Pultrusion epoxy resin composition and application thereof, epoxy resin material and preparation method and application thereof

Abstract

The invention relates to the field of carbon fiber epoxy resin modification and preparation, in particular to a pultrusion epoxy resin composition and application thereof, an epoxy resin material and a preparation method and application of the epoxy resin material. Wherein the component A comprises an epoxy resin mixture, a diluent, a coupling agent, a modified carbon nanotube and a release agent; the epoxy resin mixture comprises at least two of polyfunctional epoxy resin, rigid particle modified bisphenol epoxy resin, hydantoin epoxy resin and alicyclic epoxy resin; the component B comprises a curing agent, a toughening agent, a composite accelerant and a catalyst; the composite accelerant is selected from at least two of modified imidazole, chromium acetylacetonate and triphenyl ethyl phosphonium bromide; the composition overcomes the defects that the viscosity of an epoxy resin system is relatively high and all the components need to be mixed at relatively high temperature, and the heat resistance and the strength retention rate are high while the toughness is improved.

Description

Technical Field

[0001] The invention relates to the field of carbon fiber epoxy resin modification and preparation, and in particular to a pultruded epoxy resin composition and application thereof, an epoxy resin material and a preparation method and application thereof. Background Art

[0002] Epoxy resin has the advantages of excellent mechanical properties, good bonding properties and strong process adaptability. It is the most widely used type of resin in the resin matrix of high-performance composite materials and has the most application fields. Among them, due to its high production efficiency and low cost, pultruded epoxy resin is a common matrix for carbon fiber composite materials and can be used in wind power, building structural materials, carbon fiber composite wires, military industry and other fields. However, epoxy resin has the disadvantage of insufficient toughness after curing and cannot effectively exert the performance of carbon fiber. In particular, the high Tg epoxy resin system is more brittle, which limits the application of resin-based carbon fiber composite materials.

[0003] In the prior art, the most studied toughening modification of resin matrix is ​​to add synthetic rubber, thermoplastic resin, nanoparticles, etc. to achieve toughening purpose. For example, CN201810108691.5 uses alicyclic epoxy resin, anhydride curing agent, nano-silica and silicone rubber core-shell particle toughening agent to prepare a low-viscosity and high-heat-resistant epoxy resin composition. After curing, it has good heat resistance and a glass transition temperature of 220-260°C, but its elongation at break is less than 1%, reflecting the poor toughness of the resin system. CN201110183270.7 A high-temperature resistant epoxy resin composition for rapid pultrusion and its preparation method. The use of latent curing agent in combination with mixed amine curing agent can make the pultruded product have a lower curing temperature and quickly cure within a certain period of time, shorten the curing time, and thus improve the pultrusion speed and production efficiency; but the amine curing agent has a short application period and low toughness. CN202211376902.6 discloses a pultruded epoxy resin composition for wind turbine blades, which uses liquid petroleum resin (unsaturated polyester resin) to reduce the viscosity of epoxy resin, and uses polymer polyols to increase the elongation at break of pultruded epoxy resin castings to prevent cracks in pultruded plates. However, the added additives have compatibility issues, resulting in low glass transition temperature and low tensile strength. CN201910933400.0 uses polyimide resins containing active reactive groups for toughening and ensuring that the pultruded resin of the carbon fiber cable core has high heat resistance, electrical insulation, etc. However, the interface bonding between thermoplastic resin and carbon fiber is weak, and the load on the carbon fiber precursor cannot be effectively transferred to the resin, forming an overall force, resulting in poor performance. Summary of the invention

[0004] In summary, in the carbon fiber composite resin system currently reported to be toughened by a single method, it is difficult to effectively solve the contradiction between toughness and heat resistance, curing speed and application period. The compatibility problem of the toughening agent will lead to poor overall performance, low elongation at break, poor processability or heat resistance, and other defects.

[0005] Therefore, the purpose of the present invention is to overcome the poor comprehensive performance of the pultruded epoxy resin system in the prior art, and the balance contradiction between toughness, heat resistance, curing speed and tensile strength. For the first time, a pultruded epoxy resin composition and its application, an epoxy resin material and its preparation method and application are proposed.

