CN112547126B

CN112547126B - Ruthenium carbene compound, composition, preparation method and application thereof

Info

Publication number: CN112547126B
Application number: CN202011520977.8A
Authority: CN
Inventors: 王建辉; 杨鲜锋; 毕淑梦
Original assignee: Shanghai Zhonghua Technology Co ltd
Current assignee: Shanghai Zhonghua Technology Co ltd
Priority date: 2020-12-21
Filing date: 2020-12-21
Publication date: 2023-03-21
Anticipated expiration: 2040-12-21
Also published as: CN112547126A

Abstract

The invention discloses a ruthenium carbene compound, and a composition, a preparation method and application thereof. The invention specifically discloses a catalyst composition, which comprises a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5% -65%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin. The ruthenium carbene compound composition has good catalytic action on olefin metathesis reaction, is convenient to use, does not need to be prepared and used at present, can be stored for a long time, and is suitable for continuous automatic production.

Description

Ruthenium carbene compound, composition, preparation method and application thereof

Technical Field

The invention provides a ruthenium carbene compound, and a composition, a preparation method and application thereof.

Background

Olefin metathesis is a type of reaction in which the carbon-carbon double bond of an olefin is cleaved and recombined to form a new structural molecule under the catalytic action of a metal compound. This reaction allows the carbon-carbon double bonds, which have large bond energies and are not easily broken, to be coupled, exchanged, or transposed with each other under mild reaction conditions, and has good atom economy, which has become an important means for synthesizing olefins and constructing other compounds from olefins. The olefin metathesis reaction greatly expands the imagination space of people in constructing compound frameworks, and a new synthetic process established by the olefin metathesis reaction is simple, quick and efficient, has few byproducts, meets the requirements of green chemistry, and is greatly concerned in the chemical related field. The olefin metathesis reaction has great application potential in the aspects of chemical industry, food, medicine and biotechnology industry, and has been successfully applied to the aspects of synthesis of complex natural products, research and development of new anticancer drugs and the like. In addition, olefin metathesis reactions have also found important applications in the synthesis of specific, functionalized polymeric materials.

At present, metal carbene complexes of ruthenium, molybdenum and tungsten are known to have catalytic effects on olefin metathesis reactions. Among them, carbene complexes 1 to 5 (shown below) centered on ruthenium metal are commonly used as olefin metathesis catalysts. Particularly, the ruthenium carbene complex 2,4 and 5 obtained by replacing one tricyclohexylphosphine with azacyclo-carbene has higher catalytic activity and stability. In a word, the ruthenium complex has simple synthesis process, relatively stable structure, good functional group applicability and low requirement on reaction conditions, and can perform catalytic reaction under the condition of impurities such as oxygen, water and the like, thereby becoming a common catalyst for olefin metathesis reaction and ring-opening metathesis polymerization.

Structure types of commonly used ruthenium carbene olefin metathesis catalysts

Although these commercial ruthenium carbene catalysts (1 to 5) have high initiating activity, these catalysts can be stored only in a low-temperature, solid state for a long time, degrade at a high rate in a solution or during a reaction, and cannot be stored in a solution state for a long time. Therefore, the ruthenium carbene olefin metathesis catalyst can only be prepared at present, is very inconvenient to use, and because the commercial ruthenium carbene metathesis catalyst is dissolved by using a solvent, the volume shrinkage of the product is increased due to volatilization of the solvent in the curing process, and the use performance of the product is influenced.

For the long-term storage of ruthenium carbene catalysts, it is reported in the literature that ruthenium carbene catalysts are used as solid mixtures with paraffin wax for long-term storage of the catalysts (Taber D.F., frankowski K.J., grubbs' catalyst in paraffin: an air-stable preparation for olefin catalysis [ J ]. J.Org.Chem.,2003,68 (22): 6047-6048). 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.

The existing polydicyclopentadiene polymer is mainly prepared by a reaction injection molding process (RIM), and the catalytic system of the polydicyclopentadiene polymer is one of tungsten, molybdenum, tantalum and other one-generation catalytic systems or ruthenium metal carbene two-generation catalytic systems. The polydicyclopentadiene polymer prepared based on a first-generation catalytic system of tungsten, molybdenum, tantalum and the like is formed by mixing and molding a double-component feed liquid containing a catalyst A and a cocatalyst B, and functional fillers, copolymers, auxiliaries and other components can be added to adjust the product performance, but the preparation process needs to be filled with nitrogen for storage, and water and air are blocked to ensure the activity of the catalytic system, so that the defects of harsh storage forming conditions, high cost of die equipment, low comprehensive performance of products and the like exist. The existing commercial ruthenium carbene catalytic system can not realize continuous automatic production because of the following reasons:

1. the storage period is short: the existing commercial ruthenium carbene catalytic system can only be stored for a long time under the low-temperature and solid state, and when the ruthenium carbene catalytic system is dissolved in a common solvent to prepare a solution, the ruthenium carbene catalytic system is quickly decomposed, is difficult to store for a long time, can only be prepared and used at present, cannot be used for a continuous production line, or has the problems of inactivation, incapability of curing reaction, severe reaction, equipment blockage and the like.

2. The mixture ratio is very different: the existing commercial ruthenium catalyst system can be prepared and used after being liquefied by adding a solvent, but other components (dissolution or toxicity causes catalyst inactivation) cannot be added, so that the ratio of dicyclopentadiene to the liquid catalyst is usually over 100.

3. The existing commercial ruthenium carbene catalyst can not be directly dissolved in a resin solution, and must be dissolved by using an organic solvent such as toluene, dichloromethane and the like. In the curing process, the volume shrinkage of the solvent volatilization product is increased, and the service performance of the solvent volatilization product is influenced.

Disclosure of Invention

The invention aims to overcome the defects that the existing ruthenium carbene catalyst has single type, needs to be prepared when in use, is difficult to store and is not suitable for continuous automatic production, and provides a ruthenium carbene compound, a composition, a preparation method and application thereof. The ruthenium carbene compound composition has good catalytic action on olefin metathesis reaction, is convenient to use, does not need to be prepared and used at present, can be stored for a long time, and is suitable for continuous automatic production.

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

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

R ^1-1 is C ₆ -C ₁₀ And (4) an aryl group.

In one embodiment, some of the catalyst compositions are defined as follows, and in the undefined cases and other embodiments (hereinafter referred to as "embodiments"), the chlorinated paraffin preferably has a chlorine content of 5% to 60%, for example, 5%, 42%, 52% or 60%, and the chlorine content is a mass percentage of chlorine atoms to the mass of the chlorinated paraffin.

In a certain embodiment, the amount concentration of the ruthenium carbene compound represented by formula I or a salt thereof in the chlorinated paraffin may be 0.08mol/L to 0.7mol/L, preferably 0.1mol/L to 0.6mol/L, such as 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.55mol/L, or 0.6mol/L.

In a certain embodiment, said C ₄ -C ₁₈ Alkyl or by R ^1-1 Substituted C ₄ -C ₁₈ C in alkyl ₄ -C ₁₈ Alkyl may independently be C ₄ -C ₁₀ Alkyl, preferably C ₄ -C ₆ Alkyl radicals, e.g. C ₄ Alkyl radical, C ₅ Alkyl or C ₆ Alkyl, in turn, for example n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, preferably n-butyl or n-hexyl.

In one embodiment, the quilt R ^1-1 Substituted C ₄ -C ₁₈ In the alkyl radical, R ^1-1 The number of (B) may be 1, 2 or 3, and when 2 or 3, the same or different.

In one embodiment, said C ₆ -C ₁₀ Aryl may be phenyl or naphthyl.

In a certain embodiment, R ¹ And R ² And may independently be n-butyl or n-hexyl.

In a certain embodiment, R ¹ And R ² Can independently be C ₄ -C ₁₈ An alkyl group.

In a certain embodiment, R ¹ And R ² May be the same or different.

In a certain scheme, the ruthenium carbene compound shown in the formula I can be any one of the following structures,

in one embodiment, the catalyst composition can be composed of a ruthenium carbene compound or a salt thereof as shown in formula I, and chlorinated paraffin; the ruthenium carbene compound shown in the formula I and the chlorinated paraffin are defined in any scheme.

In one embodiment, the catalyst composition may be any combination of the following:

combination A1:

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

combination A2:

combination A3:

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

combination A4:

and chlorinated paraffin, the chlorinated paraffin has a chlorine content of 42%;

combination A5:

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

combination A6:

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

combination A7:

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

combination B1:

and chlorinated paraffin with a chlorine content of 5%,

the mass concentration of the substance in the chlorinated paraffin was 0.1mol/L;

combination B2:

and chlorinated paraffin having a chlorine content of 42%,

the mass concentration of the substance in the chlorinated paraffin was 0.3mol/L;

combination B3:

and chlorinated paraffin having a chlorine content of 52%,

the mass concentration of the substance in the chlorinated paraffin was 0.35mol/L;

combination B4:

and chlorinated paraffin having a chlorine content of 60%,

the mass concentration of the substance in the chlorinated paraffin was 0.6mol/L;

combination B5:

and chlorinated paraffin with a chlorine content of 5%,

combination B6:

and chlorinated paraffin having a chlorine content of 42%,

the amount concentration of the substance in the chlorinated paraffin was 0.25mol/L;

combination B7:

and chlorinated paraffin having a chlorine content of 52%,

combination B8:

and chlorinated paraffin having a chlorine content of 60%,

combination B9:

and chlorinated paraffin having a chlorine content of 52%,

combination B10:

and chlorinated paraffin having a chlorine content of 42%,

combination B11:

and chlorinated paraffin with a chlorine content of 5%,

the amount concentration of the substance in the chlorinated paraffin was 0.55mol/L;

combination B12:

and chlorinated paraffin having a chlorine content of 60%,

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

combination B13:

and chlorinated paraffin having a chlorine content of 52%,

the amount concentration of the substance in the chlorinated paraffin was 0.35mol/L.

The invention provides a preparation method of the catalyst composition, which comprises the following steps: and (2) mixing the ruthenium carbene compound shown as the formula I or the salt thereof with chlorinated paraffin to obtain the catalyst composition.

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

wherein R is ¹ And R ² As defined in any of the previous schemes.

the invention provides a preparation method of the ruthenium carbene compound shown in the formula I, which comprises the following steps: in an organic solvent, in the presence of alkali, carrying out the following reaction on a compound shown as a formula II and a compound shown as a formula III to obtain the ruthenium carbene compound shown as the formula I,

wherein R is ¹ And R ² As defined in any of the previous schemes.

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

In one embodiment, the olefin metathesis reaction may be a ring-closing metathesis reaction, a cross-metathesis reaction, or a ring-opening metathesis polymerization reaction. The ring-opening metathesis polymerization reaction can be used for preparing resin materials. The resin material can be polydicyclopentadiene polymer or polydicyclopentadiene/epoxy resin composite material.

