CN1850872A - Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene - Google Patents

Abstract

The present invention provides a composite catalytic system for preparing wide/bimodal distribution high-density polyethylene, which consists of three groups of a pre-transition metal compound with the following structural formula [1] and a metallocene-ether-inorganic salt The sub-adduct is used as the active component, and the supported aluminoxane is composed, and the olefin polymerization or copolymerization is carried out to prepare the bimodal distribution high-density polyethylene.

Description

A Composite Catalytic System for Preparation of Broad/Bimodal Distribution High Density Polyethylene

Technical field:

The invention relates to a composite catalytic system for preparing wide/bimodal distribution high-density polyethylene, its preparation method and its application in olefin polymerization.

Background technique:

Methods for preparing polymers with bimodal/broad molecular weight distribution include melt blending, staged reaction, and single reactor methods. The melt blending method is to blend two resins with different molecular weights by melting. This method has the problems of poor uniformity and high operating costs. The segmented reaction method mostly uses polymerization reactors connected in series, and different processes are used in different reaction stages. It also has the problem of high operating cost and complicated operation. The single-reactor mixed catalyst method is to use the performance difference of the different active centers of the two catalysts and the different chain termination speeds to broaden the molecular weight distribution of the resin.

The current method of producing wide/bimodal distribution HDPE is mainly to use two or more polymerization reactors with different concentrations of chain transfer agents in series. In this polymerization process, the reactor with a small amount of hydrogen added High molecular weight polymers are produced, high hydrogen addition reactors are used to produce low molecular weight polymers, and finally broad/bimodal polymer distributions are obtained.

The polymer obtained by the single-site catalyst (SSC) has a narrow molecular weight distribution, uniform distribution of branch chains, and good mechanical properties, but the processing performance is poor due to the narrow molecular weight distribution. By compounding with other catalysts, the single-site catalyst can be improved. Processability of catalyst resins.

There have been reports about the compounding of traditional Ziegler/Natta catalysts and single active site catalysts, such as Mobil's WO 99/03899, this type of catalyst is much better than Ziegler/Natta catalyst copolymerization performance due to metallocene catalyst copolymerization performance, and Ziegler The molecular weight of the polymer obtained by /Natta catalyst is relatively large, resulting in very low or even no branching in the high molecular weight part of the obtained resin, while the branching of the low molecular weight part is relatively high, and this material cannot reach the processing performance and strength. Balanced, did not achieve the desired compounding effect.

The compounding between different types of single-site catalysts has also been reported. US6340730B1 uses a non-cene catalyst and a semi-cene catalyst for compounding, wherein the non-cene catalyst synthesizes a high molecular weight low-density part, and the semi-cene catalyst synthesizes a low molecular weight high Density products, the average density of the polymer is about 0.950g/cm ³ . Hexene/ethylene is about 0.011 (molar ratio). The same non-metallocene catalyst in another patent US6265513B1 has a wider molecular weight distribution of the polymer, Mw/Mn>10, and is not a single-site catalyst.

Therefore, how to take advantage of the narrow molecular weight distribution of polymers obtained by single-site catalysts and select suitable single-site catalysts for compounding is very important to improve the processability of polymers.

Invention content:

One of the purposes of the present invention is to provide a composite catalytic system suitable for preparing wide/bimodal distribution high-density polyethylene in a single reactor, and the second purpose of the present invention is to provide the preparation of a composite catalytic system suitable for slurry or gas phase polymerization processes Method; The third object of the present invention is to provide a polymerization method for high-density polyethylene resin with wide/bimodal molecular weight distribution using the composite catalytic system.

The present invention is a composite catalytic system for preparing wide/bimodal distribution high-density polyethylene, comprising the following components;

A. (1) An early transition metal complex for ethylene polymerization, having the following general formula [1]:

Wherein: M is an early transition metal of group 4, preferably zirconium and titanium;

n is greater than or equal to 2;

m is an integer satisfying the M valence;

X is selected from one of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, areneoxy, acid radical, amine, preferably hydrogen, halogen, alkyl, allyl, cyclopentadienyl, alkoxy One of radicals and aromatic hydrocarbon oxy groups; most preferably chlorine, bromine, iodine, methoxy, ethoxy, isopropoxy, isobutoxy, butoxy, phenoxy, o-tolyloxy, m-phenoxy, p-phenoxy, naphthyloxy. When m is 2 or more, multiple X groups may be the same or different.

