CN115947761A

CN115947761A - Ruthenium carbene catalyst, composition containing ruthenium carbene catalyst, and preparation method and application of ruthenium carbene catalyst

Info

Publication number: CN115947761A
Application number: CN202211715065.5A
Authority: CN
Inventors: 杨鲜锋; 方佳兴; 童弢; 王建辉
Original assignee: Shanghai Zhonghua Technology Co ltd
Current assignee: Shanghai Zhonghua Technology Co ltd
Priority date: 2022-12-27
Filing date: 2022-12-27
Publication date: 2023-04-11

Abstract

The invention provides a ruthenium carbene catalyst, a composition containing the same, a preparation method and application thereof. Specifically discloses a ruthenium carbene compound shown as a formula LG or a salt thereof, wherein R is ₁ 、R ₂ And R ₃ Are each independently C ₆ ‑C ₁₈ An alkyl group. The ruthenium carbene catalyst of the invention exists in a liquid state at normal temperature, and is suitable for continuous production.

Description

Ruthenium carbene catalyst, composition containing ruthenium carbene catalyst, and preparation method and application of ruthenium carbene catalyst

Technical Field

The invention relates to a ruthenium carbene catalyst, a composition containing the same, a preparation method and application thereof.

Background

The olefin double decomposition reaction is a unique carbon skeleton rearrangement reaction, unsaturated bonds are mutually exchanged, coupled and rearranged to synthesize new carbon-carbon bonds by converting C = C or C ≡ C in a carbene metal center catalytic polymerization monomer, and the double decomposition reaction is an important means in organic synthesis and has a great significance. In recent years, olefin metathesis reaction has attracted much attention, because it is a new carbon-carbon synthesis means, and because the synthesis route of olefin metathesis reaction is simple, it has better compatibility with most organic functional groups, and the involved side reactions are less, it has higher reaction conversion rate, and the reaction conditions in the synthesis process are mild, so it is very suitable for industrial application.

Common catalyst systems for ring-opening metathesis polymerization of olefins in olefin metathesis reaction include W and Mo dual-component catalysts and Ru single-component catalysts. Compared with a bi-component catalyst, the Ru metal carbene catalyst has higher catalytic activity and better stability, and is particularly a Ru catalyst containing a nitrogen heterocyclic carbene ligand. The Ru catalyst has a stable structure, good functional group applicability and low requirement on reaction conditions, and can catalyze the reaction in the presence of impurities such as oxygen, water and the like, so that the Ru catalyst becomes a common catalyst suitable for olefin metathesis reaction and ring-opening metathesis polymerization reaction.

The existing commercial ruthenium carbene catalyst can only be stored for a long time at low temperature and in a solid state, and can be deactivated at a higher speed in a solution, so that the stability is poor. Therefore, these commercial products can only be prepared at present, and once the catalyst is dissolved by using the solvent, the solvent is volatilized in the subsequent curing process to generate air holes and shrink the volume of the product, thereby seriously affecting the performance of the product.

For long-term storage of ruthenium carbene catalysts, solid mixtures of ruthenium carbene catalysts with paraffin waxes are reported in the literature (Taber D.F., frankowski K.J., grubb's catalyst in paraffin: an air-stable preparation of alkane catalysts [ J ]. J.Org.Chem.,2003,68 (22): 6047-6048.) for long-term storage of the catalysts. However, when the catalyst is used, the solid mixture is dissolved first or added directly to the reaction solution. When the method is applied to the ring-opening metathesis polymerization of olefin bodies, the method still needs to be prepared and is not suitable for the continuity of production.

Aiming at the defects of the ruthenium carbene catalyst, a novel ruthenium carbene catalyst composition which is liquid at normal temperature is synthesized in the patent CN112547126A, the influence of a solvent is removed, the catalyst is used without being prepared, and the catalyst can be stored for a long time and is suitable for automatic production. However, the catalyst is solid at normal temperature and can be liquid only by being combined with chlorinated paraffin, and secondly, the catalyst is mainly improved aiming at the N-heterocyclic carbene ligand, the activity and the stability of the catalyst are greatly determined by the ligand, the catalyst is not inactivated in the synthesis process, and meanwhile, the process for preparing the N-heterocyclic carbene ligand is complex, and the production cost is increased.

In order to simplify the synthesis process patent CN110105400A of the ruthenium carbene catalyst, the P ligand of the catalyst is replaced by the N ligand, the needed catalyst can be synthesized by only two steps, and meanwhile, the raw materials are easy to obtain. In the patent, N ligand is used for replacing P ligand of ruthenium carbene catalyst to prepare the temperature-sensitive ruthenium carbene catalyst, and the inventor repeats the example 2 and the example 3, and finds that the ruthenium carbene catalyst is still solid at normal temperature and can not solve the problem of manufacturability.

Disclosure of Invention

Aiming at the defects that the existing ruthenium carbene catalyst is complex in preparation process and is not suitable for continuous production, the invention provides a ruthenium carbene catalyst, a composition containing the ruthenium carbene catalyst, a preparation method and application of the ruthenium carbene catalyst. The ruthenium carbene catalyst has the advantages of simple preparation process, stable product performance, existence of liquid state at normal temperature, and suitability for continuous production.

The invention provides a ruthenium carbene compound shown as a formula LG or a salt thereof,

wherein R is ₁ 、R ₂ And R ₃ Are each independently C ₆ -C ₁₈ An alkyl group.

In some embodiments, the C ₆ -C ₁₈ Alkyl is independently C ₆ -C ₁₀ Alkyl, preferably C ₆ Alkyl radical, C ₈ Alkyl or C ₁₀ An alkyl group; more preferably C ₈ Alkyl or C ₁₀ An alkyl group.

In some embodiments, the C ₆ Alkyl is n-hexyl or 4-methylpentyl.

In some embodiments, the C is ₈ Alkyl is n-octyl, 2-ethylhexyl or 5-methylheptyl; 2-ethylhexyl is preferred.

In some embodiments, the C is ₁₀ The alkyl group is an n-decyl group.

In some embodiments, the R is ₁ 、R ₂ And R ₃ The same or different.

In some embodiments, the ruthenium carbene compound according to formula LG is selected from any one of the following structures:

the invention also provides a preparation method of the ruthenium carbene compound shown in the formula LG, which comprises the following first method or second method:

the method comprises the following steps: carrying out substitution reaction between the compound 2 and the compound 3 in an organic solvent under an inert atmosphere, wherein the substitution reaction is as shown in the specification;

the second method comprises the following steps: in an organic solvent, under an inert atmosphere, the compound 4 and the compound 3 are subjected to substitution reaction as shown in the specification;

wherein R is ₁ 、R ₂ And R ₃ As defined above.

In some embodiments, in the first method, the organic solvent may be a solvent conventional in the art for such reactions, preferably a haloalkane solvent, and more preferably dichloromethane.

In some embodiments, in method one, the inert atmosphere may be an inert gas conventional in the art for such reactions, preferably nitrogen.

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

In some embodiments, in the first method, the volume molar ratio of the organic solvent to the compound 2 may be a volume molar ratio conventional in such reactions in the art, preferably 2L/mol to 8L/mol, and more preferably 4L/mol.

In some embodiments, in method one, the reaction temperature of the substitution reaction may be a reaction temperature conventional in the art for such reactions, preferably room temperature.

In some embodiments, in method one, the reaction time of the substitution reaction is based on TLC monitoring that the reaction is completely performed, preferably 1h to 5h, and more preferably 2h.

In some embodiments, the first method further comprises the following post-processing steps: rotary evaporation and/or column chromatography (preferably using petroleum ether/dichloromethane mixed solution as developing agent).

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

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

In some embodiments, in the second method, the volume molar ratio of the organic solvent to the compound 4 may be a volume molar ratio conventional in such reactions in the art, and is preferably 10L/mol to 50L/mol, and is further preferably 23.5L/mol.

In some embodiments, in method two, the reaction temperature of the substitution reaction may be a reaction temperature conventional in such reactions in the art, preferably 30 ℃ to 100 ℃, and more preferably 70 ℃.

In some embodiments, in method two, the reaction time of the substitution reaction is based on TLC monitoring that the reaction is completely occurring, preferably 1h to 5h, preferably 2h.

In some embodiments, the second method further comprises the following post-treatment steps: cooling (preferably to room temperature), column chromatography (preferably with a petroleum ether/dichloromethane mixed solution as a developing solvent), and rotary evaporation.

In some embodiments, the first method further comprises the steps of: under an inert atmosphere, carrying out substitution reaction on the compound 1 and pyridine as shown in the specification;

in some embodiments, the pyridine is anhydrous pyridine.

In some embodiments, the inert atmosphere may be an inert gas conventional in the art for such reactions, preferably nitrogen.

In some embodiments, the volume molar ratio of the pyridine to the compound 1 may be a volume molar ratio conventional in such reactions in the art, preferably from 2L/mol to 20L/mol, preferably 5L/mol.

In some embodiments, the reaction temperature of the substitution reaction is room temperature.

In some embodiments, the reaction time for the substitution reaction may be a reaction temperature conventional in such reactions in the art, preferably from 2h to 10h, preferably 5h.

In some embodiments, the substitution reaction is performed under stirring conditions.

In some embodiments, the substitution reaction further comprises a post-treatment step of: precipitation (preferably with petroleum ether), filtration, washing (preferably with petroleum ether) and drying (preferably vacuum drying).

The invention also provides a catalyst composition which comprises the ruthenium carbene compound shown as the formula LG or the salt thereof and chlorinated paraffin.

In some embodiments, the mass ratio of the ruthenium carbene compound or salt thereof to the chlorinated paraffin is from 1.

In some embodiments, the chlorinated paraffin has a chlorine content of 5% to 60%, the percentage referring to the mass fraction of chlorine atoms in the chlorinated paraffin; for example 5%, 27%, 52% or 60%.

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

In some embodiments, the catalyst composition is selected from any one of the following combinations:

combination 1:

and chlorinated paraffin having a chlorine content of 5%, 27%, 52%, or 60%; />

And (3) combination 2:

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

and (3) combination:

and chlorinated paraffin, the chlorinated paraffin having a chlorine content of 5%.

and (4) combination:

and chlorinated paraffin with a chlorine content of 5%; said +>

In the chlorinated paraffinThe molar concentration is 0.1mol/L;

and (3) combination 5:

and chlorinated paraffin with a chlorine content of 27%; is/are>

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

and (4) combination 6:

and chlorinated paraffin with chlorine content of 52%; is/are>

The molar concentration in the chlorinated paraffin is 0.4mol/L;

and (3) combination 7:

and chlorinated paraffin with a chlorine content of 60%; is/are>

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

And (4) combination 8:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 9:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 10:

and chlorinated paraffin with a chlorine content of 5%; is/are>

The molar concentration in the chlorinated paraffin is 0.5mol/L;

combination 11:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 12:

and chlorinated paraffin with a chlorine content of 5%; said +>

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

Combination 13:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 14:

and chlorinated paraffin with a chlorine content of 5%; said +>

The molar concentration in the chlorinated paraffin is 0.45mol/L;

and (3) combining 15:

and chlorinated paraffin with a chlorine content of 5%; is/are>

The molar concentration in the chlorinated paraffin was 0.6mol/L.

The invention also provides a preparation method of the catalyst composition, which comprises the following steps: and (2) mixing the ruthenium carbene compound or the ruthenium carbene salt shown in the formula LG with chlorinated paraffin in an inert atmosphere to obtain the ruthenium carbene compound.

In some embodiments, the inert atmosphere in the process for preparing the catalyst composition may be an inert gas conventional to such reactions in the art, preferably nitrogen or argon.

In some embodiments, the method of making the catalyst composition further comprises using a haloalkane. The haloalkane is preferably dichloromethane.

In some embodiments, the method of preparing the catalyst composition comprises mixing with stirring.

In some embodiments, when the preparation method of the catalyst composition further comprises using halogenated alkane, the addition sequence of the preparation method of the catalyst composition is the ruthenium carbene compound or the salt thereof shown in the formula LG, the halogenated alkane and the chlorinated paraffin in sequence.

In some embodiments, the method of preparing the catalyst composition further comprises the following post-treatment steps: and (5) performing rotary steaming.

The invention also provides application of the ruthenium carbene compound shown as the formula LG or the salt thereof or the catalyst composition in catalyzing olefin metathesis reaction.

In some embodiments, the olefin metathesis reaction is a ring-closing metathesis reaction, a cross metathesis reaction, or a ring-opening metathesis polymerization reaction.

