CN104592425B - A kind of cycloheptatriene base rare-earth metal catalyst, preparation method and application - Google Patents

Abstract

The invention discloses a cycloheptatrienyl rare earth metal catalyst, a preparation method and an application, and belongs to the field of catalysts. The steps of the method are as follows: first, add tropolone, p-toluenesulfonyl chloride and triethylamine into the reactor, react for a period of time under a nitrogen atmosphere, then add amino substituents therein, and react overnight, After recrystallization to obtain the pure product, after reacting with the solution of Et ₃ OBF ₄ for several hours, add the amino substituent dropwise, stir overnight, and purify by column chromatography to obtain the cycloheptatrienyl ligand; secondly, add the ligand dropwise into a toluene solution in which _LnR3 is dissolved, stirred at room temperature for a period of time, filtered, concentrated, and recrystallized to obtain a cycloheptatrienyl rare earth metal catalyst. The catalyst raw material is easy to get, and can be applied to the polymerization of various monomers, including the homopolymerization and copolymerization of olefins, alkynes, and polar monomers, or the copolymerization with _CO respectively; the preparation method of the catalyst The method is simple, economical and environment-friendly, has a wide range of applications and is suitable for industrialized production.

Description

A cycloheptatrienyl rare earth metal catalyst, preparation method and application

technical field

The invention relates to a cycloheptatrienyl rare earth metal catalyst, a preparation method and an application, and belongs to the technical field of catalysts.

Background technique

The conjugation effect refers to an electronic effect that changes the distribution of π electrons (or p electrons) in the system due to the interaction between atoms in the conjugated system. It is an important electronic effect in organic chemistry. It can change the distribution of electron cloud density in the molecule (coplanarization), reduce the internal energy, average the bond length, increase the refractive index, and make the whole molecule more stable. The research on the structure and properties of these molecules is of great significance both in theory and in practice, so this kind of compounds has aroused people's wide interest.

Cycloheptatrienyl ligands have been widely used as non-cene ligands in the field of coordination chemistry. This ligand is a highly conjugated 10π electron system, which opens up a new field of non-benzene ring aromatic compounds. In recent years, the preparation of transition metal complexes with cycloheptatrienyl as ligand has been widely concerned by scientists. Saman Damavandi et al. first reported the application of cycloheptatrienyl transition titanium metal catalysts in olefin polymerization to catalyze ethylene polymerization. The Philip J. Bailey research group synthesized cycloheptatrienyl metal organic compounds of magnesium, aluminum and indium; Brookhart et al. also synthesized cycloheptatrienyl ligand-supported nickel metal complexes; Peter W. Roesky and Siegfried Blechert et al. reported calcium and zinc cycloheptatrienyl metal complexes, and used them to catalyze the hydroamination reaction of terminal olefins with amino substituents, which has high activity; Selvarajan Nagendran et al. reported the synthesis of germanium Cycloheptatrienyl metal complexes, Nathan M.West research group successfully synthesized cycloheptatrienyl ligand supported platinum metal complexes. In summary, the catalysts synthesized by this ligand and some main group metals (such as Zn, Mg, Ca, Al, etc.) and transition metals (Ni, Ti, Pt, etc.) have been obtained in organic small molecule reactions and ethylene polymerization. application. However, the preparation route of the cycloheptatrienyl metal complex is relatively complicated, usually starting from the cycloheptatrienyl ligand, reacting with KH at -78°C to remove the hydrogen atom on the cycloheptatriene ligand, and then Add metal halide reaction. This process takes a long time to react, making this method not possible for a large-scale industrial process. Therefore, those skilled in the art are eager to find a method for preparing cycloheptatrienyl metal compounds that is more economical, environmentally friendly and suitable for industrialization. At present, cycloheptatrienyl rare earth metal catalysts, preparation methods and applications in polymerization reactions have not been reported.

Contents of the invention

One of the objects of the present invention is to provide a cycloheptatrienyl rare earth metal catalyst; the second object of the present invention is to provide a preparation method of a cycloheptatrienyl rare earth metal catalyst; the third object of the present invention is to provide a cycloheptatrienyl rare earth metal catalyst Application of a cycloheptatrienyl rare earth metal catalyst.

The purpose of the present invention is achieved by the following technical solutions:

A cycloheptatrienyl rare earth metal catalyst, the structural formula of the cycloheptatrienyl rare earth metal catalyst has the following two types: I and II:

In formulas I and II, R ₁ , R ₂ and R ₈ are initiator groups linked to rare earth metals; L ₁ and L ₂ are coordination groups linked to rare earth metals; R ₄ , R ₁₀ and R ₁₀ ' are Substituent groups on the N atom of the cycloheptatriene skeleton; R ₃ , R ₉ and R ₉ ' are substituent groups on the double bond of the cycloheptatriene skeleton; R ₅ , R ₆ , R ₇ , R ₁₁ , R ₁₁ ', R ₁₂ , R ₁₂ ', R ₁₃ and R ₁₃ 'are substituents on the cycloheptatriene ligand skeleton; Ln ₁ and Ln ₂ are rare earth metals;

Among them, R ₁ , R ₂ and R ₈ are all preferably alkyl, trimethylsilyl, amine, imino, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, One of Cl, Br or I;

L ₁ and L ₂ are preferably phosphorus-based ligands (such as triphenylphosphine), ether ligands (such as tetrahydrofuran, ether), neutral amine-based ligands (such as pyridine), imidazole, carbazole, oxazole, DMF a kind of

R ₄ is preferably 2,6-dimethylbenzene, 2,6-diisopropylbenzene, 2-tert-butylbenzene, 2-methyl-6-tert-butylbenzene, 2,6-diphenylbenzene, Pentafluorobenzene, 2,6-dibromobenzene, 3,5-trifluoromethylbenzene, 2-methylbenzene, 2-methyl-6-trifluoromethylbenzene, 2,6-difluorobenzene A sort of;

R is preferably _one of isopropyl, tert-butyl and n-butyl;

