A ruthenium carbene catalyst, compositions containing the same, methods of making and using the same

Abstract

The application provides a ruthenium carbene catalyst, a composition containing the same, a preparation method and application thereof. Specifically disclosed is a ruthenium carbene compound as shown in the formula LG or a salt thereof, wherein R1, R2 and R3 are independently C6-C 18 alkyl. The ruthenium carbene catalyst of the application exists in a liquid state at normal temperature and is suitable for continuous production.

Description

Technical Field

[0001] This invention relates to a ruthenium carbene catalyst, a composition containing the same, a method for its preparation, and its applications. Background Technology

[0002] Olefin metathesis is a unique carbon skeleton rearrangement reaction that transforms C=C or C≡C bonds in monomers through carbene metal center catalysis, leading to the exchange coupling and rearrangement of unsaturated bonds to synthesize new carbon-carbon bonds. It is a crucial and important technique in organic synthesis. In recent years, olefin metathesis has attracted widespread attention, partly because it is a novel carbon-carbon synthesis method, and partly because its synthetic routes are simple, compatible with most organic functional groups, involve few side reactions, exhibit high conversion rates, and require relatively mild reaction conditions, making it highly suitable for industrial applications.

[0003] Common catalyst systems for olefin ring-opening metathesis polymerization in olefin metathesis reactions include W / Mo binary catalysts and Ru single-component catalysts. Compared to binary catalysts, 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 less demanding in terms of reaction conditions, capable of catalyzing reactions even in the presence of impurities such as oxygen and water. Therefore, they have become commonly used catalysts for olefin metathesis and ring-opening metathesis polymerization reactions.

[0004] 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 the subsequent curing process can cause porosity and product volume shrinkage, severely impacting their performance.

[0005] 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.

[0006] To address the shortcomings of ruthenium carbene catalysts, patent CN112547126A synthesized a novel ruthenium carbene catalyst composition 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 itself is solid at room temperature and must be combined with chlorinated paraffin to become liquid. Furthermore, its main focus is on improving the 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.

[0007] To simplify the synthesis process of ruthenium carbene catalysts, patent CN110105400A reports replacing the P ligand with N ligand in the catalyst, requiring only two steps to synthesize the desired catalyst, while the raw materials are readily available. In this patent, N ligands are used to replace the P ligand in the ruthenium carbene catalyst to prepare a temperature-sensitive ruthenium carbene catalyst. The inventors repeated Examples 2 and 3, finding that it remained a solid at room temperature, failing to resolve the processability issues. Summary of the Invention

[0008] To address the shortcomings of existing ruthenium carbene catalysts, such as complex preparation processes and unsuitability for continuous production, this invention provides a ruthenium carbene catalyst, a composition containing it, its preparation method, and its applications. The ruthenium carbene catalyst of this invention has a simple preparation process, stable product performance, and exists in a liquid state at room temperature, making it suitable for continuous production.

[0009] This invention provides a ruthenium carbene compound or a salt thereof as shown in formula LG.

[0010]

[0011] Among them, R1, R2, and R3 are independently C6-C 18 alkyl.

[0012] In some embodiments, the C6-C 18 Alkyl groups are independently C6-C 10 Alkyl groups, preferably C6 alkyl, C8 alkyl, or C6 alkyl. 10 Alkyl; more preferably C8 alkyl or C 10 alkyl.

[0013] In some embodiments, the C6 alkyl group is n-hexyl or 4-methylpentyl.

[0014] In some embodiments, the C8 alkyl group is n-octyl, 2-ethylhexyl, or 5-methylheptyl; preferably 2-ethylhexyl.

[0015] In some implementations, the C 10 The alkyl group is n-decyl.

[0016] In some implementations, R1, R2, and R3 may be the same or different.

[0017] In some embodiments, the ruthenium carbene compound as shown in Formula LG is selected from any of the following structures:

[0018]

[0019] The present invention also provides a method for preparing the ruthenium carbene compound shown in Formula LG, which includes either method one or method two:

[0020] Method 1: Compound 2 and compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0021]

[0022] Method 2: Compound 4 and Compound 3 undergo a substitution reaction as shown below in an organic solvent under an inert atmosphere;

[0023]

[0024] The definitions of R1, R2, and R3 are as described above.

[0025] In some embodiments, in method one, the organic solvent can be a conventional solvent for such reactions in the art, preferably a haloalkane solvent, and more preferably dichloromethane.

[0026] In some embodiments, in method one, the inert atmosphere can be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0027] In some embodiments, in method one, the molar ratio of compound 3 to compound 2 can be a conventional molar ratio for such reactions in the art, preferably (1 to 10):1, and more preferably 2:1.

[0028] In some embodiments, in method one, 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.

[0029] In some embodiments, in method one, the reaction temperature of the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably room temperature.

[0030] In some embodiments, 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.

[0031] In some embodiments, method one 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).

[0032] In some embodiments, in method two, the organic solvent may be a conventional solvent for such reactions in the art, preferably an alkane solvent, such as n-hexane (or, for example, dried n-hexane).

[0033] In some embodiments, in method two, the molar ratio of compound 3 to compound 4 can be a conventional molar ratio for such reactions in the art, preferably (1 to 5):1, and more preferably 1:1.

[0034] In some embodiments, in method two, the volume molar ratio of the organic solvent to 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.

[0035] In some embodiments, in method two, 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.

[0036] In some embodiments, 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.

[0037] In some embodiments, method two 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.

[0038] In some embodiments, method one further includes the following step: under an inert atmosphere, compound 1 undergoes a substitution reaction with pyridine as shown below;

[0039]

[0040] In some embodiments, the pyridine is anhydrous pyridine.

[0041] In some embodiments, the inert atmosphere may be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0042] In some embodiments, the volume molar ratio of the pyridine to the compound 1 may 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.

[0043] In some embodiments, the substitution reaction is carried out at room temperature.

[0044] In some embodiments, the reaction time of the substitution reaction can be the conventional reaction temperature for such reactions in the art, preferably 2 to 10 hours, and more preferably 5 hours.

[0045] In some embodiments, the substitution reaction is carried out under stirred conditions.

[0046] In some embodiments, 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).

[0047] The present invention also provides a catalyst composition comprising the ruthenium carbene compound or a salt thereof as shown in Formula LG, and chlorinated paraffin.

[0048] In some embodiments, the mass ratio of the ruthenium carbene compound or its salt to the chlorinated paraffin is 1:1 to 1:10.

[0049] In some embodiments, the chlorinated paraffin contains 5% to 60% chlorine, where the percentage refers to the mass fraction of chlorine atoms in the chlorinated paraffin; for example, 5%, 27%, 52%, or 60%.

[0050] In some embodiments, the molar concentration of the ruthenium carbene compound or its salt in the chlorinated paraffin is 0.08 mol / L to 0.7 mol / L; for example, 0.1 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.4 mol / L, 0.45 mol / L, 0.5 mol / L, or 0.6 mol / L.

[0051] In some embodiments, the catalyst composition is selected from any combination of the following:

[0052] Combination 1: and chlorinated paraffin, wherein the chlorinated paraffin contains 5%, 27%, 52% or 60% chlorine;

[0053] Combination 2: and chlorinated paraffin, wherein the chlorinated paraffin contains 5% chlorine;

[0054] Combination 3: and chlorinated paraffin, wherein the chlorinated paraffin contains 5% chlorine.

[0055] In some embodiments, the catalyst composition is selected from any combination of the following:

[0056] Combination 4: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L;

[0057] Combination 5: and chlorinated paraffin with a chlorine content of 27%; The molar concentration of the chlorinated paraffin is 0.2 mol / L;

[0058] Combination 6: and chlorinated paraffin with a chlorine content of 52%; The molar concentration of the chlorinated paraffin is 0.4 mol / L;

[0059] Combination 7: and chlorinated paraffin with a chlorine content of 60%; The molar concentration of the chlorinated paraffin is 0.6 mol / L;

[0060] Combination 8: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L;

[0061] Combination 9: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.3 mol / L;

[0062] Combination 10: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.5 mol / L;

[0063] Combination 11: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.6 mol / L;

[0064] Combination 12: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L;

[0065] Combination 13: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.25 mol / L;

[0066] Combination 14: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.45 mol / L;

[0067] Combination 15: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.6 mol / L.

[0068] The present invention also provides a method for preparing the above-mentioned catalyst composition, which includes the following steps: mixing the ruthenium carbene compound or its salt as shown in Formula LG with chlorinated paraffin under an inert atmosphere.

[0069] In some embodiments, the inert atmosphere in the preparation method of the catalyst composition can be an inert gas conventional for such reactions in the art, preferably nitrogen or argon.

[0070] In some embodiments, the preparation method of the catalyst composition further includes the use of a haloalkane. The haloalkane is preferably dichloromethane.

[0071] In some embodiments, the mixing method in the preparation method of the catalyst composition is stirring.

[0072] In some embodiments, when the preparation method of the catalyst composition further includes the use of haloalkanes, the order of feeding in the preparation method of the catalyst composition is, in sequence, the ruthenium carbene compound or its salt as shown in Formula LG, the haloalkanes, and the chlorinated paraffins.

[0073] In some embodiments, the preparation method of the catalyst composition further includes the following post-processing step: rotary evaporation.

[0074] The present invention also provides the use of the ruthenium carbene compound as shown in Formula LG or its salt or the catalyst composition described above in the catalytic metathesis reaction of olefins.

[0075] In some embodiments, the olefin metathesis reaction is a ring-closed metathesis reaction, a cross metathesis reaction, or a ring-opening metasomatic polymerization reaction.

[0076] In some embodiments, the ring-closure metathesis reaction includes the following steps: under an inert atmosphere and in the presence of a catalyst, the compound shown in Formula A1 undergoes a ring-closure metathesis reaction as shown below to obtain the compound shown in Formula A2.

[0077] The catalyst is a ruthenium carbene compound or a salt thereof as shown in Formula LG, or a catalyst composition thereof.

[0078]

[0079] in,

[0080] X is O, S, -N(R) 7 )-、-C(R 8 (R) 9 )-

[0081] R 7 It is hydrogen, C1-C6 alkyl, -S(=O)2R 7-1 -C(=O)R 7-2 or -C(=O)OR 7-3

[0082] R 8 and R 9 Independently hydrogen, C1-C6 alkyl, -C(=O)R 8-1 or -C(=O)OR 8-2 ;

[0083] Or, R 8 and R 9 The atoms between them form unsubstituted or substituted groups of 1, 2 or 3 R. 8-3 The substituted heterocycles are 3-6 membered heterocycles whose heteroatoms are selected from one or more of N, O and S, and whose number of heteroatoms is 1, 2 or 3;

[0084] R 7-1 R 7-2 R 7-3 R 8-1 and R 8-2 Independently hydrogen, C1-C6 alkyl, unsubstituted or surrounded by 1, 2 or 3 Rs 7-1-1 Replacement C6-C 10 Aryl;

[0085] R 8-3 and R 7-1-1 It is independently a hydroxyl, halogen, C1-C6 alkyl, or C1-C6 alkoxy group;

[0086] n1 and n2 are independently 0, 1, 2 or 3.

