A radically polymerizable epoxy resin composition, and a method for preparing and using the same

Abstract

The application discloses a free radical polymerizable epoxy resin composition and a preparation method and application thereof. The composition comprises the following components in parts by weight: A) 50-120 parts, preferably 70-90 parts, of an epoxy resin, B) 20-50 parts, preferably 30-40 parts, of an active diluent, C) 5-50 parts, preferably 25-40 parts, of an amine curing agent, and D) 0.1-5 parts, preferably 0.5-2 parts, of a reaction aid; the active diluent is a compound containing a vinyl group and only one epoxy group. The epoxy resin composition provided by the application has the advantages of low initial viscosity, long operable time, fast curing speed, strong mechanical property and high toughness, and has significant application advantages in the fields of wind power blades, especially offshore super-long wind power blades and automobile part manufacturing.

Description

Technical Field

[0001] This invention relates to an epoxy resin composition, and more particularly to a free radical polymerizable epoxy resin composition, its preparation method, and its application. Background Technology

[0002] Epoxy resins, with their high heat resistance and low shrinkage, offer significant advantages over unsaturated resin systems, leading to their widespread application in wind turbine blade materials. Wind turbine blades are primarily composed of epoxy resin and glass fiber composites. In vacuum infusion molding, not only is a low viscosity of the epoxy resin required for better impregnation of the glass fiber, but a long working time is also necessary to ensure that the viscosity of the several-ton infusion material does not rise before fully impregnating the glass fiber. Traditional epoxy resin systems suffer from high initial viscosity, low infusion efficiency, slow curing speed, and long mold dwell time, which constrains the development of larger wind turbine blades, especially for ultra-long offshore wind turbine blades.

[0003] To reduce the viscosity of the system, low-molecular-weight compounds with one or more epoxy groups are typically added as epoxy reactive diluents. However, due to the high mechanical strength requirements of epoxy resins for wind turbine blades, monofunctional reactive diluents (such as C12-C14 glycidyl ethers, 1,4-butanediol diglycidyl ether, etc.) are generally unsuitable for this epoxy system because their participation in end-capping reduces product strength. Multifunctional reactive diluents (such as 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, etc.) react too quickly, significantly shortening the processing time, and therefore also fail to meet the requirements of epoxy resins for wind turbine blades. Furthermore, shortening the curing time of epoxy resin compositions plays a crucial role in saving construction time and improving production efficiency, which is a major technical problem that researchers are striving to solve.

[0004] Chinese patent CN106380785A discloses a vacuum-infused epoxy resin composition system that can be applied to the preparation of composite materials for onshore wind turbine blades. However, it still has problems such as high initial viscosity (approximately 300 cP), low infusion efficiency, and long curing time (≥7 hours), which are not conducive to the production of ultra-long blades in the vacuum infusion molding process. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a free-radical polymerizable epoxy resin composition, its preparation method, and its applications. This invention uses a compound containing vinyl groups and one and only one epoxy group as a reactive diluent for the epoxy resin. By adjusting the amount added, the epoxy resin composition simultaneously possesses advantages such as low initial viscosity, long working time, fast curing speed, strong mechanical properties, and high toughness. This results in significant application advantages in wind turbine blades, especially ultra-long offshore wind turbine blades, and in the manufacturing of automotive parts.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0007] Based on the first aspect of the present application, first, a free radical polymerizable epoxy resin composition is provided, comprising the following components by weight:

[0008] A) epoxy resin 50-120 parts, preferably 70-90 parts, for example 55 parts, 60 parts, 75 parts, 80 parts, 90 parts, 100 parts, 110 parts, 115 parts, etc.,

[0009] B) active diluent 20-50 parts, preferably 30-40 parts, for example 25 parts, 28 parts, 32 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, etc.,

[0010] C) amine curing agent 5-50 parts, preferably 25-40 parts, for example 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, etc.,

[0011] D) reaction aid 0.1-5 parts, preferably 0.5-2 parts; for example 0.5 parts, 1 part, 1.2 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 4 parts, etc.,

[0012] The active diluent is a compound containing a vinyl group and only one epoxy group.

[0013] As a preferred embodiment of the present application, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin;

[0014] Preferably, the viscosity of the epoxy resin is 2000-12000 mPa·s, preferably 5000-10000 mPa·s. For example, the epoxy resin can be one or more of Nanya E51, E54, F170.

