Compositions, composite epoxy resins and applications

Abstract

The present application relates to the technical field of resin, in particular to a composition, a composite epoxy resin and application.The composition comprises component A and component B, the weight ratio of component A to component B is 100:(100-150); wherein, the component A comprises 70-90 parts by weight of matrix epoxy resin, 5-25 parts by weight of 2 functional group epoxy diluent, 0.5-3 parts by weight of coupling agent and 0.3-1.5 parts by weight of fiber impregnation aid; the component B comprises 100-130 parts by weight of amine curing agent, 0-25 parts by weight of epoxy curing accelerator.The composition can be cured below 80 DEG C, the curing temperature is low, and the composite epoxy resin formed by curing has excellent flexibility.

Description

Technical Field

[0001] This invention relates to the field of resin technology, and more specifically to a composition, a composite epoxy resin, and its applications. Background Technology

[0002] Epoxy resins are widely used in various industrial sectors, particularly in automotive manufacturing and sporting goods, due to their excellent mechanical properties, superior adhesion, good electrical insulation, and chemical stability. However, while standard epoxy resin systems offer high strength, they have limitations in toughness and flexibility, restricting their effectiveness in applications requiring high impact resistance, fatigue resistance, and dynamic load adaptability. The automotive industry, in particular, demands higher standards for materials, requiring both high strength to ensure safety and improved toughness to absorb more impact energy and reduce damage. In sporting goods, such as tennis rackets, skis, and bicycle frames, there is a strong need for lightweight, high resilience, and durability, requirements that traditional epoxy resins often struggle to meet simultaneously.

[0003] To address these issues, researchers have explored various strategies to enhance the flexibility of epoxy resins, including introducing elastomer toughening agents, developing special curing systems, and preparing nanocomposites. Despite some progress, challenges remain regarding cost-effectiveness, processing complexity, and balancing overall performance. CN109852004A discloses an epoxy resin system composed of alicyclic epoxy resin, multifunctional hydantoin epoxy resin, diluent, toughening agent, moisture-resistant agent, flexible curing agent, and accelerator. The curing temperature is between 100-200℃, requiring 3-4 step temperature increments. This high curing temperature and long time result in high energy consumption, making it unsuitable for mass production of automotive and sporting goods components. Furthermore, the cured resin cannot maintain flexibility consistently, failing to meet the performance requirements of areas subject to frequent impacts, pipe connections, or hinged components.

[0004] Therefore, there is an urgent need to develop flexible epoxy resin products with significantly improved flexibility and lower curing temperature, while also being easy to process and cost-effective. This is of great significance for improving the long-term reliability of epoxy resins in automotive parts and sporting goods applications. Summary of the Invention

[0005] This invention addresses the problems of insufficient flexibility and high curing temperature of existing epoxy resin materials, which make it difficult to meet the performance and production requirements of automotive and sporting goods components. It provides a composition, a composite epoxy resin, and its application.

[0006] To achieve the above objectives, a first aspect of the present invention provides a composition comprising: component A and component B, wherein the weight ratio of component A to component B is 100:(100-150); wherein,

[0007] Component A comprises 70-90 parts by weight of a matrix epoxy resin, 5-25 parts by weight of a difunctional epoxy diluent, 0.5-3 parts by weight of a coupling agent, and 0.3-1.5 parts by weight of a fiber impregnation aid.

[0008] Component B includes 100-130 parts by weight of an amine curing agent and 0-25 parts by weight of an epoxy curing accelerator.

[0009] A second aspect of the present invention provides a composite epoxy resin, which is obtained by curing a raw material containing the composition described in the first aspect above.

[0010] The curing reaction conditions include: a reaction temperature of 50-80℃ and a reaction time of 3-4 hours.

[0011] A third aspect of the present invention provides the application of the compositions described in the first aspect or the composite epoxy resins described in the second aspect in automotive aftermarket parts and sporting goods.

[0012] The composition provided by this invention includes a resin component with a specific composition, a diluent, a coupling agent, and a curing agent. It can be cured at a temperature below 80°C. The curing temperature is low and the curing time is short. The composite epoxy resin formed by the curing reaction has high flexibility, an elongation at break of ≥90%, and good fiber wettability. It can be used in the manufacture of composite material parts (such as fiber-reinforced composite materials) and can be widely used in fields such as automotive modification parts and sports equipment where high flexibility of materials is required. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] A first aspect of the present invention provides a composition comprising: component A and component B, wherein the weight ratio of component A to component B is 100:(100-150); wherein,

[0015] Component A comprises 70-90 parts by weight of a matrix epoxy resin, 5-25 parts by weight of a difunctional epoxy diluent, 0.5-3 parts by weight of a coupling agent, and 0.3-1.5 parts by weight of a fiber impregnation aid.