In some embodiments, the ring-closing metathesis reaction comprises the steps of: under the inert atmosphere and in the presence of a catalyst, carrying out ring-closing metathesis reaction on the compound shown as the formula A1 to obtain a compound shown as the formula A2,

the catalyst is the ruthenium carbene compound shown as the formula LG or the salt thereof or the catalyst composition;

wherein the content of the first and second substances,

x is O, S, -N (R) ⁷ )-、-C(R ⁸ )(R ⁹ )-

R ⁷ Is hydrogen, C ₁ -C ₆ Alkyl, -S (= O) ₂ R ^7-1 、-C(＝O)R ^7-2 OR-C (= O) OR ^7-3

R ⁸ And R ⁹ Independently of one another is hydrogen, C ₁ -C ₆ Alkyl, -C (= O) R ^8-1 OR-C (= O) OR ^8-2 ；

Or, R ⁸ And R ⁹ With atoms in between them forming unsubstituted or substituted by 1,2 or 3R ^8-3 The substituted heteroatom is one or more selected from N, O and S, and the number of the heteroatoms is 1,2 or 3;

R ^7-1 、R ^7-2 、R ^7-3 、R ^8-1 and R ^8-2 Independently of one another is hydrogen, C ₁ -C ₆ Alkyl, unsubstituted or substituted by 1,2 or 3R ^7-1-1 Substituted C ₆ -C ₁₀ An aryl group;

R ^8-3 and R ^7-1-1 Independently of one another, hydroxy, halogen, C ₁ -C ₆ Alkyl or C ₁ -C ₆ An alkoxy group;

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

In some embodiments, X is-N (R) ⁷ )-；R ⁷ to-S (= O) ₂ R ^7-1 ；

R ^7-1 Is unsubstituted orBy 1,2 or 3R ^7-1-1 Substituted C ₆ -C ₁₀ Aryl (which may be phenyl);

each R ^7-1-1 Are each independently C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl groups).

In some embodiments, the compound of formula A1 is

In some embodiments, the conditions and operation of the ring-closing metathesis reaction may be those conventional in the art for such reactions.

In some embodiments, the ring-closing metathesis reaction is conducted in the absence of a solvent or in the presence of a solvent.

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

In some embodiments, the inert atmosphere in the ring-closing metathesis reaction may be a conventional inert gas for such reactions in the art, preferably nitrogen.

In some embodiments, in the ring-closing metathesis reaction, when the catalyst is the ruthenium carbene compound represented by formula LG or a salt thereof as described above, the ruthenium carbene compound represented by formula LG is

/>

In some embodiments, when the catalyst is the above-described catalyst composition in the ring-closing metathesis reaction, the catalyst composition is combination 5 above.

In some embodiments, the molar ratio of the ruthenium carbene compound according to formula LG or the salt thereof or the ruthenium carbene compound according to formula LG and the compound according to formula A1 in the catalyst composition may be a molar ratio customary in such reactions in the art, preferably (0.01% to 1%) to 1, further preferably 0.2% to 1.

In some embodiments, the reaction temperature of the ring-closing metathesis reaction may be a reaction temperature conventional in the art for such reactions, preferably from 30 ℃ to 100 ℃, further preferably 40 ℃.

In some embodiments, the reaction temperature of the ring closing metathesis reaction is subject to TLC monitoring that the reaction is completely occurring, preferably 1h to 5h, and more preferably 2h.

In some embodiments, the ring-closing metathesis reaction further includes a post-treatment step of: column chromatography (preferably using petroleum ether/ethyl acetate (5.

In some embodiments, when the ring-closing metathesis reaction is carried out in the presence of a solvent, the work-up step further comprises rotary evaporation and/or column chromatography.

In some embodiments, the cross-metathesis reaction may include the steps of: under the inert atmosphere and in the presence of a catalyst, carrying out cross metathesis reaction on a compound containing a segment B1 and a compound containing a segment B2 as shown in the specification to obtain a compound containing a segment B3,

in some embodiments, the compound comprising fragment B1 and the compound comprising fragment B2 may be independently

Wherein R is ⁴ Is C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl), - (CH) ₂ ) _n3 -OC(＝O)-R ^4-1 Or, unsubstituted or substituted by 1,2 or 3R ^4-2 Substituted C ₆ -C ₁₀ Aryl (which may be phenyl);

n3 is 0, 1 or 2;

R ^4-1 is unsubstituted or substituted by 1,2 or 3R ^4-1-1 Substituted C ₆ -C ₁₀ Aryl (which may be phenyl);

R ^4-2 and R ^4-1-1 Independently is hydroxy or C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl).

In some embodiments, the compound comprising fragment B1 and the compound comprising fragment B2 may be the same or different.

In some embodiments, the conditions and operation of the cross-metathesis reaction may be those conventional in the art for such reactions.

In some embodiments, the cross-metathesis reaction is carried out in the absence of a solvent or in the presence of a solvent.

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

In some embodiments, the inert atmosphere in the cross-metathesis reaction may be an inert gas conventional in the art for such reactions, preferably nitrogen.

In some embodiments, in the cross-metathesis reaction, when the catalyst is the ruthenium carbene compound represented by formula LG or a salt thereof described above, the ruthenium carbene compound represented by formula LG is

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

In some embodiments, the molar ratio of the ruthenium carbene compound according to formula LG or the salt thereof or the ruthenium carbene compound according to formula LG and the compound according to formula B1 in the catalyst composition may be a molar ratio customary in such reactions in the art, preferably (0.1% to 10%) 1, further preferably 2.5% 1.

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

In some embodiments, the reaction temperature of the cross-metathesis reaction may be a reaction temperature conventional in the art for such reactions, preferably from 30 ℃ to 100 ℃, further preferably 45 ℃.

In some embodiments, the reaction time of the cross-metathesis reaction is based on TLC monitoring that the reaction is completely occurring, preferably 4h to 20h, and more preferably 6h.

In some embodiments, when the cross-metathesis reaction is carried out in the presence of a solvent, the post-treatment step further comprises reduced pressure rotary evaporation and/or column chromatography.

In some embodiments, the ring-opening metathesis polymerization reaction includes the steps of: in an inert atmosphere, in the presence of a catalyst, carrying out ring-opening metathesis polymerization reaction on a compound containing a fragment C1 as shown in the specification to obtain a compound containing a fragment C2; the catalyst is the ruthenium carbene compound shown as the formula LG or the salt thereof or the catalyst composition,

ring A is 3-15 membered cyclic olefin containing 1,2 or 3 olefinic bonds;

n≥3。

in some embodiments, the ring-opening metathesis polymerization reaction is conducted in the absence of a solvent.

In some embodiments, the compound containing form C1 is

Wherein R is ⁵ And R ⁶ Independently of one another is hydrogen, halogen, C ₁ -C ₆ Alkyl or C ₁ -C ₆ An alkoxy group;

the A ring is 3-8 membered monocyclic cycloolefin containing 1,2 or 3 olefinic bonds, or 6-15 membered polycyclic cycloolefin containing 1,2 or 3 olefinic bonds.

In some embodiments, the compound containing form C1 is

R ⁵ And R ⁶ Is hydrogen;

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

In some embodiments, the compound containing form C1 is

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

In some embodiments, in the ring-opening metathesis polymerization reaction, when the catalyst is the ruthenium carbene compound represented by the formula LG or a salt thereof, the ruthenium carbene compound represented by the formula LG is

/>

Preferably in a manner which is +>

In some embodiments, in the ring-opening metathesis polymerization reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5.

In some embodiments, in the ring-opening metathesis polymerization reaction, the molar ratio of the ruthenium carbene compound represented by formula LG or a salt thereof or the ruthenium carbene compound represented by formula LG to the compound represented by formula C1 in the catalyst composition is a molar ratio which is conventional in the art, and is preferably (0.01% to 1%): 1, and is further preferably 0.01%:1.

On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.

In the present invention, the catalyst is a compound itself without being bound with chlorinated paraffin or paraffin, unless otherwise specified.

In the present invention, the room temperature means 0 to 40 ℃.

In the present invention, the "halogen" means fluorine, chlorine, bromine or iodine. In the present invention, the "salt" refers to a salt prepared by reacting the compound of the present invention with an acid, for example: hydrochloride, hydrobromide, sulfate, and the like.

In the present invention, the "alkyl group" means a straight-chain or straight-chain alkyl group having the specified number of carbon atoms, for example, C ₁ -C ₆ Alkyl is C ₁ -C ₄ Alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl radical.

In the present invention, the "alkoxy" group means a group-O-R ^X Wherein R is ^X Is an alkyl group as defined above.

The term "cycloalkene" refers to a cyclic olefin having one or more carbon-carbon double bonds, which may be monocyclic or polycyclic (including bicyclic). The cyclic olefin of the present invention is preferably a 3-15 membered cyclic olefin having 1,2 or 3 olefinic bonds, more preferably a 3-8 membered cyclic olefin having 1,2 or 3 olefinic bondsMonocyclic cycloalkenes or 6-15 membered polycyclic cycloalkenes containing 1,2 or 3 olefinic bonds. Examples of the cyclic olefin include cyclopropene, cyclobutene, cyclopentene, cyclohexene, and,

And the like.

In the invention, the group of the heterocycle without one hydrogen atom is the heterocycloalkyl. Thus, the heterocycle of the present invention is a ring obtained by obtaining one hydrogen atom from the heterocycloalkyl group of the present invention.

The term "heterocycloalkyl" refers to a saturated monocyclic group having heteroatoms, preferably 3-6 membered saturated monocyclic ring containing 1,2 or 3 ring heteroatoms independently selected from N, O and S. Examples of heterocycloalkyl groups are: pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothienyl, tetrahydropyridinyl, tetrahydropyrrolyl, azetidinyl, thiazolidinyl, oxazolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, and the like.

In the present invention, the "aryl group" means a hydrocarbon group having an aromatic property, such as C ₆ -C ₁₀ Aryl is phenyl or naphthyl.

In the present invention, the open expression "comprising" can be converted into the closed expression "consisting of 823030A".

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

The positive progress effects of the invention are as follows: the ruthenium carbene catalyst has the advantages of simple preparation process and stable product performance, and is suitable for continuous production.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.

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

EXAMPLE 1,3 preparation of bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (trioctylphosphine) ruthenium dichloride catalyst

To a dry 100mL single-neck flask equipped with a magnetic stirrer, 50mL of anhydrous pyridine was added under nitrogen, followed by 8.49g (10.0 mmol) of ruthenium compound 1 (formula: C) ₄₆ H ₆₅ Cl ₂ N ₂ PRu, molecular weight: 848.97 Stirring to dissolve the catalyst solids. The reaction mixture was further stirred at room temperature for 5.0 hours. At this time, the solution turned dark green. The stirring was stopped and the reaction mixture was added dropwise to a beaker containing 200mL of petroleum ether with constant vigorous stirring. In this process, a green precipitate gradually precipitated from the reaction solution. After the reaction, the reaction solution was filtered to obtain a green solid. The solid was washed three times with petroleum ether to remove adsorbed pyridine and dried in vacuo to give green intermediate 2 weighing 6.5g (8.94 mmol) in 89.4% yield.

Analyzing data:

C ₃₈ H ₄₂ Cl ₂ N ₄ theoretical value (calculated value) of Ru: c,62.80 (62.62); h,5.83 (5.60); n,7.71 (7.61).

¹ H NMR(400MHz,CDCl ₃ ):δ19.67(s,1H,CHPh),8.84(br.s,2H,pyridine),8.39(br.s,2H,pyridine),8.07(d,2H,ortho CH,J _H-H ＝8Hz),7.15(t,1H,para CH,J _H-H ＝7Hz),6.83-6.04(br.mulitiple peaks,9H,pyridine,Mes-CH),3.37(br.d,4H,CH ₂ CH ₂ ),2.79(br.s,6H,Mes-CH ₃ ),2.45(br.s,6H,Mes-CH ₃ ),2.04(br.s,6H,Mes-CH ₃ ).

¹³ C{1H}NMR(C ₆ D ₆ ):δ314.90(m,Ru＝CHPh),219.10(s,Ru-C(N) ₂ ),152.94,150.84,139.92,138.38,136.87,135.99,134.97,131.10,130.11,129.88,128.69,123.38,51.98,51.37,21.39,20.96,19.32

To a dry 100mL flask was added 3.63g (5.00 mmol) of complex 2 under nitrogen, 20mL of dichloromethane and stirred to dissolve it. Then, 3.71g (10.00 mmol) of trioctylphosphine (formula: C) was added to the flask ₂₄ H ₅₁ P; molecular weight: 370.65 g/mol) and the reaction mixture was stirred at room temperature for 2h. During this process, the solution gradually changed from green to brownish red. After the reaction is finished, removing the solvent by rotary evaporation, carrying out column chromatography on the residue (taking petroleum ether/dichloromethane mixed solution as a developing agent), and removing the solvent to obtain the reddish brown viscous catalyst LG-1 (molecular formula: C) ₅₂ H ₈₃ Cl ₂ N ₂ PRu, molecular weight: 939.19 g/mol). 3.46g (3.68 mmol) of a reddish brown viscous liquid are obtained, yield: 73.7 percent.

Analyzing data:

C ₅₂ H ₈₃ Cl ₂ N ₂ theoretical value of PRu (calculated): c,66.50 (66.61); h,8.91 (8.82); n,2.98 (2.95).