In one embodiment, the ring-closing metathesis reaction may include the steps of: in the presence of the catalyst composition, the compound shown as the formula A1 is subjected to ring-closing metathesis reaction shown as the following formula to obtain a compound shown as the formula A2,

wherein X is O, S, a fragment

Or fragments thereof

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

In one embodiment, X may be R ⁷ -N or a fragment

Wherein R is ⁷ Is hydrogen, C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ 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 (may be C) ₁ -C ₄ 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 to 3R ^8-3 Substituted "heteroatom is selected from one or more of N, O and S, 3-6 member heterocycle (can be tetrahydrofuran ring, tetrahydrothiophene ring, tetrahydropyrrole ring, piperidine ring, piperazine ring, morpholine ring, pyran ring or dioxane) with heteroatom number of 1-3";

R ^7-1 、R ^8-2 、R ^7-3 、R ^8-1 and R ^8-2 Independently of one another is hydrogen, C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl), unsubstituted or substituted by 1 to 3R ^7-1-1 Substituted C ₆ -C ₁₀ Aryl (which may be phenyl);

R ^8-3 and R ^7-1-1 Independently of one another, hydroxy, halogen, C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl) or C ₁ -C ₆ Alkoxy (may be C) ₁ -C ₄ Alkoxy groups).

In one embodiment, X may be R ⁷ -N；

R ⁷ is-S (= O) ₂ R ^7-1 ；

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

R ^7-1-1 is C ₁ -C ₄ An alkyl group.

In one embodiment, the compound of formula A1 can be

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

In one embodiment, the ring-closing metathesis reaction may be carried out in the absence of a solvent.

In one embodiment, the cross-metathesis reaction may include the steps of: in the presence of the catalyst composition, the compound containing the segment B1 and the compound containing the segment B2 are subjected to cross metathesis reaction as shown in the specification to obtain a compound containing the segment B3,

in a certain embodiment, the compound containing the compound of the segment B1 and the compound containing the segment B2 can 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 1-3R ^4-2 Substituted C ₆ -C ₁₀ Aryl (which may be phenyl);

n3 is 0, 1 or 2;

R ^4-1 is hydrogen, C ₁ -C ₆ Alkyl (can be C) ₁ -C ₄ Alkyl), unsubstituted or substituted by 1 to 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 groups).

In a certain embodiment, the compound containing tablet B1 and the compound containing tablet B2 can be independently

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

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

Or

In a certain embodiment, the compound containing tablet B1 and the compound containing tablet B2 may be the same or different.

In certain embodiments, the conditions and operations of the cross-metathesis reaction can be those conventional in the art for such reactions.

In one embodiment, the cross-metathesis reaction can be carried out in the absence of a solvent.

In one embodiment, the ring-opening metathesis polymerization reaction may include the steps of: in the presence of the catalyst composition, the compound containing the segment C1 is subjected to ring-opening metathesis polymerization reaction shown as follows to obtain a compound containing a segment C2,

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

n≥3。

in a certain embodiment, the compound containing the fragment C1 can be

Wherein R is ⁵ And R ⁶ Can independently be hydrogen, halogen (e.g. fluorine, chlorine, bromine or iodine), C ₁ -C ₆ Alkyl (may be C) ₁ -C ₄ Alkyl, e.g. methyl) or C ₁ -C ₆ Alkoxy (may be C) ₁ -C ₄ Alkoxy, such as methoxy);

the A ring is a 3-8 membered monocyclic cycloolefin having 1, 2 or 3 olefinic bonds (which may be a 3-8 membered monocyclic cycloolefin having 1 olefinic bond, for example

n4 is 1, 2,3, 4,5 or 6), or a 6-to 15-membered polycyclic cycloalkene containing 1, 2 or 3 olefinic bonds (which may be a 7-to 10-membered polycyclic cycloalkene containing 1 or 2 olefinic bonds, for example

In a certain embodiment, the compound containing the fragment C1 can be

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 a certain embodiment, the compound containing the fragment C1 can be

In certain embodiments, the conditions and operations of the ring-opening metathesis polymerization reaction can be those conventional in the art for such reactions.

In one embodiment, the ring-opening metathesis polymerization reaction may be carried out in the absence of a solvent.

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 invention, when the chlorine content of the chlorinated paraffin is less than 5%, the chlorinated paraffin is in a gel state, and needs to be diluted and dissolved by a large amount of solvent before use, so that the chlorinated paraffin is inconvenient to use. When the chlorine content is more than 65%, the liquid paraffin is in a high-viscosity state and even in a solid state (75% of commercial chlorinated paraffin is solid), which is not beneficial to the measurement of the catalyst, is difficult to be uniformly mixed with the substrate, causes local polymerization, and cannot complete the compression molding process.

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

in the invention, the ruthenium carbene compound shown as the formula I or the salt thereof can have one or more chiral carbon atoms, so that optical purity isomers, such as pure enantiomers, racemes or mixed isomers, can be obtained by separation. Pure single isomers can be obtained by separation methods in the art, such as chiral crystallization to form salts, or by chiral preparative column separation.

In the invention, if stereoisomers exist in the ruthenium carbene compound shown in the formula I or the salts thereof, the ruthenium carbene compound can exist in the form of a single stereoisomer or a mixture (such as raceme) of the stereoisomers. The term "stereoisomer" refers to either a cis-trans isomer or an optical isomer. The stereoisomers can be separated, purified and enriched by an asymmetric synthesis method or a chiral separation method (including but not limited to thin layer chromatography, rotary chromatography, column chromatography, gas chromatography, high pressure liquid chromatography and the like), and can also be obtained by chiral resolution in a mode of forming bonds (chemical bonding and the like) or salifying (physical bonding and the like) with other chiral compounds and the like. The term "single stereoisomer" means that the mass content of one stereoisomer of the compound according to the invention is not less than 95% relative to all stereoisomers of the compound.

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

The term "halogen" refers to fluorine, chlorine, bromine or iodine.

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

The term "alkoxy" refers to the group-O-RX, wherein RX is alkyl as defined above.

The term "aryl" refers to a hydrocarbon radical having aromatic character, such as C ₆ -C ₁₀ Aryl, examples of which include phenyl or naphthyl.

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, and more preferably a 3-8 membered monocyclic cyclic olefin having 1, 2 or 3 olefinic bonds or a 6-15 membered polycyclic cyclic olefin having 1, 2 or 3 olefinic bonds. Examples of the cyclic olefin include cyclopropene, cyclobutene, cyclopentene, cyclohexene, and,

And the like.

The group of the "heterocycle" of the present invention which is deprived of a hydrogen atom is a heterocycloalkyl group. 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 open expression "including" can be converted into the closed expression "consisting of 8230 \8230;.

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

The positive progress effects of the invention are as follows:

(1) The catalyst composition is convenient to use and does not need to be prepared and used at present.

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

(3) The catalyst composition of the ruthenium carbene compound has good catalytic action on olefin metathesis reaction, and can realize catalytic olefin metathesis reaction without additional solvent.

(4) The catalyst composition is in liquid state, so that the production process is suitable for more processes, such as two-component RIM process. Compared with a single-component RIM process, in the double-component RIM process, the feed liquid can be stored separately, and the storage period is prolonged.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The instruments and materials involved in the examples are described below:

hydrogen and carbon nuclear magnetic resonance spectra were obtained using a Bruker AV 400 (400 MHz) instrument. Chemical shifts are expressed in ppm with TMS as internal standard. Recording chemical shifts, splits (s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br: broad) and coupling constants (J, unit: hz)

The used solvents such as column chromatography silica gel, diatomaceous earth, dichloromethane, tetrahydrofuran, etc. are available from Schenssi Biotechnology Ltd of Tianjin. CDC1 for testing ₃ Is available from Shanghai cypress card Co. (PCy) ₃ ) ₂ C1 ₂ Ru = CHPh (1) was purchased from tianjin kayverdachi ltd.

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

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

The synthesis of the catalyst I-1 containing the butyl substituent comprises the following steps:

1) Preparation of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9)

To a 500mL three-necked flask equipped with a dropping funnel, 3.73mL of an aqueous glyoxal (8) (40%) solution and 80mL of methanol were sequentially added, and the mixture was stirred to dissolve the glyoxal. To the dropping funnel was added 9.12mL of m-trimethylamine (7), 10mL of methanol, and slowly added dropwise to the flask. The reaction solution was stirred for 12 hours while controlling the temperature to about 22 ℃. In this process, a bright yellow precipitate slowly precipitated from the reaction solution. After the reaction is finished, filtering the reaction solution to obtain a yellow solid, washing the solid with water for three times, washing the solid with methanol for one time, and drying the solid in vacuum to obtain a yellow crystal product 9. Weighing 6.5g and yield 70%. Calcd (found) for C ₂₀ H ₂₄ N ₂ ；C,82.15(82.12)；H,8.27(8.20). ¹ H-NMR(400MHz,CDCl ₃ ):δ(ppm):2.15(s,12H,CH ₃ ),2.30(s,6H,CH ₃ ),6.96(s,4H,CHar),8.10(s,2H,CHar). ¹³ C-NMR(100MHz,CDCl ₃ )δ(ppm):18.0,20.9,126.4,128.9,134.0,147.4,162.9。

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

To a dry 100mL ampoule was added 2.92g (10.0 mmol) of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46 g/mol) and 50mL of tetrahydrofuran under nitrogen protection and dissolved with stirring. Then, the ampoule was placed in an ethanol cold bath at-78 deg.CIn (1), stirring and cooling. After the reaction solution was sufficiently cooled, 13.75mL (22.0 mmol) of butyllithium (1.6M in hexane) solution was slowly added dropwise via syringe. After the addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. The solution gradually changed from turbid to yellow and transparent in the process. After the reaction, the reaction solution was cooled to 0 ℃ and 20mL of saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, after separating the organic phase, the aqueous phase was further extracted with 20mL of ethyl acetate three times, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off to give a yellow solid identified as N, N' -bis (2, 4, 6-trimethylphenyl) decane-5, 6-diamine (10) (CF: C) ₂₈ H ₄₄ N ₂ (ii) a Mw 408.67 g/mol); weight 3.91g (9.57 mmol), yield: 97 percent. Calcd (found) for C ₂₈ H ₄₄ N ₂ ；C,82.29(82.31)；H,10.85(11.01)；N,6.85(6.87). ¹ H-NMR(600MHz,CDCl ₃ ):δ(ppm):0.89(t,6H,3J(H,H)＝7.0Hz,CH ₃ ),1.31(m,8H,CH ₂ ),1.50(m,2H,CH ₂ ),1.74(m,2H,CH ₂ ),2.04(s,12H,CH ₃ ),2.22(s,6H,CH ₃ ),3.02(br,2H,NH),3.12(m,2H,CH),6.73(s,4H,CHar). ¹³ C-NMR(150MHz,CDCl ₃ )δ(ppm):14.3,18.9,20.6,23.2,29.7,31.2,58.1,128.9,129.7,130.3,142.0。

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

4.32g (10.6 mmol) of N, N' -bis (2, 4, 6-trimethylphenyl) decane-5, 6-diamine (10) (Mw: 408.67 g/mol), 1.125g (10.73 mmol) of NH ₄ BF ₄ (Mw: 104.8431 g/mol) and 19mL CH (OEt) ₃ The mixture was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oily phase was separated and 100mL of CH was used ₂ Cl ₂ Dissolving, filtering to remove insoluble substances to obtain clear solution, removing solvent by rotary evaporation, and vacuum drying to obtain brownA viscous oil of 4, 5-dibutyl-1, 3-bis (trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C) ₂₉ H ₄₃ BF ₄ N ₂ (ii) a Mw:506.48 g/mol). After passing through a celite column chromatography using dichloromethane as solvent, the solvent was removed by rotary evaporation and cooled for a long time to give 4.53g (8.94 mmol) of crystalline material in 84% yield. Calcd (found) for C ₂₉ H ₄₃ BF ₄ N ₂ ；C,68.77(68.62)；H,8.56(8.51)；N,5.53(5.32). ¹ H NMR(600MHz,CDCl ₃ )δ(ppm):8.33(s,1H,N-CH-N),6.94(s,4H,HMes),4.19(m bd,2H,CH-Bu),2.31(s,6H,CH ₃ Mes),2.27(s,12H,CH ₃ Mes),1.75(m,bd,4H,CH ₂ -CH ₂ ),1.26(m,bd 6H,CH ₂ -CH ₂ -),1.09(m,bd 2H,CH ₂ -CH ₂ -),0.81(t,6H,3J(H,H)＝7.27Hz,CH ₂ -CH ₃ ) ¹³ C NMR(150MHz,CDCl ₃ )δ(ppm):158.2,140.5,135.7,134.7,130.5,129.0,69.5,33.0,27.1,22.4,21.9,21.0,18.4,18.1,13.7.