[0087] In some implementations, X is -N(R) 7 )-;R 7 is -S(=O)2R 7-1 ;

[0088] R 7-1 For not replaced or by 1, 2 or 3 R 7-1-1 Replacement C6-C 10 Aryl (may be phenyl);

[0089] Each R 7-1-1 Each is independently a C1-C6 alkyl group (which may be a C1-C4 alkyl group).

[0090] In some embodiments, the compound shown in Formula A1 is

[0091] In some embodiments, the conditions and operations of the closed-loop metathesis reaction may be the conditions and operations conventional for this type of reaction in the art.

[0092] In some embodiments, the closed-loop metathesis reaction is carried out under solvent-free or solvent-containing conditions.

[0093] In some embodiments, when the ring-closure metathesis reaction is carried out in the presence of a solvent, the solvent may be a conventional solvent for such reactions in the art, preferably a haloalkane solvent, and more preferably dichloromethane.

[0094] In some embodiments, in the closed-loop metathesis reaction, the inert atmosphere can be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0095] In some embodiments, in the closed-ring metathesis reaction, when the catalyst is a ruthenium carbene compound or a salt thereof as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is...

[0096] In some embodiments, in the closed-loop metathesis reaction, when the catalyst is the above-described catalyst composition, the catalyst composition is the above-described combination 5.

[0097] In some embodiments, the molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG in the catalyst composition to the compound of formula A1 may be a conventional molar ratio for such reactions in the art, preferably (0.01% to 1%):1, more preferably 0.2%:1.

[0098] In some embodiments, the reaction temperature of the closed-loop metathesis reaction can be the conventional reaction temperature for such reactions in the art, preferably 30°C to 100°C, and more preferably 40°C.

[0099] In some embodiments, the reaction temperature of the closed-loop metathesis reaction is determined by TLC monitoring to ensure the reaction is complete, preferably from 1 hour to 5 hours, and more preferably 2 hours.

[0100] In some embodiments, the closed-ring metathesis reaction further includes the following post-processing step: column chromatography (preferably using petroleum ether / ethyl acetate (5:1)).

[0101] In some embodiments, when the ring-closure metathesis reaction is carried out under solvent conditions, the post-treatment step further includes rotary evaporation and / or column chromatography.

[0102] In some embodiments, the cross-metathesis reaction may include the following steps: under an inert atmosphere and in the presence of a catalyst, a compound containing fragment B1 and a compound containing fragment B2 undergo a cross-metathesis reaction as shown below to obtain a compound containing fragment B3.

[0103] The catalyst is a ruthenium carbene compound or a salt thereof as shown in Formula LG, or a catalyst composition thereof.

[0104]

[0105] In some embodiments, the compound containing fragment B1 and the compound containing fragment B2 can be independently […].

[0106] Among them, R 4 It is a C1-C6 alkyl group (which can be C1-C4 alkyl) and -(CH2). n3 -OC(=O)-R 4-1 , or, not replaced or by 1, 2 or 3 Rs 4-2 Replacement C6-C 10 Aryl (may be phenyl);

[0107] n3 is 0, 1, or 2;

[0108] R 4-1 For not replaced or by 1, 2 or 3 R 4-1-1 Replacement C6-C 10 Aryl (may be phenyl);

[0109] R 4-2 and R 4-1-1 It can be independently hydroxyl or C1-C6 alkyl (may be C1-C4 alkyl).

[0110] In some embodiments, the compound containing fragment B1 and the compound containing fragment B2 can be independently […].

[0111] In some embodiments, the compound containing fragment B1 and the compound containing fragment B2 may be the same or different.

[0112] In some embodiments, the conditions and operations of the cross-metathesis reaction may be the conditions and operations conventional for this type of reaction in the art.

[0113] In some embodiments, the cross metathesis reaction is carried out under solvent-free or solvent-containing conditions.

[0114] In some embodiments, when the cross-metathesis reaction is carried out in the presence of a solvent, the solvent may be a conventional solvent for such reactions in the art, preferably a haloalkane solvent, and more preferably dichloromethane.

[0115] In some embodiments, the inert atmosphere in the cross-metathesis reaction can be a conventional inert gas for such reactions in the art, preferably nitrogen.

[0116] In some embodiments, in the cross-metathesis reaction, when the catalyst is a ruthenium carbene compound or a salt thereof as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is...

[0117] In some embodiments, in the cross metathesis reaction, when the catalyst is the above-described catalyst composition, the catalyst composition is combination 5 described above.

[0118] In some embodiments, the molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG in the catalyst composition to the compound of formula B1 may be a conventional molar ratio for such reactions in the art, preferably (0.1% to 10%):1, more preferably 2.5%:1.

[0119] In some embodiments, the molar ratio of the compound containing fragment B2 to the compound containing fragment B1 may be a conventional molar ratio for such reactions in the art, preferably (1 to 5):1, and more preferably 2:1.

[0120] In some embodiments, the reaction temperature of the cross-metathesis reaction can be the conventional reaction temperature for such reactions in the art, preferably 30°C to 100°C, and more preferably 45°C.

[0121] In some embodiments, the reaction time of the cross-metathesis reaction is based on TLC monitoring to ensure the reaction is complete, preferably 4 to 20 hours, and more preferably 6 hours.

[0122] In some embodiments, when the cross-metathesis reaction is carried out under solvent conditions, the post-processing step further includes rotary evaporation under reduced pressure and / or column chromatography.

[0123] In some embodiments, the ring-opening metathesis polymerization reaction includes the following steps: under an inert atmosphere and in the presence of a catalyst, a compound containing segment C1 undergoes a ring-opening metathesis polymerization reaction as shown below to obtain a compound containing segment C2; the catalyst is a ruthenium carbene compound as shown in Formula LG as described above, or a salt thereof, or a catalyst composition as described above.

[0124]

[0125] The A ring is a 3-15 membered ring olefin containing 1, 2 or 3 olefinic bonds;

[0126] n≥3.

[0127] In some embodiments, the ring-opening metathesis polymerization reaction is carried out under solvent-free conditions.

[0128] In some embodiments, the compound containing fragment C1 is

[0129] Among them, R 5 and R 6 It is independently hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy;

[0130] The A ring is a 3-8 member monocyclic cyclic olefin containing 1, 2, or 3 olefin bonds, or a 6-15 member polycyclic cyclic olefin containing 1, 2, or 3 olefin bonds.

[0131] In some embodiments, the compound containing fragment C1 is

[0132] R 5 and R 6 It is hydrogen;

[0133] The A ring is a 7-10 membered polycyclic cyclic olefin containing 1, 2 or 3 olefinic bonds.

[0134] In some embodiments, the compound containing fragment C1 is

[0135] In some embodiments, the inert atmosphere in the ring-opening metathesis polymerization reaction is a conventional inert atmosphere in the art, preferably nitrogen.

[0136] In some embodiments, in the ring-opening metathesis polymerization reaction, when the catalyst is a ruthenium carbene compound or a salt thereof as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is... Preferred

[0137] In some embodiments, when the catalyst is the catalyst composition, the catalyst composition is Combination 5 in the ring-opening metathesis polymerization reaction.

[0138] In some embodiments, in the ring-opening metathesis polymerization reaction, the molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG in the catalyst composition to the compound of formula C1 is a conventional molar ratio in the art, preferably (0.01% to 1%):1, more preferably 0.01%:1.

[0139] 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.

[0140] Unless otherwise specified, the catalysts described in this invention are all compounds that are not bound to chlorinated paraffin or paraffin.

[0141] In this invention, room temperature refers to 0 to 40°C.

[0142] In this invention, "halogen" refers to fluorine, chlorine, bromine, or iodine. In this invention, "salt" refers to a salt prepared by reacting the compounds of this invention with an acid, such as hydrochloride, hydrobromide, sulfate, etc.

[0143] In this invention, "alkyl" refers to a straight-chain or linear alkyl group having a specified number of carbon atoms. For example, C1-C6 alkyl groups are C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0144] In this invention, "alkoxy group" refers to the -OR group. X , where R X It is an alkyl group as defined above.

[0145] The term "cyclic olefin" refers to a cyclic olefin having one or more carbon-carbon double bonds, which can be monocyclic or polycyclic (including bicyclic). The cyclic olefins of the present invention are preferably 3-15 membered cyclic olefins containing 1, 2, or 3 olefin bonds, more preferably 3-8 membered monocyclic cyclic olefins containing 1, 2, or 3 olefin bonds, or 6-15 membered polycyclic cyclic olefins containing 1, 2, or 3 olefin bonds. Examples of cyclic olefins include cyclopropylene, cyclobutene, cyclopentene, cyclohexene, etc. wait.

[0146] In this invention, the group formed by the loss of a hydrogen atom from a "heterocyclic ring" is a heterocyclic alkyl group. Therefore, the ring formed by the gain of a hydrogen atom by a heterocyclic alkyl group in this invention is the heterocyclic ring of this invention.

[0147] The term "heterocyclic alkyl" refers to a saturated monocyclic group having heteroatoms, preferably a 3- to 6-membered saturated monocyclic group containing one, two, or three cyclic heteroatoms independently selected from N, O, and S. Examples of heterocyclic alkyl groups include: pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl, tetrahydropyridyl, tetrahydropyrrolidinyl, azacyclic butyl, thiazolyl, azoleyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazine, etc.

[0148] In this invention, "aryl" refers to an aromatic hydrocarbon group, such as C6-C. 10 The aryl group is either phenyl or naphthyl.

[0149] In this invention, the open-ended expression "comprising" can be converted into the closed-ended expression "composed of".

[0150] The reagents and raw materials used in this invention are all commercially available.

[0151] The positive and progressive effects of this invention are: the preparation process of the ruthenium carbene catalyst of this invention is simple, the product performance is stable, and it is suitable for continuous production. Detailed Implementation

[0152] 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.

[0153] In the examples described below, compound 1 was purchased from Adamas. It is known in the art that the following reaction steps do not result in a change of configuration.

[0154] Example 1: Preparation of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(trioctylphosphine)ruthenium dichloride catalyst

[0155]

[0156] 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%.

[0157] Analyze the data:

[0158] C 38 H 42 Theoretical (calculated) values ​​of Cl2N4Ru: C, 62.80 (62.62); H, 5.83 (5.60); N, 7.71 (7.61).

[0159] 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).

[0160] 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

[0161] 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%.

[0162] Analyze the data:

[0163] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2PRu: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0164] 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).

[0165] Example 2: Preparation of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(tris(2-ethylhexyl)phosphine)ruthenium dichloride catalyst

[0166]

[0167] Under nitrogen protection, 3.71 g (5.00 mmol) of complex 2 was added to a dry 100 mL flask, and 20 mL of dichloromethane was stirred until dissolved. Then, 2.86 g (10.00 mmol) of tris(2-ethylhexyl)phosphine (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 which the solution gradually changed from green to brownish-red. 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-2 (molecular formula: C). 52 H 83 Cl2N2Pru; molecular weight: 939.19 g / mol). 3.46 g (3.68 mmol) of a reddish-brown viscous liquid was obtained, yield: 73.7%.

[0168] Analyze the data:

[0169] C 52 H 83 Theoretical (calculated) values ​​of Cl2N2Pru: C, 66.50 (66.61); H, 8.91 (8.82); N, 2.98 (2.95).