[0016] Component B includes 100-130 parts by weight of an amine curing agent and 0-25 parts by weight of an epoxy curing accelerator.

[0017] The inventors of this invention discovered in their research that a composite epoxy resin with excellent flexibility can be formed by using a composition comprising a resin component with specific components, a diluent, a coupling agent, and a curing agent, and by curing at a relatively low temperature below 80°C for 3-4 hours. The composite epoxy resin has a tensile strength ≤5MPa, a tensile elongation at break ≥90%, and good fiber wettability. As an epoxy resin matrix for fiber composite materials, it can significantly improve the flexibility of the composite material and solve the problem that existing epoxy resin compositions are difficult to balance low curing temperature and high flexibility of the cured product.

[0018] According to the present invention, in the composition, preferably, the weight ratio of component A to component B is 100:(105-145), which can better balance the low curing temperature of the composition and the high flexibility of the cured product.

[0019] According to the present invention, in the composition, preferably, component A comprises 72-88 parts by weight of a matrix epoxy resin, 6-23 parts by weight of a difunctional epoxy diluent, 0.8-2.5 parts by weight of a coupling agent and 0.4-1.3 parts by weight of a fiber impregnation aid, which is more conducive to improving the process performance of the composition in vacuum induction process, RTM (resin transfer molding) process or hand lay-up process, and improving the adhesion between the cured product of the composition and the fiber.

[0020] According to the present invention, in the composition, preferably, component B includes 103-128 parts by weight of an amine curing agent and 1-22 parts by weight of an epoxy curing accelerator, which is more conducive to the curing of the composition at a lower temperature and to improving the flexibility of the cured product.

[0021] According to the present invention, in component A of the composition, the matrix epoxy resin provides the cured product of the composition with suitable viscosity and excellent mechanical properties. Preferably, the epoxy value of the matrix epoxy resin is 0.45-0.65. Preferably, the viscosity of the matrix epoxy resin at 25°C is 1500-20000 cp.

[0022] In this invention, the epoxy value of the epoxy resin is determined by the method specified in GB / T 4612-2008.

[0023] In this invention, the viscosity of the epoxy resin at 25°C is determined by the method specified in ASTM D-2983-23 and using a Brookfield viscometer.

[0024] According to the present invention, more preferably, the matrix epoxy resin can be at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic epoxy resin that meets the above-mentioned index requirements. The source of the matrix epoxy resin is not particularly limited in the present invention; it can be obtained in-house using known methods or commercially available products. For example, the bisphenol A type epoxy resin can be DER-331 or DER332 epoxy resin from OLN Corporation (USA); the bisphenol F type epoxy resin can be DER354 epoxy resin from OLN Corporation (USA), or NPEF-180 or NPEF-185 epoxy resin from Nan Ya Plastics Industry Co., Ltd.; the phenolic epoxy resin can be DEN431, DEN438, SNE-630, or SNE-625S epoxy resin from Hunan Celway New Material Technology Co., Ltd.

[0025] According to a preferred embodiment of the present invention, the matrix epoxy resin is a bisphenol A type epoxy resin.

[0026] According to the present invention, in component A of the composition, the coupling agent can improve the adhesion between the cured product of the composition and the fiber. Preferably, the coupling agent is a silane coupling agent.

[0027] More preferably, the coupling agent is selected from epoxy silane coupling agents (e.g., KH-560) and / or amino silane coupling agents (e.g., KH-550).

[0028] According to the present invention, in component A of the composition, the difunctional epoxy diluent is a reactive diluent, which can reduce the viscosity of each component in the composition after mixing and make the cured product of the composition have high impact strength.

[0029] In this invention, the difunctional epoxy diluent refers to an epoxy diluent containing two epoxy groups in its molecular chain. Preferably, the difunctional epoxy diluent is a glycidyl ether diluent. More preferably, the difunctional epoxy diluent may be selected from at least one of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,4-butanediol diglycidyl ether.

