CN112662130B - Resin composition, resin material and preparation method thereof - Google Patents

Abstract

The invention discloses a resin composition, a resin material and a preparation method thereof. The invention specifically discloses a resin composition, which comprises: 5-98 parts of dicyclopentadiene, 3-95 parts of epoxy resin, 0.5-65 parts of epoxy resin curing agent, and curing accelerator in parts by weight. 0.5-25 parts and 0.01-15 parts of catalyst composition; Described catalyst composition comprises ruthenium carbene compound or its salt as shown in formula I, and chlorinated paraffin; The chlorine content of described chlorinated paraffin is 5 %-65%, the chlorine content is the percentage of the mass of chlorine atoms in the mass of chlorinated paraffin. The resin composition of the present invention can be stored for a long time, and the resin material obtained by the resin composition has good mechanical properties such as tensile strength, tensile modulus and elongation at break. In addition, the preparation process of the resin material is suitable for Industrialized continuous production.

Description

Resin composition, resin material and preparation method thereof

Technical Field

The invention relates to a resin composition, a resin material and a preparation method thereof.

Background Art

Polydicyclopentadiene (PDCPD) is a homopolymer or copolymer with a cross-linked network structure formed by the severance and recombination of olefin carbon-carbon double bonds of dicyclopentadiene monomers under the action of olefin metathesis catalysts. It has excellent weather resistance, wear resistance, surface finishing, electrical insulation, acid and alkali resistance, and waterproof properties. PDCPD composite products are mostly made of various parts using reaction injection molding (RIM) and have been successfully used in many fields such as engineering machinery, lightweight automobiles, and chlor-alkali industry.

At present, polydicyclopentadiene composite materials prepared based on tungsten-molybdenum catalyst system can be formed by RIM process with high automation level. However, due to defects in the catalytic system, oxygen and moisture need to be blocked during the processing to ensure catalyst activity and stable product quality. The reaction molding conditions have high requirements, the product applicability is poor, and it is not easy to add fillers, long fibers or continuous fibers to prepare structurally reinforced composite materials or functionally modified products, which limits the promotion scope of polydicyclopentadiene materials.

In addition, commercial PDCPD composite materials based on ruthenium carbene catalytic systems usually have higher catalytic activity and stability, simple synthesis process, good functional group applicability, and reaction conditions do not require air and moisture isolation, making them a hot topic in the development of polydicyclopentadiene application technology. However, the existing ruthenium catalytic system cannot achieve continuous automated production for the following reasons:

1. Short storage period: Existing commercial ruthenium carbene catalytic systems can only be stored for a long time at low temperature and in a solid state. When dissolved in common solvents to prepare solutions, they decompose rapidly and are difficult to store for a long time. They can only be prepared and used immediately and cannot be used in continuous production lines. Otherwise, they will become inactivated and unable to solidify, or the reaction will be so violent that the equipment will be blocked.

2. Poor compatibility: The existing commercial products of ruthenium carbene catalytic system polydicyclopentadiene and other resin systems such as epoxy have obvious phase separation, the products are hard and brittle, low in strength, and have obvious defects, making them difficult to promote and use.

As we all know, epoxy resin is a classic thermosetting resin product. The cross-linked network structure formed after curing gives the material excellent mechanical strength and high elastic modulus. However, it has disadvantages such as small fracture strain, poor impact resistance, narrow process adaptability, long production cycle, and difficulty in demolding, which are still the pain points of the industry today.

Compared with thermosetting resins such as epoxy resin and other engineering plastics, polydicyclopentadiene composite products have excellent impact resistance and corrosion resistance, good process applicability, and high degree of automation. However, their mechanical strength, especially the elastic modulus, is low, which to a certain extent restricts their promotion in high-end application fields.

Chinese patent application CN106243279A discloses a multi-color, aging-resistant, spray-free polydicyclopentadiene composite material and its preparation method and application. The invention is based on a ruthenium carbene catalyst and is prepared by adding a certain amount of copolymers, functional fillers, environmentally friendly color pastes or high-mesh color powders to a dicyclopentadiene system. The product has good appearance color and relatively balanced mechanical properties and is mainly used in the sanitary ware field. However, the ruthenium carbene solid catalyst in this technology is mixed with a co-solvent or other components and molded by a single-component RIM injection process. The raw material storage period is short and the reaction activity is significantly reduced. In actual production, it needs to be prepared and used immediately, which is difficult to meet the requirements of continuous production.

Chinese patent CN1027509C provides a method for preparing a thermosetting polymer, which uniformly mixes dicyclopentadiene monomer with a metathesis catalyst and a co-catalyst, adds a certain amount of additives, fillers, etc., and obtains a polydicyclopentadiene composite material through two-component reaction injection molding. However, its catalytic system is a metal carbene complex such as tungsten, molybdenum, and tantalum. During the reaction, the two-component feed liquid needs to undergo a ring-opening polymerization reaction under anhydrous and oxygen-free conditions. The molding conditions are harsh, the process adaptability is poor, and it is difficult to achieve the addition of high-content fillers or modified additives, which limits the application of this type of technology.

Chinese patent application CN103709375A discloses a high-performance epoxy resin composition containing a dicyclopentadiene alicyclic structure. In the invention, two mixed epoxy resins are used as the matrix, an anhydride curing agent, dicyclopentadiene monomer (DCPD), a accelerator, an antioxidant and a composite light stabilizer are added to prepare an epoxy resin composition with good toughness, anti-aging performance and weather resistance, which can be widely used in the field of carbon fiber composite materials. The DCPD used in the patent application is used as a chain terminator of the addition method, which is to reduce the three-dimensional cross-linked structure in the epoxy resin cured product and increase the chain structure to achieve a toughening effect.

Summary of the invention

The object of the present invention is to provide a resin composition, a resin material and a preparation method thereof. The resin composition of the present invention can be stored for a long time, and the resin material prepared from the resin composition has good mechanical properties such as tensile strength, tensile modulus and elongation at break. In addition, the preparation process of the resin material is suitable for industrial continuous production.

The present invention provides a resin composition, which comprises, by weight: 5-98 parts of dicyclopentadiene, 3-95 parts of epoxy resin, 0.5-65 parts of epoxy resin curing agent, 0.5-25 parts of curing accelerator and 0.01-15 parts of catalyst composition;

The catalyst composition comprises a ruthenium carbene compound or a salt thereof as shown in formula I, and chlorinated paraffin; the chlorinated paraffin has a chlorine content of 5% to 65%, where the chlorine content is the percentage of the mass of chlorine atoms to the mass of the chlorinated paraffin;

wherein R ¹ and R ² are independently C ₄ -C ₁₈ alkyl or C ₄ -C ₁₈ alkyl substituted by R ^1-1 ;

R ^1-1 is independently a C ₆ -C ₁₀ aryl group.

In a certain embodiment, some of the resin composition are defined as follows, and the undefined contents are the same as other embodiments (hereinafter referred to as "a certain embodiment"). The chlorine content of the chlorinated paraffin is preferably 5%-60%, for example 5%, 42%, 52% or 60%, and the chlorine content is the percentage of the mass of chlorine atoms to the mass of the chlorinated paraffin.

In a certain embodiment, the molar concentration of the ruthenium carbene compound or its salt as shown in Formula I in the chlorinated paraffin may be 0.08 mol/L to 0.7 mol/L, preferably 0.1 mol/L to 0.6 mol/L, for example 0.1 mol/L, 0.2 mol/L, 0.25 mol/L, 0.3 mol/L, 0.35 mol/L, 0.55 mol/L or 0.6 mol/L.

In a certain embodiment, the C ₄ -C ₁₈ alkyl group or the C ₄ -C ₁₈ alkyl group substituted by _R ^1-1 may independently be a C ₄ -C ₁₀ alkyl group, preferably a C ₄ -C ₆ alkyl group, such as a C ₄ alkyl group, a C ₅ alkyl group or _{a C 6 alkyl} group, such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, more preferably n-butyl or n-hexyl.

In a certain embodiment, in the C ₄ -C ₁₈ alkyl substituted by R ^1-1 , the number of R ^1-1 is 1, 2 or 3, and when there are plural R 1-1, they may be the same or different.

In one embodiment, the C ₆ -C ₁₀ aryl group may be phenyl or naphthyl.

In one embodiment, ^R1 and ^R2 can be independently n-butyl or n-hexyl.

In one embodiment, R ¹ and R ² may independently be C ₄ -C ₁₈ alkyl.

In one embodiment, ^R1 and ^R2 may be the same or different.

In one embodiment, the ruthenium carbene compound as shown in Formula I can be any of the following structures:

In a certain embodiment, the catalyst composition may be composed of a ruthenium carbene compound or a salt thereof as shown in Formula I, and chlorinated paraffin; the ruthenium carbene compound as shown in Formula I and chlorinated paraffin are as described in any of the above embodiments.

In a certain embodiment, the catalyst composition can be any combination of the following:

和氯化石蜡，所述的氯化石蜡的含氯量为5％、42％、52％或60％；Combination A1:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%, 42%, 52% or 60%;

和氯化石蜡，所述的氯化石蜡的含氯量为5％、42％、52％或60％；Combination A2:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%, 42%, 52% or 60%;

和氯化石蜡，所述的氯化石蜡的含氯量为52％；Combination A3:

and chlorinated paraffin, wherein the chlorinated paraffin has a chlorine content of 52%;

和氯化石蜡，所述的氯化石蜡的含氯量为42％；Combination A4:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 42%;

和氯化石蜡，所述的氯化石蜡的含氯量为5％；Combination A5:

and chlorinated paraffin, wherein the chlorinated paraffin has a chlorine content of 5%;

和氯化石蜡，所述的氯化石蜡的含氯量为60％；Combination A6:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 60%;

和氯化石蜡，所述的氯化石蜡的含氯量为52％。Combination A7:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%.

In a certain embodiment, the catalyst composition can be any combination of the following:

和含氯量为5％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.1mol/L；Combination B1:

and chlorinated paraffin with a chlorine content of 5%,

The molar concentration of the substance in chlorinated paraffin is 0.1 mol/L;

和含氯量为42％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.3mol/L；Combination B2:

and chlorinated paraffin with a chlorine content of 42%,

The molar concentration of the substance in chlorinated paraffin is 0.3 mol/L;

和含氯量为52％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.35mol/L；Combination B3:

and chlorinated paraffin with a chlorine content of 52%,

The molar concentration of the substance in chlorinated paraffin is 0.35 mol/L;

和含氯量为60％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.6mol/L；Combination B4:

and chlorinated paraffin with a chlorine content of 60%,

The molar concentration of the substance in chlorinated paraffin is 0.6 mol/L;

和含氯量为5％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.1mol/L；Combination B5:

and chlorinated paraffin with a chlorine content of 5%,

The molar concentration of the substance in chlorinated paraffin is 0.1 mol/L;

和含氯量为42％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.25mol/L；Combination B6:

and chlorinated paraffin with a chlorine content of 42%,

The molar concentration of the substance in chlorinated paraffin is 0.25 mol/L;

和含氯量为52％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.3mol/L；Combination B7:

and chlorinated paraffin with a chlorine content of 52%,

The molar concentration of the substance in chlorinated paraffin is 0.3 mol/L;

和含氯量为60％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.6mol/L；Combination B8:

and chlorinated paraffin with a chlorine content of 60%,

The molar concentration of the substance in chlorinated paraffin is 0.6 mol/L;

和含氯量为52％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.3mol/L；Combination B9:

and chlorinated paraffin with a chlorine content of 52%,

The molar concentration of the substance in chlorinated paraffin is 0.3 mol/L;

和含氯量为42％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.35mol/L；Combination B10:

and chlorinated paraffin with a chlorine content of 42%,

The molar concentration of the substance in chlorinated paraffin is 0.35 mol/L;

和含氯量为5％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.55mol/L；Combination B11:

and chlorinated paraffin with a chlorine content of 5%,

The molar concentration of the substance in chlorinated paraffin is 0.55 mol/L;

和含氯量为60％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.2mol/L；Combination B12:

and chlorinated paraffin with a chlorine content of 60%,

The molar concentration of the substance in chlorinated paraffin is 0.2 mol/L;

和含氯量为52％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.35mol/L。Combination B13:

and chlorinated paraffin with a chlorine content of 52%,

The molar concentration of the substance in chlorinated paraffin is 0.35 mol/L.

In a certain embodiment, the purity of the dicyclopentadiene can be ≥90%, preferably ≥98%.

In a certain embodiment, the amount of dicyclopentadiene used is preferably 10-95 parts by weight, such as 10 parts, 55 parts, 80 parts or 95 parts.

In a certain embodiment, the epoxy resin is preferably used in an amount of 5-90 parts by weight, such as 5 parts, 20 parts, 45 parts or 90 parts.

In a certain embodiment, the epoxy resin curing agent is preferably used in an amount of 1-60 parts by weight, such as 1.14 parts, 3 parts, 18.76 parts, or 57.93 parts.

In a certain embodiment, the amount of the curing accelerator is preferably 1-10 parts by weight, such as 1.56 parts, 6.40 parts, 9.70 parts or 3 parts.

In a certain embodiment, the amount of the catalyst composition used is preferably 0.03-11 parts by weight, such as 0.03 parts, 0.57 parts, 0.67 parts or 10.94 parts.

In a certain embodiment, the sum of the volume fractions of the cyclopentadiene and the epoxy resin may be 100 parts.

In a certain embodiment, the volume ratio of the cyclopentadiene to the epoxy resin may be 0.1:1-20:1, for example, 1:9, 4:1, 11:9 or 19:1.

In a certain embodiment, the epoxy resin can be an epoxy resin in the art, and can also be one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether epoxy resin, glycidyl ester epoxy resin and phenolic epoxy resin, preferably bisphenol A epoxy resin.

In a certain embodiment, the epoxy value of the epoxy resin is preferably 0.48-0.54.

In a certain embodiment, the epoxy resin curing agent may be an epoxy resin curing agent in the art, and may be one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, modified methyltetrahydrophthalic anhydride, modified methylhexahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (MNA) and dodecylsuccinic anhydride, preferably one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride.

In a certain embodiment, the curing accelerator may be a curing accelerator in the art, and may be one or more of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), dimethylaminomethylphenol (DMPZ-10), 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, preferably one or more of 2-methylimidazole, 2-ethylimidazole and 2,4,6-tris(dimethylaminomethyl)phenol.

In a certain embodiment, the resin composition further comprises one or more of a comonomer, a functional filler and an auxiliary agent.

The comonomer may be a conventional comonomer in the art, or one or more of norbornene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene, propylene, isoprene, styrene, butadiene, maleic anhydride, cyclopentadiene, methyl-5-norbornene-2,3-dicarboxylic anhydride and tert-butyl 5-norbornene-2-carboxylate, preferably one or more of ethylene, ethyl methacrylate and tert-butyl 5-norbornene-2-carboxylate.

In terms of weight, the amount of the comonomer used may be 0.5-13 parts, preferably 1-10 parts, such as 1.37 parts, 5 parts or 10 parts.