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

Example 2: preparation of 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tris (2-ethylhexyl) phosphine) ruthenium dichloride catalyst

To a dry 100mL flask was added 3.71g (5.00 mmol) of complex 2 under nitrogen, and 20mL of dichloromethane was stirred to dissolve it. Then, 2.86g (10.00 mmol) of tris (2-ethylhexyl) phosphine (formula: C) was added to the flask ₂₄ H ₅₁ P; molecular weight: 370.65 g/mol) and the reaction mixture was stirred at room temperature for 2h, the solution gradually changed from green to red brown. Removing solvent by rotary evaporation, performing column chromatography (with petroleum ether/dichloromethane mixed solution as developer) on the residue, and removing solvent to obtain reddish brown viscous catalyst LG-2 (molecular formula: C) ₅₂ H ₈₃ Cl ₂ N ₂ Pru; molecular weight 939.19 g/mol). 3.46g (3.68 mmol) of a reddish brown viscous liquid are obtained, yield: 73.7 percent.

Analyzing data:

C ₅₂ H ₈₃ Cl ₂ N ₂ theoretical value (calculated value) of Pru: c,66.50 (66.61); h,8.91 (8.82); n,2.98 (2.95).

Example 3: preparation of 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tridecylphosphine) ruthenium dichloride catalyst

To a dry 100mL flask was added 3.63g (5.00 mmol) of complex 2 under nitrogen, and 20mL of dichloromethane was stirred to dissolve it. Then, 4.55g (10.00 mmol) of tridecylphosphine (formula: C) ₃₀ H ₆₃ P; molecular weight: 454.81 g/mol) and the reaction mixture stirred at room temperature for 2h, the solution turned from green to red-brown. Removing solvent by rotary evaporation, performing column chromatography (with petroleum ether/dichloromethane mixed solution as developer) on the residue, and removing solvent to obtain reddish brown viscous catalyst LG-3 (molecular formula: C) ₅₈ H ₉₅ Cl ₂ N ₂ PRu; molecular weight: 1023.36 g/mol). 3.64g (3.56 mmol) of a reddish brown viscous liquid are obtained, yield: 71.2 percent.

Analyzing data:

C ₅₈ H ₉₅ Cl ₂ N ₂ theoretical value of PRu (calculated): c,68.07 (68.05); h,9.36 (9.33); n,2.74 (2.75).

¹ H NMR(400MHz,CDCl ₃ ):δ18.80(s.,1H,CHPh),7.81(d., ³ J＝6.46Hz.2H),7.33(t., ³ J＝7.65Hz,1H),7.04(t., ³ J＝7.80Hz,2H),6.90(s.,2H),6.24(s.,2H),4.01(m.,2H),3.85(m.,2H),2.57(s.,6H),2.23(s.,3H),2.18(s.,6H),1.86(s.,3H),1.35-0.97(br.mulitiple peaks,60H),0.78(t.,9H)。

Example 4: preparation of 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (trioctylphosphine) ruthenium dichloride catalyst

Under a nitrogen atmosphere, 1.33g (1.70 mmol) of the ruthenium compound 4, 0.63g (1.71 mmol) of trioctylphosphine and 40mL of dry n-hexane were added to the flask, and the mixture was stirred to dissolve the white solid, then the temperature was raised to 70 ℃ and the mixture was refluxed for 2.0 hours. The color of the precipitate gradually changed to reddish brown in the course of the reaction. Cooling to room temperature, performing column chromatography, eluting with petroleum ether and dichloromethane to obtain wine red solution, and spin-drying to obtain 1.41g (1.50 mmol) of brown liquid catalyst LG-1 (molecular formula: C) ₅₂ H ₈₃ Cl ₂ N ₂ PRu molecular weight: 939.19 g/mol), yield 88%.

Analyzing data:

Example 5: preparation of 1, 3-bis (2, 4, 6-trimethylphenyl) -2- (imidazolidinylidene) (benzylidene) (tris (2-ethylhexyl) phosphine) ruthenium dichloride catalyst

Under a nitrogen atmosphere, 1.33g (1.70 mmol) of the ruthenium compound 4, 0.63g (1.71 mmol) of tris (2-ethylhexyl) phosphine, and 40mL of dry n-hexane were added to the flask, and the mixture was stirred to dissolve the white solid, then the temperature was raised to 70 ℃ and the mixture was refluxed for 2.0 hours. The color of the precipitate gradually changed to reddish brown during this process. Cooling to room temperature, performing column chromatography, eluting with petroleum ether and dichloromethane to obtain wine red solution, and spin-drying to obtain 1.41g (1.50 mmol) of brown liquid catalyst LG-2 (molecular formula: C) ₅₂ H ₈₃ Cl ₂ N ₂ PRu formula 939.19 g/mol), yield 88%.

Analyzing data:

Examples 6-17 preparation of catalyst compositions

To a dry flask, ruthenium catalyst LG and a certain amount of dichloromethane were added under nitrogen or argon, and stirred to be dissolved. Then, chlorinated paraffin was added to the flask and stirred until the mixture gradually became a uniform, reddish brown solution. Removing dichloromethane by rotary evaporation to obtain the catalyst LG and chlorinated liquid paraffin solution.

/>

The mass ratio of the ruthenium catalyst LG to chlorinated paraffin is preferably 1.

The present inventors tried to dissolve commercial second generation Grubbs catalyst, the catalysts obtained in examples 1 and 2 of the present invention, respectively, in commercially available liquid paraffin. The results show that the commercial second generation Grubbs catalyst is insoluble in liquid paraffin; the catalysts obtained in examples 1 and 2 of the present invention were soluble in liquid paraffin, but the resulting catalyst compositions were gel-like substances and did not change into liquid state even when heated to 60 to 70 ℃.

A commercial second-generation Grubbs catalyst was weighed out and dissolved in a paraffin solution having a chlorine content of 52% to prepare a second-generation Grubbs catalyst solution having a concentration of 0.25 mol/L. It was found that the commercial second generation Grubbs catalysts have reduced solubility in chlorinated paraffin solutions at ambient temperatures below 10 ℃, are prone to precipitation during storage, have reduced catalytic activity, and are not conducive to industrial applications. Meanwhile, commercial second-generation Grubbs catalyst is dissolved in paraffin solution with chlorine content of 52% to prepare second-generation Grubbs catalyst solution with concentration of 0.05mol/L, and after the second-generation Grubbs catalyst solution is placed at room temperature for two weeks, more crystals are observed to be separated out; when the catalyst of the present invention was dissolved in a paraffin solution having a chlorine content of 52%, no precipitation occurred either at an ambient temperature of less than 10 ℃ or when the solution was left at room temperature for two weeks.

The chlorinated paraffin in the invention preferably has a chlorine content of 5% to 60% (mass fraction of chlorine atoms). The common chlorinated paraffin with chlorine content less than 5% has the phenomenon of gel solidification and can not be liquefied; the chlorine content is more than 60%, the viscosity of the chlorinated paraffin is too high, and even the chlorinated paraffin is in a solid state, and the liquefaction target of the catalyst cannot be realized. The molar concentration of the ruthenium carbene catalyst or a salt thereof in the chlorinated paraffin is preferably 0.08mol/L to 0.7mol/L.

Effects of the embodiment

Ruthenium metal catalysts are commonly used in olefin metathesis reactions, such as: ring-closing metathesis reaction, cross metathesis reaction or ring-opening metathesis polymerization reaction, and the results of the olefin metathesis reaction were used to evaluate the catalytic activity of the ruthenium metal catalyst.

Effect example 1: catalyst LG-1 is used for catalyzing N, N-diallyl-4-methylbenzenesulfonamide ring-closing metathesis reaction

Under nitrogen, 25.10mg of N, N-diallyl-4-methylbenzenesulfonamide and 1.0mL of freshly treated methylene chloride were added to a 5mL single-neck flask, followed by 0.188mg of the catalyst LG-1 prepared above (in a molar ratio to the reaction substrate of 0.2%) were added. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, and the residue is separated by column chromatography with petroleum ether/ethyl acetate (5. ¹ H NMR(400MHz,CDCl ₃ )δ(ppm):2.42(s,3H),4.12(d, ³ J _H-H ＝4.5Hz,4H),5.65(d, ³ J _H-H ＝4.5Hz,2H),7.32(d, ³ J _H-H ＝8.3Hz,2H),7.72(d, ³ J _H-H ＝8.3Hz,2H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7.

Effect example 2: catalyst LG-1 catalyzes allyl benzoate and styrene to carry out cross metathesis reaction

Under a nitrogen blanket, 16.2mg of allyl benzoate, 20.8mg of styrene, 1.0mL of freshly treated methylene chloride and 2.35mg of the catalyst LG-1 prepared above (in a 2.5% molar ratio to allyl benzoate) were charged to a 5mL Schlenk flask. The reaction mixture was heated to 45 ℃ and stirred for 6h. Then, the solvent was removed by rotary evaporation under reduced pressure, and the residue was separated by column chromatography to give a cross-metathesis product, phenylpropenyl benzoate, weighing 22.4mg (purity 92.7%), yield 94%. 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: catalyst/chlorinated liquid paraffin mixture HG-2 for catalyzing ring-closing metathesis reaction of N, N-diallyl-4-methylbenzenesulfonamide

To a 5mL single-neck flask, 251mg of N, N-diallyl-4-methylbenzenesulfonamide and 0.01mL (0.2 mol/L) of the catalyst/chlorinated liquid paraffin mixture HG-2 prepared above (wherein the molar ratio of the catalyst to the reaction substrate was 0.2%) were added under a nitrogen atmosphere. The reaction mixture was heated to 40 ℃ and stirred for 2h. When the reaction temperature is reduced to room temperature, the mixture is separated by column chromatography by taking petroleum ether/ethyl acetate (5). ¹ HNMR(400MHz,CDCl3)δ(ppm):2.42(s,3H),4.12(d, ³ J _H-H ＝4.5Hz,4H),5.65(d, ³ J _H-H ＝4.5Hz,2H),7.32(d, ³ J _H-H ＝8.3Hz,2H),7.72(d, ³ J _H-H ＝8.3Hz,2H)； ¹³ C NMR(100MHz,CDCl ₃ )δ(ppm):21.8,55.1,125.7,127.7,130.0,134.6,143.7。

Effect example 4: catalyst/chlorinated liquid paraffin mixture HG-2 for catalyzing allyl benzoate and styrene to carry out cross double decomposition reaction

To a 5mL Schlenk bottle were added under nitrogen, 162mg of allyl benzoate, 208mg of styrene, and 0.125mL (0.2 mol/L) of the catalyst/chlorinated liquid paraffin mixture HG-2 prepared above (which was a mixture ofThe molar ratio of the catalyst to the reaction substrate in (1) was 2.5%). The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give allyl benzoate as a cross-metathesis product, 225.9mg (92.1% purity), 94.8% yield. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d, ³ J _H-H ＝7.2Hz,2H,HAr),7.61(t, ³ J _H-H ＝7.2Hz,1H,HAr),7.50(q, ³ J _H-H ＝6.8Hz,4H,HAr),7.38(t, ³ J _H-H ＝6.8Hz,2H,HAr),7.31(t, ³ J _H-H ＝4.8Hz,1H,HAr),6.79(d, ³ J _H-H ＝16Hz,1H,Ph＝CH),6.50(dt, ³ J _H-H ＝16Hz, ³ J _H-H ＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd, ³ J _H-H ＝6.4Hz, ³ J _H-H ＝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)。

The following table compares the activities of the commercially available second-generation Grubbs catalyst 2 (GII) and the ruthenium carbene catalyst of the present invention in ring-closing metathesis and cross-metathesis reactions, and finds that the catalyst and the catalyst/chlorinated liquid paraffin mixture designed by the present invention have similar catalytic activities in catalyzing olefin ring-closing metathesis and cross-metathesis reactions with the second-generation Grubbs catalyst, which indicates that the long-carbon-chain phosphine-substituted tricyclohexylphosphine has a smaller influence on the catalytic activity of the catalyst. Meanwhile, the comparison shows that the influence of the existence of the chlorinated paraffin on the activity of the catalyst is small, and the new-structure catalyst designed in the invention can still be used under the protection of the chlorinated paraffin.

Effect examples 5 to 10:

effect examples 5, 6 and 7 the same procedure as in effect example 1 was followed, using only different catalysts, with the yields shown in the following table.

Effect examples 8, 9 and 10 the same procedure as in effect example 2 was followed, using only different catalysts, with the yields shown in the following table.

Effect example 11

Effect example this effect example differs from effect example 1 only in that the reaction was carried out in the absence of dichloromethane. It was found that ring closing metathesis using catalyst LG-1 catalyzed N, N-diallyl-4-methylbenzenesulfonamide in the absence of dichloromethane, a yield comparable to effect example 1 was achieved, indicating that chlorinated paraffins and solvents can be avoided using the catalysts of the present application.

Effect example 12

The mixture of ruthenium metal catalyst and chlorinated liquid paraffin is placed for a certain time at room temperature for stability verification

The composition HG-2 standing at room temperature for 6 months catalyzes a ring-closing metathesis reaction of N, N-diallyl-4-methylbenzenesulfonamide.

