Cycloolefin / epoxy resin mixtures, prepregs, composites and methods of making

Abstract

The application discloses a cyclic olefin / epoxy resin mixture, a prepreg, a composite material and a preparation method. The cyclic olefin / epoxy resin mixture, with the total amount of liquid epoxy resin and solid epoxy resin being 100 parts by weight, comprises the following components: liquid epoxy resin: 15-50 parts by weight; solid epoxy resin: 50-85 parts by weight; cyclic olefin resin: 5-25 parts by weight; modified ruthenium carbene catalyst: 0.0005-0.08 parts by weight; the modified ruthenium carbene catalyst comprises a ruthenium carbene compound or a salt thereof as shown in formula LG; wherein R1, R2 and R3 are independently C6-C 18 alkyl. Compared with the existing prepreg, the residual stress of the fiber prepreg prepared from the cyclic olefin / epoxy resin mixture is reduced, the warping deformation of the composite material cured and formed therefrom is obviously improved, the mechanical properties are improved, and the defects in the prior art can be overcome.

Description

Technical Field

[0001] This invention specifically relates to a cyclic olefin / epoxy resin mixture, a fiber prepreg, a composite material, and a preparation method thereof. Background Technology

[0002] Prepreg, as an intermediate material in composite materials, is a prepreg sheet product made by impregnating reinforcing fibers in a matrix. Commonly used reinforcing materials include carbon fiber, glass fiber, and aramid fiber. The matrix materials used are mainly polyester resin, epoxy resin, and thermoplastic resin. Prepreg composites are widely used in structural materials for aircraft, automobiles, industrial production equipment, and sports and leisure equipment industries due to their high specific strength, specific modulus of elasticity, good wear resistance, and corrosion resistance. Considering cost, processability, and the overall performance of composite materials, epoxy resin is usually used as the matrix resin in prepregs.

[0003] Current technologies primarily use epoxy resin as the main resin system with the addition of other additives to prepare prepregs. However, the performance of the resulting fiber prepreg composites is limited by the resin itself. Epoxy resin is a three-dimensional network thermosetting polymer, and the composites prepared from it have poor impact resistance (toughness), affecting their applications. Generally, rubber, elastomers, or block polymers are selected for modification, but the addition amount of these toughening agents is often very high, typically exceeding 20%. Improving the impact toughness of fiber prepreg composites often leads to significant losses in strength and modulus, and a substantial increase in cost. While using inorganic rigid particles for toughening modification does not result in a loss of strength and modulus, the toughness is not significantly improved. Furthermore, the poor compatibility of inorganic rigid particles with epoxy resin makes uniform dispersion difficult, leading to large defects in the epoxy resin and affecting its performance.

[0004] While existing technologies can improve product performance by adding various additives, these additives are often expensive, and improper control of the amount added can negatively impact overall quality and performance, even preventing the resin from curing properly. For example, epoxy resin products are relatively brittle, resulting in fiber prepregs with low impact resistance. Common modification methods involve toughening the epoxy resin itself, primarily by adding rubber particles and elastomers. However, this method is ineffective if the amount of additive is too small, while excessive amounts can lead to thickening, poor processability, decreased product quality, increased dispersion difficulty, and higher costs.

[0005] When using epoxy prepreg to prepare composite materials with a small thickness in current technology, warping deformation is prone to occur. This is often caused by residual stress during the prepreg molding process. The residual stress is caused by the large curing shrinkage rate of epoxy resin, the mismatch between the thermal expansion coefficients of epoxy resin and fiber, and uneven curing.

[0006] Chinese patent document CN113736211A describes a solution impregnation method for preparing dicyclopentadiene / epoxy resin composites using liquid epoxy. This method uses a large amount of organic solvents, causing severe environmental pollution, and the resin content of the prepared prepreg is difficult to control. Furthermore, the catalyst used can only be added to the dicyclopentadiene resin solution at temperatures below 60°C, resulting in a resin composite with high viscosity and uneven resin distribution on the fiber surface, failing to meet the quality requirements of the finished prepreg.

[0007] Ru metal carbene catalysts exhibit higher catalytic activity and better stability, especially Ru catalysts containing nitrogen-containing heterocyclic carbene ligands. These Ru catalysts have relatively stable structures, good functional group adaptability, and are not demanding in terms of reaction conditions. They can catalyze reactions even in the presence of impurities such as oxygen and water, and show good performance in ring-opening metathesis polymerization (ROMP) of compositions containing dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), and other cyclic olefins. However, existing commercially available ruthenium carbene catalysts can only be stored for long periods in a low-temperature, solid state. They deactivate rapidly in solution, exhibiting poor stability. Therefore, these commercially available catalysts must be prepared and used immediately. Furthermore, once solvents are used to dissolve the catalyst, solvent evaporation during subsequent curing processes can cause porosity and product volume shrinkage, severely affecting their performance.

[0008] To preserve ruthenium carbene catalysts for extended periods, the literature (Taber DF, Frankowski KJ, Grubb's catalyst in paraffin: An air-stable preparation of alkene metathesis[J]. J. Org. Chem., 2003, 68(22): 6047-6048.) reports the preparation of a solid mixture of ruthenium carbene catalyst and solid paraffin for long-term catalyst preservation. However, when using the catalyst, the solid mixture must first be dissolved or directly added to the reaction solution. When applied to olefin bulk ring-opening metathesis polymerization, it still requires fresh preparation and is not suitable for continuous production.

[0009] To address the shortcomings of ruthenium carbene catalysts, Chinese patent document CN112547126A discloses a novel ruthenium carbene catalyst that is liquid at room temperature. This eliminates the influence of solvents, eliminates the need for on-the-spot preparation, and allows for long-term storage, making it suitable for automated production. However, this catalyst is solid at room temperature and must be combined with chlorinated paraffin to become liquid. Furthermore, its main focus is on its nitrogen-heterocyclic carbene ligand, which largely determines the catalyst's activity and stability. The synthesis process must ensure that the catalyst does not deactivate, and the preparation of the nitrogen-heterocyclic carbene ligand is relatively complex, increasing production costs.

[0010] To simplify the synthesis process of ruthenium carbene catalysts, Chinese patent CN110105400A reports a modification of the P ligand in the catalyst, allowing for the synthesis of the desired catalyst in just two steps, with readily available raw materials. However, this patent uses N ligands to replace the P ligands in the ruthenium carbene catalyst to prepare a temperature-sensitive ruthenium carbene catalyst, which remains solid at room temperature, failing to solve the processability issues. Summary of the Invention

[0011] The technical problem this invention aims to solve is to overcome the shortcomings of existing ruthenium carbene catalysts, which are unstable and require on-the-fly preparation for bulk olefin ring-opening metathesis polymerization, making them unsuitable for continuous production. It also addresses the poor processability of existing prepregs, leading to warping deformation in cured composite materials and high production costs. This invention provides a cyclic olefin / epoxy resin mixture, a fiber prepreg, a composite material, and a preparation method thereof. The fiber prepreg prepared using the cyclic olefin / epoxy resin mixture of this invention has good processability and lower production costs. Compared to existing prepregs, the fiber prepreg prepared using the cyclic olefin / epoxy resin mixture of this invention exhibits reduced residual stress, and the warping deformation of the composite material cured from it is significantly improved. Simultaneously, its mechanical properties, particularly impact resistance, are improved to a certain extent, overcoming the aforementioned shortcomings of the prior art.

[0012] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0013] The present invention also provides a cyclic olefin / epoxy resin mixture, comprising 100 parts by weight of liquid epoxy resin and solid epoxy resin, and including the following components:

[0014] Liquid epoxy resin: 15-50 parts by weight;

[0015] The epoxy value of the liquid epoxy resin is 0.41-1.0;

[0016] Solid epoxy resin: 50-85 parts by weight;

[0017] The epoxy value of the solid epoxy resin is 0.12-0.6;

[0018] Cycloolefin resin: 5-25 parts by weight;

[0019] The cyclic olefin resin is one or more of dicyclopentadiene (DCPD), dicyclopentadiene polymer, norbornene, and ethylidene norbornene.

[0020] Hardener: 1-6 parts by weight;

[0021] Accelerator: 0.5-4 parts by weight;

[0022] Modified ruthenium carbene catalyst: 0.0005-0.08 parts by weight;

[0023] The modified ruthenium carbene catalyst comprises a ruthenium carbene compound as shown in Formula LG or a salt thereof:

[0024]

[0025] Among them, R1, R2, and R3 are independently C6-C 18 alkyl.

[0026] In this invention, in the ruthenium carbene compound or its salt as shown in Formula LG, the C6-C 18 Alkyl groups can be C6-C independently. 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C 10 Alkyl, more preferably C8 alkyl or C6 alkyl 10 alkyl.

[0027] The C6 alkyl group is preferably n-hexyl or 4-methylpentyl.

