Epoxy resin composition and application thereof

Abstract

The invention relates to the field of materials, and provides an epoxy resin composition and application thereof. The epoxy resin composition comprises the following components in parts by weight: 20-40 parts of matrix resin, 10-20 parts of an active hydroxyl polymer containing epoxy groups, 5-15 parts of bisphenol fluorene type epoxy resin, 1-3 parts of a curing agent A, 1-3 parts of a curing agent B, 5-15 parts of an epoxy diluent, 2-4 parts of a coupling agent, 0.01-0.05 part of an accelerant, 20-40 parts of spherical large-particle-size filler and 10-20 parts of spherical small-particle-size filler. The epoxy resin composition disclosed by the invention has the advantages that through the matching of various components, the curing temperature of the prepreg is reduced, the energy is saved, and the operation safety and simplicity are improved; the fluidity of the prepreg is improved, and the operability is improved; the curing strength of the prepreg is improved, so that the material has excellent properties such as high mechanical strength and high heat resistance; the curing time of the prepreg is greatly shortened, and the curing efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the field of materials, and more specifically, to an epoxy resin composition and application thereof. Background Art

[0002] Rapid-curing prepreg is an advanced composite material made of reinforcing fibers (such as carbon fiber, glass fiber, etc.) pre-impregnated with a resin matrix. Compared with the traditional manual impregnation process, prepreg can achieve higher fiber content, more uniform resin distribution and better repeatability, thereby obtaining excellent mechanical properties. The emergence of rapid-curing prepreg aims to shorten the curing time, improve production efficiency, and maintain good mechanical properties. The traditional prepreg curing process usually takes several hours; while rapid-curing prepreg can be cured in a few minutes, greatly improving productivity. Therefore, this material has a very broad application prospect in the fields of aerospace manufacturing, automobile manufacturing, wind turbine blade manufacturing, etc.

[0003] However, fast-curing prepregs still face many challenges in terms of mechanical strength. Increasing the curing rate may lead to problems such as internal stress accumulation and molecular chain defects, affecting the strength and toughness of the material. At present, the methods commonly used to improve the mechanical strength of fast-curing prepregs are: 1. Using a new epoxy resin technology system; 2. Using a new curing agent technology; 3. Using a new fiber reinforcement technology, etc. However, these existing technologies have problems such as poor fluidity, poor wettability, and high technical barriers. Summary of the invention

[0004] The present invention aims to overcome at least one defect (shortcoming) of the above-mentioned prior art and provide an epoxy resin composition and application thereof, so that the material has good fluidity and mechanical properties.

[0005] The present invention provides a high-strength fast-curing prepreg, comprising the following components in parts by weight:

[0006] 20-40 parts of base resin,

[0007] 10-20 parts of active hydroxyl polymer containing epoxy groups,

[0008] 5-15 parts of bisphenol fluorene epoxy resin,

[0009] Curing agent A1-3 parts,

[0010] Curing agent B1-3 parts,

[0011] Epoxy diluent 5-15 parts,

[0012] 2-4 parts of coupling agent,

[0013] Accelerator 0.01-0.05 parts,

[0014] 20-40 parts of spherical large particle size filler,

[0015] 10-20 parts of spherical small particle filler.

[0016] In this scheme, the active hydroxyl polymer containing epoxy groups can improve the strength of the prepreg after curing. In the bisphenol fluorene type epoxy resin, the fluorene group has a huge Cardo ring structure, which seriously hinders the rotation of the phenyl group, and the thermal motion and internal rotation of the polymer chain segment are inhibited. Therefore, the polymers containing the fluorene group structure have excellent properties such as high mechanical strength, high heat resistance, and high transparency. The composite curing agent formed by the combination of curing agent A and curing agent B can reduce the reaction activation energy, significantly reduce the curing temperature, and increase the crosslinking density. Epoxy diluent can reduce the viscosity of the bisphenol fluorene type epoxy resin curing system, increase fluidity, and improve operability without affecting the basic properties of the cured product.