_R3 is preferably 2,6-dimethylaniline, 2,6-diisopropylaniline, 2-tert-butylaniline, 2-methyl-6-tert-butylaniline, 2,6-diphenylaniline, Pentafluoroaniline, 2,6-dibromoaniline, 3,5-trifluoromethylaniline, 2-methylaniline, 2-methyl-6-trifluoromethylaniline, 2,6-difluoroaniline A sort of;

R ₉ and R ₉ ' are preferably one of oxygen atom, isopropylamine and tert-butylamine;

R ₅ , R ₁₁ and R ₁₁ ' are preferably hydrogen atom, methyl group, ethyl group, alkoxy group, isopropyl group, tert-butyl group, n-butyl group, nitro group, amino group, iodine atom, bromine atom, phenyl group, benzyl group One of nitrile, thiophenyl, anilino, phenol, thiophenyl and 3,5-difluoromethanephenylthio;

R ₆ and R ₇ are preferably one of phenyl, benzyl, anthracenyl, naphthyl, phenanthrenyl, thiophenyl, anilino, phenol, phenylthio and 3,5-difluoromethanephenylthio;

R ₁₂ , R ₁₂ ', R ₁₃ and R ₁₃ ' are preferably hydrogen atom, methyl group, ethyl group, isopropyl group, tert-butyl group, n-butyl group, alkoxy group, nitrile group, amino group, iodine atom, bromine atom, One of nitro and nitrile;

Ln ₁ and Ln ₂ are preferably scandium (Sc), lutetium (Lu), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nb), promethium (Pm), samarium (Sm) , europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) or ytterbium (Yb);

A preparation method of a cycloheptatrienyl rare earth metal catalyst, the method steps are as follows:

(1) preparation of cycloheptatrienyl ligand;

First, take tropolone and p-toluenesulfonyl chloride into the reactor, add a good solvent at room temperature, preferably dichloromethane, start stirring the mixture, then add triethylamine dropwise to the mixture, at this time A yellow muddy substance will be produced; another good solvent is added to dilute the reaction; after stirring for about 32 hours at room temperature under the atmosphere of nitrogen protection, compound a is obtained. Wherein the mol ratio of tropolone, p-toluenesulfonyl chloride and triethylamine is 1:1:1;

Next, the amine substituent was slowly added dropwise to a at low temperature; the mixture was stirred overnight at room temperature. After recrystallization with a good solvent and a poor solvent, the product b containing double bond O is obtained;

Finally, slowly add the CH ₂ Cl ₂ solution of product b into the Et ₃ OBF ₄ solution, stir at room temperature for a certain period of time, then slowly drop the amino substituent into the above reaction flask, and wait for the reaction to recover After reaching room temperature, stir overnight to obtain a mixture c containing the target product; add 25-35 mL of a good solvent to the mixture c, separate to obtain an aqueous phase and an organic phase, add 5-10 g of a solid desiccant to the organic phase, and filter. Spin dry to get the crude product. The cycloheptatrienyl ligand is obtained by purifying the product through column chromatography;

(2) prepare cycloheptatrienyl rare earth metal catalyst;

First, the reactor is placed in a glove box, the cycloheptatriene ligand described in step (1) is added dropwise to the solution in which the metal source is dissolved, and the reaction is stirred at room temperature for 6 hours to obtain a mixture, which is filtered , taking the obtained liquid and concentrating to obtain a cycloheptatrienyl rare earth catalyst crude product, and recrystallizing the crude product to obtain a cycloheptatrienyl rare earth metal catalyst;

Wherein, the temperature of reaction is 20～25 DEG C, and the mol ratio of cycloheptatrienyl ligand and metal source is 1:1 or 2:1; In step (1), the preferred dichloromethane of good solvent; Preferred anhydrous magnesium sulfate ( MgSO ₄ ) to dry the organic phase; the metal source in step (2) is preferably ditetrahydrofuran-tris(trimethylsilylmethyl)-rare earth metal compound, the molecular formula is [Ln(CH ₂ SiMe ₃ ) ₃ (THF) ₂ ];

An application of a cycloheptatrienyl rare earth metal catalyst, the cycloheptatrienyl rare earth metal catalyst forms a catalytic system with an alkylaluminum reagent and an organic boron salt, and is used to catalyze the homogeneous reaction of olefins, alkynes, and polar monomers. Polymerization and copolymerization, or copolymerization of olefins, alkynes, and polar monomers with _CO2 ;

Wherein, the molar ratio of the alkylaluminum reagent, organoboron salt and cycloheptatrienyl rare earth metal catalyst is 2-100:1-100:1; the alkylaluminum reagent is an alkylaluminum with a molecular _formula of AlR3 and a molecular formula of HAlR ₂ alkylaluminum hydride, alkylaluminum chloride or aluminoxane with molecular formula AlR ₂ Cl, R is an alkyl group;

The steps of the homopolymerization reaction are as follows:

The reaction bottle is placed in a glove box, and the cycloheptatrienyl rare earth catalyst, 5-10 mL of good solvent, aluminum alkyl, olefin, alkyne or polar monomer, organoboron salt are added successively in the reaction bottle. After reacting under stirring for 0.3-6h, take out the reaction bottle, add a chain terminator to stop the reaction; pour the reaction solution into ethanol to settle, and precipitate solid matter, and remove the solvent in a vacuum oven at 30°C To constant weight, obtain the homopolymer product;

Among them, the molar ratio of alkenes, alkynes or polar monomers, alkylaluminum reagents, organic boron salts and cycloheptatrienyl rare earth catalysts is 200-600:2-100:1-100:1; the reaction temperature is 25- 90°C.