[0028] The C8 alkyl group is preferably n-octyl, 2-ethylhexyl, or 5-methylheptyl, more preferably 2-ethylhexyl.

[0029] Wherein, the C 10 The alkyl group is preferably n-decylalkyl.

[0030] In this invention, in the ruthenium carbene compound or its salt represented by formula LG, R1, R2 and R3 may be the same or different.

[0031] In this invention, the ruthenium carbene compound represented by formula LG is selected from any of the following structures:

[0032]

[0033] In this invention, the preparation method of the ruthenium carbene compound or its salt as shown in Formula LG includes the following method one or method two:

[0034] Method 1: Compound 2 and compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0035]

[0036] Method 2: Compound 4 and Compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0037]

[0038] The definitions of R1, R2, and R3 are as described above.

[0039] In Method 1, the organic solvent can be a conventional solvent for this type of reaction in the art, preferably a haloalkane solvent, and more preferably dichloromethane.

[0040] In Method 1, the inert atmosphere can be a conventional inert gas for this type of reaction in the art, preferably nitrogen.

[0041] In Method 1, the molar ratio of compound 3 to compound 2 can be a conventional molar ratio for such reactions in the art, preferably (1-10):1, and more preferably 2:1.

[0042] In Method 1, the volume-molar ratio of the organic solvent to the compound 2 can be a conventional volume-molar ratio for such reactions in the art, preferably from 2 L / mol to 8 L / mol, and more preferably 4 L / mol.

[0043] In Method 1, the reaction temperature of the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably room temperature. Room temperature generally refers to 0-40°C.

[0044] In Method 1, the reaction time of the substitution reaction is based on the TLC monitoring to ensure the reaction is complete, preferably 1 to 5 hours, and more preferably 2 hours.

[0045] Method 1 further includes the following post-processing steps: rotary evaporation and / or column chromatography (preferably using a petroleum ether / dichloromethane mixed solution as the developing solvent).

[0046] In Method 2, the organic solvent can be a conventional solvent for such reactions in the art, preferably an alkane solvent, such as n-hexane (or, for example, dried n-hexane).

[0047] In Method 2, the molar ratio of compound 3 to compound 4 can be a conventional molar ratio for such reactions in the art, preferably (1-5):1, and more preferably 1:1.

[0048] In Method 2, the volume-molar ratio of the organic solvent to the compound 4 can be a conventional volume-molar ratio for such reactions in the art, preferably from 10 L / mol to 50 L / mol, and more preferably 23.5 L / mol.

[0049] In Method 2, the reaction temperature of the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably 30°C to 100°C, and more preferably 70°C.

[0050] In Method 2, the reaction time of the substitution reaction is based on the TLC monitoring to ensure the reaction is complete, preferably 1 to 5 hours, and more preferably 2 hours.

[0051] Method 2 further includes the following post-processing steps: cooling (preferably cooling to room temperature), column chromatography (preferably using a petroleum ether / dichloromethane mixed solution as the developing solvent), and rotary evaporation.

[0052] Method 1 further includes the following step: under an inert atmosphere, compound 1 undergoes a substitution reaction with pyridine as shown below;

[0053]

[0054] The pyridine is generally anhydrous pyridine.

[0055] The inert atmosphere can be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0056] The volume-molar ratio of pyridine to compound 1 can be a conventional volume-molar ratio for such reactions in the art, preferably from 2 L / mol to 20 L / mol, more preferably 5 L / mol.

[0057] The reaction temperature for the substitution reaction is generally room temperature. Room temperature generally refers to 0-40℃.

[0058] The reaction time for the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably 2h to 10h, more preferably 5h.

[0059] The substitution reaction is generally carried out under stirring conditions.

[0060] The substitution reaction further includes the following post-processing steps: precipitation (preferably using petroleum ether), filtration, washing (preferably using petroleum ether), and drying (preferably vacuum drying).

[0061] In this invention, the viscosity of the cyclic olefin / epoxy resin mixture at 70°C can be 10,000-60,000 cPs, for example 54,000 cPs, preferably 10,000-40,000 cPs, for example 20,000 cPs, 23,000 cPs, 24,000 cPs, 26,000 cPs, 27,000 cPs, 30,000 cPs, 32,000 cPs, 35,000 cPs or 37,000 cPs.

[0062] In this invention, the epoxy value of the liquid epoxy resin is preferably 0.47-1, for example 0.48-0.51, 0.87-0.95, 0.83-1 or 0.47-0.53.

[0063] In this invention, the viscosity of the liquid epoxy resin at 25°C can be 200-18000 cPs, for example 200-14000 cPs, 300-450 cPs, 2000-5000 cPs, 3000-6000 cPs, 2000-3500 cPs, 2000-6000 cPs or 11000-15000 cPs.

[0064] In this invention, the epoxy value of the solid epoxy resin is preferably 0.2-0.53, for example 0.21, 0.2-0.22 or 0.46-0.53.

[0065] In this invention, the softening point of the solid epoxy resin at 25°C can be 50-90°C, for example 62°C, 63°C, 66°C, 70°C, 75°C, 76°C, 80°C, 85°C or 87°C.

[0066] In this invention, when the cyclic olefin resin includes a dicyclopentadiene polymer, the dicyclopentadiene polymer may be one or more of tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), and pentacyclopentadiene (PCPD). TeCPD is an abbreviation for tetracyclopentadiene as defined in this invention; PCPD is an abbreviation for pentacyclopentadiene as defined in this invention, and neither has any other special meaning.

[0067] In this invention, the cyclic olefin resin is preferably a mixture of tricyclopentadiene, dicyclopentadiene and tricyclopentadiene, or a mixture of tricyclopentadiene and norbornene NB.

[0068] When the cyclic olefin resin is a mixture of dicyclopentadiene and tricyclopentadiene, the weight ratio of the dicyclopentadiene to the tricyclopentadiene is preferably (5-15):(5-15), for example, 10:5.

[0069] When the cyclic olefin resin is a mixture of tricyclopentadiene and norbornene NB, the weight ratio of the tricyclopentadiene to the norbornene NB is preferably (5-15):(5-15), for example 10:5.

[0070] In this invention, TCPD, TePCD, and PCPD are prepared by the following method:

[0071] (1) 5 kg of dicyclopentadiene was added to the reactor and heated to 200 °C under nitrogen protection and kept for 0.5 h to obtain a liquid mixture of DCPD, TCPD, TeCPD and PCPD.

[0072] (2) Cool the liquid mixture to 120°C and feed it into the first distillation column for negative pressure distillation. The substance obtained at the top of the column is DCPD, and the bottom of the column is a mixture of TCPD, TeCPD and PCPD. The bottom material is then transported to the second distillation column for further negative pressure distillation. The substance obtained at the top of the column is TCPD, and the bottom of the column is a mixture of TeCPD and PCPD.

[0073] (3) The bottom material of the tower is subjected to negative pressure distillation, and the resulting fraction is TeCPD. The residue contains PCPD.

[0074] (4) Wash the residue with toluene and collect the washing liquid. Remove the toluene solvent by vacuum distillation to obtain PCPD.

[0075] In this invention, the liquid epoxy resin, or the solid epoxy resin, may be a conventional resin in the art, such as one or more of glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester epoxy resin, and alicyclic epoxy resin.

[0076] The glycidyl ether type epoxy resin may be one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin and phenolic epoxy resin, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin or phenolic epoxy resin.

[0077] The glycidylamine type epoxy resin may be one or more of 4,4-diaminodiphenylmethane tetraglycidylamine, diglycidyl-p-aminophenol, triglycidyl-p-aminophenol, and tetraglycidyl-diaminodiphenylmethane.

[0078] The glycidyl ester epoxy resin may be one or more of the following: 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester, isophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester.

[0079] The alicyclic epoxy resin may be one or more of 1,2-epoxy-4-vinylcyclohexane, methyl 3,4-epoxycyclohexane carboxylate, bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate, bis((3,4-epoxycyclohexyl)methyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, and (N,N,N,N,-tetracyclooxypropyl-4,4-diaminodiphenylmethane).

[0080] In some preferred embodiments of the present invention, the solid epoxy resin is bisphenol A type epoxy resin YN2301 and bisphenol A type epoxy resin NPES301; wherein, the weight ratio of bisphenol A type epoxy resin YN2301 and bisphenol A type epoxy resin NPES301 is (30-70):(10-30), for example 55:20.

[0081] In this invention, the curing agent can be a conventional epoxy resin latent curing agent in the art, such as one or more of aliphatic amines, aromatic amines, dicyandiamide, imidazoles, organic acid anhydrides, organic hydrazides and Lewis acids, preferably dicyandiamide.