[0017] It can be understood that the epoxy resin composition of the present scheme reduces the curing temperature of the prepreg through the combination of various components, saves energy, improves the safety and simplicity of operation; increases the fluidity of the prepreg and improves the operability; increases the curing strength of the prepreg, so that it has excellent properties such as high mechanical strength and high heat resistance.

[0018] In some embodiments, the particle size of the spherical large-particle filler is 50-100 nm; the particle size of the spherical small-particle filler is 10-25 nm; and the weight ratio of the particle size of the spherical large-particle filler to the spherical small-particle filler is 2:1.

[0019] In some embodiments, the base resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0020] In some embodiments, the curing agent A is selected from one or more of methylnadic anhydride (MNA), HK-021 anhydride, and methyltetrahydrophthalic anhydride (MeTHPA).

[0021] In some embodiments, the curing agent B is selected from one or more of cyanate curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide curing agents and latent curing agents. Specifically, the latent curing agent is, for example, terephthalic acid dihydrazide.

[0022] In some embodiments, the epoxy resin diluent is selected from one or more of alkylene glycidyl ether (HK-66), phenyl glycidyl ether (690), C12-14 alkyl glycidyl ether (AGE) and propylene oxide o-cresyl ether (D-691).

[0023] In some embodiments, the coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0024] In some embodiments, the promoter is selected from one or more of BF3 and its complexes, SnCl4, AlCl3 and Bronsted salts.

[0025] In some embodiments, the spherical large particle size filler is selected from one or more of glass powder, silica powder, ceramic powder, silicon dioxide, zirconium oxide, aluminum oxide and magnesium oxide.

[0026] In some embodiments, the particle size of the spherical small-particle filler is selected from one or more of glass powder, silica powder, ceramic powder, silicon dioxide, zirconium oxide, aluminum oxide and magnesium oxide.

[0027] Another object of the present invention is to provide a prepreg, the prepreg comprising a reinforcing material and any one of the epoxy resin compositions described above attached to the reinforcing material. In some embodiments, compared to conventional prepregs, the curing time of the prepreg of the present invention is greatly shortened, and the curing temperature is also reduced.

[0028] Another object of the present invention is to provide a laminate comprising at least one sheet of the above-mentioned prepreg.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The epoxy resin composition of the present invention reduces the curing temperature of the prepreg through the coordination of various components, saves energy, and improves the safety and simplicity of operation; increases the fluidity of the prepreg and improves the operability; increases the curing strength of the prepreg, so that the material has excellent properties such as high mechanical strength and high heat resistance; greatly shortens the curing time of the prepreg and improves the curing efficiency. DETAILED DESCRIPTION

[0031] In order to enable those skilled in the art to better understand the technical solution of the present application, the present application is further described in detail below in conjunction with specific embodiments.

[0032] The present invention provides an epoxy resin composition, comprising the following components in parts by weight:

[0033] 20-40 parts of base resin,

[0034] 10-20 parts of active hydroxyl polymer containing epoxy groups,

[0035] 5-15 parts of bisphenol fluorene epoxy resin,

[0036] Curing agent A1-3 parts,

[0037] Curing agent B1-3 parts,

[0038] Epoxy diluent 5-15 parts,

[0039] 2-4 parts of coupling agent,

[0040] Accelerator 0.01-0.05 parts,

[0041] 20-40 parts of spherical large particle size filler,

[0042] 10-20 parts of spherical small particle filler.

[0043] In some embodiments, the reactive hydroxyl polymer containing epoxy groups is prepared as follows:

[0044] It is prepared by the reaction of hydroxymethyl bisphenol A and epichlorohydrin in the presence of an alkaline catalyst;

[0045]

[0046] The preparation of bisphenol fluorene epoxy resin is as follows:

[0047] ① Add bisphenol fluorene to toluene and dissolve it completely; then drop 2,2,6,6-tetramethylpiperidin-1-oxyl radical, 1,8-dicyano-4-phenyl-1,3,5-triazine, and sodium bromide in sequence; after sufficient reaction, obtain mixture A. The relevant structural formula is as follows:

[0048]

[0049] ② Then slowly drip an excess of active hydroxyl polymer containing epoxy groups into the mixed solution A, heat it to 35-50°C, and drip the condensation agent N,N'-dicyclohexylcarbodiimide and the phase transfer catalyst hexadecyltrimethylammonium bromide while stirring. After the reaction is complete, the bisphenol fluorene epoxy resin can be obtained. The relevant reaction formula is as follows:

[0050]

[0051] In some embodiments, the particle size of the spherical large-particle filler is 50-100 nm; the particle size of the spherical small-particle filler is 10-25 nm; and the weight ratio of the particle size of the spherical large-particle filler to the spherical small-particle filler is 2:1.

