CN106008767A - Alcohol oxymethylene bridged bimetallic half-metallocene catalyst and preparation method and application - Google Patents

Abstract

The invention provides an alcohol oxymethylene bridged bimetallic half-metallocene catalyst and a preparation method and application. The catalyst has the following structure, wherein M1 and M2 are the same or different and each represents a metal atom selected from the group consisting of IIIB, IVB, VB, and VIB; X and X 'are the same or different and are halogen atoms selected from the group consisting of Cl, Br and F; n is a positive integer greater than or equal to 1. The alcohol oxymethylene bridged bimetallic half-metallocene catalyst has a low cost and high activity at a temperature of 30 DEG C to 200 DEG C; a comonomer has a high insertion amount, and an olefin polymerization product has a low density and excellent performances.

Description

Alcohol oxymethylene bridged double metallocene catalyst, preparation method and application

technical field

The invention belongs to the field of olefin polymerization catalysts and olefin coordination polymerization, in particular to alcohol oxymethylene bridged double metallocenes for ethylene or propylene homopolymerization, ethylene/α-olefin copolymerization or propylene/α-olefin copolymerization Catalysts and applications.

Background technique

Metallocene catalysts have received widespread attention because of their single active center, catalyst activity, polymer stereoregularity, molecular weight, and molecular weight distribution can be controlled by changing the ligand structure; and the polymers synthesized by metallocene catalysts have excellent properties. Performance has been unanimously approved.

Polyolefin products have many advantages, such as easy processing, good thermal stability, good weather resistance, good chemical corrosion resistance and long service life, etc., and are very popular in the market. However, polyolefins (such as PE, PP, etc.) have poor low temperature resistance and high crystallinity, which limits their application range. If a certain amount of advanced α-olefin (such as 1-octene, etc.) is inserted into the polyolefin molecular chain to prepare a block copolymer, the structure and properties of the polyolefin will change significantly: the polymer density can be made higher than that of ordinary polyolefin The density is between 0.85 and 0.92g/ ^cm3 ; the glass transition temperature is low, the low temperature resistance is good, and the dispersion, weather resistance, flexibility, flexibility and processing performance are good. The performance of ethylene/1-octene copolymer is superior to that of ethylene/propylene copolymer and ethylene/1-butene copolymer, and ethylene/1-octene copolymer replaces ethylene/propylene copolymer and ethylene/1-butene The era of copolymers is coming.

Chien[Chien J, et al.Journal of Polymer Science, Part A: Polymer Chemistry, 1991,29,1603] adopts rac-anti-Et(Me ₄ C ₅ )(Ind)TiCl ₂ /rac-syn-Et(Me ₄ C ₅ )(Ind)TiCl ₂ Equimolar Mixture and rac-anti-Et(Me ₄ C ₅ )(Ind)TiMe ₂ Asymmetrically Bridged Metallocene Catalysts to Synthesize Thermoplastics with Crystalline-Amorphous Stereomultiblock Structure PP elastomer. Gauthier [Gauthier W J. Macromolecules, 1995,28,3779] uses Me ₂ C(Cp)(Ind)TiCl ₂ , Me ₂ Si(Cp)(Ind)ZrCl ₂ and Me ₂ Si(Cp)(Ind)HfCl ₂ Metallocene catalysts synthesized PP elastomers. _Resconi [ _{Resconi L} , _{etal.Chemical Reviews} , _{2000,100,1253} ] _synthesized heavy It is a completely amorphous PP elastomer with an average relative molecular weight of 100,000-400,000 and good elastic and optical properties.

Patent [application number: DE 19850898] using 1-(9-fluorenyl)-1,2,3,6-tetrahydro-1,3,3-trimethylcyclopentadiene zirconium dichloride/MAO catalyst The system prepares ethylene/propylene/5-ethylidene-2-norbornene copolymer, the polymerization temperature is 20-80°C, the polymerization pressure is 0.3-3.0MPa, the mass fraction of ethylene in the copolymer is 0.4-0.9, and the mass fraction of propylene is 0.095-0.59, and the mass fraction of non-conjugated dienes is 0.005-0.12. Patent [application number: WO 2000022005] uses metallocene catalysts to synthesize EPM with high molecular weight, narrow molecular weight distribution and low T _g . The polymerization temperature is 30-80°C, the polymerization pressure is 0.07-21MPa, and the ethylene mass fraction of EPM is 0.35-0.8 , the mass fraction of propylene is 0.15-0.6.