[0170] 1H 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).

[0171] Example 3: Preparation of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(tridecylphosphine)ruthenium dichloride catalyst

[0172]

[0173] 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, 4.55 g (10.00 mmol) of tridecylphosphine (molecular formula: C64) was added to the flask. 30 H 63 P; molecular weight: 454.81 g / mol), and the reaction mixture was stirred at room temperature for 2 h, during which the solution changed from green to brownish-red. 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-3 (molecular formula: C). 58 H 95 Cl2N2PRu; molecular weight: 1023.36 g / mol). 3.64 g (3.56 mmol) of a reddish-brown viscous liquid was obtained, yield: 71.2%.

[0174] Analyze the data:

[0175] C 58 H 95 Theoretical (calculated) values ​​of Cl2N2PRu: C, 68.07 (68.05); H, 9.36 (9.33); N, 2.74 (2.75).

[0176] 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,60H),0.78(t.,9H).

[0177] Example 4: Preparation of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(trioctylphosphine)ruthenium dichloride catalyst

[0178]

[0179] 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%.

[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., 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).

[0183] Example 5: Preparation of 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinedimethyl)(benzylmethyl)(tris(2-ethylhexyl)phosphine)ruthenium dichloride catalyst

[0184]

[0185] Under nitrogen protection, 1.33 g (1.70 mmol) of ruthenium compound 4, 0.63 g (1.71 mmol) of tris(2-ethylhexyl)phosphine, and 40 mL of dry n-hexane were added to a flask. The mixture was stirred until the white solid dissolved, and then heated to 70 °C and refluxed with stirring for 2.0 h. During this process, the color of the precipitate gradually changed 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-2 (molecular formula: C 52 H 83 Cl2N2PRu (molecular formula: 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] Examples 6-17 Preparation of Catalyst Compositions

[0190] Under nitrogen or argon atmosphere, ruthenium catalyst LG and a certain amount of dichloromethane are added to a dry flask and stirred until dissolved. Then, chlorinated paraffin is added to the flask and stirred until the mixture gradually becomes a homogeneous, reddish-brown solution. Rotary evaporation removes the dichloromethane to obtain catalyst LG and a chlorinated liquid paraffin solution.

[0191]

[0192]

[0193] The preferred mass ratio of ruthenium catalyst LG to chlorinated paraffin is 1:1 to 1:10. When there is less chlorinated paraffin, the shelf life of the catalyst will be affected. When there is more chlorinated paraffin, it will lead to waste of chlorinated paraffin and increase costs.

[0194] This invention attempts to dissolve commercially available second-generation Grubbs catalysts, as well as the catalysts prepared in Examples 1 and 2 of this invention, in commercially available liquid paraffin. The results show that the commercially available second-generation Grubbs catalyst is insoluble in liquid paraffin; the catalysts prepared in Examples 1 and 2 of this invention are soluble in liquid paraffin, but the resulting catalyst composition is a gel-like substance that does not transform into a liquid state even when heated to 60-70°C.

[0195] A commercially available second-generation Grubbs catalyst was dissolved in a paraffin solution with a chlorine content of 52% to prepare a second-generation Grubbs catalyst solution with a concentration of 0.25 mol / L. It was found that the solubility of the commercially available second-generation Grubbs catalyst in chlorinated paraffin solution decreased at ambient temperatures below 10°C, making it prone to precipitation during storage and reducing catalytic activity, which is detrimental to industrial applications. Furthermore, when a commercially available second-generation Grubbs catalyst solution with a chlorine content of 52% was dissolved to prepare a second-generation Grubbs catalyst solution with a concentration of 0.05 mol / L, after being left at room temperature for two weeks, a significant amount of crystal precipitation was observed. However, when the catalyst of this invention was dissolved in a paraffin solution with a chlorine content of 52%, no precipitation occurred, regardless of whether the ambient temperature was below 10°C or after two weeks of storage at room temperature.

[0196] In this invention, the chlorine content of the chlorinated paraffin is preferably 5%-60% (mass fraction of chlorine atoms). Commonly used chlorinated paraffins with a chlorine content less than 5% exhibit gelation and solidification, making liquefaction impossible; those with a chlorine content greater than 60% have excessively high viscosity, even remaining in a solid state, thus failing to achieve the catalyst liquefaction target. The molar concentration of the ruthenium carbene catalyst or its salt in the chlorinated paraffin is preferably 0.08 mol / L-0.7 mol / L.

[0197] Effect Example

[0198] Ruthenium metal catalysts are commonly used in olefin metathesis reactions, such as ring-closed metathesis reactions, cross metathesis reactions, or ring-opening metasomatic polymerization reactions. The results of olefin metathesis reactions are used to evaluate the catalytic activity of ruthenium metal catalysts.

[0199] Example 1: Catalyst LG-1 catalyzes the ring-closure metathesis reaction of N,N-diallyl-4-methylbenzenesulfonamide.

[0200]

[0201] Under nitrogen protection, 25.10 mg of N,N-diallyl-4-methylbenzenesulfonamide and 1.0 mL of freshly treated dichloromethane were added to a 5 mL single-necked flask, followed by 0.188 mg of the catalyst LG-1 prepared above (molar ratio to substrate: 0.2%). The reaction mixture was heated to 40 °C and stirred for 2 h. After cooling to room temperature, the solvent was removed by rotary evaporation under reduced pressure. The residue was eluent with petroleum ether / ethyl acetate (5:1) and separated by column chromatography to obtain the product 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole, weighing 21.97 mg (purity 93.4%), with a yield of 98.4%. 1 H NMR (400MHz, CDCl3) δ (ppm): 2.42 (s, 3H), 4.12 (d, 3 J H-H =4.5Hz, 4H), 5.65(d, 3 J H-H =4.5Hz, 2H), 7.32(d, 3 J H-H =8.3Hz,2H),7.72(d, 3 J H-H =8.3Hz, 2H); 13 C NMR (100MHz, CDCl3) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

[0202] Example 2: Catalyst LG-1 catalyzes the cross-metathesis reaction between allyl benzoate and styrene.

[0203]

[0204] Under nitrogen protection, 16.2 mg of allyl benzoate, 20.8 mg of styrene, 1.0 mL of freshly treated dichloromethane, and 2.35 mg of the catalyst LG-1 prepared above (molar ratio of allyl benzoate to 2.5%) were added to a 5 mL Schlenk flask. The reaction mixture was heated to 45 °C and stirred for 6 h. Then, the solvent was removed by rotary evaporation under reduced pressure, and the residue was separated by column chromatography to obtain the cross-metathesis product styrene benzoate, weighing 22.4 mg (purity 92.7%), with a yield of 94%. 1 H NMR (400MHz, CDCl3): δ8.12(d,J=7.2Hz,2H,HAr),7.61(t,J=7.2Hz,1H,HAr),7.50(q,J=6.8Hz,4H,HAr),7.38(t,J=6.8Hz,2H,HAr),7 .31(t,J=4.8Hz,1H,HAr),6.79(d,J=16Hz,1H,Ph=CH),6.50(dt,J=16Hz,J=6.4Hz,1H,CH=CH2),5.02(dd,J=6.4Hz,J=1.2Hz,2H,CH2); 13 C-NMR (400MHz, CDCl3): δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53 (E / Z≧20 / 1).

[0205] Example 3: Catalysis of N,N-diallyl-4-methylbenzenesulfonamide ring-closure metathesis reaction catalyzed by catalyst / chlorinated liquid paraffin mixture HG-2

[0206]

[0207] Under nitrogen protection, 251 mg of N,N-diallyl-4-methylbenzenesulfonamide and 0.01 mL (0.2 mol / L) of the catalyst / chlorinated liquid paraffin mixture HG-2 prepared above (where the molar ratio of catalyst to reactant is 0.2%) were added to a 5 mL single-necked flask. The reaction mixture was heated to 40 °C and stirred for 2 h. After cooling to room temperature, the mixture was separated by column chromatography using petroleum ether / ethyl acetate (5:1) as the eluent to obtain the product 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole, weighing 218.8 mg (purity 93.5%), with a yield of 98.0%. 1HNMR (400MHz, CDCl3) δ (ppm): 2.42 (s, 3H), 4.12 (d, 3 J H-H =4.5Hz, 4H), 5.65(d, 3 J H-H =4.5Hz, 2H), 7.32(d, 3 J H-H =8.3Hz,2H),7.72(d, 3 J H-H =8.3Hz, 2H); 13 C NMR (100MHz, CDCl3) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

[0208] Example 4: Catalyst / chlorinated liquid paraffin mixture HG-2 catalyzes the cross-metathesis reaction of allyl benzoate and styrene.

[0209]

[0210] Under nitrogen protection, 162 mg of allyl benzoate, 208 mg of styrene, and 0.125 mL (0.2 mol / L) of the catalyst / chlorinated liquid paraffin mixture HG-2 prepared above (where the molar ratio of catalyst to substrate is 2.5%) were added to a 5 mL Schlenk flask. The reaction mixture was heated to 45 °C and stirred for 6 h. The reaction mixture was separated by column chromatography to obtain the cross-metathesis product styrene benzoate, weighing 225.9 mg (purity 92.1%), with a yield of 94.8%. 1 H NMR (400MHz, CDCl3): δ 8.12 (d, 3 J H-H =7.2Hz,2H,HAr),7.61(t, 3 J H-H =7.2Hz, 1H, HAr), 7.50(q, 3 J H-H =6.8Hz, 4H, HAr), 7.38(t, 3 J H-H =6.8Hz,2H,HAr),7.31(t, 3 J H-H =4.8Hz, 1H, HAr), 6.79(d, 3 J H-H =16Hz, 1H, Ph=CH), 6.50(dt, 3 J H-H =16Hz, 3 JH-H =6.4Hz,1H,CH=CH2),5.02(dd, 3 J H-H =6.4Hz, 3 J H-H =1.2Hz, 2H, CH2); 13 C-NMR (400MHz, CDCl3): δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53 (E / Z≧20 / 1).

[0211] The table below compares the activities of commercially available second-generation Grubbs catalyst 2 (GII) and the ruthenium carbene catalyst of this invention in catalyzing ring-closure metathesis and cross-metathesis reactions. It is found that the catalyst designed in this invention and the catalyst / chlorinated liquid paraffin mixture exhibit similar catalytic activity to the second-generation Grubbs catalyst in catalyzing olefin ring-closure metathesis and cross-metathesis reactions, indicating that the substitution of tricyclohexylphosphine with long-chain phosphine has a relatively small impact on the catalyst's catalytic activity. Furthermore, the comparison shows that the presence or absence of chlorinated paraffin has a relatively small impact on the catalyst's activity; the novel catalyst structure designed in this invention can still be used without the protection of chlorinated paraffin.

[0212] Examples of effects 5-10:

[0213] Examples 5, 6 and 7 use the same method as Example 1 above, but with different catalysts. The yields are shown in the table below.

[0214] Examples 8, 9 and 10 use the same method as Example 2 above, but with different catalysts. The yields are shown in the table below.

