A solid epoxy vinyl ester resin composition and its preparation method and application

Abstract

The present invention discloses a solid epoxy vinyl ester resin composition and a preparation method and application thereof. The solid epoxy vinyl ester resin composition comprises bisphenol A epoxy vinyl ester resin, polyether polyol glycidyl ether acrylate, hyperbranched polymer and thermal initiator. The bisphenol A epoxy vinyl ester resin is obtained by esterification reaction between bisphenol A epoxy resin and unsaturated monocarboxylic acid; the polyether polyol glycidyl ether acrylate is obtained by esterification reaction between polyether polyol glycidyl ether and unsaturated monocarboxylic acid. The formula does not need to use a crosslinking monomer, the composition does not contain a crosslinking monomer, and the void ratio is low. The proportion of unsaturated double bonds in the formula is low, and the shrinkage rate is low; embedding a hyperbranched polymer in the molecular structure further reduces the shrinkage rate of the system, improves the interface performance between the resin and the fiber, and is suitable for preparing carbon fiber prepreg.

Description

Technical Field

[0001] The invention belongs to the field of polymer technology, and specifically relates to a solid epoxy vinyl ester resin composition and a preparation method and application thereof. Background Art

[0002] Carbon fiber prepreg has the advantages of low resin content, light weight and high strength, and is widely used in aviation, aerospace, rail transportation and other fields. Carbon fiber prepreg is mostly an epoxy resin system, which contains ester bonds in the molecular structure and has poor long-term resistance to seawater and salt spray, which limits its application in marine vessels.

[0003] Epoxy vinyl ester resin is prepared by reacting epoxy resin with monocarboxylic acid, and the reaction product is dissolved in a cross-linking monomer, which retains the advantages of high mechanical properties and good fatigue performance of epoxy resin. Epoxy vinyl ester resin introduces methyl protection near the ester bond to improve the seawater and salt spray resistance through steric hindrance. However, epoxy vinyl ester resin has the disadvantages of high shrinkage and poor interface performance with carbon fiber. The main reason is that the unsaturated double bond (-C=C-) in the resin molecular structure becomes an unsaturated single bond (-CC-) during the curing process, which causes the resin to shrink. The volume shrinkage rate of epoxy vinyl ester resin is 6-8%, and epoxy vinyl ester resin contains prepolymers, cross-linking monomers, etc. The cross-linking monomer is usually an ester monomer or styrene, which is volatile and not suitable for prepreg systems. In addition, epoxy vinyl ester resin uses free radical curing, lacks amino groups compared to epoxy resin systems, and has poor interface performance with carbon fiber. Although epoxy vinyl ester resin-based carbon fiber composites have excellent seawater and salt spray resistance, they cannot give full play to the advantages of light weight and high strength of carbon fiber prepregs.

[0004] Carbon fiber prepreg is prepared by preparing resin film under high temperature conditions, hot pressing resin film and fiber, etc. Epoxy vinyl ester resin contains cross-linking monomers such as styrene, which are easy to volatilize under high temperature conditions, and the unsaturated double bonds are cross-linked and cured under high temperature conditions, which cannot meet the prepreg molding process. The cross-linking monomers in epoxy vinyl ester resin are easily expanded by heat, and the void ratio of the prepared carbon fiber prepreg reaches 3-5% after curing, which reduces the mechanical properties of carbon fiber composite materials. Summary of the invention

[0005] To solve the above problems, the present invention provides a solid epoxy vinyl ester resin composition for carbon fiber prepreg that does not contain a cross-linking monomer and has low shrinkage, low exothermic peak and long storage period, as well as a preparation method and application thereof. The solid epoxy vinyl ester resin composition is suitable for prepreg molding process, especially for the preparation of marine ship carbon fiber composite material parts by prepreg molding process.

[0006] The technical scheme of the present invention is to reduce the unsaturated double bond ratio in the epoxy vinyl ester resin, introduce a hyperbranched polymer to reduce the resin shrinkage, exothermic peak, extend the storage period, and improve the interface performance of the composite material. The prepared solid epoxy vinyl ester resin composition has a low unsaturated double bond ratio, low shrinkage, low heat release, long storage period, seawater resistance, good salt spray performance, low porosity, and good interface performance.

[0007] In order to achieve the above-mentioned purpose of the invention, the first aspect of the present invention provides a solid epoxy vinyl ester resin composition, comprising bisphenol A epoxy vinyl ester resin, polyether polyol glycidyl ether acrylate, hyperbranched polymer and thermal initiator, and does not contain cross-linking monomer; the molar ratio of the bisphenol A epoxy vinyl ester resin to the polyether polyol glycidyl ether acrylate is 1:1 to 20:1; the molar ratio of the bisphenol A epoxy vinyl ester resin to the hyperbranched polymer is 33.7:1-109:1.

[0008] Preferably, the molar ratio of the bisphenol A epoxy vinyl ester resin to the polyether polyol glycidyl ether acrylate is 2.5:1 to 18.7:1.

[0009] Preferably, the bisphenol A epoxy vinyl ester resin is obtained by esterification reaction of bisphenol A epoxy resin and unsaturated monocarboxylic acid.

[0010] Preferably, the polyether polyol glycidyl ether acrylate is obtained by esterification reaction of polyether polyol glycidyl ether and unsaturated monocarboxylic acid.

[0011] Preferably, the unsaturated double bond content of the solid epoxy vinyl ester resin composition is 0.15 mol / 100 g to 0.40 mol / 100 g.

[0012] Preferably, the solid epoxy vinyl ester resin composition is made of the following raw materials in percentage by mass:

[0013]

[0014] More preferably, the solid epoxy vinyl ester resin composition comprises the following raw materials in percentage by mass:

[0015]

[0016] Preferably, the active oxygen content of the thermal initiator is 4-9%.