Bergemann [Bergemann C, et al. Journal of Molecular Catalysis A: Chemical, 1996, 105, 87] used Me ₂ Si(H ₄ Ind) ₂ ZrCl ₂ /MAO to compare ethylene and propylene at 0.1-150MPa, 120-220°C , the copolymerization of 1-butene, 1-hexene and 1-decene, it is found that the higher the carbon number is, the more difficult it is to copolymerize α-olefin with ethylene, and the ratio of reactivity ratio of ethylene and 1-butene is r _e /r _b ＝53.45/0.02, the ratio of reactivity ratio when ethylene and 1-hexene are copolymerized is r _e /r _h ＝62.70/0.02, the ratio of reactivity ratio when ethylene and 1-decene is copolymerized is r _e /r _d = 80.02/0.01. Shan [Shan CLP, et al. macromolecular chemistry and physics, 2000, 201, 2195] used a supported metallocene catalyst Et(Ind) ₂ ZrCl ₂ to catalyze the copolymerization of ethylene and 1-hexene at a pressure of 10 MPa, and the catalytic activity was as high as 4341.7 kg P/(molZr.h), the molar content of 1-hexene in the copolymer is about 3%. Losio [Losio S, et al. Macromolecules, 2008, 41, 1104] used a bridged metallocene catalyst to catalyze the copolymerization of ethylene and 4-methyl-1-pentene, and the amount of comonomer inserted was between 0.15mol% and 5.59mol% between.

The above research results show that despite the use of metallocene catalysts (except those with restricted geometry) and high α-olefin feed ratio, the copolymerization ability of α-olefins (above C ₄ ) and ethylene is still low.

However, the patent [Application No.: US5218071] uses an ethyl-bridged metallocene/MAO catalytic system under normal pressure to 5.0 MPa, with toluene as a solvent, to catalyze the copolymerization of ethylene and α-olefins to synthesize the polyolefin elastomer Tafmer. The molar content of α-olefin in the molecular chain of the product is high (up to 9%), the density of the product is low, which is 0.85-0.92g/cm ³ , and the molecular weight distribution is 1.2-4.0; Silicone compounds are added. Lin [Lin SA, et al. macromolecular chemistry and physics, 2001, 202, 1935] Synthesized ethylene/1-butene with high randomness and high molecular weight using monotanocene Cp*Ti(OR) ₃ /mMAO catalytic system The copolymer elastomer has a reactivity ratio of r _e /r _b = 1.08/0.29 when ethylene and 1-butene are copolymerized, and the molar content of 1-butene in the copolymer reaches 25.4%. DuPont-Dow Elastomets developed polyolefin elastomer Engage by using limited geometry metallocene catalysts, including 8 new varieties that can be blow molded and extruded, and belong to high melt strength ethylene/1-butene, Ethylene/1-hexene copolymer.

Patent 201510082857.7 discloses that a double metallocene compound is composed of a bridging C3-C30 hydrocarbon group or its derivatives, a C3-C30 cycloalkyl group or its derivatives, a C6-C30 aryl group or its derivatives, or a C6-C30 hetero The ring aryl group or its derivatives are connected to form a double metallocene catalyst, which has high catalytic activity and can effectively catalyze the homo (co)polymerization of ethylene and the homo (co)polymerization of propylene. However, patent 201510082857.7 does not involve alcohol oxymethylene bridged double metallocene catalysts.

In summary, adding organosilicon compounds, electron donors or Cp*M(OR) type ₃ metallocene catalysts to the catalyst system, metallocene catalysts (constrained geometric configuration)/MAO (or other co-catalysts) catalytic system When catalyzing the copolymerization of ethylene and C ₄ or higher α-olefins, the molar content of α-olefins in the copolymer can be significantly increased, and the density of the copolymer is low.

Although there are many reports on the use of metallocene catalysts to catalyze the copolymerization of ethylene and α-olefins, the molecular structure of metallocenes is becoming more and more complex, which is a challenge for industrial production costs. The invention discloses a double metallocene catalyst, which combines a single metallocene catalyst with a simple structure and a phenolic oxygen group or a secondary amino group. When catalyzing olefin polymerization at high temperature, the catalyst has high catalytic activity, and can also increase the insertion amount of comonomer α-olefin in the copolymer and improve the performance of polyolefin.

Contents of the invention

The object of the present invention is to provide a kind of alcohol oxymethylene bridged double metallocene catalyst, and it is used for ethylene homopolymerization, propylene homopolymerization, ethylene and α-olefin copolymerization or propylene and α-olefin copolymerization Application and preparation method.