The steps of the copolymerization reaction are as follows:

Place the reaction bottle in a glove box, add the cycloheptatrienyl rare earth catalyst, 1 to 40 mL of good solvent, aluminum alkyl, reactant a or reactant b, organoboron salt in turn in the reaction bottle, and stir After reacting for 3 to 24 hours, the reaction bottle was taken out, and a chain terminator was added to terminate the reaction; the reaction solution was poured into ethanol to settle, and a solid substance was precipitated, and the solid substance was removed with a vacuum oven at 30°C until constant Heavy, obtain the copolymerization product;

Wherein, the molar ratio of reactant a or reactant b, alkylaluminum reagent, organoboron salt and cycloheptatrienyl rare earth catalyst is 200-5000:2-100:1-100:1; the reaction temperature is 25-70 ℃; reactant a is two kinds of branched olefins, cycloalkenes, alkynes, and polar monomers, and reactant b is one of branched alkenes, cycloalkenes, alkynes, polar monomers, and CO ₂ .

The aluminum alkyl is preferably trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, tricyclohexylaluminum, One of octyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-tolyl aluminum and diethyl benzyl aluminum;

The alkyl aluminum hydride is preferably dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride aluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, diphenylaluminum hydride, di-p-cresylaluminum hydride, dibenzylaluminum hydride, ethylbenzylaluminum hydride and ethylp- One of the tolyl aluminum;

The alkyl aluminum chloride is preferably: dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisopropylaluminum chloride, diisopropylaluminum chloride, Isobutyl aluminum, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dichloride One of benzyl aluminum, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride;

The aluminoxane is preferably: one of methylalumoxane, ethylalumoxane, n-propylalumoxane and n-butylalumoxane;

The organoboron salt is preferably triphenyl(methyl)-tetrakis(pentafluorophenyl)boron salt ([Ph ₃ C][B(C ₆ F ₅ ) ₄ ]), phenyl-dimethylamino-tetrakis (Pentafluorophenyl) boron salt ([PhMe ₂ NH][B(C ₆ F ₅ ) ₄ ]), phenyl-dimethylamino-tetraphenyl boron salt ([PhMe ₂ NH][BPh ₄ ]) or One of tris(pentafluorophenyl)boron salts (B(C ₆ F ₅ ) ₃ );

The branched olefins are preferably ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, styrene, α-methylstyrene, 3-chloromethylstyrene, 1,3- One of butadiene, isoprene, 1,3-cyclohexadiene, 1,5-pentadiene, 1,6-hexadiene and divinylbenzene;

The cycloolefin is preferably one of norbornene, polar norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene and dicyclopentadiene;

The alkyne is preferably one of acetylene, phenylacetylene, p-phenyleneacetylene and diethynyl arenes;

The polar monomers are divided into alkylene oxides and lactones, wherein alkylene oxides are preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, heterocyclic Oxybutylene, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexylidene glycidyl ether, trifluoropropylene oxide, internal The ester is one of ε-caprolactone, β-butyrolactone, δ-valerolactone, lactide, glycolide and 3-methyl-glycolide;

The chain terminator preferably contains 5% ethanol of 2,6-di-tert-butyl-4-methylphenol, and the volume of ethanol is 100%, wherein, 2,6-di-tert-butyl-4-methyl The volume ratio of phenol is 5%; the good solvent is preferably toluene.

Beneficial effect

(1) The cycloheptatrienyl rare earth metal catalyst of the present invention is based on tropolone as the initial raw material, and the raw material is cheap and easy to obtain, and is easy to modify;

(2) The preparation method of the cycloheptatrienyl rare earth metal catalyst of the present invention has high economic efficiency and good environmental protection, and is suitable for industrialized production;

(3) The catalytic system formed by cycloheptatrienyl rare earth metal catalyst, alkylaluminum reagent and organic boron salt according to the present invention can carry out homopolymerization and Copolymerization or copolymerization of branched olefins, cyclic olefins, alkynes, polar monomers and _CO2 to obtain a series of new polymer materials with specific structures;

(4) The cycloheptatrienyl rare earth metal catalyst of the present invention can make the homopolymerization yield of ε-caprolactone reach 74.9% when catalyzing the polymerization of L-lactide and ε-caprolactone, The yield of homopolymerization of L-lactide can reach 100%.

(5) When the cycloheptatrienyl rare earth metal catalyst of the present invention catalyzes the polymerization of isoprene, the yield can reach 100%, and the selectivity of the cis 1,4-structure can reach up to 94.34%. This is a new type of isoprene rubber material that has not been reported yet. Further research on its physical and chemical properties will help to find suitable applications for it.

Description of drawings

Fig. 1 is a crystal structure diagram characterized by X-ray single crystal diffraction of cycloheptatrienyl scandium catalyst.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but is not limited thereto.

The main reagent information mentioned in the following examples is shown in Table 1; the main instruments and equipment information are shown in Table 2.

Table 1

Table 2

In the following examples, the polymerization activity is calculated by the formula Activity=(m·yeild)/(n _cat ·time). Among them, Activity is active polymerization, the unit is kg mol ^-1 h ^-1 , m is the mass of branched alkenes, cycloalkenes, alkynes, polar monomers or CO ₂ , yield is the yield, and n _cat is the catalyst The amount of substance, time is the time used for polymerization.

The microstructure of polyisoprene can be given by ¹ H-NMR and ¹³ C-NMR spectra, and the specific calculation formula of selectivity is as follows:

(1) Selectivity (proportion) of 1,4-polyisoprene:

Mol 1,4-IP%＝{I _H1 /(I _H1 +0.5I _H2 )}×100

(2) Selectivity (proportion) of 3,4-polyisoprene:

Mol 3,4-IP%＝{0.5I _H2 /(I _H1 +0.5I _H2 )}×100

(3) Selectivity (proportion) of cis 1,4-polyisoprene:

Mol cis-1,4-IP%＝{I _C1 /(I _C1 +I _C2 +I _C3 )}×100

(4) Selectivity (proportion) of anti-1,4-polyisoprene:

Mol trans-1,4-IP%＝{I _C3 /(I _C1 +I _C2 +I _C3 )}×100

(5) Selectivity (proportion) of 3,4-polyisoprene:

Mol 3,4-IP%＝{I _C2 /(I _C1 +I _C2 +I _C3 )}×100

Wherein, IP is polyisoprene, I _H1 is the integral at 5.13ppm in the ¹ H spectrum; I _H2 is the integral at 4.72ppm in the ^1H spectrum; I _C1 is the integral at 23.2ppm in the ¹³ C spectrum; I _C2 is the integral at 18.5 ppm in the ¹³ _C spectrum; IC3 is the integral at 15.9 ppm in the ¹³ C spectrum.