To a 5mL single-neck flask, 251mg of N, N-diallyl-4-methylbenzenesulfonamide was added under nitrogen, and 0.01mL (0.20 mol/L) of the ruthenium catalyst/chlorinated paraffin composition HG-2 was added after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. When the reaction temperature is reduced to room temperature, the reaction mixture is separated by column chromatography with petroleum ether/ethyl acetate (5).

Effect example 3 compared with effect example 11, it can be found that after the catalyst/chlorinated paraffin mixture is stored for 6 months, the catalytic activity of the HG-2 catalyst is slightly reduced compared with that of the freshly prepared chlorinated liquid paraffin mixture HG-2, but the catalytic activity is still higher, and the requirement of general catalytic reaction is met.

Effect example 13

Catalyst LG-1 catalyzes dicyclopentadiene to carry out ring-opening metathesis reaction

132g of dicyclopentadiene monomer and then 94mg of the above-prepared catalyst LG-1 (in a molar ratio to the reaction substrate of 0.01 mol%) were charged into a 250ml single-neck flask under a nitrogen blanket. Stirring until the color is uniform, defoaming the solution, pouring a mold, curing and molding by adopting a curing program of 80 ℃/3h, cooling to room temperature, and demolding to obtain a sample plate with the thickness of 4mm and smooth and flat surface. Cutting a sample to perform mechanical property test, wherein the result is as follows: the tensile strength is 58.7MPa, the tensile modulus is 2031MPa, and the elongation at break is 6.12%.

Effect example 14

Catalyst/chlorinated liquid paraffin mixture HG-2 for catalyzing dicyclopentadiene to perform ring-opening metathesis reaction

To a 250mL single-neck flask, 132g of dicyclopentadiene monomer was added under nitrogen protection, followed by 5mL of the catalyst/chlorinated liquid paraffin mixture HG-2 prepared above (in a molar ratio to the reaction substrate of 0.01 mol%). Stirring until the color is uniform, defoaming the solution, pouring a mold, curing and molding by adopting a curing program of 80 ℃/3h, cooling to room temperature, and demolding to obtain a sample plate with the thickness of 4mm and smooth and flat surface. Cutting a sample to perform mechanical property test, wherein the result is as follows: tensile strength 57.3MPa, tensile modulus 1987MPa, and elongation at break 7.92%.

For comparison with the effect case of the invention, the commercially available Grubbs secondary catalyst is used for catalyzing dicyclopentadiene to carry out ring-opening metathesis reaction, the experimental conditions are controlled to be consistent, and the mechanical properties of the finally obtained product are as follows: the tensile strength is 58.6MPa, the tensile modulus is 2035MPa, and the elongation at break is 5.34%. The three sets of data above show that: in the ring-opening metathesis reaction, the long-carbon-chain phosphine substituted tricyclohexylphosphine and chlorinated paraffin have small influence on the catalytic activity of the catalyst, and the catalyst with the new structure designed in the invention can still catalyze the ring-opening metathesis reaction under the protection of no chlorinated paraffin.

Effect example 15

In the examples of the effects, the tensile strength, tensile modulus and elongation at break of the obtained resin material were measured with reference to GB/T2567;

the notched impact strength is determined with reference to ISO-180;

the mass loss rate of the cured material compared with the used raw material =1- (mass of the obtained resin material/mass of the used raw material);

surface mark average depth determination method: and measuring all the depths of the left marks on the surface of the product by using a vernier caliper, and taking an average value.

Effect example 15.1 original formulation

Preparation of component A: adding 90 parts by mass of DCPD and 10 parts by mass of TCPD into a stirring kettle, replacing the atmosphere in the kettle with high-purity nitrogen, heating to 60 ℃, stirring for 2 hours (stirring speed: 250 rpm), cooling to room temperature, then discharging in a sealed manner, and storing the product in a raw material barrel in a nitrogen seal manner;

preparation of polycycloolefin resin material: respectively packaging the prepared component A and the component B (ruthenium carbene catalyst Ru-II) into corresponding charging pots (the tank bodies are filled with nitrogen in advance), and using special RIM equipment to carry out 500 parts of flow of the component A and the component B: 1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The resulting material had a tensile strength of 51MPa, a tensile modulus of 1902MPa, an elongation at break of 7.9% and a notched impact strength (ISO-180) of 19kJ/m ² (ii) a The mass loss rate of the cured material is 0.9wt% compared with the used raw materials; the average depth of surface scratches was 0.13mm (4 mm resin plate).

Effect example 15.2 increasing TeCPD

Preparation of component A: adding 55 parts by mass of DCPD, 35 parts by mass of TCPD and 10 parts by mass of TeCPD into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

The obtained material has the tensile strength of 56MPa, the tensile modulus of 2048MPa, the elongation at break of 6.5 percent and the notch impact strength of 14kJ/m ² (ISO-180); the mass loss rate of the cured material is 0.6wt% compared with the used raw materials; the average depth of surface scratches was 0.11mm (4 mm resin plate).

Effect example 15.3 increasing macrocyclic monomers

Preparation of component A: adding 55 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD and 5 parts by mass of PCPD into a stirring kettle, replacing the atmosphere in the kettle with high-purity nitrogen, heating to 60 ℃, stirring for 2 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

The resulting material had a tensile strength of 59MPa, a tensile modulus of 2105MPa, an elongation at break of 7.5% and a notched impact strength of 11kJ/m ² (ISO-180); the mass loss rate of the cured material is 0.5wt% compared with the used raw materials; the average depth of surface scratches was 0.10mm (4 mm resin plate).

Effect example 15.4 addition of elastomer

Preparing a component A: adding 87 parts by mass of DCPD, 8 parts by mass of TCPD, 2 parts by mass of SEBS (Kraton G1652) and 3 parts by mass of EPDM (Keltan 8550C) into a stirring kettle, heating to 80 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 24 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

The resulting material had a tensile strength of 35MPa, a tensile modulus of 1590MPa, an elongation at break of 19.5% and a notched impact strength (ISO-180) of 48kJ/m ² (ii) a The mass loss rate of the cured material is 0.3wt% compared with the used raw materials; the average depth of surface scratches was 0.08mm (4 mm resin plate).

Effect example 15.5 increasing elastomer and macrocycle

Preparation of component A: adding 50 parts by mass of DCPD, 30 parts by mass of TCPD, 10 parts by mass of TeCPD, 5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102) and 2.5 parts by mass of EPDM (Keltan 8550C) into a stirring kettle, heating to 80 ℃ after the atmosphere in the stirring kettle is high-purity nitrogen, stirring for 24 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal mode;

The obtained material has tensile strength of 43MPa, tensile modulus of 1710MPa, elongation at break of 16.6% and notched impact strength (ISO-180) of 50kJ/m ² (ii) a Compared with the used raw materials, the material has the mass loss rate of 0.3wt% after being cured; the average depth of surface marks was 0.08mm (4 mm resin plate)

Effect example 15.6 Filler addition

Preparation of component A: adding 50 parts by mass of DCPD, 25 parts by mass of TCPD, 7.5 parts by mass of TeCPD, 2.5 parts by mass of PCPD, 2.5 parts by mass of SEBS (Kraton D1102), 2.5 parts by mass of EPDM (Keltan 8550C) and 10 parts by mass of carbon black (800 meshes) into a stirring kettle, heating to 80 ℃ after the atmosphere in the stirring kettle is high-purity nitrogen, stirring for 24 hours (stirring speed: 250 rpm), cooling to room temperature, then discharging in a sealed manner, and storing the product in a raw material barrel in a nitrogen seal manner;

The resulting material had a tensile strength of 33MPa, a tensile modulus of 3015MPa and an elongation at break of 1.8%.

Effect example 15.7 addition of chopped glass fiber and color paste

Preparation of component A: adding 50 parts by mass of DCPD, 26 parts by mass of TCPD, 10 parts by mass of TeCPD, 3 parts by mass of PCPD, 2.5 parts by mass of SEPS 4030, 2.5 parts by mass of EPDM (Keltan 8550C), 5 parts by mass of glass fiber, 0.5 part by mass of black color paste (BK 9007-UC) and 0.5 part of anti-aging agent (BASF 168) into a stirring kettle, heating to 80 ℃ after the atmosphere in the kettle is high-purity nitrogen, stirring for 24 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal mode.

The resulting material had a tensile strength of 48MPa, a tensile modulus of 4525MPa and an elongation at break of 4.8%.

Effect example 15.8 storage stability test

preparation of polycycloolefin resin material: respectively packaging the prepared component A and the component B into corresponding charging pots (the tank bodies are filled with nitrogen in advance), standing for 6 months at room temperature, and then using special RIM equipment to perform 500 parts of flow of the component A and the component B: 1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The resulting material had a tensile strength of 51MPa, a tensile modulus of 1890MPa, an elongation at break of 9.2% and a notched impact strength of 19kJ/m ² (ii) a The mass loss rate of the cured material is 0.8wt% compared with the used raw materials; the average depth of surface scratches was 0.12mm (4 mm resin plate).

Comparative example 15.1G2 compares with example 1

Preparation of component A: adding 90 parts by mass of DCPD and 10 parts by mass of TCPD into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

preparing a component B: adding 10 parts by mass of Grubbs second-generation catalyst (shown as a structural formula G2) into a stirring kettle under the protection of dry nitrogen atmosphere, then injecting 90 parts by mass of dichloromethane into the stirring kettle, stirring for 10min, and discharging to a material tank corresponding to the special RIM equipment (the tank body is filled with nitrogen in advance);

preparation of polycycloolefin resin material: respectively packaging the prepared component A and the component B into corresponding material tanks (the tank bodies are filled with nitrogen in advance), and using special RIM equipment to perform the following steps of (1) preparing the component A and the component B according to the ratio of 150:1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The obtained material has a tensile strength of 51MPa, a tensile modulus of 1880MPa, an elongation at break of 5.9% and a notched impact strength of 16kJ/m ² (ii) a The mass loss rate of the cured material is 1.4wt% (VOCs) compared with the used raw materials; the average depth of surface scratches was 0.24mm (4 mm resin plate).

Comparative example 15.2 Ru-II with solution

Preparing a component A: adding 90 parts by mass of DCPD and 10 parts by mass of TCPD into a stirring kettle, heating to 60 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 2 hours (stirring speed: 250 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

preparing a component B: adding 10 parts by mass of Ru-II into a stirring kettle under the protection of dry nitrogen atmosphere, then injecting 90 parts by mass of dichloromethane into the stirring kettle, stirring for 10min, and discharging to a material tank corresponding to the special RIM equipment (the tank body is filled with nitrogen in advance);

preparation of polycycloolefin resin material: respectively packaging the prepared component A and the component B into corresponding charging pots (the tank bodies are filled with nitrogen in advance), and using special RIM equipment to enable the two streams of the component A and the component B to flow according to the flow ratio of 150:1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The resulting material had a tensile strength of 50MPa, a tensile modulus of 1892MPa, an elongation at break of 6.1% and a notched impact strength of 14kJ/m ² (ii) a Compared with the used raw materials, the material has the mass loss rate of 1.5wt% after being cured; the average depth of surface scratches was 0.24mm (4 mm resin plate).

Comparative example 15.3 comparative catalyst stability

preparing a component B: adding 10 parts by mass of Grubbs second-generation catalyst (shown as a structural formula G2) into a stirring kettle under the protection of dry nitrogen, then injecting 90 parts by mass of dichloromethane into the stirring kettle, stirring for 10min, discharging into a charging bucket corresponding to the special RIM equipment (the tank body is filled with nitrogen in advance), and standing for 24 hours;

preparation of polycycloolefin resin material: respectively packaging the prepared component A and the component B into corresponding charging pots (the tank bodies are filled with nitrogen in advance), and using special RIM equipment to perform the following steps of (1) mixing the component A and the component B according to the ratio of 20:1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The obtained material was in the form of gel.

Comparative example 15.4 Properties of pure DCPD as cycloolefin monomer

Preparation of polycycloolefin resin material: respectively packaging the component A (DCPD) and the component B (ruthenium carbene catalyst Ru-II) into corresponding charging tanks (a tank body is filled with nitrogen in advance, and the tank body is kept warm for 12 hours at 40 ℃ in advance), and using special RIM equipment to separate the A stream and the B stream according to the weight ratio of 500:1, and injecting the mixture into a mold, wherein the temperature of the mold is 80 ℃, and the curing time is 3 hours.

The resulting material had a tensile strength of 47MPa, a tensile modulus of 1762MPa, an elongation at break of 7.9% and a notched impact strength (ISO-180) of 22kJ/m ² (ii) a The mass loss rate of the cured material is 1.2wt% compared with the used raw materials; the average depth of surface scratches was 0.14mm (4 mm resin plate).

Comparative example 15.5

Preparation of component A: adding 30 parts by mass of DCPD, 40 parts by mass of TCPD, 25 parts by mass of TeCPD and 5 parts by mass of PCPD into a stirring kettle, replacing the atmosphere in the kettle with high-purity nitrogen, heating to 90 ℃, stirring for 24 hours (stirring speed: 500 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

the composition of component A thus obtained precipitates a large amount of solids at the bottom and cannot be used for the continuous production of polycycloolefin resin materials.

