Epoxy-cycloolefin resin composition, thermosetting resin material and method for producing the same

Abstract

Disclosed are an epoxy-cycloolefin resin composition, a thermosetting resin material and a preparation method thereof. The resin composition comprises composition A, composition B and composition C; the composition A comprises liquid epoxy resin 50-95 parts, cycloolefin monomer composition 5.0-50 parts and functional auxiliary 0.1-4 parts; the cycloolefin monomer composition comprises dicyclopentadiene and one or more of tricyclopentadiene, tetracyclopentadiene and pentacyclopentadiene; the composition B comprises epoxy resin curing agent 90-97 parts and curing accelerator 3-10 parts; the composition C comprises ruthenium carbene compound or salt thereof 0.01-1.0 parts; the weight fraction ratio of the composition A, the composition B and the composition C is 100:(50-120):(0.001-1). The resin composition of the present application can be stored for a long time, has high flash point, and the thermosetting resin material prepared from the resin composition has excellent mechanical properties and good toughening effect.

Description

Technical Field

[0001] This invention relates to an epoxy-cycloolefin resin composition, a thermosetting resin material, and a method for preparing the same. Background Technology

[0002] Epoxy resin is a widely used high-performance thermosetting polymer material. Before curing, the epoxy resin molecule contains highly chemically active functional groups such as epoxy groups, hydroxyl groups, and ether bonds. A suitable epoxy curing agent and accelerator compound system can be used to crosslink it to form a three-dimensional network structure. The resulting thermosetting resin material has excellent properties such as low deformation shrinkage, high hardness, and good chemical stability, and is therefore widely used in casting materials, laminates, and electronic appliances.

[0003] Cycloolefin resins, represented by dicyclopentadiene (DCPD), can be synthesized into thermosetting polycyclic cyclic olefin resin materials through ring-opening metathesis polymerization (ROMP) in the presence of catalysts such as ruthenium carbene or traditional tungsten / molybdenum metal-organic complexes. These materials possess both high strength and toughness. After curing, a resin system composed of cyclic olefin resins and epoxy resins in appropriate proportions can form an interpenetrating network (IPN), which can effectively enhance the toughness of thermosetting epoxy resin materials.

[0004] However, current cyclic olefin resins with DCPD as the monomer (cyclic olefin mass fraction not less than 20 wt.%), when mixed with liquid epoxy resin to form compound resins, suffer from low flash points. This leads to the generation of volatile organic compounds (VOCs) during production and transportation, posing a safety hazard of deflagration and causing significant odor issues during the preparation of thermosetting polymer materials. Furthermore, while compound resins obtained by simply using DCPD as the cyclic olefin monomer in combination with epoxy resin can improve the toughness of cured thermosetting materials, they significantly sacrifice the material's strength properties. However, since commonly used ruthenium carbene catalysts or their compositions are generally solids, they are difficult to use directly in continuous production processes. Therefore, in practical applications, solvents with sufficient solubility for ruthenium carbene catalysts and which do not undergo vigorous polymerization reactions are often used to prepare the catalyst as a solution. This solution results in a low flash point for the catalyst components, increasing VOC emissions during production and easily leading to catalyst deactivation.

[0005] CN 112547126A discloses an application of a ruthenium carbene composition, which discloses a dicyclopentadiene / epoxy resin composite material formulation: dicyclopentadiene and epoxy resin are mixed to form component A, and a ruthenium carbene catalyst composition, methyl-5-norbornene-2,3-dicarboxylic anhydride (epoxy curing agent, comonomer), coupling agent KH560 and anti-aging agent are formed to form component B.

[0006] CN 112547126A discloses an application of a ruthenium carbene composition, which also discloses a dicyclopentadiene / epoxy resin composite material formulation: dicyclopentadiene and epoxy resin are mixed to form component A, and ruthenium carbene catalyst-chlorinated paraffin composition, methyltetrahydrophthalic anhydride (epoxy resin curing agent), 2-methylimidazolium (curing agent accelerator), glass fiber, and silane coupling agent A172 are composed of component B.

[0007] CN 112662129A discloses a resin composition, a composite material and a method for preparing the same, wherein a formulation for preparing polydicyclopentadiene is disclosed: dicyclopentadiene, graphite powder and triphenylphosphine are mixed as component A, and a catalyst-chlorinated paraffin composition and methyl-5-norbornene-2,3-dicarboxylic anhydride (comonomer) are mixed as component B.

[0008] CN 113736211A discloses a dicyclopentadiene / epoxy resin composite, the material preparation process of which is as follows: a) mixing epoxy resin and DCPD evenly; b) pouring the mixed epoxy curing agent and accelerator (which may also contain solvent) composition into the epoxy resin and DCPD mixture and stirring evenly; c) adding a toluene solution of ruthenium carbene catalyst into the aforementioned mixed resin, mixing evenly, and casting the resin plate; d) obtaining the thermosetting resin by applying suitable curing conditions.

[0009] CN 114276491A discloses a method for preparing a stable liquid catalyst composition using unsaturated acid anhydrides containing C=C structures and having no more than 20 carbon atoms in the molecule and / or esters containing C=C structures and having no more than 20 carbon atoms in the molecule as solvents / dispersants for ruthenium carbene catalysts. When used in conjunction with liquid cyclic olefin / cyclic olefin compositions, it can realize the continuous and automated production of thermosetting cyclic olefin resins.

[0010] As can be seen from the above description of the prior art, the prior art generally does not meet the requirements of having both a high flash point and the ability to toughen the cured epoxy resin material. Furthermore, when DCPD is used alone as a cyclic olefin component to be compounded with epoxy resin, a high content of DCPD is required to ensure that the toughness of the cured thermosetting material meets the requirements. Moreover, the flash point of the compounded resin mixture is relatively low, which is not conducive to safe production and VOCs control in the production site. The mechanical properties of the material after the DCPD-epoxy compound resin is cured are lower than those of the material after the pure epoxy resin is cured. Summary of the Invention

[0011] To address the aforementioned technical problems, this invention provides an epoxy-cycloolefin resin composition, a thermosetting resin material, and a method for preparing the same. The resin composition of this invention can be stored for extended periods, has a high flash point, and the thermosetting resin material prepared from this composition exhibits excellent mechanical properties and good toughening effect.