The functional filler can be a conventional functional filler in the art, or one or more of carbon black, graphite powder, mica powder, montmorillonite, titanium dioxide, silica, glass fiber, basalt fiber, carbon fiber, polyethylene fiber and aramid fiber, preferably one or more of glass fiber, carbon black and carbon fiber.

In terms of weight, the amount of the functional filler can be 1-13 parts, preferably 2-10 parts, such as 2.50 parts, 5 parts or 9.66 parts.

The auxiliary agent may be a conventional auxiliary agent in the art, or one or more of a polymerization regulator, an anti-aging agent, a coupling agent, a color powder, a cosolvent, a heat stabilizer, a flame retardant and a release agent, preferably one or more of a polymerization regulator, an anti-aging agent, a coupling agent, a color powder and a cosolvent.

The polymerization regulator can be a conventional polymerization regulator in the art, and can also be one or more of triphenylphosphine, triethyl phosphite, tributyl phosphite, ethylene glycol dimethyl ether, benzophenone and isopropyl ether, preferably triethyl phosphite. In parts by weight, the amount of the polymerization regulator can be a conventional amount in the art, and can also be 0.5-3 parts, for example, 1 part.

The anti-aging agent may be a conventional anti-aging agent in the art, or one or more of 2,6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, Tinuvin 571, Tinuvin 765, Tinuvin B75, Tinuvin B88, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531 and UV-770, preferably one or more of 2,6-di-tert-butyl-4-methylphenol, 2-methylaniline, Tinuvin B75 and 2-hydroxy-4-methoxybenzophenone. The amount of the anti-aging agent may be a conventional amount in the art, or 1-5 parts, for example, 2 parts, by weight.

The coupling agent can be a conventional coupling agent in the art, or a silane coupling agent, such as silane coupling agent A172. The amount of the coupling agent can be a conventional amount in the art, or 0.3-1 part, such as 0.64 part, by weight.

The toner can be a conventional toner in the art. The toner can be used in an amount conventionally used in the art, and can be 0.1-0.5 parts, such as 0.34 parts, by weight.

The co-solvent can be a conventional co-solvent in the art, such as acetone. The amount of the co-solvent can be a conventional amount in the art, and can also be 1-2 parts, such as 1.56 parts by weight.

The heat stabilizer can be a conventional heat stabilizer in the art. The amount of the heat stabilizer used can be a conventional amount in the art by weight.

The flame retardant can be a conventional flame retardant in the art. The amount of the flame retardant can be a conventional amount in the art by weight.

The release agent can be a conventional release agent in the art. The amount of the release agent used can be a conventional amount in the art by weight.

In a certain embodiment, the composition can be any of the following combinations:

Combination C1: dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator and catalyst composition;.

Combination C2: dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator, catalyst composition, comonomer, functional filler and color powder;

Combination C3: dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator, catalyst composition, comonomer, functional filler, anti-aging agent and coupling agent;

Combination C4: dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator, catalyst composition, comonomer, functional filler, polymerization regulator and cosolvent;

The definitions of the dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator, catalyst composition, comonomer, functional filler, polymerization regulator, anti-aging agent, coupling agent, color powder and cosolvent are the same as those in any of the previous schemes.

In a certain embodiment, the composition can be any of the following combinations:

Combination D1: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator and 0.03-11 parts of catalyst composition;

Combination D2: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler and 0.1-0.5 parts of color powder;

Combination D3: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 1-5 parts of anti-aging agent and 0.3-1 parts of coupling agent;

Combination D4: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 0.5-3 parts of polymerization regulator and 1-2 parts of cosolvent;

和含氯量为5％的氯化石蜡；Combination D5: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator and 0.03-11 parts of catalyst composition; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4,6-tris(dimethylaminomethyl)phenol; the catalyst composition is

and chlorinated paraffin containing 5% chlorine;

和含氯量为42％的氯化石蜡；所述的共聚单体为乙烯、甲基丙烯酸乙酯和5-降冰片烯-2-羧酸叔丁酯中的一种或多种；所述的功能填料为玻璃纤维、炭黑和碳纤维中的一种或多种；Combination D6: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler and 0.1-0.5 parts of color powder; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4,6-tris(dimethylaminomethyl)phenol; the catalyst composition is

and chlorinated paraffin with a chlorine content of 42%; the comonomer is one or more of ethylene, ethyl methacrylate and tert-butyl 5-norbornene-2-carboxylate; the functional filler is one or more of glass fiber, carbon black and carbon fiber;

和含氯量为60％的氯化石蜡；所述的共聚单体为乙烯、甲基丙烯酸乙酯和5-降冰片烯-2-羧酸叔丁酯中的一种或多种；所述的功能填料为玻璃纤维、炭黑和碳纤维中的一种或多种；所述的抗老化剂为2,6-二叔丁基-4-甲基苯酚、2-甲基苯胺、Tinuvin B75和2-羟基-4-甲氧基二苯甲酮中的一种或多种；所述的偶联剂为硅烷偶联剂；Combination D7: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 1-5 parts of anti-aging agent and 0.3-1 parts of coupling agent; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4,6-tris(dimethylaminomethyl)phenol; the catalyst composition is

and chlorinated paraffin with a chlorine content of 60%; the comonomer is one or more of ethylene, ethyl methacrylate and tert-butyl 5-norbornene-2-carboxylate; the functional filler is one or more of glass fiber, carbon black and carbon fiber; the anti-aging agent is one or more of 2,6-di-tert-butyl-4-methylphenol, 2-methylaniline, Tinuvin B75 and 2-hydroxy-4-methoxybenzophenone; the coupling agent is a silane coupling agent;

和含氯量为5％的氯化石蜡；所述的共聚单体为乙烯、甲基丙烯酸乙酯和5-降冰片烯-2-羧酸叔丁酯中的一种或多种；所述的功能填料为玻璃纤维、炭黑和碳纤维中的一种或多种；所述的聚合调节剂为亚磷酸三乙酯；所述的助溶剂为丙酮；Combination D8: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 0.5-3 parts of polymerization regulator and 1-2 parts of cosolvent; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl-5-norbornene-2,3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4,6-tris(dimethylaminomethyl)phenol; the catalyst composition is

and chlorinated paraffin with a chlorine content of 5%; the comonomer is one or more of ethylene, ethyl methacrylate and tert-butyl 5-norbornene-2-carboxylate; the functional filler is one or more of glass fiber, carbon black and carbon fiber; the polymerization regulator is triethyl phosphite; the cosolvent is acetone;

和含氯量为5％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.1mol/L；Combination D9: 80 parts of dicyclopentadiene, 20 parts of bisphenol A epoxy resin, 13 parts of methyl-5-norbornene-2,3-dicarboxylic anhydride, 3 parts of 2,4,6-tris(dimethylaminomethyl)phenol and 0.67 parts of a catalyst composition; the catalyst composition is

and chlorinated paraffin with a chlorine content of 5%,

The molar concentration of the substance in chlorinated paraffin is 0.1 mol/L;

和含氯量为42％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.25mol/L；Combination D10: 95 parts of dicyclopentadiene, 5 parts of bisphenol A epoxy resin, 1.14 parts of methyl hexahydrophthalic anhydride, 9.70 parts of 2-ethylimidazole, 0.57 parts of catalyst composition, 1.37 parts of tert-butyl 5-norbornene-2-carboxylate, 5 parts of carbon fiber and 0.34 parts of toner; the catalyst composition is

and chlorinated paraffin with a chlorine content of 42%,

The molar concentration of the substance in chlorinated paraffin is 0.25 mol/L;

和含氯量为60％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.6mol/L；Combination D11: 55 parts of dicyclopentadiene, 45 parts of bisphenol A epoxy resin, 57.93 parts of methyltetrahydrophthalic anhydride, 6.40 parts of 2-methylimidazole, 0.03 parts of catalyst composition, 10 parts of ethylene, 9.66 parts of glass fiber, 2 parts of 2-methylaniline and 0.64 parts of silane coupling agent A172; the catalyst composition is

and chlorinated paraffin with a chlorine content of 60%,

The molar concentration of the substance in chlorinated paraffin is 0.6 mol/L;

和含氯量为5％的氯化石蜡，

在氯化石蜡中的物质的量浓度为0.1mol/L。Combination D12: 10 parts of dicyclopentadiene, 90 parts of bisphenol A epoxy resin, 18.76 parts of methyl-5-norbornene-2,3-dicarboxylic anhydride, 1.56 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 10.94 parts of catalyst composition, 5 parts of ethyl methacrylate, 2.50 parts of carbon black, 1 part of triethyl phosphite and 1.56 parts of acetone; the catalyst composition is

and chlorinated paraffin with a chlorine content of 5%,

The molar concentration of the substance in chlorinated paraffin is 0.1 mol/L.

The present invention provides a resin material, which is prepared using the resin composition of any of the above schemes as a raw material.

In a certain embodiment, the epoxy resin and dicyclopentadiene are preferably cross-linked and polymerized to form an interpenetrating network structure.

The present invention provides a method for preparing the above-mentioned resin material, which comprises the following steps: using the resin composition of any of the above schemes as a raw material, uniformly mixing the dicyclopentadiene, epoxy resin, epoxy resin curing agent, curing accelerator and catalyst composition therein, optionally adding one or more of comonomers, functional fillers and auxiliary agents, and curing and molding to obtain the resin material.

In a certain embodiment, the preparation method may adopt RIM process.

In a certain embodiment, the conditions and operations of the RIM process may be conventional conditions and operations in the art, and may include the following steps:

(1) Dicyclopentadiene and epoxy resin are mixed to form liquid A;

(2) mixing the catalyst composition, the epoxy resin curing agent and the curing accelerator to prepare liquid B;

(3) optionally adding one or more of a comonomer, a functional filler and an additive to liquid A or liquid B;

(4) introducing liquid A and liquid B into the storage system for standby use;

(5) Liquid A and Liquid B complete reaction injection molding in the RIM equipment;

(6) Curing to obtain a resin material.

In one embodiment, in step (4), the material storage system may be a material storage tank of the RIM equipment.

In one embodiment, in step (4), the temperature of the storage system may be -10°C to 40°C, preferably -5°C to 25°C.

In one embodiment, in step (5), the mass ratio of liquid A to liquid B may be 1:1-20:1, more preferably 1:1-15:1, such as 3:1, 3:2, 8:1 or 15:1, more preferably 1:1-10:1.

In one embodiment, in step (5), the liquid A and liquid B can be mixed online and injected into the mold to complete the reaction injection molding.

In one embodiment, in step (5), the injection speed of the reaction injection molding can be 200 mL/min-100 L/min, preferably 500 mL/min-30 L/min, for example 500 mL/min, 2 L/min, 5 L/min, 30 L/min.

In one embodiment, in step (5), the injection pressure of the reaction injection molding may be 0.1-20 bar, preferably 6-25 bar, for example 6 bar, 10 bar, 15 bar or 25 bar.

In one embodiment, in step (6), the curing temperature may be 70-180°C, preferably 70-100°C, for example 80°C.

In one embodiment, in step (6), the curing time may be 1-120 min, for example 2 h.

The present invention also provides a resin material prepared according to the preparation method.

In the present invention, unless otherwise specified, "min" means minute, "h" means hour, and "°C" means degree Celsius.

Unless otherwise specified, the terms used in the present invention have the following meanings:

In the present invention, the ruthenium carbene compound or its salt as shown in Formula I may have one or more chiral carbon atoms, so it can be separated to obtain optically pure isomers, such as pure enantiomers, or racemates, or mixed isomers. Pure single isomers can be obtained by separation methods in the art, such as chiral crystallization into salts, or separation by chiral preparative columns.

In the present invention, the ruthenium carbene compound or its salt as shown in Formula I, if stereoisomers exist, can exist in the form of a single stereoisomer or a mixture thereof (e.g., a racemate). The term "stereoisomer" refers to cis-trans isomers or optical isomers. These stereoisomers can be separated, purified and enriched by asymmetric synthesis methods or chiral separation methods (including but not limited to thin layer chromatography, rotary chromatography, column chromatography, gas chromatography, high pressure liquid chromatography, etc.), and can also be obtained by chiral separation by bonding (chemical bonding, etc.) or salification (physical bonding, etc.) with other chiral compounds. The term "single stereoisomer" means that the mass content of one stereoisomer of the compound of the present invention relative to all stereoisomers of the compound is not less than 95%.

The term "salt" includes salts prepared by reacting the compound of the present invention with an acid, for example, hydrochloride, hydrobromide, sulfate and the like.

The term "alkyl" refers to a straight or branched chain alkyl group having a specified number of carbon atoms. For example, _C1 - _C6 alkyl is a straight or branched chain alkyl group containing 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, and the like.

The term "aryl" refers to a hydrocarbon group having aromaticity, such as a _C6 - _C10 aryl group, examples of which include phenyl or naphthyl.

In the present invention, the open-ended expression "including" can be converted into the closed-ended expression "consisting of...".

On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

The reagents and raw materials used in the present invention are commercially available.

The positive and progressive effects of the present invention are:

(1) The catalyst composition in the resin composition of the present invention is easy to use and does not need to be prepared immediately before use.

(2) The catalyst composition in the resin composition of the present invention has a long storage period and can still maintain its original catalytic activity after storage for 6 months.

(3) The resin composition of the present invention can be stored for a long time, and the mechanical properties of the resin material obtained after storage for 6 months do not change significantly.

(4) The resin material prepared by the present invention realizes the compounding of the epoxy system and the polydicyclopentadiene resin system, has good compatibility, and the product has both high mechanical strength, high modulus and good impact resistance.

(5) The catalyst composition of the present invention is used to prepare resin materials. Since the catalyst composition is in liquid form, the production process can be applied to more processes, such as a two-component RIM process. Compared with a single-component RIM process, in a two-component RIM process, the feed liquid can be stored separately, which increases the storage cycle and is suitable for industrial continuous production.

DETAILED DESCRIPTION

The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

The instruments and raw materials involved in the embodiments are described as follows:

H NMR and C NMR spectra were measured by Bruker AV 400 (400 MHz). Chemical shifts were expressed in ppm with TMS as the internal standard. Chemical shifts, splitting (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad peak) and coupling constants (J, unit: Hz) were recorded.

The silica gel, diatomaceous earth, dichloromethane, tetrahydrofuran and other solvents used in column chromatography were purchased from Tianjin Xiensi Biochemical Technology Co., Ltd. CDC1 ₃ for testing was purchased from Shanghai Boka Co., Ltd. (PCy ₃ ) ₂ C1 ₂ Ru＝CHPh (1) was purchased from Tianjin Kaimeiweide Technology Co., Ltd.

Tetrahydrofuran is obtained by distillation under nitrogen protection after sodium reflux until the benzophenone solution turns blue; dichloromethane is obtained by distillation under nitrogen protection after calcium hydride treatment.