Comparative example 15.6

Preparation of component A: adding 60 parts by mass of DCPD, 25 parts by mass of TeCPD and 15 parts by mass of PCPD into a stirring kettle, heating to 90 ℃ after the atmosphere in the replacement kettle is high-purity nitrogen, stirring for 24 hours (stirring speed: 500 rpm), cooling to room temperature, sealing and discharging, and storing the product in a raw material barrel in a nitrogen seal manner;

a small amount of solid powder is separated out from the bottom of the composition of the component A, and the saturated solution at the upper layer is a colorless clear solution.

Effect example 16

In this effect example, the flash point was tested in accordance with GB/T261-2021.

In the embodiment with the effect, DCPD is dicyclopentadiene, TCPD is tricyclopentadiene, teCPD is tetracyclopentadiene, and PCPD is pentacyclopentadiene.

The preparation method of TCPD/TePCD/PCPD comprises the following steps:

(1) Putting 5kg of dicyclopentadiene into a reaction kettle, heating to 200 ℃ under the protection of nitrogen, and keeping for 0.5h to obtain a liquid mixture of DCPD, TCPD, teCPD and PCPD;

(2) Cooling the liquid mixture to 120 ℃, feeding the liquid mixture into a first rectifying tower, and carrying out negative pressure rectification to obtain a substance at the tower top, namely DCPD, and a tower kettle is a mixture of TCPD, teCPD and PCPD; conveying the tower bottom material to a second rectifying tower, and continuing to perform further negative pressure rectification to obtain TCPD at the tower top, wherein the tower bottom is a mixture of TeCPD and PCPD;

(3) Performing negative pressure distillation on the tower bottom material to obtain a fraction TeCPD, wherein the residue contains PCPD;

(4) And washing the residue with toluene, collecting washing liquid, and distilling off the toluene solvent by reduced pressure distillation to obtain the PCPD.

The structure of the Ru-I ruthenium carbene catalyst used in this effect example is as follows:

effect example 16.1

1. Preparing a resin composition:

preparing a component A: adding 66 parts by mass of Yannong YN-1828 bisphenol A epoxy resin (purchased from Yannong lake chemical Co., ltd. Of Jiangsu, with an epoxy value of 0.51-0.54), 18 parts by mass of DCPD, 15 parts by mass of TCPD and 1 part by mass of TPP into a mixing kettle, filling nitrogen into the mixing kettle as a protective gas, heating to 50 ℃, stirring for 1h, cooling, and then discharging in a sealed manner to a special material tank for the component A;

preparing a component B: adding 22.7 parts by mass of MNA, 72.7 parts by mass of MeTHPA and 4.6 parts by mass of DMP-30 accelerator into a mixing kettle, filling nitrogen serving as protective gas into the mixing kettle, heating to 35 ℃, stirring for 1 hour, cooling, and then discharging materials to a special material tank for the component B in a closed manner;

and C, component C: and adding a liquid ruthenium carbene catalyst Ru-I into a special material tank for the component C.

The flash points (closed cups) of the three components are:

fraction A63 deg.C

B-fraction >100 DEG C

C component >100 deg.C

2. Preparation of thermosetting resin material:

(1) 100 parts of the component A, 72 parts of the component B and 0.05 part of the component C are injected into a static mixer at room temperature (20-25 ℃) and mixed uniformly;

(2) Vacuumizing and defoaming the uniformly mixed resin;

(3) Injecting the defoamed mixed resin into a mold through a VARI process, heating to 80 ℃, and curing for 5 hours;

(4) And after the solidification is finished, cooling the die to room temperature, and demoulding to obtain the prepared thermosetting cycloolefin-epoxy resin material.

3. The material performance is as follows:

the tensile strength of the obtained material is 71.6MPa, the modulus is 3054MPa, the elongation at break is 5.1 percent (the test standard is GB/T2567-2021), and the unnotched impact strength is 24kJ/m ² (test standard ISO-180).

Effect example 17

The structure of the ruthenium carbene compound used in the effect example is as follows:

test standards, raw materials and equipment:

resin substrate plate tensile test standard: GBT 2567-2008 resin casting body performance test method

Plate specification: thickness 4mm, length 200mm and width 150mm

Testing standard of the composite material plate: GBT 1447-2005 fiber reinforced plastic tensile property test method GBT 1449-2005 fiber reinforced plastic bending property test method

Specification of the carbon fiber composite material plate: 350 x 2mm

Specification of the glass fiber composite material plate: 350 x 3.5mm

And (3) testing equipment: the material universal mechanical testing machine manufacturer: instron model: 5984

Dicyclopentadiene (DCPD): purchased from Guangdong Xinhuayue petrochemical group shares company

In the embodiment with the effect, DCPD is dicyclopentadiene, TCPD is tricyclopentadiene, teCPD is tetracyclopentadiene and PCPD is pentacyclopentadiene.

The preparation method of TCPD/TePCD/PCPD comprises the following steps:

(4) The residue was washed with toluene, and the washing liquid was collected, and the toluene solvent was distilled off by reduced pressure distillation to obtain PCPD.

The RTM and VARI processes share a set of equipment, and the equipment is formed by assembling a vacuum pump, a gas storage tank, a control panel and a gas pipe component, and a RIM process adopts a reaction injection molding machine.

Effect example 17.1

RTM (resin transfer molding) process for preparing carbon fiber reinforced resin matrix composite board

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 1:

TABLE 1

Kind of raw material	Dosage of
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Polymerization regulator: triphenylphosphine	2 portions of
Catalyst: ruthenium carbene compounds	0.05 part

(2) Preparation of the sheets and testing

Injecting the resin mixture into an RTM mold cavity in which the unidirectional carbon fiber woven cloth is placed by adopting an RTM process, and performing injection curing molding to obtain a prefabricated part; the glue injection pressure is as follows: 3bar, temperature: 80 ℃, time: 60min; the carbon fiber is 12K-T700 unidirectional fiber woven cloth, and the fiber surface density is 300g/m ² And 7 layers of woven cloth are laid in a mold cavity in a co-lamination mode, the thickness of the prefabricated part is 2mm, and the volume content of carbon fibers is about 40%. The mass percentage of the carbon fiber is about 65%.

Effect example 17.2

Carbon fiber reinforced PDCPD resin composite board prepared by RTM process

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 2:

TABLE 2

Kind of raw material	Dosage of
		DCPD	45 portions of
TCPD	30 portions of
		TeCPD	20 portions of
PCPD	5 portions of
		Polymerization regulators: triphenylphosphine and its use	4 portions of
Catalyst: ruthenium carbene compounds	0.5 portion

(2) Preparation of the sheets and testing

Injecting the resin mixture into an RTM mold cavity in which the unidirectional carbon fiber woven cloth is placed by adopting an RTM process, and performing injection curing molding to obtain a prefabricated part; the glue injection pressure is as follows: 3bar, temperature: 80 ℃, time: 60min; the carbon fiber is 12K-T700 unidirectional fiber woven cloth, and the fiber surface density is 300g/m ² And 7 layers of woven cloth are laid in a mold cavity in a co-lamination mode, the thickness of the prefabricated part is 2mm, the volume content of carbon fibers is about 40%, and the mass ratio of the fibers is about 65%.

Effect example 17.3

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 3:

TABLE 3

(2) Preparation of the sheets and testing

Effect example 17.4

RTM (resin transfer molding) process for preparing glass fiber reinforced resin matrix composite board

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 4:

TABLE 4

Kind of raw material	Amount of the composition
		DCPD	60 portions of
TCPD	30 portions of
		TeCPD	10 portions of
PCPD	0 portion of
		Polymerization regulators: triphenylphosphine	2 portions of
Catalyst: ruthenium carbene compounds	1 part of

(2) Preparation of the sheets and testing

Injecting the resin mixture into an RTM mold cavity in which the unidirectional glass fiber woven cloth is placed by adopting an RTM process, and performing injection curing molding to obtain a prefabricated part; the glue injection pressure is as follows: 3bar, temperature: 80 ℃, time: 60min; the used glass fiber is unidirectional glass fiber woven cloth with the monofilament diameter of 17um, and the fiber areal density is 1250g/m ² And 4 layers of woven cloth are laid in a mould cavity in a co-lamination mode, the thickness of the prefabricated part is 3.4mm, the volume content of glass fiber is about 50%, and the mass ratio of the fiber is about 75%.

Effect example 17.5

Glass fiber reinforced resin matrix composite board prepared by VARI process

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 5:

TABLE 5

Kind of raw material	Dosage of
		DCPD	50 portions of
TCPD	20 portions of
		TeCPD	20 portions of
PCPD	10 portions of
		Polymerization regulators: triphenylphosphine	2 portions of
Catalyst: ruthenium carbene compounds	0.5 portion

(2) Preparation of the sheets and testing

Injecting the resin mixture into a VARI mold cavity in which the unidirectional glass fiber woven cloth is placed by adopting a VARI process and utilizing vacuum negative pressure, and performing injection curing molding to obtain a prefabricated part; temperature: 80 ℃, time: 60min; the used glass fiber is unidirectional glass fiber woven cloth with the monofilament diameter of 17um, and the fiber areal density is 1250g/m ² And 4 layers of woven cloth are laid in a mould cavity in a co-lamination mode, the thickness of the prefabricated part is 3.6mm, and the volume content of the glass fiber is about 48%. The mass ratio of the fiber is about 73 percent.

Effect example 17.6

Glass fiber reinforced resin matrix composite board prepared by VARI process

DCPD modified resin by VARI process

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 6:

TABLE 6

Kind of raw material	Dosage of
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Polymerization regulators: triphenylphosphine and its use	0.76 portion
Catalyst: ruthenium carbene compounds	0.02 portion
		Bisphenol A epoxy resin	233 parts of
Epoxy curing agent: methyl tetrahydrophthalic anhydride	211 portions of
		Accelerant DMP-30	10.3 portions of

(2) Preparation of the sheets and testing

Injecting the resin mixture into a VARI die cavity with the unidirectional glass fiber woven cloth by adopting a VARI process and utilizing vacuum negative pressure, and performing injection curing molding to obtain a prefabricated part; temperature: 80 ℃, time: 60min; the used glass fiber is unidirectional glass fiber woven cloth with the monofilament diameter of 17um, and the fiber areal density is 1250g/m ² And 4 layers of woven cloth are laid in a mould cavity in a co-lamination mode, the thickness of the prefabricated part is 3.6mm, and the volume content of the glass fiber is about 48%. The mass ratio of the fiber is about 73 percent.

Effect example 17.7

Polydicyclopentadiene (PDCPD) polymer pure material resin plate

Resin mixtures were prepared according to the raw material types and added parts by mass shown in table 7:

TABLE 7

Kind of raw material	Dosage of
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Triphenylphosphine	5 portions of
Catalyst: ruthenium carbene compounds	0.5 portion

Preparing a PDCPD resin prefabricated part with the thickness of 3.8mm by closed-die injection molding of RIM equipment, wherein the molding pressure is 5bar, and the glue injection speed is about 120g/min; the article was completed with a total thickness of 4mm.

Effect example 17.8

(1) Preparing a resin mixture according to the types and the added parts by mass of the raw materials shown in the table 8:

TABLE 8

Kind of raw material	Amount of the composition
		DCPD	100 portions of
Polymerization regulators: triphenylphosphine	2 portions of
		Catalyst: ruthenium carbene compounds	0.05 part

(2) Preparation of the sheets and testing

The partial operation and conditions were the same as in example 17.1.

Comparative example 17.1

Polydicyclopentadiene (PDCPD) pure material resin plate

Resin mixtures were prepared according to the raw material types and the added parts by mass shown in table 9:

TABLE 9

Kind of raw material	Dosage of
		DCPD	100 portions of
Triphenylphosphine	5 portions of
		Commercial G2 catalyst (Sigma-Aldrich)	0.5 portion
Toluene solvent	1 part of

Preparing a PDCPD resin prefabricated part with the thickness of 3.8mm by RIM equipment closed mold injection molding, wherein the molding pressure is 5bar, and the glue injection speed is about 120g/min; forming temperature: 80 ℃, time: 60min; the article was completed with a total thickness of 4mm. Although the resin plate prepared from the PDCPD pure material resin plate has lower cost and smooth and beautiful surface, the material has poorer mechanical property and is difficult to meet the technical requirements of functionalization and light weight of an application end.

Comparative example 17.2

Resin mixtures were prepared according to the raw material types and added parts by mass shown in table 10:

TABLE 10

Kind of raw material	Dosage of
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Triphenylphosphine and its use	5 portions of
Commercial G2 catalyst (Sigma-Aldrich)	0.5 portion
		Toluene solvent	1 part of

Injecting a resin mixture into a mold cavity in which the unidirectional carbon fiber woven cloth is placed through closed mold injection molding of RTM equipment, and performing injection curing molding to obtain a prefabricated part; the carbon fiber is 12K-T700 unidirectional fiber woven cloth, and the fiber surface density is 300g/m ² 7 layers of woven cloth are laid in a mould cavity in a co-lamination mode, the thickness of the prefabricated part is 2mm, and the volume content of carbon fibers is about 40%. The mass ratio of the fiber is about 65 percent.