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

[0013] This invention provides an epoxy-cyclic olefin resin composition, which, by weight, comprises: composition A, composition B, and composition C;

[0014] The composition A comprises: 50-95 parts of liquid epoxy resin, 5.0-50 parts of cyclic olefin monomer composition, and 0.1-4 parts of functional additives; the cyclic olefin monomer composition comprises one or more of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), tetracyclopentadiene (TeCPD), and pentacyclopentadiene (PCPD);

[0015] The composition B comprises: 90-97 parts of epoxy resin curing agent and 3-10 parts of curing accelerator;

[0016] The composition C comprises 0.01 to 1.0 parts of a ruthenium carbene compound or a salt thereof;

[0017] The weight fraction ratio of composition A, composition B and composition C is 100:(50-120):(0.001-1).

[0018] In this invention, the closed-cup flash point of the compositions A, B, and C is preferably not lower than 60°C.

[0019] In this invention, the weight fraction ratio of composition A, composition B and composition C can be 100:(60-80):(0.01-0.1), for example 100:72:0.05 or 100:71.64:0.05.

[0020] In this invention, the liquid epoxy resin can be conventional in the art, preferably one or more of bisphenol A type epoxy resin, bisphenol A type phenolic epoxy resin, bisphenol F type epoxy resin, o-cresol type epoxy resin and p-aminophenol epoxy resin, preferably bisphenol A type epoxy resin.

[0021] In this invention, the amount of liquid epoxy resin can be 50-70 parts, preferably 60-70 parts, for example 65.8 parts or 66 parts.

[0022] In this invention, the epoxy value of the liquid epoxy resin can be 0.2 to 0.6, preferably 0.51 to 0.54.

[0023] In this invention, the liquid epoxy resin may be of the type Yangnong YN-1828.

[0024] In this invention, the amount of the cyclic olefin monomer composition can be 10 to 35 parts, preferably 33 parts.

[0025] In this invention, the amount of dicyclopentadiene (DCPD) in the cyclic olefin monomer composition can be 1 to 20 parts, for example 5 parts, 10 parts or 18 parts.

[0026] In this invention, when the cyclic olefin monomer composition includes tricyclopentadiene (TCPD), the amount of tricyclopentadiene (TCPD) can be 0 to 55 parts, preferably 10 to 20 parts, for example 10 parts or 15 parts.

[0027] In this invention, when the cyclic olefin monomer composition includes tetracyclopentadiene (TeCPD), the amount of tetracyclopentadiene (TeCPD) can be 0 to 30 parts, preferably 2 to 10 parts, for example 5 parts, 8 parts or 10 parts.

[0028] In this invention, when the cyclic olefin monomer composition includes pentacyclopentadiene (PCPD), the amount of pentacyclopentadiene (PCPD) can be 0 to 30 parts, preferably 2 to 10 parts, for example 3 parts or 5 parts.

[0029] In this invention, the cyclic olefin monomer composition may include 1 to 20 parts of dicyclopentadiene (DCPD) and 10 to 20 parts of tricyclopentadiene (TCPD), for example, 18 parts of dicyclopentadiene (DCPD) and 15 parts of tricyclopentadiene (TCPD).

[0030] In this invention, the cyclic olefin monomer composition may include 1-20 parts of dicyclopentadiene (DCPD), 10-20 parts of tricyclopentadiene (TCPD), and 2-10 parts of tetracyclopentadiene (TeCPD), for example, 18 parts of dicyclopentadiene (DCPD), 10 parts of tricyclopentadiene (TCPD), and 5 parts of tetracyclopentadiene (TeCPD).

[0031] In this invention, the cyclic olefin monomer composition may include 1-20 parts of dicyclopentadiene (DCPD), 10-20 parts of tricyclopentadiene (TCPD), 2-10 parts of tetracyclopentadiene (TeCPD), and 2-10 parts of pentacyclopentadiene (PCPD), for example, 10 parts of dicyclopentadiene (DCPD), 15 parts of tricyclopentadiene (TCPD), 5 parts of tetracyclopentadiene (TeCPD), and 3 parts of pentacyclopentadiene (PCPD); or, 5 parts of dicyclopentadiene (DCPD), 15 parts of tricyclopentadiene (TCPD), 8 parts of tetracyclopentadiene (TeCPD), and 5 parts of pentacyclopentadiene (PCPD); or, 10 parts of dicyclopentadiene (DCPD), 10 parts of tricyclopentadiene (TCPD), 10 parts of tetracyclopentadiene (TeCPD), and 3 parts of pentacyclopentadiene (PCPD).

[0032] In this invention, the cyclic olefin monomer composition may also include other types of cyclic olefin compounds, such as ethylidene norbornene and / or methyldicyclopentadiene.

[0033] The amount of the ethylidene norbornene and / or the methyldicyclopentadiene can be 0 to 20 parts.

[0034] In this invention, the amount of the functional additive can be 0.5 to 3 parts, preferably 0.5 to 1.5 parts, for example 1 part or 1.2 parts.

[0035] In this invention, the functional additives may be one or more of polymerization regulators, antioxidants, light stabilizers, coupling agents, functional fillers, basalt fibers, polyethylene fibers, aramid fibers, chopped glass fibers, and colorants, preferably polymerization regulators and / or antioxidants.

[0036] The polymerization regulator may be an organophosphorus compound, preferably one or more of triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenylphosphine (TPP), trioctylphosphine, and tricyclohexylphosphine.

[0037] The amount of the polymerization regulator can be 0.1 to 2 parts, preferably 0.5 to 1.0 parts.

[0038] The amount of the antioxidant can be 0 to 0.5 parts, for example, 0.2 parts.

[0039] In this invention, the functional additive is preferably 1 part of triphenylphosphine (TPP) and 0.2 parts of antioxidant.

[0040] The functional filler may be one or more of the following: aluminum hydroxide, magnesium hydroxide, magnesium aluminum hydrotalcite powder, red phosphorus, zinc borate, graphite powder, carbon nanotubes, mica sheets, titanium dioxide, montmorillonite, fumed silica, and carbon fiber powder.