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

4.94g (9.75 mmol) of 4, 5-dibutyl-1, 3-di (trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (II-1) (CF: C) were added to the dry flask under nitrogen protection ₂₉ H ₄₃ BF ₄ N ₂ (ii) a Mw:506.48 g/mol), 1.05g (9.34 mmol) of potassium tert-butoxide (Mw: 112.2 g/mol) and 50mL of dry tetrahydrofuran, and the resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.30 mmol) of Grubbs I (1) (Mw: 836.98 g/mol) as a ruthenium complex and 60mL of dry toluene, and the resulting mixture was heated to 70 ℃ and stirred for 4 hours. The solvent was removed by rotary evaporation, and the resulting solid material was subjected to silica gel column chromatography (petroleum ether/dichloromethane (1). Removing solvent by vacuum rotary evaporationPreparing a viscous brownish red solid substance I-1 (Cf: C) ₅₄ H ₈₁ Cl ₂ N ₂ PRu, mw: 961.20). Weighing 3.97g (4.13 mmol); yield: 78 percent. Calcd (found) for C ₅₄ H ₈₁ Cl ₂ N ₂ PRu；C,67.48(67.41)；H,8.49(8.51)；N,2.91(2.95). ¹ H NMR(600MHz,CDCl ₃ ):δ0.70-2.81(m,51H),2.01(s,6H,CH ₃ ),2.28(s,12H,CH ₃ ),3.77(s,2H,NCHCHN),6.68-7.30(m,9H),19.39(s,1H,RuCHAr). ³¹ P-NMR(81.0MHz,CDCl ₃ ):δ29.3.

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

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

1) Preparation of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9)

To a 500mL three-necked flask equipped with a dropping funnel, 3.73mL of an aqueous glyoxal (8) (40%) solution and 80mL of methanol were sequentially added, and the mixture was stirred to dissolve the glyoxal. To the dropping funnel was added 9.12mL of m-trimethylamine (7), 10mL of methanol, and slowly added dropwise to the flask. The reaction mixture was stirred for 12 hours while controlling the temperature of the reaction mixture to about 22 ℃. In this process, a bright yellow precipitate slowly precipitated from the reaction solution. After the reaction is finished, filtering the reaction solution to obtain a yellow solid, washing the solid with water for three times, washing the solid with methanol for one time, and drying the solid in vacuum to obtain a yellow crystal product 9. Weighing 6.5g and yield 70%. Calcd (found) for C ₂₀ H ₂₄ N ₂ C,82.15(82.12)；H,8.27(8.20). ¹ H-NMR(400MHz,CDCl ₃ ):δ(ppm):2.15(s,12H,CH ₃ ),2.30(s,6H,CH ₃ ),6.96(s,4H,CHar),8.10(s,2H,CHar). ¹³ C-NMR(100MHz,CDCl ₃ )δ(ppm):18.0,20.9，126.4,128.9,134.0,147.4,162.9。

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

To a dry 100mL ampoule was added 2.92g (0.01mol mw, 292.46g/mol) of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9), 50mL of tetrahydrofuran under nitrogen with stirring to dissolve it. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction mixture was sufficiently cooled, 9.16mL (0.022 mol) of a hexyllithium (2.2M toluene solution) solution was slowly added dropwise thereto with a syringe. After the addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. During this process the solution gradually changed from cloudy to yellow and transparent. After the reaction was completed, the reaction solution was cooled to 0 ℃,20 mL of saturated ammonium chloride solution was added to the reaction solution, the solution was layered, after separating the organic phase, the aqueous phase was further extracted three times with 20mL of ethyl acetate, the organic phases were combined, dried with anhydrous sodium sulfate, and the solvent was distilled off to obtain 4.32g (9.584 mmol mw 450.76g/mol) of a yellow oil (12), yield: 96 percent. Calcd (found) for C ₃₂ H ₅₂ N ₂ C,82.70(82.61)；H,11.28(11.41)；N,6.03(5.95). ¹ H-NMR(400MHz,CDCl ₃ ):δ(ppm):0.87(t,6H, ³ J(H,H)＝5.8Hz,CH ₃ ),1.26(m,12H,CH ₂ ),1.47(m,4H,CH ₂ ),1.72(m,4H,CH ₂ ),2.03(s,12H,CH ₃ ),2.21(s,6H,CH ₃ ),2.93(br,2H,NH),3.11(m,2H,CH),6.73(s,4H,CHar). ¹³ C-NMR(100MHz,CDCl ₃ )δ(ppm):14.1,18.2,21.9,22.7,27.0,29.3,30.5,31.8,65.0,126.0,128.7,129.2,142.2。

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

4.32g (9.584 mmol) of N7, N8-bis (2, 4, 6-trimethyl) phenyltetradecane-7, 8-diamine (12) (Mw: 450.76 g-mol)(13)、NH ₄ BF ₄ ( Mw:104.84g/mol;1.125g,10.73mmol,. About.10% molar excess) and 19mL CH (OEt) ) ₃ The mixture was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oily phase was separated and 100mL of CH was used ₂ Cl ₂ Dissolving, filtering to remove insoluble substances to obtain a clear solution, performing rotary evaporation to remove the solvent, and performing vacuum drying to obtain a brown viscous oily substance which is 4, 5-dihexyl-1, 3-bis (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-2), performing once diatomite column chromatography by using dichloromethane as a solvent, performing rotary evaporation to remove the solvent, and performing long-time cooling to obtain 4.53g (8.05mmol, mw, 562.59g/mol) of a crystalline substance with the yield of 75%. Calcd (found) for C ₃₃ H ₅₁ BF ₄ N ₂ ；C,70.45(70.52)；H,9.14(9.31)；N,4.98(5.02). ¹ H NMR(400MHz,CO(CD ₃ ) ₂ )δ(ppm):8.45(s,1H,N-CH-N),6.99(s,4H,HMes),4.19(m bd,2H,CH-hexyl),2.35(s,12H,CH ₃ Mes),2.32(s,6H,CH ₃ Mes)，1.21-1.28(m,bd 20H,CH ₂ -CH ₂ -),0.85(t,6H, ³ J(H,H)＝5.9Hz,CH ₂ -CH ₃ ) ¹³ C NMR(100MHz,CO(CD ₃ ) ₂ )δ(ppm):144.2(N-C-N),140.3(CAr),135.6(CHAr),135.4(CHAr),129.7(CHAr),129.6(CHAr),129.4(CHAr),129.2(CAr),66.5(CH-hexyl),66.1(CH-Hexyl),28.3(CH ₃ -Mes),17.8(CH ₃ Mes),31.8(CH ₂ ),29.3(CH ₂ ),27.3(CH ₂ ),25.6(CH ₂ ),22.7(CH ₂ ),14.1(CH ₃ -hexyl)； ¹⁹ F NMR(376MHz,CO(CD ₃ ) ₂ )δ(ppm):-151.7.

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

Adding 4, 5-dihexyl into a dry flask under the protection of nitrogen1, 3-bis (trimethylphenyl) -4, 5-dihydro-1H-imidazolium tetrafluoroborate (II-2) (Mw: 562.9g/mol; 4.94g; 8.78mmol), potassium tert-butoxide (Mw: 112.2g/mol; 1.05g; 9.33mmol) and 50mL of dry tetrahydrofuran. The resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.37mmol, mw 836.98g/mol) of ruthenium complex Grubbs I (1) and 60mL of dry toluene, and dissolved with stirring. The reaction mixture was heated to 70 ℃ and kept at this temperature with stirring for 2.5h. And (3) after the reaction liquid is cooled to room temperature, performing silica gel column chromatography by using petroleum ether/dichloromethane (1). The solvent was removed by rotary evaporation in vacuo to give a viscous brownish red solid I-2,3.97g (0.39 mmol) (Cf: C) ₅₈ H ₈₉ Cl ₂ N ₂ PRu, mw 1017.3). Yield: 72.6 percent. ¹ H NMR(400MHz,CDCl ₃ ):δ0.88-2.44(m,59H),1.93(s,6H,CH ₃ ),2.34(s,12H,CH ₃ ),4.03(s,2H,NCHCHN),7.04-7.38(m,9H),19.16(s,1H,RuCHAr). ³¹ P-NMR(81.0MHz,CDCl ₃ ):δ29.2.

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

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

To a dry 250mL ampoule was added 2.92g of N, N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46g/mol;10.0 mmol), 100mL of tetrahydrofuran under nitrogen and dissolved with stirring. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction solution was sufficiently cooled, 4.17mL (10.0 mmol) of a solution of hexyllithium (2.4M in toluene) was slowly added dropwise via a syringe. The reaction solution was again cooled to-78 ℃ and 6.25mL (10.0 mmol) of butyllithium (1.6M in hexane) solution was slowly added dropwise via syringe. After the dropwise addition, the reaction mixture was slowly warmed to room temperature with stirring, andstirring was continued for 0.5h. Then, the reaction solution was cooled to 0 ℃ and 20mL of a saturated ammonium chloride solution was added to the reaction solution, followed by stirring for about 10 minutes. Standing until the solution is layered, separating out an organic phase, continuously extracting the aqueous phase with 20mL ethyl acetate for three times, combining the organic phases, and drying with anhydrous sodium sulfate. The solvent was removed by rotary evaporation to give an orange viscous oil which was identified as N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) ₃₀ H ₄₈ N ₂ (ii) a Mw of 436.73 g/mol), a weight of 4.28g (9.80 mmol), and a yield of 98%.