Example 1

(1) Preparation of cycloheptatrienyl ligand

First, weigh 5.3 g (43 mmol) of tropolone and 8.2 g (43 mmol) of p-toluenesulfonyl chloride into the reactor, add 60 mL of dichloromethane at room temperature, start stirring the mixture, and then add 6 mL of (43mmol) triethylamine, this moment will produce yellow muddy substance. Another 60 mL of dichloromethane was added. Compound a was obtained after stirring for about 32 h at room temperature under an atmosphere of nitrogen protection.

Next, isopropylamine (60 mL) was slowly added dropwise into a (10.92 g, 40.0 mmol) at low temperature. After the mixture was stirred overnight at room temperature, it was rotary evaporated under reduced pressure, and the obtained substance was dissolved in 2 mol/L NaOH (60 mL) and CH ₂ Cl ₂ (120 mL), separated into layers, and the organic phase was separated. The aqueous phase was extracted ₂ more times with _CH2Cl2 (120 mL). The organic phases were combined, washed with 20 mL of concentrated brine, dried with anhydrous MgSO ₄ , filtered with suction, and the filtrate was spin-dried, and the obtained solid was recrystallized with CH ₂ Cl ₂ and n-hexane to obtain a yellow solid b, which was cycloheptane Alkenyl ligand, yield 80.9%.

(2) Preparation of Cycloheptatrienyl Scandium Catalyst

First, the reactor was placed in a glove box, and the cycloheptatriene ligand (665.9 mg, 4.08 mmol) prepared in step (1) was added dropwise to a solution of Sc(CH ₂ SiMe ₃ ) ₃ (thf) ₂ ( 920mg, 2.04mmol) of toluene solution, reacted for 6h under stirring to obtain mixture c; wherein, the reaction temperature was 25°C;

Next, the mixture c was filtered, and the resulting liquid was concentrated to obtain a crude cycloheptatrienyl scandium catalyst product, which was recrystallized to obtain 0.720 g of a yellow powder, which was cycloheptatrienyl scandium catalyst d , the yield was 65%. As shown in the accompanying drawing, it is a crystal structure diagram characterized by X-ray single crystal diffraction of cycloheptatrienyl scandium catalyst d.

The following examples 5 to 11 and examples 16 to 18 are applications of the cycloheptatrienyl scandium catalyst d described in example 1.

Example 2

(1) Preparation of cycloheptatrienyl ligand

First, weigh 5.3 g (43 mmol) of tropolone and 8.2 g (43 mmol) of p-toluenesulfonyl chloride into the reactor, add 60 mL of dichloromethane at room temperature, and then add 4.4 g (6 mL, 43mmol) triethylamine, and another 60mL of dichloromethane was added. Under the protection of nitrogen at room temperature, after stirring for about 32 h, compound a was obtained. The operation of compound b is the same as in Example 1. Next, slowly add the CH ₂ Cl ₂ solution of product b (1.37g, 9.20mmol) into the Et ₃ OBF ₄ (1.75g, 9.21mmol) solution, stir at room temperature for 3h, and spot the plate until the new product When the point no longer changed, the reaction was cooled to 0°C, and then isopropylamine (20 mL) was slowly added dropwise into the above reaction flask. After the reaction returned to room temperature, it was stirred overnight to obtain a mixture e containing the target product. The oily substance after rotary evaporation under reduced pressure was dissolved in NaOH (10 mL) and CH ₂ Cl ₂ (20 mL), and the organic phase was separated. The aqueous phase was extracted twice with _CH2Cl2 ( ₂₀ mL). The organic phases were combined, washed with 20 mL of concentrated brine, and dried over anhydrous MgSO ₄ . Suction filter and spin dry. The crude product was obtained. The product was purified by column chromatography to obtain 1.39 g of the cycloheptatrienyl ligand f with a yield of 47.9%.

(2) Preparation of Cycloheptatrienyl Scandium Catalyst

First, the reactor was placed in the glove box, and the cycloheptatrienyl ligand f (613.0mg, 3mmol) prepared in step (1) was added dropwise to the dissolved Sc(CH ₂ SiMe ₃ ) ₃ (thf) ₂ (676.2mg, 1.5mmol) in a toluene solution, reacted for 6h under stirring to obtain a mixture g; wherein, the reaction temperature was 25°C;

Next, after the mixture g is filtered, it is concentrated to obtain a crude product of the cycloheptatrienyl scandium catalyst, and the crude product is recrystallized to obtain 0.530 g of a yellow powder, which is the cycloheptatrienyl scandium catalyst h, producing The rate is 58%.

The following examples 12-15 are the polymerization application of cycloheptatrienyl scandium catalyst h described in example 2.

Example 3

(1) Preparation of cycloheptatrienyl ligand

The operation of compounds a and b is the same as in Example 1. Afterwards, the CH ₂ Cl ₂ solution of product b (1.37g, 9.20mmol) was slowly added to the Et ₃ OBF ₄ (1.75g, 9.21mmol) solution, and after stirring at room temperature for 3h, spot the plate to confirm that there was new The product is formed until the new product point no longer changes, the reaction is cooled to 0°C, and then isopropylamine (20mL) is slowly added dropwise at a rate of 1s/drop into the above reaction flask, and the reaction is returned to room temperature , stirred overnight to obtain mixture e containing the desired product. The product was purified by column chromatography to obtain 1.39 g of the cycloheptatrienyl ligand f with a yield of 47.9%.

(2) Preparation of Cycloheptatrienyl Lutetium Catalyst

First, the reactor was placed in the glove box, and the cycloheptatrienyl ligand f (326.9 mg, 3.0 mmol) prepared in step (1) was added dropwise to the solution of Lu(CH ₂ SiMe ₃ ) ₃ (thf) ₂ (676.2mg, 1.5mmol) in toluene solution, reacted for 6h under stirring to obtain mixture i; wherein, the reaction temperature was 25°C;

Next, after the mixture i was filtered, it was concentrated to obtain a crude cycloheptatrienyllutetium catalyst product, which was recrystallized at -33°C to obtain 0.699g of cycloheptatrienyllutetium catalyst j, The yield was 63%.