R ¹ -R ⁸ are the same or different, and are hydrogen atom, halogen atom, C ₁ -C ₂₀ aliphatic hydrocarbon group, C ₃ -C ₂₀ cyclic hydrocarbon group or C ₆ -C ₂₀ aromatic hydrocarbon group, any of the hydrocarbon groups A hydrogen or carbon atom may optionally be replaced by a heteroatom such as a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom; specifically a hydrogen atom, methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-amyl, n-hexyl, isohexyl, tert-hexyl, phenyl, tricyclodecanyl, 2-phenyl- Isopropyl, methoxy, ethoxy or tert-propoxy.

R ⁹ -R ¹⁰ are the same or different, selected from substituted or unsubstituted C ₁ -C ₂₀ aliphatic hydrocarbon groups or C ₆ -C ₃₀ aromatic hydrocarbon groups; specifically n-hexyl, phenyl, nitro-substituted phenyl, halogen substituted phenyl, alkyl substituted phenyl, naphthyl, biphenyl or trityl; two or more groups in R ¹ -R ¹⁰ can combine with each other to form a ring.

Y is a bridging group, which is a C ₁ -C ₂₀ aliphatic hydrocarbon group or a C ₆ -C ₂₀ aromatic hydrocarbon group, any hydrogen or carbon atom on the hydrocarbon group can optionally be replaced by a halogen atom, oxygen, nitrogen, Boron, sulfur, phosphorus, silicon atoms and other heteroatom substitution; specifically methylene, ethylene, propylene, butylene, ethylene, isopropylidene, isobutylene, phenyl, substituted phenyl .

(2) A metallocene-ether-inorganic salt three-component adduct, disclosed in CN98103034.3, has the following general formula: Cp'Cp"MQ ₂ ·RXR'·nM'Q _2/n

In the formula, Cp'Cp"MQ ₂ is a metallocene compound, and Cp' and Cp" are metallocene ligands selected from cyclopentadiene derivatives, and the cyclopentadiene derivatives include cyclopentadiene Base, indenyl, fluorenyl; preferably cyclopentadienyl or substituted cyclopentadienyl, the ligands can be the same or different, and the hydrogen atoms in the ligands can be substituted by one or more substituents, the substituents are selected from Alkyl, alkoxy, silyl, aryl or aralkoxy from C ₁ to C ₁₂ ; preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl.

The metallocene ligands Cp', Cp" can also be connected by a bridging group, the bridging group can be a C ₁ ~ C ₄ carbon bridge, a silicon bridge or a germanium bridge; there can also be no bridge Linked, that is, non-bridged metallocene compounds, preferably non-bridged metallocene compounds.

M is selected from any one of Group IVB elements in the periodic table, preferably Zr or Ti, most preferably Zr; Q is selected from halogen, preferably chlorine.

RXR is ether or cyclic ether, R and R' can be the same or different, selected from C ₁ ~ C ₆ alkyl, X is oxygen; RXR' is preferably ether, tetrahydrofuran, the best tetrahydrofuran; inorganic salt M'Q ₂ In _/n , M' is selected from alkali metals or alkaline earth metals; n=1 or 2, when M' is an alkali metal, n=2; when M' is an alkaline earth metal, n=1; M' is preferably lithium or magnesium , preferably lithium.

The molar ratio between the transition metal complex (1) and the metallocene adduct (2) is 0.01-300:1, preferably 0.1-100:1, more preferably 0.1-50:1, most preferably 0.1-30:1.

B. Carrier-loaded aluminoxane; the molar ratio of aluminum in component B to active centers included in (1) and (2) in component A is 10-2000; preferably 20-500;

The adducts in the present invention are formed when a certain substance forms a crystal, and another substance is sequentially added to the crystal defect of the substance, and one substance is combined with another substance by intermolecular force.