[0215]

[0216] Example 11

[0217] The difference between this effect example and effect example 1 is only that the reaction was carried out in the absence of dichloromethane. It was found that, in the absence of dichloromethane, using catalyst LG-1 to catalyze the ring-closure metathesis reaction of N,N-diallyl-4-methylbenzenesulfonamide achieved a yield comparable to that of effect example 1, indicating that the catalyst of this application can avoid the use of chlorinated paraffins and solvents.

[0218] Example 12

[0219] The stability of the ruthenium metal catalyst / chlorinated liquid paraffin mixture was verified by placing it at room temperature for a certain period of time.

[0220] The composition HG-2, which was placed at room temperature for 6 months, catalyzed the ring-closure metathesis reaction of N,N-diallyl-4-methylbenzenesulfonamide.

[0221]

[0222] Under nitrogen protection, 251 mg of N,N-diallyl-4-methylbenzenesulfonamide and 0.01 mL of ruthenium catalyst / chlorinated paraffin composition HG-2 (0.20 mol / L) stored for 6 months were added to a 5 mL single-necked flask. The reaction mixture was heated to 40 °C and stirred for 2 h. After cooling to room temperature, the reaction mixture was separated by column chromatography using petroleum ether / ethyl acetate (5:1) as the eluent to obtain 218 mg (93.2% purity) of 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole, with a yield of 97.7%.

[0223] Comparing Example 3 with Example 11, it can be found that after 6 months of storage of the catalyst / chlorinated paraffin mixture, the conversion rate of the HG-2 catalyst is slightly lower than that of the newly prepared chlorinated liquid paraffin mixture HG-2, but the catalytic activity is still high and meets the requirements of general catalytic reactions.

[0224] Example 13

[0225] Catalyst LG-1 catalyzes the ring-opening metathesis reaction of dicyclopentadiene.

[0226]

[0227] Under nitrogen protection, 132 g of dicyclopentadiene monomer was added to a 250 ml single-necked flask, followed by 94 mg of the previously prepared catalyst LG-1 (molar ratio to substrate: 0.01 mol%). The mixture was stirred until uniform in color, then degassed, poured into a mold, and cured at 80 °C for 3 hours. After cooling to room temperature, the sample was demolded to obtain a smooth, flat sample plate with a thickness of 4 mm. Mechanical property tests were performed on the cut sample, yielding the following results: tensile strength 58.7 MPa, tensile modulus 2031 MPa, and elongation at break 6.12%.

[0228] Example 14

[0229] HG-2, a catalyst / chlorinated liquid paraffin mixture, catalyzes the ring-opening metathesis reaction of dicyclopentadiene.

[0230]

[0231] Under nitrogen protection, 132 g of dicyclopentadiene monomer was added to a 250 ml single-necked flask, followed by 5 mL of the catalyst / chlorinated liquid paraffin mixture HG-2 prepared above (molar ratio of 0.01 mol% to the reaction substrate). The mixture was stirred until the color was uniform, the solution was degassed, poured into a mold, and cured at 80℃ for 3 hours. After cooling to room temperature, the sample was demolded to obtain a smooth, flat sample plate with a thickness of 4 mm. The sample was cut and its mechanical properties were tested. The results were: tensile strength 57.3 MPa, tensile modulus 1987 MPa, and elongation at break 7.92%.

[0232] To compare the effects with the experimental results of this invention, a commercially available Grubbs second-generation catalyst was used to catalyze the ring-opening metathesis reaction of dicyclopentadiene. Under consistent experimental conditions, the mechanical properties of the final product were as follows: tensile strength 58.6 MPa, tensile modulus 2035 MPa, and elongation at break 5.34%. These three sets of data indicate that in the ring-opening metathesis reaction, the substitution of tricyclohexylphosphine and chlorinated paraffin by long-chain phosphine has a relatively small impact on the catalytic activity of the catalyst. The novel catalyst structure designed in this invention can still catalyze the ring-opening metathesis reaction without the protection of chlorinated paraffin.

[0233] Example 15

[0234] In this embodiment, the tensile strength, tensile modulus and elongation at break of the obtained resin material were measured in accordance with GB / T2567.

[0235] Notched impact strength was determined according to ISO-180.

[0236] The mass loss rate of the cured material compared to the raw materials used = 1 - (mass of the obtained resin material / mass of the raw materials used);

[0237] Method for determining the average depth of surface marks: Measure the depth of all marks on the surface of the product using vernier calipers and take the average value.

[0238] Example 15.1 Original Formula

[0239] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0240] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0241] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1902 MPa, an elongation at break of 7.9%, and a notched impact strength (ISO-180) of 19 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.9 wt%; the average depth of surface marks was 0.13 mm (4 mm resin board).

[0242]

[0243] Example 15.2: Adding TeCPD

[0244] Preparation of component A: Add 55 parts by mass of DCPD, 35 parts by mass of TCPD and 10 parts by mass of TeCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, seal and discharge the material, and store the product in a nitrogen-sealed raw material tank.

[0245] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0246] The obtained material has a tensile strength of 56 MPa, a tensile modulus of 2048 MPa, an elongation at break of 6.5%, and a notched impact strength of 14 kJ / m. 2 (ISO-180); The mass loss rate of the material after curing compared with the raw materials used is 0.6wt%; The average depth of surface marks is 0.11mm (4mm resin board).

[0247] Example 15.3: Increased macrocyclic monomer

[0248] Preparation of component A: Add 55 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD and 5 parts by mass of PCPD to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 60°C and stir for 2 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed raw material tank.

[0249] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0250] The obtained material has a tensile strength of 59 MPa, a tensile modulus of 2105 MPa, an elongation at break of 7.5%, and a notched impact strength of 11 kJ / m. 2 (ISO-180); The mass loss rate of the material after curing compared with the raw materials used is 0.5wt%; The average depth of surface marks is 0.10mm (4mm resin board).

[0251] Example 15.4: Adding an elastomer

[0252] Preparation of component A: Add 87 parts by mass of DCPD, 8 parts by mass of TCPD, 2 parts by mass of SEBS (Kraton G1652) and 3 parts by mass of EPDM (Keltan 8550C) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed container.

[0253] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0254] The obtained material has a tensile strength of 35 MPa, a tensile modulus of 1590 MPa, an elongation at break of 19.5%, and a notched impact strength (ISO-180) of 48 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.3wt%; the average depth of surface marks was 0.08mm (4mm resin board).

[0255] Example 15.5: Adding elastomer and macrocycle

[0256] Preparation of component A: Add 50 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD, 5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102), and 2.5 parts by mass of EPDM (Keltan 8550C) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the product in a sealed container and store it under nitrogen.

[0257] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0258] The obtained material has a tensile strength of 43 MPa, a tensile modulus of 1710 MPa, an elongation at break of 16.6%, and a notched impact strength (ISO-180) of 50 kJ / m. 2 The mass loss rate of the cured material compared to the raw materials used was 0.3 wt%; the average depth of surface marks was 0.08 mm (4 mm resin board).

[0259] Example 15.6: Adding filler

[0260] Preparation of component A: Add 50 parts by mass of DCPD, 25 parts by mass of TCPD, 7.5 parts by mass of TeCPD, 2.5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102), 2.5 parts by mass of EPDM (Keltan 8550C), and 10 parts by mass of carbon black (800 mesh) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the material in a sealed container and store the product in a nitrogen-sealed container.

[0261] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0262] The obtained material has a tensile strength of 33 MPa, a tensile modulus of 3015 MPa, and an elongation at break of 1.8%.

[0263] Example 15.7: Adding short glass fibers and colorant

[0264] Preparation of component A: Add 50 parts by mass of DCPD, 26 parts by mass of TCPD, 10 parts by mass of TeCPD, 3 parts by mass of PCPD, 2.5 parts by mass of SEPS 4030, 2.5 parts by mass of EPDM (Keltan 8550C), 5 parts by mass of glass fiber, 0.5 parts by mass of black pigment (BK 9007-UC), and 0.5 parts by mass of antioxidant (BASF168) to a stirred tank. After replacing the atmosphere in the tank with high-purity nitrogen, heat to 80°C and stir for 24 hours (stirring speed: 250 rpm). After cooling to room temperature, discharge the product in a sealed container and store it under nitrogen.

[0265] Preparation of polycyclic olefin resin materials: The prepared components A and B (ruthenium carbene catalyst Ru-II) are respectively packaged into corresponding tanks (the tanks are pre-filled with nitrogen). The two streams of A and B are mixed at a ratio of 500:1 using a special RIM device and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0266] The obtained material has a tensile strength of 48 MPa, a tensile modulus of 4525 MPa, and an elongation at break of 4.8%.

[0267] Example 15.8 Storage Stability Experiment

[0268] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0269] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen) and left to stand at room temperature for 6 months. Then, the two streams of A and B are mixed at a ratio of 500:1 using a dedicated RIM device and injected into the mold. The mold temperature is 80°C and the curing time is 3 hours.

[0270] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1890 MPa, an elongation at break of 9.2%, and a notched impact strength of 19 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 0.8 wt%; the average depth of surface marks was 0.12 mm (4 mm resin board).

[0271] Comparison of Comparative Example 15.1G2 and Example 1

[0272] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0273] Preparation of component B: Under a dry nitrogen atmosphere, 10 parts by mass of Grubbs second-generation catalyst (as shown in structural formula G2) are added to a stirred tank, and then 90 parts by mass of dichloromethane are injected into the stirred tank. After stirring for 10 minutes, the material is discharged into the corresponding tank of the dedicated RIM equipment (the tank is pre-filled with nitrogen).

[0274] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 150:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0275] The obtained material has a tensile strength of 51 MPa, a tensile modulus of 1880 MPa, an elongation at break of 5.9%, and a notched impact strength of 16 kJ / m. 2 The material's mass loss rate after curing was 1.4 wt% (VOCs) compared to the raw materials used; the average depth of surface marks was 0.24 mm (4 mm resin board).

[0276]

[0277] Comparative Example 15.2 Ru-II in solution

[0278] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0279] Preparation of component B: Under a dry nitrogen atmosphere, add 10 parts by mass of Ru-II to the stirred tank, then inject 90 parts by mass of dichloromethane into the stirred tank, stir for 10 minutes, and then discharge the material into the corresponding tank of the dedicated RIM equipment (the tank is pre-filled with nitrogen).

[0280] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 150:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0281] The obtained material has a tensile strength of 50 MPa, a tensile modulus of 1892 MPa, an elongation at break of 6.1%, and a notched impact strength of 14 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 1.5wt%; the average depth of surface marks was 0.24mm (4mm resin board).

[0282] Comparative Example 15.3: Catalyst Stability

[0283] Preparation of component A: Add 90 parts by mass of DCPD and 10 parts by mass of TCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 60°C, stir for 2 hours (stirring speed: 250 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed container.

[0284] Preparation of component B: Under a dry nitrogen atmosphere, 10 parts by mass of Grubbs second-generation catalyst (as shown in structural formula G2) were added to a stirred tank, and then 90 parts by mass of dichloromethane were injected into the stirred tank. After stirring for 10 minutes, the material was discharged into the corresponding tank of the dedicated RIM equipment (the tank was pre-filled with nitrogen) and allowed to stand for 24 hours.

[0285] Preparation of polycyclic olefin resin material: The prepared components A and B are packaged into their respective containers (the containers are pre-filled with nitrogen). Using a dedicated RIM device, the two streams of A and B are mixed at a ratio of 20:1 and then injected into the mold. The mold temperature is 80℃ and the curing time is 3 hours.