[0030] According to a preferred embodiment of the present invention, the 2-functionalized epoxy diluent is selected from at least one of polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0031] According to the present invention, in component A of the composition, the fiber wetting agent can reduce air bubbles formed during the mixing process of the components in the composition and improve the adhesion between the composition and the fiber. Preferably, the fiber wetting agent can be selected from at least one of polysiloxane coupling agents, titanate coupling agents, and aluminate coupling agents. For example, KH-560 (γ-glycidyl etheroxypropyltrimethoxysilane), BYK-C 8001, BYK-P9912, and BYK-P9920 from Hong Kong Haiyi Enterprise Development Co., Ltd.

[0032] According to a preferred embodiment of the present invention, the fiber impregnation aid is a polysiloxane coupling agent.

[0033] According to the present invention, in component B of the composition, the amine curing agent enables the composition to cure at a lower temperature, thereby improving the flexibility of the cured product. Preferably, the amine curing agent may be selected from at least one of aliphatic amines, polyether amines, and polyamides, and more preferably a polyether amine curing agent.

[0034] According to the present invention, the fatty amine curing agent may be at least one selected from ethylenediamine, N-hydroxyethylpiperazine, diethylaminopropylamine, 3-diethylaminopropylamine, N,N-di(3-aminopropyl)ethylethylamine and N,N-di(3-aminopropyl)ethylethylamine.

[0035] According to the present invention, the polyetheramine curing agent may be at least one selected from polyetheramines containing one active amine functional group, two active amine functional groups, and three active amine functional groups. For example, D230, D400, D2000, M600, and T403 from Shenzhen Jiadida New Material Technology Co., Ltd.

[0036] According to the present invention, the polyamide curing agent may be at least one selected from, but not limited to, dimer fatty acid polyamides, cashew nut shell oil-modified polyamides, and glycidyl methacrylate polyamides. For example, WSCM-4140 and WSCM-4141 from Zhejiang Wansheng Co., Ltd.

[0037] According to a preferred embodiment of the present invention, the amine curing agent is WSCM-4141.

[0038] According to the present invention, when component B of the composition contains the epoxy curing accelerator, the curing temperature of the composition can be further reduced. Preferably, the epoxy curing accelerator can be selected from at least one of tertiary amines and their salts, alcohols, and phenols. For example, the epoxy curing accelerator can be at least one of benzyldimethylamine, tetramethylethylenediamine, benzyl alcohol, triethanolamine, bisphenol A, and styrene-modified phenol.

[0039] According to a preferred embodiment of the present invention, in the composition, component A comprises 75-80 parts by weight of bisphenol A type epoxy resin DER-332, 15-22 parts by weight of neopentyl glycol diglycidyl ether or 1,6-hexanediol diglycidyl ether, 1.5-5 parts by weight of aminosilane coupling agent KH-550, and 0.5-1 parts by weight of fiber impregnation aid BYK-P 9912; component B comprises 105-120 parts by weight of polyetheramine curing agent D400 and / or D2000, and 10-20 parts by weight of epoxy curing accelerator styrene-modified phenol; the weight ratio of component A to component B is 100:(110-140). The composition can be cured at below 80°C for 3-4 hours to form a composite epoxy resin with high flexibility, a tensile strength not exceeding 4 MPa, and a tensile elongation at break not less than 130%.

[0040] According to the present invention, the composition can be obtained by thoroughly mixing its components, and can exist in the form of a mixture, or the components can be packaged separately and mixed before use.

[0041] A second aspect of the present invention provides a composite epoxy resin, which is obtained by curing a raw material containing the composition described in the first aspect above.

[0042] The curing reaction conditions include: a reaction temperature of 50-80℃ and a reaction time of 3-4 hours.

[0043] According to a preferred embodiment of the present invention, the composite epoxy resin can be prepared using the composition provided by the present invention through the following steps:

[0044] (1) The components contained in component A of the composition are first mixed to obtain component A; and the components contained in component B of the composition are second mixed to obtain component B;

[0045] (2) Mix component A and component B in a third process to obtain a reaction system. Then, perform degassing and curing reactions on the reaction system in sequence to obtain the composite epoxy resin.

[0046] The mixing temperatures of the first, second, and third mixtures are selected to ensure good dispersion of each component, facilitate addition, and achieve uniform mixing.

[0047] Preferably, the first mixing is carried out in the range of 50-60°C; the second mixing is carried out in the range of 20-35°C; and the third mixing is carried out in the range of 25-35°C.