Example 1: Synthesis of 1,3-bis(2,4,6-trimethylphenyl)-2-(4,5-dibutylimidazolidinyl)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium (I-1) containing butyl substituent catalyst

The synthesis of catalyst I-1 containing butyl substituents includes the following steps:

1) Preparation of N,N′-bis(2,4,6-trimethyl)phenylethyleneimine (9)

Add 3.73mL of glyoxal (8) aqueous solution (40%) and 80mL of methanol to a 500mL three-necked flask equipped with a dropping funnel, and stir to dissolve the glyoxal. Add 9.12mL of m-trimethylbenzene (7) and 10mL of methanol to the dropping funnel, and slowly drop them into the flask. Control the reaction liquid temperature to about 22°C and stir for 12h. During this process, a bright yellow precipitate slowly precipitates from the reaction liquid. After the reaction is completed, filter the reaction liquid to obtain a yellow solid, wash the solid three times with water and once with methanol, and vacuum dry to obtain a yellow crystalline product 9. Weight 6.5g, yield 70%. Analytical Data.Calcd(found)for:C ₂₀ H ₂₄ N ₂ ; C, 82.15 (82.12); H, 8.27 (8.20). ¹ H-NMR (400MHz, CDCl ₃ ): δ (ppm): 2.15 (s, 6H, CH ₃ ), 6.96 (s, 4H, CHar), 8.10 (s, 2H, CHar). ¹³ C-NMR (100MHz, CDCl ₃ ) δ (ppm): 18.0, 20.9, 126.4, 128.9, 134.0, _147.4 , 162.9.

2) Preparation of N,N'-bis(2,4,6-trimethylphenyl)decane-5,6-diamine (10)

Under nitrogen protection, add 2.92g (10.0mmol) N,N'-di(2,4,6-trimethyl)phenylethyleneimine (9) (Mw: 292.46g/mol) and 50mL tetrahydrofuran to a dry 100mL ampoule and stir to dissolve. Then, place the ampoule in a -78℃ ethanol cold bath and stir to cool. After the reaction solution is fully cooled, slowly add 13.75mL (22.0mmol) of butyl lithium (1.6M hexane solution) solution with a syringe. After the addition is complete, the reaction mixture is slowly cooled to room temperature under stirring and continued to stir for 1.5h. During this process, the solution gradually changes from turbid to transparent yellow. After the reaction was completed, the reaction solution was cooled to 0°C, 20 mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, and after the organic phase was separated, the aqueous phase was continuously extracted with 20 mL of ethyl acetate for three times. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain a yellow solid, which was identified as NN`-bis(2,4,6-trimethylphenyl)decane-5,6-diamine (10) (CF: C ₂₈ H ₄₄ N ₂ ; Mw: 408.67 g/mol); weight: 3.91 g (9.57 mmol), yield: 97%. Analytical Data. Calcd (found) for: C ₂₈ H ₄₄ N ₂ ; C, 82.29 (82.31); H, 10.85 (11.01); N, 6.85 (6.87). ¹ H-NMR (600MHz, CDCl ₃ ): δ (ppm): 0.89 (t, 6H, 3J (H, H) = 7.0Hz, CH ₃ ), 1. 31(m,8H,CH ₂ ),1.50(m,2H,CH ₂ ),1.74(m,2H,CH ₂ ),2.04(s,12H,CH ₃ ),2.22(s,6H,CH ₃ ),3.02(br,2H,NH),3.12(m,2H,CH),6.73(s,4H,CHar). ¹³ C-NMR(15 0MHz,CDCl ₃ ) δ (ppm): 14.3, 18.9, 20.6, 23.2, 29.7, 31.2, 58.1, 128.9, 129.7, 130.3, 142.0.

3) Preparation of 4,5-dibutyl-1,3-di(trimethylphenyl)-4,5-dihydro-1H-imidazolium tetrafluoroborate (II-1)

A mixture of 4.32 g (10.6 mmol) N,N'-bis(2,4,6-trimethylphenyl)decane-5,6-diamine (10) (Mw: 408.67 g/mol), 1.125 g (10.73 mmol) _NH4BF4 (Mw: 104.8431 g/mol) and 19 mL CH(OEt) ₃ was heated to 125°C and stirred for 15 h. During this period _, the solution gradually turned brownish red. After cooling to room temperature, the mixture was washed with petroleum ether (50×3 mL), the lower layer of oil was separated, dissolved with 100 mL of CH ₂ Cl ₂ , the insoluble matter was removed by filtration, a clear solution was obtained, the solvent was removed by rotary evaporation, and the brown viscous oil was obtained by vacuum drying, which was 4,5-dibutyl-1,3-di(trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C ₂₉ H ₄₃ BF ₄ N ₂ ; Mw: 506.48 g/mol). The mixture was subjected to diatomaceous earth column chromatography using dichloromethane as solvent, and the solvent was removed by rotary evaporation. After long-term cooling, 4.53 g (8.94 mmol) of crystalline substance was obtained, with a yield of 84%. Analytical Data. Calcd (found) for: C ₂₉ H ₄₃ BF ₄ N ₂ ; C, 68.77 (68.62); H, 8.56 (8.51); N, 5.53 (5.32). ¹ H NMR (600MHz, CDCl ₃ ) δ (ppm): 8.33 (s, 1H, N-CH-N), 6.94 (s, 4H, HMes) ,4.19(m bd,2H,CH-Bu),2.31(s,6H,CH ₃ Mes),2.27(s,12H,CH ₃ Mes),1.75(m,bd,4H,CH ₂ -CH ₂ ),1.26(m,bd 6H,CH ₂ -CH ₂ -),1.09(m,bd 2H,CH ₂ -CH ₂ -), 0.81 (t, 6H, 3J (H, H) = 7.27Hz, CH ₂ -CH ₃ ) ¹³ C NMR (150MHz, CDCl ₃ ) δ (ppm): 158.2, 140.5, 135.7, 134.7, 130.5, 129.0, 69.5, 33.0, 27.1, 22.4, 21.9, 21.0 ,18.4,18.1,13.7.

4) Preparation of 4,5-dibutyl-1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(benzylidene)(tricyclohexylphosphine)ruthenium dichloride catalyst (I-1)

Under nitrogen protection, 4.94 g (9.75 mmol) of 4,5-dibutyl-1,3-di(trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C ₂₉ H ₄₃ BF ₄ N ₂ ; Mw: 506.48 g/mol), 1.05 g (9.34 mmol) of potassium tert-butoxide (Mw: 112.2 g/mol) and 50 mL of dry tetrahydrofuran were added to a dry flask, and the resulting mixture was stirred at room temperature for 4 hours. The tetrahydrofuran solvent was removed by rotary evaporation, and a solid substance was obtained by vacuum drying. 4.44 g (5.30 mmol) of ruthenium complex Grubbs I (1) (Mw: 836.98 g/mol) and 60 mL of dry toluene were added to the resulting solid, and the resulting mixture was heated to 70°C and stirred for 4 hours. The solvent was removed by rotary evaporation, and the obtained solid material was subjected to silica gel column chromatography (petroleum ether/dichloromethane (1:1) as the developing solvent) to obtain a wine red solution. The solvent was removed by vacuum rotary evaporation to obtain a viscous brown-red solid material I-1 (Cf: C ₅₄ H ₈₁ Cl ₂ N ₂ PRu, Mw: 961.20). Weight: 3.97 g (4.13 mmol); yield: 78%. Analytical Data. Calcd (found) for: C ₅₄ H ₈₁ Cl ₂ N ₂ PRu; C, 67.48 (67.41); H, 8.49 (8.51); N, 2.91 (2.95). ¹ H NMR (600MHz, CDCl ₃ ): δ0.70-2.81 (m, 51H), 2.01 (s, 6H, CH ₃ ), 2. 28(s,12H,CH ₃ ),3.77(s,2H,NCHCHN),6.68-7.30(m,9H),19.39(s,1H,RuCHAr). ³¹ P-NMR (81.0MHz, CDCl ₃ ): δ29.3.

Example 2: Synthesis of the catalyst containing hexyl substituent 1,3-bis(2,4,6-trimethylphenyl)-2-(4,5-dihexylimidazolidinyl)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium (I-2)

The synthesis of catalyst I-2 containing hexyl substituents comprises the following steps:

1) Preparation of N,N′-bis(2,4,6-trimethyl)phenylethyleneimine (9)

Add 3.73mL of glyoxal (8) aqueous solution (40%) and 80mL of methanol to a 500mL three-necked flask equipped with a dropping funnel, and stir to dissolve the glyoxal. Add 9.12mL of m-trimethylbenzene (7) and 10mL of methanol to the dropping funnel, and slowly drop them into the flask. Control the reaction liquid temperature to about 22°C and stir for 12h. During this process, a bright yellow precipitate slowly precipitates from the reaction liquid. After the reaction is completed, filter the reaction liquid to obtain a yellow solid, wash the solid three times with water and once with methanol, and vacuum dry to obtain a yellow crystalline product 9. Weight 6.5g, yield 70%. Analytical Data.Calcd(found)for:C ₂₀ H ₂₄ N ₂ C,82.15(82.12);H,8.27(8.20). ¹ H-NMR(400MHz,CDCl ₃ ): δ(ppm):2.15(s,12H,CH ₃ ),2.30(s,6H,CH ₃ ),6.96(s,4H,CHar),8. 10 (s, 2H, CHar). ¹³ C-NMR (100MHz, CDCl ₃ ) δ (ppm): 18.0, 20.9, 126.4, 128.9, 134.0, 147.4, 162.9.

2) Preparation of N7,N8-di(2,4,6-trimethyl)phenyltetradecane-7,8-diamine (12)

Under nitrogen protection, add 2.92g (0.01mol; Mw: 292.46g/mol) N,N'-di(2,4,6-trimethyl)phenylethyleneimine (9) and 50mL tetrahydrofuran to a dry 100mL ampoule and stir to dissolve. Then, place the ampoule in a -78℃ ethanol cold bath and stir to cool. After the reaction solution is fully cooled, slowly add 9.16mL (0.022mol) of hexyllithium (2.2M toluene solution) solution with a syringe. After the addition is complete, the reaction mixture is slowly cooled to room temperature under stirring and continued to stir for 1.5h. During this process, the solution gradually changes from turbid to transparent yellow. After the reaction was completed, the reaction solution was cooled to 0°C, 20 mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, and the aqueous phase was extracted three times with 20 mL of ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was evaporated to obtain 4.32 g (9.584 mmol; Mw: 450.76 g/mol) of a yellow oil (12). The yield was 96%. Analytical Data. Calcd (found) for: C ₃₂ H ₅₂ N ₂ C, 82.70 (82.61); H, 11.28 (11.41); N, 6.03 (5.95). ¹ H-NMR (400MHz, CDCl ₃ ): δ (ppm): 0.87 (t, 6H, ³ J (H, H) = 5.8Hz, CH ₃ ), 1.2 6(m,12H,CH ₂ ),1.47(m,4H,CH ₂ ),1.72(m,4H,CH ₂ ),2.03(s,12H,CH ₃ ),2.21(s,6H,CH ₃ ),2.93(br,2H,NH),3.11(m,2H,CH),6.73(s,4H,CHar). ¹³ C-NMR(10 0MHz,CDCl ₃ ) δ (ppm): 14.1, 18.2, 21.9, 22.7, 27.0, 29.3, 30.5, 31.8, 65.0, 126.0, 128.7, 129.2, 142.2.

3) Preparation of 4,5-dihexyl-1,3-di(trimethylphenyl)-4,5-dihydro-1H-imidazolium tetrafluoroborate (II-2)

A mixture of 4.32 g (9.584 mmol) N7,N8-bis(2,4,6-trimethyl)phenyltetradecane-7,8-diamine (12) (Mw: 450.76 g/mol) (13), _NH4BF4 (Mw: 104.84 g/mol; 1.125 g, 10.73 mmol, 10 _% molar excess) and 19 mL CH(OEt) ₃ was heated to 125°C and stirred for 15 h. During this time, the solution gradually turned brown-red. After cooling to room temperature, the mixture was washed with petroleum ether (50×3 mL), the lower layer of oil was separated, dissolved with 100 mL of CH ₂ Cl ₂ , and the insoluble matter was filtered to obtain a clear solution. The solvent was removed by rotary evaporation and vacuum dried to obtain a brown viscous oil, which is 4,5-dihexyl-1,3-di(trimethylphenyl)-4,5-dihydro-1H-imidazolium tetrafluoroborate (II-2). The mixture was subjected to diatomaceous earth column chromatography using dichloromethane as solvent, and the solvent was removed by rotary evaporation. After long-term cooling, 4.53 g (8.05 mmol; Mw: 562.59 g/mol) of crystalline material was obtained, with a yield of 75%. Analytical Data.Calcd(found)for:C ₃₃ H ₅₁ BF ₄ N ₂ ；C,70.45(70.52)；H,9.14(9.31)；N,4.98(5.02). ¹ H NMR(400MHz,CO(CD ₃ ) ₂ )δ(ppm):8.45(s,1H,N-CH-N),6.99(s,4H,HMes),4.19(m bd,2H,CH-hexyl),2.35(s,12H,CH ₃ Mes),2.32(s,6H,CH ₃ Mes)，1.21-1.28(m,bd 20H,CH ₂ -CH ₂ -),0.85(t,6H, ³ J(H,H)＝5.9Hz,CH ₂ -CH ₃ ) ¹³ C NMR(100MHz,CO(CD ₃ ) ₂ )δ(ppm):144.2(NCN),140.3(CAr),135.6(CHAr),135.4(CHAr),129.7(CHAr),129.6(CHAr),129.4(CHAr),129.2(CAr),66.5(CH-hexyl),66.1(CH-H exyl), 28.3 (CH ₃ -Mes), 17.8 (CH ₃ Mes), 31.8 (CH ₂ ), 29.3 (CH ₂ ), 27.3 (CH ₂ ), 25.6 (CH ₂ ), 22.7 (CH ₂ ), 14.1 (CH ₃ -hexyl); ¹⁹ F NMR (376MHz, CO (CD ₃ ) ₂ ) δ (ppm): -151 .7.

4) Preparation of catalyst 1,3-bis(2,4,6-trimethylphenyl)-2-(4,5-dihexylimidazolidinyl)(benzylidene)(tricyclohexylphosphine)dichlororuthenium catalyst (I-2)

Under nitrogen protection, add 4,5-dihexyl-1,3-di(trimethylphenyl)-4,5-dihydro-1H-imidazolium tetrafluoroborate (II-2) (Mw: 562.9 g/mol; 4.94 g, 8.78 mmol), potassium tert-butoxide (Mw: 112.2 g/mol; 1.05 g, 9.33 mmol) and 50 mL of dry tetrahydrofuran into a dry flask. Stir the resulting mixture at room temperature for 4 hours. Remove the tetrahydrofuran solvent by rotary evaporation and dry in vacuo to obtain a solid. Add 4.44 g (5.37 mmol; Mw: 836.98 g/mol) of ruthenium complex Grubbs I (1) and 60 mL of dry toluene to the resulting solid and stir to dissolve it. Heat the reaction mixture to 70°C and maintain this temperature with stirring for 2.5 hours. After the reaction solution cooled to room temperature, petroleum ether/dichloromethane (1:1) was used as the developing solvent and subjected to silica gel column chromatography to obtain a wine red solution. The solvent was removed by vacuum rotary evaporation to obtain a viscous brown-red solid substance I-2, 3.97 g (0.39 mmol) (Cf: C ₅₈ H ₈₉ Cl ₂ N ₂ PRu, Mw: 1017.3). Yield: 72.6%. ¹ H NMR (400 MHz, CDCl ₃ ): δ0.88-2.44 (m, 59H), 1.93 (s, 6H, CH ₃ ), 2.34 (s, 12H, CH ₃ ), 4.03 (s, 2H, NCHCHN), 7.04-7.38 (m, 9H), 19.16 (s, 1H, RuCHAr). ³¹ P-NMR (81.0 MHz, CDCl ₃ ): δ29.2.