[0017] More preferably, the thermal initiator is selected from one or more of benzoyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate.

[0018] Further preferably, the thermal initiator is tert-butyl perbenzoate with an active oxygen content of 8%.

[0019] Preferably, the molecular weight of the hyperbranched polymer is 1000-10000.

[0020] More preferably, the hyperbranched polymer is selected from one or more of carboxyl-terminated hyperbranched polyesters, hydroxyl-terminated hyperbranched polyesters and unsaturated double-bond-terminated hyperbranched polyurethanes.

[0021] More preferably, the hyperbranched polymer is a hydroxyl-terminated hyperbranched polyester with a molecular weight of 2000 to 6000 and 20 to 50 hydroxyl groups per mol.

[0022] Preferably, the bisphenol A epoxy resin has an epoxy equivalent of 180 to 515 g / mol.

[0023] More preferably, the bisphenol A epoxy resin is selected from one or more of E51 epoxy resin, E44 epoxy resin and E20 epoxy resin; the epoxy equivalent of the E51 epoxy resin is 180-200 g / mol; the epoxy equivalent of the E44 epoxy resin is 210-240 g / mol; the epoxy equivalent of the E20 epoxy resin is 485-515 g / mol.

[0024] Further preferably, the bisphenol A epoxy resin is E51 epoxy resin and E44 epoxy resin in a mass ratio of 20-50:50-80.

[0025] Preferably, the unsaturated monocarboxylic acid is selected from methacrylic acid and / or acrylic acid.

[0026] Preferably, the polyether polyol glycidyl ether is a low viscosity epoxy resin.

[0027] More preferably, the molecular weight of the polyether polyol glycidyl ether is 100-800, the viscosity is 5-200 mPa.s, and the epoxy equivalent is 50-400 g / mol.

[0028] More preferably, the polyether polyol glycidyl ether is selected from one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, 1,6-hexanediol glycidyl ether and cardanol glycidyl ether.

[0029] Preferably, the inhibitor 1# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

[0030] Preferably, the catalyst is selected from one or more of benzyltrimethylammonium chloride, triphenylphosphine, benzyltriethylammonium chloride, benzyltriethylammonium chloride ammonium bromide, imidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole.

[0031] Preferably, the polymerization inhibitor 2# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

[0032] The second aspect of the present invention provides a method for preparing the solid epoxy vinyl ester resin composition according to the first aspect, comprising the following steps:

[0033] (1) mixing bisphenol A epoxy resin and polyether polyol glycidyl ether, heating to 90-100° C. and stirring evenly to obtain a first reactant;

[0034] (2) adding a hyperbranched polymer and an organic unsaturated monocarboxylic acid to the first reactant, controlling the temperature of the reaction system to 85-95° C., and stirring uniformly to obtain a second reactant;

[0035] (3) adding inhibitor 1# to the second reactant, stirring evenly, adding a catalyst, and reacting at 120-125° C. for 4.0-5.0 hours, controlling the acid value of the reaction system to be less than 7 mg KOH / g during the reaction, to obtain a third reactant;

[0036] (4) adding inhibitor 2# to the third reactant, cooling to 68-70° C. and stirring evenly to obtain a fourth reactant;

[0037] (5) Add a thermal initiator to the fourth reactant and stir evenly again to obtain a solid epoxy vinyl ester resin composition.

[0038] Preferably, the molar ratio of the bisphenol A epoxy resin to the polyether polyol glycidyl ether in step (1) is 1:1 to 20:1;

[0039] More preferably, the molar ratio of the bisphenol A epoxy resin to the polyether polyol glycidyl ether is 2.5:1 to 18.7:1.

[0040] Preferably, the bisphenol A epoxy resin in step (1) has an epoxy equivalent of 180 to 515 g / mol;

[0041] More preferably, the bisphenol A epoxy resin is selected from one or more of E51 epoxy resin, E44 epoxy resin and E20 epoxy resin, the epoxy equivalent of the E51 epoxy resin is 180-200 g / mol, the epoxy equivalent of the E44 epoxy resin is 210-240 g / mol, and the epoxy equivalent of the E20 epoxy resin is 485-515 g / mol;

[0042] More preferably, the bisphenol A epoxy resin is an E51 epoxy resin and an E44 epoxy resin in a mass ratio of 20-50:50-80.

[0043] Preferably, the polyether polyol glycidyl ether in step (1) is a low-viscosity epoxy resin;

[0044] More preferably, the polyether polyol glycidyl ether has a molecular weight of 100-800, a viscosity of 5-200 mPa.s, and an epoxy equivalent of 50-400 g / mol;

[0045] Further preferably, the polyether polyol glycidyl ether is selected from one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, 1,6-hexanediol glycidyl ether and cardanol glycidyl ether.

[0046] Preferably, the molar ratio of the bisphenol A epoxy resin in step (1) to the hyperbranched polymer in step (2) is 33.7:1-109:1;

[0047] Preferably, the molecular weight of the hyperbranched polymer in step (2) is 1000-10000.

[0048] More preferably, the hyperbranched polymer is selected from one or more of carboxyl-terminated hyperbranched polyesters, hydroxyl-terminated hyperbranched polyesters and terminal unsaturated double-bond hyperbranched polyurethanes;

[0049] Further preferably, the hyperbranched polymer is a hydroxyl-terminated hyperbranched polyester with a molecular weight of 2000 to 6000 and 20 to 50 hydroxyl groups per mol.

[0050] Preferably, the unsaturated monocarboxylic acid in step (2) is selected from methacrylic acid and / or acrylic acid.

[0051] Preferably, the stirring time in step (2) is 18-22 minutes.

[0052] Preferably, the inhibitor 1# in step (3) is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

[0053] Preferably, the stirring time in step (3) is 8 - 12 minutes.