[0082] In this invention, the accelerator can be one or more of the conventional epoxy resin latent curing accelerators in the art, such as imidazole compounds and their derivatives and salts, urea derivatives, organic guanidine derivatives, phosphorus-containing compounds, transition metal complexes and composite accelerators, tertiary amines, tertiary amine salts, quaternary phosphine salts, Lewis acid-amine complexes and acetylacetone transition metal complexes, preferably organic urea accelerators.

[0083] In this invention, the liquid epoxy resin is preferably in the form of 15-48 parts by weight, for example 16 parts, 20 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts or 47 parts.

[0084] In this invention, the weight percentage of the solid epoxy resin is preferably 52-85 parts, for example 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 84 parts.

[0085] In this invention, the weight ratio of the liquid epoxy resin to the solid epoxy resin can be (15-50):(50-85), preferably (15-48):(52-85), for example 45:55, 35:65, 20:80 or 30:70.

[0086] In this invention, the weight percentage of the cyclic olefin resin is preferably 6-25 parts, for example 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or 24 parts.

[0087] In this invention, the curing agent is preferably 3-6 parts by weight, for example 3.5 parts, 4.31 parts, 4.87 parts, 5.18 parts, 5.3 parts, 5.53 parts or 5.86 parts.

[0088] In this invention, the accelerator is preferably 1-4 parts by weight, for example 1.24 parts, 1.52 parts, 1.73 parts, 1.82 parts, 2.01 parts, 2.37 parts, 3.2 parts or 3.6 parts.

[0089] In this invention, the modified ruthenium carbene catalyst is preferably 0.001-0.08 parts by weight, for example 0.02 parts, 0.003 parts, 0.035 parts, 0.038 parts, 0.04 parts, 0.05 parts, 0.06 parts or 0.07 parts.

[0090] In this invention, the cyclic olefin / epoxy resin mixture preferably further includes other additives. These other additives are generally commercially available conventional prepreg resin additives, such as one or more of defoamers, toughening agents, tackifiers, leveling agents, wetting and dispersing agents, coupling agents, and color pastes.

[0091] The defoamer can be a conventional defoamer in the art, such as defoamer with the model number BYKA530.

[0092] The toughening agent may be a conventional organic toughening agent and / or an inorganic toughening agent in the art. The organic toughening agent may be a conventional organic toughening agent in the art, such as a butadiene-styrene-methyl methacrylate block copolymer. The inorganic toughening agent may be a conventional inorganic toughening agent in the art, such as calcium carbonate.

[0093] The tackifier may be a conventional tackifier in the art.

[0094] The leveling agent may be a conventional leveling agent in the art.

[0095] The wetting and dispersing agent may be a conventional wetting and dispersing agent in the art, such as the wetting and dispersing agent with model number BYK9010.

[0096] The coupling agent may be a conventional coupling agent in the art, such as γ-glycidoxypropyltrimethoxysilane (KH560).

[0097] The colorant can be a conventional colorant in the art.

[0098] When the cyclic olefin / epoxy resin mixture also includes other additives, the weight parts of the other additives can be 0-40 parts, preferably 0-38 parts, for example 2 parts, 4 parts, 8 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 37 parts.

[0099] When the other additives are defoamers, wetting and dispersing agents and coupling agents, the weight ratio of the defoamer, the wetting and dispersing agent and the coupling agent can be (0.2-1):(0.2-1):(0.2-1), for example 0.6:0.6:0.8 or 0.2:0.6:0.8.

[0100] When the other additives are defoamers, wetting and dispersing agents, coupling agents and toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent and the toughening agent can be (0.3-1):(0.3-1):(0.3-1):(5-40), for example 0.6:0.6:0.8:35.

[0101] When the other additives are defoamers, wetting and dispersing agents, coupling agents and organic toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent and the organic toughening agent can be (0.3-1):(0.3-1):(0.3-1):(5-20), for example 0.6:0.6:0.8:10.

[0102] When the other additives include defoamers, the defoamer is preferably 0.1-1 parts by weight, for example 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts or 0.9 parts.

[0103] When the other additives include toughening agents, the toughening agent is preferably present in 5-30 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 18 parts, 20 parts or 25 parts.

[0104] When the toughening agent includes an organic toughening agent and an inorganic toughening agent, the weight ratio of the organic toughening agent to the inorganic toughening agent can be (5-20):(10-30), for example, 10:25.

[0105] When the other additives include a tackifier, the weight percentage of the tackifier may be conventional in the art.

[0106] When the other additives include leveling agents, the weight percentage of the leveling agent may be conventional in the art.

[0107] When the other additives include wetting and dispersing agents, the weight of the wetting and dispersing agents is preferably 0.1-1 parts, for example 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts or 0.9 parts.

[0108] When the other additives include coupling agents, the weight of the coupling agent is preferably 0.1-1 parts, for example 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts or 0.9 parts.

[0109] When the other additives include color paste, the weight percentage of the color paste can be conventional in the art.

[0110] The present invention also provides a method for preparing the cyclic olefin / epoxy resin mixture as described above, comprising the following steps:

[0111] S1. The solid epoxy resin is melted and cooled, then mixed with a portion of the liquid epoxy resin and the cyclic olefin resin to obtain component A;

[0112] S2. The curing agent, the accelerator, the modified ruthenium carbene catalyst, and the remaining liquid epoxy resin are mixed and ground to obtain component B;

[0113] S3. Component B is mixed and dispersed with component A to obtain the cyclic olefin / epoxy resin mixture.

[0114] In S1, preferably, the solid epoxy resin is melted and cooled, and then mixed sequentially with a portion of the liquid epoxy resin and the cyclic olefin to obtain component A.

[0115] In S1, the melting temperature can be 120-150°C, preferably 120-140°C, for example 130°C.

[0116] In S1, the temperature after cooling can be 70-100℃, preferably 80-100℃, for example 90℃.

[0117] In S2, the grinding process can be repeated 2-3 times.

[0118] In S2, the grinding equipment can be conventional equipment in the art, such as a three-roll mill.

[0119] In S2, when a three-roll mill is selected as the grinding equipment, the distance between the front rollers of the three-roll mill can be 20-100μm, preferably 20-40μm, such as 25μm, 30μm or 35μm.

[0120] In S2, when a three-roll mill is selected as the grinding equipment, the back roller spacing of the three-roll mill can be 30-110μm, preferably 30-50μm, such as 30μm, 35μm or 40μm.

[0121] In S2, the grinding speed can be 30-120 r / min, preferably 30-80 r / min, for example 40 r / min, 50 r / min, 60 r / min or 70 r / min.

[0122] Preferably, in S2, when the grinding equipment is a three-roll mill, the front roller spacing is 20-40μm; the rear roller spacing is 30-50μm; and the rotation speed is 30-80r / min.

[0123] Preferably, in S2, when the grinding equipment is a three-roll mill, the front roller spacing is 25μm, the rear roller spacing is 35μm, and the rotation speed is 60r / min.

[0124] In S3, the dispersion method can be a conventional method in the art, such as using a high-speed disperser.

[0125] In S3, when a high-speed disperser is used for dispersion, the rotation speed of the high-speed disperser can be 200-1000 r / min, preferably 400-1000 r / min, for example 700 r / min.

[0126] In S3, the dispersion time can be 15-30 minutes, preferably 20-30 minutes, for example 25 minutes.

[0127] In S3, the dispersion temperature can be 30-70°C, preferably 40-60°C, for example 50°C.

[0128] The present invention also provides a fiber prepreg comprising the cyclic olefin / epoxy resin mixture and reinforcement as described above;

[0129] The resin content in the fiber prepreg is 25-40 wt%; the percentage is the weight of the resin in the fiber prepreg relative to the total weight of the fiber prepreg.

[0130] In this invention, the reinforcing material can be a fiber conventional in the art, such as organic fiber and / or inorganic fiber.

[0131] The organic fiber may be one or more of carbon fiber, aramid fiber and aromatic polyamide fiber.

[0132] The inorganic fiber may be glass fiber and / or basalt fiber.

[0133] In this invention, the fiber areal density of the reinforcing body can be 50-600 gsm, for example 100-300 gsm, preferably 150 gsm.

[0134] In this invention, when the reinforcing body is carbon fiber, the fiber areal density of the carbon fiber is preferably 150 gsm.

[0135] In this invention, the resin content in the fiber prepreg is preferably 30-40 wt%, for example 36 wt%, where the percentage is the weight percentage of the resin in the fiber prepreg to the total weight of the fiber prepreg.

[0136] The present invention also provides a method for preparing a fiber prepreg, which includes the following steps: impregnating the reinforcing body with the cyclic olefin resin / epoxy resin mixture as described above.

[0137] In this invention, the impregnation temperature can be a conventional impregnation temperature in the art.

[0138] In this invention, the immersion time can be the immersion time conventional in the art.

[0139] In this invention, the fiber prepreg can be prepared into a general-purpose prepreg or a highly flame-retardant prepreg by changing the types and proportions of each component added in the cyclic olefin / epoxy resin mixture and changing the process parameters, according to actual application requirements.