[0015] As a preferred embodiment of the present application, the active diluent has the following molecular structure expression:

[0016]

[0017] Wherein, R1 is selected from hydrogen, methyl or ethyl; R2 is selected from C1-C6 alkyl, C1-C6 alkoxy, C6-C 20 For example, the active diluent can be one or more of glycidyl methacrylate, ethyl glycidyl methacrylate, p-phenyl glycidyl methacrylate, benzyl glycidyl methacrylate.

[0018] As a preferred embodiment of the present application, the amine curing agent is selected from one or more of alicyclic amines, aliphatic amines, aromatic amines, preferably 4,4-diaminodicyclohexyl methane (HMDA), isophorone diamine (IPDA), methylcyclohexane diamine (HTDA), 1,3-cyclohexane dimethylamine (1,3-BAC), m-xylylenediamine (MXDA), 3,3'-dimethyl-4,4-diaminodicyclohexyl methane (DMDC), 1,2-cyclohexane diamine (DCH-99), polyether amine, 4,4'-diaminodiphenyl methane (MDA).

[0019] As a preferred embodiment of the present application, the reaction aid includes a free radical initiator and a free radical promoter;

[0020] Preferably, the free radical initiator is selected from one or more of organic peroxides, azo initiators, preferably t-butyl peroxy-2-ethylhexanoate (TBPO), t-butyl peroxybenzoate (TBPB), dibenzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP);

[0021] Preferably, the free radical promoter is selected from one or more of organic metal salts, tertiary amines, preferably cobalt iso-octoate, potassium iso-octoate, copper iso-octoate, pentamethyldiethylene triamine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine.

[0022] As a preferred embodiment of the present application, the sum of the mass ratio of the free radical initiator and the free radical promoter is 1:(0.001-10), preferably 1:(0.1-1), for example, it can be 1:0.1, 1:0.2, 1:0.4, 1:0.5, 1:0.6, 1:0.8, 1:2, 1:3, 1:4, 1:5, etc.

[0023] Based on the second aspect of the present application, a method for preparing the free radical polymerizable epoxy resin composition as described above is also provided, characterized in that it comprises the following steps:

[0024] The epoxy resin, the active diluent, the amine curing agent, and the reaction aid are mixed and stirred, and then vacuum degassed, and cured.

[0025] The vacuum degassing condition is that the vacuum degree is 0.05-0.1 MPa, preferably 0.08-0.1 MPa, and the temperature is 5-45℃, preferably 25-35℃.

[0026] The curing condition is that the pre-curing temperature is 30-55℃, and the time is 30-240 min, preferably the temperature is 35-45℃, and the time is 60-120 min; the post-curing temperature is 60-100℃, and the time is 30-240 min, preferably the temperature is 70-85℃, and the time is 60-120 min.

[0027] Based on the third aspect of the present application, there is further provided a free radical polymerizable epoxy resin composition composite material as described previously, characterized in that it is obtained by curing after compounding the epoxy resin composition and fibers;

[0028] Preferably, the mass ratio of the epoxy resin composition to fibers is 1:(2-6), such as 1:2, 1:3, 1:4, 1:5, 1:6, etc.

[0029] Preferably, the fibers are one or more of glass fibers, carbon fibers, aramid fibers, bamboo fibers.

[0030] As a preferred embodiment of the present application, the compounding of the epoxy resin composition and fibers is performed by one of vacuum infusion molding, hand lay-up molding, filament winding molding, pultrusion molding, prepreg molding.

[0031] As a preferred embodiment of the present application, the curing conditions after compounding the epoxy resin composition and fibers are: pre-curing temperature 30-55℃, time 30-240min, preferably temperature 35-45℃, time 60-120min; post-curing temperature 60-100℃, time 30-240min, preferably temperature 70-85℃, time 60-120min.

[0032] Based on the fourth aspect of the present application, there is further provided an application of the free radical polymerizable epoxy resin composition composite material as described previously in wind turbine blades, pressure vessels, automobile parts, especially in wind turbine blades with single machine power not less than 3MW.

[0033] The advantages of the present application are:

[0034] 1) The selected active diluent has moderate reactivity with respect to the epoxy resin curing system for the first time, which can effectively prolong the operable time before curing under the condition of adjusting the addition amount, achieving the beneficial effects of viscosity reduction and operation time extension.