The preparation method of the metallocene adduct provided by the present invention is: using ether as a solvent, at -10 to 30°C, preferably -5 to 10°C, making a cyclopentadiene-type metallocene ligand compound and an alkaline reagent The reaction generates a ligand anion, and then reacts the generated ligand anion with a metal halide of the general formula MQ ₄ at -78 to 30°C. While the metallocene compound is formed, the metallocene compound and the inorganic salt released by the reaction Form metallocene adducts with ether solvents, preferably remove 50-98% of the solvents, add alkanes to disperse the residue, filter and dry to obtain metallocene adduct solid products.

The cyclopentadiene-type metallocene ligand compound in the above preparation method includes cyclopentadiene and its derivatives, such as fluorene or indene, and the cyclopentadiene and its derivatives can also contain one or more substituents, preferably Mono-substituted cyclopentadiene, multi-substituted cyclopentadiene, indene, fluorene; substituents are selected from C ₁ ~C ₁₂ alkyl, alkoxy, silyl, aryl or aralkoxy, preferably C ₁ ～C ₁₂ alkyl; more preferred cyclopentadiene type compounds are cyclopentadiene, n-propyl cyclopentadiene, methyl butyl cyclopentadiene, tetramethyl cyclopentadiene, pentamethyl Cyclopentadiene, indene.

The ether solvent is an ether or cyclic ether with the general formula RXR', wherein R and R' can be the same or different, selected from C ₁ -C ₆ alkyl groups, and X is oxygen; the preferred ether is diethyl ether or tetrahydrofuran , a more preferred ether is tetrahydrofuran.

The basic reagent is an organic compound of alkali metal or alkaline earth metal, preferably alkyllithium, aryllithium, most preferably butyllithium.

M in the MQ ₄ metal compound is selected from any element of Group IVB in the periodic table, preferably zirconium or titanium, most preferably zirconium; Q is a halogen, preferably chlorine.

The alkanes are selected from C ₅ -C ₁₂ alkanes, preferably petroleum ether with a boiling range of 60-90°C. The amount of alkane added is preferably 1 to 10 times the volume of the adduct slurry.

The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene of the present invention is to support the above-mentioned early transition metal compound and metallocene adduct together with a cocatalyst in a certain molar ratio on an inorganic or organic carrier. The carrier is inorganic oxide, inorganic chloride, polymer or their mixture, and silicon dioxide (silica gel) is the best.

Described promoter refers to aluminoxane, and its structural formula is:

or

Wherein R represents a C ₁ to C ₁₂ hydrocarbon group, preferably a methyl group, a represents an integer of 4 to 30, preferably an integer of 10 to 30, and the aluminoxane is preferably methylaluminoxane MAO, modified methylaluminoxane mmao.

The loading method of the present invention is that the cocatalyst is first loaded on the carrier to obtain the cocatalyst B component supported by the carrier, and then the above-mentioned pre-transition metal compound and the metallocene adduct of the two catalyst active components are mixed in a certain proportion Loaded on B component. The molar ratio of the aluminum on component B to the active centers included in (1) and (2) in component A is 10-2000, preferably 20-500.

The loading method of the present invention is as follows;

(1) Treatment of the carrier: calcining the carrier under nitrogen at a temperature of 200-800° C. for 1-24 hours. The calcined carrier can be used directly.

(2) Loading of aluminoxane: under nitrogen, add the above-mentioned treated carrier, aluminoxane and solvent, heat up to 30-80°C, preferably 40-60°C, and stir for 3-6 hours , and then washed several times with a solvent, and dried in vacuum to obtain a fluid solid powder. Wherein the solvent can adopt aromatic or aliphatic hydrocarbons, such as toluene, benzene, xylene, hexane, heptane, cyclohexane, etc., preferably toluene.