Example 4

(1) Preparation of cycloheptatrienyl ligand

The operation of compound a is the same as in Example 1. After that, isopropylamine (60 mL) was slowly added dropwise into a (10.92 g, 40.0 mmol) at 0°C. The mixture was stirred overnight at room temperature. After recrystallization of the obtained solid with CH ₂ Cl ₂ and n-hexane, a yellow solid b was obtained. Finally, the CH ₂ Cl ₂ solution of product b (1.37g, 9.20mmol) was slowly added to the Et ₃ OBF ₄ (1.75g, 9.21mmol) solution, and after stirring at room temperature for 3h, spot the plate to confirm that there was new When the product was formed, the reaction was cooled to 0°C, and then isopropylamine (20 mL) was slowly added dropwise into the reaction flask. After the reaction returned to room temperature, it was stirred overnight to obtain a mixture e containing the target product. The product was purified by column chromatography to obtain 1.39 g of the cycloheptatrienyl ligand f with a yield of 47.9%.

(2) Preparation of Cycloheptatrienyl Yttrium Catalyst

First, the reactor was placed in the glove box, and the cycloheptatrienyl ligand f (1175.2 mg, 4.7 mmol) prepared in step (1) was added dropwise to the solution of Y(CH ₂ SiMe ₃ ) ₃ (thf) ₂ (1162.8mg, 2.4mmol) in toluene solution, reacted for 6h under stirring to obtain mixture k; wherein, the reaction temperature was 25°C;

Next, after filtering the mixture k, it was concentrated to obtain a crude cycloheptatrienyllutetium catalyst product, which was recrystallized at -33°C to obtain 0.989g of cycloheptatrienyllutetium catalyst 1, The yield was 63%.

Example 5

Put the reactor in the glove box, add 20 μmol of cycloheptatrienyl scandium catalyst d, 40 μmol of ^iPrOH to the eggplant bottle, add 2mL of THF, stir at room temperature for 10-30min, and then add 3mL containing 8mmol of L-lactide Add THF solution into the catalyst mixture, stir and react for 2.5h, the reaction temperature is 25°C, after the solution becomes viscous, add 10% HCl ethanol solution by volume fraction to stop the reaction, then pour into ethanol to settle, filter, The white polymer was obtained by washing, and the solid was vacuum-dried at 30° C., and the solvent was removed to a constant weight to obtain polylactide, with a net weight of 0.055 g, a conversion rate of 5.8%, and a polymerization activity of 1.64 kg·mol ^-1 ·h ^{- 1} ; GPC analysis of polylactide has a number average molecular weight M _n =23×10 ⁴ , and a molecular weight distribution M _w /M _n =1.58.

Example 6

Put the reactor in a glove box, add 20 μmol of cycloheptatrienyl scandium catalyst d, 40 μmol of EtONa, and 2 mL of CH ₂ Cl ₂ into the eggplant bottle, and stir at room temperature for 10 to 30 minutes, then add 3 mL of 8 mmol L- _{The CH2Cl2} solution of lactide was added to the catalyst mixture, stirred and reacted for 2.5h, the reaction temperature was 25°C, and the rest of the operations were the same as in Example 5 to obtain polylactide, with a net weight of 1.179g, a conversion rate of 100%, and a polymerization activity of It is 23.58 kg·mol ^-1 ·h ^-1 ; the number average molecular weight of polylactide M _n =15×10 ⁴ by GPC analysis, and the molecular weight distribution M _w /M _n =1.31.

Example 7

Put the reactor in a glove box, add 20 μmol of cycloheptatrienyl scandium catalyst d, 40 μmol of EtONa, and 2 mL of THF to the eggplant bottle, and stir for 10 to 30 minutes, then add 3 mL of THF containing 8 mmol ε-caprolactone solution, and then added to the catalyst mixture, stirred and reacted for 2.5h, and the rest of the operations were the same as in Example 5 to obtain 0.683g of polycaprolactone, with a conversion rate of 74.9%, and a polymerization activity of 13.68kg·mol ^-1 ·h ^-1 ; GPC analysis The number average molecular weight M _n of polycaprolactone = 9×10 ⁴ , and the molecular weight distribution M _w /M _n = 1.69.

Example 8

Put the reactor in a glove box, add 20 μmol of cycloheptatrienyl scandium catalyst d, 40 μmol of EtONa, and 2 mL of CH ₂ Cl ₂ into the eggplant bottle, and stir for 10 to 30 minutes, then add 3 mL of 4 mmol of L- Lactide and 4 mmol of ε-caprolactone in CH ₂ Cl ₂ solution were added to the catalyst mixture, stirred for 4 hours, and the remaining operations were the same as in Example 5 to obtain a copolymer of L-lactide and ε-caprolactone , net weight 0.859g, polymerization activity 34.36kg·mol ^-1 ·h ^-1 ; GPC analysis of the number average molecular weight of the copolymer M _n =8×10 ⁴ , molecular weight distribution M _w /M _n =1.33.

Example 9

Put the reactor in the glove box, add 25 μmol of cycloheptatrienyl scandium catalyst d, 5 mL of toluene, 50 μmol of Al ⁱ Bu ₃ , 5 mmol of phenylacetylene and 25 μmol of [PhNHMe ₂ ][B(C ₆ F ₅ ) ₄ ], after reacting at 50°C for 0.3h, take out the eggplant bottle, add 30mL of ethanol containing 5% 2,6-di-tert-butyl-4-methylphenol to stop the reaction; settle the reaction solution with ethanol , precipitated a white solid substance, the solid substance was vacuum-dried at 30° C., and the solvent was removed to a constant weight to obtain polyphenylene vinylene with a net weight of 0.29 g and a conversion rate of 57%; the number average molecular weight M _n of polyphenylene vinylene was analyzed by GPC = 2×10 ⁴ , molecular weight distribution M _w /M _n = 1.73.