[0048] Preferably, the first, second, and third mixing are carried out at atmospheric pressure. In this invention, atmospheric pressure refers to one standard atmosphere, or a conventional pressure at which no additional pressure needs to be applied to the reactor.

[0049] According to the present invention, the initial viscosity of the composite epoxy resin is ≤1000cps, more preferably 300-800cps, which is beneficial for the composite epoxy resin to be used in vacuum induction or RTM process to prepare fiber composite parts.

[0050] In this invention, the initial viscosity of the epoxy resin is determined according to the method specified in ASTM D-2983-23 and using a Brookfield viscometer.

[0051] According to the present invention, the composite epoxy resin has excellent flexibility. Preferably, the tensile elongation at break of the epoxy resin is ≥90%, more preferably 100-150%.

[0052] In this invention, the tensile elongation at break is determined according to the method specified in GB / T 2567-2021.

[0053] According to the present invention, the tensile strength of the composite epoxy resin is ≤5MPa, preferably 2-4.5MPa.

[0054] In this invention, the tensile strength is determined according to the method specified in GB / T 2567-2021.

[0055] The composite epoxy resin provided by this invention has high flexibility and good fiber wettability. It can be used in the manufacture of composite materials (such as fiber-reinforced composite materials) and can well meet the process requirements of vacuum flow, RTM, hand lay-up molding and other processes of fiber-reinforced composite materials. It can significantly improve the flexibility of composite materials.

[0056] A third aspect of the present invention provides the application of the compositions described in the first aspect or the composite epoxy resins described in the second aspect in automotive aftermarket parts and sporting goods.

[0057] According to the present invention, the composition provided by the present invention has a low curing temperature, a short curing time, and a short pre-curing operation time (30-60 min). It has high epoxy resin preparation efficiency and can well meet the requirements of mass production of products. The cured composite epoxy resin has high flexibility and can be widely used in fields such as automotive modification parts and sports equipment where high flexibility of materials is required.

[0058] The present invention will be described in detail below through examples. Unless otherwise specified, the following examples and comparative examples are all conventional methods; the reagents and materials mentioned are commercially available unless otherwise specified.

[0059] Bisphenol A type epoxy resins: DER-331 epoxy resin (epoxy value 0.56, viscosity at 25℃ 11000cps) and DER332 epoxy resin (epoxy value 0.57, viscosity at 25℃ 5000cps), purchased from OLN Corporation, USA.

[0060] Bisphenol F type epoxy resins: DER354 epoxy resin (epoxy value 0.58, viscosity at 25℃ 3800cps), purchased from OLN Corporation, USA; NPEF-180 epoxy resin (epoxy value 0.55, viscosity at 25℃ 6000cps) and NPEF-185 epoxy resin (epoxy value 0.56, viscosity at 25℃ 7000cps), purchased from Nan Ya Plastics Industrial Co., Ltd.

[0061] Phenolic epoxy resins: DEN-431 epoxy resin (epoxy value 0.57, viscosity at 25℃ 1500cps), DEN438 epoxy resin (epoxy value 0.56, viscosity at 52℃ 35000cps), SNE-630 epoxy resin (epoxy value 0.58, viscosity at 25℃ 2000cps), and SNE-625S epoxy resin (epoxy value 0.60, viscosity at 25℃ 11000cps), purchased from Hunan Servi New Material Technology Co., Ltd.

[0062] 2. Functional group epoxy diluents: polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, purchased from Anhui Xinyuan Technology Co., Ltd.

[0063] Coupling agents: aminosilane coupling agent KH-550 and epoxysilane coupling agent KH-560, purchased from Hong Kong Haiyi Enterprise Development Co., Ltd.

[0064] Fiber impregnation auxiliaries: KH-560, BYK-C 8001, BYK-P 9912, BYK-P 9920, purchased from Hong Kong Haiyi Enterprise Development Co., Ltd.

[0065] Amine curing agents: N,N-di(3-aminopropyl)ethylethylamine, 3-diethylaminopropylamine; D230, D400, D2000, M600, purchased from Shenzhen Jiadida New Material Technology Co., Ltd.; WSCM-4140, WSCM-4141, purchased from Zhejiang Wansheng Co., Ltd.