[0035] 2) The selected active diluent contains a compound containing a vinyl group and only one epoxy group, which can control the low reactivity at low temperature in the early stage, and greatly improve the reactivity through the free radical polymerization of the double bond under the condition of medium-high temperature in the later stage, realizing rapid curing, overcoming the difficulty of fast reaction in the early stage and low curing degree in the later stage of conventional epoxy resin compositions, and having good process adaptability.

[0036] 3) The polymerization of the double bond in the active diluent is beneficial to greatly improving the crosslinking strength of the system, thereby rapidly establishing high Tg and high mechanical properties of the epoxy resin composition.

[0037] 4) The epoxy resin composition has the advantages of low initial viscosity, long workable time, fast curing speed, strong mechanical property and high toughness, solves the contradiction that the workable time and curing time of traditional products are difficult to be considered, and can be widely applied to the processing of wind power blades, especially offshore super-long wind power blades and automobile parts. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The viscosity growth curve of the epoxy resin composition prepared for example 3 at 25℃.

[0039] Figure 2 The test sample bar of the epoxy resin composition cast body prepared for example 3.

[0040] Figure 3 The test sample plate of the epoxy resin composite material prepared for application example 3. DETAILED DESCRIPTION

[0041] The application will be further described below through specific examples, and the examples described in the application are only used to illustrate the application and do not limit the scope of the application.

[0042] The main raw material information used in the following examples of the application is as follows:

[0043] Bisphenol A type epoxy resin (E51), South Asia Epoxy Resin (Kunshan) Co., Ltd.;

[0044] Bisphenol A type epoxy resin (E54), South Asia Epoxy Resin (Kunshan) Co., Ltd.;

[0045] Bisphenol A type epoxy resin (F170), South Asia Epoxy Resin (Kunshan) Co., Ltd.;

[0046] Glycidyl methacrylate (GMA), Wanhua Chemical Group Co., Ltd.;

[0047] Polyetheramine (D230), Wanhua Chemical Group Co., Ltd.;

[0048] 4,4'-diaminodicyclohexyl methane (HMDA), Wanhua Chemical Group Co., Ltd.;

[0049] Isophorone diamine (IPDA), Wanhua Chemical Group Co., Ltd.;

[0050] Methylcyclohexanediamine (HTDA): Xiamen Greda Chemical Co., Ltd.;

[0051] N,N-dimethylcyclohexylamine: Wanhua Chemical Group Co., Ltd.;

[0052] Potassium isooctoate, cobalt isooctoate, copper isooctoate, Omei Ke International Co., Ltd.;

[0053] Tert-butyl peroxy-2-ethylhexanoate (TBPO), Lanzhou Auxiliary Factory;

[0054] Tert-butyl peroxybenzoate (TBPB), Lanzhou Auxiliary Factory;

[0055] Methyl ethyl ketone peroxide (MEKP): Sigma-Aldrich;

[0056] Benzoyl peroxide (BPO): Aladdin;

[0057] Glass fiber (EKU1150), Chongqing International Composite Material Co., Ltd.;

[0058] Carbon fiber (T800): Toray (China) Investment Co., Ltd.;

[0059] Aramid fiber (Twaron): Teijin Limited;

[0060] C12-14 alkyl glycidyl ether (AGE): Sigma-Aldrich;

[0061] 1,4-Butanediol diglycidyl ether: Sigma-Aldrich.

[0062] Other raw materials are commercially available products unless otherwise specified.

[0063] The test methods used in the following examples of the present application are as follows:

[0064] (1) Viscosity: Referring to ISO 2555-2018, using a Brookfield viscometer, model DV2TLVTJ0;

[0065] (2) Volume shrinkage: Referring to ISO3521-1997, using a METTLER densimeter, model DM45;

[0066] (3) Tensile strength: Referring to ISO527-2, using an Instron universal tensile testing machine, model Instron5980;

[0067] (4) Bending strength: Referring to ISO-178, using an Instron universal tensile testing machine, model Instron5980;

[0068] (5) Shear strength: Referring to ASTM-7078, using an Instron universal tensile testing machine, model Instron5980;

[0069] (6) Heat distortion temperature: Referring to ISO75-2, using a high-iron heat distortion temperature tester, model HV-3000;

[0070] (7) Impact strength: Referring to ISO-179, using an Instron pendulum impact tester, model CEAST 9050;

[0071] (8) Fracture toughness: Referring to ISO 15024:2001, using a Mettler fracture toughness tester, model Landmark 250.