[0006] The first aspect of the present invention provides a pultruded epoxy resin composition, which comprises component A and component B; wherein component A comprises an epoxy resin mixture, a diluent, a coupling agent, modified carbon nanotubes and a release agent; the epoxy resin mixture comprises at least two of a multifunctional epoxy resin, a rigid particle modified bisphenol epoxy resin, a hydantoin epoxy resin and an alicyclic epoxy resin; component B comprises a curing agent, a toughening agent, a composite accelerator and a catalyst; the composite accelerator is selected from at least two of modified imidazole, chromium acetylacetonate and triphenylethylphosphonium bromide. The composition solves the defects of the epoxy resin system having a high viscosity and requiring the components to be mixed at a high temperature, and has high heat resistance and strength retention rate while improving toughness.

[0007] The second aspect of the present invention provides use of the epoxy resin composition of the present invention in processing and preparing epoxy resin materials.

[0008] The third aspect of the present invention provides a method for preparing an epoxy resin material, which is prepared using the epoxy resin composition of the present invention. The method comprises: (1) subjecting the epoxy resin mixture in component A, a diluent, a coupling agent, modified carbon nanotubes and a release agent to a first contact to obtain a mixture I; (2) subjecting the curing agent, a toughening agent, a composite accelerator and a catalyst in component B to a second contact to obtain a mixture II; and (3) subjecting the mixture I to a third contact with the mixture II, and curing to obtain the epoxy resin material.

[0009] A fourth aspect of the present invention provides application of the epoxy resin material prepared by the preparation method of the present invention in a carbon fiber composite material.

[0010] Through the above technical solution, the present invention has the following beneficial effects:

[0011] 1. The pultruded epoxy resin composition provided by the present invention realizes effective dispersion and compatibility of various components of the system, is easy to operate, and has a wide range of applications. The epoxy resin material prepared by the composition has a glass transition temperature of 160-190°C, which can achieve the beneficial effects of simultaneously improving toughness, heat resistance and strength;

[0012] 2. Use epoxy resin mixture and control the viscosity of the mixture to be less than 10000CP to ensure the processability of pultrusion and wettability of carbon fiber;

[0013] 3. The composite accelerator is used to adjust the curing temperature and use time, so that the epoxy resin system has the advantages of high activity, fast curing speed and long application period (>24h);

[0014] 4. By adding toughening agents, the obtained epoxy resin material has the advantages of high toughness and high strength while being resistant to high temperatures, and having small shrinkage upon curing. DETAILED DESCRIPTION

[0015] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0016] The invention provides a pultruded epoxy resin composition, which comprises component A and component B; wherein component A comprises an epoxy resin mixture, a diluent, a coupling agent, a modified carbon nanotube and a release agent; the epoxy resin mixture comprises at least two of a multifunctional epoxy resin, a rigid particle modified bisphenol epoxy resin, a hydantoin epoxy resin and an alicyclic epoxy resin; component B comprises a curing agent, a toughening agent, a composite accelerator and a catalyst; the composite accelerator is selected from at least two of modified imidazole, chromium acetylacetonate and triphenylethylphosphonium bromide.

[0017] In the present invention, in the pultruded epoxy resin composition, the weight ratio of component A to component B is in a wide range, and according to a preferred embodiment of the present invention, the weight ratio of component A to component B is 1:(0.9-1.2) by weight. By adopting the above preferred embodiment, the heat resistance and toughness of the resin system can be ensured, and the defects of the epoxy resin system having high viscosity and requiring the components to be mixed at a higher temperature can be solved.

[0018] In the present invention, the weight ratio of the epoxy resin mixture, diluent, coupling agent, modified carbon nanotubes and release agent in component A can be selected in a wide range by weight. According to a preferred embodiment of the present invention, the weight ratio of the epoxy resin mixture, diluent, coupling agent, modified carbon nanotubes and release agent in component A is 100:(5-20):(2-6):(2-6):(1-3) by weight. By adopting the above preferred embodiment, the toughness and strength can be improved while adjusting the viscosity.