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

To a dry 250mL ampoule was added 1.46g (5.0 mmol) of N-N' -bis (2, 4, 6-trimethyl) phenylenediimine (9) (Mw: 292.46 g/mol) and 100mL of tetrahydrofuran under nitrogen, and the mixture was dissolved with stirring. Then, the ampoule was placed in an ethanol cooling bath at-78 ℃ and stirred for cooling. After the reaction solution was sufficiently cooled, a solution of 7.5mL (6.0 mmol) of hexylmagnesium bromide (0.8M, THF solution) was slowly added dropwise via a syringe. After the addition was complete, the reaction mixture was stirred slowly at room temperature and continued for 1.5h. During the process, the solution gradually changes from orange red to yellow and transparent. The reaction mixture was cooled to-78 deg.C and 3.75mL (6.0 mmol) of butyllithium (1.6M in hexane) solution was slowly added dropwise via syringe. After the dropwise addition was complete, the reaction mixture was slowly allowed to warm to room temperature with stirring and stirring was continued for 0.5h. The reaction solution was cooled to 0 ℃,20 mL of a saturated ammonium chloride solution was added to the reaction solution, the solution was separated into layers, after separating the organic phase, the aqueous phase was further extracted three times with 20mL of ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was distilled off to leave N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) as an orange viscous oil ₃₀ H ₄₈ N ₂ (ii) a Mw of 436.73 g/mol) and a weight of 2.13g (4.87 mol) was obtained, showing a yield of 97.4%.

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

4.19g (9.58 mmol) of N, N' -bis (2, 4, 6-trimethylphenyl) dodecane-5, 6-diamine (14) (CF: C) ₃₀ H ₄₈ N ₂ ；Mw:436.73g/mol)(13)、NH ₄ BF ₄ (Mw: 104.84g/mol;1.125g, 10.73mmol) and 19mL CH (OEt) ₃ The mixture was heated to 125 ℃ and stirred for 15h. During this time, the solution gradually turned a brownish red color. After cooling to room temperature, the mixture was washed with petroleum ether (50X 3 mL) and the lower oil was separated and washed with 100mL CH ₂ Cl ₂ Dissolving, filtering to remove insoluble substances to obtain clear solution, removing solvent by rotary evaporation, and vacuum drying to obtain brown viscous oil which is 4-butyl-5-hexyl-1, 3-bis (2, 4,6 trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (15) (CF: C) ₃₁ H ₄₇ BF ₄ N ₂ (ii) a Mw 534.53 g/mol). Weighing 3.85g (7.20 mmol) and yield 75%. Performing primary chromatography with a diatomite column by using dichloromethane as a solvent, removing the solvent by rotary evaporation, and standing for a long time to obtain a crystalline substance.

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

4.69g (8.776 mmol) of 4-butyl-5-hexyl-1, 3-bis (2, 4, 6-trimethylphenyl) -4, 5-dihydroimidazolium tetrafluoroborate (15) (CF: C) are added to the dry flask under nitrogen protection ₃₁ H ₄₇ BF ₄ N ₂ (ii) a Mw 534.53 g/mol), 1.047g (9.33 mmol) of potassium tert-butoxide (Mw: 112.21 g/mol), 50mL of dry tetrahydrofuran, and the resulting mixture was stirred at room temperature for 4 hours. And (4) removing the tetrahydrofuran solvent by rotary evaporation, and drying in vacuum to obtain a solid substance. To the resulting solid were added 4.44g (5.37 mmol) of Grubbs I (Mw: 836.98 g/mol) as a ruthenium complex and 60mL of dry toluene, and the mixture was stirred to dissolveAnd (5) solving. The reaction mixture was heated to 70 ℃ and stirred for 2.5h while maintaining this temperature. And (3) after the reaction liquid is cooled to room temperature, performing silica gel column chromatography by using petroleum ether/dichloromethane (1). Removing solvent by vacuum rotary evaporation, and vacuum drying to obtain pink solid (I-3) (CF: C) ₅₆ H ₈₅ Cl ₂ N ₂ PRu; mw: 989.25), 3.82g (3.87 mmol), yield 72%.

With reference to the preparation methods of examples 1 and 2, the R substituent group obtained by the preparation was-C ₁₀ H ₂₁ (straight chain), -C ₁₄ H ₂₉ (straight chain), -C ₁₈ H ₃₇ (straight chain) and

the catalyst of (1).

Preparation of the catalyst composition:

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

The chlorine content of the liquid chlorinated paraffin is as follows: 5% -65%;

the concentration ranges of the catalyst composition are: 0.08mol/L to 0.7mol/L;

the liquid chlorinated paraffin can be purchased or manufactured by self, and the self-manufacturing method refers to the following two methods: (1) Adding the measured liquid paraffin into a reaction kettle, introducing chlorine gas for reaction, washing with NaOH aqueous solution and aqueous solution in sequence until the acid value (mgkOH/g) is less than or equal to 0.3, decompressing and dehydrating until the water content is less than 2%, and discharging to obtain a finished product; (2) Adding metered liquid paraffin into a reaction kettle, dropwise adding thionyl chloride while stirring, refluxing for 5-7 h, and recovering excessive thionyl chloride under normal pressure. Washing with water and NaOH aqueous solution in sequence, reducing pressure and dehydrating until the water content is less than 2%, and discharging to obtain the finished product.

Examples of the preparation of the catalyst compositions are shown in table 1.

TABLE 1 preparation examples of catalyst compositions

Comparative example 1:

weighing 2.6g of commercial Grubbs2 ^nd The catalyst was dissolved in 12.2mL of a paraffin solution having a chlorine content of 52% to prepare Grubbs2 at a concentration of 0.25mol/L ^nd A catalyst solution. Commercial Grubbs2 were found to be present at ambient temperatures below 10 deg.C ^nd The solubility of the catalyst in the chlorinated paraffin solution is reduced, the catalyst is easy to separate out in the storage process, the catalytic activity is reduced, and the industrial application is not facilitated. Meanwhile, commercial Grubbs2 ^nd Catalyst was dissolved in a paraffin solution having a chlorine content of 52% to prepare Grubbs2 at a concentration of 0.05mol/L ^nd The catalyst solution was allowed to stand at room temperature for two weeks, and was observed to precipitate from a large number of crystals. The experiment also shows that under normal temperature and pressure, the Grubbs2 is commercialized ^nd The catalyst began to decompose after about 2 hours in toluene solvent, losing catalytic activity.

In addition, the catalyst with the R substituent group of methyl, ethyl or propyl is dissolved in the liquid chlorinated paraffin, so that the crystal of the catalyst is easily separated out in the long-time standing process, and the using effect is influenced.

Comparative example 2:

the present inventors attempted to commercialize Grubbs2 ^nd The catalyst and the catalysts obtained in examples 1 and 2 of the present invention were dissolved in commercially available liquid paraffin, respectively. The results show that Grubbs2 is commercially available ^nd The catalyst is insoluble in liquid paraffin; the catalysts prepared in examples 1 and 2 of the present invention were soluble in liquid paraffin, but the formed catalyst compositions were gel-like substances and were not transformed into liquid state even when heated to 60-70 ℃.

Comparative example 3:

the invention tries the chlorinated paraffin with different chlorine contents, when the chlorine content of the chlorinated paraffin is lower than 5 percent, the chlorinated paraffin is in a gel state, and needs a large amount of solvent to be diluted and dissolved before use, so the use is inconvenient. When the chlorine content is more than 65%, the liquid paraffin is in a high-viscosity state and even in a solid state (75% of commercial chlorinated paraffin is solid), which is not beneficial to the measurement of the catalyst, is difficult to be uniformly mixed with the substrate, causes local polymerization, and cannot complete the compression molding process.

Effect example 1

To evaluate the catalytic activity of the catalyst composition for ring-closing metathesis reactions, N-diallyl-4-methylbenzenesulfonamide (16) was selected as a substrate for testing.

Effect example 1.1:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.02mL of the catalyst composition prepared in example 4. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 219.7mg (0.984 mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 98.4%. 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 1.2:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.006mL of the catalyst composition prepared in example 6. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the mixture was separated by column chromatography using petroleum ether/ethyl acetate (5) as eluent to give the product 17, weighing 219.95mg (0.985mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 98.8％。 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 1.3:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.008mL of the catalyst composition prepared in example 9. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 218.8mg (0.98mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 98%. 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 1.4:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.007mL of the catalyst composition prepared in example 10. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 219.1mg (0.981mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 98.1%. 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

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

Effect example 2.1:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19 and 0.083mL of the catalyst composition prepared in example 5. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 228.8mg (0.96mmol ₁₆ H ₁₄ O ₂ Mw, 238.3), yield 96%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 2.2:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19 and 0.071mL of the catalyst composition prepared in example 6. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 229.2mg (0.962mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 96.2%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH2)； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 2.3:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19, 0.25mL of the catalyst composition prepared in example 8. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was separated by column chromatography to give a cross-metathesis product 20 weighing 224.2mg (0.941mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 94.1%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 2.4:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19 and 0.10mL of the catalyst composition prepared in example 9. The reaction mixture was heated to 45 ℃ and stirred for 6h. The reaction mixture was then separated by column chromatography to give a cross-metathesis product 20 weighing 224.5mg (0.942mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 94.2%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 3

To evaluate the use of the catalyst composition in ring-opening metathesis polymerization, dicyclopentadiene was selected as the monomer for testing.

Effect example 3.1:

200g of DCPD monomer was added dropwise to 0.6mL of the catalyst composition prepared in example 6, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 59.0MPa, tensile modulus 1919.2MPa and elongation at break 7.87%.

Effect example 3.2:

200g of DCPD monomer was added dropwise to 0.35mL of the catalyst composition prepared in example 7, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 59.3MPa, tensile modulus 1919.7MPa and elongation at break 7.82%.

Effect example 3.3:

200g of DCPD monomer was added dropwise to 1.0mL of the catalyst composition prepared in example 9, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 58.5MPa, tensile modulus 1911.6MPa and elongation at break 7.67%.

Effect example 3.4:

200g of DCPD monomer was added dropwise to 0.42mL of the catalyst composition prepared in example 11, and the mixture was stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 80 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 58.9MPa, tensile modulus 1912.2MPa and elongation at break 7.61%.

Comparative example 3.1:

200g of DCPD monomer was weighed out, and 0.2g of Grubbs2 dissolved in toluene solvent was added dropwise ^nd And mixing and stirring the catalyst uniformly, then carrying out defoaming treatment, and pouring a mold. And setting a curing program of 60-100 ℃/2h for curing and forming to obtain a sample plate with the thickness of slightly less than 4mm (about 3.96 mm), wherein the surface of the plate has obvious flow mark phenomenon. This is mainly caused by the evaporation of the solvent toluene during the curing process. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 59.4MPa, tensile modulus 1913.4MPa and elongation at break 7.42%.