Example 3: Preparation of 4-butyl-5-hexyl-1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(benzylidene)(tricyclohexylphosphine)ruthenium dichloride (I-3)

1.1) Preparation of N,N'-bis(2,4,6-trimethylphenyl)dodecane-5,6-diamine (14)

Under nitrogen protection, add 2.92g N,N'-di(2,4,6-trimethyl)phenylethyleneimine (9) (Mw: 292.46g/mol; 10.0mmol) to a dry 250mL ampoule and stir with 100mL tetrahydrofuran to dissolve it. Then, place the ampoule in a -78℃ ethanol cold bath and stir to cool. After the reaction solution is fully cooled, slowly add 4.17mL (10.0mmol) of hexyl lithium (2.4M toluene solution) solution with a syringe. Cool the reaction solution to -78℃ again, and slowly add 6.25mL (10.0mmol) of butyl lithium (1.6M hexane solution) solution with a syringe. After the addition is complete, the reaction mixture is slowly heated to room temperature under stirring and continued to stir for 0.5h. Then, cool the reaction solution to 0℃, add 20mL of saturated ammonium chloride solution to the reaction solution, and stir for about 10 minutes. After the solution was allowed to stand for stratification, the organic phase was separated, and the aqueous phase was extracted three times with 20 mL of ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation to obtain an orange viscous oil, which was identified as N,N'-di(2,4,6-trimethylphenyl)dodecane-5,6-diamine (14) (CF:C ₃₀ H ₄₈ N ₂ ; Mw: 436.73 g/mol), weighing 4.28 g (9.80 mmol), with a yield of 98%.

1.2) Preparation of N,N'-bis(2,4,6-trimethylphenyl)dodecane-5,6-diamine (14) by Grignard reagent

Under nitrogen protection, add 1.46g (5.0mmol) N-N'-di(2,4,6-trimethyl)phenylethyleneimine (9) (Mw: 292.46g/mol) and 100mL tetrahydrofuran to a dry 250mL ampoule and stir to dissolve. Then, place the ampoule in an ethanol cold bath at -78℃ and stir to cool. After the reaction solution is fully cooled, slowly add 7.5mL (6.0mmol) of hexylmagnesium bromide (0.8M, THF solution) solution with a syringe. After the addition is complete, the reaction mixture is slowly heated to room temperature under stirring and continued to stir for 1.5h. During this process, the solution gradually changes from orange-red to yellow and transparent. Cool the reaction mixture to -78℃ and slowly add 3.75mL (6.0mmol) of butyllithium (1.6M hexane solution) solution with a syringe. After the addition is complete, slowly heat the reaction mixture to room temperature under stirring and continue to stir for 0.5h. The reaction solution was cooled to 0°C, 20 mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, and after the organic phase was separated, the aqueous phase was continuously extracted with 20 mL of ethyl acetate for three times, and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was evaporated to obtain an orange viscous oily substance N,N'-di(2,4,6-trimethylphenyl)dodecane-5,6-diamine (14) (CF:C ₃₀ H ₄₈ N ₂ ; Mw: 436.73 g/mol), weighing 2.13 g (4.87 mol), with a yield of 97.4%.

2) Preparation of 4-butyl-5-hexyl-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (II-3)

A mixture of 4.19 _g (9.58 mmol) N,N'-bis(2,4,6-trimethylphenyl)dodecane-5,6-diamine (14) (CF: _C30H48N2 ; Mw: 436.73 g/mol) (13), _NH4BF4 (Mw: 104.84 g/mol; 1.125 g, _10.73 mmol) and 19 mL CH(OEt) ₃ was heated to 125 _° C and stirred for 15 h. During this period, the solution gradually turned brownish red. After cooling to room temperature, the mixed solution was washed with petroleum ether (50×3 mL), the lower layer of oil was separated, dissolved with 100 mL of CH ₂ Cl ₂ , the insoluble matter was removed by filtration, a clear solution was obtained, the solvent was removed by rotary evaporation, and the brown viscous oil was obtained by vacuum drying, which was 4-butyl-5-hexyl-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (15) (CF: C ₃₁ H ₄₇ BF ₄ N ₂ ; Mw: 534.53 g/mol). The weight was 3.85 g (7.20 mmol), and the yield was 75%. The mixture was subjected to diatomaceous earth column chromatography using dichloromethane as solvent, and the solvent was removed by rotary evaporation. A crystalline substance was obtained after long-term storage.

3) Preparation of 4-butyl-5-hexyl-1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(benzylidene)(tricyclohexylphosphine)ruthenium dichloride (I-3)

Under nitrogen protection, 4.69 g (8.776 mmol) of 4-butyl-5-hexyl-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium tetrafluoroborate (15) (CF: C ₃₁ H ₄₇ BF ₄ N ₂ ; Mw: 534.53 g/mol), 1.047 g (9.33 mmol) of potassium tert-butoxide (Mw: 112.21 g/mol), and 50 mL of dry tetrahydrofuran were added to a dry flask, and the resulting mixture was stirred at room temperature for 4 hours. The tetrahydrofuran solvent was removed by rotary evaporation, and the solid was dried in vacuo to obtain a solid. 4.44 g (5.37 mmol) of ruthenium complex Grubbs I (Mw: 836.98 g/mol) and 60 mL of dry toluene were added to the resulting solid, and stirred to dissolve. The reaction mixture was heated to 70°C and maintained at this temperature with stirring for 2.5 hours. After the reaction solution cooled to room temperature, it was subjected to silica gel column chromatography using petroleum ether/dichloromethane (1:1) as the developing solvent to obtain a wine red solution. The solvent was removed by vacuum rotary evaporation and vacuum dried to obtain a pink solid substance (I-3) (CF: C ₅₆ H ₈₅ Cl ₂ N ₂ PRu; Mw: 989.25), weighing 3.82 g (3.87 mmol), with a yield of 72%.

的催化剂。Referring to the preparation methods of Examples 1 and 2, the R substituents are -C ₁₀ H ₂₁ (straight chain), -C ₁₄ H ₂₉ (straight chain), -C ₁₈ H ₃₇ (straight chain) and

catalyst.

Preparation of catalyst composition:

A certain amount of the above-synthesized long alkyl chain modified catalyst is weighed and added with liquid chlorinated paraffin to prepare a catalyst composition. The catalyst composition can be stored for a long time at room temperature.

The chlorine content of liquid chlorinated paraffin is: 5% to 65%;

The concentration range of the catalyst composition is: 0.08 mol/L to 0.7 mol/L;

Liquid chlorinated paraffin can be purchased or made by yourself. The following two methods are used for making it by yourself: (1) Add a measured amount of liquid paraffin to a reactor, introduce chlorine gas to react, wash with NaOH aqueous solution and aqueous solution in sequence until the acid value (mgkOH/g) is ≤0.3, dehydrate under reduced pressure until the water content is less than 2%, and the finished product is obtained; (2) Add a measured amount of liquid paraffin to a reactor, add thionyl chloride dropwise under stirring, reflux for 5 to 7 hours, recover the excess thionyl chloride under normal pressure, wash with water and NaOH aqueous solution in sequence, dehydrate under reduced pressure until the water content is less than 2%, and the finished product is obtained.

The preparation example of the catalyst composition is shown in Table 1.

Table 1 Preparation Example of Catalyst Composition

Comparative Example 1:

Weigh 2.6g of commercial Grubbs ^2nd catalyst and dissolve it in 12.2mL paraffin solution with a chlorine content of 52% to prepare a Grubbs ^2nd catalyst solution with a concentration of 0.25mol/L. It was found that when the ambient temperature was lower than 10°C, the solubility of the commercial Grubbs ^2nd catalyst in the chlorinated paraffin solution decreased, and it was easy to precipitate during storage, and the catalytic activity decreased, which was not conducive to industrial application. At the same time, the commercial Grubbs ^2nd catalyst was dissolved in a paraffin solution with a chlorine content of 52% to prepare a Grubbs ^2nd catalyst solution with a concentration of 0.05mol/L. After being placed at room temperature for two weeks, more crystals were observed to precipitate. The experiment also found that at room temperature and pressure, the commercial Grubbs ^2nd catalyst began to decompose in toluene solvent after about 2 hours and lost its catalytic activity.

In addition, in the present invention, the catalyst whose R substituent is methyl, ethyl or propyl is dissolved in liquid chlorinated paraffin, and crystals of the catalyst are easily precipitated during long-term storage, which affects the use effect.

Comparative Example 2:

The present invention attempts to dissolve the commercial Grubbs ^2nd catalyst and the catalysts prepared in Examples 1 and 2 of the present invention in commercially available liquid paraffin. The results show that the commercial Grubbs ^2nd catalyst is insoluble in liquid paraffin; the catalysts prepared in Examples 1 and 2 of the present invention are soluble in liquid paraffin, but the catalyst composition formed therefrom is a gel-like substance that will not be converted into a liquid state even when heated to 60-70°C.

Comparative Example 3:

The present invention tries chlorinated paraffins with different chlorine contents. When the chlorine content of the chlorinated paraffin is less than 5%, it is in a gel state, and a large amount of solvent needs to be added to dilute and dissolve before use, which is inconvenient to use. When the chlorine content is higher than 65%, the liquid paraffin is in a high viscosity state, or even in a solid state (75% of commercial chlorinated paraffin is solid), which is not conducive to the amount of the catalyst, and it is difficult to mix evenly with the substrate, resulting in local polymerization, and the molding process cannot be completed.

Effect Example 1

In order to evaluate the catalytic activity of the catalyst composition for the ring-closing metathesis reaction, N,N-diallyl-4-methylbenzenesulfonamide (16) was selected as the substrate for testing.

Effect example 1.1:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.02 mL of the catalyst composition prepared in Example 4 were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction temperature was cooled to room temperature, the mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 219.7 mg (0.984 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 98.4%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect example 1.2:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.006 mL of the catalyst composition prepared in Example 6 were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction temperature was cooled to room temperature, the mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 219.95 mg (0.985 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 98.8%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect example 1.3:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.008 mL of the catalyst composition prepared in Example 9 were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction temperature was cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 218.8 mg (0.98 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 98%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 1.4:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.007 mL of the catalyst composition prepared in Example 10 were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction temperature was cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 219.1 mg (0.981 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 98.1%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 2

In order to evaluate the catalytic activity of the catalyst composition for the cross-metathesis reaction of olefin molecules, allyl benzoate (18) and styrene (19) were selected as substrates for activity testing.

Effect Example 2.1:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19 and 0.083 mL of the catalyst composition prepared in Example 5 were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. The reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 228.8 mg (0.96 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 96%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 2.2:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19 and 0.071 mL of the catalyst composition prepared in Example 6 were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. The reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 229.2 mg (0.962 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 96.2%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH2); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 2.3:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19, and 0.25 mL of the catalyst composition prepared in Example 8 were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. The reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 224.2 mg (0.941 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 94.1%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 2.4:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19 and 0.10 mL of the catalyst composition prepared in Example 9 were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. Then, the reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 224.5 mg (0.942 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 94.2%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 3

In order to evaluate the application of the catalyst composition in the ring-opening metathesis polymerization reaction, dicyclopentadiene was selected as a monomer for testing.

Effect Example 3.1:

Take 200g DCPD monomer, add 0.6mL of the catalyst composition prepared in Example 6 dropwise, and mix and stir until the color is uniform. Degas the solution, cast it into a mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 59.0MPa, tensile modulus 1919.2MPa, and elongation at break 7.87%.

Effect Example 3.2:

Take 200g DCPD monomer, add 0.35mL of the catalyst composition prepared in Example 7 dropwise, and mix and stir until the color is uniform. Degas the solution, cast it into a mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 59.3MPa, tensile modulus 1919.7MPa, and elongation at break 7.82%.

Effect Example 3.3:

Take 200g DCPD monomer, add 1.0mL of the catalyst composition prepared in Example 9 dropwise, and mix and stir until the color is uniform. Degas the solution, cast it into a mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 58.5MPa, tensile modulus 1911.6MPa, and elongation at break 7.67%.

Effect Example 3.4:

Take 200g of DCPD monomer, add 0.42mL of the catalyst composition prepared in Example 11 dropwise, and mix and stir until the color is uniform. Degas the solution, cast it into a mold, and cure it at 80℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 58.9MPa, tensile modulus 1912.2MPa, and elongation at break 7.61%.

Comparative Example 3.1:

Weigh 200g DCPD monomer, add 0.2g Grubbs ^2nd catalyst dissolved in toluene solvent dropwise, mix and stir evenly, degas, and cast into mold. Then set the curing program of 60-100℃/2h for curing molding to obtain a sample plate with a thickness slightly less than 4mm (about 3.96mm), and there are obvious flow marks on the surface of the plate. This is mainly caused by the volatilization of solvent toluene during the curing process. Finally, cut the specimens for mechanical properties testing. The results are: tensile strength 59.4MPa, tensile modulus 1913.4MPa, elongation at break 7.42%.

Comparative Example 3.2:

In order to make an application control experiment with the present invention, the present invention strictly prepares the solid paraffin mixture of Grubbs 2 ^{nd catalyst according to the document (Taber DF, Frankowski K.J., Grubbs`catalyst in paraffin: An air-stable preparation for alkenemetathesis [J]. J. Org. Chem., 2003, 68 (22): 6047-6048). Take 200g DCPD monomer, add 1.4g Grubbs 2 nd catalyst} solid paraffin mixture (0.15mmol/g, 0.21mmol), find that the solid paraffin mixture is insoluble in DCPD monomer, and stirring for 12 hours still can not mix evenly. Raise the temperature to 40 ° C, find that during the stirring process, polymerization occurs around the solid paraffin, and the undissolved solid paraffin mixture is wrapped, and the solution cannot be degassed and poured into a mold. The polymerization experiment failed, indicating that the solid paraffin mixture of Grubbs 2 ^nd catalyst reported in the document must be in the presence of a solvent to play a catalytic role.

Long-term storage stability test

After the catalyst compositions prepared in Examples 4 to 11 were stored at room temperature for six months, a storage stability verification experiment was performed.

Effect Example 4

After the catalyst was stored in chlorinated paraffin solution for 6 months, its catalytic activity for ring-closing metathesis reaction was evaluated, and N,N-diallyl-4-methylbenzenesulfonamide (16) was selected as the substrate for the test.