[0140] The present invention also provides a composite material comprising fibers and a three-dimensional network structure formed on the surface of the fibers by crosslinking and polymerization of a cyclic olefin / epoxy resin mixture as described above.

[0141] In this invention, the fiber can be a conventional fiber in the art, such as carbon fiber.

[0142] The present invention also provides a method for preparing a composite material, the steps of which include: curing the fiber prepreg as described above into a mold.

[0143] In this invention, the curing process for curing molding can be "heating at 70-90℃ for 0.8-1.2h, heating at 90-130℃ for 0.8-1.2h, heating at 110-150℃ for 0.8-1.2h", or "heating at 70-90℃ for 0.8-1.2h, heating at 90-130℃ for 1.5-3h".

[0144] In this invention, preferably, the curing process of the curing molding can be "heating at 80°C for 1 hour, heating at 120°C for 1 hour, and heating at 140°C for 1 hour", or "heating at 80°C for 1 hour and heating at 120°C for 2 hours".

[0145] In this invention, the curing pressure can be 0.5-2 MPa, for example 1 MPa.

[0146] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0147] The reagents and raw materials used in this invention are all commercially available.

[0148] The positive and progressive effects of this invention are as follows:

[0149] 1. The components in the cyclic olefin / epoxy resin mixture of the present invention are well-matched, resulting in fiber prepregs with good processability and low production costs. Specifically:

[0150] In preparing cyclic olefin / epoxy resin mixtures, this invention uses a modified ruthenium carbene catalyst as a liquid catalyst, eliminating the need for on-the-spot preparation and exhibiting good storage stability and a long shelf life (>6 months). This catalyst can be uniformly dispersed in the epoxy curing agent components. When the catalyst is mixed with the cyclic olefin at a certain temperature, a rapid polymerization reaction can occur, releasing heat to promote the curing of the epoxy resin and lower its curing temperature. Furthermore, it can be mixed with the resin at 60-80℃ without reacting with the cyclic olefin during use. Using liquid and solid epoxy resins with different epoxy values ​​allows for better matching of the production requirements of the prepreg product.

[0151] 2. The mechanical properties of the fiber prepreg of the present invention, especially the impact properties, are improved to a certain extent. Furthermore, compared with ordinary epoxy prepreg, the residual stress generated by chemical shrinkage and other reasons during the molding process of the fiber prepreg is reduced, which significantly improves the warping deformation of composite material structural parts.

[0152] 3. The cyclic olefin / epoxy resin mixture system of the present invention can be flexibly supplemented with a series of functional additives such as flame retardants and toughening agents as needed. Furthermore, the cyclic olefin / epoxy resin mixture system of the present invention can be used to prepare fiber prepregs by solution impregnation and melt impregnation methods. The process has a wide range of applications, is simple to operate, has low cost, and a high safety factor, which is conducive to industrial production applications. Detailed Implementation

[0153] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0154] In the following examples and comparative examples, "parts" refers to "parts by weight".

[0155] The brands of the key raw material manufacturers are as follows:

[0156] Liquid epoxy resin, bisphenol A type, YN1828, epoxy value (0.48-0.51), viscosity at 25℃ 11000-15000 cPs, produced by Jiangsu Yangnong Chemical. Glycidylamine type epoxy resin (triglycidyl-p-aminophenol) S500, epoxy value (0.87-0.95), viscosity at 25℃ is 2000-6000 cPs, produced by Nantong Xinxina; Glycidyl ester type epoxy resin (4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester) S186, epoxy value (0.83-1), viscosity at 25℃ is 2000-3500 cPs, produced by Nantong Xinxina; Alicyclic epoxy resin (bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate) S28, epoxy value (0.47-0.53), viscosity at 25℃ is 400-750 cPs, produced by Nantong Xinxina.

[0157] The solid epoxy resins are: bisphenol A type epoxy resin YN2301, with an epoxy equivalent of 479.4 g / mol (epoxy value of 0.21) and a softening point of 66℃, produced by Jiangsu Yangnong Chemical; bisphenol A type epoxy resin NPES301, with an epoxy value of (0.2-0.22) and a softening point of 63℃, produced by Nan Ya; and phenolic epoxy resin (o-cresol epoxy resin) NPCN702, with an epoxy value of (0.46-0.53) and a softening point of 70℃, produced by Nan Ya.

[0158] The organic urea accelerator is the UR2T curing accelerator product manufactured by Air Products.

[0159] Defoamer: BYKA530 from BYK Chemicals.

[0160] Wetting and dispersing agent: BYKW9010 from BYK Chemicals.

[0161] Coupling agent: KH560 coupling agent from Nanjing Nengde New Materials.

[0162] The manufacturer of dicyclopentadiene is Guangdong Xinhua Yue Petrochemical Co., Ltd.

[0163] The preparation process of tricyclopentadiene (TCPD) used in this invention is as follows:

[0164] (1) 5 kg of the above-mentioned dicyclopentadiene (DCPD) from Guangdong Xinhua Yue Petrochemical Co., Ltd. was put into a reactor and heated to 200°C under nitrogen protection for 0.5 h to obtain a liquid mixture of DCPD, TCPD, TeCPD and PCPD.

[0165] (2) Cool the liquid mixture to 120°C and feed it into the first distillation column for negative pressure distillation. The substance obtained at the top of the column is DCPD, and the bottom of the column is a mixture of TCPD, TeCPD and PCPD. The bottom material is transported to the second distillation column for further negative pressure distillation. The substance obtained at the top of the column is TCPD.

[0166] Unless otherwise specified above, the reagents used in the examples and comparative examples are products from any manufacturer.

[0167] There are no particular limitations on the preparation of components A and B in the following examples and comparative examples, as long as they are well dispersible.

[0168] The specific structural formula, preparation method, and analytical data of the modified ruthenium carbene catalyst (novel P-ligand ruthenium carbene catalyst) used in this invention are as follows:

[0169] (1) Structural formula:

[0170]

[0171] (2) Preparation method and analytical data:

[0172] Method 1:

[0173]

[0174] Under nitrogen protection, 50 mL of anhydrous pyridine was added to a dry 100 mL single-necked flask equipped with a magnetic stirrer, followed by 8.49 g (10.0 mmol) of ruthenium compound 1 (molecular formula: C). 46 H 65 Cl2N2PRu (molecular weight: 848.97) was stirred to dissolve the catalyst solid. The reaction mixture was stirred at room temperature for 5.0 h. At this point, the solution turned dark green. Stirring was stopped, and the reaction mixture was added dropwise to a beaker containing 200 mL of petroleum ether while continuously and vigorously stirring. During this process, a green precipitate slowly precipitated from the reaction solution. After the reaction was completed, the reaction solution was filtered to obtain a green solid. The solid was washed three times with petroleum ether to remove adsorbed pyridine, and dried under vacuum to obtain green intermediate product 2, weighing 6.5 g (8.94 mmol), with a yield of 89.4%.

[0175] Analyze the data:

[0176] C 38 H 42 Theoretical (calculated) values ​​of Cl2N4Ru: C, 62.80 (62.62); H, 5.83 (5.60); N, 7.71 (7.61).

[0177] 1H NMR (400MHz, CDCl3): δ19.67(s,1H,CHPh),8.84(br.s,2H,pyridine),8.39(br.s,2H,pyridine),8.07(d,2H,ortho CH,J H-H =8Hz), 7.15(t,1H,para CH,J H-H =7Hz),6.83-6.04(br.mulitiple peaks,9H,pyridine,Mes-CH),3.37(br.d,4H,CH2CH2),2.79(br.s,6H,Mes-CH3),2.45(br.s,6H,Mes-CH3),2.04(br.s,6H,Mes-CH3).

[0178] 13 C{1H}NMR(C6D6): δ314.90(m,Ru=CHPh),219.10(s,Ru-C(N)2),152.94,150.84,139.92,138.38,13 6.87,135.99,134.97,131.10,130.11,129.88,128.69,123.38,51.98,51.37,21.39,20.96,19.32

[0179] Under nitrogen protection, 3.63 g (5.00 mmol) of complex 2 was added to a dry 100 mL flask, followed by stirring in 20 mL of dichloromethane until dissolved. Then, 3.71 g (10.00 mmol) of trioctylphosphine (molecular formula: C) was added to the flask. 24 H 51 P; molecular weight: 370.65 g / mol), and the reaction mixture was stirred at room temperature for 2 h. During this process, the solution gradually changed from green to brownish-red. After the reaction was complete, the solvent was removed by rotary evaporation, and the residue was subjected to column chromatography (using a petroleum ether / dichloromethane mixture as the developing solvent) to remove the solvent, yielding a reddish-brown viscous catalyst LG-1 (molecular formula: C). 52 H 83 Cl2N2PRu (molecular weight: 939.19 g / mol) yielded 3.46 g (3.68 mmol) of a reddish-brown viscous liquid, with a yield of 73.7%.