Example 10

Put the reactor in the glove box, add 25 μmol scandium cycloheptatriene catalyst d, 5 mL toluene, 50 μmol AlMe ₃ , 5 mmol propylene oxide and 25 μmol [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], reaction time 5h, reaction temperature 50 ℃, all the other operations are with embodiment 9, obtain polypropylene oxide, net weight 0.26g, transformation efficiency 90%; GPC analyzes the number average molecular weight M _n of polypropylene oxide =17 * 10 ⁴ , molecular weight distribution M _w /M _n = 1.62.

Example 11

The reactor was placed in a glove box, and 21 μmol of cycloheptatrienyl scandium catalyst d, 25 mL of toluene, 42 μmol of Al ⁱ Bu ₃ , 53 mmol of norbornene, 53 mmol of 1,4-butadiene, and 21 μmol of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], the reaction time is 3h, the reaction temperature is 25°C, and the rest of the operations are the same as in Example 9 to obtain a copolymer of norbornene and 1,4-butadiene, the conversion rate 79%; GPC analysis of the number average molecular weight of the copolymer M _n =3.5×10 ⁴ , molecular weight distribution M _w /M _n =1.69.

Example 12

The reactor was placed in a glove box, and 25 μmol cycloheptatrienyl scandium catalyst h, 5 mL toluene, 50 μmol Al ⁱ Bu ₃ , 15 mmol isoprene and 25 μmol [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], the reaction time was 6 hours, the reaction temperature was 25°C, and the rest of the operations were the same as in Example 9 to obtain polyisoprene with a net weight of 0.714 g, a conversion rate of 70%, and a polymerization activity of 4.8 kg·mol ^-1 · h ^-1 ; GPC analysis showed that the number average molecular weight of polyisoprene was Mn=10×10 ³ , and the molecular weight distribution M _w /M _n =1.54; the cis 1,4-polymerization selectivity was 84%.

Example 13

The reactor was placed in a glove box, and 25 μmol cycloheptatrienyl scandium catalyst h, 5 mL toluene, 50 μmol Al ⁱ Bu ₃ , 5 mmol isoprene and 25 μmol [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], the reaction time was 6 hours, the reaction temperature was 25°C, and the rest of the operations were the same as in Example 9 to obtain polyisoprene with a net weight of 0.335 g, a conversion rate of 98.5%, and a polymerization activity of 2.2 kg·mol ^-1 · h ^-1 ; GPC analysis showed that the number average molecular weight of polyisoprene was Mn=15×10 ³ , and the molecular weight distribution M _w /M _n =1.76; the cis 1,4-polymerization selectivity was 94.34%.

Example 14

The reactor was placed in a glove box, and 25 μmol cycloheptatrienyl scandium catalyst h, 10 mL toluene, 2.5 mmol Ali Bu ₃ , 5 mmol isoprene and 2.5 mmol [ ^PhNHMe ₂ ][B( C ₆ F ₅ ) ₄ ], reaction time 3 h, reaction temperature 25°C, and other operations were the same as in Example 9 to obtain polyisoprene with a net weight of 0.306 g, a conversion rate of 90%, and a polymerization activity of 4.1 kg·mol ^-1 · h ^-1 ; GPC analysis showed that the number average molecular weight of polyisoprene was Mn=18×10 ³ , and the molecular weight distribution M _w /M _n =1.98; the cis 1,4-polymerization selectivity was 89%.

Example 15

The reactor was placed in a glove box, and 25 μmol cycloheptatrienyl scandium catalyst h, 10 mL toluene, 2.5 mmol Ali Bu ₃ , 5 mmol isoprene and 2.5 mmol [ ^PhNHMe ₂ ][B( C ₆ F ₅ ) ₄ ], the reaction time was 3 hours, the reaction temperature was 90°C, and the rest of the operations were the same as in Example 9 to obtain polyisoprene with a net weight of 0.34 g, a conversion rate of 100%, and a polymerization activity of 4.5 kg·mol ^-1 · h ^-1 ; GPC analysis showed that the number average molecular weight of polyisoprene was Mn=12×10 ³ , and the molecular weight distribution M _w /M _n =2.27; the cis 1,4-polymerization selectivity was 76%.

Example 16

Put the reactor in the glove box, weigh 2g of norbornene monomer into a 50mL eggplant bottle with a 20mL clean vial, add 4.57mL of toluene, add 0.5μmol cycloheptatrienyl scandium catalyst d with a syringe, and drop AlMe ₃ toluene solution 8 μL. After 1h, take out the glove box and use 30mL degradation reaction solution with acidic ethanol (ethanol:concentrated hydrochloric acid=20:1), filter, and wash with ethanol to filter out the solid; after the solid is crushed as much as possible, vacuum-dry in a vacuum oven at 30°C, remove the solvent to With constant weight, 0.04 g of polynorbornene was obtained, the yield was 2.0%, and the polymerization activity was 40.0 kg·mol ^-1 ·h ^-1 ; the number average molecular weight of polynorbornene by GPC analysis was Mn=15×10 ³ , and the molecular weight distribution M _w /M _n = 1.27.

Example 17

The reactor was placed in a glove box, and 25 μmol cycloheptatrienyl scandium catalyst d, 5 mL toluene, 250 μmol Al ⁱ Bu ₃ , 10 mmol styrene and 25 μmol [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], the reaction time is 4h, and the reaction temperature is 25°C. The remaining operations were the same as in Example 9 to obtain polystyrene; the net weight was 0.382 g, the conversion rate was 36.7%, and the polymerization activity was 3.82 kg·mol ⁻¹ ·h ⁻¹ ; the number average molecular weight of polystyrene analyzed by GPC was Mn=90×10 ³ , molecular weight distribution M _w /M _n = 1.49.