[0054] Preferably, the catalyst in step (3) is selected from one or more of benzyltrimethylammonium chloride, triphenylphosphine, benzyltriethylammonium chloride, benzyltriethylammonium chloride bromide, imidazole, 1 - methylimidazole, and 2 - ethyl - 4 - methylimidazole.

[0055] Preferably, the catalyst in step (3) is slowly added within 20 minutes.

[0056] Preferably, the polymerization inhibitor 2# in step (4) is selected from one or more of hydroquinone, p - benzoquinone, tert - butylhydroquinone, 2,6 - di - tert - butyl - 4 - methylphenol, methylhydroquinone, and p - methoxyphenol.

[0057] Preferably, the stirring time in step (4) is 8 - 12 minutes.

[0058] Preferably, the active oxygen content of the thermal initiator in step (5) is 4 - 9%;

[0059] More preferably, the thermal initiator is selected from one or more of benzoyl peroxide, tert - butyl peroxybenzoate, and tert - butyl peroxy - 2 - ethylhexanoate;

[0060] Further preferably, the thermal initiator is tert - butyl peroxybenzoate with an active oxygen content of 8%.

[0061] Preferably, the stirring time in step (5) is 8 - 12 minutes.

[0062] Preferably, the solid epoxy vinyl ester resin composition is made from the following raw materials in mass percentages:

[0063]

[0064]

[0065] More preferably, the solid epoxy vinyl ester resin composition is made from the following raw materials in mass percentages:

[0066]

[0067] The third aspect of the present invention provides the use of the solid epoxy vinyl ester resin composition described in the first aspect or the solid epoxy vinyl ester resin composition prepared by the preparation method described in the second aspect in the preparation of carbon fiber prepregs.

[0068] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0069] (1) The unsaturated double bond content of conventional epoxy vinyl ester resin is 0.50-0.80 mol / 100 g, while the unsaturated double bond content of the epoxy vinyl ester resin prepared by the present invention is 0.15-0.40 mol / 100 g, and the unsaturated double bond ratio is more than 20% lower, which is beneficial to increase the resin storage period and reduce the shrinkage rate. The formula contains an initiator, which can release free radicals during storage to initiate the cross-linking and curing of unsaturated double bonds, reduce the unsaturated double bond ratio, reduce the resin activity, and increase the resin storage period; reduce the unsaturated double bond ratio, reduce the heat release, reduce the stress concentration phenomenon during the molding process, and the product has good dimensional stability, which is suitable for molding large-sized composite parts.

[0070] (2) Compared with conventional epoxy vinyl ester resins, bisphenol A epoxy vinyl ester resins are combined with polyether polyol glycidyl ether acrylate to reduce the viscosity of the system, so there is no need to use a cross-linking monomer, the product does not contain a cross-linking monomer, and the void ratio is low. Styrene and low-flash point acrylate cross-linking monomers expand and volatilize when heated, which easily produces voids. The void ratio has a great influence on the mechanical properties of the composite material, and the present invention does not contain such a cross-linking monomer.

[0071] (3) The product has low shrinkage and good interface performance. The volume shrinkage of conventional epoxy vinyl ester resin is 6-8%, while the volume shrinkage of the epoxy vinyl ester resin prepared by the present invention is 2-4%. On the one hand, the proportion of unsaturated double bonds in the formula is low, and the shrinkage is low; on the other hand, hyperbranched polymers are embedded in the molecular structure, and the hyperbranched polymers further reduce the shrinkage of the system. The surface of the hyperbranched polymer contains polar groups such as hydroxyl groups, which improves the interface performance between the resin and the fiber.

[0072] (4) The ester group in the product molecular structure is protected by a methyl group, which plays a steric hindrance role. The retention rate of the flexural strength after boiling water reaches more than 92%, which is suitable for the preparation of carbon fiber composite materials for marine ships.

[0073] (5) It is solid at room temperature and easy to store. The formula contains a thermal initiator and can be used after heating when preparing carbon fiber prepreg. No batching operation is required. It is easy to use and highly efficient.

[0074] (6) During the preparation process, no three wastes are generated, which is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 This is the viscosity-temperature curve of the solid epoxy vinyl ester resin composition of Example 3 of the present invention.

[0076] Figure 2 This is the 120°C viscosity-time curve of the solid epoxy vinyl ester resin composition of Example 3 of the present invention.

[0077] Figure 3This is the 100°C viscosity-time curve of the solid epoxy vinyl ester resin composition of Example 3 of the present invention. DETAILED DESCRIPTION

[0078] In the present invention, "epoxy resin" refers to a molecule containing two or more epoxy groups -CH(O)CH-(

[0079] ) polymer, epoxy resin can undergo esterification reaction with unsaturated monocarboxylic acid, and the reaction formula of esterification reaction is In the present invention, "bisphenol A type epoxy resin" is a compound prepared from bisphenol A and epichlorohydrin under alkaline conditions such as NaOH, and has the structural formula The most reactive group in bisphenol A epoxy resin is the epoxy group, which can undergo esterification reaction with the carboxyl group. In the present invention, the polyether polyol glycidyl ether is an epoxy resin formed by condensation of polyether polyol and epichlorohydrin, and has epoxy groups at both ends of the molecular structure, which can also undergo esterification reaction with the carboxyl group.

[0080] The present invention provides a solid epoxy vinyl ester resin composition, which is made of the following raw materials in percentage by mass:

[0081]

[0082] In the present invention, the formula contains two epoxy resins, among which the polyether polyol glycidyl ether has a low viscosity, which reduces the viscosity of the system and is conducive to the esterification reaction. At the same time, the viscosity of the composite is greatly reduced compared with the use of bisphenol A epoxy resin alone, and the viscosity index requirements of the prepreg process can be met without adding a cross-linking monomer. Preferably, the mass ratio of bisphenol A epoxy resin to polyether polyol glycidyl ether is (35-65): (3-28); more preferably, the mass ratio of bisphenol A epoxy resin to polyether polyol glycidyl ether is (40-60): (3-8).