[0019] In the present invention, the weight ratio of the curing agent, toughening agent, composite accelerator and catalyst in component B is relatively wide. According to a preferred embodiment of the present invention, the weight ratio of the curing agent, toughening agent, composite accelerator and catalyst in component B is 100: (10-20): (1-4): (1-5). By adopting the above preferred embodiment, it can be ensured that the curing system has a fast curing speed and a long pot life (> 24h), while improving toughness and strength.

[0020] According to a preferred embodiment of the present invention, the epoxy resin mixture in component A is a mixture of a multifunctional epoxy resin and a rigid particle-modified bisphenol epoxy resin.

[0021] According to a preferred embodiment of the present invention, the weight ratio of the multifunctional epoxy resin to the rigid particle modified bisphenol epoxy resin in component A is 3-1.

[0022] According to a preferred embodiment of the present invention, the viscosity of the multifunctional epoxy resin in component A after mixing with the rigid particle modified bisphenol epoxy resin is less than 10000 CP.

[0023] By adopting the aforementioned preferred embodiment, it can be ensured that the heat resistance and system viscosity meet the process requirements.

[0024] According to a preferred embodiment of the present invention, the rigid particles in component A are rubber particles and / or core-shell particles with a particle size of 10-100 nm.

[0025] According to a preferred embodiment of the present invention, the bisphenol epoxy resin in component A is selected from bisphenol A and / or bisphenol F epoxy resins having a viscosity less than 5000 CP.

[0026] By adopting the above-mentioned preferred implementation mode, the mixing and toughening effects can be optimized and the viscosity of the system can be ensured to meet the process requirements.

[0027] According to a preferred embodiment of the present invention, the multifunctional epoxy resin in component A is selected from a multifunctional epoxy resin with a viscosity of less than 6100 CP; more preferably, a glycidylamine type epoxy resin with a viscosity of less than 6100 CP. By adopting the above preferred embodiment, the heat resistance can be ensured while the viscosity of the system meets the process requirements.

[0028] In the present invention, there is no special requirement for the selection of the diluent in component A. According to a preferred embodiment of the present invention, the diluent is selected from at least one of glycidylamine, glycidyl ester, and glycidyl ether. Glycidylamine is used as an example in the embodiment, but the scope of the present invention is not limited thereto. By adopting the aforementioned preferred embodiment, it is possible to ensure heat resistance while reducing the viscosity of the system and improving the wettability of the resin system to the fiber.

[0029] In the present invention, there is no special requirement for the selection of the coupling agent of component A. According to a preferred embodiment of the present invention, the coupling agent is selected from at least one of KH550, KH570 and KH591. KH550 is used as an example in the embodiment, but the scope of the present invention is not limited thereto. By adopting the aforementioned preferred embodiment, the compatibility of the components of the mixed system and the interface strength of the fiber can be improved.

[0030] In the present invention, there is no special requirement for the selection of the modified carbon nanotubes described in component A. According to a preferred embodiment of the present invention, the modified carbon nanotubes are selected from at least one of hydroxylated multi-walled carbon nanotubes, carboxylated multi-walled carbon nanotubes and amino multi-walled carbon nanotubes. The hydroxylated multi-walled carbon nanotubes are used as an example in the embodiment, but the scope of the present invention is not limited thereto. According to a preferred embodiment of the present invention, the particle size of the hydroxylated multi-walled carbon nanotubes is 20-30nm and the length is 10-30nm. By adopting the aforementioned preferred embodiment, the resin system can achieve better toughening effect and mechanical properties.

[0031] In the present invention, there is no special requirement for the selection of the release agent of component A. According to a preferred embodiment of the present invention, the release agent is selected from at least one of a stearic acid release agent, a silicone resin and an epoxy-modified silicone oil. The stearic acid release agent is used as an exemplary embodiment in the embodiment, but the scope of the present invention is not limited thereto. By adopting the aforementioned preferred embodiment, the friction of the solidified material in the mold can be reduced, and the traction force of the pultrusion process can be reduced.