Effect Example 4.1:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.01 mL of the catalyst composition prepared in Example 4 after storage for 6 months were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 217.7 mg (0.0975 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 97.5%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 4.2:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.0057 mL of the catalyst composition prepared in Example 6 after storage for 6 months were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 21.8.1 mg (0.978 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 97.8%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 4.3:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.008 mL of the catalyst composition prepared in Example 9 after storage for 6 months were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as the eluent to obtain product 17, weighing 217 mg (0.972 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 97.2%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 4.4:

Under nitrogen protection, 251 mg (1.0 mmol; Cf: C ₁₃ H ₁₇ NO ₂ S; Mw: 251.1) of substrate 16 and 0.0067 mL of the catalyst composition prepared in Example 10 after storage for 6 months were added to a 5 mL single-mouth bottle. The reaction mixture was heated to 40°C and stirred for 2 h. After the reaction cooled to room temperature, the reaction mixture was separated by column chromatography using petroleum ether/ethyl acetate (5:1) as eluent to obtain product 17, weighing 217.7 mg (0.975 mmol; Cf: C ₁₁ H ₁₃ NO ₂ S; Mw: 223.3), with a yield of 97.5%. ¹ H NMR (400MHz, CDCl ₃ ) δ (ppm): 2.42 (s, 3H), 4.12 (d, ³ J _HH = 4.5Hz, 4H), 5.65 (d, ³ J _HH = 4.5Hz, 2H), 7.32 (d, ³ J _HH = 8.3Hz, 2H), 7.72 (d, ³ J _HH = 8.3Hz, 2H ); ¹³ C NMR (100MHz, CDCl ₃ ) δ (ppm): 21.8, 55.1, 125.7, 127.7, 130.0, 134.6, 143.7.

Effect Example 5

After the catalyst was stored in a chlorinated paraffin solution for 6 months, its catalytic activity for the cross-metathesis reaction of olefin molecules was evaluated. Allyl benzoate (18) and styrene (19) were selected as substrates for activity testing.

Effect Example 5.1:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19, and 0.083 mL of the catalyst composition prepared in Example 5 after storage for 6 months were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. After the reaction solution cooled to room temperature, the reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 226.6 mg (0.95 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 95.1%. ¹ H NMR (400MHz, CDCl ₃ ): 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, CDCl ₃ ): 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).

Effect Example 5.2:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19, and 3.61 mL of the catalyst composition prepared in Example 6 after storage for 6 months were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. After the reaction solution cooled to room temperature, the reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 22.69 mg (0.0952 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 95.2%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 5.3:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19, and 0.25 mL of the catalyst composition prepared in Example 8 after storage for 6 months were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. After the reaction solution cooled to room temperature, the reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 222.8 mg (0.935 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 93.5%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 5.4:

Under nitrogen protection, 162 mg (1.0 mmol; Cf: C ₁₀ H ₁₀ O ₂ , Mw: 162.2) of substrate 18, 208 mg (2.0 mmol; Cf: C ₈ H ₈ , Mw: 104.2) of styrene 19, and 0.10 mL of the catalyst composition prepared in Example 9 after storage for 6 months were added to a 5 mL Schlenk bottle. The reaction mixture was heated to 45° C. and stirred for 6 h. After the reaction solution cooled to room temperature, the reaction mixture was separated by column chromatography to obtain a cross-metathesis product 20, weighing 223.3 mg (0.937 mmol; Cf: C ₁₆ H ₁₄ O ₂ , Mw: 238.3), with a yield of 93.7%. ¹ H NMR (400MHz, CDCl ₃ ): 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＝CH ₂ ), 5.02 (dd, J＝6.4Hz, J＝1.2Hz, 2H, CH ₂ ); ¹³ C-NMR (400MHz, CDCl ₃ ): 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).

Effect Example 6

After the catalyst was stored in chlorinated paraffin solution for 6 months, its catalytic activity for ring-opening metathesis polymerization was evaluated, and dicyclopentadiene was selected as the monomer for the test.

Effect Example 6.1:

Take 200g DCPD monomer, add dropwise 0.6mL of the catalyst composition prepared in Example 6 after storage for 6 months, and mix and stir until the color is uniform. Degas the solution, cast the mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 54.5MPa, tensile modulus 1905.3MPa, and elongation at break 8.11%.

Effect Example 6.2:

Take 200g DCPD monomer, add dropwise 0.35mL of the catalyst composition prepared in Example 7 after storage for 6 months, and mix and stir until the color is uniform. Degas the solution, cast the mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 54.9MPa, tensile modulus 1907.2MPa, and elongation at break 8.04%.

Effect Example 6.3:

Take 200g DCPD monomer, add dropwise 1.0mL of the catalyst composition prepared in Example 9 stored for 6 months, and mix and stir until the color is uniform. Degas the solution, cast the mold, and cure it at 60-100℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 54.3MPa, tensile modulus 1892.3MPa, and elongation at break 8.03%.

Effect Example 6.4:

Take 200g of DCPD monomer, add dropwise 0.42mL of the catalyst composition prepared in Example 11 stored for 6 months, and mix and stir until the color is uniform. Degas the solution, cast the mold, and cure it at 80℃/2h to obtain a sample plate with a thickness of 4mm and a smooth surface. Finally, cut the specimens for mechanical property testing. The results are: tensile strength 54.8MPa, modulus 1893.1MPa, and elongation at break 7.98%.

Effect Example 7: Preparation of dicyclopentadiene/epoxy resin composition

The information of raw materials or reagents involved in the following effect examples is as follows:

Bisphenol A epoxy resin YN1828: purchased from Jiangsu Yangnong Jinhu Chemical Co., Ltd., with an epoxy value of 0.51-0.54.

Dicyclopentadiene: DCPD.

4,4'-Diaminodiphenyl sulfone: DDS.

2,4,6-Tris(dimethylaminomethyl)phenol: DMP-30.

The formulas of the raw materials in Effect Examples 7.1-7.7 and Comparative Examples 7.1-7.4 are shown in Table 2 and Table 3, respectively.

Chlorinated paraffins:

The chlorine content is 5%, and the density is 0.82;

The chlorine content is 42%, and the density is 1.16;

The chlorine content is 52%, and the density is 1.24;

The chlorine content is 60% and the density is 1.45.

Calculation of mass of catalyst composition:

The mass of the catalyst in the effect examples (7.1-7.10) = the molar concentration of the catalyst composition * the molecular weight of the catalyst * the volume of the catalyst composition in the effect example

The mass of the catalyst composition = the mass of the catalyst in the effect example (7.1-7.10) * (the volume of the chlorinated paraffin with the chlorine content determined in the corresponding example * the density) / the mass of the catalyst in the corresponding example + the mass of the catalyst in the effect example (7.1-7.10)

Table 2

Table 3

Effect examples 7.1-7.7:

The preparation process of the dicyclopentadiene/epoxy resin composition is as follows:

(1) premixing dicyclopentadiene and epoxy resin to form a uniform solution;

(2) adding a curing agent and a curing accelerator, and performing mechanical grinding using a three-roll grinder;

(3) When the average particle size of the solid particles in the mixed solution is less than 30 μm, the catalyst composition is added, stirred and mixed, and then mixed using a three-roll mill until the solution has a uniform color;

(4) The mixed solution obtained in step (3) is placed in a vacuum drying oven to remove bubbles, and is cast and cured using a curing procedure of 80° C./1 h, 120° C./2 h, 150° C./2 h, and 180° C./2 h to obtain a thermosetting resin composition plate for copper clad laminates.

Comparative Example 7.1:

The preparation process of the epoxy resin of Comparative Example 7.1 is as follows:

(1) adding 4,4′-diaminodiphenyl sulfone (DDS) curing agent and 2,4,6-tris(dimethylaminomethyl)phenol to epoxy resin and performing mechanical grinding using a three-roll mill;

(2) When the average particle size of the solid particles in the mixed solution is less than 30 μm, the mixed solution is placed in a vacuum drying oven to remove bubbles, and the mixed solution is cast and cured using a curing procedure of 80°C/1h, 120°C/2h, 150°C/2h, and 180°C/2h to obtain an epoxy resin cured sheet.

Comparative Example 7.2:

The preparation process of the polydicyclopentadiene resin of Comparative Example 7.2 is as follows:

(1) 1,3-bis(2,4,6-trimethylphenyl)-2-(4,5-dibutylimidazolidinyl)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium liquefaction catalyst is added to dicyclopentadiene, and the mixture is stirred at room temperature for 2 minutes until the color is uniform;

(2) The mixed solution obtained in step (1) is placed in a vacuum drying oven to remove bubbles, and is poured and cured using a curing procedure of 80° C./1 h and 120° C./2 h to obtain a polydicyclopentadiene resin cured sheet.

Comparative Example 7.3:

The preparation process of the dicyclopentadiene/epoxy resin composition of Comparative Example 7.3 is as follows:

(1) premixing dicyclopentadiene and epoxy resin to form a uniform solution;

(2) adding 4,4′-diaminodiphenyl sulfone (DDS) curing agent and 2,4,6-tris(dimethylaminomethyl)phenol, and mechanically grinding using a three-roll mill;

(3) When the average particle size of the solid particles in the mixed solution is less than 30 μm, the mixed solution is placed in a vacuum drying oven to remove bubbles, and poured and cured using a curing procedure of 80° C./1 h, 120° C./2 h, 150° C./2 h, and 180° C./2 h to obtain a thermosetting resin composition sheet for copper clad laminates.

Comparative Example 7.4:

The preparation process of the dicyclopentadiene/epoxy resin composition of Comparative Example 7.4 is as follows:

(1) premixing dicyclopentadiene and epoxy resin to form a uniform solution;

(2) adding 4,4′-diaminodiphenyl sulfone (DDS) curing agent and 2,4,6-tris(dimethylaminomethyl)phenol, and mechanically grinding using a three-roll mill;

(3) When the average particle size of the solid particles in the mixed solution is less than 30 μm, add the Grubbs second-generation catalyst completely dissolved in toluene, stir and mix first, and then use a three-roll mill to mix until the solution has a uniform color;

(4) The mixed solution obtained in step (3) is placed in a vacuum drying oven to remove bubbles, and is cast and cured using a curing procedure of 80° C./1 h, 120° C./2 h, 150° C./2 h, and 180° C./2 h to obtain a thermosetting resin composition plate for copper clad laminates.

The present invention tests the dielectric properties of the plates prepared in Example 7.1-7.7 and Comparative Example 7.1-7.4. The results are shown in Table 4.

Table 4

The following points can be seen from the above table:

(1) Compared with Comparative Example 7.1, as the content of dicyclopentadiene increases in Examples 7.1-5, the dielectric constant and dielectric loss factor are significantly reduced, indicating that the introduction of the non-polar alicyclic chain structure of dicyclopentadiene can improve the dielectric properties of epoxy resin.

(2) Compared with Comparative Example 7.3, the initial decomposition temperature (Td 5%) in Example 7.3 is significantly increased, indicating that in the dicyclopentadiene/epoxy resin composite, the use of the dual-cure system can make the two resins completely cured and cross-linked to form an interpenetrating polymer network structure, thereby giving it good heat resistance; (in Comparative Example 7.3, no catalyst was added, and dicyclopentadiene could only exist in the composition in the form of a monomer without cross-linking and curing).

(3) From Example 7.3, Example 7.6 and Example 7.7, it can be seen that the use of different epoxy curing agents can prepare polydicyclopentadiene/epoxy resin composites with reduced dielectric properties.

(4) Compared with Comparative Example 7.4, the use of the ruthenium carbene catalyst composition in Examples 7.1-7.7 can also fully cure dicyclopentadiene and cross-link with the epoxy resin to obtain a composite with excellent performance.

Effect Example 8: Preparation of polydicyclopentadiene polymer

In effect examples 8-10, the actual amount of each component in liquid B = (the sum of the weight parts of liquid A) * (the weight parts of each component in liquid B) / [(the mass ratio of liquid A to liquid B) * (the sum of the weight parts of liquid B)]

Effect Example 8.1:

The catalyst composition prepared by the present invention has the same formula as that of Example 8, and the resin components are subjected to RIM reaction injection molding to obtain a polydicyclopentadiene polymer.

The weight parts of each component raw material are as follows:

Dicyclopentadiene monomer 99.95 copies Catalyst composition 0.05 Comonomer: Ethylene 10 servings Anti-aging agent: Tinuvin B75 5 servings

The preparation process of polydicyclopentadiene polymer is:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer to form Liquid A.

2. Preparation of Liquid B: Weigh and mix the catalyst composition, comonomer and anti-aging agent to form Liquid B.

3. Importing the storage system: After stirring evenly to fully mix the components, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use.

4. Injection molding: Run the RIM injection equipment to mix the A and B liquids online and inject them into the mold to complete the reaction injection molding to obtain the polydicyclopentadiene composite material.

5. Curing and demoulding: After the mold is heated and cured, demoulding and material removal are completed to complete the preparation of polymer products.

The mass ratio of liquid A to liquid B is about 9:1. RIM equipment is used for reaction injection molding, the injection speed is 500ml/min, the injection pressure is 6bar, the mold is kept at 80℃ for 2h after resin filling, and the mold is cured and molded. The test is completed by demolding and taking out the parts. Sample cutting and board making, the specific test results are shown in Table 5.

Effect Example 8.2:

The catalyst composition prepared by the present invention has the same formula as Example 8, and the polydicyclopentadiene polymer is prepared by RIM reaction injection molding, and the resin system formula used is the same as that of Example 8.1. After the A and B liquids are evenly mixed, they are placed in the two-component storage tank of the RIM equipment and stored under natural conditions for 6 months, and then the composite material product is prepared by RIM process, and the process parameters are the same as those of Example 1. Samples are cut and plates are made, and the specific test results are shown in Table 5.

Effect Example 8.3:

The catalyst composition prepared by the present invention has the same formula as that of Example 10, and is subjected to RIM reaction injection molding to prepare a polydicyclopentadiene polymer.

The weight parts of each component raw material are as follows:

Dicyclopentadiene monomer 80 servings Catalyst composition 20 servings Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 3 servings Functional filler: glass fiber 5 servings Auxiliary agent: Silane coupling agent A172 2 servings Additives: Color powder 2 servings

The preparation process of polydicyclopentadiene polymer is:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer and functional filler glass fiber to form Liquid A, and stir and mix;

2. Preparation of Liquid B: weigh and mix the catalyst composition, comonomer and additive to form Liquid B;

3. Importing the storage system: After stirring evenly to fully mix the components, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use;

4. Injection molding: Run the RIM injection equipment to mix the A and B liquids online and inject them into the mold to complete the reaction injection molding to obtain the polydicyclopentadiene composite material.

5. Curing and demoulding: After the mold is heated and cured, demoulding and material removal are completed to complete the preparation of the composite material product.

The mass ratio of liquid A to liquid B is about 5:1. RIM equipment is used for reaction injection molding, the injection speed is 2L/min, the injection pressure is 15bar, and the mold is kept at 80℃ for 2h for curing after resin filling. The mold is demoulded and the test is completed. Sample cutting and board making, the specific test results are shown in Table 5.

Effect Example 8.4:

The catalyst composition prepared in Example 4 was used to uniformly mix the components of the resin formulation and then subjected to RIM reaction injection molding to prepare a polydicyclopentadiene polymer.