[0083] In the present invention, bisphenol A epoxy resin and unsaturated monocarboxylic acid undergo esterification reaction to generate bisphenol A epoxy vinyl ester resin with an unsaturated double bond as the terminal group. In the present invention, the epoxy equivalent of bisphenol A epoxy resin is 180 to 515 g / mol. Preferably, the bisphenol A epoxy resin includes but is not limited to one or more of E51 epoxy resin, E44 epoxy resin and E20 epoxy resin. Further preferably, the bisphenol A epoxy resin is E51 epoxy resin and E44 epoxy resin in a mass ratio of 20-50:50-80.

[0084] In the present invention, polyether polyol glycidyl ether and unsaturated monocarboxylic acid undergo esterification reaction to generate polyether polyol glycidyl ether acrylate with an unsaturated double bond as the terminal group. In the present invention, the polyether polyol glycidyl ether is a low-viscosity epoxy resin, which reduces the viscosity of the system and provides excellent impact toughness and flexibility. Preferably, the molecular weight of the polyether polyol glycidyl ether is 100-800, the viscosity is 5-200mPa.s, and the epoxy equivalent is 50-400g / mol. Further preferably, the polyether polyol glycidyl ether includes but is not limited to one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, 1,6-hexanediol glycidyl ether and cardanol glycidyl ether.

[0085] In the present invention, the hyperbranched polymer has a tree-like structure, and the surface polar groups improve the interfacial properties between the resin and the carbon fiber, and the molecular weight of the hyperbranched polymer is 1000-10000. In the present invention, the hyperbranched polymer includes but is not limited to one or more of carboxyl-terminated hyperbranched polyesters, hydroxyl-terminated hyperbranched polyesters, and terminal unsaturated double-bond hyperbranched polyurethanes. Preferably, in the present invention, the hyperbranched polymer is a hydroxyl-terminated hyperbranched polyester with a molecular weight of 2000 to 6000 and 20-50 hydroxyl groups per mol. In a specific embodiment, the hyperbranched polymer selects a hydroxyl-terminated hyperbranched polyester with a molecular weight of 2400 as shown below, and the number of hydroxyl groups per mol is 20-24:

[0086]

[0087] In the present invention, the unsaturated double bond content of the solid epoxy vinyl ester resin composition is 0.15 to 0.40 mol / 100g.

[0088] In some specific embodiments of the present invention, the molar ratio of bisphenol A epoxy vinyl ester resin to polyether polyol glycidyl ether acrylate is 2.5:1, 5.6:1 or 18.7:1, and the molar ratio of bisphenol A epoxy vinyl ester resin to hyperbranched polymer is 33.7:1, 43.2:1, 49.6:1, 53.7:1 or 109:1.

[0089] In the present invention, the initiator can release free radicals during the storage of the solid epoxy vinyl ester resin composition, which can trigger the cross-linking and curing of unsaturated double bonds, reduce the proportion of unsaturated double bonds, reduce the activity of the resin, and improve the shelf life of the resin. In the present invention, the active oxygen content of the thermal initiator is 4-9%. Preferably, the thermal initiator includes but is not limited to one or more of benzoyl peroxide, tert-butyl perbenzoate and tert-butyl peroxy-2-ethylhexanoate. In a specific embodiment, the thermal initiator is tert-butyl perbenzoate with an active oxygen content of 8%.

[0090] In the present invention, the organic unsaturated monocarboxylic acid includes but is not limited to methacrylic acid and / or acrylic acid.

[0091] In the present invention, the inhibitor 1# includes but is not limited to one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

[0092] In the present invention, the catalyst includes but is not limited to one or more of benzyltrimethylammonium chloride, triphenylphosphine, benzyltriethylammonium chloride, benzyltriethylammonium chloride ammonium bromide, imidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole.

[0093] In the present invention, the inhibitor 2# includes, but is not limited to, one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

[0094] The present invention also provides a method for preparing the above-mentioned solid epoxy vinyl ester resin composition, comprising the following steps:

[0095] (1) mixing bisphenol A epoxy resin and polyether polyol glycidyl ether, heating to 90-100° C. and stirring evenly to obtain a first reactant;

[0096] (2) adding a hyperbranched polymer and an organic unsaturated monocarboxylic acid to the first reactant, controlling the temperature of the reaction system to 85-95° C., and stirring uniformly to obtain a second reactant;

[0097] (3) adding inhibitor 1# to the second reactant, stirring evenly, adding a catalyst, and reacting at 120-125° C. for 4.0-5.0 hours, controlling the acid value of the reaction system to be less than 7 mg KOH / g during the reaction, to obtain a third reactant;

[0098] (4) adding inhibitor 2# to the third reactant, cooling to 68-70° C. and stirring evenly to obtain a fourth reactant;

[0099] (5) Add a thermal initiator to the fourth reactant and stir evenly again to obtain a solid epoxy vinyl ester resin composition.

[0100] In the present invention, stirring is continued until the reactants are uniformly stirred. Preferably, the stirring time in step (2) is 18-22 minutes; and the stirring time in steps (3), (4) and (5) is 8-12 minutes.

[0101] The solid epoxy vinyl ester resin composition prepared by the present invention has a low ratio of unsaturated double bonds, and has the advantages of low shrinkage, low heat release, long storage period, good seawater resistance and salt spray performance, low porosity, and good interface performance. Compared with conventional epoxy vinyl ester resins, the ratio of unsaturated double bonds is more than 20% lower, which is beneficial to improving the resin storage period, good product dimensional stability, low product shrinkage, and interface performance, and is suitable for molding high-performance large-size composite material parts. The ester group in the molecular structure of epoxy vinyl ester resin is protected by methyl, which plays a steric hindrance protection role, and the seawater resistance and salt spray performance are greatly improved compared with the epoxy resin prepreg system, and is suitable for preparing marine ship carbon fiber composite material parts. It is solid at room temperature and easy to store. The formula contains a thermal initiator, and it can be used after heating when preparing carbon fiber prepreg, without the need for batching operation, and is easy to use and efficient.