[0180] Analyze the data:

[0181] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2PRu: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0182] 1 H NMR(400MHz, CDCl3): δ18.80(s.,1H,CHPh),7.81(d., 3 J = 6.46 Hz.2H), 7.33 (t., 3 J = 7.65 Hz, 1H), 7.04 (t., 3 J=7.80Hz,2H),6.90(s.,2H),6.24(s.,2H),4.01(m.,2H),3.85(m.,2H),2.57 (s.,6H),2.23(s.,3H),2.18(s.,6H),1.86(s.,3H),1.35-0.97(br.mulitiple peaks,48H),0.78(t.,9H).

[0183] Method 2:

[0184]

[0185] Under nitrogen protection, 1.33 g (1.70 mmol) of ruthenium compound 4, 0.63 g (1.71 mmol) of trioctylphosphine, and 40 mL of dry n-hexane were added to a flask. The mixture was stirred until the white solid dissolved, then heated to 70 °C and refluxed with stirring for 2.0 h. During this process, the precipitate gradually changed color to reddish-brown. After cooling to room temperature, column chromatography was performed using petroleum ether and dichloromethane as eluents to give a wine-red solution. Upon rotary evaporation, 1.41 g (1.50 mmol) of a reddish-brown viscous liquid catalyst LG-1 (molecular formula: C 52 H 83 Cl2N2PRu (molecular weight: 939.19 g / mol), yield 88%.

[0186] Analyze the data:

[0187] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2Pru: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0188] 1 H NMR(400MHz, CDCl3): δ18.80(s.,1H,CHPh),7.81(d., 3 J = 6.46 Hz.2H), 7.33 (t., 3 J = 7.65 Hz, 1H), 7.04 (t., 3J=7.80Hz,2H),6.90(s.,2H),6.24(s.,2H),4.01(m.,2H),3.85(m.,2H),2.57 (s.,6H),2.23(s.,3H),2.18(s.,6H),1.86(s.,3H),1.35-0.97(br.mulitiple peaks,48H),0.78(t.,9H).

[0189] Example 1

[0190] Preparation of cycloolefin / epoxy resin mixtures:

[0191] Component A: Melt 55 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 35 parts of liquid epoxy resin YN1828, 24 parts of TCPD, and 22 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, 0.8 parts of coupling agent KH560, 10 parts of organic toughening agent butadiene-styrene-methyl methacrylate block copolymer, and 10 parts of inorganic toughening agent calcium carbonate), stir evenly, and set aside.

[0192] Component B: Add 5.53 parts of epoxy curing agent dicyandiamide, 2.01 parts of accelerator UR2T, and 0.06 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 70μm, rear roller spacing 80μm, and rotation speed 40r / min.

[0193] A / B component mixing: Add the above-mentioned component B to component A, and disperse it at 50°C using a high-speed disperser (speed of 700 r / min) for 25 min to make it uniformly mixed. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 25500 cPs.

[0194] Preparation of finished fiber prepreg:

[0195] Unidirectional carbon fibers with a fiber areal density of 150 gsm were selected, and prepregs with a resin content of 36% were produced using the conventional melt impregnation method.

[0196] Preparation of composite materials:

[0197] Several sheets of carbon fiber prepreg were cut and molded under the process conditions of 80℃ / 1h + 120℃ / 1h + 140℃ / 1h and 1MPa pressure. The mechanical properties of the resulting composite material are shown in Table 5-1.

[0198] Example 2

[0199] Preparation of cycloolefin / epoxy resin mixtures:

[0200] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD, and 12 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, 0.8 parts of coupling agent KH560, and 10 parts of organic toughening agent butadiene-styrene-methyl methacrylate block copolymer) and stir until homogeneous, then set aside.

[0201] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0202] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0203] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-1.

[0204] Example 3

[0205] Preparation of cycloolefin / epoxy resin mixtures:

[0206] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0207] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0208] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0209] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-1.

[0210] Example 4

[0211] Preparation of cycloolefin / epoxy resin mixtures:

[0212] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0213] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25 μm, rear roller spacing 35 μm, and rotation speed 60 r / min.

[0214] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0215] The preparation process of the finished fiber prepreg is the same as in Example 1.

[0216] Preparation of composite materials:

[0217] Several sheets of carbon fiber prepreg were cut and molded under the process conditions of 80℃ / 1h + 120℃ / 2h and 1MPa pressure. The mechanical properties of the composite material are shown in Table 5-1.

[0218] Example 5

[0219] Preparation of cycloolefin / epoxy resin mixtures:

[0220] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0221] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.005 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0222] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0223] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-1.

[0224] Example 6

[0225] Preparation of cycloolefin / epoxy resin mixtures:

[0226] Component A: Melt 80 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 10 parts of liquid epoxy resin YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0227] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0228] The mixing process for components A and B is the same as in Example 1, and the cyclic olefin / epoxy resin mixture at 70°C is 54000 cPs.

[0229] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-2.

[0230] Example 7

[0231] Preparation of cycloolefin / epoxy resin mixtures:

[0232] Component A: Melt 75 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 15 parts of liquid epoxy resin S-28, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0233] Component B: Add 5.25 parts of epoxy curing agent dicyandiamide, 1.76 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin S-28, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0234] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 20,000 cPs.

[0235] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-1.

[0236] Example 8

[0237] Preparation of cycloolefin / epoxy resin mixtures:

[0238] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 15 parts of DCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0239] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.041 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0240] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0241] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 5-1.

[0242] Example 9

[0243] Preparation of cycloolefin / epoxy resin mixtures:

[0244] Component A: Melt 75 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 15 parts of liquid epoxy resin S-500, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0245] Component B: Add 5.3 parts of epoxy curing agent dicyandiamide, 1.78 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0246] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 28000 cPs.

[0247] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-1.

[0248] Example 10

[0249] Preparation of cycloolefin / epoxy resin mixtures:

[0250] Component A: Melt 75 parts of solid epoxy resin NPES301 at 120-150℃; after cooling to 80-100℃, add 15 parts of liquid epoxy resin S-186, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0251] Component B: Add 5.3 parts of epoxy curing agent dicyandiamide, 1.78 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin S-186, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0252] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23500 cPs.

[0253] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-1.

[0254] Example 11

[0255] Preparation of cycloolefin / epoxy resin mixtures:

[0256] Component A: Melt 60 parts of solid epoxy resin NPCN702 at 120-150℃; after cooling to 80-100℃, add 30 parts of liquid epoxy resin YN1828, 10 parts of DCPD, 5 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0257] Component B: Add 5.3 parts of epoxy curing agent dicyandiamide, 1.78 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0258] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 21000 cPs.

[0259] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-1.

[0260] Example 12

[0261] Preparation of cycloolefin / epoxy resin mixtures:

[0262] Component A: Melt 55 parts of solid epoxy resin YN2301 and 20 parts of solid epoxy resin NPES301 at 120-150℃; after cooling to 80-100℃, add 15 parts of liquid epoxy resin S-500, 15 parts of norbornene NB, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0263] Component B: Add 5.3 parts of epoxy curing agent dicyandiamide, 1.78 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin S-500. After stirring evenly, grind the mixture 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0264] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 20,500 cPs.

[0265] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-1.

[0266] Example 13

[0267] Preparation of cycloolefin / epoxy resin mixtures:

[0268] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy resin YN1828, 10 parts of TCPD, 5 parts of norbornene NB, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0269] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0270] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 21500 cPs.

[0271] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-1.

[0272] Example 14

[0273] Preparation of cycloolefin / epoxy resin mixtures:

[0274] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy YN1828, 15 parts of TCPD, and 1.4 parts of other additives (including 0.2 parts of defoamer, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0275] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0276] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0277] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-2.

[0278] Example 15

[0279] Preparation of cycloolefin / epoxy resin mixtures:

[0280] Component A: Melt 40 parts of solid epoxy resin YN2301 and 20 parts of tetrabromoethylene epoxy resin NPEB-400 at 120-150℃; after cooling to 80-100℃, add 30 parts of liquid epoxy YN1828, 15 parts of TCPD, 40 parts of aluminum hydroxide and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0281] Component B: Add 4.2 parts of epoxy curing agent dicyandiamide, 1.53 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 45μm, rear roller spacing 55μm, and rotation speed 40r / min.

[0282] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 34000 cPs.

[0283] Preparation of high flame retardant fiber prepreg finished product:

[0284] Unidirectional glass fibers with a fiber areal density of 400 gsm were selected, and prepregs with a resin content of 40% were produced using the conventional melt impregnation method.

[0285] Preparation of composite materials:

[0286] Several pieces of glass fiber prepreg were cut and molded under process conditions of 80℃ / 1h + 120℃ / 1h + 140℃ / 1h and 1MPa pressure.