[0072] The following Examples 1-5 are used to provide different epoxy resin composition castings for testing:

[0073] Example 1

[0074] Epoxy resin (E51) 50 g, glycidyl methacrylate (GMA) 30 g, polyetheramine (D230) 3 g, 4,4'-diaminodicyclohexyl methane (HMDA) 2 g, t-butyl peroxy-2-ethylhexanoate (TBPO) 0.1 g, cobalt isooctoate 1 mg, were weighed into a 100 mL round bottom flask, the composition was mixed uniformly by mechanical stirring, and the air bubbles were removed by a vacuum drying oven, the vacuum degree in the drying oven was 0.08 Mpa, and the temperature was 25°C, to obtain an epoxy resin composition.

[0075] The composition was poured into a sealed glass mold, and cured by a forced air oven at 30°C for 120 min, and then cured at 60°C for 240 min, to obtain an epoxy resin composition casting.

[0076] Example 2

[0077] Epoxy resin (E54) 120 g, glycidyl methacrylate (GMA) 50 g, polyetheramine (D230) 30 g, methylcyclohexanediamine 20 g, benzoyl peroxide (BPO) 2.5 g, cobalt isooctoate 2.5 g, were weighed into a 100 mL round bottom flask, the composition was mixed uniformly by mechanical stirring, and the air bubbles were removed by a vacuum drying oven, the vacuum degree in the drying oven was 0.08 Mpa, and the temperature was 25°C, to obtain an epoxy resin composition.

[0078] The composition was poured into a sealed glass mold, and cured by a forced air oven at 55°C for 60 min, and then cured at 100°C for 30 min, to obtain an epoxy resin composition casting.

[0079] Example 3

[0080] Epoxy resin (F170) 64 g, glycidyl methacrylate (GMA) 36 g, polyetheramine (D230) 24 g, isophorone diamine (IPDA) 8 g, methyl ethyl ketone peroxide 0.1 g, cobalt isooctoate 10 mg, were weighed into a 100 mL round bottom flask, mixed well by mechanical stirring, and bubbles were removed by a vacuum drying oven with a vacuum degree of 0.08 MPa and a temperature of 25 °C to obtain an epoxy resin composition.

[0081] The composition was poured into a closed glass mold, and cured by heating in a forced air oven at 50 °C for 60 min, and then at 80 °C for 120 min to obtain an epoxy resin composition cast body.

[0082]

Example 4

[0083] Epoxy resin (E51) 87 g, glycidyl methacrylate (GMA) 44 g, 4,4'-diamino dicyclohexyl methane (HMDA) 18 g, isophorone diamine (IPDA) 15 g, tert-butyl benzoyl peroxide (TBPB) 4 g, cobalt isooctoate 1 g, were weighed into a 100 mL round bottom flask, mixed well by mechanical stirring, and bubbles were removed by a vacuum drying oven with a vacuum degree of 0.08 MPa and a temperature of 25 °C to obtain an epoxy resin composition.

[0084] The composition was poured into a closed glass mold, and cured by heating in a forced air oven at 45 °C for 95 min, and then at 85 °C for 100 min to obtain an epoxy resin composition cast body.

[0085]

Example 5

[0086] Epoxy resin (E54) 73 g, glycidyl methacrylate (GMA) 35 g, polyetheramine (D230) 14 g, isophorone diamine (IPDA) 22 g, tert-butyl peroxy-2-ethylhexanoate (TBPO) 3 g, copper isooctoate 15 mg, were weighed into a 100 mL round bottom flask, mixed well by mechanical stirring, and bubbles were removed by a vacuum drying oven with a vacuum degree of 0.08 MPa and a temperature of 25 °C to obtain an epoxy resin composition.

[0087] The composition was poured into a closed glass mold, and cured by heating in a forced air oven at 40 °C for 80 min, and then at 70 °C for 115 min to obtain an epoxy resin composition cast body.