Comparative example 3.2:

for comparison experiments with the present invention, the present invention is strictly in accordance with the literature (Taber D.F., frankowski K.J., grubbs' catalyst in paraffin: an air-stable preparation for olefin catalysis [ J. ])]Grubbs2 were prepared J.org.chem.,2003,68 (22): 6047-6048) ^nd Paraffin wax mixtures of the catalysts. 200g of DCPD monomer is taken and added with 1.4g of Grubbs2 ^nd A paraffin wax mixture of the catalyst (0.15 mmol/g,0.21 mmol) was found to be insoluble in DCPD monomer and was not homogeneously mixed even after stirring for 12 hours. And (3) raising the temperature to 40 ℃, and finding that polymerization occurs around the solid paraffin during stirring, so that the undissolved solid paraffin mixture is wrapped, and the solution cannot be defoamed and poured into a mold. The polymerization experiment fails, indicating that Grubbs2 reported in the literature ^nd Solid paraffin mixture of catalystIt must be in the presence of a solvent to exert the catalytic action.

Long term storage stability test

Storage stability verification experiments were performed after the catalyst compositions prepared in examples 4 to 11 were stored at room temperature for six months.

Effect example 4

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

Effect example 4.1:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.01mL of the catalyst composition prepared in example 4 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, weighing 217.7mg (0.0975mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 97.5%. 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 4.2:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.0057mL of the catalyst composition prepared in example 6 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5)Column chromatography separation gave product 17, weighing 21.8.1mg (0.978mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 97.8%. 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 4.3:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.008mL of the catalyst composition prepared in example 9 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) by column chromatography to give product 17, 217mg (0.972mmol ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 97.2%. 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 4.4:

to a 5mL single-neck flask, 251mg (1.0 mmol ₁₃ H ₁₇ NO ₂ S; mw 251.1) substrate 16, 0.0067mL catalyst composition prepared in example 10 after 6 months of storage. The reaction mixture was heated to 40 ℃ and stirred for 2h. After the reaction was cooled to room temperature, the reaction mixture was eluted with petroleum ether/ethyl acetate (5) ₁₁ H ₁₃ NO ₂ S; mw: 223.3), yield 97.5%. 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 5

After the catalyst is stored in the chlorinated paraffin solution for 6 months, the catalytic activity of the catalyst on the intermolecular cross-metathesis reaction of olefins is evaluated, and allyl benzoate (18) and styrene (19) are selected as substrates to be subjected to activity test.

Effect example 5.1:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19, and 0.083mL of the catalyst composition prepared in example 5 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to give a cross metathesis product 20, weighing 226.6mg (0.95mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 95.1%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH2),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH2)； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 5.2:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19, and 3.61mL of the catalyst prepared in example 6 after 6 months storageAn agent composition. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to give a cross metathesis product 20 weighing 22.69mg (0.0952mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 95.2%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1).

Effect example 5.3:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19, and 0.25mL of the catalyst composition prepared in example 8 after 6 months of storage. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to obtain a cross metathesis product 20, weighing 222.8mg (0.935mmol ₁₆ H ₁₄ O ₂ Mw: 238.3), yield 93.5%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 5.4:

to a 5mL Schlenk flask, 162mg (1.0 mmol ₁₀ H ₁₀ O ₂ Mw 162.2) substrate 18, 208mg (2.0 mmol; cf is C ₈ H ₈ Mw 104.2) styrene 19, and 0.10mL after 6 months of storageThe catalyst composition prepared in example 9. The reaction mixture was heated to 45 ℃ and stirred for 6h. After the reaction mixture was cooled to room temperature, the reaction mixture was separated by column chromatography to give a cross metathesis product 20 weighing 223.3mg (0.937mmol ₁₆ H ₁₄ O ₂ Mw, 238.3), yield 93.7%. ¹ H NMR(400MHz,CDCl ₃ ):δ8.12(d,J＝7.2Hz,2H,HAr),7.61(t,J＝7.2Hz,1H,HAr),7.50(q,J＝6.8Hz,4H,HAr),7.38(t,J＝6.8Hz,2H,HAr),7.31(t,J＝4.8Hz,1H,HAr),6.79(d,J＝16Hz,1H,Ph＝CH),6.50(dt,J＝16Hz,J＝6.4Hz,1H,CH＝CH ₂ ),5.02(dd,J＝6.4Hz,J＝1.2Hz,2H,CH ₂ )； ¹³ C-NMR(400MHz,CDCl ₃ ):δ169.25,134.29,132.97,132.28,130.22,129.64,128.62,128.36,128.09,126.66,118.19,65.53(E/Z≧20/1)。

Effect example 6

After the catalyst is stored in the chlorinated paraffin solution for 6 months, the catalytic activity of the catalyst on the ring-opening metathesis polymerization reaction is evaluated, and dicyclopentadiene is selected as a monomer for testing.

Effect example 6.1:

200g of DCPD monomer was added dropwise to 0.6mL of the catalyst composition prepared in example 6 after storage for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.5MPa, tensile modulus 1905.3MPa, and elongation at break 8.11%.

Effect example 6.2:

200g of DCPD monomer was added dropwise to 0.35mL of the catalyst composition prepared in example 7 after storage for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.9MPa, tensile modulus 1907.2MPa, and elongation at break 8.04%.

Effect example 6.3:

200g of DCPD monomer was added dropwise to 1.0mL of the catalyst composition prepared in example 9 stored for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 60-100 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.3MPa, tensile modulus 1892.3MPa and elongation at break 8.03%.

Effect example 6.4:

200g of DCPD monomer was added dropwise to 0.42mL of the catalyst composition prepared in example 11 stored for 6 months, and mixed and stirred until the color became uniform. And (3) defoaming the solution, pouring a mold, and curing and molding by adopting a curing program of 80 ℃/2h to obtain a sample plate with a thickness of 4mm and a smooth and flat surface. And finally, cutting a sample strip for mechanical property testing. The result is: tensile strength 54.8MPa, modulus 1893.1MPa, and elongation at break 7.98%.

Effect example 7: preparation of Dicyclopentadiene/epoxy resin compositions

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

bisphenol a epoxy resin YN1828: purchased from Jiangsu Yangyang Hu chemical Co., ltd, and having an epoxy value of 0.51 to 0.54.

Dicyclopentadiene (2): DCPD.

4,4' -diaminodiphenyl sulfone: a DDS.

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

The formulations of the raw materials of effect examples 7.1 to 7.7 and comparative examples 7.1 to 7.4 are shown in tables 2 and 3, respectively.

Chlorinated paraffin:

the chlorine content is 5 percent, and the density is 0.82;

the chlorine content is 42 percent, and the density is 1.16;

the chlorine content is 52 percent, and the density is 1.24;

the chlorine content was 60% and the density was 1.45.

Mass calculation of the catalyst composition:

effect example (7.1 to 7.10) mass of catalyst = mass concentration of substance of catalyst composition x catalyst molecular weight:volumeof catalyst composition in effect example

Mass of catalyst composition = mass of catalyst in effect examples (7.1 to 7.10) (% by volume of chlorinated paraffin whose chlorine content was determined in the respective examples)/mass of catalyst in the respective examples + mass of catalyst in effect examples (7.1 to 7.10)

TABLE 2

TABLE 3

Effect examples 7.1 to 7.7:

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

(1) Mixing dicyclopentadiene and epoxy resin in advance to form a uniform solution;

(2) Adding a curing agent and a curing accelerator, and mechanically grinding by using a three-roll grinder;

(3) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, adding the catalyst composition, stirring and mixing the mixture firstly, and then mixing the mixture by using a three-roll grinder until the solution is uniform in color;

(4) And (4) placing the mixed solution obtained in the step (3) in a vacuum drying box to remove bubbles, and pouring and curing by adopting curing procedures of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h to obtain the thermosetting resin composition plate for the copper-clad plate.

Comparative example 7.1:

the process for preparing the epoxy resin of comparative example 7.1 is as follows:

(1) Adding 4,4' -diaminodiphenyl sulfone (DDS) curing agent and 2,4, 6-tris (dimethylaminomethyl) phenol to epoxy resin, and mechanically grinding by using a three-roll grinder;

(2) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, the mixed solution is placed in a vacuum drying oven to remove bubbles, and the epoxy resin cured plate is obtained by adopting a curing procedure of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h for casting and curing.

Comparative example 7.2:

the process for preparing the polydicyclopentadiene resin of comparative example 7.2 is as follows:

(1) Adding a1, 3-bis (2, 4, 6-trimethylphenyl) -2- (4, 5-dibutylimidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium liquefaction catalyst into dicyclopentadiene, and stirring and mixing for 2min at normal temperature until the color is uniform;

(2) And (2) placing the mixed solution obtained in the step (1) in a vacuum drying oven to remove bubbles, and pouring and curing by adopting a curing program of 80 ℃/1h and 120 ℃/2h to obtain the polydicyclopentadiene resin cured product plate.

Comparative example 7.3:

the process for preparing the dicyclopentadiene/epoxy resin composition of comparative example 7.3 is as follows:

(2) Adding 4,4' -Diamino Diphenyl Sulfone (DDS) curing agent and 2,4, 6-tri (dimethylamino methyl) phenol, and mechanically grinding by using a three-roll grinder;

(3) When the average particle size of solid particles in the mixed solution is lower than 30 mu m, the mixed solution is placed in a vacuum drying oven to remove bubbles, and the thermosetting resin composition plate for the copper-clad plate is obtained by adopting a curing procedure of 80 ℃/1h, 120 ℃/2h, 150 ℃/2h and 180 ℃/2h for casting and curing.

Comparative example 7.4:

the process for preparing the dicyclopentadiene/epoxy resin composition of comparative example 7.4 is as follows:

(3) When the average particle size of solid particles in the mixed solution is less than 30 mu m, adding Grubbs second-generation catalyst which is completely dissolved in toluene, firstly stirring and mixing, and then mixing by using a three-roll grinder until the solution is uniform in color;

The dielectric properties of the sheets prepared in effect examples 7.1 to 7.7 and comparative examples 7.1 to 7.4 were tested, and the results are shown in Table 4,

TABLE 4

From the above table, the following points can be seen:

(1) Compared with the comparative example 7.1, the dielectric constant and the dielectric loss factor are obviously reduced along with the increase of the content of the dicyclopentadiene in the examples 7.1 to 5, which shows that the dielectric property of the epoxy resin can be improved by introducing the dicyclopentadiene nonpolar alicyclic chain structure.

(2) The significant increase in initial decomposition temperature (Td 5%) in example 7.3 compared to comparative example 7.3 indicates that the use of the dual cure system in the dicyclopentadiene/epoxy resin composite enables the two resins to each be fully cured and crosslinked to form an interpenetrating polymer network structure, thereby imparting good heat resistance thereto; (comparative example 7.3 No catalyst was added, dicyclopentadiene was present in the composition only as a monomer, and no crosslinking cure was performed).

(3) From example 7.3, example 7.6 and example 7.7, it can be seen that polydicyclopentadiene/epoxy resin composites having reduced dielectric properties can be prepared using different epoxy curing agents.

(4) Compared with the comparative example 7.4, the ruthenium carbene catalyst composition used in the examples 7.1 to 7.7 can fully cure the dicyclopentadiene, and the dicyclopentadiene and the epoxy resin are subjected to co-crosslinking, so that the compound with excellent performance is obtained.