[0032] In the present invention, there is no special requirement for the selection of the curing agent in component B. According to a preferred embodiment of the present invention, the curing agent is selected from at least one of methyl hexahydrophthalic anhydride, methyl nadic anhydride and methyl tetrahydrophthalic anhydride. In the embodiments, methyl nadic anhydride is used as an example, but the scope of the present invention is not limited thereto. By adopting the aforementioned preferred embodiment, the process requirements of heat resistance of the system and fast curing speed can be taken into account.

[0033] In the present invention, there is no special requirement for the selection of the toughening agent described in component B. According to a preferred embodiment of the present invention, the toughening agent is selected from at least one of polyether polyols, liquid polysulfide rubber and liquid nitrile rubber, and further preferably polyether polyols are selected from polyethylene glycol and / or polypropylene glycol. In the embodiment, polypropylene glycol is used for exemplary description, but the scope of the present invention is not limited thereto. By adopting the aforementioned preferred embodiment, the toughness and processability (easy demolding) of the cured product can be further improved.

[0034] According to a preferred embodiment of the present invention, the composite accelerator in component B is a mixture of modified imidazole and chromium acetylacetonate.

[0035] According to a preferred embodiment of the present invention, the weight ratio of the modified imidazole to chromium acetylacetonate in component B is 1-3.

[0036] By adopting the above preferred embodiment, the curing temperature can be lowered, so that the epoxy resin system has high activity, fast curing speed and long application period;

[0037] In the present invention, there is no special requirement for the selection of the catalyst. According to a preferred embodiment of the present invention, the catalyst is selected from at least two of tetramethylammonium chloride, benzyltriethylammonium chloride and hexadecyltrimethylammonium bromide, preferably a mixture of tetramethylammonium chloride and benzyltriethylammonium chloride, and the weight ratio of tetramethylammonium chloride to benzyltriethylammonium chloride is 0.5-1. By adopting the above preferred embodiment, the curing speed and the compatibility between the components of the curing system can be improved.

[0038] The present invention provides application of the epoxy resin composition of the present invention in processing and preparing epoxy resin materials.

[0039] The present invention provides a method for preparing an epoxy resin material, which is prepared by using the epoxy resin composition of the present invention. The method comprises: (1) subjecting an epoxy resin mixture in component A, a diluent, a coupling agent, a modified carbon nanotube and a release agent to a first contact to obtain a mixture I; (2) subjecting a curing agent, a toughening agent, a composite accelerator and a catalyst in component B to a second contact to obtain a mixture II; and (3) subjecting the mixture I to a third contact with the mixture II, and curing the mixture to obtain the epoxy resin material.

[0040] In the present invention, in step (1), step (2) and / or step (3), there are no special requirements for the selection of the first contact condition, the second contact condition and / or the third contact condition, and they can be carried out with reference to the prior art.

[0041] According to a preferred embodiment of the present invention, in step (1), the first contact temperature is 40-100° C., preferably 52-65° C.; 60° C. is used as an example in the embodiment, but the scope of the present invention is not limited thereto.

[0042] According to a preferred embodiment of the present invention, in step (1), the first contact time is 60-120 min, and 90 min is used as an example in the examples, but the scope of the present invention is not limited thereto.

[0043] According to a preferred embodiment of the present invention, in step (2), the second contact temperature is 40-80°C, preferably 52-65°C; 60°C is used as an example in the embodiment, but the scope of the present invention is not limited thereto.

[0044] According to a preferred embodiment of the present invention, in step (2), the second contact time is 30-60 min, and 45 min is used as an example in the examples, but the scope of the present invention is not limited thereto.

[0045] According to a preferred embodiment of the present invention, in step (3), the third contact temperature is 20-60°C, preferably 40-50°C; 50°C is used as an example in the examples, but the scope of the present invention is not limited thereto.

[0046] According to a preferred embodiment of the present invention, in step (3), the third contact time is 20-80 min, and 60 min is used as an example in the examples, but the scope of the present invention is not limited thereto.

[0047] According to a preferred embodiment of the present invention, the contact temperature in step (3) is lower than the first contact temperature in step (1) and the second contact temperature in step (2).