(3) Loading of catalyst active components: react the carrier containing aluminoxane obtained in the above (2) and the mixture of the early transition metal compound and the metallocene adduct in a solvent, at 0-40°C, The time is 1-120 minutes, and the slurry can be directly used in the polymerization reaction; or the solvent can be removed to obtain a fluid solid catalyst for the polymerization reaction. The solvent is toluene, benzene, xylene, hexane, heptane, cyclohexane, etc., toluene, hexane or the mixture of the two are the best.

The polymerization method of the present invention is to add an organic aluminum compound as a cleaning agent in the reaction medium, then add the slurry obtained in (3) or a solid catalyst, raise the temperature, and add ethylene to polymerize.

The organoaluminum compound is one of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, monochlorodiethylaluminum, dichloroethylaluminum, or Their mixtures are preferably trimethylaluminum, triethylaluminum and triisobutylaluminum. The molar ratio of Al in the above organoaluminum compound to the active centers included in (1) and (2) in component A is 10-2000, preferably 30-200.

The polymerization temperature is 0°C to 150°C, preferably 0°C to 90°C.

The polymerization pressure is 0.1-10.0 MPa, preferably 0.1-2.0 MPa.

The reaction medium is a non-polar medium, such as: C _3-10 saturated alkanes, including paraffins and cycloalkanes, preferably n-hexane.

The catalyst system described in the present invention can be used for the polymerization or copolymerization of olefins, especially for the homopolymerization of ethylene or the copolymerization of ethylene and other α-olefins, wherein the α-olefins are propylene, butene, pentene, hexene , octene, 4-methylpentene-1; the polymerization process can adopt slurry method and gas phase method. The density of the obtained polyethylene resin is 0.967～0.948g/cm ³ , the melt index (MI _2.16kg ): 0.01～10g/10min, MI _21.6kg /MI _2.16kg = 100～200, Mw/Mn=5～20, which This resin can be used to make high density film or tubing.

Compared with the prior art, the composite catalytic system with dual active centers provided by the present invention has the following advantages: Although there are many existing technologies using the composite catalytic system, none of them can achieve the desired effect due to improper collocation. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene composed of early transition metal compounds and metallocene adducts provided by the present invention has a reasonable combination of properties of the two active centers, and achieves the preparation of wide/bimodal distribution The expected effect of high-density polyethylene not only makes the resin obtain ideal mechanical properties, but also improves the processing performance of the resin.

Detailed ways:

Further describe the present invention below in conjunction with embodiment, the scope of the present invention is not limited by these embodiment. The scope of the present invention is set forth in the claims.

Example 1

Compound A: Synthesis of (L2) ₃ Zr ₂ Cl ₄

1. Synthetic Ligand L2

Under a nitrogen atmosphere, add 2.0g (5.05mmol) of 5,5'-isopropylidene-bis(3-tert-butyl-2-hydroxybenzaldehyde) into a 250ml three-necked flask, dissolve it in 60ml of methanol, and then add 1.39 ml (12.12 mmol) of cyclohexylamine and 0.6 ml of formic acid, stirred at room temperature for 24 hours. The precipitate was filtered off and dried in vacuo to obtain 0.7 g (1.25 mmol, 24.8% yield) of Ligand L2 as a yellow powder.

Its structural formula is as follows:

Ligand L2

CI-MS: 558M ⁺

2. Synthesis of metal complexes (L2) ₃ Zr ₂ Cl ₄

Under nitrogen atmosphere, add 1.07g (1.92mmol) of ligand L2 synthesized above into the three-necked flask, add 50ml of tetrahydrofuran to dissolve, then cool down to below -70°C, slowly add 1.60ml (2.56mmol) of n-butyl lithium solution dropwise, React at this temperature for 1 hour, slowly warm up to room temperature, and react for 4 hours; transfer this solution to a constant pressure dropper, and slowly add it dropwise to 50ml of 0.48g (1.28mmol) ZrCl ₄ dissolved in it below -70°C After dripping, it was gradually raised to room temperature, then reacted for about 18 hours, and then refluxed for 5 hours; distilled under reduced pressure, evaporated to dryness, dissolved in dichloromethane, filtered off insolubles, and added to the filtrate Anhydrous diethyl ether was used to obtain 0.60 g of yellow powder of the metal complex (L2) ₃ Zr ₂ Cl ₄ .