[0286] The resulting material is gel-like.

[0287] Comparative Example 15.4: Performance of pure DCPD as a cyclic olefin monomer

[0288] Preparation of polycyclic olefin resin materials: Component A (DCPD) and component B (ruthenium carbene catalyst Ru-II) were respectively packaged into corresponding tanks (the tanks were pre-filled with nitrogen and pre-heated at 40°C for 12 hours). Using a dedicated RIM device, the two streams of A and B were mixed at a ratio of 500:1 and injected into the mold. The mold temperature was 80°C and the curing time was 3 hours.

[0289] The obtained material has a tensile strength of 47 MPa, a tensile modulus of 1762 MPa, an elongation at break of 7.9%, and a notched impact strength (ISO-180) of 22 kJ / m. 2 The mass loss rate of the material after curing compared with the raw materials used was 1.2 wt%; the average depth of surface marks was 0.14 mm (4 mm resin board).

[0290] Comparative Example 15.5

[0291] Preparation of component A: Add 30 parts by mass of DCPD, 40 parts by mass of TCPD, 25 parts by mass of TeCPD and 5 parts by mass of PCPD to a stirred tank. Replace the atmosphere in the tank with high-purity nitrogen, heat to 90°C, stir for 24 hours (stirring speed: 500 rpm), cool to room temperature, and discharge the material in a sealed container. Store the product in a nitrogen-sealed raw material tank.

[0292] The resulting composition of component A precipitates a large amount of solids at the bottom, making it unsuitable for continuous production of polycyclic olefin resin materials.

[0293] Comparative Example 15.6

[0294] Preparation of component A: Add 60 parts by mass of DCPD, 25 parts by mass of TeCPD and 15 parts by mass of PCPD to a stirred tank, replace the atmosphere in the tank with high-purity nitrogen, heat to 90°C, stir for 24 hours (stirring speed: 500 rpm), cool to room temperature, discharge the material in a sealed container, and store the product in a nitrogen-sealed raw material tank.

[0295] A small amount of solid powder precipitated at the bottom of the composition of component A, while the upper saturated solution was a colorless and clear solution.

[0296] Example 16

[0297] In this effect example, the flash point was tested according to GB / T261-2021.

[0298] In this example, DCPD is dicyclopentadiene, TCPD is tricyclopentadiene, TeCPD is tetracyclopentadiene, and PCPD is pentacyclopentadiene.

[0299] Preparation methods of TCPD / TePCD / PCPD:

[0300] (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.

[0301] (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.

[0302] (3) The bottom material of the tower is subjected to negative pressure distillation, and the resulting fraction is TeCPD. The residue contains PCPD.

[0303] (4) Wash the residue with toluene and collect the washing liquid. Remove the toluene solvent by vacuum distillation to obtain PCPD.

[0304] The structure of the Ru-I ruthenium carbene catalyst used in this effect embodiment is shown below:

[0305]

[0306] Example 16.1

[0307] 1. Preparation of resin composition:

[0308] 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.

[0309] 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.

[0310] Component C: Add liquid ruthenium carbene catalyst Ru-I to the dedicated container for Component C.

[0311] The flash points (closed cup) of the three components are as follows:

[0312] Component A 63℃

[0313] Component B >100℃

[0314] Component C > 100℃

[0315] 2. Preparation of thermosetting resin materials:

[0316] (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.

[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 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.)

[0322] Example 17

[0323] The structure of the ruthenium carbene compound used in this effect embodiment is shown below:

[0324]

[0325] Testing standards, raw materials and equipment:

[0326] Tensile testing standard for resin matrix sheets: GB / T 2567-2008 Test methods for the properties of resin castings

[0327] Sheet specifications: Thickness 4mm, Length 200mm, Width 150mm

[0328] Test standards for composite material boards: GB / T 1447-2005 Tensile properties test method for fiber reinforced plastics; GB / T 1449-2005 Flexural properties test method for fiber reinforced plastics.

[0329] Carbon fiber composite plate specifications: 350*350*2mm

[0330] Fiberglass composite panel specifications: 350*350*3.5mm

[0331] Testing equipment: Universal Testing Machine for Materials Manufacturer: Instron Model: 5984

[0332] Dicyclopentadiene (DCPD): Purchased from Guangdong Xinhua Yue Petrochemical Group Co., Ltd.

[0333] In this example, DCPD is dicyclopentadiene, TCPD is tricyclopentadiene, TeCPD is tetracyclopentadiene, and PCPD is pentacyclopentadiene.

[0334] Preparation methods of TCPD / TePCD / PCPD:

[0335] (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.

[0336] (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.

[0337] (3) The bottom material of the tower is subjected to negative pressure distillation, and the resulting fraction is TeCPD. The residue contains PCPD.

[0338] (4) Wash the residue with toluene and collect the washing liquid. Remove the toluene solvent by vacuum distillation to obtain PCPD.

[0339] The RTM and VARI processes share a single set of equipment, which consists of a vacuum pump, gas tank, control panel, and gas tubing components. The RIM process uses a reaction injection molding machine.

[0340] Example 17.1

[0341] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0342] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 1:

[0343] Table 1

[0344] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Polymerization regulator: triphenylphosphine 2 copies Catalyst: Ruthenium carbene compound 0.05 copies

[0345] (2) Preparation of the substrate and testing

[0346] The resin mixture was injected into an RTM mold cavity containing unidirectional carbon fiber woven fabric using the RTM process, and then cured to form a preform. The injection pressure was 3 bar, the temperature was 80℃, and the time was 60 min. The carbon fiber used was 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2 The mold cavity contains seven layers of woven fabric, the preform is 2mm thick, and its carbon fiber volume content is approximately 40%. The carbon fiber mass percentage is approximately 65%.

[0347] Example 17.2

[0348] RTM process for preparing carbon fiber reinforced PDCPD resin composite plates

[0349] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 2:

[0350] Table 2

[0351] Types of raw materials Dosage DCPD 45 copies TCPD 30 copies TeCPD 20 copies PCPD 5 copies Polymerization regulator: triphenylphosphine 4 copies Catalyst: Ruthenium carbene compound 0.5 copies

[0352] (2) Preparation of the substrate and testing

[0353] The resin mixture was injected into an RTM mold cavity containing unidirectional carbon fiber woven fabric using the RTM process, and then cured to form a preform. The injection pressure was 3 bar, the temperature was 80℃, and the time was 60 min. The carbon fiber used was 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2The mold cavity contains seven layers of woven fabric, the preform is 2mm thick, and its carbon fiber volume content is about 40%, and the fiber mass ratio is about 65%.

[0354] Example 17.3

[0355] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0356] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 3:

[0357] Table 3

[0358]

[0359]

[0360] (2) Preparation of the substrate and testing

[0361] The resin mixture was injected into an RTM mold cavity containing unidirectional carbon fiber woven fabric using the RTM process, and then cured to form a preform. The injection pressure was 3 bar, the temperature was 80℃, and the time was 60 min. The carbon fiber used was 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2 The mold cavity contains seven layers of woven fabric, the preform is 2mm thick, and its carbon fiber volume content is about 40%, and the fiber mass ratio is about 65%.

[0362] Example 17.4

[0363] RTM process for preparing glass fiber reinforced resin matrix composite plates

[0364] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 4:

[0365] Table 4

[0366] Types of raw materials Dosage DCPD 60 copies TCPD 30 copies TeCPD 10 copies PCPD 0 copies Polymerization regulator: triphenylphosphine 2 copies Catalyst: Ruthenium carbene compound 1 copy

[0367] (2) Preparation of the substrate and testing

[0368] The resin mixture was injected into an RTM mold cavity containing unidirectional glass fiber woven fabric using the RTM process, and then cured to obtain the preform. The injection pressure was 3 bar, the temperature was 80℃, and the time was 60 min. The glass fiber used was unidirectional glass fiber woven fabric with a single filament diameter of 17 μm and a fiber areal density of 1250 g / m². 2 Four layers of woven fabric are stacked in the mold cavity. The preform is 3.4 mm thick and has a glass fiber volume content of about 50% and a fiber mass ratio of about 75%.

[0369] Example 17.5

[0370] VARI process for preparing glass fiber reinforced resin matrix composite plates

[0371] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 5:

[0372] Table 5

[0373] Types of raw materials Dosage DCPD 50 copies TCPD 20 copies TeCPD 20 copies PCPD 10 copies Polymerization regulator: triphenylphosphine 2 copies Catalyst: Ruthenium carbene compound 0.5 copies

[0374] (2) Preparation of the substrate and testing

[0375] The VARI process utilizes vacuum negative pressure to inject a resin mixture into a VARI mold cavity containing unidirectional glass fiber woven fabric, followed by injection curing to produce a preform; temperature: 80℃, time: 60min; the glass fiber used is unidirectional glass fiber woven fabric with a single filament diameter of 17µm and a fiber areal density of 1250g / m². 2 The mold cavity contains four layers of woven fabric, with a preform thickness of 3.6 mm and a glass fiber volume content of approximately 48%. The fiber mass percentage is approximately 73%.

[0376] Example 17.6

[0377] VARI process for preparing glass fiber reinforced resin matrix composite plates

[0378] DCPD modified resin is produced using the VARI process.

[0379] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 6:

[0380] Table 6

[0381] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Polymerization regulator: triphenylphosphine 0.76 copies Catalyst: Ruthenium carbene compound 0.02 copies Bisphenol A epoxy resin 233 copies Epoxy curing agent: Methyltetrahydrophthalic anhydride 211 copies Accelerator DMP-30 10.3 copies

[0382] (2) Preparation of the substrate and testing

[0383] The VARI process utilizes vacuum negative pressure to inject a resin mixture into a VARI mold cavity containing unidirectional glass fiber woven fabric, followed by injection curing to produce a preform; temperature: 80℃, time: 60min; the glass fiber used is unidirectional glass fiber woven fabric with a single filament diameter of 17µm and a fiber areal density of 1250g / m². 2 The mold cavity contains four layers of woven fabric, with a preform thickness of 3.6 mm and a glass fiber volume content of approximately 48%. The fiber mass percentage is approximately 73%.

[0384] Example 17.7

[0385] Polydicyclopentadiene (PDCPD) polymer pure resin board

[0386] Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 7:

[0387] Table 7

[0388] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Triphenylphosphine 5 copies Catalyst: Ruthenium carbene compound 0.5 copies

[0389] A 3.8 mm thick PDCPD resin preform was prepared by closed-mold injection molding using a RIM (Resin Injection Molding) machine. The molding pressure was 5 bar and the injection speed was approximately 120 g / min. The finished product had a total thickness of 4 mm.

[0390] Example 17.8

[0391] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0392] (1) Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 8:

[0393] Table 8

[0394] Types of raw materials Dosage DCPD 100 copies Polymerization regulator: triphenylphosphine 2 copies Catalyst: Ruthenium carbene compound 0.05 copies

[0395] (2) Preparation of the substrate and testing

[0396] The operation and conditions in this part are the same as in Example 17.1.