Example 18

Put the reactor in a glove box, add 50 μmol of cycloheptatrienyl scandium catalyst d, 1 mL of toluene, and 20 mol of propylene oxide to the eggplant bottle in sequence, seal the reactor, transfer it out of the glove box, and inject CO ₂ into the reactor , adjusted the pressure to 6Mpa, then heated to 70°C, reacted for 24h, then cooled to room temperature, dissolved in chloroform, added methanol to obtain a white solid, washed with methanol, and dried in vacuum to obtain a copolymer of propylene oxide and CO ₂ ; The ratio was 43.0%, the molecular weight was M _n =31×10 ³ , and the molecular weight distribution M _w /M _n =1.40.

The present invention includes but is not limited to the above embodiments, and any equivalent replacement or partial improvement under the principle of the spirit of the present invention will be considered within the protection scope of the present invention.

Claims (8)

1. A cycloheptatrienyl rare earth metal catalyst, characterized in that: the cycloheptatrienyl rare earth metal catalyst structural formula has two kinds of following I and II: Among them, R ₁ , R ₂ and R ₈ are initiator groups linked to rare earth metals; L ₁ and L ₂ are coordination groups linked to rare earth metals; R ₄ , R ₁₀ and R ₁₀ ' are The substituent group on the N atom connected to the carbon atom of the alkenyl skeleton; R ₃ , R ₉ and R ₉ ' are the substituent groups connected to the carbon atom of the cycloheptatrienyl skeleton; R ₅ , R ₆ , R ₇ , R ₁₁ , R ₁₁ ', R ₁₂ , R ₁₂ ', R ₁₃ and R ₁₃ ' are substituents on the cycloheptatriene ligand skeleton; Ln ₁ and Ln ₂ are rare earth metals; R ₁ , R ₂ , R ₈ are all alkyl, trimethylsilyl, amino, imino, alkoxy, benzyl, cyclopentadienyl, indenyl, fluorenyl and halogen F, Cl, One of Br or I; L1 and L2 are both ether ligands and neutral amine ligands, wherein the ether ligands are one of tetrahydrofuran and ether; the neutral amine ligands are pyridine, imidazole, carbazole, One of oxazole and DMF; R ₄ is 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2-tert-butylphenyl, 2-methyl-6-tert-butylphenyl, 2,6-di Phenylphenyl, pentafluorophenyl, 2,6-dibromophenyl, 3,5-trifluoromethylphenyl, 2-methylphenyl, 2-methyl-6-trifluoromethylphenyl , one of 2,6-difluorophenyl; R ₁₀ is one of isopropyl, tert-butyl, n-butyl; R ₃ is 2,6-dimethylanilino, 2,6-diisopropylanilino, 2-tert-butylanilino, 2-methyl-6-tert-butylanilino, 2,6-di Phenylanilino, pentafluoroanilino, 2,6-dibromoanilino, 3,5-trifluoromethylanilino, 2-methylanilino, 2-methyl-6-trifluoromethylanilino , one of 2,6-difluoroaniline; Both R ₉ and R ₉ ' are one of oxygen atom, isopropylamino group and tert-butylamino group; wherein, R ₉ and R ₉ ' are the same; R ₅ , R ₁₁ and R ₁₁ ' are hydrogen atom, methyl group, ethyl group, alkoxy group, isopropyl group, tert-butyl group, n-butyl group, nitro group, amino group, iodine atom, bromine atom, phenyl group, One of benzyl, nitrile, thiophenyl, anilino, phenol, thiophenyl and 3,5-difluoromethanephenylthio; wherein, R ₁₁ and R ₁₁ ' are the same; Both R ₆ and R ₇ are one of phenyl, benzyl, anthracenyl, naphthyl, phenanthrenyl, thiophenyl, anilino, phenol, phenylthio and 3,5-difluoromethanephenylthio ; R ₁₂ , R ₁₂ ', R ₁₃ and R ₁₃ ' are hydrogen atom, methyl group, ethyl group, isopropyl group, tert-butyl group, n-butyl group, alkoxy group, nitrile group, amino group, iodine atom, bromine atom One of , nitro, nitrile; wherein, R ₁₂ and R ₁₂ ' are the same, R ₁₃ and R ₁₃ ' are the same; Ln ₁ and Ln ₂ are scandium (Sc), lutetium (Lu), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nb), promethium (Pm), samarium (Sm ), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), or ytterbium (Yb). 2. A preparation method of cycloheptatrienyl rare earth metal catalyst structural formula II as claimed in claim 1, characterized in that: the method steps and conditions are as follows: (1) Synthesis of cycloheptatrienyl ligands: First, weigh tropolone and p-toluenesulfonyl chloride into the reactor, add a good solvent dichloromethane at room temperature, start stirring the mixture, then add triethylamine dropwise to the mixture, at this time a yellow Slurry substance, another good solvent was added to dilute the reaction; at room temperature under the atmosphere of nitrogen protection, after stirring for about 32h, compound a was obtained; wherein the molar ratio of tropolone, p-toluenesulfonyl chloride and triethylamine 1:1:1; Secondly, at low temperature, the amine substituent is slowly added dropwise to a, the mixture is stirred overnight at room temperature, and after recrystallization with a good solvent and a poor solvent, the product b containing double bond O is obtained; Finally, slowly add the CH ₂ Cl ₂ solution of product b into the Et ₃ OBF ₄ solution, stir at room temperature for a certain period of time, then slowly add the amine substituent into the above mixture, and wait until the reaction returns to After room temperature, stir overnight to obtain a mixture c containing the target product; add 25-35 mL of a good solvent to the mixture c, separate layers to obtain an aqueous phase and an organic phase, add 5-10 g of a solid desiccant to the organic phase, filter, and spin dry to obtain a crude product, and then obtain the cycloheptatrienyl ligand by column chromatography purification of the product; (2) Preparation of Cycloheptatrienyl Rare Earth Metal Catalyst: First, the reactor is placed in a glove box, the cycloheptatriene ligand described in step (1) is added dropwise to the solution in which the rare earth metal source is dissolved, and the reaction is stirred at room temperature for 6 hours to obtain a mixture, which is Filtration, taking the obtained liquid and concentrating to obtain a cycloheptatrienyl rare earth catalyst crude product, and recrystallizing the crude product to obtain a cycloheptatrienyl rare earth metal catalyst. 