[0048] By adopting the aforementioned preferred embodiment, simple operation can be adopted to ensure that the system obtains a better mixing effect.

[0049] In the present invention, there is no special requirement for the curing conditions in step (3), and the curing conditions can be carried out with reference to the prior art. The following is an exemplary description, but the scope of the present invention is not limited thereby.

[0050] According to a preferred embodiment of the present invention, the curing temperature in step (3) is 100-180°C, preferably 110-150°C.

[0051] According to a preferred embodiment of the present invention, the curing time in step (3) is 1-6 hours, preferably 2-5 hours.

[0052] By adopting the aforementioned preferred embodiments, the polymer material can obtain the best comprehensive performance.

[0053] The present invention provides application of the epoxy resin material prepared by the preparation method of the present invention in a carbon fiber composite material.

[0054] The test methods and standards for epoxy resin materials in the present invention are as follows:

[0055] Tensile strength (MPa): GB / T 2567-2008;

[0056] Tensile modulus (GPa): GB / T 2567-2008;

[0057] Flexural strength (MPa): GB / T 2567-2008;

[0058] Flexural modulus (GPa): GB / T 2567-2008;

[0059] Elongation at break (%): GB / T 2567-2008;

[0060] Tg (℃): GB / T 19466.2-2004;

[0061] Viscosity (CP): GB / T 22314—2008.

[0062] Example 1

[0063] (1) 50 parts by weight of a glycidylamine epoxy resin MF4101 having a viscosity of 4000 CP and 50 parts by weight of a rigid particle modified bisphenol F epoxy resin REF-170 having a viscosity of 4000 CP (rubber particles having a rigid particle size of 50 nm) (the viscosity of the glycidylamine epoxy resin and the rigid particle modified bisphenol F epoxy resin after mixing is 4000 CP), 10 parts of a glycidylamine diluent MF-2133, 3 parts of a coupling agent KH550, 3 parts of hydroxylated multi-walled carbon nanotubes XFM2 (particle size of 20 nm and length of 10 nm), and 2 parts of a stearic acid release agent CLI-7011 are stirred at 60° C. for 90 min, and then cooled to obtain component A;

[0064] (2) 100 parts by weight of curing agent methylnadic anhydride MNA, 15 parts of polyethylene glycol (molecular weight 400), 2 parts of modified liquid imidazole Lepcu HD2004, 0.8 parts of chromium acetylacetonate, 1 part of tetramethylammonium chloride and 2 parts of benzyltriethylammonium chloride were stirred at 60° C. for 45 minutes to obtain component B;

[0065] (3) mixing component A and component B at a weight ratio of 0.98 at 50° C. for 60 minutes to obtain an epoxy resin system;

[0066] (4) curing the epoxy resin system obtained in step 3 at 150° C. for 3 h to obtain an epoxy resin material;

[0067] The performance test results are shown in Table 1.

[0068] Example 2

[0069] (1) 75 parts by weight of a glycidylamine epoxy resin MF4101 with a viscosity of 3000 CP, 25 parts by weight of a rigid particle modified bisphenol A epoxy resin E-03 with a viscosity of 5000 CP (rigid particle diameter 100 nm rubber particle) (the viscosity of the glycidylamine epoxy resin and the rigid particle modified bisphenol A epoxy resin after mixing is 3500 CP), 5 parts of a glycidylamine diluent MF-2133, 2 parts of a coupling agent KH550, 2 parts of hydroxylated multi-walled carbon nanotubes XFM2 (particle diameter 25 nm length 20 nm), and 1 part of a stearic acid release agent CLI-7011 are stirred at 60° C. for 90 min, and then cooled to obtain component A;

[0070] (2) 100 parts by weight of curing agent methylnadic anhydride MNA, 15 parts of polypropylene glycol (molecular weight 600), 0.5 parts of modified liquid imidazole Lepcu HD2004, 0.5 parts of chromium acetylacetonate, 0.5 parts of tetramethylammonium chloride and 0.5 parts of benzyltriethylammonium chloride were stirred at 60° C. for 45 minutes to obtain component B;

[0071] (3) mixing component A and component B at a weight ratio of 0.94 at 50° C. for 60 minutes to obtain an epoxy resin system;

[0072] (4) curing the epoxy resin system obtained in step 3 at 110° C. for 2 h to obtain an epoxy resin material;

[0073] The performance test results are shown in Table 1.