[0397] Comparative Example 17.1

[0398] Polydicyclopentadiene (PDCPD) virgin resin board

[0399] Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 9:

[0400] Table 9

[0401] Types of raw materials Dosage DCPD 100 copies Triphenylphosphine 5 copies Commercially available G2 catalyst (Sigma-Aldrich) 0.5 copies Toluene solvent 1 copy

[0402] A 3.8mm thick PDCPD resin preform was prepared by closed-mold injection molding using a RIM (Reinforced Molding Injection) system. The molding pressure was 5 bar, the injection speed was approximately 120g / min, the molding temperature was 80℃, and the molding time was 60min. The completed product had a total thickness of 4mm. While resin boards made from pure PDCPD resin sheets have lower costs and a smooth, aesthetically pleasing surface, their mechanical properties are poor, making it difficult to meet the functional and lightweight technical requirements of applications.

[0403] Comparative Example 17.2

[0404] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0405] Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 10:

[0406] Table 10

[0407] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Triphenylphosphine 5 copies Commercially available G2 catalyst (Sigma-Aldrich) 0.5 copies Toluene solvent 1 copy

[0408] The resin mixture is injected into a mold cavity containing unidirectional carbon fiber woven fabric using RTM closed-mold injection molding, and the preform is obtained by injection curing. The carbon fiber used is 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2 The mold cavity contains seven layers of woven fabric, with a preform thickness of 2mm and a carbon fiber volume content of approximately 40%. The fiber mass percentage is approximately 65%.

[0409] Comparative Example 17.3

[0410] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0411] Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 11:

[0412] Table 11

[0413] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Polymerization regulator: triphenylphosphine 15 copies Catalyst: Ruthenium carbene compound 0.5 copies

[0414] The resin mixture is injected into a mold cavity containing unidirectional carbon fiber woven fabric using RTM closed-mold injection molding, and then cured to obtain a preform. The carbon fiber used is 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2 The mold cavity contains seven layers of woven fabric, with a preform thickness of 2mm and a carbon fiber volume content of approximately 40%. The fiber mass percentage is approximately 65%.

[0415] Comparative Example 17.4

[0416] RTM process for preparing carbon fiber reinforced resin matrix composite plates

[0417] Prepare the resin mixture according to the types and mass proportions of raw materials shown in Table 12:

[0418] Table 12

[0419] Types of raw materials Dosage DCPD 75 copies TCPD 20 copies TeCPD 3 copies PCPD 2 copies Polymerization regulator: triphenylphosphine 5 copies Catalyst: Ruthenium carbene compound 10 copies

[0420] The resin mixture is injected into a mold cavity containing unidirectional carbon fiber woven fabric using RTM closed-mold injection molding, and then cured to obtain a preform. The carbon fiber used is 12K-T700 unidirectional fiber woven fabric with a fiber areal density of 300 g / m². 2The mold cavity contains seven layers of woven fabric, the preform is 2mm thick, and its carbon fiber volume content is about 40%, and the fiber mass ratio is about 65%.

[0421] Table 13 Data Performance Comparison Table

[0422]

[0423] The results show that the products obtained by fiber-reinforced PDCPD boards prepared entirely using the RTM / VARI process have significantly improved mechanical properties compared to pure resin boards, and can meet higher-level requirements for thinner and lighter designs.

[0424] Example 17.9:

[0425] For the sheet products prepared in Effective Examples 17.1-17.8 and Comparative Examples 17.1-17.4, planar areas were selected on the products for sample preparation and relevant tests were completed to evaluate the surface quality of the products. The data and results are shown in Table 13.

[0426] Example 17.10:

[0427] Prepare resin plates for tensile testing and conduct stability tests.

[0428] Example 17.10-1

[0429] Component A is a mixture of 75 parts DCPD, 20 parts TCPD, 3 parts TeCPD, 2 parts PCPD, and 2 parts polymerization regulator (triphenylphosphine).

[0430] The catalyst, 0.05 parts of ruthenium carbene compound, was used as component B.

[0431] (1) Mix components A and B and inject the mixture into a flat casting mold to prepare a test plate with a thickness of 4 mm. The test is conducted using a universal testing machine for materials, according to the standard GBT 2567-2008, to test its tensile properties.

[0432] (2) After the above-mentioned raw materials of components A and B were placed for three months, the experiment was repeated to test their performance. The effect data are shown in Table 14.

[0433] Example 17.10-2

[0434] Component A is a mixture of 75 parts DCPD, 20 parts TCPD, 3 parts TeCPD, 2 parts PCPD, and 2 parts polymerization regulator (triphenylphosphine).

[0435] 0.05 parts of commercially available G2 catalyst (Sigma-Aldrich) and 1 part of toluene were used as component B.

[0436] (1) Mix components A and B and inject the mixture into a flat casting mold to prepare a test plate with a thickness of 4 mm. The test is conducted using a universal testing machine for materials, according to the standard GBT 2567-2008, to test its tensile properties.

[0437] (2) After the above-mentioned raw materials of components A and B were placed for three months, the experiment was repeated to test their performance. The effect data are shown in Table 14.

[0438] Table 14 Comparison of Mechanical Performance Data

[0439]

[0440] According to the performance data in Table 14, the ruthenium carbene compound used in this invention has excellent stability and still has good mechanical properties after being stored for 3 months.

[0441] Example 18

[0442] In this effect embodiment, "parts" refers to "parts by weight".

[0443] The brands of the key raw material manufacturers are as follows:

[0444] 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.

[0445] 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.

[0446] The organic urea accelerator is the UR2T curing accelerator product manufactured by Air Products.

[0447] Defoamer: BYKA530 from BYK Chemicals.

[0448] Wetting and dispersing agent: BYKW9010 from BYK Chemicals.

[0449] Coupling agent: KH560 coupling agent from Nanjing Nengde New Materials.

[0450] The manufacturer of dicyclopentadiene is Guangdong Xinhua Yue Petrochemical Co., Ltd.

[0451] The preparation process of tricyclopentadiene (TCPD) used in this effect embodiment is as follows:

[0452] (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.

[0453] (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.

[0454] Unless otherwise specified above, the reagents used in this effect example are products from any manufacturer.

[0455] In this example, there are no particular restrictions on the preparation of components A and B, as long as they are well dispersible.

[0456] The specific structural formula of the modified ruthenium carbene catalyst (novel P-ligand ruthenium carbene catalyst) used in this effect embodiment is as follows:

[0457]

[0458] Example 18.1

[0459] Preparation of cycloolefin / epoxy resin mixtures:

[0460] 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.

[0461] 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.

[0462] 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.

[0463] Preparation of finished fiber prepreg:

[0464] 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.

[0465] Preparation of composite materials:

[0466] 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.

[0467] Example 18.2

[0468] Preparation of cycloolefin / epoxy resin mixtures:

[0469] 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.

[0470] 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.

[0471] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0472] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-1.

[0473] Example 18.3

[0474] Preparation of cycloolefin / epoxy resin mixtures:

[0475] 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.

[0476] 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.

[0477] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0478] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-1.

[0479] Example 18.4

[0480] Preparation of cycloolefin / epoxy resin mixtures:

[0481] 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.

[0482] 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.

[0483] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0484] The preparation process of the finished fiber prepreg is the same as in Example 18.1.

[0485] Preparation of composite materials:

[0486] 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.

[0487] Example 18.5

[0488] Preparation of cycloolefin / epoxy resin mixtures:

[0489] 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.

[0490] 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.

[0491] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0492] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-1.

[0493] Example 18.6

[0494] Preparation of cycloolefin / epoxy resin mixtures:

[0495] 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.

[0496] 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.

[0497] The mixing process of components A and B is the same as in Example 18.1, where the cyclic olefin / epoxy resin mixture at 70°C produces 54,000 cPs.

[0498] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-2.

[0499] Example 18.7

[0500] Preparation of cycloolefin / epoxy resin mixtures:

[0501] 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.

[0502] 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.

[0503] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 20000 cPs.

[0504] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-1.

[0505] Example 18.8

[0506] Preparation of cycloolefin / epoxy resin mixtures:

[0507] 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.

[0508] 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.

[0509] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23000 cPs.

[0510] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 5-1.

[0511] Example 18.9

[0512] Preparation of cycloolefin / epoxy resin mixtures:

[0513] 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.

[0514] 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.

[0515] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 28000 cPs.

[0516] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-1.

[0517] Example 18.10

[0518] Preparation of cycloolefin / epoxy resin mixtures:

[0519] 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.

[0520] 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.

[0521] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 23500 cPs.

[0522] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-1.

[0523] Example 18.11

[0524] Preparation of cycloolefin / epoxy resin mixtures:

[0525] 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.

[0526] 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.

[0527] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 21000 cPs.

[0528] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-1.

[0529] Example 18.12

[0530] Preparation of cycloolefin / epoxy resin mixtures:

[0531] 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;

[0532] 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.

[0533] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 20500 cPs.

[0534] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-1.

[0535] Example 18.13

[0536] Preparation of cycloolefin / epoxy resin mixtures:

[0537] 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;

[0538] 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.

[0539] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 21500 cPs.

[0540] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-1.

[0541] Example 18.14

[0542] Preparation of cycloolefin / epoxy resin mixtures:

[0543] 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.

[0544] 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.

[0545] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0546] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-2.

[0547] Example 18.15

[0548] Preparation of cycloolefin / epoxy resin mixtures:

[0549] 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;

[0550] 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.

[0551] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 34000 cPs.

[0552] Preparation of high flame retardant fiber prepreg finished product:

[0553] 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.

[0554] Preparation of composite materials:

[0555] Several pieces of glass fiber prepreg were cut and molded under process conditions of 80℃ / 1h + 120℃ / 1h + 140℃ / 1h and 1MPa pressure.

[0556] 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.

[0557] Comparative Example 18.1

[0558] Preparation of epoxy resin mixtures:

[0559] 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;

[0560] 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.

[0561] The mixing process of components A and B is the same as in Example 18.1, and the viscosity of the epoxy resin mixture at 70°C is 26000 cPs.

[0562] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.4. The mechanical properties of the prepared composite material are shown in Table 4-2.

[0563] Comparative Example 18.2

[0564] Preparation of epoxy resin mixtures:

[0565] 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;

[0566] 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.

[0567] The mixing process of components A and B is the same as in Example 18.1, and the viscosity of the epoxy resin mixture at 70°C is 26000 cPs.

[0568] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-2.

[0569] Comparative Example 18.3

[0570] Preparation of cycloolefin / epoxy resin mixtures:

[0571] 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.

[0572] 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.

[0573] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0574] The preparation process of the fiber prepreg and the composite material are the same as in Example 18.1. The mechanical properties of the prepared composite material are shown in Table 4-2.

[0575] Comparative Example 18.4

[0576] Preparation of cycloolefin / epoxy resin mixtures:

[0577] 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.

[0578] Component B: 5.18 parts of epoxy curing agent dicyandiamide, 1.73 parts of accelerator UR2T, and 0.0375 parts of commercially available Grubbs2 nd The 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.

[0579] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 24000 cPs.

[0580] 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.

[0581] Comparative Example 18.5

[0582] Preparation of cycloolefin / epoxy resin mixtures:

[0583] 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;

[0584] 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.

[0585] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 130,000 cPs.

[0586] 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.