Comparative example 17.3

Resin mixtures were prepared according to the raw material types and the added parts by mass shown in table 11:

TABLE 11

Kind of raw material	Dosage of
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Polymerization regulators: triphenylphosphine	15 portions of
Catalyst: ruthenium carbene compounds	0.5 part of

Injecting the resin mixture into a mold cavity in which the unidirectional carbon fiber woven cloth is placed by closed mold injection molding of RTM equipment, and performing injection curing molding to obtain a prefabricated part; the carbon fiber is 12K-T700 unidirectional fiber woven cloth, and the fiber surface density is 300g/m ² And 7 layers of woven cloth are laid in a mold cavity in a co-lamination mode, the thickness of the prefabricated part is 2mm, and the volume content of carbon fibers is about 40%. The mass ratio of the fiber is about 65%.

Comparative example 17.4

Resin mixtures were prepared according to the raw material types and the added parts by mass shown in table 12:

TABLE 12

Kind of raw material	Amount of the composition
		DCPD	75 portions of
TCPD	20 portions of
		TeCPD	3 portions of
PCPD	2 portions of
		Polymerization regulators: triphenylphosphine	5 portions of
Catalyst: ruthenium carbene compounds	10 portions of

Injecting the resin mixture into the fabric containing the unidirectional carbon fibers by using RTM equipment to perform closed mold injection moldingIn the die cavity of the weaving cloth, the prefabricated part is prepared by injection, solidification and molding; the carbon fiber is 12K-T700 unidirectional fiber woven cloth, and the fiber surface density is 300g/m ² And 7 layers of woven cloth are laid in a mold cavity in a co-lamination mode, the thickness of the prefabricated part is 2mm, the volume content of carbon fibers is about 40%, and the mass ratio of the fibers is about 65%.

TABLE 13 data Performance comparison Table

The result shows that the mechanical property of the product obtained by the fiber reinforced PDCPD plate prepared by the RTM/VARI process is greatly improved compared with that of a pure resin plate, and the design requirements of higher-level thinning and light weight can be met.

Effect example 17.9:

for the plate products prepared in the examples 17.1 to 17.8 and the comparative examples 17.1 to 17.4, the flat area on the product was selected for sampling and the relevant test was completed, the surface quality of the product was evaluated, and the data and the results are shown in table 13.

Effect example 17.10:

tensile test resin plate was prepared and subjected to stability test

Effect example 17.10-1

75 parts of DCPD, 20 parts of TCPD, 3 parts of TeCPD, 2 parts of PCPD and 2 parts of polymerization regulator (triphenylphosphine) are mixed to be used as a component A;

and (2) mixing the following catalyst: 0.05 part of a ruthenium carbene compound is used as a B component.

(1) Mix A, B component and pour the mixed liquid into dull and stereotyped pouring mould, prepare and survey the board, panel thickness 4mm, the test adopts the omnipotent mechanical testing machine of material, the test standard: GBT 2567-2008, whose tensile properties were tested.

(2) The raw materials of the component A and the component B are placed for three months and then the performance of the raw materials is tested by repeating the experiment once again, and the effect data is shown in a table 14.

Effect examples 17.10-2

commercial G2 catalyst (Sigma-Aldrich) 0.05 part and toluene 1 part were used as the B component.

(2) The raw materials of the component A and the component B are placed for three months, and then the experiment is repeated to test the performance, and the effect data is shown in Table 14.

TABLE 14 mechanical Property data comparison Table

As can be seen from the effect data in table 14, the ruthenium carbene compound used in the present invention has excellent stability and still has good mechanical properties after being left for 3 months.

Effect example 18

The "parts" described in the effect examples refer to "parts by weight".

The grades of important raw material manufacturers are as follows:

liquid epoxy resin bisphenol A epoxy resin YN1828, epoxy value (0.48-0.51), 25 ℃ viscosity 11000-15000cPs, and Jiangsu Yangyang agricultural chemical production. Glycidyl amine type epoxy resin (triglycidyl p-aminophenol) S500, epoxy value (0.87-0.95), viscosity at 25 ℃ of 2000-6000cPs, produced by Nantong Xinjiang; glycidyl ester type epoxy resin (4, 5-epoxyhexane-1, 2-dicarboxylic acid diglycidyl ester) S186 having an epoxy value (0.83-1) and a viscosity of 2000-3500cPs at 25 ℃ manufactured by Nantong Xinxinna; alicyclic epoxy resin (bis (7-oxabicyclo [4.1.0] -3-heptamethyl) adipate) S28, epoxy value (0.47-0.53), viscosity at 25 ℃ of 400-750cPs, produced by Nantong Xinjiang.

The solid epoxy resin is bisphenol A epoxy resin YN2301, the epoxy equivalent is 479.4g/mol (the epoxy value is 0.21), the softening point is 66 ℃, and the solid epoxy resin is produced by Jiangsu Yangyang agricultural chemical industry; bisphenol A epoxy resin NPES301 with an epoxy value of 0.2-0.22 and a softening point of 63 ℃ is produced in south Asia; novolac epoxy resin (o-cresol epoxy resin) NPCN702 with an epoxy value of 0.46-0.53 and a softening point of 70 ℃ is produced in south Asia.

The organic urea accelerator is a UR2T curing accelerator product produced in air chemical industry.

Defoaming agent: BYKA530, an antifoaming agent of birk chemistry.

Wetting and dispersing agent: BYKW9010, a wetting dispersant from birk chemistry.

Coupling agent: KH560 as coupling agent for new Nanjing Needde material.

Manufacturer of dicyclopentadiene: guangdong Xinhuayue petrochemical company Limited.

The preparation process of Tricyclopentadiene (TCPD) adopted in the effect example is as follows:

(1) Adding 5kg of dicyclopentadiene (DCPD) of the Guangdong Xinhuayue petrochemical Co., ltd into a reaction kettle, heating to 200 ℃ under the protection of nitrogen, and keeping for 0.5h to obtain a liquid mixture of the DCPD, the TCPD, the TeCPD and the PCPD;

(2) Cooling the liquid mixture to 120 ℃, feeding the liquid mixture into a first rectifying tower, and carrying out negative pressure rectification to obtain a substance at the tower top, namely DCPD, and a tower kettle is a mixture of TCPD, teCPD and PCPD; and (4) conveying the tower bottom material to a second rectifying tower, and continuing to perform further negative pressure rectification to obtain TCPD at the tower top.

Except for the above specific description, the reagents used in the effect examples are all products produced by any manufacturers.

The preparation of the components A and B in the effect examples is not particularly limited as long as the dispersibility is good.

The specific structural formula of the modified ruthenium carbene catalyst (novel P ligand ruthenium carbene catalyst) used in the effect example is as follows:

effect example 18.1

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 55 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 35 parts of liquid epoxy resin YN1828, 24 parts of TCPD, and 22 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010,0.8 part of coupling agent KH560, 10 parts of organic toughening agent butadiene-styrene-methyl methacrylate block copolymer and 10 parts of inorganic toughening agent calcium carbonate), and uniformly stirring for later use;

and B component: adding 5.53 parts of dicyandiamide as an epoxy curing agent, 2.01 parts of UR2T as an accelerator and 0.06 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 70 μm, the pitch of the back roller is 80 μm, and the rotating speed is 40r/min.

Mixing the components A and B: adding the component B into the component A, and dispersing for 25min at 50 ℃ by using a high-speed dispersion machine (the rotating speed is 700 r/min) to uniformly mix, wherein the viscosity of the cycloolefin/epoxy resin mixture is 25500cPs at 70 ℃.

Preparing a fiber prepreg finished product:

unidirectional carbon fibers with the fiber areal density of 150gsm are selected, and a prepreg with the resin content of 36% is produced by adopting a conventional melt impregnation method.

Preparing a composite material:

cutting a plurality of carbon fiber prepregs, and carrying out compression molding under the process conditions of 80 ℃/1h +120 ℃/1h +140 ℃/1h and 1MPa pressure. The mechanical properties of the composite material obtained are shown in Table 5-1.

Effect example 18.2

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD and 12 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010,0.8 part of coupling agent KH560 and 10 parts of organic toughening agent butadiene-styrene-methyl methacrylate block copolymer) and uniformly stirring for later use;

and B component: adding 5.18 parts of dicyandiamide as an epoxy curing agent, 1.73 parts of an accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The mixing process of the A/B components was the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture was 24000cPs at 70 ℃.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those of the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 5-1.

Effect example 18.3

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: adding 5.18 parts of dicyandiamide epoxy curing agent, 1.73 parts of accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The mixing process of the A/B components was the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture was 23000cPs at 70 ℃.

Effect example 18.4

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 65 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy resin YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.18 parts of dicyandiamide as an epoxy curing agent, 1.73 parts of an accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the front roller interval is 25um, the back roll interval is 35um, and the rotational speed is 60r/min.

The A/B component mixing process is the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ is 23000cPs.

The preparation process of the fiber prepreg finished product is the same as that of the embodiment 18.1.

Preparing a composite material:

cutting a plurality of carbon fiber prepregs, and carrying out compression molding under the process conditions of 80 ℃/1h +120 ℃/2h and 1MPa pressure. The mechanical properties of the composite are shown in Table 5-1.

Effect example 18.5

Preparation of cycloolefin/epoxy resin mixture:

and B component: adding 5.18 parts of dicyandiamide as an epoxy curing agent, 1.73 parts of UR2T as an accelerant and 0.005 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

Effect example 18.6

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 80 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 10 parts of liquid epoxy resin YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

The same effect as in example 18.1 was obtained by mixing the A/B components in such a manner that the cycloolefin/epoxy resin mixture had 54000cPs at 70 ℃.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those of the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 5-2.

Effect example 18.7

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 75 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 15 parts of liquid epoxy resin S-28, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: adding 5.25 parts of dicyandiamide as an epoxy curing agent, 1.76 parts of UR2T as an accelerant and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin S-28, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the back roller is 35 μm, and the rotating speed is 60r/min.

The process for mixing the A/B components is as described in example 18.1, the viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ being 20000cPs.

Effect example 18.8

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy resin YN1828, 15 parts of DCPD and 2 parts of other additives (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.18 parts of dicyandiamide as an epoxy curing agent, 1.73 parts of an accelerant UR2T and 0.041 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

Effect example 18.9

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 75 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 15 parts of liquid epoxy resin S-500, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: adding 5.3 parts of dicyandiamide epoxy curing agent, 1.78 parts of accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the back roller is 35 μm, and the rotating speed is 60r/min.

The A/B component mixing procedure is as in example 18.1, with a viscosity of the cycloolefin/epoxy resin mixture of 28000cPs at 70 ℃.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those of the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 4-1.

Effect example 18.10

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: melting 75 parts of solid epoxy resin NPES301 at 120-150 ℃; cooling to 80-100 ℃, adding 15 parts of liquid epoxy resin S-186, 15 parts of TCPD and 2 parts of other additives (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.3 parts of dicyandiamide as an epoxy curing agent, 1.78 parts of UR2T as an accelerant and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin S-186, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The A/B component mixing procedure is as in example 18.1, with a viscosity of the cycloolefin/epoxy resin mixture of 23500cPs at 70 ℃.

Effect example 18.11

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: 60 parts of solid epoxy resin NPCN702 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 30 parts of liquid epoxy resin YN1828, 10 parts of DCPD, 5 parts of TCPD and 2 parts of other additives (comprising 0.6 part of defoamer BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.3 parts of dicyandiamide as an epoxy curing agent, 1.78 parts of an accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The process for mixing the A/B components is the same as that of example 18.1, the viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ is 21000cPs.

Effect example 18.12

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: melting 55 parts of solid epoxy resin YN2301 and 20 parts of solid epoxy resin NPES301 at 120-150 ℃; cooling to 80-100 ℃, adding 15 parts of liquid epoxy resin S-500, 15 parts of norbornene NB and 2 parts of other additives (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.3 parts of dicyandiamide as an epoxy curing agent, 1.78 parts of UR2T as an accelerant and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin S-500, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The process for mixing the components A/B is the same as that of example 18.1, the viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ being 20500cPs.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those in the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 4-1.

Effect example 18.13

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy resin YN1828, 10 parts of TCPD, 5 parts of norbornene NB and 2 parts of other additives (comprising 0.6 part of defoamer BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560), and uniformly stirring for later use;

The mixing process of the A/B components was the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture was 21500cPs at 70 ℃.

Effect example 18.14

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy YN1828, 15 parts of TCPD and 1.4 parts of other auxiliary agents (comprising 0.2 part of antifoaming agent, 0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.18 parts of dicyandiamide as an epoxy curing agent, 1.73 parts of an accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the back roller is 35 μm, and the rotating speed is 60r/min.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those of the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 4-2.