[0088]

Example 6

[0089] An epoxy resin (E54) 67 g, glycidyl methacrylate (GMA) 33 g, methylcyclohexane diamine 28 g, t-butyl peroxy benzoate (TBPB) 2 g, N,N-dimethyl aniline 25 mg were weighed into a 100 mL round bottom flask, the composition was mixed uniformly by mechanical stirring, and the bubbles were removed by a vacuum drying oven, the vacuum degree in the drying oven was 0.08 MPa, and the temperature was 25°C, to obtain an epoxy resin composition.

[0090] The composition was poured into a closed glass mold, and cured by a forced air oven at 55°C for 65 min, and then cured at 100°C for 30 min, to obtain an epoxy resin composition cast body.

[0091]

Example 7

[0092] An epoxy resin (E54) 67 g, glycidyl methacrylate (GMA) 33 g, methylcyclohexane diamine 28 g, t-butyl peroxy benzoate (TBPB) 2 g, N,N-dimethyl aniline 25 mg were weighed into a 100 mL round bottom flask, the composition was mixed uniformly by mechanical stirring, and the bubbles were removed by a vacuum drying oven, the vacuum degree in the drying oven was 0.08 MPa, and the temperature was 25°C, to obtain an epoxy resin composition.

[0093] The composition was poured into a closed glass mold, and cured by a forced air oven at 55°C for 65 min, and then cured at 100°C for 30 min, to obtain an epoxy resin composition cast body.

[0094]

Example 8

[0095] An epoxy resin (E51) 75 g, glycidyl methacrylate (GMA) 39 g, isophorone diamine (IPDA) 26 g, t-butyl peroxy benzoate (TBPB) 1 g, N,N-dimethyl cyclohexane amine 10 mg were weighed into a 200 mL round bottom flask, the composition was mixed uniformly by mechanical stirring, and the bubbles were removed by a vacuum drying oven, the vacuum degree in the drying oven was 0.08 MPa, and the temperature was 25°C, to obtain an epoxy resin composition.

[0096] The composition was poured into a closed glass mold, and cured by a forced air oven at 55°C for 65 min, and then cured at 100°C for 30 min, to obtain an epoxy resin composition cast body.

[0097]

Example 9

[0098] An epoxy resin composition cast body was prepared according to the substantially same method as Example 3, except that no glycidyl methacrylate was added.

[0099] Comparative Example 2

[0100] An epoxy resin composition cast was prepared in substantially the same manner as Example 3, except that the amount of glycidyl methacrylate added was modified to 18 g.

[0101] Comparative Example 3

[0102] An epoxy resin composition cast was prepared in substantially the same manner as Example 3, except that the amount of glycidyl methacrylate added was modified to 65 g.

[0103] Comparative Example 4

[0104] An epoxy resin composition cast was prepared in substantially the same manner as Example 3, except that the glycidyl methacrylate was replaced with C12-14 alkyl glycidyl ether (AGE) of the same mass.

[0105] Comparative Example 5

[0106] An epoxy resin composition cast was prepared in substantially the same manner as Example 3, except that the glycidyl methacrylate was replaced with 1,4-butanediol diglycidyl ether of the same mass.

[0107] The epoxy resin compositions and their casts prepared in Examples 1-8 and Comparative Examples 1-5 were subjected to the performance tests in Table 1, and the test results are as follows:

[0108] Table 1, Performance test results of epoxy resin compositions and their casts

[0109]

[0110]

[0111] As can be seen from the test results in Table 1, the epoxy resin compositions provided by the present application can all complete curing and achieve good tensile strength, bending strength, impact strength, fracture toughness and other product mechanical property requirements and higher heat distortion temperature within a heating time of <360 min, and the excellent ones can achieve the curing degree meeting the application requirements in the field within a heating time of 90 min, which has a significant advantage and difference compared with the curing time of 7-8 h in the prior art. Comparative Example 1 does not add any active diluent, which has a too high initial viscosity, a short workable time and a large application difficulty, and the epoxy resin composition product obtained under the same heating and curing conditions as Example 3 is brittle and has very low toughness, which cannot meet the use requirements. Comparative Example 2 adds a small amount of GMA, which has a certain contribution to the initial viscosity and workable time, but the reaction in the system is mainly the reaction of epoxy due to the low amount of GMA, resulting in a low overall curing degree within a short heating time, and the product performance is still brittle, which cannot meet the use requirements, and according to industry experience, the heating and curing time needs to be greatly prolonged to improve the crosslinking degree of the system. Comparative Example 3 adds an excessive amount of GMA, and the product has a large internal stress due to the main free radical reaction in the heating and curing process, resulting in a sharp decrease in toughness, which also cannot meet the use requirements. Comparative Examples 4 and 5 respectively use the single- and double-active diluents commonly used in the industry, which do not have too much contribution to the workable time, and the curing degree is also not high within a short heating time, and the product mechanical properties cannot meet the use requirements.