[0587] Comparative Example 18.6

[0588] Preparation of cycloolefin / epoxy resin mixtures:

[0589] 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.

[0590] 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.

[0591] The mixing process of components A and B is the same as in Example 18.1, where the viscosity of the cyclic olefin / epoxy resin mixture at 70°C is 8000 cPs.

[0592] 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%).

[0593] The main conditional parameters involved in the effective examples 18.1-18.15 and comparative examples 18.1-18.6 are listed in Tables 18.1-18.3 below.

[0594] Table 18.1 Conditions and parameters involved in the preparation of component A

[0595]

[0596]

[0597]

[0598]

[0599] Table 18.2 Conditions and parameters involved in the preparation of component B

[0600]

[0601]

[0602] Table 18.3 Conditions and parameters involved in the preparation of composite materials

[0603]

[0604]

[0605] Note: In Table 3, " / " indicates that the parameter is not set.

[0606] Example 18.16

[0607] Test subjects: Composite materials prepared in Effective Examples 18.1-18.15 and Comparative Examples 18.1-18.6.

[0608] 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.

[0609] Evaluation method for warpage: 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 18.1-18.4, 18.6-18.15: virtually no warpage; Example 18.5: slight warpage; Comparative Examples 18.1-18.3: significant warpage.

[0610] Test results are shown in Tables 4-1 and 4-2 below.

[0611] Table 4-1 Summary of the mechanical properties of the composite materials obtained in the examples

[0612]

[0613] Note: In Table 4-1, A indicates that there is basically no warping deformation; B indicates slight warping deformation.

[0614] Table 4-2 Summary of the mechanical properties of the composite materials obtained in the examples

[0615]

[0616] Note: In Table 4-2, A indicates that there was basically no warping deformation. Examples 18.1-18.15 are all carbon fiber prepregs, and example 18.15 is a glass fiber prepreg.

[0617] Table 4-3 Summary of the mechanical properties of the composite materials obtained in the comparative examples

[0618]

[0619] 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.

[0620] From the tables above, we can see that:

[0621] Example 18.1 can be used as a comparative example to illustrate this effect;

[0622] Compared with Effective Example 18.2, Effective Example 18.1 shows that the inorganic toughening agent added in Effective Example 18.1 is well dispersed in the resin system and can also play a reinforcing role.

[0623] Compared with Effect Example 18.3, Effect Example 18.1, with the addition of both organic and inorganic toughening agents, has a toughening effect and tensile properties that are similar to Effect Example 18.3.

[0624] Compared with Effect Example 18.3, the fiber prepreg in Effect Example 18.4 was cured at 80℃ / 1h + 120℃ / 2h, and its mechanical properties were basically the same as those in Effect Example 18.3.

[0625] Compared to Example 18.3, Example 18.5 showed a significant decrease in mechanical properties due to incomplete curing of TCPD caused by the low amount of modified ruthenium carbene catalyst added. Comparative Example 18.3, which did not contain any catalyst, exhibited even worse mechanical properties.

[0626] Compared with Effect Example 18.3, Effect Example 18.6 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.

[0627] Compared to Effect Example 18.3, Effect Example 18.7 showed a slight decrease in tensile strength and a slight increase in modulus, which is related to the properties of the liquid epoxy resin itself.

[0628] Compared with Effective Example 18.3, the tensile strength and modulus of Effective Example 18.8 decreased, while the impact strength remained basically the same.

[0629] Compared with Comparative Example 18.2, the epoxy-reinforced fiber prepreg in Comparative Example 18.1 was not fully cured at 80℃ / 1h+120℃ / 2h, and its tensile strength and modulus were significantly lower than those of Comparative Example 18.2.

[0630] Compared to Comparative Example 18.2, Example 18.1 demonstrates how the inorganic toughening agent, cyclic olefin resin, and organic toughening agent synergistically toughen the epoxy resin, thereby improving the impact strength of the prepreg product. The simultaneous addition of the organic toughening agent and cyclic olefin resin resulted in a significant 15.6% increase in impact strength, but a 5.07% decrease in tensile strength.

[0631] Compared to Comparative Example 18.2, in Effect Example 18.2, 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.

[0632] Compared with Comparative Example 18.2, only 15 parts of tricyclopentadiene were added in Effect Example 18.3 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.

[0633] Compared with the effect example 18.3, the comparative example 18.3 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.

[0634] Compared to Effective Example 18.3, the commercially available Grubbs second-generation catalyst used in Comparative Example 18.4 immediately polymerized with TCPD when added to the resin mixture, making it impossible to prepare prepreg.

[0635] The viscosity of the cyclic olefin / epoxy resin mixture prepared in Comparative Example 18.5 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.

[0636] The viscosity of the cyclic olefin / epoxy resin mixture prepared in Comparative Example 18.6 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 prepregs (generally, the resin content is controlled between 25-40 wt%).

[0637] Comparative Example 1

[0638]

[0639] Under nitrogen protection, 3.63 g (5.00 mmol) of complex 2 was added to a dry 100 mL flask and dissolved in 20 mL of dichloromethane by stirring. Then, 0.76 g (10.00 mmol) of trimethylphosphine (Cf: C3H9P; Mw: 76.0 g / mol) was added to the flask, 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 to obtain 2.42 g of solid particles (Cf: C3H9P; Mw: 76.0 g / mol). 31 H 41 Cl2N2PRu Mw: 644.54 g / mol). The final product was a solid, which did not meet the requirements for a liquid state.

Claims

1. A ruthenium carbene compound as shown in formula LG, or a salt thereof, LG in, R1, R2, and R3 are each independently C8-C 18 alkyl.

2. The ruthenium carbene compound or its salt as shown in Formula LG according to claim 1, characterized in that, It meets one or more of the following conditions: (1) The C8-C 18 Alkyl groups are independently C8-C 10 Alkyl; and (2) R1, R2 and R3 are the same or different.

3. The ruthenium carbene compound or its salt as shown in formula LG according to claim 1, characterized in that, The C8-C 18 The alkyl group is independently a C8 alkyl group or a C6 alkyl group. 10 alkyl.

4. The ruthenium carbene compound or its salt as shown in formula LG according to claim 1, characterized in that, The C8-C 18 The alkyl group is independently a C8 alkyl group.

5. The ruthenium carbene compound or its salt as shown in formula LG as claimed in claim 3, characterized in that, It meets one or more of the following conditions: (1) The C8 alkyl group is n-octyl, 2-ethylhexyl, or 5-methylheptyl; and (2) The C 10 The alkyl group is n-decyl.

6. The ruthenium carbene compound or a salt thereof as shown in formula LG as claimed in claim 5, characterized in that, The C8 alkyl group is 2-ethylhexyl.

7. The ruthenium carbene compound or a salt thereof as shown in formula LG according to claim 1, characterized in that, The ruthenium carbene compound represented by formula LG is selected from any of the following structures: 。 8. A method for preparing a ruthenium carbene compound as shown in formula LG according to any one of claims 1-7, 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; ， in, The definitions of R1, R2 and R3 are as described in any one of claims 1-7.

9. The method for preparing the ruthenium carbene compound as shown in Formula LG according to claim 8, characterized in that, It meets one or more of the following conditions: (1) In Method 1, the organic solvent is a haloalkane solvent; (2) In Method 1, the inert atmosphere is nitrogen; (3) In Method 1, the molar ratio of compound 3 to compound 2 is (1-10):1; (4) In Method 1, the volume molar ratio of the organic solvent to Compound 2 is 2 L / mol to 8 L / mol; (5) In Method 1, the reaction temperature of the substitution reaction is room temperature; (6) In Method 1, the reaction time of the substitution reaction is 1 h to 5 h; (7) Method 1 further includes the following post-processing steps: rotary evaporation and / or column chromatography; (8) In Method 2, the organic solvent is an alkane solvent; (9) In method two, the molar ratio of compound 3 to compound 4 is (1-5):1; (10) In Method 2, the volume molar ratio of the organic solvent to Compound 4 is 10 L / mol to 50 L / mol; (11) In Method 2, the reaction temperature of the substitution reaction is 30 °C to 100 °C; (12) In Method 2, the reaction time of the substitution reaction is 1 h to 5 h; and (13) Method 2 also includes the following post-processing steps: cooling, column chromatography and rotary evaporation.

10. The method for preparing the ruthenium carbene compound as shown in Formula LG according to claim 9, characterized in that, It meets one or more of the following conditions: (1) In Method 1, the organic solvent is dichloromethane; (2) In Method 1, the molar ratio of compound 3 to compound 2 is 2:1; (3) In Method 1, the volume molar ratio of the organic solvent to Compound 2 is 4 L / mol; (4) In Method 1, the reaction time for the substitution reaction is 2 h; (5) In the post-processing step of the method one, the column chromatography uses a petroleum ether / dichloromethane mixed solution as the developing solvent; (6) In Method 2, the organic solvent is n-hexane; (7) In method two, the molar ratio of compound 3 to compound 4 is 1:1; (8) In Method 2, the volume molar ratio of the organic solvent to Compound 4 is 23.5 L / mol; (9) In Method 2, the reaction temperature of the substitution reaction is 70 °C; (10) In Method 2, the reaction time for the substitution reaction is 2 h; (11) In the post-processing step of Method Two, cooling is cooling to room temperature; and (12) In the post-processing step of the second method, the column chromatography uses a petroleum ether / dichloromethane mixed solution as the developing solvent.

11. The method for preparing the ruthenium carbene compound as shown in Formula LG according to claim 8, characterized in that, Method 1 further includes the following step: under an inert atmosphere, compound 1 undergoes a substitution reaction with pyridine as shown below; 。 12. The method for preparing the ruthenium carbene compound as shown in Formula LG according to claim 11, characterized in that, It meets one or more of the following conditions: (1) The pyridine is anhydrous pyridine; (2) The inert atmosphere is nitrogen; (3) The volume molar ratio of the pyridine to compound 1 is 2 L / mol to 20 L / mol; (4) The reaction temperature of the substitution reaction is room temperature; (5) The reaction time of the substitution reaction is 2 h to 10 h; (6) The substitution reaction is carried out under stirring conditions; and (7) The substitution reaction further includes the following post-processing steps: precipitation, filtration, washing and drying.

13. The method for preparing the ruthenium carbene compound as shown in Formula LG according to claim 12, characterized in that, It meets one or more of the following conditions: (1) The volume molar ratio of the pyridine to compound 1 is 5 L / mol; (2) The reaction time for the substitution reaction is 5 h; (3) In the post-treatment step of the substitution reaction, precipitation is carried out using petroleum ether; (4) In the post-treatment step of the substitution reaction, washing is performed using petroleum ether; and (5) In the post-treatment step of the substitution reaction, the drying is vacuum drying.

14. A catalyst composition comprising a ruthenium carbene compound or a salt thereof as shown in formula LG as claimed in any one of claims 1-7, and chlorinated paraffin.

15. The catalyst composition according to claim 14, characterized in that, It meets one or more of the following conditions: (1) The chlorinated paraffin contains 5% to 60% chlorine, where the percentage refers to the mass fraction of chlorine atoms in the chlorinated paraffin; and (2) The molar concentration of the ruthenium carbene compound or its salt in the chlorinated paraffin is 0.08 mol / L-0.7 mol / L.