[0041] In this invention, the epoxy resin curing agent can be a conventional epoxy resin curing agent in the art, preferably one or more of methyltetrahydrophthalic anhydride (MeTHPA), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride (MNA), dicyandiamide, linear phenolic resin, 4,4'-diaminodiphenyl sulfone (DDS), and trimellitic anhydride.

[0042] In this invention, the amount of epoxy resin curing agent can be 92 to 96 parts, for example 95.4 parts.

[0043] In a preferred embodiment, the epoxy resin curing agent is 22.7 parts of methyl nadic anhydride (MNA) and 72.7 parts of methyl tetrahydrophthalic anhydride (MeTHPA).

[0044] In a preferred embodiment, the epoxy resin curing agent is 22.2 parts of methyl nadic anhydride (MNA) and 72.7 parts of methyl tetrahydrophthalic anhydride (MeTHPA).

[0045] In this invention, the curing accelerator is a conventional curing accelerator in the art, preferably one or more of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) and DCMU-P accelerator.

[0046] In this invention, the amount of the curing accelerator can be 3 to 5 parts, for example 4.6 parts.

[0047] In this invention, the amount of the ruthenium carbene compound or its salt may be 0.02 to 0.5 parts, for example 0.05 parts.

[0048] In this invention, the ruthenium carbene compound or its salt may include a ruthenium carbene compound or its salt as shown in Formula I:

[0049]

[0050] Among them, R1, R2, and R3 are independently C6-C 18 alkyl.

[0051] Wherein, the ruthenium carbene compound or its salt as shown in Formula I, the C6-C 18 Alkyl groups can be C6-C independently. 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C6 alkyl. 10 Alkyl; more preferably C8 alkyl or C6 alkyl. 10 alkyl.

[0052] The C6 alkyl group is preferably n-hexyl or 4-methylpentyl.

[0053] The C8 alkyl group is preferably n-octyl, 2-ethylhexyl, or 5-methylheptyl; more preferably 2-ethylhexyl.

[0054] The C 10 The alkyl group is preferably n-decyl.

[0055] Wherein, the ruthenium carbene compound or its salt as shown in Formula I, wherein R1, R2 and R3 are the same or different.

[0056] The ruthenium carbene compound represented by Formula I is selected from any of the following structures:

[0057]

[0058] The ruthenium carbene compound or its salt as shown in Formula I is preferably in liquid form.

[0059] The method for preparing the ruthenium carbene compound or its salt as shown in Formula I includes either Method I or Method II:

[0060] Method 1: Compound 2 and compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0061]

[0062] Method 2: Compound 4 and Compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0063]

[0064] The definitions of R1, R2, and R3 are as described above.

[0065] In Method 1, the organic solvent can be a conventional solvent for such reactions in the art, preferably a haloalkane solvent, and more preferably dichloromethane.

[0066] In Method 1, the inert atmosphere can be a conventional inert gas for this type of reaction in the art, preferably nitrogen.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] In Method 1, the reaction time of the substitution reaction is based on TLC monitoring to ensure the reaction is complete, preferably 1 to 5 hours, and more preferably 2 hours.

[0071] 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).

[0072] 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).

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In Method 2, the reaction time of the substitution reaction is based on TLC monitoring to ensure the reaction is complete, preferably 1 to 5 hours, and more preferably 2 hours.

[0077] 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.

[0078] Method 1 further includes the following step: under an inert atmosphere, compound 1 undergoes a substitution reaction with pyridine as shown below;

[0079]

[0080] The pyridine is anhydrous pyridine.

[0081] The inert atmosphere can be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0082] The volume molar ratio of the pyridine to the compound 1 can be a conventional volume molar ratio for such reactions in the art, preferably from 2 L / mol to 20 L / mol, and more preferably 5 L / mol.

[0083] The substitution reaction was carried out at room temperature.

[0084] The reaction time for the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably 2 h to 10 h, more preferably 5 h.

[0085] The substitution reaction was carried out under stirring conditions.

[0086] 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).

[0087] In this invention, when using the ruthenium carbene compound or its salt as shown in Formula I, it is preferable that the ruthenium carbene compound or its salt is not dissolved in a solvent.

[0088] In this invention, the ruthenium carbene compound or its salt may also include a ruthenium carbene compound or its salt as shown in Formula II:

[0089] ;

[0090] Among them, R 1 and R 2 Independently for C4-C 18 Alkyl or R 1-1 Replacement C4-C 18 Alkyl; the R 1-1 For C6-C 10 Aryl.

[0091] In this invention, when the ruthenium carbene compound or its salt is a ruthenium carbene compound represented by Formula II, the ruthenium carbene compound or its salt is generally dissolved in a solvent for use.

[0092] The solvent may be conventional in the art, such as chlorinated paraffin, methyl nadic anhydride, or tetrahydrophthalic anhydride.

[0093] The weight ratio of the ruthenium carbene compound or its salt to the solvent can be conventional in the art, and preferably 1:9.

[0094] In this invention, the ruthenium carbene compound or its salt may also include compounds as shown in Formula III and / or Formula IV:

[0095]

[0096] In this invention, when the ruthenium carbene compound or its salt is a ruthenium carbene compound represented by Formula III and / or Formula IV, the ruthenium carbene compound is generally dissolved in a solvent for use.

[0097] The solvent is preferably toluene, dichloromethane, tetrahydrofuran, or methylnadic anhydride, and more preferably methylnadic anhydride.

[0098] The weight ratio of the ruthenium carbene compound or its salt to the solvent can be conventional in the art, and preferably 14:86.

[0099] In this invention, the preparation method of composition A can be conventional in the art, and preferably it is to mix the liquid epoxy resin, the cyclic olefin monomer composition and the functional additive.

[0100] The mixing is generally carried out by stirring in a mixing vessel.

[0101] The mixing is generally carried out under an inert atmosphere, such as a nitrogen atmosphere.

[0102] The mixing temperature can be conventional in the art, preferably 35-90°C, and more preferably 40-60°C.

[0103] The mixing time can be conventional in the art, preferably 0.5 to 2 hours.

[0104] In this invention, the preparation method of composition B can be conventional in the art, and preferably it is to mix the epoxy resin curing agent and the curing accelerator.

[0105] The mixing is generally carried out by stirring in a mixing vessel.

[0106] The mixing is generally carried out under an inert atmosphere, such as a nitrogen atmosphere.