[0052] In some embodiments, the base resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0053] In some embodiments, the curing agent A is selected from one or more of methylnadic anhydride (MNA), HK-021 anhydride, and methyltetrahydrophthalic anhydride (MeTHPA). The curing agent B is selected from one or more of cyanate curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, and latent curing agents. Specifically, the latent curing agent is, for example, terephthalic acid dihydrazide.

[0054] In some embodiments, the epoxy resin diluent is selected from one or more of alkylene glycidyl ether (HK-66), phenyl glycidyl ether (690), C12-14 alkyl glycidyl ether (AGE) and propylene oxide o-cresyl ether (D-691).

[0055] In some embodiments, the coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. The accelerator is selected from one or more of BF3 and its complex, SnCl4, AlCl3 and Bronsted acid salt.

[0056] In some embodiments, the spherical large particle size filler is selected from one or more of glass powder, silica powder, ceramic powder, silicon dioxide, zirconium oxide, aluminum oxide and magnesium oxide. The spherical small particle size filler is selected from one or more of glass powder, silica powder, ceramic powder, silicon dioxide, zirconium oxide, aluminum oxide and magnesium oxide.

[0057] Another object of the present invention is to provide a prepreg, comprising a reinforcing material and any one of the above-mentioned epoxy resin compositions attached to the reinforcing material.

[0058] Another object of the present invention is to provide a laminate comprising at least one sheet of the above-mentioned prepreg.

[0059] Example 1

[0060] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 20 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0061] Example 2

[0062] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0063] Example 3

[0064] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0065] Example 4

[0066] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 20 parts of bisphenol A epoxy resin, 20 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0067] Example 5

[0068] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 20 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 10 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0069] Example 6

[0070] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 20 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 15 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0071] Example 7

[0072] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 20 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 40 parts of spherical large-particle silica and 20 parts of spherical small-particle silica.

[0073] Example 8

[0074] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 40 parts of spherical large-particle silica and 20 parts of spherical small-particle silica.

[0075] Example 9

[0076] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 25 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0077] Example 10

[0078] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 35 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0079] Embodiment 11

[0080] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 25 parts of spherical large-particle silica and 12.5 parts of spherical small-particle silica.

[0081] Example 12

[0082] The present embodiment provides an epoxy resin composition, comprising the following components in parts by weight: 35 parts of bisphenol A epoxy resin, 15 parts of active hydroxyl polymer containing epoxy groups, 10 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0083] Embodiment 13

[0084] This embodiment provides a prepreg, including a reinforcing material and an epoxy resin composition attached to the reinforcing material, wherein the epoxy resin composition is provided by Embodiments 1 to 12.

[0085] Embodiment 14

[0086] This embodiment provides a method for preparing a prepreg, which is used to prepare the prepreg provided in Example 13. The preparation method comprises:

[0087] ① Preparation of epoxy resin composition matrix for prepreg.

[0088] Put the base resin, active hydroxyl polymer containing epoxy group, bisphenol fluorene epoxy resin, curing agent A, epoxy resin diluent into the reaction kettle, and after uniform dispersion, dissolve the curing agent B, coupling agent and accelerator and put them into the reaction kettle; after uniform dispersion, put spherical large-particle silica and spherical small-particle silica into the stirring state, stir well for 60-120 minutes, and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg. Specifically, in this embodiment, it is preferably stirred for 100 minutes.