Its structural formula is as follows:

Example 2

Metallocene compound B: Preparation of (Me ₄ Cp) ₂ ZrCl ₂ adduct:

Under a nitrogen atmosphere, add 20g (0.164mol) of newly distilled tetramethylcyclopentadiene to the three-necked flask, add 200ml of tetrahydrofuran to dissolve, then cool down to below -70°C, and slowly add 65.6ml (0.164mol) of n-butyl Lithium-based solution (2.5M), react at this temperature for 1 hour, slowly warm up to room temperature, and react for 4 hours; transfer this solution to a constant pressure dropper, and slowly add it dropwise to the dissolved 19.1g (0.082mol) ZrCl in _100ml of tetrahydrofuran solution, after dripping, gradually rise to room temperature, then react for about 18 hours; Distill under reduced pressure, evaporate to dryness, disperse with hexane, filter, wash 2 times with hexane, 39 g of purple metallocene adduct B powder was obtained, Zr%=18 (ICP), calculated as Zr, the yield was 94.1%.

Example 3

Metallocene compound C: Preparation of (n-BuMeCp) ₂ ZrCl ₂ adduct:

Under a nitrogen atmosphere, add 20 g (0.147 mol) of newly distilled methyl butyl cyclopentadiene to the three-necked flask, add 200 ml of tetrahydrofuran to dissolve, then lower the temperature to below -70°C, and slowly add 58.9 ml (0.147 mol) of n-butyl Lithium solution (2.5M), react at this temperature for 1 hour, slowly warm up to room temperature, and react for 4 hours; transfer this solution to a constant pressure dropper, and slowly add it dropwise to dissolve 16.43g ( 0.074mol) ZrCl in _100ml of tetrahydrofuran solution, after dripping, gradually rise to room temperature, then react for about 18 hours; vacuum distillation, evaporate to dryness, disperse with hexane, filter, wash 2 times with hexane to obtain 35g of yellow metallocene adduct C powder, Zr%=175 (ICP), calculated as Zr, the yield is 91%.

Example 4

Preparation of loaded MAO (SMAO):

Add 20 grams of activated 955 silica gel into a 250ml glass bottle replaced with nitrogen (activation condition 600°C, 4 hours), add 30ml of toluene, raise the temperature of the system to 50°C, add dropwise the toluene solution of MAO (containing 11g of MAO, where The a value is 15), reacted for 4 hours, filtered, washed 3 times with 30ml toluene, then washed 2 times with hexane, and dried to obtain a white carrier with good fluidity, Al%: ~ 14 (ICP method measurement).

Example 5

Preparation of supported catalyst D:

In the 250ml glass bottle replaced with nitrogen, add the SMAO prepared by 2g embodiment 4, add 20ml toluene, start stirring, add dropwise the toluene solution of 10ml compound A (containing 70mg compound A, Al/Zr=100) at room temperature, stir The reaction was carried out for 30 min, filtered, washed with 30 ml of hexane, filtered, and dried to obtain a light yellow powder catalyst D with good fluidity.

Example 6

Preparation of supported catalyst E:

In the 250ml glass bottle replaced with nitrogen, add the SMAO prepared by 2g embodiment 4, add 20ml toluene, start stirring, add dropwise the toluene solution of 10ml compound B (containing 105mg compound B, Al/Zr=50) at room temperature, stir The reaction was carried out for 30 min, filtered, washed with 30 ml of hexane, filtered, and dried to obtain a light yellow powder catalyst E with good fluidity.

Example 7

Preparation of supported catalyst F:

In the 250ml glass bottle replaced with nitrogen, add the SMAO prepared by 2g embodiment 5, add 20ml toluene, start stirring, add dropwise the toluene solution of 10ml compound C (containing 108mg compound C, Al/Zr=50) at room temperature, stir The reaction was carried out for 30 min, filtered, washed with 30 ml of hexane, filtered, and dried to obtain a light yellow powder catalyst F with good fluidity.