[0107] The mixing temperature can be conventional in the art, preferably 30-40°C.

[0108] The mixing time can be conventional in the art, preferably 0.5 to 2 hours.

[0109] In this invention, when the ruthenium carbene compound or its salt is a ruthenium carbene compound represented by Formula III, it is preferable to dissolve the ruthenium carbene compound in a solvent before adding it to composition B.

[0110] The present invention also provides a method for preparing a thermosetting resin material, which includes the following steps: curing the epoxy-cycloolefin resin composition into shape.

[0111] In this invention, the preparation method may employ RTM or VARI processes.

[0112] In this invention, the curing temperature can be 70℃ to 180℃, for example 80℃.

[0113] In this invention, the curing time can be 1 to 6 hours, preferably 3 to 5 hours.

[0114] In this invention, the curing process is preferably a gradient temperature curing process.

[0115] In a preferred embodiment, the curing process involves first curing at 80°C for 3 hours, and then curing at 140°C for 2 hours.

[0116] In this invention, it is preferable to mix and vacuum degas the composition A, composition B and composition C before curing and molding.

[0117] The mixing is preferably performed in a static mixer.

[0118] The mixing temperature is preferably 20–30°C, and more preferably 20–25°C.

[0119] The present invention also provides a thermosetting resin material, which is prepared by the preparation method described above.

[0120] In a preferred embodiment, the liquid epoxy resin and the cyclic olefin monomer composition are each crosslinked and polymerized to form an interpenetrating network structure.

[0121] 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.

[0122] The reagents and raw materials used in this invention are all commercially available.

[0123] The positive and progressive effects of this invention are as follows:

[0124] (1) The resin composition of the present invention can be stored for a long time, has good stability and high flash point;

[0125] (2) The thermosetting resin material prepared by the resin composition of the present invention compensates for the decrease in mechanical properties of the prepared thermosetting material caused by the introduction of cyclic olefin monomers in some compound resins, while still having a good toughening effect on the cured epoxy resin matrix. Detailed Implementation

[0126] 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.

[0127] 1. In the following examples and comparative examples, the flash point was tested in accordance with GB / T261-2021.

[0128] 2. In the following examples and comparative examples, DCPD is dicyclopentadiene, TCPD is tricyclopentadiene, TeCPD is tetracyclopentadiene, and PCPD is pentacyclopentadiene.

[0129] Preparation methods of TCPD / TePCD / PCPD:

[0130] (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.

[0131] (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.

[0132] (3) The bottom material of the column is subjected to negative pressure distillation, and the resulting fraction is TeCPD. The residue contains PCPD.

[0133] (4) Wash the residue with toluene and collect the washing liquid. Remove the toluene solvent by vacuum distillation to obtain PCPD.

[0134] 3. The structures of the Ru-I ruthenium carbene catalysts used in Examples 1-5, Examples 8-9, and Comparative Examples 2-4 are shown below:

[0135]

[0136] The preparation method of this Ru-I ruthenium carbene catalyst is as follows:

[0137] Method 1

[0138] Synthesis of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(trioctylphosphine)ruthenium dichloride catalyst Ru-I:

[0139]

[0140] 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 65Cl2N2PRu (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%.

[0141] C 38 H 42 Theoretical (calculated) values ​​of Cl2N4Ru: C, 62.80 (62.62); H, 5.83 (5.60); N, 7.71 (7.61).

[0142] 1 H 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).

[0143] 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

[0144] 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 tri-n-octylphosphine (Cf:C) was added to the flask. 24 H 51P; Mw: 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 liquid catalyst Ru-I (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%.

[0145] Analyze the data:

[0146] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2PRu: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0147] 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).

[0148] Method 2

[0149]

[0150] 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 83Cl2N2PRu (molecular weight: 939.19 g / mol), yield 88%.

[0151] Analyze the data:

[0152] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2Pru: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0153] 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).

[0154] In this invention, the Ru-I ruthenium carbene catalyst prepared is in liquid state.

[0155] 4. Examples and Comparative Examples

[0156] Example 1

[0157] 1. Preparation of resin composition:

[0158] Group A formulation: Add 66 parts by weight of Yangnong YN-1828 bisphenol A type epoxy resin (purchased from Jiangsu Yangnong Jinhu Chemical Co., Ltd., epoxy value 0.51-0.54), 18 parts by weight of DCPD, 15 parts by weight of TCPD and 1 part by weight of TPP to the mixing vessel. Pour nitrogen into the mixing vessel as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Group A.

[0159] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0160] Component C: Add liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0161] The flash points (closed cup) of the above three components are as follows:

[0162] Component A 63℃

[0163] Component B >100℃

[0164] Component C > 100℃

[0165] 2. Preparation of thermosetting resin materials:

[0166] (1) Inject 100 parts of component A, 72 parts of component B and 0.05 parts of component C into a static mixer at room temperature (20-25°C) and mix thoroughly.

[0167] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0168] (3) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0169] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0170] 3. Material properties:

[0171] The obtained material has a tensile strength of 71.6 MPa, a modulus of 3054 MPa, an elongation at break of 5.1% (test standard GB / T 2567-2021), and an unnotched impact strength of 24 kJ / m. 2 (The testing standard is ISO-180.)

[0172] Example 2

[0173] 1. Preparation of resin composition:

[0174] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 18 parts by weight of DCPD, 10 parts by weight of TCPD, 5 parts by weight of TeCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0175] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0176] Component C: Add ruthenium carbene catalyst Ru-I to the dedicated container for component C.

[0177] The flash points (closed cup) of the above three components are as follows:

[0178] Component A 65℃

[0179] Component B >100℃

[0180] Component C > 100℃

[0181] 2. Preparation of thermosetting resin materials:

[0182] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0183] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0184] (3) The degassed mixed resin was injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0185] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0186] 3. Material properties:

[0187] The obtained material has a tensile strength of 72.6 MPa, a modulus of 3098 MPa, an elongation at break of 5.1% (test standard GB / T 2567-2021), and an unnotched impact strength of 24 kJ / m. 2 (The testing standard is ISO-180.)