[0112] In addition, the epoxy resin composition prepared in Example 3 (before heating and curing) was placed in an environment of 25℃, the viscosity change was monitored, and the viscosity growth curve was plotted, as shown in Figure 1 It can be seen that the epoxy resin composition provided by the present application has a workable time of up to 350 min or more. When used in the present application, the term "workable time" refers to the time when the viscosity of the epoxy resin composition reaches 500 mPa·s (25℃). In addition, the test sample of the cast body of the epoxy resin composition prepared in Example 3 is shown in Figure 2 .

[0113]

Application Examples 1-8

[0114] The epoxy resin compositions were prepared according to the formulations in Examples 1-8, and were respectively compounded and cured with fibers by vacuum infusion molding, and the vacuum degree was 0.1 MPa, to obtain the epoxy resin composites in Application Examples 1-8. The compounding and curing conditions in each application example are shown in Table 2.

[0115] Table 2, compounding and curing conditions in application examples

[0116] Fiber type Mass ratio Pre-curing Post-curing Application Example 1 Glass fiber 1:2 30°C for 30 min 60°C for 240 min Application Example 2 Glass fiber 1:3 40°C for 90 min 100°C for 60 min Application Example 3 Glass fiber 1:6 55°C for 30 min 80°C for 120 min Application Example 4 Carbon fiber 1:2 30°C for 60 min 60°C for 120 min Application Example 5 Carbon fiber 1:4 40°C for 120 min 70°C for 60 min Application Example 6 Carbon fiber 1:5 55°C for 240 min 100°C for 30 min Application Example 7 Aramid fiber 1:3 45°C for 120 min 80°C for 30 min Application Example 8 Aramid fiber 1:5 35°C for 30 min 100°C for 60 min

[0117] wherein "mass ratio" represents the mass ratio of the epoxy resin composition to the fiber.

[0118] [Comparative Application Example 1]

[0119] An epoxy resin composite was prepared in substantially the same manner as in Application Example 3, except that the epoxy resin composition used was replaced with the epoxy resin composition prepared in Comparative Example 1.

[0120] [Comparative Application Example 2]

[0121] An epoxy resin composite was prepared in substantially the same manner as in Application Example 3, except that the epoxy resin composition used was replaced with the epoxy resin composition prepared in Comparative Example 2.

[0122] [Comparative Application Example 3]

[0123] An epoxy resin composite was prepared in substantially the same manner as in Application Example 3, except that the epoxy resin composition used was replaced with the epoxy resin composition prepared in Comparative Example 3.

[0124] [Comparative Application Example 4]

[0125] An epoxy resin composite was prepared in substantially the same manner as in Application Example 3, except that the epoxy resin composition used was replaced with the epoxy resin composition prepared in Comparative Example 4.

[0126] [Comparative Application Example 5]

[0127] An epoxy resin composite was prepared in substantially the same manner as in Application Example 3, except that the epoxy resin composition used was replaced with the epoxy resin composition prepared in Comparative Example 5.

[0128] Test specimens of the epoxy resin composite prepared in Application Example 3 were prepared as shown in Figure 3 In addition, the epoxy resin composites in Application Examples 1 to 8 and Comparative Application Examples 1 to 5 were subjected to the performance tests in Table 3, and the test results were as follows:

[0129] Table 3, Performance test results of epoxy resin composites

[0130]

[0131]

[0132] The above description is merely preferred embodiments of the present application, and it is to be noted that those skilled in the art can make several improvements and supplements without departing from the method of the present application, and these improvements and supplements should also be considered as falling within the scope of protection of the present application.

Claims

1. A radically polymerizable epoxy resin composition, characterized by comprising: Comprise the following components by weight parts: A) epoxy resin 50-120 parts, B) active diluent 20-50 parts, C) amine curing agent 5-50 parts, D) reaction aid 0.1-5 parts; The active diluent is a compound comprising a vinyl group and only one epoxy group; The active diluent has the following molecular structure expression: Wherein, R1 is selected from hydrogen, methyl, or ethyl; R2 is selected from C1-C6 alkyl, C1-C6 alkoxy, C6-C6 alkyl, C6 ... 20 Aryl groups.