[0089] ②Preparation of prepreg

[0090] The epoxy resin matrix obtained in step ① is added to the coating machine, and the temperature of the ink sol device is set to 80°C, and the epoxy resin matrix is ​​prepared into an epoxy resin matrix resin film at the above temperature; then the epoxy resin matrix resin film and the 2116 glass fiber cloth are introduced into the prepreg equipment together, the resin film and the glass fiber cloth are compounded, and the temperature of the hot roller in the equipment is set to 150°C to obtain a high-strength and fast-curing prepreg of 2116RC45.

[0091] Embodiment 15

[0092] This embodiment provides a laminate containing at least one prepreg provided in Example 13.

[0093] Example 16

[0094] This embodiment provides a method for preparing a laminate, which is used to prepare the laminate provided in embodiment 15. The preparation method comprises:

[0095] Five prepregs were stacked, and a matte release film was covered on each of the upper and lower sides of the stack. The stack was placed in a programmable temperature and pressure controlled vacuum press. 2 The product is cured at the set temperature under the pressure condition to produce a laminate with a thickness of 0.5 mm.

[0096] Comparative Example 1

[0097] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 40 parts of bisphenol A epoxy resin, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0098] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0099] 40 parts of bisphenol A epoxy resin, 5 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, and 5 parts of HK-66 were added to the reactor. After uniform dispersion, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 part of BF3 were added to the reactor. After uniform dispersion, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica were added under stirring. After full stirring for 100 minutes, the epoxy resin matrix of the high-strength fast-curing prepreg was obtained by filling.

[0100] Comparative Example 2

[0101] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 35 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0102] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0103] 35 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 1 part of methyl nadic anhydride, and 5 parts of HK-66 are put into the reactor. After uniform dispersion, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 part of BF3 are put into the reactor. After uniform dispersion, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica are put into the reactor under stirring. Stir thoroughly for 100 minutes and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg.

[0104] Comparative Example 3

[0105] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 2 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0106] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0107] 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy group, 2 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66 are put into the reactor, and after uniform dispersion, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 part of BF3 are put into the reactor; after uniform dispersion, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica are put into the reactor under stirring. Stir thoroughly for 100 minutes, and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg.

[0108] Comparative Example 4

[0109] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 20 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0110] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0111] 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy group, 20 parts of bisphenol fluorene epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66 are put into the reactor, and after being evenly dispersed, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 part of BF3 are put into the reactor; after being evenly dispersed, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica are put into the reactor under stirring. Stir thoroughly for 100 minutes, and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg.

[0112] Comparative Example 5

[0113] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol S epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0114] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0115] 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy group, 5 parts of bisphenol S epoxy resin, 1 part of methyl nadic anhydride, 5 parts of HK-66 are put into the reactor, and after being evenly dispersed, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 part of BF3 are put into the reactor; after being evenly dispersed, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica are put into the reactor under stirring. Stir thoroughly for 100 minutes, and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg.

[0116] Comparative Example 6

[0117] This comparative example provides an epoxy resin composition, comprising the following components in parts by weight: 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy groups, 5 parts of bisphenol fluorene epoxy resin, 5 parts of HK-66, 1 part of terephthalic acid dihydrazide, 2 parts of γ-aminopropyltriethoxysilane, 0.01 parts of BF3, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica.

[0118] The following method is used to prepare the epoxy resin composition matrix for prepreg:

[0119] 30 parts of bisphenol A epoxy resin, 10 parts of active hydroxyl polymer containing epoxy group, 5 parts of bisphenol fluorene epoxy resin, 5 parts of HK-66 are put into the reactor, and after being evenly dispersed, 1 part of dissolved terephthalic acid dihydrazide, 2 parts of γ-aminopropyl triethoxysilane, and 0.01 parts of BF3 are put into the reactor; after being evenly dispersed, 20 parts of spherical large-particle silica and 10 parts of spherical small-particle silica are put into the reactor under stirring. Stir thoroughly for 100 minutes, and fill to obtain the epoxy resin matrix of high-strength fast-curing prepreg.

[0120] The epoxy resin composition matrices of Comparative Examples 1 to 6 were prepared into prepregs by the method of Example 14, and further prepared into laminates by the method of Example 16.