[0188] Example 3

[0189] 1. Preparation of resin composition:

[0190] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 10 parts by weight of DCPD, 15 parts by weight of TCPD, 5 parts by weight of TeCPD, 3 parts by weight of PCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0191] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0192] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0193] The flash points (closed cup) of the above three components are as follows:

[0194] Component A 78℃

[0195] Component B >100℃

[0196] Component C > 100℃

[0197] 2. Preparation of thermosetting resin materials:

[0198] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0199] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0200] (3) The degassed mixed resin was injected into the mold using VARI, heated to 80°C, and cured for 5 hours;

[0201] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0202] 3. Material properties:

[0203] The obtained material has a tensile strength of 73.0 MPa, a modulus of 3140 MPa, an elongation at break of 4.9% (test standard GB / T 2567-2021), and an unnotched impact strength of 22 kJ / m. 2 (The testing standard is ISO-180.)

[0204] Example 4

[0205] 1. Preparation of resin composition:

[0206] Component A preparation: Add 65.8 parts by weight of YN1828 bisphenol A type epoxy resin, 5 parts by weight of DCPD, 15 parts by weight of TCPD, 8 parts by weight of TeCPD, 5 parts by weight of PCPD, 1 part by weight of TPP and 0.2 parts by weight of antioxidant 264 to the mixing vessel. Pour nitrogen into the mixing vessel as a protective gas, heat to 50°C, stir for 4 hours, cool, and then seal and discharge the material into the dedicated container for Component A.

[0207] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0208] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0209] The flash points (closed cup) of the above three components are as follows:

[0210] Component A 99℃

[0211] Component B >100℃

[0212] Component C > 100℃

[0213] 2. Preparation of thermosetting resin materials:

[0214] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0215] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0216] (3) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0217] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0218] 3. Material properties:

[0219] The obtained material has a tensile strength of 73.7 MPa, a modulus of 3180 MPa, an elongation at break of 4.8% (test standard GB / T 2567-2021), and an unnotched impact strength of 21 kJ / m. 2 (The testing standard is ISO-180.)

[0220] Example 5

[0221] 1. Preparation of resin composition:

[0222] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 18 parts by weight of DCPD, 15 parts by weight of TCPD and 1 part by weight of TPP to the mixing vessel, fill the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A (nitrogen protection).

[0223] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, fill the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B (nitrogen protection).

[0224] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to a dedicated container for Component C, and seal it with nitrogen gas.

[0225] The flash points (closed cup) of the above three components are as follows:

[0226] Component A 63℃

[0227] Component B >100℃

[0228] Component C > 100℃

[0229] 2. Preparation of thermosetting resin materials:

[0230] (1) Store components A, B, and C in their respective containers and leave them at room temperature (20-25°C) for 6 months;

[0231] (2) Inject 100 parts by weight, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix thoroughly;

[0232] (3) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0233] (4) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0234] (5) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0235] 3. Material properties:

[0236] The obtained material has a tensile strength of 71.6 MPa, a modulus of 3057 MPa, an elongation at break of 5.2% (test standard GB / T 2567-2021), and an unnotched impact strength of 24 kJ / m. 2 (The testing standard is ISO-180.)

[0237] Example 6

[0238] 1. Preparation of resin composition:

[0239] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 10 parts by weight of DCPD, 15 parts by weight of TCPD, 5 parts by weight of TeCPD, 3 parts by weight of PCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0240] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0241] Component C: A composition of ruthenium carbene catalyst Ru-II and chlorinated paraffin 52, wherein Ru-II catalyst comprises 10 parts by mass and chlorinated paraffin 52 comprises 90 parts by mass.

[0242] The structural formula of the ruthenium carbene catalyst Ru-II is shown below:

[0243]

[0244] The flash points (closed cup) of the above three components are as follows:

[0245] Component A 78℃

[0246] Component B >100℃

[0247] Component C > 100℃

[0248] 2. Preparation of thermosetting resin materials:

[0249] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.5 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix thoroughly;

[0250] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0251] (3) The degassed mixed resin was injected into the mold using VARI, heated to 80°C, and cured for 5 hours;

[0252] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0253] 3. Material properties:

[0254] The obtained material has a tensile strength of 72.9 MPa, a modulus of 3110 MPa, an elongation at break of 4.7% (test standard GB / T 2567-2021), and an unnotched impact strength of 22 kJ / m. 2 (The testing standard is ISO-180.)

[0255] Example 7

[0256] 1. Preparation of resin composition:

[0257] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 10 parts by weight of DCPD, 15 parts by weight of TCPD, 5 parts by weight of TeCPD, 3 parts by weight of PCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0258] Component B preparation: 22.2 parts by mass of MNA, 72.7 parts by mass of MeTHPA and 4.6 parts by mass of DMP-30 accelerator were added to a mixing vessel. Nitrogen gas was introduced into the mixing vessel as a protective gas, heated to 35°C, stirred for 1 hour, and cooled to obtain component B.

[0259] Add 0.5 parts by mass of component C to component B, stir for 0.5 hours to obtain a mixture of components B and C, and then seal and discharge the mixture into a dedicated container for component B.

[0260] Component C consists of 14 parts by mass of G2 ruthenium carbene catalyst and 86 parts by mass of MNA.

[0261] The structural formula of the G2 ruthenium carbene catalyst is shown below:

[0262]

[0263] The flash points (closed cup) of the above three components are as follows:

[0264] Component A 78℃

[0265] Component B >100℃

[0266] Component C > 100℃

[0267] 2. Preparation of thermosetting resin materials:

[0268] (1) Pour 100 parts by weight of component A and 72 parts by weight of components B and C into a static mixer at room temperature (20-25°C) and mix thoroughly;

[0269] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0270] (3) The degassed mixed resin was injected into the mold using VARI, heated to 80°C, and cured for 5 hours;

[0271] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0272] 3. Material properties:

[0273] The obtained material has a tensile strength of 73.0 MPa, a modulus of 3134 MPa, an elongation at break of 5.0% (test standard GB / T 2567-2021), and an unnotched impact strength of 21 kJ / m. 2 (The testing standard is ISO-180.)

[0274] Example 8

[0275] 1. Preparation of resin composition:

[0276] Component A preparation: Add 66 parts by weight of YN1828 bisphenol A epoxy resin, 10 parts by weight of DCPD, 10 parts by weight of TCPD, 10 parts by weight of TeCPD, 3 parts by weight of PCPD and 1 part by weight of TPP to the mixing vessel. Pour nitrogen into the mixing vessel as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component A.