[0287] The mechanical properties of the composite material are: tensile strength 525 MPa, tensile modulus 25 GPa, elongation at break 1.7%, and impact strength 153 KJ / m. 2 The UL94 test achieved V0.

[0288] Comparative Example 1

[0289] Preparation of epoxy resin mixtures:

[0290] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy YN1828 and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0291] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide and 1.73 parts of accelerator UR2T to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0292] The mixing process for components A and B is the same as in Example 1, and the viscosity of the epoxy resin mixture at 70°C is 26000 cPs.

[0293] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 4. The mechanical properties of the prepared composite materials are shown in Table 4-2.

[0294] Comparative Example 2

[0295] Preparation of epoxy resin mixtures:

[0296] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy YN1828 and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0297] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide and 1.73 parts of accelerator UR2T to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0298] The mixing process for components A and B is the same as in Example 1, and the viscosity of the epoxy resin mixture at 70°C is 26000 cPs.

[0299] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-2.

[0300] Comparative Example 3

[0301] Preparation of cycloolefin / epoxy resin mixtures:

[0302] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0303] Component B: Add 5.18 parts of epoxy curing agent dicyandiamide and 1.73 parts of accelerator UR2T to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0304] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0305] The preparation processes for the fiber prepreg and the composite materials are the same as in Example 1. The mechanical properties of the prepared composite materials are shown in Table 4-2.

[0306] Comparative Example 4

[0307] Preparation of cycloolefin / epoxy resin mixtures:

[0308] Component A: Melt 65 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 25 parts of liquid epoxy YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0309] Component B: 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.0375 parts of commercially available Grubbs2 ndThe catalyst was added to 10 parts of liquid epoxy resin YN1828, stirred evenly, and then ground 2-3 times using a three-roll mill. During this process, the roller spacing of the three-roll mill was controlled as follows: the front roller spacing was 25μm, the rear roller spacing was 35μm, and the rotation speed was 60r / min.

[0310] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0311] When component B is added to component A, the resin system undergoes rapid polymerization. This is because the commercially available Grubbs second-generation catalyst is a solid powder, which has poor compatibility with liquid epoxy resin and is difficult to disperse uniformly in the epoxy. When mixed with TCPD in component A, rapid polymerization occurs immediately.

[0312] Comparative Example 5

[0313] Preparation of cycloolefin / epoxy resin mixtures:

[0314] Component A: Melt 90 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 15 parts of TCPD and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir evenly for later use;

[0315] Component B: Add 4.31 parts of epoxy curing agent dicyandiamide, 1.24 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0316] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 130,000 cPs.

[0317] The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is too high, far exceeding the viscosity required for the prepreg preparation process (10,000-40,000 cPs), thus making it impossible to prepare the finished prepreg product.

[0318] Comparative Example 6

[0319] Preparation of cycloolefin / epoxy resin mixtures:

[0320] Component A: Melt 45 parts of solid epoxy resin YN2301 at 120-150℃; after cooling to 80-100℃, add 45 parts of liquid epoxy YN1828, 15 parts of TCPD, and 2 parts of other additives (including 0.6 parts of defoamer BYKA530, 0.6 parts of wetting and dispersing agent BYKW9010, and 0.8 parts of coupling agent KH560) and stir until homogeneous, then set aside.

[0321] Component B: Add 5.86 parts of epoxy curing agent dicyandiamide, 2.37 parts of accelerator UR2T, and 0.038 parts of modified ruthenium carbene catalyst to 10 parts of liquid epoxy resin YN1828, stir evenly, and then grind 2-3 times using a three-roll mill. During this process, control the roller spacing of the three-roll mill as follows: front roller spacing 25μm, rear roller spacing 35μm, and rotation speed 60r / min.

[0322] The mixing process for components A and B is the same as in Example 1. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 8000 cPs.

[0323] The viscosity of the cyclic olefin / epoxy resin mixture is too low at 70°C, and the resin content in the finished prepreg is less than 20 wt%, which does not meet the required resin content standard for prepreg (generally, the resin content is controlled between 25-40 wt%).

[0324] The main conditional parameters involved in Examples 1-15 and Comparative Examples 1-6 are listed in Tables 1-3 below.

[0325] Table 1. Conditions and parameters involved in the preparation of component A

[0326]

[0327]

[0328] Table 2. Conditions and parameters involved in the preparation of component B

[0329]

[0330] Table 3. Conditions and parameters involved in the preparation of composite materials

[0331]

[0332] Note: In Table 3, " / " indicates that the parameter is not set.

[0333] Example 1

[0334] Test subjects: Composite materials prepared in Examples 1-15 and Comparative Examples 1-6.

[0335] Test methods: The test standard for tensile properties (e.g., tensile strength, tensile modulus, elongation at break) is ASTM D3039, and the test standard for impact properties (e.g., impact strength) is ISO 180.

[0336] Evaluation method for warpage deformation: Place the composite material on a flat table and visually observe the warpage height on one side for comparison. Use the presence or absence of warpage to describe the appearance. Examples 1-4, 6-15: virtually no warpage deformation; Example 5: slight warpage deformation; Comparative Examples 1-3: obvious warpage deformation.

[0337] Test results are shown in Tables 4-1 and 4-2 below.

[0338] Table 4-1 Summary of the mechanical properties of the composite materials obtained in the examples

[0339]

[0340]

[0341] Note: In Table 4-1, A indicates that there is basically no warping deformation; B indicates slight warping deformation.

[0342] Table 4-2 Summary of the mechanical properties of the composite materials obtained in the examples

[0343]

[0344] Note: In Table 4-2, A indicates that there was basically no warping deformation. Examples 1-15 are all carbon fiber prepregs, and Example 15 is a glass fiber prepreg.

[0345] Table 4-3 Summary of the mechanical properties of the composite materials obtained in the comparative examples

[0346]

[0347] Note: In Table 4-3, " / " indicates that the data could not be measured. C: indicates significant warping deformation. The above comparative examples are all carbon fiber prepregs.

[0348] It can be seen from the above table 1-4:

[0349] This Example 1 can be used as a comparative example;

[0350] Compared with Example 2, Example 1 shows that the inorganic toughening agent added in Example 1 is well dispersed in the resin system and can also play a reinforcing role.

[0351] Compared with Example 3, Example 1, which simultaneously added organic / inorganic toughening agents, had a toughening effect and tensile properties similar to Example 3.

[0352] Compared with Example 3, the fiber prepreg in Example 4 was cured at 80℃ / 1h + 120℃ / 2h, and its mechanical properties were basically the same as those in Example 3.

[0353] Compared to Example 3, Example 5 showed a significant decrease in mechanical properties due to incomplete curing of TCPD caused by the lower amount of modified ruthenium carbene catalyst added. Comparative Example 3, which did not add any catalyst, exhibited even worse mechanical properties.

[0354] Compared with Example 3, Example 6 has a higher viscosity than the viscosity required by the prepreg preparation process (10000-40000 cPs), resulting in a lot of dry yarn and increased porosity during the preparation of the prepreg product, which leads to a deterioration in the mechanical properties of the composite material.

[0355] Compared with Example 3, the tensile strength of Example 7 decreased slightly while the modulus increased slightly, which is related to the properties of the liquid epoxy resin itself.

[0356] Compared with Example 3, the tensile strength and modulus of Example 8 decreased, while the impact strength remained basically the same.

[0357] Compared with Comparative Example 2, the epoxy-reinforced fiber prepreg in Comparative Example 1 was not fully cured at 80℃ / 1h + 120℃ / 2h, and its tensile strength and modulus were significantly lower than those of Comparative Example 2.

[0358] Compared to Comparative Example 2, Example 1 shows that the inorganic toughening agent synergistically toughens the epoxy resin with the cyclic olefin resin and the organic toughening agent, thereby improving the impact strength of the prepreg product. The simultaneous addition of the organic toughening agent and the cyclic olefin resin resulted in a significant 15.6% increase in impact strength, but a 5.07% decrease in tensile strength.

[0359] Compared to Comparative Example 2, Example 2 showed that the simultaneous addition of the organic toughening agent and cyclic olefin resin significantly improved the impact strength of the product by 19.5%, but decreased the tensile strength by 9.4%. The results indicate that the organic toughening agent severely compromises the tensile strength of the product while improving its impact toughness.

[0360] Compared with Comparative Example 2, only 15 parts of tricyclopentadiene were added in Example 3 to achieve a toughening effect, with an impact strength increase of 17.7% and a tensile strength decrease of only 1.98%, indicating that tricyclopentadiene improves the impact toughness of the product while basically not changing the tensile strength of the product.

[0361] Compared with Example 3, Comparative Example 3 added tricyclopentadiene, but did not add a corresponding proportion of the novel P-ligand ruthenium carbene catalyst, resulting in insufficient curing of the composite board during the molding process and overall low tensile properties.