2. The radically polymerizable epoxy resin composition according to claim 1, characterized in that, Comprise the following components by weight parts: A) epoxy resin 70-90 parts, B) active diluent 30-40 parts, C) amine curing agent 25-40 parts, D) reaction aid 0.5-2 parts.

3. The radically polymerizable epoxy resin composition according to claim 1, characterized in that, The epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin.

4. The radically polymerizable epoxy resin composition according to claim 3, characterized in that, The viscosity of the epoxy resin is 2000-12000 mPa·s.

5. The radically polymerizable epoxy resin composition according to claim 1, characterized in that, The amine curing agent is selected from alicyclic amine, aliphatic amine, aromatic amine.

6. The radically polymerizable epoxy resin composition according to claim 5, characterized in that, The amine curing agent is selected from one or more of 4,4-diamino dicyclohexyl methane, isophorone diamine, methylcyclohexane diamine, 1,3-cyclohexane diamine, m-xylene diamine, 3,3'-dimethyl-4,4-diamino dicyclohexyl methane, 1,2-cyclohexane diamine, polyether amine, 4,4'-diamino diphenyl methane.

7. The radically polymerizable epoxy resin composition according to any one of claims 1 to 6, characterized in that, The reaction aid comprises a free radical initiator and a free radical promoter.

8. The radically polymerizable epoxy resin composition according to claim 7, characterized in that, The free radical initiator is selected from organic peroxide, azo initiator.

9. The radically polymerizable epoxy resin composition according to claim 8, characterized in that, The free radical initiator is selected from one or more of tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxybenzoate, dibenzoyl peroxide, methyl ethyl ketone peroxide.

10. The radically polymerizable epoxy resin composition according to claim 7, characterized in that, The free radical promoter is selected from organic metal salt, tertiary amine.

11. The radically polymerizable epoxy resin composition according to claim 10, characterized in that, The free radical promoter is selected from one or more of cobalt isooctoate, potassium isooctoate, copper isooctoate, pentamethyldiethylene triamine, N,N-dimethyl aniline, N,N-dimethyl cyclohexylamine.

12. The radically polymerizable epoxy resin composition according to claim 7, characterized in that, The mass ratio of the free radical initiator and the free radical promoter is 1:(0.001-10).

13. The radically polymerizable epoxy resin composition according to claim 12, characterized in that, The mass ratio of the free radical initiator and the free radical promoter is 1:(0.1-1).

14. A process for preparing a radically polymerizable epoxy resin composition as claimed in any one of claims 1 to 13, characterized in that, Comprise the following steps: According to weight parts, the epoxy resin, active diluent, amine curing agent, reaction aid are mixed and stirred, vacuum degassing, curing.

15. A free-radically polymerizable epoxy resin composition composite material, characterized by, Cured by the free radical polymerizable epoxy resin composition and fiber composite of any one of claims 1-13.

16. The free-radical polymerizable epoxy resin composition composite according to claim 15, characterized in that, The mass ratio of the epoxy resin composition and the fiber is 1:(2-6).

17. The free-radical polymerizable epoxy resin composition composite of claim 16, wherein, The fiber is one or more of glass fiber, carbon fiber, aramid fiber, bamboo fiber.

18. The free radical polymerizable epoxy resin composition composite of claim 15, wherein, The composite molding of the epoxy resin composition and the fiber adopts one of vacuum infusion molding, hand lay-up molding, winding molding, pultrusion molding, prepreg molding.

19. The free radical polymerizable epoxy resin composition composite according to any one of claims 15-18, characterized in that, The curing condition of the epoxy resin composition and the fiber after compounding is: pre-curing temperature 30-55℃, time 30-240min; post-curing temperature 60-100℃, time 30-240min.

20. The free radical polymerizable epoxy resin composition composite of claim 19, wherein, The curing condition of the epoxy resin composition and the fiber after compounding is: pre-curing temperature 35-45℃, time 60-120min; post-curing temperature 70-85℃, time 60-120min.

21. Use of a free-radically polymerizable epoxy resin composition composite according to any one of claims 15 to 20 in wind turbine blades, pressure vessels, automotive parts.

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