The olefin polymerization alcohol oxymethylene bridged double metallocene catalyst provided by the present invention has a structure conforming to the general formula (1);

In general formula (1), R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ' are the same or different, independently selected from hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 haloaryl, C2-C20 heterocycloalkyl and C6-C20 arheteroalkyl ; Wherein, the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ are mutually closed to form a single ring or a fused ring or not Closed; for example, a single ring is a C3-C20 cycloalkane, a C3-C20 heterocycloalkane or a benzene ring; a fused ring is a C8-C20 fused ring, such as naphthalene and pyrene;

Among them, M ₁ and M ₂ are the same or different metal atoms, respectively selected from one of IIIB, IVB, VB, VIB or VIII, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd;

Wherein, X, X' are the same or different halogen atoms, selected from Cl, Br, F;

Wherein, n is a positive integer greater than or equal to 1;

Wherein, R6 is a C1 _- C30 hydrocarbon group or its derivatives, a C3-C30 cycloalkyl group or its derivatives, a C6-C30 aryl group or its derivatives, a C2-C30 heterocycloalkyl group or its derivatives , or R6 does not exist; derivatives refer to more complex products derived from hydrogen atoms or atomic groups replaced by other atoms or atomic groups _; for example, R6 can be substituted or unsubstituted 0-C20 alkyl, C3-C20 Cycloalkyl, C6-C20 aryl, C3-C20 heterocycloalkyl, substituents can be C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 Haloaryl, C1-C20 alkoxy, C3-C20 cycloalkoxy or _C6 -C20 aryloxy, or R6 can be C2-C20 alkane containing N, S, O and other heteroatoms C3-C20 cycloalkyl group, C6-C20 aryl group, C3-C20 heterocycloalkyl group;

In one aspect of the present invention, described double metallocene catalyst is:

Cat.1

Cat.2

Cat.3

Cat.4

Cat.5

Cat.6

Cat.7

Cat.8

Cat.9

Cat.10

Cat.11

Cat.12

Cat.13

Cat.14

Cat.15

Cat.16

Cat.17

Cat.18

Cat.19

The present invention also provides a catalyst for olefin polymerization, which is composed of a main catalyst and a co-catalyst, wherein the main catalyst is the above-mentioned alcohol oxymethylene bridging double metallocene catalyst.

In one aspect of the present invention, the cocatalyst is aluminum alkyl, methylalumoxane (MAO) or modified methylalumoxane (mMAO), etc.

In yet another aspect of the present invention, the molar ratio of the main catalyst to the co-catalyst is 1:(100-5000).

The present invention provides the preparation method of described general formula (1) alcohol oxymethylene bridging double metallocene catalyst, it is characterized in that comprising the following steps:

1) in an organic solvent, dissolve the compound having general formula (2a) and (2b);

Among them, R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ' are the same or different substituents, independently representing a hydrogen atom, Alkyl of C1-C20, cycloalkyl of C3-C20, aryl of C6-C20, haloaryl of C6-C20, heterocycloalkyl of C2-C20 and arheteroalkyl of C6-C20, wherein Substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ are closed to each other to form a single ring or fused ring or not closed; The compound of general formula (2a) or (2b) is preferably selected from cyclopentadiene and its derivatives, indene and its derivatives, fluorene and its derivatives;

At -80°C-120°C, react for 0.5h-12h, react with the added n-butyllithium to form negative ions; then, at -50°C-150°C, react with transition metal halide MX _m for 1h-10h , to obtain the compound according to the general formula (3),

Wherein M is a metal atom selected from groups IIIB, IVB, VB, VIB or VIII, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd; wherein, X is a halogen atom selected from Cl, Br, F;

Among the metal halides MX _m , M is a transition metal atom selected from groups IIIB, IVB, VB, VIB or VIII, preferably Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, One of Co, Ni or Pd; wherein, X is a halogen atom selected from Cl, Br, F; m is 2, 3 or 4.

Preferably, the molar ratio of the compound having the structure (2a) or (2b) to the metal halide MX _m is 1:0.4-1.6;

2) Dissolving the compound conforming to the general formula (3) in an organic solvent, adding a diol compound with a specific structure of carbon atoms from C2 to C30, and reacting at -20°C-110°C for 0.5h-24h; removing Solvent post-drying obtains the compound that meets aforementioned general formula (1),

Diol compounds with carbon atoms from C2 to C20 are preferably ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, decanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexane Dimethanol, 1,4-tere-xylylenedimethanol, 1,3-m-xylylenedimethanol, 1,2-o-phthalylenedimethanol, 1,1'-biphenyl-4,4'-dimethanol, 1,1' - Biphenyl-3,4'-dimethanol, 1,1'-biphenyl-2,2'-dimethanol.

In one aspect of the present invention, the molar ratio of the compound conforming to the general formula (3) to the diol compound having carbon atoms ranging from C2 to C20 is 1.5-2.5:1.

The organic solvent used in the process of synthesizing the catalyst is saturated alkanes, saturated naphthenes or aromatics or their mixtures; Chloromethane or their mixtures.

The present invention provides the above-mentioned alcohol oxymethylene double metallocene catalyst or the application of the above-mentioned catalyst. Wherein, the provided double metallocene catalyst or catalyst is used to catalyze the homopolymerization or copolymerization of non-polar olefins. Wherein said non-polar olefin is a C2-C20 α-olefin, preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, dodec-1-ene, deca Oct-1-ene, Styrene, Cyclopentene, 3-Methyl-1-butene, 4-Methyl-1-pentene, Isoprene, 1,3-Butadiene, α-Methyl Styrene, norbornene.