[0362] Compared to Example 3, the commercially available Grubbs second-generation catalyst used in Comparative Example 4 immediately polymerized with TCPD when added to the resin mixture, making it impossible to prepare prepreg.

[0363] The viscosity of the cyclic olefin / epoxy resin mixture prepared in Comparative Example 5 was too high at 70°C, far exceeding the viscosity required for the prepreg preparation process (10,000-40,000 cPs), making it impossible to prepare the prepreg product.

[0364] The viscosity of the cyclic olefin / epoxy resin mixture prepared in Comparative Example 6 was too low at 70°C, and the resin content in its prepreg product was less than 20 wt%, which did not meet the required resin content standard for prepreg (generally, the resin content is controlled between 25-40 wt%).

Claims

1. A cyclic olefin / epoxy resin mixture, characterized in that, Based on 100 parts by weight of liquid epoxy resin and solid epoxy resin, it comprises the following components: Liquid epoxy resin: 20-50 parts by weight; The epoxy value of the liquid epoxy resin is 0.41-1.0; Solid epoxy resin: 50-80 parts by weight; The epoxy value of the solid epoxy resin is 0.12-0.6; Cycloolefin monomers: 5-25 parts by weight; The cyclic olefin monomer is one or more of dicyclopentadiene, dicyclopentadiene polymer, norbornene, and ethylidene norbornene. Hardener: 1-6 parts by weight; Accelerator: 0.5-4 parts by weight; Modified ruthenium carbene catalyst: 0.02-0.08 parts by weight; The modified ruthenium carbene catalyst comprises a ruthenium carbene compound as shown in Formula LG or a salt thereof: LG, Among them, R1, R2, and R3 are independently C6-C 18 alkyl; Other additives: 0-40 parts; when the other additives include toughening agents, the toughening agents are 5-20 parts by weight. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 10,000-40,000 cPs.

2. The cyclic olefin / epoxy resin mixture as described in claim 1, characterized in that, It satisfies one or more of the following conditions ai: a. A method for preparing the ruthenium carbene compound or its salt as shown in Formula LG, comprising either method one or method two: Method 1: Compound 2 and compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere; ； Method 2: Compound 4 and compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere; ； The definitions of R1, R2, and R3 are as described in claim 1; b. The viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 20000 cPs, 23000 cPs, 24000 cPs, 26000 cPs, 27000 cPs, 30000 cPs, 32000 cPs, 35000 cPs or 37000 cPs. c. The epoxy value of the liquid epoxy resin is 0.47-1; d. The viscosity of the liquid epoxy resin at 25°C is 200-18000 cPs; e. The epoxy value of the solid epoxy resin is 0.2-0.53; f. The liquid epoxy resin, or the solid epoxy resin, is one or more of glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester epoxy resin, and alicyclic epoxy resin. g. The curing agent is one or more of the following: aliphatic amines, aromatic amines, dicyandiamides, imidazoles, organic acid anhydrides, organic acylhydrazides, and Lewis acids; h. The accelerator is one or more of the following: imidazole compounds and their derivatives, urea derivatives, organic guanidine derivatives, phosphorus-containing compounds, transition metal complexes and composite accelerators, tertiary amines, tertiary amine salts, quaternary phosphine salts, Lewis acid-amine complexes, and acetylacetone transition metal complexes. i. The cyclic olefin / epoxy resin mixture also includes other additives, which are one or more of the following: defoamer, toughening agent, tackifier, leveling agent, wetting and dispersing agent, coupling agent and color paste.

3. The cyclic olefin / epoxy resin mixture according to claim 1, characterized in that, The accelerator is a salt of an imidazole compound.

4. The cycloolefin / epoxy resin mixture according to claim 1, characterized in that, In the ruthenium carbene compound or its salt as shown in Formula LG, the C6-C 18 Alkyl groups are independently C6-C 10 alkyl.

5. The cycloolefin / epoxy resin mixture according to claim 1, characterized in that, In the ruthenium carbene compound or its salt as shown in Formula LG, R1, R2, and R3 may be the same or different.

6. The cyclic olefin / epoxy resin mixture according to claim 1, characterized in that, The ruthenium carbene compound represented by formula LG is selected from any of the following structures: ， 。 7. The cycloolefin / epoxy resin mixture according to claim 1, characterized in that, When the cyclic olefin monomer includes a dicyclopentadiene polymer, the dicyclopentadiene polymer is one or more of tricyclopentadiene, tetracyclopentadiene, and pentacyclopentadiene.

8. The cycloolefin / epoxy resin mixture according to claim 1, characterized in that, The cyclic olefin monomer is a mixture of tricyclopentadiene, dicyclopentadiene, and tricyclopentadiene, or a mixture of tricyclopentadiene and norbornene NB.

9. The cycloolefin / epoxy resin mixture according to claim 2, characterized in that, It satisfies one or more of the following conditions ah; a. The C6-C 18 The alkyl group is independently C6 alkyl, C8 alkyl or C 10 alkyl; b. The epoxy value of the liquid epoxy resin is 0.48-0.51 or 0.87-0.95; c. The viscosity of the liquid epoxy resin at 25°C is 200-14000 cPs; d. The epoxy value of the solid epoxy resin is 0.21 or 0.46-0.53; e. When the cyclic olefin monomer is a mixture of dicyclopentadiene and tricyclopentadiene, the weight ratio of the dicyclopentadiene to the tricyclopentadiene is (5-15):(5-15). f. When the cyclic olefin monomer is a mixture of tricyclopentadiene and norbornene NB, the weight ratio of the tricyclopentadiene to the norbornene NB is (5-15):(5-15). g. The curing agent is dicyandiamide; h. The accelerator is a urea-based accelerator.

10. The cyclic olefin / epoxy resin mixture according to claim 2, characterized in that, It satisfies one or more of the following conditions ac; a. The epoxy value of the liquid epoxy resin is 0.83-1 or 0.47-0.53; b. The viscosity of the liquid epoxy resin at 25°C is 300-450 cPs or 2000-5000 cPs. c. The epoxy value of the solid epoxy resin is 0.2-0.

22.

11. The cyclic olefin / epoxy resin mixture according to claim 2, characterized in that, The viscosity of the liquid epoxy resin at 25°C is 3000-6000 cPs.

12. The cycloolefin / epoxy resin mixture according to claim 2, characterized in that, The viscosity of the liquid epoxy resin at 25°C is 2000-3500 cPs.

13. The cyclic olefin / epoxy resin mixture according to claim 2, characterized in that, The viscosity of the liquid epoxy resin at 25°C is 2000-6000 cPs or 11000-15000 cPs.

14. The cyclic olefin / epoxy resin mixture according to claim 9, characterized in that, The C6 alkyl group is n-hexyl or 4-methylpentyl.

15. The cycloolefin / epoxy resin mixture as described in claim 9, characterized in that, The C8 alkyl group is n-octyl, 2-ethylhexyl, or 5-methylheptyl.

16. The cyclic olefin / epoxy resin mixture according to claim 9, characterized in that, The C8 alkyl group is 2-ethylhexyl.

17. The cycloolefin / epoxy resin mixture according to claim 9, characterized in that, The C 10 The alkyl group is n-decyl.

18. The cycloolefin / epoxy resin mixture as described in claim 9, characterized in that, When the cyclic olefin monomer is a mixture of dicyclopentadiene and tricyclopentadiene, the weight ratio of the dicyclopentadiene to the tricyclopentadiene is 10:

5.

19. The cycloolefin / epoxy resin mixture according to claim 9, characterized in that, When the cyclic olefin monomer is a mixture of tricyclopentadiene and norbornene NB, the weight ratio of tricyclopentadiene to norbornene NB is 10:

5.

20. The cycloolefin / epoxy resin mixture according to claim 2, characterized in that, It satisfies one or more of the following conditions ae; a. The glycidyl ether type epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin and phenolic epoxy resin; b. The glycidylamine type epoxy resin is one or more of 4,4-diaminodiphenylmethane tetraglycidylamine, diglycidyl-p-aminophenol, triglycidyl-p-aminophenol, and tetraglycidyl-diaminodiphenylmethane. c. The glycidyl ester epoxy resin is one or more of 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester, isophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester. d. The alicyclic epoxy resin is one or more of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexane carboxylate, bis(7-oxabicyclo[4.1.0]3-heptylmethyl) adipate, bis((3,4-epoxycyclohexyl)methyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, and N,N,N,N,-tetracyclooxypropyl-4,4-diaminodiphenylmethane; e. When the cyclic olefin / epoxy resin mixture also includes other additives, the other additives are in the amount of 0-38 parts by weight.

21. The cyclic olefin / epoxy resin mixture according to claim 20, characterized in that, When the other additives are defoamers, wetting and dispersing agents and coupling agents, the weight ratio of the defoamer, the wetting and dispersing agent and the coupling agent is (0.2-1):(0.2-1):(0.2-1).

