAS#: 108-94-1), propylene glycol methyl ether (CAS#: 107-98-2), ethylene glycol methyl ether (CAS#: 109-86-4), toluene (CAS#: 108-88-3). Epoxy resin used as control: bisphenol A epoxy resin (NPEL-128, Nan Ya Plastics Industry Co., Ltd.). Rubber used as control: PDMS silicone rubber (Dow Corning DC184), hydrogenated nitrile rubber (Japan Zeon HNBR 2020).

[0042] Example 1

[0043] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0044] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0045] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0046] Example 2

[0047] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 20 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0048] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0049] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0050] Example 3

[0051] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 40 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0052] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0053] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0054] Example 4

[0055] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 10 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0056] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0057] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0058] Example 5

[0059] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 30 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0060] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0061] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0062] Example 6

[0063] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of ARLANXEO Levapren NPG VP, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0064] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0065] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0066] Example 7

[0067] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC DP, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0068] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0069] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0070] Example 8

[0071] In parts by mass, 50 parts of acetone, 100 parts of bis((3,4-epoxycyclohexyl)methyl)adipate, 40 parts of Sumitomo BF-7M, 10 parts of DuPont VAMAC Ultra LT, 5 parts of p-aminodiphenylmethane and 1 part of 2-ethyl-4-methylimidazole were added into a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0072] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0073] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0074] Example 9

[0075] In parts by mass, 60 parts of N,N-dimethylformamide, 100 parts of a polymerization product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and caprolactone, 35 parts of Sumitomo BF-E, 15 parts of DuPont VAMACDP, 10 parts of dicyandiamide, and 0.8 parts of 2-methylimidazole were added to a container in sequence, and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0076] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0077] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0078] Example 10

[0079] 70 parts of cyclohexanone, 100 parts of 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 32 parts of ARLANXEO Levapren NPG VP, 18 parts of DuPont VAMAC Ultra LT, 15 parts of p-aminodiphenylmethane and 0.7 parts of 2-ethyl-4-methylimidazole were added to a container in sequence by mass and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0080] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0081] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0082] Embodiment 11

[0083] In a container, 75 parts of propylene glycol methyl ether, 100 parts of 4-vinyl-1-cyclohexene diepoxide, 30 parts of Sumitomo BF-E, 20 parts of DuPont VAMAC DP, 20 parts of dicyandiamide and 0.6 parts of 2-methylimidazole were added in sequence by mass and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0084] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0085] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0086] Example 12

[0087] 85 parts of ethylene glycol methyl ether, 100 parts of diglycidyl hexahydrophthalate, 28 parts of Sumitomo BF-7M, 22 parts of DuPont VAMAC Ultra LT, 25 parts of p-aminodiphenylmethane and 0.4 parts of 2-ethyl-4-methylimidazole were added to a container in sequence by mass and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0088] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0089] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0090] Embodiment 13

[0091] In parts by mass, 90 parts of toluene, 100 parts of 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 25 parts of Sumitomo BF-E, 25 parts of DuPont VAMAC DP, 25 parts of dicyandiamide and 0.3 parts of 2-methylimidazole were added into a container in sequence and stirred evenly to obtain a cold-resistant and impact-resistant epoxy resin composition.

[0092] 400g / m2 was impregnated with the obtained cold-resistant and impact-resistant epoxy resin composition. 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain a cold-resistant and impact-resistant epoxy resin prepreg with a thickness of 0.4 mm.

[0093] Four sheets of the obtained cold-resistant and impact-resistant epoxy resin prepregs were combined into a laminate, and a PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain a cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm.

[0094] Comparative Example 1

[0095] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence and stirred evenly to obtain an epoxy resin composition.

[0096] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0097] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0098] Comparative Example 2

[0099] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 50 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain an epoxy resin composition.

[0100] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0101] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0102] Comparative Example 3

[0103] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence and stirred evenly to obtain an epoxy resin composition.

[0104] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0105] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0106] Comparative Example 4

[0107] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 30 parts of Sumitomo BF-7B, 40 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added into a container in sequence, and stirred evenly to obtain an epoxy resin composition.