[0066] Epoxy curing accelerators: benzyl dimethylamine, tetramethylethylenediamine, benzyl alcohol, triethanolamine, bisphenol A, and stylated phenol, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0067] Example 1

[0068] (1) Component A: 50 parts of bisphenol A type epoxy resin DER-331, 25 parts of bisphenol F type epoxy resin DER354, 22 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 0.6 parts of fiber impregnating agent BYK-P 9912, and 2.5 parts of aminosilane coupling agent KH-550 were added sequentially into the reaction vessel and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0069] Component B: 50 parts of polyetheramine curing agent D400, 50 parts of D2000, and 10 parts of benzyl dimethylamine were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B; the above quantities "parts" refer to parts by weight.

[0070] (2) Curing: Mix component A and component B at a mass ratio of 100:110 evenly and degas under vacuum. After injecting into the mold, cure at 50°C for 1 hour and at 80°C for 2 hours to obtain composite epoxy resin (denoted as P1).

[0071] Example 2

[0072] (1) Component A: 60 parts of bisphenol F type epoxy resin DER354, 20 parts of phenolic epoxy resin SNE-625S epoxy resin, 18 parts of epoxy resin diluent neopentyl glycol diglycidyl ether, 0.8 parts of fiber impregnating agent BYK-P 9912, and 2 parts of aminosilane coupling agent KH-550 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0073] Component B: 50 parts of polyetheramine curing agent M600, 50 parts of polyamide curing agent WSCM-4141, and 20 parts of benzyl alcohol were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B;

[0074] (2) Curing: Mix component A and component B at a mass ratio of 100:120 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P2).

[0075] Example 3

[0076] (1) Component A: 75 parts of bisphenol A type epoxy resin DER-332, 15 parts of phenolic epoxy resin SNE-630, 8 parts of epoxy resin diluent 1,4-butanediol diglycidyl ether, 0.8 parts of fiber impregnating agent BYK-P9912 and 2 parts of epoxy silane coupling agent KH-560 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0077] Component B: 30 parts of N,N-di(3-aminopropyl)ethyl ethylamine, 50 parts of polyetheramine D2000, 50 parts of polyamide curing agent WSCM-4141, and 15 parts of styrene-modified phenol were added sequentially to the reaction vessel and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B;

[0078] (2) Curing: Mix component A and component B at a mass ratio of 100:145 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P3).

[0079] Example 4

[0080] (1) Component A: 65 parts of bisphenol F type epoxy resin NPEF-180, 15 parts of phenolic epoxy resin SNE-625S, 18 parts of epoxy resin diluent polypropylene glycol diglycidyl ether, 0.6 parts of fiber impregnating agent BYK-P 9920, and 2 parts of epoxy silane coupling agent KH-560 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0081] Component B: 20 ​​parts of 3-diethylaminopropylamine, 60 parts of polyetheramine D2000, 50 parts of polyetheramine D400, and 15 parts of triethanolamine are added sequentially to the reaction vessel and stirred at room temperature and pressure for 1 hour until homogeneous.

[0082] (2) Curing: Mix component A and component B at a mass ratio of 100:145 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P4).

[0083] Example 5

[0084] (1) Component A: 70 parts of bisphenol F type epoxy resin NPEF-185, 15 parts of phenolic epoxy resin DEN431, 14 parts of epoxy resin diluent polyethylene glycol diglycidyl ether, 1 part of fiber impregnating agent BYK-C8001, and 1 part of aminosilane coupling agent KH550 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0085] Component B: 70 parts of polyetheramine D400, 50 parts of polyamide WSCM-4140, and 5 parts of tetramethylethylenediamine were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B;

[0086] (2) Curing: Mix component A and component B at a mass ratio of 100:125 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P5).

[0087] Example 6

[0088] (1) Component A: 80 parts of bisphenol F type epoxy resin DER354, 10 parts of phenolic epoxy resin DEN438, 8 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 1 part of fiber impregnating agent BYK-P9920, and 2 parts of aminosilane coupling agent KH-550 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0089] Component B: 100 parts of polyetheramine M600, 25 parts of 3-diethylaminopropylamine, and 25 parts of benzyl alcohol were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B.

[0090] (2) Curing: Mix component A and component B at a mass ratio of 100:150 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P6).