Effect example 18.15

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 40 parts of solid epoxy resin YN2301 and 20 parts of tetrabrominated epoxy resin NPEB-400 at 120-150 ℃; cooling to 80-100 ℃, adding 30 parts of liquid epoxy YN1828, 15 parts of TCPD,40 parts of aluminum hydroxide and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560), and uniformly stirring for later use;

and B component: adding 4.2 parts of dicyandiamide as an epoxy curing agent, 1.53 parts of an accelerant UR2T and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 45 μm, the pitch of the rear roller is 55 μm, and the rotation speed is 40r/min.

The process for mixing the components A/B is the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ is 34000cPs.

Preparing a high-flame-retardant fiber prepreg finished product:

unidirectional glass fibers with a fiber areal density of 400gsm were selected and a conventional melt impregnation process was used to produce a prepreg with a resin content of 40%.

Preparing a composite material:

cutting a plurality of pieces of glass fiber prepreg, and carrying out compression molding under the process conditions of 80 ℃/1h +120 ℃/1h +140 ℃/1h and 1MPa pressure.

The mechanical properties of the composite material are as follows: the tensile strength is 525MPa, the tensile modulus is 25GPa, the elongation at break is 1.7 percent, and the impact strength is 153KJ/m ² . UL94 tests reach V0.

Comparative example 18.1

Preparation of epoxy resin mixture:

the component A comprises: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy YN1828 and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: adding 5.18 parts of dicyandiamide epoxy curing agent and 1.73 parts of accelerant UR2T into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The A/B component mixing process was the same as that of example 18.1, and the viscosity of the epoxy resin mixture at 70 ℃ was 26000cPs.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those in the embodiment 18.4 with the effect. The mechanical properties of the composite material prepared therefrom are shown in Table 4-2.

Comparative example 18.2

Preparation of epoxy resin mixture:

and (2) component A: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy YN1828 and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.18 parts of dicyandiamide epoxy curing agent and 1.73 parts of accelerant UR2T into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The preparation process of the fiber prepreg finished product and the preparation process of the composite material are the same as those in the embodiment 18.1. The mechanical properties of the composite material prepared therefrom are shown in Table 4-2.

Comparative example 18.3

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

Comparative example 18.4

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: 65 parts of solid epoxy resin YN2301 is melted at 120-150 ℃; cooling to 80-100 ℃, adding 25 parts of liquid epoxy YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: 5.18 parts of dicyandiamide epoxy hardener, 1.73 parts of an accelerator UR2T and 0.0375 part of commercially available Grubbs2 ^nd The catalyst is added into 10 parts of liquid epoxy resin YN1828, and after being uniformly stirred, the mixture is ground for 2 to 3 times by a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The A/B component mixing process was the same as that of example 18.1, and the viscosity of the cycloolefin/epoxy resin mixture was 24000cPs at 70 ℃.

When the B component is added to the A component, the resin system undergoes depolymerization. The reason for this is that the commercial Grubbs' second generation catalyst is a solid powder, has poor compatibility with liquid epoxy resins, is difficult to disperse uniformly in the epoxy, and undergoes immediate depolymerization upon mixing with the TCPD in component A.

Comparative example 18.5

Preparation of cycloolefin/epoxy resin mixture:

and (2) component A: melting 90 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and the component B comprises: adding 4.31 parts of dicyandiamide as an epoxy curing agent, 1.24 parts of UR2T as an accelerant and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the rear roller is 35 μm, and the rotation speed is 60r/min.

The mixing process of the A/B components was as in example 18.1, the viscosity of the cycloolefin/epoxy resin mixture was 130000cPs at 70 ℃.

The viscosity of the cycloolefin/epoxy resin mixture at 70 ℃ is too high and is much higher than the viscosity (10000-40000 cPs) required by the prepreg preparation process, so that the preparation of a prepreg finished product cannot be carried out.

Comparative example 18.6

Preparation of cycloolefin/epoxy resin mixture:

the component A comprises: melting 45 parts of solid epoxy resin YN2301 at 120-150 ℃; cooling to 80-100 ℃, adding 45 parts of liquid epoxy YN1828, 15 parts of TCPD and 2 parts of other auxiliary agents (comprising 0.6 part of defoaming agent BYKA530,0.6 part of wetting dispersant BYKW9010 and 0.8 part of coupling agent KH 560) and uniformly stirring for later use;

and B component: adding 5.86 parts of dicyandiamide as an epoxy curing agent, 2.37 parts of UR2T as an accelerator and 0.038 part of modified ruthenium carbene catalyst into 10 parts of liquid epoxy resin YN1828, uniformly stirring, and grinding for 2-3 times by using a three-roll grinder. The roll spacing of the three-roll grinder is controlled in the process as follows: the pitch of the front roller is 25 μm, the pitch of the back roller is 35 μm, and the rotating speed is 60r/min.

The A/B component mixing procedure is as in example 18.1, with a viscosity of the cycloolefin/epoxy resin mixture of 8000cPs at 70 ℃.

The viscosity of the cycloolefin/epoxy mixture at 70 ℃ is too low and the resin content of the finished prepreg is less than 20% by weight, which does not meet the required prepreg resin content criteria (typically the resin content is controlled to be 25-40% by weight).

Effects examples 18.1 to 18.15 and comparative examples 18.1 to 18.6 are given in the following tables 18.1 to 18.3 with respect to the main condition parameters.

TABLE 18.1 Condition parameters relating to the preparation of component A

/>

/>

/>

TABLE 18.2 Condition parameters relating to the preparation of component B

/>

Table 18.3 conditional parameters relating to composite preparation

/>

Remarking: in table 3 "/" indicates that the parameter is not set.

Effect example 18.16

Test objects: effects the composite materials obtained in examples 18.1 to 18.15 and comparative examples 18.1 to 18.6.

The test method comprises the following steps: the test criteria for tensile properties (e.g. tensile strength, tensile modulus, elongation at break) are: ASTM D3039, impact performance (e.g., impact strength) test standards are: ISO180.

Evaluation method of warp deformation: the composite material was placed on a flat table top and the warpage height of one side was visually observed for comparison. Whether warping is used for the appearance description. Examples 18.1 to 18.4, 18.6 to 18.15, no substantial buckling deformation occurred; example 18.5: micro buckling deformation; comparative examples 18.1 to 18.3: significant warpage.

And (3) testing results: as shown in tables 4-1 and 4-2 below.

TABLE 4-1 summary of mechanical Properties of the composites obtained in the examples

Remarking: a in Table 4-1: indicating that substantially no buckling deformation occurred; b: indicating a slight warp deformation.

TABLE 4-2 summary of mechanical properties of the composites prepared in the examples

Remarking: a in Table 4-2: indicating that substantially no buckling deformation occurred. Effect examples 18.1 to 18.15 are all carbon fiber prepregs, and effect example 18.15 is a glass fiber prepreg.

TABLE 4-3 summary of mechanical properties of composites prepared in comparative examples

Remarking: the "/" in tables 4-3 indicates that the data could not be measured. C: indicating significant buckling deformation. The comparative examples above are all carbon fiber prepregs.

From the above tables, it can be seen that:

this effect example 18.1 can be compared as a comparative example;

effect example 18.1 compared with effect example 18.2, in effect example 18.1, the inorganic toughening agent is added and well dispersed in the resin system, and can also play a role in reinforcement.

Effect example 18.1 compared with effect example 18.3, when the organic/inorganic toughening agent was added, the toughening effect and tensile property were close to those of effect example 18.3.

Compared with effect example 18.3, the fiber prepreg in effect example 18.4 is cured at 80 ℃/1h +120 ℃/2h, and the mechanical properties are basically consistent with those of effect example 18.3.

Compared with the effect example 18.3, the effect example 18.5 has the advantage that the TCPD is not completely cured due to the small addition amount of the modified ruthenium carbene catalyst, and the mechanical property is obviously reduced. In contrast, comparative example 18.3, in which no catalyst was added, had poorer mechanical properties.

Compared with the effect example 18.3, the effect example 18.6 has the advantages that the viscosity is higher than the viscosity (10000-40000 cPs) required by the prepreg preparation process, so that a lot of dry yarns appear in the preparation process of a prepreg finished product, the porosity is increased, and the mechanical property of the composite material is poor.

Effect example 18.7 had a slight decrease in tensile strength and a slight increase in modulus compared to effect example 18.3, which is related to the properties of the liquid epoxy resin itself.

Effect example 18.8 showed a decrease in tensile strength and modulus and substantially the same impact strength as effect example 18.3.

Compared with comparative example 18.2, the epoxy reinforced fiber prepreg in comparative example 18.1 is not cured sufficiently at 80 ℃/1h +120 ℃/2h, and the tensile strength and modulus are obviously reduced compared with comparative example 18.2.

Effect example 18.1 compared to comparative example 18.2, the inorganic toughening agent synergistically toughens the epoxy resin with the cycloolefin resin and the organic toughening agent, so that the impact strength of the prepreg product is improved. The organic flexibilizer and the cycloolefin are added simultaneously, so that the impact strength of the product is improved by 15.6 percent, the amplitude is larger, but the tensile strength is reduced by 5.07 percent.

Compared with the comparative example 18.2, the organic toughening agent is added with the cycloolefin resin at the same time, so that the impact strength of the product is obviously improved by 19.5%, but the tensile strength is reduced by 9.4%. The results show that the organic toughening agent seriously loses the tensile strength of the product when improving the impact toughness of the product

Compared with the comparative example 18.2, the effect of toughening can be achieved by only adding 15 parts of tricyclopentadiene in the example 18.3, the impact strength is improved by 17.7%, and the tensile strength is only reduced by 1.98%, which shows that the tricyclopentadiene can improve the impact toughness of the product while the tensile strength of the product is not changed basically.

Compared with the effect example 18.3, in the comparative example 18.3, the tricyclopentadiene is added, but the ruthenium carbene catalyst with the novel P ligand in the corresponding proportion is not added, so that the composite plate is insufficiently cured in the mould pressing process, and the tensile property is integrally lower.

In contrast to effect example 18.3, the commercial Grubbs' secondary catalyst used in comparative example 18.4, when added to the resin mixture, immediately exposed to depolymerization with TCPD and failed to produce a prepreg.

The viscosity of the cycloolefin/epoxy resin mixture prepared in comparative example 18.5 at 70 ℃ is too high and is much higher than the viscosity (10000-40000 cPs) required by the prepreg preparation process, and the preparation of the prepreg finished product cannot be carried out.

Comparative example 18.6 the cycloolefin/epoxy resin mixture prepared had too low a viscosity at 70 c and had a resin content in the finished prepreg of less than 20% by weight and failed to meet the required resin content standards for prepregs (typically the resin content was controlled at 25-40% by weight).

Comparative example 1

To a dry 100mL flask was added 3.63g (5.00 mmol) of complex 2 under nitrogen, and 20mL of dichloromethane was stirred to dissolve it. Then, 0.76g (10.00 mmol) of trimethylphosphine (Cf: C) was added to the flask ₃ H ₉ P; mw:76.0 g/mol) and the reaction mixture was stirred at room temperature 2h. During this process, the solution gradually changed from green to brownish red. After the reaction was completed, the solvent was removed by rotary evaporation to obtain 2.42g (Cf: C) of solid particles ₃₁ H ₄₁ Cl ₂ N ₂ PRu Mw:644.54 g/mol). The obtained product is solid and does not meet the liquid requirement.

Claims

1. A ruthenium carbene compound represented by the formula LG or a salt thereof,

2. The ruthenium carbene compound, or a salt thereof, according to claim 1, having the formula LG, wherein it satisfies one or more of the following conditions:

(1) Said C is ₆ -C ₁₈ Alkyl is independently C ₆ -C ₁₀ Alkyl, preferably C ₆ Alkyl radical, C ₈ Alkyl or C ₁₀ An alkyl group; more preferably C ₈ Alkyl or C ₁₀ An alkyl group; and

(2) Said R is ₁ 、R ₂ And R ₃ The same or different.

3. The ruthenium carbene compound, or a salt thereof, according to formula LG of claim 2, characterized in that it satisfies one or more of the following conditions:

(1) Said C is ₆ Alkyl is n-hexyl or 4-methylpentyl;

(2) Said C is ₈ Alkyl is n-octyl, 2-ethylhexyl or 5-methylheptyl; preferably 2-ethylhexyl; and

(3) Said C is ₁₀ The alkyl group is an n-decyl group.

4. The ruthenium carbene compound according to formula LG, or a salt thereof, according to claim 1, wherein the ruthenium carbene compound according to formula LG is selected from any one of the following structures:

5. a process for the preparation of a ruthenium carbene compound according to formula LG as claimed in any of claims 1 to 4, which comprises the following process one or process two:

wherein R is ₁ 、R ₂ And R ₃ Is as defined in any one of claims 1 to 4.