[0277] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0278] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0279] The flash points (closed cup) of the above three components are as follows:

[0280] Component A 80℃

[0281] Component B >100℃

[0282] Component C > 100℃

[0283] 2. Preparation of thermosetting resin materials:

[0284] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0285] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0286] (3) The degassed mixed resin was injected into the mold using VARI and cured by gradient temperature increase: (1) 80℃, cured for 3h; (2) 140℃, cured for 2h;

[0287] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0288] 3. Material properties:

[0289] The obtained material has a tensile strength of 81.0 MPa, a modulus of 3310 MPa, an elongation at break of 3.9% (test standard GB / T 2567-2021), and an unnotched impact strength of 20 kJ / m. 2 (The testing standard is ISO-180.)

[0290] Example 9

[0291] 1. Preparation of resin composition:

[0292] Group A distribution method: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin, 18 parts by weight of DCPD, 10 parts by weight of TCPD, 5 parts by weight of TeCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0293] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0294] Component C: Add liquid ruthenium carbene catalyst as shown in formula Ru-I to a dedicated container for component C.

[0295]

[0296] Ru-I

[0297] The flash points (closed cup) of the above three components are as follows:

[0298] Component A 65℃

[0299] Component B >100℃

[0300] Component C > 100℃

[0301] 2. Preparation of thermosetting resin materials:

[0302] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0303] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0304] (3) The degassed mixed resin is injected into the mold using the VARI process and cured by gradient temperature increase: (1) 80℃, cured for 3h; (2) 140℃, cured for 2h;

[0305] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0306] 3. Material properties:

[0307] The obtained material has a tensile strength of 76 MPa, a modulus of 3190 MPa, an elongation at break of 4.4% (test standard GB / T 2567-2021), and an unnotched impact strength of 22 kJ / m. 2 (The testing standard is ISO-180.)

[0308] Comparative Example 1

[0309] 1. Preparation of resin composition:

[0310] Component A: Add sufficient YN1828 bisphenol A type epoxy resin to the dedicated container for Component A;

[0311] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0312] The flash points (closed cup) of the two components are as follows:

[0313] Component A >100℃

[0314] Component B >100℃

[0315] 2. Preparation of thermosetting resin materials:

[0316] (1) Inject 100 parts by weight of component A and 110 parts by weight of component B into a static mixer at room temperature (20-25°C) and mix them evenly;

[0317] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0318] (3) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0319] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0320] 3. Material properties:

[0321] The obtained material has a tensile strength of 78.6 MPa, a modulus of 3268 MPa, an elongation at break of 4.5% (test standard GB / T 2567-2021), and an unnotched impact strength of 12 kJ / m.2 (The testing standard is ISO-180.)

[0322] Comparative Example 2

[0323] 1. Preparation of resin composition:

[0324] Group A preparation: Add 66 parts by weight of YN1828 bisphenol A type epoxy resin (purchased from Jiangsu Yangnong Jinhu Chemical Co., Ltd., epoxy value 0.51~0.54), 33 parts by weight of DCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0325] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0326] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0327] The flash points (closed cup) of the above three components are as follows:

[0328] Component A 46℃

[0329] Component B >100℃

[0330] Component C > 100℃

[0331] 2. Preparation of thermosetting resin materials:

[0332] (1) Inject 100 parts by weight, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0333] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0334] (3) The degassed mixed resin was injected into the mold using the VARI method, heated to 80°C, and cured for 5 hours;

[0335] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0336] 3. Material properties:

[0337] The obtained material has a tensile strength of 69.4 MPa, a modulus of 2994 MPa, an elongation at break of 5.4% (test standard GB / T 2567-2021), and an unnotched impact strength of 26 kJ / m.2 (The testing standard is ISO-180.)

[0338] Comparative Example 3

[0339] 1. Preparation of resin composition:

[0340] Group A preparation: Add 49 parts by weight of YN1828 bisphenol A type epoxy resin (purchased from Jiangsu Yangnong Jinhu Chemical Co., Ltd., epoxy value 0.51~0.54), 50 parts by weight of DCPD and 1 part by weight of TPP to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 50°C, stir for 1 hour, cool, and then seal and discharge the material into the special material tank for Group A.

[0341] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0342] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0343] The flash points (closed cup) of the above three components are as follows:

[0344] Component A 41℃

[0345] Component B >100℃

[0346] Component C > 100℃

[0347] 2. Preparation of thermosetting resin materials:

[0348] (1) Inject 100 parts by weight of component A, 53 parts by weight of component B and 0.08 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0349] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0350] (3) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0351] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0352] 3. Material properties:

[0353] The obtained material has a tensile strength of 62.4 MPa, a modulus of 2887 MPa, an elongation at break of 5.5% (test standard GB / T 2567-2021), and an unnotched impact strength of 31 kJ / m. 2 (The testing standard is ISO-180.)

[0354] Comparative Example 4

[0355] 1. Preparation of resin composition:

[0356] Component A preparation: Add 94 parts by weight of YN1828 bisphenol A type epoxy resin, 2 parts by weight of DCPD, 1.5 parts by weight of TCPD, 1 part by weight of TeCPD, 0.3 parts by weight of PCPD and 0.2 parts by weight of antioxidant 264 to a mixing vessel. Pour nitrogen into the mixing vessel as a protective gas, heat to 50°C, stir for 5 hours, cool, and then seal and discharge the material into a dedicated container for Component A.

[0357] Component B preparation: Add 22.7 parts by weight of MNA, 72.7 parts by weight of MeTHPA and 4.6 parts by weight of DMP-30 accelerator to the mixing vessel, purge the mixing vessel with nitrogen as a protective gas, heat to 35°C, stir for 1 hour, cool, and then seal and discharge the material into the dedicated container for Component B.

[0358] Component C: Add sufficient liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0359] The flash points (closed cup) of the above three components are as follows:

[0360] Component A >100℃

[0361] Component B >100℃

[0362] Component C > 100℃

[0363] 2. Preparation of thermosetting resin materials:

[0364] (1) Inject 100 parts by weight of component A, 72 parts by weight of component B and 0.05 parts by weight of component C into a static mixer at room temperature (20-25°C) and mix them evenly;

[0365] (2) The above-mentioned resin, which is mixed evenly, is degassed under vacuum;

[0366] (3) The degassed mixed resin is injected into the mold using the VARI process, heated to 80°C, and cured for 5 hours;

[0367] (4) After curing, wait for the mold to cool to room temperature, and then remove the mold to obtain the prepared thermosetting cyclic olefin-epoxy resin material.