The alcohol oxymethylene bridged double metallocene catalyst or catalyst provided by the present invention is used to catalyze the polymerization of non-polar olefins. The polymerization conditions are that the polymerization temperature is 30°C-200°C, and the olefin polymerization pressure is 0.1MPa-30MPa. The reaction time is 5min-240min.

The olefin polymerization catalyst provided by the present invention has the following beneficial effects:

The alcohol oxymethylene bridged double metallocene catalyst of the present invention is low in cost and still has high activity at high temperature; when used for the copolymerization of ethylene or propylene with α-olefin or polar olefin monomer, α-olefin or Polar vinyl monomers have a high insertion rate; polyolefins have low density and better performance.

The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the following examples.

detailed description

Example 1

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, and add 3.3mL (0.04mol) cyclopentane successively at room temperature (open system under standard atmospheric pressure, the same below). Diene, 3.8mL (0.04mol) of n-butyllithium, reacted for 2h; heated to 40°C, reacted for 4h. At 0°C, add 4.4mL (0.04mol) TiCl ₄ to the intermediate, and react at 0°C for 1h; then, react at room temperature for 3h; filter with suction, wash the solid matter with n-hexane three times; filter with suction at 30°C, Compound M1 (see general formula (3)) was obtained with a yield of 95.6%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100 mL of toluene to a dry reaction flask with magnets under nitrogen protection, add 4.4 g (0.02 mol) of compound M1 and stir to dissolve, and dissolve at 10 °C Add 0.01 mol of ethylene glycol, keep at 10°C for 30 minutes, then raise the temperature to 40°C for 3 hours. After the reaction is over, filter and wash with n-hexane 50mL at 40°C several times, and suction filter; obtain the main catalyst Cat.1:

3) Ethylene polymerization: Under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.1), and 3.8 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air for three times, keep the ethylene pressure at 180°C and 2atm for 30 minutes, stop the reaction with ethanol solution containing 10% (volume fraction, the same below) hydrochloric acid, filter, wash with ethanol for 3 times, and vacuum the polymer at 40°C Dry for 24h.

4) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.1), 3.8mL MAO solution (1.5mol/L) in sequence. After exchanging air for three times, keep the polymerization at 180°C, 2 atm ethylene pressure and 2 atm propylene for 30 minutes, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 2

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 4.4g (0.02mol) of compound M1 and stir Dissolve, add 0.01mol 1,1'-biphenyl-4,4'-dimethanol at 10°C, keep at 10°C for 30min, then raise the temperature to 40°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.2:

2) Ethylene polymerization: Under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.2), and 4.0 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air for three times, keep polymerization at 160°C and 2 atm ethylene pressure for 30min, terminate the reaction with ethanol solution containing 10% (volume fraction, the same below) hydrochloric acid, filter, wash with ethanol three times, and vacuum the polymer at 40°C Dry for 24h.

3) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.2), and 4.8 mL of MAO solution (1.5 mol/L) in sequence in a 250 mL reaction flask. After exchanging air three times, keep polymerization at 160°C, ethylene pressure of 1 atm and propylene of 2 atm for 30 minutes, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 3

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 4.4g (0.02mol) of compound M1 and stir Dissolve, add 0.01mol decanediol at 10°C, keep at 10°C for 30min, then raise the temperature to 40°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.3:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.3), 4.5mL MAO solution (1.5mol/L), 5mL 3-methyl-1 -butene. After exchanging air for three times, keep polymerization at 170°C and 2 atm ethylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 4

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 4.4g (0.02mol) of compound M1 and stir Dissolve, add 0.01mol 1,4-tere-phenylenedimethanol at 10°C, keep at 10°C for 1 hour, then raise the temperature to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 30°C, and suction filter; obtain the main catalyst component Cat.4:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.4), 6.7mL MAO solution (1.5mol/L), and 5mL 1-hexene in sequence in a 250mL reaction flask. After exchanging air for three times, keep polymerization at 180°C and 2 atm ethylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 5

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, add 3.3mL (0.04mol) cyclopentadiene, 3.8mL (0.04mol) n- Butyllithium, react at 10°C for 1h; heat up to 40°C, react for 4h. Under ice-salt bath, add 9.3g (0.04mol) ZrCl ₄ to the intermediate, and react under ice-salt bath for 1h; then, react at 40°C for 4h; Under suction filtration, compound M2 (see general formula (3)) was obtained with a yield of 93.8%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100mL of toluene to a dry reaction flask with magnets under nitrogen protection, add 5.26g (0.02mol) of compound M2 and stir to dissolve, at 20°C Add 0.01 mol of 1,2-phthalene dimethanol, keep at 20°C for 30min, then raise the temperature to 50°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.5:

3) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.5), 4.2mL MAO solution (1.5mol/L), and 2g norbornene to a 250mL reaction flask in sequence. After exchanging air for three times, keep polymerization at 180°C and 2 atm ethylene pressure for 1 hour, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 6

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL of toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 0.01mol metallocene catalyst M1 and 0.01mol The metallocene catalyst M2 was stirred and dissolved, and 0.01 mol of decanediol was added at 5°C, kept at 5°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.6:

2) Ethylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.6), 10mL MAO solution (1.5mol/L), 5mL dodec-1-ene . After exchanging air for three times, keep polymerization at 160°C and 2 atm ethylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 7

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, add 3.3mL (0.04mol) cyclopentadiene, 3.8mL (0.04mol) n- Butyllithium, react at 5°C for 2h; heat up to 40°C, react for 5h. Under ice-salt bath, add 7.82g (0.04mol) YCl ₃ to the intermediate, and react under ice-salt bath for 1h; then, react at 30°C for 4h; Under suction filtration, compound M3 (see general formula (3)) was obtained with a yield of 95.6%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100mL of toluene to a dry reaction flask with magnets under nitrogen protection, add 4.5g (0.02mol) of compound M3 and stir to dissolve, at 10°C Add 0.01 mol of 1,4-tere-phenylenedimethanol, keep at 10°C for 30 minutes, then raise the temperature to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.7:

3) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.7), 7.8mL MAO solution (1.5mol/L), and 5mL 1-octene to a 250mL reaction flask in sequence. After exchanging air for three times, keep polymerization at 180°C and 3 atm ethylene pressure for 60 minutes, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer at 40°C for 24 hours in vacuum.

Example 8

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 4.4g (0.02mol) compound M3 and stir Dissolve, add 0.01mol 1,1'-biphenyl-2,2'-dimethanol at 10°C, keep at 10°C for 60min, then raise the temperature to 50°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.8:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.8), 6.5mL MAO solution (1.5mol/L), 5mL 1,3-butane Diene. After exchanging air three times, polymerize at 170°C and 3atm propylene pressure for 30min, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 9

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 0.01mol metallocene catalyst M2 and 0.01mol Metallocene catalyst M3 was stirred and dissolved, and 0.01 mol of decanediol was added at 5°C, kept at 5°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.9:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.9), 6.5mL of MAO solution (1.5mol/L), and 5mL of isoprene. After exchanging air three times, polymerize at 170°C and 3atm propylene pressure for 30min, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 10

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, add 3.3mL (0.04mol) cyclopentadiene, 3.8mL (0.04mol) n- Butyllithium, react at 10°C for 2h; heat up to 40°C, react for 5h. Under ice-salt bath, add 5.22g (0.04mol) NiCl ₂ to the intermediate, and react under ice-salt bath for 1h; then, react at 50°C for 4h; Under suction filtration, the compound M4 (see general formula (3)) was obtained with a yield of 95.6%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 3.9g (0.02mol) of compound M4 and stir to dissolve, at 10°C Add 0.01 mol of 1,4-tere-phenylenedimethanol, keep at 10°C for 30 minutes, then raise the temperature to 40°C for 4 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.10:

3) Propylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.10), 9.5mL MAO solution (1.5mol/L), and 5mL 1-hexene in sequence in a 250mL reaction flask. After exchanging air three times, polymerize for 1 hour at 180°C under propylene pressure of 2 atm, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 11

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, add 5.5mL (0.04mol) fluorene, 3.8mL (0.04mol) n-butyllithium successively at room temperature, Reaction at room temperature for 1h; warming up to 50°C, reaction for 3h. Under ice-salt bath, add 4.4mL (0.04mol) TiCl ₄ to the intermediate, and react under ice-salt bath for 1h; then, react at 50°C for 4h; Under suction filtration, the compound M5 (see general formula (3)) was obtained with a yield of 95.3%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100 mL of toluene to a dry reaction flask with a magnet under nitrogen protection, add 6.39 g (0.02 mol) of compound M5 and stir to dissolve, and dissolve at 10 ° C Add 0.01 mol of butanediol, keep at 10°C for 30 minutes, then raise the temperature to 40°C for 4 hours. After the reaction finishes, filter and wash with normal hexane 50mL several times at 40°C, and suction filter; obtain the main catalyst component Cat11:

3) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.11), 8.3mL MAO solution (1.5mol/L), 5mL octadecadecan-1- alkene. After exchanging air for three times, polymerize for 1 h at 180°C under propylene pressure of 3 atm, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 h.