6. A process for the preparation of a ruthenium carbene compound according to formula LG as claimed in claim 5, characterized in that it satisfies one or more of the following conditions:

(1) In the first method, the organic solvent is a halogenated alkane solvent, preferably dichloromethane;

(2) In the first method, the inert atmosphere is nitrogen;

(3) In process one, the molar ratio of compound 3 to compound 2 is (1 to 10): 1, preferably 2;

(4) In the first method, the volume mol ratio of the organic solvent to the compound 2 is 2L/mol to 8L/mol, preferably 4L/mol;

(5) In the first method, the reaction temperature of the substitution reaction is room temperature;

(6) In the first method, the reaction time of the substitution reaction is 1 to 5 hours, preferably 2 hours;

(7) The first method also comprises the following post-processing steps: performing rotary evaporation and/or column chromatography (preferably using petroleum ether/dichloromethane mixed solution as a developing agent);

(8) In the second method, the organic solvent is an alkane solvent, such as n-hexane;

(9) In method two, the molar ratio of compound 3 to compound 4 is (1 to 5): 1, preferably 1;

(10) In the second method, the volume molar ratio of the organic solvent to the compound 4 is 10L/mol to 50L/mol, preferably 23.5L/mol;

(11) In the second method, the reaction temperature of the substitution reaction is 30-100 ℃, and preferably 70 ℃;

(12) In the second method, the reaction time of the substitution reaction is 1h to 5h, preferably 2h; and

(13) The second method also comprises the following post-processing steps: cooling (preferably to room temperature), column chromatography (preferably with a petroleum ether/dichloromethane mixed solution as a developing solvent), and rotary evaporation.

7. The method for preparing the ruthenium carbene compound represented by the formula LG according to claim 5, further comprising the following steps: under an inert atmosphere, carrying out substitution reaction on the compound 1 and pyridine as shown in the specification;

8. the process for the preparation of a ruthenium carbene compound according to formula LG of claim 7, characterized in that it satisfies one or more of the following conditions:

(1) The pyridine is anhydrous pyridine;

(2) The inert atmosphere is nitrogen;

(3) The volume molar ratio of the pyridine to the compound 1 is 2L/mol to 20L/mol, preferably 5L/mol;

(4) The reaction temperature of the substitution reaction is room temperature;

(5) The reaction time of the substitution reaction is 2h to 10h, preferably 5h;

(6) The substitution reaction is carried out under the condition of stirring; and

(7) The substitution reaction also includes the following post-treatment steps: precipitation (preferably with petroleum ether), filtration, washing (preferably with petroleum ether) and drying (preferably vacuum drying).

9. A catalyst composition comprising a ruthenium carbene compound according to formula LG as described in any one of claims 1 to 4 or a salt thereof, and a chlorinated paraffin.

10. The catalyst composition of claim 9, wherein one or more of the following conditions are met:

(1) The chlorine content of the chlorinated paraffin is 5-60%, and the percentage refers to the mass fraction of chlorine atoms in the chlorinated paraffin; e.g., 5%, 27%, 52%, or 60%; and

(2) The molar concentration of the ruthenium carbene compound or the salt thereof in the chlorinated paraffin is 0.08-0.7 mol/L; for example, 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, or 0.6mol/L.

11. The catalyst composition of claim 9, wherein the catalyst composition is selected from any combination of:

combination 1:

and chlorinated paraffin, the chlorinated paraffin having a chlorine content of 5%, 27%, 52% or 60%;

and (3) combination 2:

and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 5%; or->

And (3) combination:

12. The catalyst composition of claim 11, wherein the catalyst composition is selected from any combination of:

and (4) combination:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

and (3) combination 5:

and chlorinated paraffin with a chlorine content of 27%; is/are>

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

and (4) combination 6:

and chlorinated paraffin with a chlorine content of 52%; is/are>

The molar concentration in the chlorinated paraffin is 0.4mol/L;

and (3) combination 7:

and chlorinated paraffin having a chlorine content of 60%; is/are>

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

And (4) combination 8:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 9:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 10:

and chlorinated paraffin with a chlorine content of 5%; is/are>

The molar concentration in the chlorinated paraffin is 0.5mol/L;

combination 11:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 12:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

Combination 13:

and chlorinated paraffin with a chlorine content of 5%; is/are>

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

combination 14:

and chlorinated paraffin with a chlorine content of 5%; is/are>

The molar concentration in the chlorinated paraffin is 0.45mol/L; or

And (3) combining 15:

and chlorinated paraffin with a chlorine content of 5%; is/are>

The molar concentration in the chlorinated paraffin was 0.6mol/L.

13. A process for preparing a catalyst composition as claimed in any one of claims 9 to 12, comprising the steps of: and mixing the ruthenium carbene compound shown as the formula LG or the salt thereof with chlorinated paraffin in an inert atmosphere.

14. A process for preparing the catalyst composition of claim 13, wherein one or more of the following conditions are met:

(1) The inert atmosphere is nitrogen or argon;

(2) The preparation method of the catalyst composition also comprises the steps of using halogenated alkane; the halogenated alkane is preferably dichloromethane;

(3) The mixing mode is stirring; and

(4) When the preparation method of the catalyst composition further comprises the use of halogenated alkane, the preparation method of the catalyst composition sequentially comprises the steps of sequentially adding the ruthenium carbene compound shown as the formula LG or the salt thereof, the halogenated alkane and the chlorinated paraffin;

(5) The preparation method of the catalyst composition also comprises the following post-treatment steps: and (5) performing rotary steaming.

15. Use of a ruthenium carbene compound according to formula LG as described in any one of claims 1 to 4 or a salt thereof or a catalyst composition according to any one of claims 9 to 12 in an olefin metathesis reaction;

the olefin metathesis reaction is preferably a ring-closing metathesis reaction, a cross-metathesis reaction or a ring-opening metathesis polymerization reaction.

16. Use according to claim 15, characterized in that it satisfies one or more of the following conditions:

(1) The ring-closing metathesis reaction comprises the following steps: carrying out ring-closing metathesis reaction on a compound shown as a formula A1 in the presence of a catalyst in an inert atmosphere to obtain a compound shown as a formula A2, wherein the catalyst is a ruthenium carbene compound shown as a formula LG in the claim 15 or a salt thereof or a catalyst composition in the claim 15;

wherein X is O, S, -N (R) ⁷ )-、-C(R ⁸ )(R ⁹ )-

R ⁷ Is hydrogen, C ₁ -C ₆ Alkyl, -S (= O) ₂ R ^7-1 、-C(＝O)R ^7-2 OR-C (= O) OR ^7-3 ；

Or, R ⁸ And R ⁹ With atoms in between them forming unsubstituted or substituted by 1,2 or 3R ^8-3 The substituted heteroatom is selected from one or more of N, O and S, and the number of the heteroatoms is 1,2 or 3;

R ^7-1 、R ^7-2 、R ^7-3 、R ^8-1 and R ^8-2 Independently of one another is hydrogen, C ₁ -C ₆ Alkyl or unsubstituted or substituted by 1,2 or 3R ^7-1-1 Substituted C ₆ -C ₁₀ An aryl group;

n1 and n2 are independently 0, 1,2 or 3;

preferably, X is-N (R) ⁷ )-；R ⁷ to-S (= O) ₂ R ^7-1 ；

R ^7-1 Is unsubstituted or substituted by 1,2 or 3R ^7-1-1 Substituted C ₆ -C ₁₀ An aryl group;

each R ^7-1-1 Are each independently C ₁ -C ₆ An alkyl group;

(2) The cross-metathesis reaction comprises the steps of: subjecting a compound containing a fragment B1 and a compound containing a fragment B2 to cross metathesis reaction in the presence of a catalyst in an inert atmosphere to obtain a compound containing a fragment B3, wherein the catalyst is a ruthenium carbene compound represented by the formula LG or a salt thereof according to claim 15 or a catalyst composition according to claim 15;

(3) The ring-opening metathesis polymerization reaction includes the steps of: in an inert atmosphere, in the presence of a catalyst, carrying out ring-opening metathesis polymerization reaction on a compound containing a fragment C1 as shown in the specification to obtain a compound containing a fragment C2; the catalyst is the ruthenium carbene compound shown as the formula LG or the salt thereof in the claim 15 or the catalyst composition in the claim 15,

ring A is 3-15 membered ring olefin containing 1,2 or 3 olefinic bonds;

n≥3。

17. use according to claim 16, characterized in that it satisfies one or more of the following conditions:

(1) The compound shown as the formula A1 is

/>

(2) The ring-closing metathesis reaction is carried out under the condition of no solvent or with solvent;

(3) When the ring-closing metathesis reaction is carried out in the presence of a solvent, the solvent is a haloalkane solvent, preferably dichloromethane;

(4) In the ring-closing double decomposition reaction, the inert atmosphere is nitrogen;

(5) In the ring-closing metathesis reaction, when the catalyst is the ruthenium carbene compound shown in the formula LG or the salt thereof, the ruthenium carbene compound shown in the formula LG is

(6) In the ring-closing metathesis reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5;

(7) The molar ratio of the ruthenium carbene compound shown as the formula LG or the salt thereof or the ruthenium carbene compound shown as the formula LG to the compound shown as the formula A1 in the catalyst composition is (0.01-1%): 1, preferably 0.2%:1;

(8) The reaction temperature of the ring-closing metathesis reaction is 30 ℃ to 100 ℃, preferably 40 ℃;

(9) The reaction temperature of the ring-closing metathesis reaction is 1h to 5h, preferably 2h;

(10) The ring-closing metathesis reaction further comprises the following post-treatment steps: column chromatography (preferably using petroleum ether/ethyl acetate (5); and

(11) When the ring-closing metathesis reaction is carried out in the presence of a solvent, the post-treatment step further comprises rotary evaporation and/or column chromatography.

18. Use according to claim 16, characterized in that it satisfies one or more of the following conditions:

(1) The compound containing the fragment B1 and the compound containing the fragment B2 are independently

Wherein R is ⁴ Is C ₁ -C ₆ Alkyl, - (CH) ₂ ) _n3 -OC(＝O)-R ^4-1 Or, unsubstituted or substituted by 1,2 or 3R ^4-2 Substituted C ₆ -C ₁₀ An aryl group;

n3 is 0, 1 or 2;

R ^4-1 is unsubstituted or substituted by 1,2 or 3R ^4-1-1 Substituted C ₆ -C ₁₀ An aryl group;

R ^4-2 and R ^4-1-1 Independently is hydroxy or C ₁ -C ₆ An alkyl group;

preferably, the compound containing segment B1 and the compound containing segment B2 are independently

(2) The compound containing fragment B1 and the compound containing fragment B2 are the same or different;

(3) The cross-metathesis reaction is carried out under solventless or solvent conditions;

(4) When the cross-metathesis reaction is carried out in the presence of a solvent, the solvent is a haloalkane solvent, preferably dichloromethane;

(5) In the cross double decomposition reaction, the inert atmosphere is nitrogen;

(6) In the cross metathesis reaction, when the catalyst is the ruthenium carbene compound shown in the formula LG or the salt thereof, the ruthenium carbene compound shown in the formula LG is

(7) In the cross-metathesis reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5;

(8) The ruthenium carbene compound or the salt thereof shown in the formula LG or the ruthenium carbene compound shown in the formula LG in the catalyst composition or the catalyst composition has the molar ratio of (0.1% to 10%) 1, preferably 2.5% to 1;

(9) The molar ratio of the compound containing the fragment B2 to the compound containing the fragment B1 is (1 to 5) 1, preferably 2;

(10) The reaction temperature of the cross-metathesis reaction is from 30 ℃ to 100 ℃, preferably 45 ℃;

(11) The reaction time of the cross metathesis reaction is 4 to 20h, preferably 6h; and

(12) When the cross-metathesis reaction is carried out in the presence of a solvent, the post-treatment step further comprises reduced pressure rotary evaporation and/or column chromatography.

19. Use according to claim 16, characterized in that it satisfies one or more of the following conditions:

(1) The ring-opening metathesis polymerization reaction is carried out under the condition of no solvent;

(2) The compound containing the tablet C1 is

Wherein R is ⁵ And R ⁶ Independently of one another hydrogen, halogen, C ₁ -C ₆ Alkyl or C ₁ -C ₆ An alkoxy group;

ring A is 3-8 membered monocyclic cycloalkene containing 1,2 or 3 olefinic bonds, or 6-15 membered polycyclic cycloalkene containing 1,2 or 3 olefinic bonds;

preferably, the compound containing the fragment C1 is

R ⁵ And R ⁶ Is hydrogen;

ring A is 7-10 membered polycyclic cyclic olefin containing 1,2 or 3 olefinic bonds;

further preferably, the compound containing tablet C1 is

(3) In the ring-opening metathesis polymerization reaction, the inert atmosphere is nitrogen;

(4) In the ring-opening metathesis polymerization reaction, when the catalyst is the ruthenium carbene compound shown in the formula LG or the salt thereof, the ruthenium carbene compound shown in the formula LG is

Preferably->

(5) In the ring-opening metathesis polymerization reaction, when the catalyst is the catalyst composition, the catalyst composition is the combination 5; and

(6) The molar ratio of the ruthenium carbene compound shown as the formula LG or the salt thereof or the ruthenium carbene compound shown as the formula LG to the compound shown as the formula C1 in the catalyst composition is (0.01-1%): 1, preferably 0.01%:1.