The weight parts of each component raw material are:

Dicyclopentadiene monomer 65 servings Catalyst composition 35 servings

The preparation process of polydicyclopentadiene polymer is:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer to form Liquid A.

2. Preparation of Liquid B: Weigh and mix the catalyst composition to form Liquid B.

3. Importing the material storage system: After stirring evenly and fully mixing, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use.

4. Injection molding: Run the RIM injection equipment to mix the A and B liquids online and inject them into the mold to complete the reaction injection molding to obtain the polydicyclopentadiene composite material.

5. Curing and demoulding: After the mold is heated and cured, demoulding and material removal are completed to complete the preparation of polymer products.

The mass ratio of liquid A to liquid B is about 2:1. RIM equipment is used for reaction injection molding, the injection speed is 200ml/min, the injection pressure is 2bar, the mold is kept at 80℃ for 2h for curing after resin filling, and the mold is demoulded to complete the test. Sample cutting and board making, the specific test results are shown in Table 5.

Effect Example 8.5:

The catalyst composition and the preparation process of the polydicyclopentadiene polymer used are the same as those in Example 8.4; the only difference is that the weight proportions of the raw materials of each component in the resin formula are as follows, wherein the dicyclopentadiene monomer, functional filler and additive are used as liquid A, the copolymerized monomer and the catalyst composition are mixed to form liquid B, and the mass ratio of liquid A to liquid B is about 3:1. Samples are cut and plates are made, and the specific test results are shown in Table 5.

Dicyclopentadiene monomer 75 servings Functional filler: graphite powder 5 servings Auxiliary agent: polymerization regulator (triphenylphosphine) 10 servings Catalyst composition 25 servings Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 30 servings

Comparative Example 8.1:

The commercial Grubbs 2 ^nd catalyst was dissolved in a toluene solution to prepare a commercial Grubbs 2 ^nd catalyst composition (the mass ratio of the commercial Grubbs 2 ^nd catalyst to toluene was 1:10), and the polydicyclopentadiene polymer was prepared by single-component RIM reaction injection molding.

The weight parts of each component raw material are as follows:

Dicyclopentadiene monomer 99.8 copies Commercial Grubbs 2nd catalyst composition 0.2 parts Comonomer: tert-butyl 5-norbornene-2-carboxylate 20 servings Functional filler: glass fiber 5 servings Additives: Anti-aging agent Tinuvin B75 3 servings

In the reaction molding process of this formula, dicyclopentadiene monomer, commercial Grubbs ^2nd catalyst composition, comonomer, additives and functional filler glass fiber are uniformly mixed, and the RIM equipment is used for reaction injection molding, the injection speed is 200ml/min, the injection pressure is 20bar, and the mold is kept at 100℃ for 30min for curing after the resin is filled, and the demolding is completed. Sample cutting and board making, the specific test results are shown in Table 5.

Comparative Example 8.2:

The polydicyclopentadiene polymer was prepared by two-component RIM reaction injection molding using a commercial tungsten-molybdenum metal carbene catalyst system.

The weight parts of each component raw material are as follows:

The preparation process of polydicyclopentadiene polymer is:

1. Preparation of Liquid A: According to the formula design scheme, 49.8 parts of dicyclopentadiene monomer and 0.18 parts of molybdenum catalyst were weighed to form Liquid A.

2. Preparation of Liquid B: According to the formula design scheme, weigh 50 parts of dicyclopentadiene monomer and 0.02 parts of diethylaluminum monochloride to form Liquid B.

3. Import storage system: After stirring evenly and fully mixing, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use

The mass ratio of liquid A to liquid B is about 1:1. RIM equipment is used for reaction injection molding, the injection speed is 2L/min, the injection pressure is 3bar, and the mold is kept at 120℃ for 10min for curing after resin filling. The test is completed by demoulding and taking out the parts. Sample cutting and board making, the specific test results are shown in Table 5.

Table 5

Serial number Tensile strength(MPa) Tensile modulus (MPa) Elongation at break (%) Effect Example 8.1 56 1952 6.17 Effect Example 8.2 51 1937 5.65 Effect Example 8.3 65 5124 4.5 Effect Example 8.4 45 1861 5.13 Effect Example 8.5 58 2073 4.8 Comparative Example 8.1 42 4527 3.15 Comparative Example 8.2 38 1692.1 8.41

Comparing Effect Example 8.1 with Effect Example 8.2, it can be seen that after the resin composition is stored for 6 months, the mechanical properties of the prepared composite material have no obvious changes, the catalytic system has a long effective period, and the storage resistance is reliable.

Comparing Effect Example 8.1 with Effect Example 8.3, it can be seen that the composite material prepared after adding glass fiber filler has higher strength than the composite material prepared without adding glass fiber filler, and can be used to strengthen plastics.

Comparing Example 8.3 with Comparative Example 8.1, the composite material prepared in Example 8.3 has better mechanical properties than the composite material prepared by the commercial Grubbs 2 ^nd catalyst. The catalytic system of Example 8.3 is stable, has a long storage period, and is more suitable for adding additional components such as functional fillers to improve the overall performance of the product.

Comparing Effect Example 8.1 with Comparative Example 8.2, the mechanical properties of the composite material prepared in Effect Example 8.1 are significantly improved compared with the commercial tungsten-molybdenum metal carbene catalyst system.

Effect Example 9: Preparation of polydicyclopentadiene/epoxy resin composite material

Effect Example 9.1:

The catalyst composition prepared in Example 7 was used to prepare an epoxy/polydicyclopentadiene composite material through RIM reaction injection molding.

The weight parts of each component raw material in liquid A are as follows:

The weight parts of each component raw material in liquid B are as follows:

The preparation process of epoxy/polydicyclopentadiene composite material is as follows:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer and bisphenol A epoxy resin to form Liquid A;

2. Preparation of Liquid B: weigh and mix the catalyst composition, epoxy resin curing agent and curing accelerator to form Liquid B;

3. Mixing of additional components: Evenly mix the functional filler, comonomer and additives into the A liquid or B liquid resin system according to the formula design;

4. Importing the storage system: After stirring evenly to fully mix the components, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use;

5. Injection molding: Run the RIM injection equipment to mix the A and B liquids online and inject them into the mold to complete the reaction injection molding to obtain the polydicyclopentadiene composite material.

6. Curing and demoulding: After the mold is heated and cured, demoulding and material removal are completed to complete the preparation of composite material products.

The mass ratio of liquid A to liquid B is about 3:2. RIM equipment is used for reaction injection molding, the injection speed is 500ml/min, the injection pressure is 6bar, and the mold is kept at 80℃ for 2h for curing after resin filling. The mold is demoulded and the test is completed. Sample cutting and board making, the specific test results are shown in Table 6.

Effect Example 9.2:

The catalyst composition prepared in Example 4 was used to prepare an epoxy/polydicyclopentadiene composite material through RIM reaction injection molding.

The weight parts of each component raw material in liquid A are as follows:

The weight percentages of the raw materials of each component in liquid B are as follows, the sum of the weight percentages of the catalyst composition, the curing agent and the curing accelerator is 100%, and the weight percentages of the other components are the weights of the components as a percentage of the total weight of the catalyst composition, the curing agent and the curing accelerator:

The RIM molding process is the same as that in Example 9.1. The mass ratio of liquid A to liquid B is about 3:1. RIM equipment is used for reaction injection molding. The injection speed is 2L/min and the injection pressure is 15bar. After the resin is filled into the mold, the mold is kept at 80℃ for 2h for curing and molding. The mold is removed and the test is completed. Sample cutting and board making are shown in Table 6 for specific test results.

Effect Example 9.3:

The catalyst composition prepared in Example 9 was used to prepare an epoxy/polydicyclopentadiene composite material through RIM reaction injection molding.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 95 copies Bisphenol A epoxy resin 5 servings Functional filler: carbon fiber powder 5 servings

The weight parts of each component raw material in liquid B are as follows:

The RIM molding process is the same as that in Example 9.1. The mass ratio of liquid A to liquid B is about 8:1. RIM equipment is used for reaction injection molding. The injection speed is 5L/min and the injection pressure is 10bar. After the resin is filled into the mold, the mold is kept at 80℃ for 2h for curing and molding. The demoulding is completed by taking out the parts. Sample cutting and board making, the specific test results are shown in Table 6.

Effect Example 9.4:

The catalyst composition prepared in Example 8 was used to prepare an epoxy/polydicyclopentadiene composite material through RIM reaction injection molding.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 80 servings Bisphenol A epoxy resin 20 servings

The weight parts of each component raw material in liquid B are as follows:

The RIM molding process is the same as that in Example 9.1. The mass ratio of liquid A to liquid B is about 15:1. RIM equipment is used for reaction injection molding. The injection speed is 30L/min and the injection pressure is 25bar. After the resin is filled into the mold, the mold is kept at 80°C for 2h for curing and molding. The mold is removed from the mold to complete the test. Sample cutting and board making, the specific test results are shown in Table 6.

Comparative Example 9.1:

The commercial Grubbs 2 ^nd catalyst was dissolved in a toluene solution to prepare a commercial Grubbs 2 ^nd catalyst composition (the mass ratio of the commercial Grubbs 2 ^nd catalyst to toluene was 1:10), and the polydicyclopentadiene composite material was prepared by single-component RIM reaction injection molding.

The weight parts of each component raw material are as follows:

In the reaction molding process of this formula, dicyclopentadiene monomer, commercial Grubbs ^2nd catalyst composition, comonomer, additives and functional filler glass fiber are uniformly mixed, and the RIM equipment is used for reaction injection molding, the injection speed is 200mL/min, the injection pressure is 20bar, and the mold is kept at 100℃ for 30min for curing after the resin is filled, and the demolding is completed. Sample cutting and board making, the specific test results are shown in Table 6.

Comparative Example 9.2:

The commercial Grubbs 2 ^nd catalyst was dissolved in a toluene solution to prepare a commercial Grubbs 2 ^nd catalyst composition (the mass ratio of the commercial Grubbs 2 ^nd catalyst to toluene was 1:10), and the polydicyclopentadiene composite material was prepared by single-component RIM reaction injection molding.

The weight parts of each component raw material are as follows:

Dicyclopentadiene monomer 88.5 copies Commercial Grubbs 2nd catalyst composition 0.5 serving Comonomer: Norbornene 8 servings Functional filler: glass fiber 3 servings

In the reaction molding process of this formula, dicyclopentadiene monomer, commercial Grubbs ^2nd catalyst, comonomer and functional filler glass fiber are uniformly mixed, and the RIM equipment is used for reaction injection molding, the injection speed is 2L/min, the injection pressure is 3bar, and the mold is kept at 120℃ for 10min for curing after the resin is filled, and the demolding is completed. Sample cutting and board making, the specific test results are shown in Table 6.

Table 6

Serial number Tensile strength(MPa) Tensile modulus (MPa) Elongation at break (%) Effect Example 9.1 65 5812 2.95 Effect Example 9.2 58 3156 4.85 Effect Example 9.3 62 4936 3.51 Effect Example 9.4 53 2074 3.97 Comparative Example 9.1 42 4527 3.15 Comparative Example 9.2 38 1692.1 8.41

Comparing Effect Example 9.1 with Effect Example 9.2, it can be seen that by adding glass fiber functional filler to the compound system, the strength and elastic modulus of the product are significantly improved, and the reinforcing effect of the fiber is obvious.

Comparing the effect example 9.1 with the comparative example 9.1, it can be seen that the composite system has higher strength than the composite material prepared by the commercial Grubbs 2 ^nd catalyst.

Comparing Example 9.2 with Comparative Example 9.2, the mechanical properties of the composite material prepared in Example 9.2 are significantly improved compared with the commercial polydicyclopentadiene product, especially the increase in elastic modulus significantly improves the product's anti-deformation ability.

Effect Example 9.3 shows that the addition of carbon fiber can significantly improve the elastic modulus and strength of the material.

By comparing Effect Example 9.4 with Effect Example 9.1 and Comparative Example 9.1, it can be seen that the addition of the epoxy resin system can improve the strength and deformation resistance of the polydicyclopentadiene resin system to a certain extent.

Effect Example 10: Preparation of polydicyclopentadiene/epoxy resin-based fiber-reinforced composite materials

In Example 10, the actual amount of fiber reinforcement = (the weight percentage of fiber reinforcement) * (the sum of the weight percentages of liquid A and liquid B)

Effect Example 10.1:

The catalyst composition prepared in Example 5 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin-based composite material through RTM process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 20 servings Bisphenol A epoxy resin 80 servings Functional filler: graphite powder 5 servings

The weight parts of each component raw material in liquid B are as follows:

Catalyst composition 0.33 Epoxy curing agent: methyltetrahydrophthalic anhydride 97.79 copies Epoxy curing accelerator: 2-methylimidazole 1.88 copies Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 15 servings Auxiliary agent: polymerization regulator triphenylphosphine 0.6 parts

The preparation process of polydicyclopentadiene/epoxy resin system is as follows:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer and bisphenol A epoxy resin to form Liquid A;

2. Preparation of Liquid B: weigh and mix the liquefaction catalyst, epoxy resin curing agent and curing accelerator to form Liquid B;

3. Mixing of additional components: Evenly mix the functional filler, comonomer and additives into the A liquid or B liquid resin system according to the formula design;

4. Molding process: After uniformly stirring to fully mix all components, mix liquid A with liquid B to obtain a polydicyclopentadiene/epoxy resin system.

The mass ratio of liquid A to liquid B is about 10:7. They are mixed evenly by mechanical stirring at a speed of 300 to 500 r/min and a stirring time of 20 to 30 min.

A fiber-reinforced resin-based composite material with a fiber mass fraction of 50% was prepared using continuous glass fiber as reinforcement. The preparation process of the composite material is as follows:

1. Mold treatment: clean the RTM mold, apply sealing agent and release agent to facilitate demoulding and improve the appearance of the product;

2. Preparation of continuous glass fiber reinforcement: According to the product design requirements, the continuous glass fiber is cut, laid and reinforced, and then placed in the RTM mold cavity after trimming. The mass of the continuous glass fiber accounts for 50% of the mass of the composite material.

3. Mold closing and glue injection: Close the mold to ensure good sealing, use RTM glue injection machine to inject the prepared epoxy/polydicyclopentadiene resin glue into the mold cavity, heat up and cure, demold and take out the parts to complete the preparation of composite materials.

The surface density of the continuous glass fiber twill fabric used in this embodiment is 250g/ ^m2 , the designed thickness of the plate is 2mm, the warp direction of the fabric is recorded as 0° direction, the composite plate ply design is [0/90] ₅ , and there are 10 layers of balanced and symmetrical ply. The fiber reinforcement is prepared by referring to this material and ply design scheme. The injection pressure during the RTM process of the composite material is 6bar, and the system curing system is 80℃5h. Sample cutting and plate making, the specific test results are shown in Table 7.