[0108] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0109] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0110] Comparative Example 5

[0111] 80 parts of butanone, 100 parts of bisphenol A epoxy resin, 30 parts of Sumitomo BF-7B, 20 parts of DuPont VAMAC VMX4017, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence by mass and stirred evenly to obtain an epoxy resin composition.

[0112] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0113] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0114] Comparative Example 6

[0115] In parts by mass, 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 50 parts of PDMS silicone rubber, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence and stirred evenly to obtain an epoxy resin composition.

[0116] The epoxy resin composition obtained was used to impregnate 400 g / m 2The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0117] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0118] Comparative Example 7

[0119] 80 parts of butanone, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 50 parts of hydrogenated nitrile rubber, 20 parts of 4,4'-diaminodiphenyl sulfone and 0.5 parts of 2-methylimidazole were added to a container in sequence by mass and stirred evenly to obtain an epoxy resin composition.

[0120] The epoxy resin composition obtained was used to impregnate 400 g / m 2 The glass fiber cloth was dried in an oven at 150°C for 3 minutes to obtain an epoxy resin prepreg with a thickness of 0.4 mm.

[0121] Four obtained epoxy resin prepregs were combined into a laminate, and one PET release film was covered on each side of the laminate. The laminate was sent into a 150°C fast press, and the pressure was increased to 200 psi. After maintaining constant temperature and pressure for 15 minutes, the material was taken out, cooled to room temperature, and then the PET release films on both sides were torn off to obtain an epoxy resin laminate with a thickness of 1.6 mm.

[0122] Table 1 Components and dosage of cold-resistant and impact-resistant epoxy resin compositions of Examples 1 to 7

[0123]

[0124] Table 2 Example 8 - Cold-resistant and impact-resistant epoxy resin composition components and amounts thereof

[0125]

[0126]

[0127] Table 3 Components and dosage of epoxy resin compositions of Comparative Examples 1 to 7

[0128]

[0129] The laminates obtained from the above-mentioned embodiments and comparative examples were subjected to performance tests, including: simply supported beam impact strength test at 23°C, simply supported beam impact strength test at -30°C, flexural strength test before aging, and flexural strength test after aging. The test results are shown in Table 4.

[0130] 1. Simply supported beam impact strength test at 23°C: The laminate was tested in accordance with the GB / T 1043.2-2018 standard, and the sample temperature was controlled at 23°C during the test.

[0131] 2. Simply supported beam impact strength test at -30℃: The laminate was tested in accordance with the GB / T 1043.2-2018 standard, and the sample temperature was controlled at -30℃ during the test.

[0132] 3. Aging test: Conduct aging test on laminated board according to ISO 4892 standard.

[0133] 4. Bending strength test: Refer to GB / T 9341-2008 standard and test the laminates before and after aging.

[0134] Table 4 Test results of Examples 1 to 14 and Comparative Examples 1 to 7.

[0135]

[0136] It can be seen from Table 4 that the comprehensive performance of the cold-resistant and impact-resistant epoxy resin laminate prepared by this scheme is better. Specifically, the simply supported beam impact strength of the cold-resistant and impact-resistant epoxy resin laminate with a thickness of 1.6 mm measured at 23°C is ≥250 kJ / m 2 , simply supported beam impact strength measured at -30℃≥217kJ / m 2 , the bending strength before aging is ≥527MPa, the bending strength after aging is ≥496MPa, and the bending strength decrease rate after aging is ≤7.62%.