22. The cycloolefin / epoxy resin mixture according to claim 20, characterized in that, When the other additives are defoamers, wetting and dispersing agents, coupling agents and toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent and the toughening agent is (0.3-1):(0.3-1):(0.3-1):(5-40).

23. The cycloolefin / epoxy resin mixture as described in claim 20, characterized in that, When the other additives are defoamers, wetting and dispersing agents, coupling agents and organic toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent and the organic toughening agent in the cyclic olefin / epoxy resin mixture is (0.3-1):(0.3-1):(0.3-1):(5-20).

24. The cycloolefin / epoxy resin mixture as described in claim 20, characterized in that, It satisfies one or more of the following conditions: ad; a. When the other additives include defoamers, the defoamer is 0.1-1 parts by weight; b. When the other additives include toughening agents, the toughening agents are in the following weight proportions: 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 18 parts, or 20 parts. c. When the other additives include wetting and dispersing agents, the weight of the wetting and dispersing agents is 0.1-1 parts; d. When the other additives include coupling agents, the weight of the coupling agent is 0.1-1 parts.

25. The cycloolefin / epoxy resin mixture as described in claim 20, characterized in that, It satisfies one or more of the following conditions: af; a. The glycidyl ether type epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin or phenolic epoxy resin. b. The other additives are present in parts by weight of 2, 4, 8, 15, 20, 25, 30, 35 or 37. c. When the other additives include defoamers, the weight parts of the defoamers are 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts, or 0.9 parts; d. When the other additives include toughening agents, and when the toughening agents include organic toughening agents and inorganic toughening agents, the weight ratio of the organic toughening agent to the inorganic toughening agent is (5-20):(10-30). e. When the other additives are wetting and dispersing agents, the weight parts of the wetting and dispersing agents are 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts, or 0.9 parts; f. When the other additives include coupling agents, the weight parts of the coupling agents are 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 0.85 parts, or 0.9 parts.

26. The cyclic olefin / epoxy resin mixture according to claim 20, characterized in that, When the other additives include defoamers, wetting and dispersing agents and coupling agents, the weight ratio of the defoamer, the wetting and dispersing agent and the coupling agent is 0.6:0.6:0.8 or 0.2:0.6:0.

8.

27. The cycloolefin / epoxy resin mixture according to claim 20, characterized in that, When the other additives include defoamers, wetting and dispersing agents, coupling agents, and toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent, and the toughening agent is 0.6:0.6:0.8:

35.

28. The cycloolefin / epoxy resin mixture according to claim 20, characterized in that, When the other additives include defoamers, wetting and dispersing agents, coupling agents, and organic toughening agents, the weight ratio of the defoamer, the wetting and dispersing agent, the coupling agent, and the organic toughening agent is 0.6:0.6:0.8:

10.

29. The cycloolefin / epoxy resin mixture as described in claim 25, characterized in that, When the toughening agent includes an organic toughening agent and an inorganic toughening agent, the weight ratio of the organic toughening agent to the inorganic toughening agent is 10:

25.

30. The cyclic olefin / epoxy resin mixture according to claim 1, characterized in that, It satisfies one or more of the following conditions: ag; a. The liquid epoxy resin is present in 25-48 parts by weight; b. The solid epoxy resin is 52-75 parts by weight; c. The weight ratio of the liquid epoxy resin to the solid epoxy resin is (15-50):(50-85). d. The cyclic olefin monomer is in the form of 6-25 parts by weight; e. The curing agent is 3-6 parts by weight; f. The accelerator is present in 1-4 parts by weight; g. The modified ruthenium carbene catalyst is present in weight parts of 0.02, 0.035, 0.038, 0.04, 0.05, 0.06, or 0.

07.

31. The cyclic olefin / epoxy resin mixture according to claim 30, characterized in that, It satisfies one or more of the following conditions: af; a. The liquid epoxy resin is present in parts by weight of 25, 28, 30, 35, 40, 45, or 47. b. The solid epoxy resin is present in parts by weight of 55, 60, 65, 70 or 75 parts; c. The weight ratio of the liquid epoxy resin to the solid epoxy resin is (15-48):(52-85). d. The weight parts of the cyclic olefin monomer are 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or 24 parts; e. The curing agent is present in parts by weight of 3.5, 4.31, 4.87, 5.18, 5.3, 5.53, or 5.

86. f. The accelerator is present in the following weight proportions: 1.24 parts, 1.52 parts, 1.73 parts, 1.82 parts, 2.01 parts, 2.37 parts, 3.2 parts, or 3.6 parts.

32. The cycloolefin / epoxy resin mixture according to claim 30, characterized in that, The weight ratio of the liquid epoxy resin to the solid epoxy resin is 45:55, 35:65, 20:80, or 30:

70.

33. A method for preparing a cyclic olefin / epoxy resin mixture as described in any one of claims 1-32, characterized in that, It includes the following steps: S1. The solid epoxy resin is melted and cooled, then mixed with a portion of the liquid epoxy resin and the cycloolefin monomer to obtain component A; S2. The curing agent, the accelerator, the modified ruthenium carbene catalyst, and the remaining liquid epoxy resin are mixed and ground to obtain component B; S3. Component B is mixed and dispersed with component A to obtain the cyclic olefin / epoxy resin mixture.

34. The method for preparing the cyclic olefin / epoxy resin mixture according to claim 33, characterized in that, It satisfies one or more of the following conditions ae; a. The solid epoxy resin is melted and cooled, and then mixed sequentially with a portion of the liquid epoxy resin and the cyclic olefin to obtain component A; b. In S1, the melting temperature is 120-150℃; c. In S1, the temperature after cooling is 70-100℃; In d and S3, the dispersion time is 15-30 minutes; In e and S3, the dispersion temperature is 30-70℃.

35. The method for preparing the cyclic olefin / epoxy resin mixture according to claim 34, characterized in that, It satisfies one or more of the following conditions: ad; a. The melting temperature is 120-140℃; b. The temperature after cooling is 80-100℃; c. The dispersion time is 20-30 minutes; d. The dispersion temperature is 40-60℃.

36. The method for preparing the cyclic olefin / epoxy resin mixture according to claim 34, characterized in that, It satisfies one or more of the following conditions: ad; a. The melting temperature is 130℃; b. The temperature after cooling is 90℃; c. The dispersion time is 25 minutes; d. The dispersion temperature is 50℃.

37. A fiber prepreg, characterized in that, It includes the cyclic olefin / epoxy resin mixture and the reinforcing agent as described in any one of claims 1-32; The resin content in the fiber prepreg is 25-40 wt%, and the percentage is the percentage of the weight of the resin in the fiber prepreg to the total weight of the fiber prepreg.

38. The fiber prepreg as described in claim 37, characterized in that, The resin content in the fiber prepreg is 30-40 wt%.

39. The fiber prepreg as described in claim 37, characterized in that, The resin content in the fiber prepreg is 36 wt%.

40. The fiber prepreg as described in claim 37, characterized in that, The reinforcing material is an organic fiber and / or an inorganic fiber.

41. The fiber prepreg as described in claim 40, characterized in that, The organic fiber is aramid fiber and / or aromatic polyamide fiber.

42. The fiber prepreg as described in claim 40, characterized in that, The inorganic fiber is one or more of carbon fiber, glass fiber, and basalt fiber.

43. The fiber prepreg as described in claim 37, characterized in that, The fiber areal density of the reinforcement is 50-600 gsm.

44. The fiber prepreg as described in claim 37, characterized in that, The fiber areal density of the reinforcement is 100-300 gsm.

45. The fiber prepreg as described in claim 37, characterized in that, The fiber areal density of the reinforcement is 150 gsm.

46. ​​The fiber prepreg as described in claim 37, characterized in that, When the reinforcement is carbon fiber, the fiber areal density of the carbon fiber is 150 gsm.

47. A method for preparing a fiber prepreg, characterized in that, It includes the following steps: impregnating the reinforcing body with the cycloolefin / epoxy resin mixture as described in any one of claims 1-32.

48. A composite material, characterized in that, It includes fibers and a three-dimensional network structure formed on the surface of the fibers by crosslinking and polymerization of a cyclic olefin / epoxy resin mixture as described in any one of claims 1-32.

49. A method for preparing a composite material, characterized in that, It includes the following steps: curing the fiber prepreg as described in claims 37-46 into shape.

50. The method for preparing the composite material as described in claim 49, characterized in that, The curing process for the curing molding is "heating at 70-90℃ for 0.8-1.2h, heating at 90-130℃ for 0.8-1.2h, heating at 110-150℃ for 0.8-1.2h", or "heating at 70-90℃ for 0.8-1.2h, heating at 90-130℃ for 1.5-3h".

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