Effect Example 10.2:

The catalyst composition prepared in Example 9 was used to prepare a carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material through RTM process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 40 servings Bisphenol A epoxy resin 60 servings Functional filler: silicon dioxide 10 servings

The weight parts of each component raw material in liquid B are as follows:

Catalyst composition 1.05 servings Epoxy curing agent: methyl hexahydrophthalic anhydride 94.21 copies Epoxy curing accelerator: DMP-30 4.74 servings Comonomer: tert-butyl 5-norbornene-2-carboxylate 10 servings Additives: Anti-aging agent (Tinuvin 571) 0.98 copies

The preparation process of the polydicyclopentadiene/epoxy resin system is the same as that of Example 10.1. The mass ratio of liquid A to liquid B is about 5:3, and the mixture is mixed evenly by mechanical stirring at a speed of 300-500 r/min and a stirring time of 20-30 min.

The preparation process of carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of Example 10.1. The difference is that the fiber reinforcement described in this example is continuous carbon fiber, the surface density of its unidirectional fabric is 160g/ ^m2 , the design thickness of the plate is 1mm, the fiber direction in the unidirectional fabric is recorded as 0° direction, and the composite plate ply design is [0/90/0] ₃ , with a total of 9 layers of balanced and symmetrical plies. The preparation of the fiber reinforcement is completed with reference to this material and ply design scheme. In this embodiment, the mass of the continuous carbon fiber accounts for 40% of the mass of the composite material; the injection pressure during the RTM process of the composite material is 3bar, and the system curing system is 120℃/2h. Sample cutting and plate making, specific test results are shown in Table 7.

Effect Example 10.3:

The catalyst composition prepared in Example 6 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum induction process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 50 servings Bisphenol A epoxy resin 50 servings Auxiliary agent: coupling agent KH560 0.65 Additives: Anti-aging agent (2,6-di-tert-butyl-4-methylphenol) 1.14 servings

The weight parts of each component raw material in liquid B are as follows:

The preparation process of the polydicyclopentadiene/epoxy resin system is the same as that of Example 10.1. The mass ratio of liquid A to liquid B is about 2:1, and the mixture is mixed evenly by mechanical stirring at a speed of 300-500 r/min and a stirring time of 20-30 min.

A fiber-reinforced resin-based composite material with a fiber mass fraction of 60% was prepared using continuous glass fiber as reinforcement. The preparation process of the composite material is as follows:

1. Prefabricated body preparation: according to the ply design plan, complete the fiber fabric cutting, ply shaping, trimming and standby;

2. Bag making: prepare vacuum bags for vacuum induction molding process and test whether the air tightness is good;

3. Glue injection: complete the injection of resin glue under vacuum negative pressure;

4. Curing and molding: Heat the preform after injection to solidify it, and demold it.

In this effect example, the type of continuous glass fiber used and the layer design are the same as those in effect example 10.1. In the vacuum infusion process, the vacuum degree of the vacuum bag should generally be greater than 920mbar; during the air tightness test, the pressure drop should be less than 50mbar in 5 minutes, and the curing system of the product is 120℃/2h. Sample cutting and board making, the specific test results are shown in Table 7.

Effect Example 10.4:

The catalyst composition prepared in Example 5 was used to prepare a continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum induction process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 60 servings Bisphenol A epoxy resin 40 servings Functional filler: graphite powder 5 servings Auxiliary agent: polymerization regulator triethyl phosphite 0.02 parts Auxiliary agent: coupling agent KH560 0.65

The weight parts of each component raw material in liquid B are as follows:

Catalyst composition 1.85 servings Epoxy curing agent: methyl hexahydrophthalic anhydride 60.83 copies Epoxy curing agent: methyl-5-norbornene-2,3-dicarboxylic anhydride 35.58 copies Epoxy curing accelerator: 2-ethylimidazole 1.73 copies Comonomer: tert-butyl 5-norbornene-2-carboxylate 5 servings

The preparation process of the polydicyclopentadiene/epoxy resin system is the same as that of Example 10.1. The mass ratio of liquid A to liquid B is about 5:2, and the mixture is mixed evenly by mechanical stirring at a speed of 300-500 r/min and a stirring time of 20-30 min.

The preparation process of continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of Example 10.3. The difference is that the fiber reinforcement described in this example is continuous carbon fiber, the surface density of its unidirectional fabric is 160g/ ^m2 , the design thickness of the plate is 1mm, the fiber direction in the unidirectional fabric is recorded as 0° direction, and the composite plate ply design is [0/90/0] ₃ , with a total of 9 layers of balanced and symmetrical ply. The preparation of the fiber reinforcement is completed by referring to this material and ply design scheme. In this embodiment, the mass of the continuous carbon fiber accounts for 70% of the mass of the composite material; the specific test results of the composite material are shown in Table 7.

Effect Example 10.5:

The catalyst composition prepared in Example 10 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material through a wet molding process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 80 servings Bisphenol A epoxy resin 20 servings Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 5 servings Comonomer: tert-butyl 5-norbornene-2-carboxylate 5 servings Functional filler: graphite powder 5 servings

The weight parts of each component raw material in liquid B are as follows:

Catalyst composition 6.25 servings Epoxy curing agent: methyltetrahydrophthalic anhydride 62.83 copies Epoxy curing agent: methyl-5-norbornene-2,3-dicarboxylic anhydride 25.67 copies Epoxy curing accelerator: DMP-30 5.24 servings Additives: Anti-aging agent BASF168 1.14 servings Auxiliary agent: coupling agent KH560 0.65 Additives: Anti-aging agent 2-hydroxy-4-methoxybenzophenone 0.985 copies

The preparation process of the polydicyclopentadiene/epoxy resin system is the same as that of Example 10.1. The mass ratio of liquid A to liquid B is about 5:2, and the mixture is mixed evenly by mechanical stirring at a speed of 300-500 r/min and a stirring time of 20-30 min.

A fiber-reinforced resin-based composite material with a fiber mass fraction of 75% was prepared using continuous glass fiber as reinforcement. The composite material was prepared using a wet molding process, and the molding process was as follows:

1. Prefabricated body preparation: according to the ply design plan, complete the fiber fabric cutting, ply shaping, trimming and standby;

2. Resin coating: evenly coating the aforementioned resin glue on the preform in the mold cavity;

3. Mould closing and pressing: close the mould of the press machine, control the pressing process, heat up and solidify the mould, and then demould and take out the parts.

In this effect example, the type of continuous glass fiber used and the layer design are the same as those in effect example 10.1. The pre-pressure during the wet molding process is 0.2MPa, the pressing pressure is 1.5MPa, and the curing system of the resin system is 120℃/20min; the sample is cut and the board is made. The specific test results are shown in Table 7.

Effect Example 10.6:

The catalyst composition prepared in Example 6 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum induction process. The resin system formula used was the same as that of Example 10.3.

After mixing liquid A, liquid B and the accessory components, they were stored at room temperature for 6 months, and then the composite material product was prepared by vacuum infusion process, and the process parameters were the same as those in Example 10.3. Samples were cut and boards were made, and the specific test results are shown in Table 7.

Comparative Example 10.1:

The catalyst composition prepared in Example 6 was used to prepare a polydicyclopentadiene/epoxy resin composite material through a RIM process.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 50 servings Bisphenol A epoxy resin 50 servings

The weight parts of each component raw material in liquid B are as follows:

Catalyst composition 1.13 copies Epoxy curing agent: methyl-5-norbornene-2,3-dicarboxylic anhydride 94.39 copies Epoxy curing accelerator: DMP-30 4.49 copies Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 5 servings Auxiliary agent: coupling agent KH560 0.65 Additives: Anti-aging agent (2,6-di-tert-butyl-4-methylphenol) 1.14 servings

The preparation process of polydicyclopentadiene/epoxy resin composite material is as follows:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer, functional filler and additives to form Liquid A;

2. Preparation of Liquid B: weigh and mix the liquefied catalyst and comonomer to form Liquid B;

3. Mixing of additional components: Evenly mix the comonomers and additives into the A liquid or B liquid resin system according to the formula design;

4. Importing the storage system: After stirring evenly to fully mix the components, introduce liquid A and liquid B into the two-component storage tank of the RIM equipment for standby use;

5. Injection molding: Run the RIM injection equipment to mix the A and B liquids online and inject them into the mold to complete the reaction injection molding to obtain the polydicyclopentadiene composite material.

6. Curing and demoulding: After the mold is heated and cured, demoulding and material removal are completed to complete the preparation of composite material products.

The mass ratio of liquid A to liquid B is about 2:1. RIM equipment is used for reaction injection molding, the injection speed is 1500ml/min, the injection pressure is 6bar, the mold is kept at 80℃ for 2h after resin filling, and the mold is cured and molded. The test is completed by demoulding and taking out the parts. Sample cutting and board making, the specific test results are shown in Table 7.

Comparative Example 10.2:

The catalyst composition prepared in Example 6 was used to prepare polydicyclopentadiene material through RIM reaction injection molding.

The weight parts of each component raw material are as follows:

Dicyclopentadiene monomer 99.7 copies Catalyst composition 0.3 parts Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 15 servings Functional filler: graphite powder 5 servings Auxiliary agent: polymerization regulator triphenylphosphine 3.2 servings

The resin system and composite material RIM molding process are the same as those in comparative example 10.1, except that the liquid A in this example contains only dicyclopentadiene monomer, and the mass ratio of liquid A to liquid B is about 5:1 to 7:1. The specific test results are shown in Table 7.

Comparative Example 10.3:

The catalyst composition prepared in Example 6 of the present invention was used to prepare continuous glass fiber reinforced polydicyclopentadiene by RTM process, and the resin system formula used was the same as that of Comparative Example 10.2. The composite material product was prepared by RTM process, and the molding method and process parameters were the same as those of Comparative Example 10.1. Samples were cut and plates were made, and the specific test results are shown in Table 7.

Comparative Example 10.4:

The existing commercially available ruthenium carbene olefin metathesis catalyst can only be stored for a long time at low temperature and in a solid state. When used, it can only be dissolved in a common solvent to prepare a solution of a certain concentration, and the catalyst in the solution state is easy to decompose, resulting in catalyst inactivation. Therefore, in the olefin polymerization process, the ruthenium carbene olefin metathesis catalyst can only be prepared on the spot.

A continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material was prepared by vacuum infusion process using a commercial ruthenium carbene catalytic system.

The weight parts of each component raw material in liquid A are as follows:

Dicyclopentadiene monomer 50 servings Bisphenol A epoxy resin 50 servings

The weight parts of each component raw material in liquid B are as follows:

Epoxy curing agent: methyl-5-norbornene-2,3-dicarboxylic anhydride 95.46 copies Epoxy curing accelerator: DMP-30 4.54 servings Comonomer: Methyl-5-norbornene-2,3-dicarboxylic anhydride 5 servings Auxiliary agent: coupling agent KH560 0.65 Additives: Anti-aging agent (2,6-di-tert-butyl-4-methylphenol) 1.14 servings

The weight parts of each component raw material in liquid C are as follows:

Commercial Grubbs 2nd catalyst 6.5 servings Solvent: Toluene 93.5 copies

The preparation process of polydicyclopentadiene/epoxy resin system is as follows:

1. Preparation of Liquid A: According to the formula design plan, weigh dicyclopentadiene monomer and bisphenol A epoxy resin to form Liquid A;

2. Preparation of Liquid B: Weigh and mix epoxy resin curing agent and curing accelerator to form Liquid B;

3. Mixing of additional components: Evenly mix the functional filler, comonomer and additives into the A liquid or B liquid resin system according to the formula design;

4. Preparation of Liquid C: Fully dissolve Grubbs ^2nd catalyst in toluene solution to form Liquid C.

5. Molding process: First mix liquid A and liquid B, then add liquid C, and mix them evenly to obtain a resin system for composite materials.

The mass ratio of liquid A, liquid B and liquid C is about 200:100:1. They are mixed evenly by mechanical stirring at a speed of 300-500 r/min and a stirring time of 20-30 min.

A fiber-reinforced resin matrix composite material with a fiber mass fraction of 60% was prepared using continuous glass fiber as reinforcement. The preparation process of the composite material is the same as that of Example 10.3. The specific test results are shown in Table 7.

Table 7

Claims (22)

1. A resin composition characterized by comprising, in parts by weight: 5-98 parts of dicyclopentadiene, 3-95 parts of epoxy resin, 0.5-65 parts of epoxy resin curing agent, 0.5-25 parts of curing accelerator and 0.01-15 parts of catalyst composition;

The catalyst composition comprises a ruthenium carbene compound or a salt thereof shown in a formula I, and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5-65%, and the chlorine content is the percentage of the mass of chlorine atoms in the chlorinated paraffin;

wherein R is ¹ And R is ² Independently C ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ An alkyl group;

R ^1-1 independently C ₆ -C ₁₀ Aryl groups.

2. The resin composition according to claim 1,

the chlorine content of the chlorinated paraffin is 5-60%, and the chlorine content is the percentage of the mass of chlorine atoms in the chlorinated paraffin;

and/or the mass concentration of the ruthenium carbene compound shown in the formula I or the salt thereof in the chlorinated paraffin is 0.08mol/L to 0.7mol/L;

and/or, the C ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl is independently C ₄ -C ₁₀ An alkyl group;

and/or, the quilt R ^1-1 Substituted C ₄ -C ₁₈ In the alkyl group, R ^1-1 Is 1, 2 or 3, and when it is 2 or 3, it is the same or different;

and/or, the C ₆ -C ₁₀ Aryl is phenyl or naphthyl;

and/or R ¹ And R is ² The same or different;

and/or, the purity of the dicyclopentadiene is more than or equal to 90%;

and/or, the dosage of dicyclopentadiene is 10-95 parts by weight;

And/or, the epoxy resin is used in an amount of 5-90 parts by weight;

and/or, the epoxy resin curing agent is used in an amount of 1-60 parts by weight;

and/or, the dosage of the curing accelerator is 1-10 parts by weight;

and/or, the catalyst composition is used in an amount of 0.03-11 parts by weight;

and/or, the sum of the volume parts of the cyclopentadiene and the epoxy resin is 100 parts;

and/or the volume fraction ratio of the cyclopentadiene to the epoxy resin is 0.1:1-20:1;

and/or the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin and phenolic epoxy resin;

and/or the epoxy value of the epoxy resin is 0.48-0.54;

and/or the epoxy resin curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, modified methyl tetrahydrophthalic anhydride, modified methyl hexahydrophthalic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride and dodecyl succinic anhydride;

And/or the curing accelerator is one or more of 2,4, 6-tri (dimethylaminomethyl) phenol, dimethylaminomethyl phenol, 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole;

and/or the composition further comprises one or more of a comonomer, a functional filler and an auxiliary agent.