[0102] The technical scheme provided by the present invention is described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present invention. The experimental methods in the following embodiments that do not specify specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer. All raw materials that do not specify the synthesis method are purchased from the market.

[0103] Example 1

[0104] 125.4g E51 epoxy resin (0.336mol), 295.9g E44 epoxy resin (0.672mol), 251.1g polypropylene glycol diglycidyl ether (0.402mol Aladdin reagent) were added to the reactor, heated to 95°C and stirred evenly. 71.7g hyperbranched polymer (0.029mol, hydroxyl-terminated hyperbranched polyester, average molecular weight 2400, hydroxyl number 20-24) and 242.8g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.224g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.973g triphenylphosphine within 20 minutes, keep warm at 122°C for 4-6h, test the acid value every 0.5h, the acid value is less than 7mg KOH / g, add 0.500g p-benzoquinone and 0.500g methylhydroquinone, cool to 68-70°C, stir for 10 minutes, add 9.86g tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0105] In implementation 1, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 2.5:1, and the unsaturated double bond content is 0.282 mol / 100g.

[0106] Example 2

[0107] 165.7g E51 epoxy resin (0.443mol), 357.6g E44 epoxy resin (0.813mol), 139.5g polypropylene glycol diglycidyl ether (0.224mol Aladdin reagent) were added to the reactor, heated to 95°C, and stirred evenly. 69.8g hyperbranched polymer (0.029mol, hydroxyl-terminated hyperbranched polyester, average molecular weight 2400, hydroxyl number 20-24) and 254.7g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.218g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.919 g of triphenylphosphine within 20 minutes, keep warm at 122 ° C, keep warm for 4-6 hours, test the acid value every 0.5 hours, the acid value is less than 7 mg KOH / g, add 0.500 g of p-benzoquinone and 0.500 g of methylhydroquinone, cool to 68-70 ° C, stir for 10 minutes, add 9.59 g of tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0108] The difference between Example 2 and Example 1 is that the weight proportion of bisphenol A epoxy resin is increased, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 5.6:1, and the unsaturated double bond content is 0.296 mol / 100g.

[0109] Example 3

[0110] 183.3g E51 epoxy resin (0.490mol), 418.9g E44 epoxy resin (0.952mol), 52.4g polypropylene glycol diglycidyl ether (0.084mol, Aladdin reagent) were added to the reactor, heated to 95°C, and stirred evenly. 69.8g hyperbranched polymer (0.029mol, aliphatic hyperbranched polyester, average molecular weight 2400, hydroxyl number 20-24) and 262.7g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.218g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.919 g of triphenylphosphine within 20 minutes, keep warm at 122 ° C, keep warm for 4-6 hours, test the acid value every 0.5 hours, the acid value is less than 7 mg KOH / g, add 0.500 g of p-benzoquinone and 0.500 g of methylhydroquinone, cool to 68-70 ° C, stir for 10 minutes, add 9.60 g of tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0111] The difference between Example 3 and Example 2 is that the weight proportion of bisphenol A epoxy resin is further increased, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 17.2:1, and the unsaturated double bond content is 0.305 mol / 100g.

[0112] Example 4

[0113] 171.3g E51 epoxy resin (0.458mol), 391.6E44 epoxy resin (0.890mol), 49.0g polypropylene glycol diglycidyl ether (0.078mol, Aladdin reagent) were added to the reactor, heated to 95°C, and stirred evenly. 130.5g hyperbranched polymer (0.025mol, hydroxyl-terminated hyperbranched polyester, average molecular weight 5200, hydroxyl number 40-45) and 245.6g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.203g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.795g triphenylphosphine within 20 minutes, keep warm at 122°C for 4-6h, test the acid value every 0.5h, the acid value is less than 7mg KOH / g, add 0.500g p-benzoquinone and 0.500g methylhydroquinone, cool to 68-70°C, stir for 10 minutes, add 8.98g tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0114] The difference between Example 4 and Example 3 is that the weight proportion of the hyperbranched polymer is increased. The weight proportion of the hyperbranched polymer in Example 3 is 7%, and the weight proportion of the hyperbranched polymer in Example 4 is 13%. The weight proportion of bisphenol A epoxy resin, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 17.3:1, and the unsaturated double bond content is 0.285 mol / 100g.

[0115] Example 5

[0116] 243.4g E51 epoxy resin (0.651mol), 356.4E44 epoxy resin (0.810mol), 52.2g polyethylene glycol diglycidyl ether (0.078mol, Aladdin reagent) were added to the reactor, heated to 95°C, and stirred evenly. 69.5g hyperbranched polymer (0.025mol, hydroxyl-terminated hyperbranched polyester, average molecular weight 5200, hydroxyl number 40-45) and 265.9g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.217g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.912 g of triphenylphosphine within 20 minutes, keep warm at 122 ° C, keep warm for 4-6 hours, test the acid value every 0.5 hours, the acid value is less than 7 mg KOH / g, add 0.500 g of p-benzoquinone and 0.500 g of methylhydroquinone, cool to 68-70 ° C, stir for 10 minutes, add 9.56 g of tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0117] In Example 5, polypropylene glycol diglycidyl ether is replaced with polyethylene glycol diglycidyl ether, the weight proportion of bisphenol A epoxy resin, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 18.7:1, and the unsaturated double bond content is 0.309 mol / 100g.