[0074] Example 3

[0075] (1) 60 parts by weight of a glycidylamine epoxy resin MF4101 having a viscosity of 6000 CP, 40 parts by weight of a rigid particle modified bisphenol F epoxy resin REF-170 having a viscosity of 3000 CP (rubber particles having a rigid particle size of 10 nm) (the viscosity of the glycidylamine epoxy resin and the rigid particle modified bisphenol F epoxy resin after mixing is 4500 CP), 20 parts of a glycidylamine diluent MF-2133, 6 parts of a coupling agent KH550, 6 parts of hydroxylated multi-walled carbon nanotubes XFM2 (particle size of 30 nm and length of 30 nm), and 3 parts of a stearic acid release agent CLI-7011 were stirred at 60° C. for 90 min, and then cooled to obtain component A;

[0076] (2) 100 parts by weight of a curing agent methylnadic anhydride MNA, 20 parts of polyethylene glycol (molecular weight 400), 3 parts of a modified liquid imidazole Lepcu HD2004, 1 part of chromium acetylacetonate, 2 parts of tetraethylammonium chloride and 3 parts of benzyltriethylammonium chloride were stirred at 60° C. for 45 minutes to obtain component B;

[0077] (3) mixing component A and component B at a weight ratio of 1.05 at 50° C. for 60 minutes to obtain an epoxy resin system;

[0078] (4) curing the epoxy resin system obtained in step (3) at 130° C. for 5 h to obtain an epoxy resin material;

[0079] The performance test results are shown in Table 1.

[0080] Example 4

[0081] All conditions are the same as those in Example 1, except that: in step (1), 50 parts by weight of the glycidylamine epoxy resin MF4101 with a viscosity of 4000 is replaced with 50 parts by weight of a high-viscosity multifunctional epoxy resin AG80 with a viscosity of 12000 (the viscosity after mixing with the rigid particle modified bisphenol A type epoxy resin is 7000 CP);

[0082] The performance test results are shown in Table 1.

[0083] Example 5

[0084] All conditions are the same as those in Example 1, except that: in step (1), 50 parts by weight of rigid particle-modified bisphenol F epoxy resin REF-170 (rigid particle diameter 70 nm core-shell particles) with a viscosity of 4000 CP is selected (the viscosity after mixing is the same as that in Example 1);

[0085] The performance test results are shown in Table 1.

[0086] Example 6

[0087] All conditions are the same as those in Example 1, except that in step (1): 20 parts by weight of a glycidylamine epoxy resin having a viscosity of 4000 and 80 parts by weight of a rigid particle-modified bisphenol F epoxy resin REF-170 (rubber particles having a rigid particle size of 50 nm) having a viscosity of 4000 CP (the viscosity after mixing is the same as that in Example 1);

[0088] The performance test results are shown in Table 1.

[0089] Example 7

[0090] All conditions are the same as in Example 1, except that: in step (2), 15 parts of liquid polysulfide rubber JLY-121;

[0091] The performance test results are shown in Table 1.

[0092] Example 8

[0093] All conditions were the same as in Example 1, except that: in step (2), 2.2 parts of modified liquid imidazole Lepcu HD2004 and 0.6 parts of chromium acetylacetonate;

[0094] The performance test results are shown in Table 1.

[0095] Example 9

[0096] All conditions were the same as in Example 1, except that: in step (2), 0.8 parts of tetramethylammonium chloride and 2.2 parts of benzyltriethylammonium chloride were used;

[0097] The performance test results are shown in Table 1.

[0098] Example 10

[0099] All conditions are the same as those in Example 1, except that: in step (4), the epoxy resin system obtained in step (3) is cured at 100° C. for 1 h to obtain an epoxy resin material;

[0100] The performance test results are shown in Table 1.