Effect example 8: preparation of polydicyclopentadiene polymers

In effect examples 8 to 10, the actual amounts of the respective components in the liquid B = (sum of parts by weight of the liquid a)/[ (mass ratio of the liquid a to the liquid B) × (sum of parts by weight of the liquid B) ]

Effect example 8.1:

the formula of the catalyst composition prepared by the invention is the same as that of example 8, and the polydicyclopentadiene polymer is prepared by RIM reaction and injection molding of each component of the resin.

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	99.95 parts of
		Catalyst composition	0.05 part
Comonomer (b): ethylene	10 portions of
		Anti-aging agent: tinuvin B75	5 portions of

The preparation process of the polydicyclopentadiene polymer comprises the following steps:

1. preparation of solution A: weighing dicyclopentadiene monomer according to a formula design scheme to form solution A.

2. And (3) preparation of a liquid B: and weighing and mixing the catalyst composition, the comonomer and the anti-aging agent to form liquid B.

3. Leading in a material storage system: uniformly stirring to fully mix the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use.

4. Injection molding: and (3) operating RIM glue injection equipment, mixing the A and B liquid materials on line, injecting the mixture into a mold to complete reaction injection molding, and preparing the polydicyclopentadiene composite material.

5. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to finish the preparation of the polymer product.

And (3) the mass ratio of the solution A to the solution B is about 9, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 500ml/min, the glue injection pressure is 6bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.

Effect example 8.2:

the formula of the catalyst composition prepared by the invention is the same as that of example 8, and the polydicyclopentadiene polymer is prepared by RIM reaction injection molding, and the formula of the resin system used by the catalyst composition is the same as that of effect example 8.1. After the feed liquids A and B are uniformly mixed, the mixture is respectively placed in a two-component storage tank of RIM equipment to be stored for 6 months under natural conditions, a composite material product is prepared by the RIM process, and the process parameters are the same as those of example 1. The panels were cut out and the specific test results are shown in table 5.

Effect example 8.3:

the catalyst composition prepared by the invention has the same formula as that of the catalyst composition in example 10, and is prepared into polydicyclopentadiene polymer through RIM reaction and injection molding,

the weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	80 portions
		Catalyst composition	20 portions of
Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	3 portions of
		Functional filler: glass fiber	5 portions of
Auxiliary agent: silane coupling agent A172	2 portions of
		Auxiliary agent: toner powder	2 portions of

1. preparation of solution A: weighing dicyclopentadiene monomer and functional filler glass fiber to form solution A according to a formula design scheme, and stirring and mixing;

2. and (3) preparation of liquid B: weighing and mixing the catalyst composition, the comonomer and the auxiliary agent to form a solution B;

3. leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use;

5. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the composite material product.

And (3) the mass ratio of the solution A to the solution B is about 5, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 2L/min, the glue injection pressure is 15bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.

Effect example 8.4:

the catalyst composition prepared in example 4 was used to prepare polydicyclopentadiene polymer by mixing the components of the resin formulation uniformly and then injection molding by RIM reaction.

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	65 portions of
		Catalyst composition	35 portions of

2. And (3) preparation of a liquid B: the catalyst composition was weighed and mixed to make solution B.

3. Leading in a material storage system: uniformly stirring to fully mix, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use.

And (3) the mass ratio of the solution A to the solution B is about 2, RIM equipment is adopted for reaction and injection molding, the injection speed is 200ml/min, the injection pressure is 2bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.

Effect example 8.5:

the catalyst composition and the preparation process of the polydicyclopentadiene polymer are the same as those in the effect example 8.4; the difference is that the resin formula comprises the following raw materials in parts by weight, wherein a dicyclopentadiene monomer, a functional filler and an auxiliary agent are used as a solution A, a comonomer is mixed with a catalyst composition to form a solution B, and the mass ratio of the solution A to the solution B is about 3. The panels were cut out and the specific test results are shown in table 5.

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

Comparative example 8.1:

commercial Grubbs2 ^nd The catalyst was dissolved in toluene solution to produce commercial Grubbs2 ^nd Catalyst composition (mass ratio of Grubbs2 commercialized) ^nd Catalyst: toluene =1:10 And is subjected to single-component RIM reaction and injection molding to obtain the polydicyclopentadiene polymer.

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	99.8 parts of
		Commercial Grubbs 2nd catalyst composition	0.2 part
Comonomer (b): 5-norbornene-2-carboxylic acid tert-butyl ester	20 portions of
		Functional filler: glass fiber	5 portions of
Auxiliary agent: anti-aging agent Tinuvin B75	3 portions of

During the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs2 are added ^nd The catalyst composition, the comonomer, the auxiliary agent and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the glue injection speed is 200ml/min, the glue injection pressure is 20bar, the mold is insulated for 30min at 100 ℃ after the resin is filled, curing molding is carried out, and the test is finished after demolding and taking out. The panels were cut out and the specific test results are shown in table 5.

Comparative example 8.2:

the polydicyclopentadiene polymer is prepared by adopting a commercial tungsten-molybdenum metal carbene catalytic system and performing double-component RIM reaction injection molding.

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	49.8 parts of
		Main catalyst: molybdenum catalyst	0.18 part
Dicyclopentadiene monomer	50 portions of
		And (3) a cocatalyst: aluminum diethyl monochloride	0.02 portion

1. preparation of solution A: according to the formulation design scheme, 49.8 parts of dicyclopentadiene monomer and 0.18 part of molybdenum catalyst are weighed to form solution A.

2. And (3) preparation of a liquid B: according to the formula design scheme, 50 parts of dicyclopentadiene monomer and 0.02 part of diethyl aluminum monochloride are weighed to form solution B.

3. Leading in a material storage system: uniformly stirring to mix thoroughly, respectively introducing solution A and solution B into two-component storage tank of RIM equipment for use

And (3) the mass ratio of the solution A to the solution B is about 1, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 2L/min, the glue injection pressure is 3bar, the mold is kept at 120 ℃ for 10min after resin filling, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in table 5.

TABLE 5

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

Compared with the effect example 8.2, the effect example 8.1 shows that after the resin composition is stored for 6 months, the mechanical property of the prepared composite material has no obvious change, the effective period of the catalytic system is long, and the storage resistance is reliable.

Compared with the effect example 8.3, the effect example 8.1 shows that the composite material prepared by adding the glass fiber filler has higher strength compared with the composite material prepared by not adding the glass fiber filler, and can be used for reinforcing plastics.

Effect example 8.3 in comparison with comparative example 8.1, compared with commercial Grubbs2 ^nd The composite material prepared by the catalyst has better mechanical property in the effect example 8.3, and the catalytic system in the effect example 8.3 is stable and has long storage period, and is more suitable for adding additional components such as functional filler and the like to improve the comprehensive performance of the product.

Compared with the comparative example 8.2, in the effect example 8.1, compared with a commercial tungsten-molybdenum metal carbene catalytic system, the mechanical property of the composite material prepared in the effect example 8.1 is remarkably improved.

Effect example 9: preparation of polydicyclopentadiene/epoxy resin composite material

Effect example 9.1:

using the catalyst composition obtained in example 7, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.

The liquid A comprises the following raw materials in parts by weight:

the liquid B comprises the following raw materials in parts by weight:

the preparation process of the epoxy/polydicyclopentadiene composite material comprises the following steps:

1. preparation of solution A: weighing dicyclopentadiene monomer and bisphenol A epoxy resin to form A liquid according to a formula design scheme;

2. and (3) preparation of a liquid B: weighing and mixing the catalyst composition, the epoxy resin curing agent and the curing accelerator to form a liquid B;

3. mixing the additional components: uniformly mixing the functional filler, the comonomer and the auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;

4. leading in a material storage system: uniformly stirring to fully mix all the components, and respectively introducing the solution A and the solution B into a two-component storage tank of RIM equipment for later use;

5. injection molding: and (3) operating RIM glue injection equipment, mixing the A and B liquid materials on line, injecting the mixture into a mold to complete reaction injection molding, and preparing the polydicyclopentadiene composite material.

6. Curing and demolding: and after the mold is heated and cured, demolding and taking materials to complete the preparation of the composite material product.

And (3) reacting and injecting the solution A and the solution B by RIM equipment at a glue injection speed of 500ml/min and a glue injection pressure of 6bar, keeping the temperature of the mold at 80 ℃ after resin filling for 2h, curing and molding, demolding and taking a piece to finish the test, wherein the mass ratio of the solution A to the solution B is about 3. The panels were cut out and the specific test results are shown in Table 6.

Effect example 9.2:

using the catalyst composition obtained in example 4, an epoxy/polydicyclopentadiene composite material was prepared by RIM reaction injection molding.

The liquid A comprises the following raw materials in parts by weight:

the weight percentage of each component raw material in the liquid B is as follows, the sum of the weight percentage of the catalyst composition, the curing agent and the curing accelerator is 100%, and the weight percentage of other components is the percentage of the weight of each component accounting for the total weight of the catalyst composition, the curing agent and the curing accelerator:

the RIM molding process was the same as in effect example 9.1. And (3) the mass ratio of the solution A to the solution B is about 3, RIM equipment is adopted for reaction and injection molding, the injection speed is 2L/min, the injection pressure is 15bar, the mold is kept at 80 ℃ after resin filling, the curing molding is carried out for 2h, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 6.

Effect example 9.3:

using the catalyst composition obtained in example 9, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	95 parts of
		Bisphenol A epoxy resin	5 portions of
Functional filler: carbon fiber powder	5 portions of

The liquid B comprises the following raw materials in parts by weight:

the RIM molding process was the same as in effect example 9.1. And (3) the mass ratio of the solution A to the solution B is about 8, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 5L/min, the glue injection pressure is 10bar, the mold is subjected to heat preservation at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 6.

Effect example 9.4:

using the catalyst composition obtained in example 8, an epoxy/polydicyclopentadiene composite material was obtained by RIM reaction injection molding.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	80 portions
		Bisphenol A epoxy resin	20 portions of

The liquid B comprises the following raw materials in parts by weight:

the RIM formation process was the same as in example 9.1. And (3) the mass ratio of the solution A to the solution B is about 15, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 30L/min, the glue injection pressure is 25bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 6.

Comparative example 9.1:

commercial Grubbs2 ^nd The catalyst was dissolved in toluene solution to produce commercial Grubbs2 ^nd Catalyst composition (mass ratio of Grubbs2 commercialized) ^nd Catalyst: toluene =1:10 And is subjected to single-component RIM reaction and injection molding to obtain the polydicyclopentadiene composite material.

The weight parts of the raw materials of each component are as follows:

during the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs2 are added ^nd The catalyst composition, the comonomer, the auxiliary agent and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the injection speed is 200mL/min, the injection pressure is 20bar, the mold is insulated for 30min at 100 ℃ after the resin is filled, curing molding is carried out, and the test is finished after demolding and taking out. The panels were cut out and the specific test results are shown in Table 6.