[0118] Comparative Example 1

[0119] 183.3g E51 epoxy resin (0.490mol) and 418.9g E44 epoxy resin (1.120mol) were put into the reactor, heated to 95°C and stirred evenly. 262.7g methacrylic acid was added, the temperature was controlled at 90°C and stirred for 20 minutes. 0.218g methyl hydroquinone was added and stirred for 10 minutes. 1.919g triphenylphosphine was slowly added within 20 minutes, and the temperature was kept at 122°C for 4-6h. The acid value was tested every 0.5h, and the acid value was less than 7mg KOH / g. 0.500g p-benzoquinone and 0.500g methyl hydroquinone were added, the temperature was lowered to 68-70°C, 52.4g styrene was added, and stirred for 10 minutes. 9.60g tert-butyl perbenzoate was added and stirred for 10 minutes. The solid epoxy vinyl ester resin composition was obtained.

[0120] The difference between Comparative Example 1 and Example 3 is that no polyether polyol glycidyl ether and hyperbranched polymer are added, styrene is used as a cross-linking monomer, and the unsaturated double bond content is 0.382 mol / 100 g.

[0121] Comparative Example 2

[0122] 183.3g E51 epoxy resin (0.490mol) and 418.9g E44 epoxy resin (1.120mol) were put into the reactor, heated to 95°C and stirred evenly. 262.7g methacrylic acid was added, the temperature was controlled at 90°C and stirred for 20 minutes. 0.218g methyl hydroquinone was added and stirred for 10 minutes. 1.919g triphenylphosphine was slowly added within 20 minutes, and the temperature was kept at 122°C for 4-6h. The acid value was tested every 0.5h, and the acid value was less than 7mg KOH / g. 0.500g p-benzoquinone and 0.500g methyl hydroquinone were added, the temperature was lowered to 68-70°C, 52.4g hydroxyethyl methacrylate was added, and the mixture was stirred for 10 minutes. 9.60g tert-butyl perbenzoate was added and stirred for 10 minutes. The mixture was put into a packaging barrel to obtain a solid epoxy vinyl ester resin composition.

[0123] The difference between Comparative Example 2 and Comparative Example 1 is that the volatile cross-linking monomer is replaced with a non-volatile cross-linking monomer, and the unsaturated double bond content is 0.371 mol / 100 g.

[0124] Comparative Example 3

[0125] 183.3g E51 epoxy resin (0.490mol), 418.9g E44 epoxy resin (1.120mol), 52.4g polypropylene glycol diglycidyl ether (0.084mol, Aladdin reagent) were put into the reactor, heated to 95°C, and stirred evenly. 262.7g methacrylic acid was added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.218g methyl hydroquinone was added and stirred for 10 minutes. 1.919g triphenylphosphine was slowly added within 20 minutes, and the temperature was kept at 122°C for 4-6h. The acid value was tested every 0.5h. The acid value was less than 7mg KOH / g. 0.500g p-benzoquinone and 0.500g methyl hydroquinone were added, the temperature was lowered to 68-70°C, and stirred for 10 minutes. 9.60g tert-butyl perbenzoate was added, and stirred for 10 minutes. The solid epoxy vinyl ester resin composition was obtained.

[0126] The difference between Comparative Example 3 and Example 3 is that no hyperbranched polymer is added, the molar ratio of bisphenol A epoxy resin to polypropylene glycol diglycidyl ether is 19.2:1, and the unsaturated double bond content is 0.328 mol / 100 g.

[0127] Comparative Example 4

[0128] 214.7g E51 epoxy resin (0.574mol) and 418.9g E44 epoxy resin (1.120mol) were added into the reactor, heated to 95°C and stirred evenly. 69.8g hyperbranched polymer (0.029mol, hydroxyl-terminated hyperbranched polyester, average molecular weight 2400, hydroxyl number 20-24) and 262.7g methacrylic acid were added, the temperature was controlled at 90°C, and stirred for 20 minutes. 0.218g methylhydroquinone was added and stirred for 10 minutes. Slowly add 1.919 g of triphenylphosphine within 20 minutes, keep warm at 122 ° C, keep warm for 4-6 hours, test the acid value every 0.5 hours, the acid value is less than 7 mg KOH / g, add 0.500 g of p-benzoquinone and 0.500 g of methylhydroquinone, cool to 68-70 ° C, stir for 10 minutes, add 9.60 g of tert-butyl perbenzoate, stir for 10 minutes, put into a packaging barrel to obtain a solid epoxy vinyl ester resin.

[0129] The difference between Comparative Example 4 and Example 3 is that polypropylene glycol diglycidyl ether is replaced by E51 epoxy resin, low-viscosity polyether polyol diglycidyl ether is not contained, and the unsaturated double bond content is 0.312 mol / 100 g.

[0130] Test example

[0131] Carbon fiber prepreg was prepared using the epoxy vinyl ester resin obtained in the above Examples 1-5 and Comparative Examples 1-4, and then a carbon fiber composite material was prepared using a vacuum assisted bag pressing process. The tensile strength, flexural strength, short beam interlaminar shear strength, and porosity of the carbon fiber composite material were tested, and the test results are shown in Table 1;

[0132] The temperature conditions for preparing the carbon fiber composite material are: 4h / 100°C+1h / 130°C+1h / 140°C+1h / 150°C

[0133] The carbon fiber composite material reinforcement material uses T700 carbon fiber, the sizing agent is epoxy vinyl ester resin, and the ply structure is 0° / 90° orthogonal ply;

[0134]

[0135] The carbon fiber composite material has a resin content of 36±0.5%.

[0136] The viscosity of solid epoxy vinyl ester resins is measured in accordance with ISO 2884-1.

[0137] Test method for storage period of solid epoxy vinyl ester resin: When the resin viscosity increases to twice the basic viscosity, the performance of the impregnated fiber is affected. The epoxy vinyl ester resin is stored in an environment of 23±2℃, and the time for the test viscosity to increase to twice is recorded as the storage period.