[0137] Compared with Example 1, the composition used in the preparation of epoxy resin laminates in Comparative Example 1 did not add E-GMA copolymer, and the low-temperature brittleness increased, resulting in a significant decrease in the -30°C impact strength and the flexural strength after aging. In Comparative Example 2, the composition used to prepare epoxy resin laminates added E-GMA copolymer exceeding the upper limit, and the rigidity decreased, resulting in a flexural strength of less than 500MPa. In Comparative Example 3, the composition used to prepare epoxy resin laminates did not add AEM rubber, and the toughness and weather resistance decreased, resulting in a significant decrease in the impact strength at 23°C and -30°C, and the flexural strength after aging. In Comparative Example 4, the composition used to prepare epoxy resin laminates added AEM rubber exceeding the upper limit, and the rigidity decreased, resulting in a flexural strength of less than 500MPa. In Comparative Example 5, the composition used to prepare epoxy resin laminates replaced the weather-resistant epoxy resin with bisphenol A epoxy resin in an equal amount, resulting in a significant decrease in anti-aging performance. In the composition used to prepare the epoxy resin laminate, the E-GMA copolymer and AEM rubber combination were replaced in equal amounts by PDMS silicone rubber with better weather resistance and low temperature resistance. However, due to the low bonding strength between silicone rubber and epoxy resin, the mechanical strength loss of the resin composition was large, and a laminate with the same impact strength and bending strength could not be obtained. In the composition used to prepare the epoxy resin laminate, the E-GMA copolymer and AEM rubber combination were replaced in equal amounts by hydrogenated nitrile rubber with better toughening effect. Although hydrogenated nitrile rubber has better weather resistance than nitrile rubber, it still cannot achieve the same performance as AEM rubber, so the bending strength still decreases significantly after aging.

[0138] In summary, this scheme uses AEM rubber and E-GMA copolymer with low brittle temperature and excellent impact strength, and compounded with weather-resistant epoxy resin to prepare a weather-resistant epoxy resin composition that still has high impact strength under low temperature conditions, thereby improving the reliability of the product prepared by the composition under severe cold conditions.

[0139] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation methods of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all implementation methods here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A cold-resistant and impact-resistant epoxy resin composition, characterized in that: The composition comprises the following components in parts by mass: 100 parts of weather-resistant epoxy resin, 20 to 40 parts of ethylene-glycidyl methacrylate copolymer, Ethylene acrylate rubber 10-30 parts, 5-30 parts of curing agent, 0.1 to 1 part of accelerator, and 50-100 parts of solvent; Wherein, the weather-resistant epoxy resin is selected from at least one of alicyclic epoxy resin and aliphatic epoxy resin.

2. The cold-resistant and impact-resistant epoxy resin composition according to claim 1, characterized in that: The weather-resistant epoxy resin is selected from at least one of bis((3,4-epoxycyclohexyl)methyl)adipate, a polymerization product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and caprolactone, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, hexahydrophthalic acid diglycidyl ester, and 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylic acid) ester.

3. The cold-resistant and impact-resistant epoxy resin composition according to claim 1, characterized in that: The ethylene-glycidyl methacrylate copolymer is at least one selected from the group consisting of an ethylene-glycidyl methacrylate binary copolymer, an ethylene-glycidyl methacrylate-vinyl acetate terpolymer, and an ethylene-glycidyl methacrylate-methyl acrylate terpolymer.

4. The cold-resistant and impact-resistant epoxy resin composition according to claim 1, characterized in that: The ethylene acrylate rubber is selected from at least one of ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methoxyethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-butyl methacrylate copolymer and ethylene-methoxyethyl methacrylate copolymer.

5. The cold-resistant and impact-resistant epoxy resin composition according to any one of claims 1 to 4, characterized in that: The curing agent is selected from at least one of aliphatic polyamine curing agents, aromatic amine curing agents, polyamide curing agents, and hydrazide curing agents.

6. The cold-resistant and impact-resistant epoxy resin composition according to claim 5, characterized in that: The curing agent is selected from aliphatic polyamine curing agents or aromatic amine curing agents containing two or more amine groups in the molecular structure.

7. The cold-resistant and impact-resistant epoxy resin composition according to claim 1, characterized in that: The accelerator is selected from at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

8. The cold-resistant and impact-resistant epoxy resin composition according to any one of claims 1 to 4, characterized in that: The solvent is selected from at least one of acetone, butanone, N,N-dimethylformamide, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether and toluene.

9. A cold-resistant and impact-resistant epoxy resin prepreg, characterized in that: The prepreg comprises a reinforcement and a resin matrix attached to the reinforcement, and the resin matrix is ​​made of the cold-resistant and impact-resistant epoxy resin composition according to any one of claims 1 to 8.

10. A cold-resistant and impact-resistant epoxy resin laminate, characterized in that: The laminate comprises at least one cold-resistant and impact-resistant epoxy resin prepreg as claimed in claim 9.

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