[0091] Example 7

[0092] (1) Component A: 50 parts of bisphenol F type epoxy resin NPEF-185, 20 parts of phenolic epoxy resin SNE-630, 8 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 10 parts of 1,4-butanediol diglycidyl ether, 1 part of fiber impregnating agent BYK-P9912, and 2 parts of epoxy silane coupling agent KH560 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0093] Component B: 40 parts of polyetheramine D400, 60 parts of D2000, 5 parts of benzyl dimethylamine, and 20 parts of benzyl alcohol were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B;

[0094] (2) Curing: Mix component A and component B at a mass ratio of 100:105 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as P7).

[0095] Example 8

[0096] The method of Example 6 was followed, except that in step (1), the aminosilane coupling agent KH-550 in component A was 0.5 parts, and component B contained only 100 parts of polyetheramine M600 and 25 parts of 3-diethylaminopropylamine. The other steps and conditions were the same as in Example 6, and a composite epoxy resin (denoted as 8) was obtained.

[0097] Example 9

[0098] The method of Example 6 was followed, except that 1,6-hexanediol diglycidyl ether was replaced with an equal weight of 1,4-butanediol diglycidyl ether, and all other steps and conditions were the same as in Example 6, to obtain a composite epoxy resin (denoted as P9).

[0099] Example 10

[0100] The method of Example 6 was followed, except that 100 parts of polyetheramine M600 and 25 parts of 3-diethylaminopropylamine were replaced with 125 parts of polyetheramine D400. All other steps and conditions were the same as in Example 6, and a composite epoxy resin (denoted as P10) was obtained.

[0101] Example 11

[0102] (1) Component A: 77 parts of bisphenol A type epoxy resin DER-332, 21.5 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 0.9 parts of fiber impregnating agent BYK-P 9912, and 1.6 parts of aminosilane coupling agent KH-550 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0103] Component B: 45 parts of polyetheramine curing agent D400, 65 parts of D2000, and 10 parts of styrene-modified phenol were added sequentially to the reaction vessel and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B; all the above quantities "parts" refer to parts by weight.

[0104] (2) Curing: Mix component A and component B at a mass ratio of 100:120 evenly and degas under vacuum. After injecting into the mold, cure at 50°C for 1 hour and at 80°C for 2 hours to obtain composite epoxy resin (denoted as P11).

[0105] Comparative Example 1

[0106] (1) Component A: 50 parts of bisphenol F type epoxy resin NPEF-185, 20 parts of phenolic epoxy resin SNE-630, 8 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 10 parts of 1,4-butanediol diglycidyl ether, 0.6 parts of fiber impregnating agent BYK-P9920, and 2 parts of epoxy silane coupling agent KH560 were added sequentially to the reaction vessel and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0107] Component B: 30 parts of polyetheramine D230, 5 parts of benzyl dimethylamine, and 20 parts of alicyclic amine EC201 were added sequentially to the reaction vessel and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B; all the quantities "parts" above refer to parts by weight.

[0108] (2) Curing: Mix component A and component B at a mass ratio of 100:55 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as DP1).

[0109] Comparative Example 2

[0110] (1) Component A: 80 parts of bisphenol F type epoxy resin NPEF-185, 18 parts of epoxy resin diluent benzyl glycidyl ether, 1 part of fiber impregnating agent BYK-P 9912, and 2 parts of epoxy silane coupling agent KH560 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0111] Component B: 50 parts of polyetheramine curing agent M600, 50 parts of polyamide curing agent WSCM-4141, and 20 parts of benzyl alcohol are added sequentially to the reaction vessel and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B; all the above quantities "parts" refer to parts by weight.

[0112] (2) Curing: Mix component A and component B at a mass ratio of 100:105 evenly and degas under vacuum. After injecting into the mold, cure at 60°C for 1 hour and at 80°C for 3 hours to obtain composite epoxy resin (denoted as DP2).

[0113] Comparative Example 3

[0114] The method of Example 6 was followed, except that 100 parts of polyetheramine M600 and 25 parts of 3-diethylaminopropylamine were replaced with 125 parts of methyl nadic anhydride. All other steps and conditions were the same as in Example 6, and a composite epoxy resin (denoted as DP3) was prepared.