[0368] 3. Material properties:

[0369] The obtained material has a tensile strength of 77.9 MPa, a modulus of 3250 MPa, an elongation at break of 4.9% (test standard GB / T 2567-2021), and an unnotched impact strength of 12 kJ / m. 2 (The testing standard is ISO-180.)

[0370] Comparative Example 5

[0371] Resin composition preparation:

[0372] Component A preparation: Add 30 parts by weight of YN1828 bisphenol A type epoxy resin, 10 parts by weight of DCPD, 40 parts by weight of TCPD, 15 parts by weight of TeCPD and 5 parts by weight of PCPD to a mixing vessel. Pour nitrogen into the mixing vessel as a protective gas, heat to 50°C, stir for 5 hours, cool, and then discharge into a dedicated container for Component A.

[0373] The resulting A-component compound resin composition is in the form of a paste, and some solids cannot be fully dissolved, making it unsuitable for continuous production.

[0374] The comparative results of Examples 1-4 and Comparative Examples 1 and 2 show that adding macrocyclic cyclic olefin monomers other than DCPD to the compound resin of cyclic olefin monomers and epoxy resin can effectively increase the flash point of the compound resin system, and can compensate for the reduction in mechanical properties of the thermosetting material after curing caused by the compounding of DCPD in epoxy resin, while retaining the toughening effect of the introduction of DCPD resin on the thermosetting epoxy resin material.

[0375] The comparative results of Example 1 and Comparative Examples 1-5 show that compounding epoxy resin with a certain proportion of cyclic olefin monomers can effectively improve the toughness of the cured resin material. However, when the DCPD content in the compounded resin system is too high, the resin system has good toughness but poor material strength; when the content of polycyclic cyclic olefin monomers in the compounded resin system is too high, it is impossible to compound a homogeneous resin composition that can be used for production. In addition, when the content of cyclic olefin components in the compounded resin is too low, it is impossible to effectively toughen the cured thermosetting epoxy resin.

[0376] The comparison of the results of Examples 8 and 9 shows that, under the same conditions of total cyclic olefin mass in resin and curing conditions, increasing the proportion of polycyclic cyclic olefin monomers in TeCPD and PCPD can significantly improve the tensile strength of the cured material after curing at high temperature (or under suitable curing conditions), while the toughness of the material is similar.

[0377] The thermosetting resin material obtained after curing the cyclic olefin-epoxy composite resin has significantly enhanced toughness (unnotched impact strength) compared to the thermosetting material cured with epoxy resin alone. Compared with the thermosetting material cured with DCPD-epoxy composite resin of the same cyclic olefin content, the mechanical properties are slightly improved, which makes up for part of the strength loss caused by the introduction of cyclic olefin monomers, while the toughness (unnotched impact strength) is basically the same.

Claims

1. An epoxy-cyclic olefin resin composition, characterized in that, The raw materials, by weight, include: composition A, composition B and composition C; The composition A comprises: 50-66 parts of liquid epoxy resin, 10-35 parts of cyclic olefin monomer composition, and 0.1-4 parts of functional additives; The cyclic olefin monomer composition comprises 1-20 parts of dicyclopentadiene, 10-20 parts of tricyclopentadiene, and 2-10 parts of tetracyclopentadiene; or, 1-20 parts of dicyclopentadiene, 10-20 parts of tricyclopentadiene, 2-10 parts of tetracyclopentadiene, and 2-10 parts of pentacyclopentadiene. The composition B comprises: 90-97 parts of epoxy resin curing agent and 3-10 parts of curing accelerator; The composition C comprises: 0.01 to 1.0 parts of a ruthenium carbene compound or a salt thereof; The weight fraction ratio of composition A, composition B, and composition C is 100:(50~120):(0.001~1). The ruthenium carbene compound or its salt thereof is a ruthenium carbene compound or its salt as shown in Formula I: ； Among them, R1, R2, and R3 are independently C6-C 18 alkyl.

2. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The epoxy-cycloolefin resin composition described herein satisfies one or more of the following conditions: (1) The closed-cup flash point of the composition A, the composition B and the composition C is not lower than 60°C; (2) The weight fraction ratio of composition A, composition B and composition C is 100:(60~80):(0.01~0.1); (3) The amount of the ruthenium carbene compound or its salt used is 0.02~0.5 parts; (4) The liquid epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol A type phenolic epoxy resin, bisphenol F type epoxy resin, o-cresol type epoxy resin and p-aminophenol epoxy resin; (5) The amount of liquid epoxy resin used is 60-66 parts; (6) The epoxy value of the liquid epoxy resin is 0.2~0.6; (7) The liquid epoxy resin is of the Yangnong YN-1828 type; (8) The amount of the functional additive is 0.5 to 3 parts; (9) The functional additives are one or more of the following: polymerization regulators, antioxidants, light stabilizers, coupling agents, functional fillers, basalt fibers, polyethylene fibers, aramid fibers, chopped glass fibers and colorants.

3. The epoxy-cycloolefin resin composition according to claim 2, characterized in that, The epoxy-cycloolefin resin composition described herein satisfies one or more of the following conditions: (1) The weight fraction ratio of the composition A, the composition B and the composition C is 100:72:0.05 or 100:71.64:0.05; (2) The amount of the ruthenium carbene compound or its salt used is 0.05 parts; (3) The liquid epoxy resin is a bisphenol A type epoxy resin; (4) The amount of liquid epoxy resin used is 65.8 parts or 66 parts; (5) The epoxy value of the liquid epoxy resin is 0.51~0.54; (6) The amount of the functional additive is 0.5 to 1.5 parts; (7) The functional additives are polymerization regulators and / or antioxidants.