[0121] The epoxy resin compositions of Examples 1 to 12 and Comparative Examples 1 to 6 were correspondingly prepared into prepregs and subjected to the following tests: a glue flow test was performed by measuring with a ruler.

[0122] The laminates prepared from the epoxy resin compositions of Examples 1 to 12 and Comparative Examples 1 to 6 were subjected to the following tests:

[0123] 1. Elastic modulus: in accordance with IPC-TM-650 2.4.22.1.

[0124] 2. Flexural strength: in accordance with IPC-TM-650 2.4.4.

[0125] The components used in the epoxy resin compositions of Examples 1 to 9 and the corresponding test results are shown in Table 1.

[0126] Table 1

[0127]

[0128] The components used in the epoxy resin compositions of Examples 10 to 12 and Comparative Examples 1 to 6 and the corresponding test results are as follows:

[0129] As shown in Table 2.

[0130]

[0131] Table 2

[0132] According to the test results corresponding to Examples 1 to 12, the epoxy resin composition of the present invention enables the prepreg to have excellent fluidity, can achieve rapid curing at above 150° C., and the cured product has excellent mechanical strength.

[0133] According to the test results corresponding to Examples 1 to 12 and Comparative Examples 1, 2 and 5, the lack of any of the active hydroxyl polymer having epoxy groups and the bisphenol fluorene epoxy resin in the epoxy resin composition will reduce the mechanical strength of the composition.

[0134] According to the test results corresponding to Examples 1 to 12 and Comparative Examples 3 and 4, it can be seen that excessive addition of bisphenol fluorene epoxy resin in the epoxy resin composition will reduce the mechanical strength of the material.

[0135] According to the test results corresponding to Examples 1 to 12 and Comparative Example 6, using only one curing agent in the epoxy resin composition will reduce the curing speed, and thus a higher curing temperature is required to accelerate the curing; while the present application can achieve rapid curing at a lower curing temperature.

[0136] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the technical solution of the present invention, and are not intended to limit the specific implementation methods of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the claims of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. An epoxy resin composition, characterized in that The composition comprises the following components in parts by weight: 20-40 parts of base resin, 10-20 parts of active hydroxyl polymer containing epoxy groups, 5-15 parts of bisphenol fluorene epoxy resin, Curing agent A1-3 parts, Curing agent B1-3 parts, Epoxy diluent 5-15 parts, 2-4 parts of coupling agent, Accelerator 0.01-0.05 parts, 20-40 parts of spherical large particle size filler, 10-20 parts of spherical small particle filler.

2. The epoxy resin composition according to claim 1, characterized in that The particle size of the spherical large-particle filler is 50-100nm; the particle size of the spherical small-particle filler is 10-25nm; and the weight ratio of the particle size of the spherical large-particle filler to the spherical small-particle filler is 2:

1.

3. The epoxy resin composition according to claim 1, characterized in that The matrix resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aliphatic glycidyl ether epoxy resin and glycidyl ester epoxy resin.

4. The epoxy resin composition according to claim 1, characterized in that The curing agent A is selected from one or more of methylnadic anhydride, HK-021 anhydride, and methyltetrahydrophthalic anhydride.

5. The epoxy resin composition according to claim 1, characterized in that The curing agent B is selected from one or more of cyanate curing agents, aliphatic polyamine curing agents, alicyclic polyamine curing agents, aromatic amine curing agents, polyamide curing agents and latent curing agents.

6. The epoxy resin composition according to claim 1, characterized in that The epoxy resin diluent is selected from one or more of alkylene glycidyl ether, phenyl glycidyl ether, C12-14 alkyl glycidyl ether and propylene oxide o-tolyl ether.

7. The epoxy resin composition according to claim 1, characterized in that The coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

8. The epoxy resin composition according to any one of claims 1 to 7, characterized in that The promoter is selected from one or more of BF3 and its complex, SnCl4, AlCl3 and Bronsted acid salts.

9. A prepreg, characterized in that: The prepreg comprises a reinforcing material and the epoxy resin composition according to any one of claims 1 to 8 attached to the reinforcing material.

10. A laminated board, characterized in that: The laminate comprises at least one prepreg according to claim 9.

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