[0138] The volume shrinkage of solid epoxy vinyl ester resin is carried out according to ISO 3521.

[0139] The tensile strength of the composites was tested according to ISO 527-2.

[0140] The flexural strength and boiling water retention rate of the composite materials were tested in accordance with ISO 14125.

[0141] The void content of composite materials is determined according to EN 2564

[0142] The interlaminar shear strength of composite short beams was tested according to ISO 14130.

[0143] Table 1 Performance test results of Examples 1-5 and Comparative Examples 1-4

[0144]

[0145] From Table 1, we can see that:

[0146] 1. Compared with the carbon fiber composite materials prepared in Comparative Example 1-2, the storage period at 25°C of Example 1-5 was greatly improved, the tensile strength, bending strength, and interlaminar shear strength were more than 50% higher, and the void ratio was significantly reduced;

[0147] 2. The carbon fiber composite material prepared in Example 4 has the highest interlaminar shear strength, which proves that the hyperbranched polymer helps to improve the interface between epoxy vinyl ester resin and carbon fiber.

[0148] 3. Compared with Comparative Examples 1-3, the volume shrinkage of Examples 1-5 and Comparative Example 4 is significantly reduced, which proves that the hyperbranched polymer can effectively reduce the shrinkage of the system.

[0149] 4. The bending and boiling water retention rate of comparative example 2 is the lowest, which proves that the inclusion of ester cross-linking monomers will reduce the water resistance of the system. The bending and boiling water retention rates of examples 1-5 of the present invention are all higher than 90%.

[0150] 5. The test examples prove that Examples 1-5 meet the requirements of the technical solution of the present invention, and the obtained solid epoxy vinyl ester resin can be used to prepare composite materials with carbon fiber prepreg.

[0151] Attached Figure 1 The viscosity-temperature curve of the epoxy vinyl ester resin in Example 3 shows that the epoxy vinyl resin composition shows an exponential decrease at 60-135°C. Figure 2 The viscosity-time curve of the epoxy vinyl ester resin composition at 120°C of Example 3 is shown in the following figure. Figure 3 This is the viscosity-time curve of the epoxy vinyl ester resin composition of Example 3 at 100°C. In a short period of time, the viscosity of the epoxy vinyl ester resin composition of Example 3 increases rapidly.

[0152] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A solid epoxy vinyl ester resin composition, characterized in that It includes bisphenol A type epoxy vinyl ester resin, polyether polyol glycidyl ether acrylate, hyperbranched polymer and thermal initiator, and does not contain cross-linking monomer; The molar ratio of the bisphenol A type epoxy vinyl ester resin to the polyether polyol glycidyl ether acrylate is 1:1 to 20:1; The molar ratio of the bisphenol A epoxy vinyl ester resin to the hyperbranched polymer is 33.7:1-109:1; The molecular weight of the hyperbranched polymer is 1000-10000; the hyperbranched polymer is selected from one or more of carboxyl-terminated hyperbranched polyester, hydroxyl-terminated hyperbranched polyester and terminal unsaturated double-bond hyperbranched polyurethane; The active oxygen content of the thermal initiator is 4-9%; the thermal initiator is selected from one or more of benzoyl peroxide, tert-butyl perbenzoate and tert-butyl peroxy-2-ethylhexanoate.

2. The solid epoxy vinyl ester resin composition according to claim 1, characterized in that The bisphenol A epoxy vinyl ester resin is obtained by esterification reaction of bisphenol A epoxy resin and unsaturated monocarboxylic acid; The polyether polyol glycidyl ether acrylate is obtained by esterification reaction of polyether polyol glycidyl ether and unsaturated monocarboxylic acid.

3. The solid epoxy vinyl ester resin composition according to claim 1, characterized in that The molar ratio of the bisphenol A epoxy vinyl ester resin to the polyether polyol glycidyl ether acrylate is 2.5:1-17.5:1; The unsaturated double bond content of the solid epoxy vinyl ester resin composition is 0.15 mol / 100 g to 0.40 mol / 100 g.

4. The solid epoxy vinyl ester resin composition according to claim 1, characterized in that The solid epoxy vinyl ester resin composition comprises the following raw materials in percentage by weight: The inhibitor 1# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole; The catalyst is selected from one or more of benzyltrimethylammonium chloride, triphenylphosphine, benzyltriethylammonium chloride, benzyltriethylammonium chloride ammonium bromide, imidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole; The inhibitor 2# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole.

5. The solid epoxy vinyl ester resin composition according to claim 4, characterized in that The solid epoxy vinyl ester resin composition comprises the following raw materials in percentage by weight:

6. A solid epoxy vinyl ester resin composition according to claim 1, characterized in that: The hyperbranched polymer is a terminal hydroxyl hyperbranched polyester with a molecular weight of 2000-6000 and contains 20-50 hydroxyl groups per mol.

7. A solid epoxy vinyl ester resin composition according to any one of claims 1 to 5, characterized in that: The epoxy equivalent of the bisphenol A epoxy resin is 180 to 515 g / mol.

8. A solid epoxy vinyl ester resin composition according to claim 7, characterized in that: The bisphenol A epoxy resin is selected from one or more of E51 epoxy resin, E44 epoxy resin and E20 epoxy resin, the epoxy equivalent of the E51 epoxy resin is 180-200 g / mol, the epoxy equivalent of the E44 epoxy resin is 210-240 g / mol, and the epoxy equivalent of the E20 epoxy resin is 485-515 g / mol.

9. A solid epoxy vinyl ester resin composition according to claim 8, characterized in that: The bisphenol A type epoxy resin is E51 type epoxy resin and E44 type epoxy resin in a mass ratio of 20-50:50-80.