16. The catalyst composition according to claim 15, characterized in that, It meets one or more of the following conditions: (1) The chlorinated paraffin contains 5%, 27%, 52%, or 60% chlorine, where the percentage refers to the mass fraction of chlorine atoms in the chlorinated paraffin; and (2) The molar concentration of the ruthenium carbene compound or its salt in the chlorinated paraffin is 0.1 mol / L, 0.2 mol / L, 0.25 mol / L, 0.3 mol / L, 0.4 mol / L, 0.45 mol / L, 0.5 mol / L or 0.6 mol / L.

17. The catalyst composition according to claim 14, characterized in that, The catalyst composition is selected from any combination of the following: Combination 1: and chlorinated paraffin, wherein the chlorinated paraffin contains 5%, 27%, 52% or 60% chlorine; Combination 2: and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%; or Combination 3: and chlorinated paraffin, wherein the chlorinated paraffin contains 5% chlorine.

18. The catalyst composition according to claim 17, characterized in that, The catalyst composition is selected from any combination of the following: Combination 4: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L; Combination 5: and chlorinated paraffin with a chlorine content of 27%; The molar concentration of the chlorinated paraffin is 0.2 mol / L; Combination 6: and chlorinated paraffin with a chlorine content of 52%; The molar concentration of the chlorinated paraffin is 0.4 mol / L; Combination 7: and chlorinated paraffin with a chlorine content of 60%; The molar concentration of the chlorinated paraffin is 0.6 mol / L; Combination 8: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L; Combination 9: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.3 mol / L; Combination 10: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.5 mol / L; Combination 11: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.6 mol / L; Combination 12: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.1 mol / L; Combination 13: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.25 mol / L; Combination 14: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.45 mol / L; or Combination 15: and chlorinated paraffin with a chlorine content of 5%; The molar concentration of the chlorinated paraffin is 0.6 mol / L.

19. A method for preparing the catalyst composition according to any one of claims 14-18, comprising the following steps: mixing the ruthenium carbene compound as shown in formula LG or a salt thereof with chlorinated paraffin under an inert atmosphere.

20. The method for preparing the catalyst composition according to claim 19, characterized in that, It meets one or more of the following conditions: (1) The inert atmosphere is nitrogen or argon; (2) The method for preparing the catalyst composition further includes the use of haloalkanes; (3) The mixing is stirring; (4) When the preparation method of the catalyst composition further includes the use of a haloalkane, the feeding sequence of the preparation method of the catalyst composition is, in sequence, the ruthenium carbene compound or its salt as shown in Formula LG, the haloalkane, and the chlorinated paraffin; and (5) The preparation method of the catalyst composition further includes the following post-processing step: rotary evaporation.

21. The method for preparing the catalyst composition according to claim 20, characterized in that, The haloalkane is dichloromethane.

22. The use of a ruthenium carbene compound as shown in formula LG as claimed in any one of claims 1-7, or a salt thereof, or a catalyst composition as claimed in any one of claims 14-18, in olefin metathesis reactions.

23. The application as described in claim 22, characterized in that, The olefin metathesis reaction is a ring-closed metathesis reaction, a cross metathesis reaction, or a ring-opening metasomatic polymerization reaction.

24. The application as described in claim 23, characterized in that, It meets one or more of the following conditions: (1) The closed-ring metathesis reaction includes the following steps: under an inert atmosphere and in the presence of a catalyst, the compound shown in Formula A1 is subjected to the closed-ring metathesis reaction shown below to obtain the compound shown in Formula A2, wherein the catalyst is a ruthenium carbene compound shown in Formula LG as described in any one of claims 1-7 or a salt thereof or a catalyst composition as described in any one of claims 14-18. ； Where X represents O, S, -N(R) 7 )-、-C(R 8 (R) 9 )- R 7 It is hydrogen, C1-C6 alkyl, -S(=O)2R 7-1 -C(=O)R 7-2 or -C(=O)OR 7-3 ; R 8 and R 9 Independently hydrogen, C1-C6 alkyl, -C(=O)R 8-1 or -C(=O)OR 8-2 ; Or, R 8 and R 9 The atoms between them form unsubstituted or substituted groups of 1, 2 or 3 R. 8-3 The substituted heterocycles are 3-6 membered heterocycles whose heteroatoms are selected from one or more of N, O and S, and whose number of heteroatoms is 1, 2 or 3. R 7-1 R 7-2 R 7-3 R 8-1 and R 8-2 Independently hydrogen, C1-C6 alkyl, or unsubstituted or surrounded by 1, 2, or 3 Rs 7-1-1 Replacement C6-C 10 Aryl; R 8-3 and R 7-1-1 Independently hydroxyl, halogen, C1-C6 alkyl, or C1-C6 alkoxy; n1 and n2 are independently 0, 1, 2 or 3; (2) The cross metathesis reaction includes the following steps: under an inert atmosphere and in the presence of a catalyst, a compound containing fragment B1 and a compound containing fragment B2 are subjected to the cross metathesis reaction shown below to obtain a compound containing fragment B3, wherein the catalyst is a ruthenium carbene compound as shown in formula LG as described in any one of claims 1-7 or a salt thereof or a catalyst composition as described in any one of claims 14-18. ； The compound containing fragment B1 and the compound containing fragment B2 are independently... , Among them, R 4 It is a C1-C6 alkyl group, -(CH2) n3 -OC(=O)-R 4-1 , or, not replaced or by 1, 2 or 3 Rs 4-2 Replacement C6-C 10 Aryl; n3 is 0, 1, or 2; R 4-1 For not replaced or by 1, 2 or 3 R 4-1-1 Replacement C6-C 10 Aryl; R 4-2 and R 4-1-1 Independently hydroxyl or C1-C6 alkyl; (3) The ring-opening metathesis polymerization reaction includes the following steps: under an inert atmosphere and in the presence of a catalyst, the compound containing segment C1 is subjected to the ring-opening metathesis polymerization reaction shown below to obtain the compound containing segment C2; the catalyst is a ruthenium carbene compound as shown in formula LG as described in any one of claims 1-7 or a salt thereof, or a catalyst composition as described in any one of claims 14-18. ； n≥3； The compound containing fragment C1 is ; Among them, R 5 and R 6 It is independently hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy; The A ring is a 3-8 member monocyclic cyclic olefin containing 1, 2, or 3 olefin bonds, or a 6-15 member polycyclic cyclic olefin containing 1, 2, or 3 olefin bonds.

25. The application as described in claim 24, characterized in that, X is -N(R) 7 )-;R 7 is -S(=O)2R 7-1 ; R 7-1 For not replaced or by 1, 2 or 3 R 7-1-1 Replacement C6-C 10 Aryl; Each R 7-1-1 Each is independently a C1-C6 alkyl group.

26. The application as described in claim 24, characterized in that, It meets one or more of the following conditions: (1) The compound shown in formula A1 is ; (2) The closed-ring metathesis reaction is carried out under solvent-free conditions or with solvent conditions. When the closed-ring metathesis reaction is carried out under solvent conditions, the solvent is a haloalkane solvent. (3) In the closed-loop metathesis reaction, the inert atmosphere is nitrogen; (4) In the closed-ring metathesis reaction, when the catalyst is the ruthenium carbene compound or its salt as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is , or ; (5) In the closed-loop metathesis reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5; (6) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG to the compound of formula A1 in the catalyst composition is (0.01%-1%):1; (7) The reaction temperature of the closed-loop metathesis reaction is 30 °C to 100 °C; (8) The reaction time of the closed-loop metathesis reaction is 1 h to 5 h; and (9) The closed-ring metathesis reaction further includes the following post-processing steps: column chromatography, or when the closed-ring metathesis reaction is carried out under solvent conditions, the post-processing steps further include rotary evaporation and / or column chromatography.

27. The application as described in claim 26, characterized in that, It meets one or more of the following conditions: (1) When the closed-ring metathesis reaction is carried out in the presence of a solvent, the solvent is dichloromethane; (2) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG to the compound of formula A1 in the catalyst composition is 0.2%:1; (3) The reaction temperature of the closed-loop metathesis reaction is 40℃; (4) The reaction time of the closed-loop metathesis reaction is 2 h; and (5) In the post-processing steps of the closed-ring metathesis reaction, the column chromatography is performed using a 5:1 petroleum ether / ethyl acetate column chromatography.

28. The application as described in claim 24, characterized in that, It meets one or more of the following conditions: (1) The compound containing fragment B1 and the compound containing fragment B2 are the same or different; (2) The cross metathesis reaction is carried out under solvent-free conditions or with solvent conditions. When the cross metathesis reaction is carried out under solvent conditions, the solvent is a haloalkane solvent. (3) In the cross-metathesis reaction, the inert atmosphere is nitrogen; (4) In the cross-metathesis reaction, when the catalyst is the ruthenium carbene compound or its salt as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is , or ; (5) In the cross metathesis reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5; (6) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG to the compound of formula B1 in the catalyst composition is (0.1%-10%):1; (7) The molar ratio of the compound containing fragment B2 to the compound containing fragment B1 is (1-5):1; (8) The reaction temperature of the cross-metathesis reaction is 30 ℃ to 100 ℃; (9) The reaction time for the cross-metathesis reaction is 4 h to 20 h; and (10) When the cross metathesis reaction is carried out in the presence of solvent, the post-treatment steps further include rotary evaporation under reduced pressure and / or column chromatography.

29. The application as described in claim 28, characterized in that, It meets one or more of the following conditions: (1) The compound containing fragment B1 and the compound containing fragment B2 are independently... or ; (2) When the cross metathesis reaction is carried out in the presence of a solvent, the solvent is dichloromethane; (3) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG to the compound of formula B1 in the catalyst composition is 2.5%:1; (4) The molar ratio of the compound containing fragment B2 to the compound containing fragment B1 is 2:1; (5) The reaction temperature of the cross-metathesis reaction is 45 °C; and (6) The reaction time of the cross metathesis reaction is 6 h.

30. The application as described in claim 24, characterized in that, It meets one or more of the following conditions: (1) The ring-opening metathesis polymerization reaction is carried out under solvent-free conditions; (2) In the ring-opening metathesis polymerization reaction, the inert atmosphere is nitrogen; (3) In the ring-opening metathesis polymerization reaction, when the catalyst is the ruthenium carbene compound or its salt as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is or ; (4) In the ring-opening metathesis polymerization reaction, when the catalyst is the catalyst composition, the catalyst composition is composition 5; and (5) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG to the compound of formula C1 in the catalyst composition is (0.01%-1%):

1.

31. The application as described in claim 30, characterized in that, It meets one or more of the following conditions: (1) The compound containing fragment C1 is ; R 5 and R 6 It is hydrogen; The A ring is a 7-10 membered polycyclic cyclic olefin containing 1, 2 or 3 olefinic bonds; (2) The molar ratio of the ruthenium carbene compound of formula LG or its salt or the ruthenium carbene compound of formula LG in the catalyst composition to the compound of formula C1 is 0.01%:1; (3) In the ring-opening metathesis polymerization reaction, when the catalyst is the ruthenium carbene compound or its salt as shown in Formula LG, the ruthenium carbene compound as shown in Formula LG is .

32. The application as described in claim 30, characterized in that, The compound containing fragment C1 is , , , or .

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