[0115] Comparative Example 4

[0116] (1) Component A: 80 parts of bisphenol F type epoxy resin DER354, 10 parts of phenolic epoxy resin DEN438, 8 parts of epoxy resin diluent 1,6-hexanediol diglycidyl ether, 1 part of fiber impregnating agent BYK-P9920, and 2 parts of aminosilane coupling agent KH-550 were added to the reaction vessel in sequence and heated to 50°C under normal pressure; stirred for 1 hour until homogeneous, and the mixture was cooled to room temperature to obtain component A;

[0117] Component B: 125 parts of methylnadic anhydride and 5 parts of benzyl dimethylamine were added to the reaction vessel in sequence and stirred at room temperature and pressure for 1 hour until homogeneous to obtain component B; the above quantities "parts" refer to parts by weight.

[0118] (2) Curing: Mix component A and component B evenly at a mass ratio of 100:130 and degas under vacuum. After injecting into the mold, cure at 100℃ for 1 hour, 150℃ for 1 hour and 180℃ for 1 hour to obtain composite epoxy resin (denoted as DP4).

[0119] Test case

[0120] The initial viscosity, tensile strength, and tensile elongation at break of the composite epoxy resins P1-P11 and DP1-DP4 prepared in the above embodiments and comparative examples were tested, and the results are shown in Table 1.

[0121] Table 1

[0122]

[0123] As shown in Table 1, the compositions of Examples 1-11 can be cured at a relatively low temperature of 50-80℃, with a curing time not exceeding 4 hours. The cured composite epoxy resins P1-P11 have an initial viscosity of less than 1000 cps at 25℃, a tensile strength of less than 5 MPa, and a tensile elongation at break of more than 90%, exhibiting excellent flexibility. They can be widely used in automotive modification parts, sporting goods, and other fields requiring high material flexibility. The composite epoxy resins formed after curing the compositions of Comparative Examples 1-3 do not possess the above properties.

[0124] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition, characterized in that, The composition comprises: component A and component B, wherein the weight ratio of component A to component B is 100:(100-150); wherein, Component A comprises 70-90 parts by weight of a matrix epoxy resin, 5-25 parts by weight of a difunctional epoxy diluent, 0.5-3 parts by weight of a coupling agent, and 0.3-1.5 parts by weight of a fiber impregnation aid. Component B includes 100-130 parts by weight of an amine curing agent and 0-25 parts by weight of an epoxy curing accelerator.

2. The composition according to claim 1, wherein, The weight ratio of component A to component B is 100:(105-145); And / or, component A comprises 72-88 parts by weight of a matrix epoxy resin, 6-23 parts by weight of a difunctional epoxy diluent, 0.8-2.5 parts by weight of a coupling agent and 0.4-1.3 parts by weight of a fiber impregnation aid; And / or, component B comprises 103-128 parts by weight of an amine curing agent and 1-22 parts by weight of an epoxy curing accelerator.

3. The composition according to claim 1 or 2, wherein, The epoxy value of the matrix epoxy resin is 0.45-0.65; And / or, the viscosity of the matrix epoxy resin at 25°C is 1500-20000 cps.

4. The composition according to claim 3, wherein, The matrix epoxy resin is selected from at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic epoxy resin.

5. The composition according to any one of claims 1-4, wherein, The 2-functional group epoxy diluent is a glycidyl ether diluent; Preferably, the 2-functionalized epoxy diluent is selected from at least one of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,4-butanediol diglycidyl ether.

6. The composition according to any one of claims 1-5, wherein, The coupling agent is a silane coupling agent, preferably an epoxy silane coupling agent and / or an amino silane coupling agent; And / or, the fiber impregnation aid is selected from at least one of polysiloxane coupling agents, titanate coupling agents, and aluminate coupling agents.

7. The composition according to any one of claims 1-6, wherein, The amine curing agent is selected from at least one of fatty amines, polyether amines, and polyamides; And / or, the epoxy curing accelerator is selected from at least one of tertiary amines and their salts, alcohols and phenols.

8. A composite epoxy resin, characterized in that, The composite epoxy resin is prepared by curing a raw material containing the composition of any one of claims 1-7; The curing reaction conditions include: a reaction temperature of 50-80℃ and a reaction time of 3-4 hours.

9. The epoxy resin according to claim 8, wherein, The initial viscosity of the composite epoxy resin at 25°C is ≤1000cps, preferably 300-800cps; And / or, the tensile strength of the composite epoxy resin is ≤5MPa, preferably 2-4.5MPa; And / or, the tensile elongation at break of the composite epoxy resin is ≥90%, preferably 100-150%.

10. The use of the composition according to any one of claims 1-7 or the composite epoxy resin according to claim 8 or 9 in automotive parts and sporting goods.

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