3. The resin composition according to claim 2,

the chlorine content of the chlorinated paraffin is 5%, 42%, 52% or 60%, and the chlorine content is the percentage of the mass of chlorine atoms in the chlorinated paraffin;

and/or the mass concentration of the ruthenium carbene compound shown in the formula I or the salt thereof in the chlorinated paraffin is 0.1mol/L to 0.6mol/L;

and/or, the C ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl is independently C ₄ -C ₆ An alkyl group;

and/or the purity of the dicyclopentadiene is more than or equal to 98%;

and/or, the dosage of dicyclopentadiene is 10 parts, 55 parts, 80 parts or 95 parts by weight;

and/or, the epoxy resin is used in an amount of 5 parts, 20 parts, 45 parts or 90 parts by weight;

and/or the epoxy resin curing agent is used in an amount of 1.14 parts, 3 parts, 18.76 parts or 57.93 parts by weight;

And/or the usage amount of the curing accelerator is 1.56 parts, 6.40 parts, 9.70 parts or 3 parts by weight;

and/or the catalyst composition is used in an amount of 0.03 parts, 0.57 parts, 0.67 parts or 10.94 parts by weight;

and/or, when the composition further comprises a comonomer, the comonomer is one or more of norbornene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene, propylene, isoprene, styrene, butadiene, maleic anhydride, cyclopentadiene, methyl-5-norbornene-2, 3-dicarboxylic anhydride, and t-butyl 5-norbornene-2-carboxylate;

and/or, when the composition further comprises a comonomer, the comonomer is used in an amount of 0.5 to 13 parts;

and/or, when the composition further comprises a functional filler, the functional filler is one or more of carbon black, graphite powder, mica powder, montmorillonite, titanium pigment, silica, glass fiber, basalt fiber, carbon fiber, polyethylene fiber and aramid fiber;

and/or, when the composition further comprises a functional filler, the functional filler is used in an amount of 1 to 13 parts;

And/or, when the composition further comprises an auxiliary agent, the auxiliary agent is one or more of a polymerization regulator, an anti-aging agent, a coupling agent, toner, a cosolvent, a heat stabilizer, a flame retardant and a release agent.

4. The resin composition according to claim 3,

the C is ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl is independently C ₄ Alkyl, C ₅ Alkyl or C ₆ An alkyl group.

5. The resin composition according to claim 4,

the C is ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl is independently n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl.

6. The resin composition according to claim 5,

the C is ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl is independently n-butyl or n-hexyl.

7. The resin composition according to claim 3 to 6,

the mass concentration of the ruthenium carbene compound shown in the formula I or the salt thereof in the chlorinated paraffin is 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.55mol/L or 0.6mol/L;

and/or the ruthenium carbene compound shown in the formula I has any structure,

And/or, when the composition further comprises a comonomer, the comonomer is one or more of ethylene, ethyl methacrylate, and tert-butyl 5-norbornene-2-carboxylate;

and/or, when the composition further comprises a comonomer, the comonomer is used in an amount of 1 to 10 parts;

and/or, when the composition further comprises a functional filler, the functional filler is one or more of glass fiber, carbon black and carbon fiber;

and/or, when the composition further comprises a functional filler, the functional filler is used in an amount of 2 to 10 parts;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a polymerization regulator, wherein the polymerization regulator is one or more of triphenylphosphine, triethyl phosphite, tributyl phosphite, ethylene glycol dimethyl ether, diphenyl ketone and isopropyl ether;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a polymerization regulator, wherein the dosage of the polymerization regulator is 0.5-3 parts by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, aniline, 2-methylaniline, BASF1010, BASF1076, BASF168, tinuvin 571, tinuvin 765, tinuvin B75, tinuvin B88, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-531 and UV-770;

And/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, and the anti-aging agent is used in an amount of 1-5 parts by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a coupling agent, and the coupling agent is a silane coupling agent;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a coupling agent, wherein the coupling agent is used in an amount of 0.3-1 part by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises toner, and the dosage of the toner is 0.1-0.5 part by weight;

and/or, when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises a cosolvent, and the cosolvent is acetone;

and/or when the composition further comprises an auxiliary agent, the auxiliary agent comprises a cosolvent, wherein the cosolvent is used in an amount of 1-2 parts by weight.

8. The resin composition according to claim 7,

when the composition further comprises a comonomer, the comonomer is used in an amount of 1.37 parts, 5 parts or 10 parts;

and/or, when the composition further comprises a functional filler, the functional filler is used in an amount of 2.50 parts, 5 parts or 9.66 parts;

And/or, when the composition further comprises an auxiliary agent, wherein the auxiliary agent comprises a polymerization regulator, the polymerization regulator is triethyl phosphite;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a polymerization regulator, wherein the dosage of the polymerization regulator is 1 part by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises an anti-aging agent, wherein the anti-aging agent is used in an amount of 2 parts by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a coupling agent, wherein the coupling agent is a silane coupling agent A172;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a coupling agent, wherein the coupling agent is used in an amount of 0.64 parts by weight;

and/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises toner, and the amount of the toner is 0.34 part by weight;

And/or, when the composition further comprises an auxiliary agent, the auxiliary agent comprises a cosolvent, wherein the cosolvent is used in an amount of 1.56 parts by weight.

9. The resin composition according to claim 1 to 6,

the catalyst composition consists of a ruthenium carbene compound or a salt thereof shown in a formula I and chlorinated paraffin;

and/or, the composition is any combination of the following:

combination C1: dicyclopentadiene, epoxy resin curing agent, curing accelerator and catalyst composition;

combination C2: dicyclopentadiene, epoxy resin, an epoxy resin curing agent, a curing accelerator, a catalyst composition, a comonomer, a functional filler and toner;

combination C3: dicyclopentadiene, epoxy resin, an epoxy resin curing agent, a curing accelerator, a catalyst composition, a comonomer, a functional filler, an anti-aging agent and a coupling agent;

combination C4: dicyclopentadiene, epoxy resin curing agent, curing accelerator, catalyst composition, comonomer, functional filler, polymerization regulator and cosolvent.

10. The resin composition of claim 9, wherein the catalyst composition is any combination of:

Combination A1:

and chlorinated paraffin, wherein the chlorinated paraffin has chlorine content of 5%, 42%, 52% or 60%; />

Combination A2:

and chlorinated paraffin, wherein the chlorinated paraffin has chlorine content of 5%, 42%, 52% or 60%;

combination A3:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%;

combination A4:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 42%;

combination A5:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 5%;

combination A6:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 60%;

combination A7:

and chlorinated paraffin, wherein the chlorine content of the chlorinated paraffin is 52%;

combination B1:

and chlorine content of 5%Chlorinated Paraffin, tiger>

The concentration of the substances in the chlorinated paraffin was 0.1mol/L; />

Combination B2:

and chlorinated paraffin with chlorine content of 42%>

The mass concentration of the substances in the chlorinated paraffin is 0.3mol/L;

combination B3:

and chlorinated paraffin with chlorine content of 52%>

The mass concentration of the substances in the chlorinated paraffin is 0.35mol/L;

combination B4:

and chlorinated paraffin with chlorine content of 60%>

The concentration of the substances in the chlorinated paraffin was 0.6mol/L;

combination B5:

and chlorinated paraffin with chlorine content of 5% >

The concentration of the substances in the chlorinated paraffin was 0.1mol/L;

combination B6:

and chlorinated paraffin with chlorine content of 42%>

The mass concentration of the substances in the chlorinated paraffin is 0.25mol/L;

combination B7:

and chlorinated paraffin with chlorine content of 52%>

The mass concentration of the substances in the chlorinated paraffin is 0.3mol/L; />

Combination B8:

and chlorinated paraffin with chlorine content of 60%>

The concentration of the substances in the chlorinated paraffin was 0.6mol/L;

combination B9:

and chlorinated paraffin with chlorine content of 52%>

The mass concentration of the substances in the chlorinated paraffin is 0.3mol/L;

combination B10:

and chlorinated paraffin with chlorine content of 42%>

In chlorinated paraffinThe mass concentration of the substances is 0.35mol/L;

combination B11:

and chlorinated paraffin with chlorine content of 5%>

The mass concentration of the substances in the chlorinated paraffin is 0.55mol/L;

combination B12:

and chlorinated paraffin with chlorine content of 60%>

The mass concentration of the substances in the chlorinated paraffin is 0.2mol/L;

combination B13:

and chlorinated paraffin with chlorine content of 52%>

The concentration of the substances in chlorinated paraffin was 0.35mol/L.

11. The resin composition of claim 9, wherein the composition is any combination of:

combination D1: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator and 0.03-11 parts of catalyst composition;

Combination D2: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler and 0.1-0.5 part of toner;

combination D3: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 1-5 parts of anti-aging agent and 0.3-1 part of coupling agent;

combination D4: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 0.5-3 parts of polymerization regulator and 1-2 parts of cosolvent;

combination D5: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator and 0.03-11 parts of catalyst composition; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl-5-norbornene-2, 3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4, 6-tris (dimethylaminomethyl) phenol; the catalyst composition is

And chlorinated paraffin having chlorine content of 5%;

combination D6: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler and 0.1-0.5 part of toner; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl-5-norbornene-2, 3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4, 6-tris (dimethylaminomethyl) phenol; the catalyst composition is

And chlorinated paraffin having a chlorine content of 42%; the comonomer is one of ethylene, ethyl methacrylate and tert-butyl 5-norbornene-2-carboxylateOne or more species; the functional filler is one or more of glass fiber, carbon black and carbon fiber; />

Combination D7: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 1-5 parts of anti-aging agent and 0.3-1 part of coupling agent; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl-5-norbornene-2, 3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4, 6-tris (dimethylaminomethyl) phenol; the catalyst composition is

And chlorinated paraffin having a chlorine content of 60%; the comonomer is one or more of ethylene, ethyl methacrylate and 5-norbornene-2-carboxylic acid tert-butyl ester; the functional filler is one or more of glass fiber, carbon black and carbon fiber; the anti-aging agent is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2-methylaniline, tinuvin B75 and 2-hydroxy-4-methoxybenzophenone; the coupling agent is a silane coupling agent;

combination D8: 10-95 parts of dicyclopentadiene, 5-90 parts of epoxy resin, 1-60 parts of epoxy resin curing agent, 1-10 parts of curing accelerator, 0.03-11 parts of catalyst composition, 1-10 parts of comonomer, 2-10 parts of functional filler, 0.5-3 parts of polymerization regulator and 1-2 parts of cosolvent; the epoxy resin is bisphenol A type epoxy resin; the epoxy resin curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl-5-norbornene-2, 3-dicarboxylic anhydride; the curing accelerator is one or more of 2-methylimidazole, 2-ethylimidazole and 2,4, 6-tris (dimethylaminomethyl) phenol; the catalyst composition is

And chlorinated paraffin having chlorine content of 5%; the comonomer is one or more of ethylene, ethyl methacrylate and 5-norbornene-2-carboxylic acid tert-butyl ester; the functional filler is one or more of glass fiber, carbon black and carbon fiber; the polymerization regulator is triethyl phosphite; the cosolvent is acetone;

Combination D9: 80 parts of dicyclopentadiene, 20 parts of bisphenol A type epoxy resin, 13 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 3 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 0.67 part of a catalyst composition; the catalyst composition is

And chlorinated paraffin with chlorine content of 5%>

The concentration of the substances in the chlorinated paraffin was 0.1mol/L;

combination D10: 95 parts of dicyclopentadiene, 5 parts of bisphenol A epoxy resin, 1.14 parts of methyl hexahydrophthalic anhydride, 9.70 parts of 2-ethylimidazole, 0.57 part of catalyst composition, 1.37 parts of 5-norbornene-2-carboxylic acid tert-butyl ester, 5 parts of carbon fiber and 0.34 part of toner; the catalyst composition is

And chlorinated paraffin having a chlorine content of 42%,

the mass concentration of the substances in the chlorinated paraffin is 0.25mol/L;

combination D11: 55 parts of dicyclopentadiene, 45 parts of bisphenol A epoxy resin, 57.93 parts of methyltetrahydrophthalic anhydride, 6.40 parts of 2-methylimidazole, 0.03 part of catalyst composition, 10 parts of ethylene, 9.66 parts of glass fiber, 2 parts of 2-methylaniline and 172.64 parts of silane coupling agent A; the catalyst composition is

And chlorinated paraffin with chlorine content of 60%>

The concentration of the substances in the chlorinated paraffin was 0.6mol/L;

Combination D12: 10 parts of dicyclopentadiene, 90 parts of bisphenol A type epoxy resin, 18.76 parts of methyl-5-norbornene-2, 3-dicarboxylic anhydride, 1.56 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 10.94 parts of a catalyst composition, 5 parts of ethyl methacrylate, 2.50 parts of carbon black, 1 part of triethyl phosphite and 1.56 parts of acetone; the catalyst composition is

And chlorinated paraffin with chlorine content of 5%>

The concentration of the substances in the chlorinated paraffin was 0.1mol/L.

12. The resin composition according to claim 1,

R ¹ and R is ² Independently C ₄ -C ₁₈ An alkyl group.

13. The resin composition according to claim 12, wherein,

R ¹ and R is ² Independently n-butyl or n-hexyl.

14. A resin material prepared from the resin composition according to any one of claims 1 to 13.

15. The resinous material of claim 14, wherein the epoxy resin and dicyclopentadiene each crosslink and polymerize to form an interpenetrating network structure.

16. A method for preparing a resin material, comprising the steps of: taking the resin composition as defined in any one of claims 1-13 as a raw material, uniformly mixing dicyclopentadiene, epoxy resin, an epoxy resin curing agent, a curing accelerator and a catalyst composition, optionally adding one or more of a comonomer, a functional filler and an auxiliary agent, and curing and molding to obtain the resin material.

17. The method of claim 16, wherein the method of manufacture uses RIM technology.

18. The method of claim 17, wherein the RIM process comprises the steps of:

(1) Mixing dicyclopentadiene and epoxy resin to obtain solution A;

(2) Mixing the catalyst composition, the epoxy resin curing agent and the curing accelerator to obtain a solution B;

(3) Optionally adding one or more of a comonomer, a functional filler and an auxiliary agent to the liquid a or the liquid B;

(4) Leading the solution A and the solution B into a storage system for standby;

(5) The solution A and the solution B are subjected to reaction injection molding in RIM equipment;

(6) Solidifying to obtain the resin material.

19. The method of claim 18, wherein,

in the step (4), the storage system is a storage tank of RIM equipment;

and/or, in the step (4), the temperature of the storage system is-10-40 ℃;

and/or in the step (5), the mass ratio of the liquid A to the liquid B is 1:1-20:1;

and/or in the step (5), the solution A and the solution B are mixed and injected into a mould on line to finish reaction injection molding;

and/or, in the step (5), the glue injection speed of the reaction injection molding is 200mL/min-100L/min;

And/or, in the step (5), the glue injection pressure of the reaction injection molding is 0.1-20bar;

and/or, in the step (6), the temperature during curing is 70-180 ℃;

and/or, in the step (6), the curing time is 1-120min.

20. The method of claim 19, wherein,

in the step (4), the temperature of the storage system is-5-25 ℃;

and/or in the step (5), the mass ratio of the liquid A to the liquid B is 1:1-15:1;

and/or, in the step (5), the glue injection speed of the reaction injection molding is 500mL/min-30L/min;

and/or, in the step (5), the glue injection pressure of the reaction injection molding is 6-25bar;

and/or, in the step (6), the temperature during curing is 70-100 ℃.

21. The method of claim 20, wherein,

in the step (5), the mass ratio of the liquid A to the liquid B is 1:1-10:1.

22. A resin material produced according to the production method of any one of claims 16 to 21.