[0101] Embodiment 11

[0102] All conditions are the same as those in Example 1, except that: in step (4), the epoxy resin system obtained in step (3) is cured at 180° C. for 6 h to obtain an epoxy resin material;

[0103] The performance test results are shown in Table 1.

[0104] Example 12

[0105] All conditions are the same as in Example 1, except that: in step (1), the rubber particles with a rigid particle size of 50 nm are replaced with rubber particles with a rigid particle size of 8 nm;

[0106] The performance test results are shown in Table 1.

[0107] Example 13

[0108] All conditions were the same as in Example 1, except that: the contact temperature in step (3) was 60°C;

[0109] The performance test results are shown in Table 1.

[0110] Comparative Example 1

[0111] All conditions are the same as those in Example 1, except that: in step (1), 100 parts by weight of glycidylamine epoxy resin MF4101 with a viscosity of 4000 CP is added, and rigid particle modified bisphenol F epoxy resin REF-170 with a viscosity of 4000 CP (rigid particle size 50 nm rubber particle) is not added;

[0112] The performance test results are shown in Table 1.

[0113] Comparative Example 2

[0114] All conditions are the same as those in Example 1, except that: in step (1), 100 parts by weight of rigid particle-modified bisphenol F type epoxy resin REF-170 (rigid particle size 50 nm rubber particles) with a viscosity of 4000 CP is added, and glycidylamine type epoxy resin MF4101 with a viscosity of 4000 is not added;

[0115] The performance test results are shown in Table 1.

[0116] Comparative Example 3

[0117] All conditions were the same as in Example 1, except that: 2.8 parts of modified liquid imidazole LepcuHD2004 and 0 parts of chromium acetylacetonate were added in step (2);

[0118] The performance test results are shown in Table 1.

[0119] Comparative Example 4

[0120] All conditions were the same as in Example 1, except that: 0 parts of modified liquid imidazole Lepcu HD2004 and 2.8 parts of chromium acetylacetonate were added in step (2);

[0121] The performance test results are shown in Table 1.

[0122] Comparative Example 5

[0123] All conditions were the same as in Example 1, except that: 3 parts of tetramethylammonium chloride and 0 parts of benzyltriethylammonium chloride were added in step (2);

[0124] The performance test results are shown in Table 1.

[0125] Comparative Example 6

[0126] All conditions were the same as in Example 1, except that: 3 parts of benzyltriethylammonium chloride and 0 parts of tetramethylammonium chloride were added in step (2);

[0127] The performance test results are shown in Table 1.

[0128] Comparative Example 7

[0129] All conditions were the same as in Example 1, except that no catalyst was added in step (2);

[0130] The performance test results are shown in Table 1.

[0131] Table 1

[0132]

[0133]

[0134] It can be seen from the results in Table 1 that the epoxy resin material obtained by the technical solution of the present invention has good toughness, strength and heat resistance, and the epoxy resin material obtained by the preferred embodiment has high comprehensive performance, that is, it can better take into account tensile strength, bending strength and elongation at break. The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to this. Within the scope of the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention, and all belong to the protection scope of the present invention.

Claims

1. A pultruded epoxy resin composition, characterized in that The composition comprises component A and component B; Wherein, component A comprises an epoxy resin mixture, a diluent, a coupling agent, modified carbon nanotubes and a release agent; the epoxy resin mixture comprises at least two of a multifunctional epoxy resin, a rigid particle modified bisphenol epoxy resin, a hydantoin epoxy resin and an alicyclic epoxy resin; Component B comprises a curing agent, a toughening agent, a composite accelerator and a catalyst; the composite accelerator is selected from at least two of modified imidazole, chromium acetylacetonate and triphenylethylphosphonium bromide.

2. The composition according to claim 1, wherein In parts by weight, the weight ratio of component A to component B is (0.9-1.2); and / or In parts by weight, the weight ratio of the epoxy resin mixture, the diluent, the coupling agent, the modified carbon nanotubes and the release agent in component A is 100:(5-20):(2-6):(2-6):(1-3); and / or The weight ratio of the curing agent, toughening agent, composite accelerator and catalyst in component B is 100:(10-20):(1-4):(1-5).