Embodiment 8～10

Preparation of compound catalyst:

Add the SMAO prepared by 2g embodiment 5 in the 250ml glass bottle replaced with nitrogen, add 20ml toluene, start stirring, dropwise the toluene solution (Al/Zr=50) of the compound A of 10ml certain molar ratio and B at room temperature, B/A=0.7, 1, 2 (molar ratio), reacted for 30 min under stirring, filtered, washed with 30 ml of hexane, filtered, and dried to obtain light yellow powder with good fluidity.

Examples 11-13

Preparation of compound catalyst:

Add the SMAO prepared by 2g embodiment 5 in the 250ml glass bottle replaced with nitrogen, add 20ml toluene, start stirring, dropwise the toluene solution (Al/Zr=100) of the compound B of 10ml certain molar ratio and C at room temperature, C/A=0.3, 0.7, 1.7 (molar ratio), react under stirring for 30 min, filter, wash with 30 ml of hexane, filter, and dry to obtain light yellow powder with good fluidity.

Examples 14-37

Slurry Polymerization Test:

In a 2-liter stainless steel autoclave, after nitrogen blowing and ethylene replacement several times, add 1 liter of hexane, comonomer hexene, 2 mmoles of triethylaluminum and the above-mentioned examples 5-13 obtained Catalyst, feed ethylene, and react at 1.0Mpa, 80°C for a certain period of time. After cooling down, filter and dry to obtain polymer powder. See Table 1 for the data.

Table 1 Aggregation results Example catalyst Proportion 1-Hexene(ml) time (min) Activity (gPE/gcat) MI _2.16kg MI _21.6kg MI _21.6kg /MI _2.16kg Mw(×10 ⁴ ) Mw/Mn Density (g/cm ³ ) 14151617181920212223242526 DDEEEFFFB/AB/AB/AB/AB/A --------0.70.7111 01001020010200100510 60606060606060606060606060 1600210012561400102925662735204415601850152017201800 36.7039.800.140.046-0.1360.3120.420.0740.1660.0470.0940.075 --4.191.91-2.86--7.9512.465.319.495.98 --3041.5-21--1077511310179.7 5.925.89-2421---16.0816.8621.316.116.4 6.25.89-3.352.8-----11.349.9410.42 0.96690.96620.95310.9367------0.95780.95710.9529

continued 2728293031323334353637 B/AB/AB/AB/AB/AC/AC/AC/AC/AC/AC/A 111220.30.30.70.71.71.7 10101001010205101020 1201802406060606060606060 22002650290015601755225024302250265723432157 0.0750.0170.0190.0470.0462.462.720.5291.210.510.61 7.574.083.612.712.7116.45132.2313.9539.398.8711.15 100.924019057.758.847.3448.6126.3732.5517.418.22 -----11.6--13.6615.8- -----10.52--11.457.44- -----------

Claims (8)