3. the preparation method of cycloheptatrienyl rare earth metal catalyst as claimed in claim 2 is characterized in that: in step (1), solid desiccant is anhydrous magnesium sulfate; In step (2), metal source is ditetrahydrofuran- Tris(trimethylsilylmethyl)-rare earth metal compound, molecular formula is [Ln(CH ₂ SiMe ₃ ) ₃ (THF) ₂ ], said Ln is scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium , Europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; Me is methyl; THF is tetrahydrofuran. 4. an application of the cycloheptatrienyl rare earth metal catalyst as claimed in claim 1, characterized in that: the cycloheptatrienyl rare earth metal catalyst forms a catalytic system with an alkylaluminum reagent and an organoboron salt, and is used for Catalyze the homopolymerization and copolymerization of olefins, cyclic olefins, alkynes, and polar monomers, or the copolymerization of olefins, cyclic olefins, alkynes, and polar monomers with _CO2 ; Wherein, the molar ratio of the alkylaluminum reagent, organoboron salt and cycloheptatrienyl rare earth metal catalyst is 2 to 100:1 to 100:1; the alkylaluminum reagent is an alkylaluminum with a molecular _formula of AlR3 and a molecular formula of HAlR ₂ alkylaluminum hydride, alkylaluminum chloride or aluminoxane with molecular formula AlR ₂ Cl, R is an alkyl group. 5. the application of a kind of cycloheptatrienyl rare earth metal catalyst according to claim 4, is characterized in that: the step of described homopolymerization is as follows: The reaction bottle is placed in a glove box, and the cycloheptatrienyl rare earth catalyst, 5-10 mL of good solvent, aluminum alkyl, olefin, alkyne or polar monomer, organoboron salt are added successively in the reaction bottle. After reacting under stirring for 0.3-6h, take out the reaction bottle, add a chain terminator to stop the reaction; pour the reaction solution into ethanol to settle, and precipitate solid matter, and remove the solvent in a vacuum oven at 30°C To constant weight, obtain the homopolymer product; Among them, the molar ratio of alkenes, alkynes or polar monomers, alkylaluminum reagents, organic boron salts and cycloheptatrienyl rare earth catalysts is 200-600:2-100:1-100:1; the reaction temperature is 25- 90°C. 6. the application of a kind of cycloheptatrienyl rare earth metal catalyst according to claim 4, is characterized in that: the step of described copolymerization reaction is as follows: Place the reaction bottle in a glove box, add the cycloheptatrienyl rare earth catalyst, 1 to 40 mL of good solvent, aluminum alkyl, reactant a or reactant b, organoboron salt in turn in the reaction bottle, and stir After reacting for 3 to 24 hours, the reaction bottle was taken out, and a chain terminator was added to terminate the reaction; the reaction solution was poured into ethanol to settle, and a solid substance was precipitated, and the solid substance was removed with a vacuum oven at 30°C until constant Heavy, obtain the copolymerization product; Wherein, the molar ratio of reactant a or reactant b, alkylaluminum reagent, organoboron salt and cycloheptatrienyl rare earth catalyst is 200-5000:2-100:1-100:1; the reaction temperature is 25-70 ℃; reactant a is two kinds of branched olefins, cycloalkenes, alkynes, and polar monomers, and reactant b is one of branched alkenes, cycloalkenes, alkynes, polar monomers, and CO ₂ . 7. the application of cycloheptatrienyl rare earth metal catalyst according to claim 4, is characterized in that: The aluminum alkyl is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, tricyclohexylaluminum, One of octyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-tolyl aluminum and diethyl benzyl aluminum; The alkylaluminum hydride is dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dipentylaluminum hydride aluminum hydride, dihexylaluminum hydride, dicyclohexylaluminum hydride, dioctylaluminum hydride, diphenylaluminum hydride, di-p-cresylaluminum hydride, dibenzylaluminum hydride, ethylbenzylaluminum hydride and ethylp- One of the tolyl aluminum; The alkylaluminum chloride is: dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisopropylaluminum chloride, diisopropylaluminum chloride, Isobutyl aluminum, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dichloride One of benzyl aluminum, ethyl benzyl aluminum chloride and ethyl p-tolyl aluminum chloride; The aluminoxane is: one of methylalumoxane, ethylalumoxane, n-propylalumoxane and n-butylalumoxane; The organoboron salt is triphenyl(methyl)-tetrakis(pentafluorophenyl)boron salt ([Ph ₃ C][B(C ₆ F ₅ ) ₄ ]), phenyl-dimethylamino-tetrafluorophenyl One of (pentafluorophenyl) boron salts ([PhMe ₂ NH][B(C ₆ F ₅ ) ₄ ]) and tris(pentafluorophenyl) boron salts (B(C ₆ F ₅ ) ₃ ); The olefins are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, styrene, α-methylstyrene, 3-chloromethylstyrene, 1,3-butanediene One of ene, isoprene, 1,3-cyclohexadiene, 1,5-pentadiene, 1,6-hexadiene and divinylbenzene; The cyclic olefin is one of norbornene, polar norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene and dicyclopentadiene; The alkyne is one of acetylene, phenylacetylene, p-phenyleneacetylene and diethynyl arenes; The polar monomers are divided into alkylene oxides and lactones, wherein alkylene oxides are ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, heterocyclic Oxybutylene, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexylidene glycidyl ether, trifluoropropylene oxide, internal The ester is one of ε-caprolactone, β-butyrolactone, δ-valerolactone, lactide, glycolide and 3-methyl-glycolide. 8. The application of a cycloheptatrienyl rare earth metal catalyst according to claim 5 or 6, characterized in that: the chain terminator is a compound containing 2,6-di-tert-butyl-4-methylphenol Ethanol, based on the volume of ethanol as 100%, wherein the volume ratio of 2,6-di-tert-butyl-4-methylphenol is 5%; the good solvent is toluene.