10. A solid epoxy vinyl ester resin composition according to any one of claims 1 to 5, characterized in that: The polyether polyol glycidyl ether is a low-viscosity epoxy resin.

11. A solid epoxy vinyl ester resin composition according to claim 10, characterized in that: The molecular weight of the polyether polyol glycidyl ether is 100-800, the viscosity is 5-200 mPa.s, and the epoxy equivalent is 50-400 g / mol.

12. A solid epoxy vinyl ester resin composition according to claim 11, characterized in that: The polyether polyol glycidyl ether is selected from one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, 1,6-hexanediol glycidyl ether and cardanol glycidyl ether.

13. A solid epoxy vinyl ester resin composition according to claim 1, characterized in that: The thermal initiator is tert-butyl perbenzoate, and the active oxygen content is 8%.

14. A solid epoxy vinyl ester resin composition according to any one of claims 1 to 5, characterized in that: The unsaturated monocarboxylic acid is selected from methacrylic acid and / or acrylic acid.

15. A method for preparing the solid epoxy vinyl ester resin composition according to any one of claims 1 to 14, characterized in that: The steps include: (1) mixing bisphenol A epoxy resin and polyether polyol glycidyl ether, heating to 90-100° C. and stirring evenly to obtain a first reactant; (2) adding a hyperbranched polymer and an unsaturated monocarboxylic acid to the first reactant, controlling the temperature of the reaction system to 85-95° C., and stirring uniformly to obtain a second reactant; the molecular weight of the hyperbranched polymer is 1000-10000; the hyperbranched polymer is selected from one or more of a carboxyl-terminated hyperbranched polyester, a hydroxyl-terminated hyperbranched polyester, and an unsaturated double-bond-terminated hyperbranched polyurethane; (3) adding a polymerization inhibitor 1# to the second reactant, stirring evenly, adding a catalyst, and reacting at 120-125° C. for 4.0-5.0 hours, and controlling the acid value of the reaction system to be less than 7 mg KOH / g during the reaction, to obtain a third reactant; wherein the polymerization inhibitor 1# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole; and the catalyst is selected from one or more of benzyltrimethylammonium chloride, triphenylphosphine, benzyltriethylammonium chloride, benzyltriethylammonium chloride bromide, imidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole; (4) adding a polymerization inhibitor 2# to the third reactant, cooling the mixture to 68-70° C. and stirring the mixture to obtain a fourth reactant; wherein the polymerization inhibitor 2# is selected from one or more of hydroquinone, p-benzoquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-cresol, methylhydroquinone and p-hydroxyanisole; (5) adding a thermal initiator to the fourth reactant and stirring again to obtain a solid epoxy vinyl ester resin composition; the active oxygen content of the thermal initiator is 4 to 9%; the thermal initiator is selected from one or more of benzoyl peroxide, tert-butyl perbenzoate and tert-butyl peroxy-2-ethylhexanoate.

16. The preparation method according to claim 15, characterized in that: The molar ratio of the bisphenol A epoxy resin to the polyether polyol glycidyl ether in step (1) is 1:1 to 20:1; The bisphenol A epoxy resin in step (1) has an epoxy equivalent of 180 to 515 g / mol; The polyether polyol glycidyl ether in step (1) is a low-viscosity epoxy resin; The molar ratio of the bisphenol A epoxy resin in step (1) to the hyperbranched polymer in step (2) is 33.7:1-109:1; The unsaturated monocarboxylic acid in step (2) is selected from methacrylic acid and / or acrylic acid; The stirring time in step (2) is 18-22 minutes; The stirring time in step (3) is 8-12 minutes; The catalyst in step (3) is slowly added within 20 minutes; The stirring time in step (4) is 8-12 minutes; The stirring time in step (5) is 8-12 minutes.

17. The preparation method according to claim 16, characterized in that: In step (1), the molar ratio of the bisphenol A epoxy resin to the polyether polyol glycidyl ether is 2.5:1-17.5:

1.

18. The preparation method according to claim 16, characterized in that: The bisphenol A epoxy resin in step (1) is selected from one or more of E51 epoxy resin, E44 epoxy resin and E20 epoxy resin, the epoxy equivalent of the E51 epoxy resin is 180-200 g / mol, the epoxy equivalent of the E44 epoxy resin is 210-240 g / mol, and the epoxy equivalent of the E20 epoxy resin is 485-515 g / mol.

19. The preparation method according to claim 18, characterized in that: The bisphenol A epoxy resin in step (1) is E51 epoxy resin and E44 epoxy resin in a mass ratio of 20-50:50-80.

20. The preparation method according to claim 16, characterized in that: The molecular weight of the polyether polyol glycidyl ether is 100-800, the viscosity is 5-200 mPa.s, and the epoxy equivalent is 50-400 g / mol.

21. The preparation method according to claim 20, characterized in that: The polyether polyol glycidyl ether is selected from one or more of polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, 1,6-hexanediol glycidyl ether and cardanol glycidyl ether.

22. The preparation method according to claim 15, characterized in that: The hyperbranched polymer is a terminal hydroxyl hyperbranched polyester with a molecular weight of 2000-6000 and contains 20-50 hydroxyl groups per mol.

23. The preparation method according to claim 15, characterized in that: The thermal initiator in step (5) is tert-butyl perbenzoate, with an active oxygen content of 8%.

24. The preparation method according to claim 15, characterized in that: The solid epoxy vinyl ester resin composition comprises the following raw materials in percentage by weight:

25. The preparation method according to claim 24, characterized in that: The solid epoxy vinyl ester resin composition comprises the following raw materials in percentage by weight:

26. Use of the solid epoxy vinyl ester resin composition according to any one of claims 1 to 14 or the solid epoxy vinyl ester resin composition prepared by the preparation method according to any one of claims 15 to 25 in preparing carbon fiber prepreg.

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