Comparative example 9.2:

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	88.5 portions of
		Commercial Grubbs 2nd catalyst composition	0.5 portion
Comonomer (b): norbornene based on carbon dioxide	8 portions of
		Functional filler: glass fiber	3 portions of

During the reaction forming process of the formula, dicyclopentadiene monomer and commercialized Grubbs2 are added ^nd The catalyst, the comonomer and the functional filler glass fiber are uniformly mixed, reaction and injection molding are carried out by RIM equipment, the glue injection speed is 2L/min, the glue injection pressure is 3bar, the mold is insulated for 10min at 120 ℃ after the resin is filled, curing molding is carried out, and the test is finished after demolding and taking out. The panels were cut out and the specific test results are shown in Table 6.

TABLE 6

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

Compared with the effect example 9.2, the effect example 9.1 shows that the strength and the elastic modulus of the product are obviously improved and the reinforcing effect of the fiber is obvious when the glass fiber functional filler is added into the complex system.

Effect example 9.1 in comparison with comparative example 9.1, it can be seen that the formulated system is comparable to commercial Grubbs2 ^nd The composite material prepared by the catalyst has higher strength.

Compared with the comparative example 9.2, in the effect example 9.2, compared with the commercial polydicyclopentadiene product, the mechanical property of the composite material prepared in the effect example 9.2 is obviously improved, and especially the deformation resistance of the product is obviously improved due to the increase of the elastic modulus.

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

Effect example 9.4 in comparison with effect example 9.1 and comparative example 9.1, it is understood that the addition of the epoxy resin system can improve the strength and deformation resistance of the polydicyclopentadiene resin system to some extent.

Effect example 10: preparation of polydicyclopentadiene/epoxy resin-based fiber-reinforced composite material

In effect example 10, the actual amount of the fiber reinforcement = (the amount of the fiber reinforcement in parts by weight) = (the sum of the amounts of the liquid a and the liquid B in parts by weight)

Effect example 10.1:

the catalyst composition prepared in example 5 is used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin based composite material by an RTM process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	20 portions of
		Bisphenol A epoxy resin	80 portions
Functional filler: graphite powder	5 portions of

The liquid B comprises the following raw materials in parts by weight:

catalyst composition	0.33
		Epoxy curing agent: methyl tetrahydrophthalic anhydride	97.79 portions
Epoxy curing accelerator: 2-methylimidazole	1.88 parts
		Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	15 portions of
Auxiliary agent: polymerization regulator triphenyl phosphine	0.6 part

The preparation process of the polydicyclopentadiene/epoxy resin system comprises the following steps:

2. and (3) preparation of a liquid B: weighing and mixing a liquefaction catalyst, an epoxy resin curing agent and a curing accelerator to form a liquid B;

4. the molding process comprises the following steps: and uniformly stirring to fully mix all the components, and mixing the solution A and the solution B to obtain a polydicyclopentadiene/epoxy resin system.

The mass ratio of the solution A to the solution B is about 10: and 7, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

And (3) preparing the fiber reinforced resin matrix composite material with the fiber mass fraction of 50% by taking continuous glass fibers as a reinforcement. The preparation process of the composite material comprises the following steps:

1. treating the die: the RTM mould is cleaned, and a hole sealing agent and a release agent can be coated to facilitate demoulding and improve the apparent effect of a product;

2. preparation of continuous glass fiber reinforcement: finishing continuous glass fiber cutting, laying and reinforcement shaping according to product design requirements, trimming and then placing in an RTM mold cavity; wherein the mass of the continuous glass fiber accounts for 50% of the mass of the composite material;

3. mold closing and glue injection: closing the mold to ensure good sealing, injecting the prepared epoxy/polydicyclopentadiene resin glue solution into the mold cavity by using an RTM glue injection machine, heating for curing, demolding and taking out the parts to finish the preparation of the composite material.

The continuous glass fiber twill used in this example had an areal density of 250g/m ² The design thickness of the board is 2mm, the warp direction of the fabric is marked as 0 degree direction, and the ply design of the composite board is [0/90 ]] ₅ There are 10 layers of balanced symmetrical ply. Fiber reinforcement preparation is accomplished with reference to this material and ply design. The glue injection pressure in the RTM process forming process of the composite material is 6bar, and the system curing system is 80 ℃ for 5h. The panels were cut out and the specific test results are shown in Table 7.

Effect example 10.2:

the catalyst composition prepared in example 9 was used to prepare a carbon fiber-reinforced polydicyclopentadiene/epoxy resin composite material by an RTM process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	40 portions of
		Bisphenol A epoxy resin	60 portions of
Functional filler: silicon dioxide	10 portions of

The liquid B comprises the following raw materials in parts by weight:

catalyst composition	1.05 parts
		Epoxy curing agent: methylhexahydrophthalic anhydride	94.21 portions
Epoxy curing accelerator: DMP-30	4.74 portions
		Comonomer (b): 5-norbornene-2-carboxylic acid tert-butyl ester	10 portions of
Auxiliary agent: anti-aging agent (Tinuvin 571)	0.98 portion of

The process for preparing polydicyclopentadiene/epoxy resin system was the same as in effect example 10.1. The mass ratio of the solution A to the solution B is about 5:3, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

The preparation process of the carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of the effect example 10.1. Except that the fiber reinforcement described in the present embodiment is continuous carbon fiber, and the area density of the unidirectional fabric is 160g/m ² The design thickness of the board is 1mm, the direction of the unidirectional fabric along the fiber direction is marked as 0 degree, and the ply design of the composite board is [0/90/0 ]] ₃ And 9 layers are uniformly and symmetrically layered. Fiber reinforcement preparation is accomplished with reference to this material and ply design. In the embodiment, the mass of the continuous carbon fiber accounts for 40% of the mass of the composite material; the glue injection pressure in the RTM process forming process of the composite material is 3bar, and the system curing system is 120 ℃/2h. The panels were cut out and the specific test results are shown in Table 7.

Effect example 10.3:

the catalyst composition prepared in example 6 was used to prepare a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material by a vacuum flow guiding process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	50 portions of
		Bisphenol A epoxy resin	50 portions of
Auxiliary agent: coupling agent KH560	0.65 portion
		Auxiliary agent: anti-aging agent (2, 6-di-tert-butyl-4-methylphenol)	1.14 parts

The liquid B comprises the following raw materials in parts by weight:

catalyst composition	1.13 parts of
		Epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride	94.39 parts
Epoxy curing accelerator: DMP-30	4.49 parts
		Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	5 portions of

The process for preparing polydicyclopentadiene/epoxy resin system was the same as in effect example 10.1. The mass ratio of the solution A to the solution B is about 2:1, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

And (3) preparing the fiber reinforced resin matrix composite material with the mass fraction of the fiber of 60 percent by taking the continuous glass fiber as a reinforcement. The preparation process of the composite material comprises the following steps:

1. preparing a prefabricated body: according to the design scheme of the laying layer, finishing cutting, laying layer shaping and trimming of the fiber fabric for later use;

2. bag making: preparing a vacuum bag used in the vacuum flow guide forming process, and detecting good air tightness;

3. injecting glue: under the action of vacuum negative pressure, the resin glue solution is poured;

4. curing and forming: and heating the preformed blank after glue injection to solidify the preformed blank, and demoulding to take the part.

In this effect example, the type of continuous glass fiber used and the ply design are the same as in effect example 10.1. In the vacuum diversion process, the vacuum degree of the vacuum bag is generally more than 920mbar; during air tightness detection, the requirement that the pressure drop is less than 50mbar within 5min is met, and the curing system of the product is 120 ℃/2h. The panels were cut out and the specific test results are shown in Table 7.

Effect example 10.4:

the catalyst composition prepared in example 5 is used for preparing a continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum diversion process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	60 portions of
		Bisphenol A epoxy resin	40 portions of
Functional filler: graphite powder	5 portions of
		Auxiliary agent: polymerization regulator triethyl phosphite	0.02 portion
Auxiliary agent: coupling agent KH560	0.65 portion

The liquid B comprises the following raw materials in parts by weight:

catalyst composition	1.85 parts of
		Epoxy curing agent: methylhexahydrophthalic anhydride	60.83 portions
Epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride	35.58 parts
		Epoxy curing accelerator: 2-ethylimidazole	1.73 parts
Comonomer (b): 5-norbornene-2-carboxylic acid tert-butyl ester	5 portions of

The preparation process of polydicyclopentadiene/epoxy resin system is the same as that of effect example 10.1. The mass ratio of the solution A to the solution B is about 5:2, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

The preparation process of the continuous carbon fiber reinforced polydicyclopentadiene/epoxy resin composite material is the same as that of the effect example 10.3. The difference is that the fiber reinforcement described in the effect example is continuous carbon fiber, and the area density of the unidirectional fabric is 160g/m ² The design thickness of the board is 1mm, the direction of the unidirectional fabric along the fiber direction is marked as 0 degree, and the ply design of the composite board is [0/90/0 ]] ₃ And 9 layers are uniformly and symmetrically layered. Completing fiber reinforcement with reference to the material and ply designAnd (4) preparing a body. In the embodiment, the mass of the continuous carbon fiber accounts for 70% of the mass of the composite material; the results of the composite material testing are shown in Table 7.

Effect example 10.5:

using the catalyst composition prepared in example 10, a continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite was prepared by a wet molding process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	80 portions
		Bisphenol A epoxy resin	20 portions of
Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	5 portions of
		Comonomer (b): 5-norbornene-2-carboxylic acid tert-butyl ester	5 portions of
Functional filler: graphite powder	5 portions of

The liquid B comprises the following raw materials in parts by weight:

catalyst composition	6.25 parts of
		Epoxy curing agent: methyl tetrahydrophthalic anhydride	62.83 portions
Epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride	25.67 parts
		Epoxy curing accelerator: DMP-30	5.24 parts of
Auxiliary agent: anti-aging agent BASF168	1.14 parts
		Auxiliary agent: coupling agent KH560	0.65 portion
Auxiliary agent: anti-aging agent 2-hydroxy-4-methoxybenzophenone	0.985 parts of

The same procedure as in effect example 10.1 was used to prepare a polydicyclopentadiene/epoxy resin system. The mass ratio of the solution A to the solution B is about 5:2, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

And (3) preparing the fiber reinforced resin matrix composite material with the mass fraction of the fiber of 75 percent by taking the continuous glass fiber as a reinforcement. The composite material is prepared by adopting a wet-process die pressing process, and the forming process comprises the following steps:

2. resin coating: uniformly coating the resin glue solution on the prefabricated body in the die cavity;

3. die assembly and press forming: and (3) closing the mold by a press, controlling the pressing process, heating, curing and molding, and demolding and taking out the workpiece.

In this effect example, the type of continuous glass fiber used and the ply design are the same as in effect example 10.1. The prepressing pressure in the wet-method mould pressing process is 0.2MPa, the pressing pressure is 1.5MPa, and the curing system of a resin system is 120 ℃/20min; the panels were cut out and the specific test results are shown in Table 7.

Effect example 10.6:

the catalyst composition prepared in the example 6 is adopted to prepare the continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material through a vacuum diversion process, and the formula of the resin system used by the composite material is the same as that of the effect example 10.3.

And mixing the solution A, the solution B and the accessory components, placing the mixture at room temperature for 6 months, and preparing a composite material product by adopting a vacuum diversion process, wherein the process parameters are the same as those of the effect example 10.3. The panels were cut out and the specific test results are shown in Table 7.