4. The epoxy-cycloolefin resin composition according to claim 3, characterized in that, The epoxy-cycloolefin resin composition described herein satisfies one or more of the following conditions: (1) The amount of the functional additive is 1 part or 1.2 parts; (2) The polymerization regulator is an organophosphorus compound; (3) The amount of the polymerization regulator is 0.1 to 2 parts; (4) The amount of the antioxidant is 0 to 0.5 parts; (5) The functional additive is 1 part triphenylphosphine and 0.2 parts antioxidant; (6) The functional filler is one or more of aluminum hydroxide, magnesium hydroxide, magnesium aluminum hydrotalcite powder, red phosphorus, zinc borate, graphite powder, carbon nanotubes, mica sheets, titanium dioxide, montmorillonite, fumed silica and carbon fiber powder.

5. The epoxy-cycloolefin resin composition according to claim 4, characterized in that, The epoxy-cycloolefin resin composition described herein satisfies one or more of the following conditions: (1) The polymerization regulator is one or more of triethyl phosphite, tripropyl phosphite, tributyl phosphite, triphenylphosphine, trioctylphosphine and tricyclohexylphosphine; (2) The amount of the polymerization regulator is 0.5~1.0 parts; (3) The amount of the antioxidant is 0.2 parts.

6. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The cyclic olefin monomer composition satisfies one or more of the following conditions: (1) The amount of the cyclic olefin monomer composition used is 33 parts; (2) In the cyclic olefin monomer composition, the amount of dicyclopentadiene is 5 parts, 10 parts or 18 parts; (3) The cyclic olefin monomer composition further includes ethylidene norbornene and / or methyldicyclopentadiene.

7. The epoxy-cycloolefin resin composition according to claim 6, characterized in that, The cyclic olefin monomer composition satisfies one or two of the following conditions: (1) When the cyclic olefin monomer composition includes tricyclopentadiene, the amount of tricyclopentadiene is 10 parts or 15 parts; (2) The amount of the ethylidene norbornene and / or the methyldicyclopentadiene is 0 to 20 parts.

8. The epoxy-cycloolefin resin composition according to claim 7, characterized in that, The cyclic olefin monomer composition satisfies one or two of the following conditions: (1) When the cyclic olefin monomer composition includes tetracyclopentadiene, the amount of tetracyclopentadiene is 5 parts, 8 parts or 10 parts; (2) When the cyclic olefin monomer composition includes pentacyclopentadiene, the amount of pentacyclopentadiene is 3 parts or 5 parts.

9. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The cyclic olefin monomer composition satisfies any one of the following conditions: (1) The cyclic olefin monomer composition comprises 18 parts of dicyclopentadiene, 10 parts of tricyclopentadiene and 5 parts of tetracyclopentadiene; (2) The cyclic olefin monomer composition comprises 10 parts of dicyclopentadiene, 15 parts of tricyclopentadiene, 5 parts of tetracyclopentadiene and 3 parts of pentacyclopentadiene, or 5 parts of dicyclopentadiene, 15 parts of tricyclopentadiene, 8 parts of tetracyclopentadiene and 5 parts of pentacyclopentadiene, or 10 parts of dicyclopentadiene, 10 parts of tricyclopentadiene, 10 parts of tetracyclopentadiene and 3 parts of pentacyclopentadiene.

10. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The composition B satisfies one or more of the following conditions: (1) The epoxy resin curing agent is one or more of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, dicyandiamide, linear phenolic resin, 4,4'-diaminodiphenyl sulfone and trimellitic anhydride. (2) The amount of the epoxy resin curing agent is 92-96 parts; (3) The curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol and DCMU-P accelerator; (4) The amount of the curing accelerator is 3 to 5 parts.

11. The epoxy-cycloolefin resin composition according to claim 10, characterized in that, The composition B satisfies one or two of the following conditions: (1) The amount of the epoxy resin curing agent is 95.4 parts; (2) The amount of the curing accelerator is 4.6 parts.

12. The epoxy-cycloolefin resin composition according to claim 11, characterized in that, The composition B satisfies one or two of the following conditions: (1) The epoxy resin curing agent is 22.7 parts of methylnadic anhydride and 72.7 parts of methyltetrahydrophthalic anhydride; (2) The epoxy resin curing agent is 22.2 parts of methyl nadic anhydride and 72.7 parts of methyl tetrahydrophthalic anhydride.

13. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The C6-C 18 Alkyl groups are independently C6-C 10 alkyl; And / or, R1, R2 and R3 may be the same or different.

14. The epoxy-cycloolefin resin composition according to claim 13, characterized in that, The C6-C 18 The alkyl group is independently C6 alkyl, C8 alkyl or C 10 alkyl.

15. The epoxy-cycloolefin resin composition according to claim 14, characterized in that, The C6 alkyl group is n-hexyl or 4-methylpentyl.

16. The epoxy-cycloolefin resin composition according to claim 14, characterized in that, The C6-C 18 The alkyl group is independently a C8 alkyl group or a C8 alkyl group. 10 alkyl.

17. The epoxy-cycloolefin resin composition according to claim 16, characterized in that, The C8 alkyl group is n-octyl, 2-ethylhexyl, or 5-methylheptyl; And / or, the C 10 The alkyl group is n-decyl.

18. The epoxy-cycloolefin resin composition according to claim 17, characterized in that, The C8 alkyl group is 2-ethylhexyl.

19. The epoxy-cycloolefin resin composition according to claim 13, characterized in that, The ruthenium carbene compound as shown in Formula I is selected from any of the following structures: ， 。 20. The epoxy-cycloolefin resin composition according to claim 1, characterized in that, The method for preparing the ruthenium carbene compound or its salt as shown in Formula I includes either Method I or Method II: 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 any one of claims 1 or 13-19.

21. A method for preparing a thermosetting resin material, characterized in that, It includes the following steps: The epoxy-cyclic olefin resin composition as described in any one of claims 1-20 can be cured and molded.

22. The method for preparing the thermosetting resin material according to claim 21, characterized in that, It meets one or more of the following conditions: (1) The preparation method described herein employs either the RTM process or the VARI process; (2) The curing temperature is 70℃~180℃; (3) The curing time is 1 to 6 hours.

23. The method for preparing the thermosetting resin material according to claim 22, characterized in that, It meets one or two of the following conditions: (1) The curing temperature is 80℃; (2) The curing time is 3~5h.

24. A thermosetting resin material, characterized in that, It is prepared according to the preparation method described in any one of claims 21-23.

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