1. A composite catalytic system for preparing wide/bimodal distribution high-density polyethylene, characterized in that, comprises the following components; A. (1) An early transition metal complex for ethylene polymerization, having the following general formula [1]: in: M is a Group 4 pre-transition metal; n is an integer greater than or equal to 2, m is an integer satisfying M valence, X is selected from one of hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, areneoxy, acid radical, amine, and when m is 2 or greater, multiple X groups can be the same or different; R ¹ -R ⁸ are the same or different, and are hydrogen atom, halogen atom, C ₁ -C ₂₀ aliphatic hydrocarbon group, C ₃ -C ₂₀ cyclic hydrocarbon group or C ₆ -C ₂₀ aromatic hydrocarbon group, any of the hydrocarbon groups A hydrogen or carbon atom may optionally be replaced by a halogen atom, oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom; R ⁹ -R ¹⁰ are the same or different, selected from substituted or unsubstituted C ₁ -C ₂₀ aliphatic hydrocarbon groups or C ₆ -C ₃₀ aromatic hydrocarbon groups; Two or more groups in R ¹ -R ¹⁰ can combine with each other to form a ring; Y is a bridging group, which is a C ₁ -C ₂₀ aliphatic hydrocarbon group or a C ₆ -C ₂₀ aromatic hydrocarbon group, any hydrogen or carbon atom on the hydrocarbon group can optionally be replaced by a halogen atom, oxygen, nitrogen, Boron, sulfur, phosphorus, silicon atom substitution; (2) a metallocene-ether-inorganic salt three-component adduct has the following general formula: Cp′Cp″MQ ₂ ·RXR′·nM′Q _2/n In the formula, Cp'Cp"MQ ₂ is a metallocene compound, wherein Cp', Cp" are metallocene compound ligands, selected from cyclopentadiene derivatives, and the cyclopentadiene derivatives include cyclopentadiene Dienyl, indenyl, fluorenyl; the ligands can be the same or different, and the hydrogen atoms in the ligands can be replaced by one or more substituents, and the substituents are selected from C ₁ to C ₁₂ alkyl, alkoxy, Silyl, aryl or aralkoxy; M is selected from any one of Group IVB elements in the periodic table; Q is selected from halogen; RXR' is ether or cyclic ether, R and R' can be the same or different, selected from C ₁ ~ C ₆ alkyl, X is oxygen; M'Q _2/n is an inorganic salt, M' is selected from alkali metals or alkaline earth metals; n=1 or 2, when M' is an alkali metal, n=2; when M' is an alkaline earth metal, n=1; The molar ratio between the transition metal complex (1) and the metallocene adduct (2) is 0.01 to 300:1; B. Aluminoxane supported by a carrier; the molar ratio of aluminum in component B to active centers included in (1) and (2) in component A is 10-2000. 2. the composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 1, is characterized in that: transition metal complex in component A (1), described M is an early transition metal Zirconium, titanium; X is chlorine, bromine, iodine, methoxy, ethoxy, isopropoxy, isobutoxy, butoxy, phenoxy, o-phenoxy, m-phenoxy, p-phenyl Oxygen or naphthyloxy; R ¹ -R ⁸ are selected from hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl , isohexyl, tert-hexyl, phenyl, tricyclodecanyl, 2-phenyl-isopropyl, methoxy, ethoxy or tert-propoxy; R ⁹ -R ¹⁰ are selected from n-hexyl, phenyl, nitro-substituted phenyl, halophenyl, alkyl-substituted phenyl, naphthyl, biphenyl or trityl; Y is selected from methylene, ethylene, propylene, butylene, ethylene, isopropylidene, isobutylene, phenyl, substituted phenyl; Metallocene-ether-inorganic salt three-component adduct in component A (2), Cp', Cp" are preferably cyclopentadienyl or substituted cyclopentadienyl, and the substituents are preferably methyl, ethyl Base, propyl group, isopropyl group, butyl group, isobutyl group, M is zirconium; Q is chlorine, RXR' is preferably tetrahydrofuran, and M' in M'Q _2/n is preferably lithium; transition metal complex (1) The molar ratio between the metallocene adduct (2) and the metallocene adduct (2) is preferably 0.1 to 50:1; the molar ratio of aluminum in component B to the active centers included in (1) and (2) in component A is preferably 20- 500. 3. the composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 1, is characterized in that, the carrier described in component B is inorganic oxide, inorganic chloride, polymer or their mixture. 4. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 3, characterized in that, the carrier described in component B is silica gel. 5. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 1, wherein the general structural formula of aluminoxane is:

or

Wherein R represents a C ₁ -C ₁₂ hydrocarbon group, and a represents an integer of 4-30. 6. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 5, characterized in that R in the aluminoxane is preferably a methyl group, and a is preferably an integer of 10-30. 7. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 1, characterized in that an organoaluminum compound can be added in the olefin polymerization system. 8. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to claim 7, wherein the organoaluminum compound is selected from trimethylaluminum, triethylaluminum, triiso One of butylaluminum, trihexylaluminum, diethylaluminum monochloride, ethylaluminum dichloride or a mixture thereof.