Example 12

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 6.39g (0.02mol) compound M5 and stir Dissolve, add 0.01mol 1,4-cyclohexanedimethanol at 10°C, keep at 10°C for 60min, then raise the temperature to 50°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.12:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.12), 7.6mL of MAO solution (1.5mol/L), and 5mL of styrene. After exchanging air three times, polymerize at 70°C and propylene pressure of 2 atm for 30 minutes, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 13

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 6.39g (0.02mol) compound M5 and stir Dissolve, add 0.01mol 1,1'-biphenyl-4,4'-dimethanol at 20°C, keep at 20°C for 1 hour, then raise the temperature to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.13:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.13), 5.6mL of MAO solution (1.5mol/L), and 5mL of 1-octene. After exchanging air for three times, keep polymerization at 60°C and 3 atm propylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 14

1) Preparation of metallocene catalyst: under the protection of anhydrous, oxygen and nitrogen, add 100mL toluene to a 250mL reaction flask, add 4.7mL (0.04mol) indene, 3.8mL (0.04mol) n-butyllithium successively at 10°C , react at 10°C for 1h; heat up to 40°C, react for 3h. Under ice-salt bath, add 9.35g (0.04mol) ZrCl ₄ to the intermediate, and react under ice-salt bath for 1h; then, react at 40°C for 4h; Under suction filtration, compound M6 (see general formula (3)) was obtained with a yield of 96.8%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalysts: Add 100mL of toluene to a dry reaction flask with magnets under nitrogen protection, add 6.32g (0.02mol) of compound M8 and stir to dissolve, at 20°C Add 0.01mol of butanediol, keep at 30°C for 30min, then raise the temperature to 50°C for 3h. After the reaction finishes, filter and wash several times with normal hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.14:

3) Ethylene copolymerization: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.14), 9.3mL MAO solution (1.5mol/L), and 5mL cyclopentene to a 250mL reaction flask in sequence. After exchanging air three times, keep polymerization at 30°C and 3 atm ethylene pressure for 1 hour, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 15

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 6.32g (0.02mol) compound M6 and stir Dissolve, add 0.01mol 1,4-tere-phenylenedimethanol at 30°C, keep at 30°C for 1 hour; then raise the temperature to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.15:

2) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.15), 8.8mL MAO solution (1.5mol/L), and 5mL 1-hexene into a 250mL reaction flask in sequence. After exchanging air three times, polymerize at 160°C and 2 atm ethylene pressure for 30 minutes, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and vacuum-dry the polymer at 40°C for 24 hours.

Example 16

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 6.32g (0.02mol) compound M6 and stir Dissolve, add 0.01mol 1,1'-biphenyl-4,4'-dimethanol at room temperature, keep the reaction at room temperature for 1h, then raise the temperature to 50°C for 3h. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.16:

2) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.16), 9.3mL MAO solution (1.5mol/L), and 5mL 1-butene into a 250mL reaction flask in sequence. After exchanging air for three times, keep polymerization at 180°C and 2 atm ethylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 17

1) Preparation of metallocene catalyst: under anhydrous, oxygen-free and nitrogen protection, add 100mL toluene to a 250mL reaction flask, add 4.7mL (0.04mol) indene, 3.8mL (0.04mol) n-butyllithium in sequence at 30°C , react at 30°C for 1h; heat up to 50°C, react for 2h. Under ice-salt bath, add 7.82g (0.04mol) YCl ₃ to the intermediate, and react under ice-salt bath for 1h; then, react at 50°C for 4h; Under suction filtration, compound M7 (see general formula (3)) was obtained with a yield of 97.3%.

2) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with a magnet under nitrogen protection, add 5.62g (0.02mol) metallocene catalyst M7 and stir to dissolve, 20 Add 0.01mol 1,1'-biphenyl-4,4'-dimethanol at ℃, keep 20℃ for 30min, then raise the temperature to 50℃ for 3h. After the reaction finishes, filter and wash several times with normal hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.17:

3) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.17), 8.7mL of MAO solution (1.5mol/L), and 5g of norbornene. After exchanging air for three times, keep polymerization at 130°C and 2 atm propylene pressure for 1 hour, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 18

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 0.01mol metallocene catalyst M7 and 0.01mol Metallocene catalyst M6 was stirred and dissolved, and 0.01mol 1,1'-biphenyl-4,4'-dimethanol was added at 5°C, kept at 5°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.18:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.18), 6.5mL of MAO solution (1.5mol/L), and 5mL of cyclopentene. After exchanging air three times, polymerize at 170°C and 3atm propylene pressure for 30min, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 19

1) Preparation of alcohol oxymethylene bridged double metallocene catalysts: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 0.01mol metallocene catalyst M7 and 0.01mol Metallocene catalyst M3 was stirred and dissolved, and 0.01mol of 1,1'-biphenyl-4,4'-dimethanol was added at 5°C, kept at 5°C for 60 minutes, and then heated to 50°C for 3 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.19:

2) Propylene copolymerization: Under anhydrous and oxygen-free conditions, in a 250 mL reaction flask, add 100 mL of toluene, 10 mg of main catalyst (Cat.19), 6.5 mL of MAO solution (1.5 mol/L), and 5 mL of isoprene in sequence. After exchanging air three times, polymerize at 170°C and 3atm propylene pressure for 30min, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 20

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with magnets under nitrogen protection, add 179.4mg (0.0004mol) metallocene catalyst dimethylsilyl Bisindenyl zirconium chloride was stirred and dissolved, and 0.0002 mol of 1,4-cyclohexanedimethanol was added at 20°C, kept at 30°C for 30 minutes, and then heated to 50°C for 3 hours. After the reaction, filter and wash with 50mL of n-hexane several times at 40°C, and filter with suction; the main catalyst component Cat.20

2) Copolymerization of ethylene: under anhydrous and oxygen-free conditions, add 100mL toluene, 10mg main catalyst (Cat.20), 9.3mL MAO solution (1.5mol/L), and 5mL 1-decene to a 250mL reaction flask in sequence. After exchanging air for three times, keep polymerization at 160°C under 3 atm ethylene pressure for 1 hour, terminate the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24 hours.

Example 21

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 179.4mg (0.0004mol) metallocene catalyst Dimethylsilyl bis-indenyl zirconium chloride, stirring and dissolving, add 0.0002mol decanediol at room temperature, keep room temperature for 1h reaction; then raise the temperature to 50°C for 3h reaction. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.21:

2) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL toluene, 10mg main catalyst (Cat.21), 8.7mL MAO solution (1.5mol/L), and 5mL 1-hexene in sequence. After exchanging air three times, polymerize at 180°C and 2 atm propylene pressure for 30min, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 22

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: Add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 179.4mg (0.0004mol) metallocene catalyst Dimethylsilylbisindenyl zirconium chloride was stirred and dissolved. Added 0.0002 mol of 1,1'-biphenyl-4,4'-dimethanol at room temperature, kept at room temperature for 1 hour, and then heated to 40°C for 4 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.22:

2) Propylene copolymerization: Under anhydrous and oxygen-free conditions, add 100 mL of toluene, 10 mg of main catalyst (Cat.22), 9.6 mL of MAO solution (1.5 mol/L), and 5 mL of norbornene into a 250 mL reaction flask in sequence. After exchanging air for three times, keep polymerization at 160°C and 3atm propylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

Example 23

1) Preparation of alcohol oxymethylene bridged double metallocene catalyst: add 100mL toluene to a dry reaction flask with magnets under anhydrous, oxygen-free and nitrogen protection, add 200mg metallocene catalyst (CGC), stir Add 0.0002 mol of 1,1'-biphenyl-4,4'-dimethanol at room temperature, keep the reaction at room temperature for 1 hour, then raise the temperature to 80°C for 5 hours. After the reaction finishes, filter and wash several times with n-hexane 50mL at 40°C, and suction filter; obtain the main catalyst component Cat.23:

3) Propylene copolymerization: under anhydrous and oxygen-free conditions, in a 250mL reaction flask, add 100mL of toluene, 10mg of main catalyst (Cat.22), 9.6mL of MAO solution (1.5mol/L), and 5mL of norbornene. After exchanging air for three times, keep polymerization at 160°C and 3atm propylene pressure for 1h, stop the reaction with ethanol solution containing 10% hydrochloric acid, filter, wash with ethanol three times, and dry the polymer in vacuum at 40°C for 24h.

The result of polymerization reaction in each embodiment is shown in Table 1:

Table 1:

Claims (9)