3. The composition according to claim 1 or 2, wherein In component A, The epoxy resin mixture is a mixture of a multifunctional epoxy resin and a rigid particle modified bisphenol type epoxy resin; Preferably, the weight ratio of the multifunctional epoxy resin to the rigid particle modified bisphenol epoxy resin is 3-1; and / or The viscosity of the multifunctional epoxy resin after mixing with the rigid particle modified bisphenol type epoxy resin is less than 10000CP; More preferably, The rigid particles are rubber particles and / or core-shell particles with a particle size of 10-100 nm; and / or The rigid particle modified bisphenol type epoxy resin is selected from bisphenol A and / or bisphenol F type epoxy resins having a viscosity less than 5000 CP; and / or The multifunctional epoxy resin is selected from a multifunctional epoxy resin having a viscosity of less than 6100 CP; more preferably, a glycidylamine type epoxy resin having a viscosity of less than 6100 CP; and / or The diluent is selected from at least one of glycidylamine, glycidyl ester, and glycidyl ether, preferably glycidylamine; and / or The coupling agent is selected from at least one of KH550, KH570 and KH591; and / or The modified carbon nanotubes are selected from at least one of hydroxylated multi-walled carbon nanotubes, carboxylated multi-walled carbon nanotubes and aminated multi-walled carbon nanotubes, preferably hydroxylated multi-walled carbon nanotubes, more preferably hydroxylated multi-walled carbon nanotubes having a particle size of 20-30 nm and a length of 10-30 nm; and / or The release agent is selected from at least one of stearic acid release agent, silicone resin and epoxy-modified silicone oil.

4. The composition according to any one of claims 1 to 3, wherein In component B, The curing agent is selected from at least one of methylhexahydrophthalic anhydride, methylnadic anhydride and methyltetrahydrophthalic anhydride; and / or The toughening agent is selected from at least one of polyether polyol, liquid polysulfide rubber and liquid nitrile rubber, preferably polyether polyol, and more preferably polyether polyol is selected from polyethylene glycol and / or polypropylene glycol; and / or The composite accelerator is a mixture of modified imidazole and chromium acetylacetonate, and the weight ratio of the modified imidazole to the chromium acetylacetonate is 1-3; and / or The catalyst is selected from at least two of tetramethylammonium chloride, benzyltriethylammonium chloride and hexadecyltrimethylammonium bromide, preferably a mixture of tetramethylammonium chloride and benzyltriethylammonium chloride, and the weight ratio of tetramethylammonium chloride to benzyltriethylammonium chloride is 0.5-1.

5. Use of the epoxy resin composition according to any one of claims 1 to 4 in processing and preparing epoxy resin materials.

6. A method for preparing an epoxy resin material, characterized in that: Prepared by using the epoxy resin composition according to any one of claims 1 to 4, the method comprises: (1) contacting the epoxy resin mixture in component A, a diluent, a coupling agent, modified carbon nanotubes, and a release agent to obtain a mixture I; (2) subjecting the curing agent, toughening agent, composite accelerator and catalyst in component B to a second contact to obtain a mixture II; (3) The mixture I and the mixture II are brought into contact with each other for the third time and cured to obtain an epoxy resin material.

7. The method according to claim 6, wherein: In step (1), the first contact conditions include: temperature 40-100°C, preferably 52-65°C; and / or time 60-120 min; and / or In step (2), the second contact conditions include: temperature 40-80°C, preferably 52-65°C; and / or time 30-60 min; and / or In step (3), the third contact conditions include: temperature 20-60°C, preferably 40-50°C; and / or time 20-80 min.

8. The method according to claim 6 or 7, wherein: The contact temperature in step (3) is lower than the first contact temperature in step (1) and the second contact temperature in step (2).

9. The method according to any one of claims 6 to 8, wherein: The curing conditions in step (3) include: temperature 100-180° C., preferably 110-150° C.; and / or time 1-6 h, preferably 2-5 h.

10. Use of the epoxy resin material prepared by the preparation method according to any one of claims 6 to 9 in carbon fiber composite materials.

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