Comparative example 10.1:

using the catalyst composition obtained in example 6, a polydicyclopentadiene/epoxy resin composite material was obtained by a RIM process.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	50 portions of
		Bisphenol A epoxy resin	50 portions of

The liquid B comprises the following raw materials in parts by weight:

the preparation process of the polydicyclopentadiene/epoxy resin composite material comprises the following steps:

1. preparation of solution A: weighing dicyclopentadiene monomer, functional filler and auxiliary agent according to a formula design scheme to form solution A;

2. and (3) preparation of a liquid B: weighing and mixing a liquefaction catalyst and a comonomer to form a solution B;

3. mixing the additional components: uniformly mixing a comonomer and an auxiliary agent into a resin system of the liquid A or the liquid B according to a formula design scheme;

And the mass ratio of the solution A to the solution B is about 2, RIM equipment is adopted for reaction and injection molding, the glue injection speed is 1500ml/min, the glue injection pressure is 6bar, the mold is insulated at 80 ℃ for 2h after the resin is filled, the curing molding is carried out, and the demolding and the piece taking are carried out to finish the test. The panels were cut out and the specific test results are shown in Table 7.

Comparative example 10.2:

using the catalyst composition obtained in example 6, polydicyclopentadiene material was prepared by RIM reaction injection molding.

The weight parts of the raw materials of each component are as follows:

dicyclopentadiene monomer	99.7 parts of
		Catalyst composition	0.3 part
Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	15 portions of
		Functional filler: graphite powder	5 portions of
Auxiliary agent: polymerization regulator triphenyl phosphine	3.2 parts of

The resin system and the RIM forming process method of the composite material are the same as the comparative example 10.1; the difference is that the solution a in the present embodiment only contains dicyclopentadiene monomer, and the mass ratio of the dicyclopentadiene monomer to the solution B is about 5. The specific test results are shown in table 7.

Comparative example 10.3:

the continuous glass fiber reinforced polydicyclopentadiene is prepared by the RTM process by adopting the catalyst composition prepared in the embodiment 6 of the invention, and the formula of the resin system used by the catalyst is the same as that of the comparative example 10.2. The RTM process is adopted to prepare the composite material product, and the forming method and the process parameters are the same as those of the effect example 10.1. The panels were cut out and the specific test results are shown in Table 7.

Comparative example 10.4:

the existing commercial ruthenium carbene olefin metathesis catalyst can only be stored for a long time under the condition of low temperature and solid state. When in use, the catalyst can only be dissolved in a common solvent to prepare a solution with a certain concentration, and the catalyst in the solution state is easy to decompose, so that the catalyst is deactivated. Therefore, ruthenium carbene olefin metathesis catalysts have only been currently formulated in olefin polymerization processes.

A commercial ruthenium carbene catalytic system is adopted, and a vacuum flow guide process is carried out to prepare the continuous glass fiber reinforced polydicyclopentadiene/epoxy resin composite material.

The liquid A comprises the following raw materials in parts by weight:

dicyclopentadiene monomer	50 portions of
		Bisphenol A epoxy resin	50 portions of

The liquid B comprises the following raw materials in parts by weight:

epoxy curing agent: methyl-5-norbornene-2, 3-dicarboxylic anhydride	95.46 parts
		Epoxy curing accelerator DMP-30	4.54 parts of
Comonomer (b): methyl-5-norbornene-2, 3-dicarboxylic anhydride	5 portions of
		Auxiliary agent: coupling agent KH560	0.65 portion
Auxiliary agent: anti-aging agent (2, 6-di-tert-butyl-4-methylphenol)	1.14 parts

The liquid C comprises the following raw materials in parts by weight:

commercial Grubbs 2nd catalyst	6.5 parts of
		Solvent: toluene	93.5 parts

2. and (3) preparation of a liquid B: weighing and mixing an epoxy resin curing agent and a curing accelerator to form a solution B;

4. and C, preparation of a solution C: mixing Grubbs2 ^nd The catalyst is fully dissolved in the toluene solution to form a solution C.

5. The molding process comprises the following steps: and mixing the solution A and the solution B, adding the solution C, and uniformly mixing to obtain the resin system for the composite material.

The mass ratio of the solution A to the solution B to the solution C is about 200:100:1, uniformly mixing by adopting a mechanical stirring mode, wherein the rotating speed is 300-500 r/min, and the stirring time is 20-30 min.

And (3) preparing the fiber reinforced resin matrix composite material with the mass fraction of the fiber of 60 percent by taking the continuous glass fiber as a reinforcement. The preparation process of the composite material is the same as that of effect example 10.3. The specific test results are shown in table 7.

TABLE 7

Serial number	Tensile strength	Modulus of elasticity	Elongation at break
				Effect example 10.1	557MPa	48GPa	3.41％
Effect example 10.2	1865MPa	75GPa	2.74％
				Effect example 10.3	712MPa	57GPa	3.06％
Effect example 10.4	2184MPa	136GPa	1.89％
				Effect example 10.5	852MPa	64GPa	2.83％
Effect example 10.6	703MPa	53GPa	3.31％
				Comparative example 10.1	63MPa	2917MPa	4.42％
Comparative example 10.2	48MPa	2162MPa	5.71％
				Comparative example 10.3	469MPa	36GPa	4.2％
Comparative example 10.4	708MPa	55GPa	3.05％

Claims

1.A catalyst composition is characterized by comprising a ruthenium carbene compound shown as a formula I or a salt thereof and chlorinated paraffin; the chlorine content of the chlorinated paraffin is 5-65%, and the chlorine content is the mass percentage of chlorine atoms in the chlorinated paraffin;

R ^1-1 is C ₆ -C ₁₀ And (3) an aryl group.

2. The catalyst composition of claim 1,

the chlorine content of the chlorinated paraffin is 5-60%;

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

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

and/or, the said quilt R ^1-1 Substituted C ₄ -C ₁₈ In the alkyl radical, R ^1-1 The number of (A) is 1, 2 or 3, and when 2 or 3, they are the same or different;

and/or, said C ₆ -C ₁₀ Aryl is phenyl or naphthyl.

3. The catalyst composition of claim 2,

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

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

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

4. The catalyst composition of claim 3, wherein the ruthenium carbene compound represented by formula I or a salt thereof is present in the chlorinated paraffin in an amount of 0.1mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.55mol/L, or 0.6mol/L;

and/or, said C ₄ -C ₆ Alkyl is C ₄ Alkyl radical, C ₅ Alkyl or C ₆ An alkyl group.

5. The catalyst composition of claim 4, wherein C is ₄ -C ₆ Alkyl is n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl.

6. The catalyst composition of claim 5, wherein C is ₄ -C ₆ Alkyl is n-butyl or n-hexyl.

7. The catalyst composition of claim 1, wherein the ruthenium carbene compound of formula I is of any one of the following structures,

8. the catalyst composition of claim 1, wherein the catalyst composition consists of the ruthenium carbene compound or a salt thereof, as represented by formula I, and a chlorinated paraffin.

9. The catalyst composition of claim 8, wherein the catalyst composition is any combination of:

combination A1:

combination A2:

combination A3:

combination A4:

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

combination A5:

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

combination A6:

combination A7:

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

combination B1:

and chlorinated paraffin with a chlorine content of 5%,

combination B2:

and chlorinated paraffin having a chlorine content of 42%,

combination B3:

and chlorinated paraffin with chlorine content of 52%,

combination B4:

and chlorinated paraffin having a chlorine content of 60%,

combination B5:

and chlorinated paraffin with a chlorine content of 5%,

combination B6:

and chlorinated paraffin having a chlorine content of 42%,

combination B7:

and chlorinated paraffin having a chlorine content of 52%,

combination B8:

and chlorinated paraffin having a chlorine content of 60%,

combination B9:

and chlorinated paraffin having a chlorine content of 52%,

combination B10:

and chlorinated paraffin having a chlorine content of 42%,

combination B11:

and chlorinated paraffin with a chlorine content of 5%,

combination B12:

and chlorinated paraffin having a chlorine content of 60%,

combination B13:

and chlorinated paraffin having a chlorine content of 52%,

10. Use of a catalyst composition according to any one of claims 1 to 9 for catalysing an olefin metathesis reaction.

11. The use of claim 10, wherein the olefin metathesis reaction is a ring-closing metathesis reaction, a cross-metathesis reaction, or a ring-opening metathesis polymerization reaction.

12. The use of claim 11, wherein the ring closing metathesis reaction comprises the steps of: in the presence of a catalyst, carrying out ring-closing metathesis reaction on a compound shown as a formula A1 as shown in the specification to obtain a compound shown as a formula A2; the catalyst is the catalyst composition of any one of claims 1 to 9,

wherein X is O, S, a fragment

Or fragments thereof

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

13. The use of claim 12, wherein the ring closing metathesis is carried out in the absence of a solvent;

and/or X is R ⁷ -N or a fragment

Wherein R is 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 to 3R ^8-3 The substituted heteroatom is one or more selected from N, O and S, and the number of the heteroatoms is 1-3;

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 1-3R ^7-1-1 Substituted C ₆ -C ₁₀ An aryl group;

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

14. The use of claim 13, wherein the ring closing metathesis reaction comprises the steps of: x is R ⁷ -N；

Wherein R is ⁷ is-S (= O) ₂ R ^7-1 ；

R ^7-1-1 is C ₁ -C ₄ An alkyl group.

15. The use according to claim 14, wherein the compound of formula A1 is

16. The use of claim 11, wherein the cross-metathesis reaction comprises the steps of: in the presence of a catalyst, carrying out cross metathesis reaction on a compound containing a fragment B1 and a compound containing a fragment B2 as shown in the specification to obtain a compound containing a fragment B3; the catalyst is the catalyst composition of any one of claims 1-9,

17. the use of claim 16, wherein the cross-metathesis reaction is carried out in the absence of a solvent;

and/or the compound containing the section B1 and the compound containing the section B2 are the same or different;

and/or the compound containing the section B1 and the compound containing the section B2 are independently

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

n3 is 0, 1 or 2;

R ^4-1 is hydrogen, C ₁ -C ₆ Alkyl, unsubstituted or substituted by 1-3R ^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.

18. The use of claim 17, wherein said compound containing tablet B1 and said compound containing tablet B2 are independently

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

n3 is 0, 1 or 2;

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

19. The use of claim 18, wherein said compound comprises compound of formula B1 and compound of formula B2Independently is

20. The use according to claim 11, wherein the ring-opening metathesis polymerisation reaction comprises the steps of: in the presence of a catalyst, carrying out ring-opening metathesis polymerization reaction on a compound containing the segment C1 as shown in the specification to obtain a compound containing the segment C2; the catalyst is the catalyst composition of any one of claims 1-9,

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

n≥3。

21. the use according to claim 20, wherein the ring-opening metathesis polymerisation is carried out in the absence of a solvent;

and/or 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;

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

22. The use of claim 21, wherein said compound containing segment C1 is

R ⁵ And R ⁶ Is hydrogen;

23. The use of claim 22, wherein the compound containing segment C1 is