1. a kind of alcohol oxymethylene bridging double metallocene catalyst that is used for olefin polymerization, is made up of procatalyst and cocatalyst; It is characterized in that, the structure of described procatalyst meets general formula (1): In general formula (1), R ₁ , R ₁ ′, R ₂ , R ₂ ′, R ₃ , R ₃ ′, R ₄ , R ₄ ′, R ₅ , R ₅ ′ are the same or different substituents, respectively independently represent hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 halogenated aryl, C2-C20 heterocycloalkyl or C6-C20 aryl Heteroalkyl, wherein substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ are closed to each other to form a single or condensed ring Or not closed; M1 or _M2 are the same or different metal atoms, respectively selected from _one of IIIB, IVB, VB, VIB or VIII; X or X' are the same or different halogen atoms, selected from Cl, Br, F; n is a positive integer greater than or equal to 1; R6 is a C1-C20 hydrocarbon group or its derivatives, a C3-C30 cycloalkyl group or its derivatives, a C6-C20 aryl group or its derivatives. derivatives, C2-C30 heterocycloalkyl or derivatives thereof, or R6 does not exist. 2. a catalyst for olefin polymerization, is made up of procatalyst and cocatalyst, it is characterized in that: wherein procatalyst is alcohol oxymethylene bridging double metallocene catalyst according to claim 1, described The co-catalyst is aluminum alkyl or methyl aluminoxane; the molar ratio of main catalyst to co-catalyst is 1:(100-5000). 3. prepare the method for alcohol oxymethylene bridging double metallocene catalyst as claimed in claim 1, it is characterized in that comprising the following steps: 1) in an organic solvent, dissolve the compound having general formula (2a) or (2b); Among them, R ₁ , R ₁ ', R ₂ , R ₂ ', R ₃ , R ₃ ', R ₄ , R ₄ ', R ₅ , R ₅ ' are the same or different substituents, each independently representing a hydrogen atom , C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 haloaryl, C2-C20 heterocycloalkyl and C6-C20 arheteroalkyl, Wherein the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ are mutually closed to form a single ring or fused ring or not closed; Compounds of general formula (2a) or (2b), selected from cyclopentadiene and its derivatives, indene and its derivatives, fluorene and its derivatives; At -80°C-120°C, react for 0.5h-12h, react with the added n-butyllithium to form negative ions; then, at -50°C-150°C, react with transition metal halide MX _m for 1h-10h , obtain the compound that meets general formula (3); Where M represents a metal atom, selected from IIIB, IVB, VB, VIB or VIII; X is a halogen atom, selected from Cl, Br, F; Among the metal halides MX _m ; M represents a metal atom, selected from IIIB, IVB, VB, VIB or VIII; X is a halogen atom, selected from Cl, Br, F; m is 2, 3 or 4; The molar ratio of the compound having a structure conforming to the general formula (2a) or (2b) to the metal halide MX _m is 1:0.4-1.6; 2) Dissolve the compound conforming to the general formula (3) in an organic solvent, add a dihydric alcohol with a carbon number of C2-C30, and react at -20°C-110°C for 0.5h-24h; remove the solvent and dry Obtain the catalyst that meets general formula (1), i.e. alcohol oxymethylene bridged double metallocene catalyst; In general formula (1), R ₁ , R ₁ ′, R ₂ , R ₂ ′, R ₃ , R ₃ ′, R ₄ , R ₄ ′, R ₅ , R ₅ ′ are the same or different, each independently representing hydrogen atom, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 haloaryl, C2-C20 heterocycloalkyl and C6-C20 arheteroalkyl , wherein the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₁ ', R ₂ ', R ₃ ', R ₄ ', R ₅ ' are mutually closed to form a single ring or fused ring or not closed ; M ₁ and M ₂ are selected from IIIB, IVB, VB, VIB or Group VIII metal atoms; X and X' are selected from Cl, Br, F; R6 is a hydrocarbon group whose carbon number is C1-C20 or its derivatives, C3 -C30 cycloalkyl or its derivatives, C6-C20 aryl or its derivatives, C2-C30 heterocycloalkyl or its derivatives, or R6 does not exist; n is a positive integer greater than or equal to 1; The molar ratio of the compound conforming to the general formula (3) to the diol compound is 1.5-2.5:1. 4. the preparation method of alcohol oxymethylene bridged double metallocene catalyst according to claim 3 is characterized in that: the solvent used in the synthesis process is saturated alkane, saturated cycloalkane, aromatic hydrocarbon or their mixed solutions . 5. the preparation method of alcohol oxymethylene bridged double metallocene catalyst according to claim 3 is characterized in that: the compound that meets general formula (2a) or (2b) is cyclopentadiene and derivatives thereof , indene and its derivatives, or fluorene and its derivatives. 6. the preparation method of alcohol oxymethylene bridging double metallocene catalyst according to claim 3 is characterized in that: dibasic alcohol is the aliphatic alcohol that carbon number is C2-C30, the cycloalkane of C3-C30 Alcohol, C6-C30 aryl alcohol or C2-C30 heterocycloalkyl alcohol. 7. the preparation method of alcohol oxymethylene bridging double metallocene catalyst according to claim 3 is characterized in that: M in general formula ( ₁ ), M ₂ are Ti, Zr, Hf, Sc, Y, Nd, La, Sm, Ru, Rh, Fe, Co, Ni or Pd. 8. The application of the alcohol oxymethylene bridged double metallocene catalyst according to claim 1 is characterized in that it catalyzes nonpolar olefin homopolymerization or copolymerization; wherein said nonpolar olefin is C2- C30 alkenes. 9. The application according to claim 8, characterized in that the polymerization conditions are: the polymerization temperature is 30°C-200°C, the olefin polymerization pressure is 0.1MPa-30MPa, and the polymerization reaction time is 5min-300min.