CN100441602C - A Composite Catalytic System for Preparation of Broad/Bimodal Distribution High Density Polyethylene - Google Patents

Abstract

The present invention provides a composite catalytic system for preparing wide/bimodal distribution high-density polyethylene, which is composed of a semi-metallocene compound having the following structural formula [1] and a metallocene-ether-inorganic salt three-component The adduct is used as an active component, and is composed of a supported organoaluminoxane; and catalyzed olefin polymerization or copolymerization to prepare 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, a preparation method and application.

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 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 molecular weight distribution of the polymer obtained by the single-site catalyst (SSC) is narrow, the branch chain distribution is uniform, and the mechanical properties are good. However, due to the narrow molecular weight distribution of the polymer, its processing performance is relatively poor. By compounding with other catalysts, it can be Improves processability of single site 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. In the obtained resin, the branching degree of the high molecular weight part is low, or even unbranched, while the branching degree of the low molecular weight part is high. This material cannot achieve processing performance and strength. balanced combination.

There are also reports on the compounding of single-site catalysts. 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 product. The average density of the polymer is around 0.950 g/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, specifically, it is a composite catalytic system that is obtained by using a semi-metallocene catalyst and a metallocene catalyst. /Composite catalytic system of bimodal distribution high-density polyethylene; the second purpose of the present invention is to provide the preparation method of the composite catalytic system suitable for slurry or gas phase polymerization process; the third purpose of the present invention is to provide the above-mentioned composite catalytic system Polymerization process for the preparation of high density polyethylene resins with broad/bimodal molecular weight distribution.

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

A. (1) A hemicene compound for ethylene polymerization, having the following general formula [1]: disclosed in CN01141472.3:

In the formula [1], R ₁ is a substituent on the salicylidene benzene ring selected from hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₆ -C ₁₂ aryl, Preferably hydrogen or C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl or tert-butyl, the substituent can be 3 to 6, preferably 3 or 6, and the substituent is located adjacent to the hydroxyl group bit or counter bit.

In formula [1], R ₂ is a substituent on N, selected from C ₁ -C ₈ alkyl, cycloalkyl or C ₆ -C ₁₂ aryl, preferably C ₁ -C ₈ cycloalkyl, more Cyclohexyl is preferred.

R ₃ is a substituent on the cyclopentadiene skeleton, selected from hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₆ -C ₁₂ aryl, preferably hydrogen or C ₁ -C 12 _C4 alkyl, specifically hydrogen, methyl, ethyl, more preferably hydrogen; M is selected from Ti, Zr or Hf, preferably Zr.

A metallocene-ether-inorganic salt three-component adduct in the composite catalytic system for preparing wide/bimodal distribution high-density polyethylene according to the present invention is disclosed in CN98103034.3, and its composition is 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 derivative groups, and the cyclopentadiene derivative groups include cyclopentadiene Base, indenyl, fluorenyl; preferably cyclopentadienyl or substituted cyclopentadienyl, Cp', Cp" can be the same or different, and can contain one or more substituents, the substituents are selected from C ₁ ~ C ₁₂ alkyl, alkoxy, silyl, aryl or aralkoxy, preferably C ₁ to C ₁₂ alkyl, most preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl.

The metallocene ligands Cp', Cp" can also be connected by a bridging group, and 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; the preferred ether is diethyl ether or tetrahydrofuran, more preferably tetrahydrofuran.

M'Q _2/n is an inorganic salt, and M' is selected from alkali metals or alkaline earth metals; preferably lithium or magnesium, preferably lithium; n=1 or 2, when M' is an alkali metal, n=2; M' When it is an alkaline earth metal, n=1; preferably n=2.

The molar ratio of the above hemilocene compound to the metallocene adduct is 0.01-300:1, preferably 0.1-100:1, more preferably 0.1-50:1, most preferably 0.1-30:1.

B. Carrier-supported 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 described in the present invention are formed when a certain substance forms a crystal, and another substance is added to the crystal defects of the substance in an orderly manner. combined.

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, substituting The group is selected from C ₁ to C ₁₂ alkyl, alkoxy, silyl, aryl or aralkoxy, preferably C ₁ to C ₁₂ alkyl; more preferred cyclopentadiene-type metallocene ligand The compounds are cyclopentadiene, n-propylcyclopentadiene, methylbutylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, 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, and are selected from C ₁ -C ₆ alkyl groups, and X is oxygen; the preferred ether is diethyl ether or tetrahydrofuran , more preferably tetrahydrofuran.

The alkaline reagent is an organic compound of an alkali metal or an alkaline earth metal, preferably an alkyllithium or an aryllithium, and butyllithium is the best. 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 described in the present invention is to load the above-mentioned semi-locene compound and metallocene adduct together with a co-catalyst 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 organoaluminoxane is preferably methylaluminoxane MAO, modified methylaluminoxane Alkane 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 semi-locene compound and the metallocene adduct of the two catalyst active components are loaded in a certain proportion on the B component. The molar ratio of aluminum on component B to active centers 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., and 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 unreasonable collocation. The composite catalytic system for preparing wide/bimodal distribution high-density polyethylene composed of semi-locene 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 high The expected effect of density polyethylene not only makes the resin obtain ideal mechanical properties, but also improves the processing performance of the resin.

Description of drawings:

Accompanying drawing 1 is the GPC (135 ℃ high temperature GPC, the solvent is o-dichlorobenzene) curve comparison diagram of the PE obtained by using the metallocene catalyst, the semi-metallocene catalyst and the composite catalyst obtained after the above two catalysts are used for ethylene polymerization. Wherein curve 1 is the GPC curve figure of the PE that embodiment 11 half metallocene catalyst polymerization obtains; Curve 2 is the GPC curve figure of the PE that embodiment 13 metallocene catalyst polymerization obtains; Curve 3 is the PE that embodiment 17 composite catalyst polymerization obtains GPC curve chart.

Specific implementation methods:

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

Synthesis of compound (A):

Bis(3-tert-butylsalicylidenecyclohexyl)-(cyclopentadienyl)zirconium chloride.

(1) Preparation of ligand compound 3-tert-butyl salicylidene cyclohexylamine:

Take 17.8g (0.1mol) of 3-tert-butylsalicylaldehyde and 0.2mol of cyclohexylamine and add it to 100ml of ethanol medium, heat to reflux under stirring, react for 2 hours, cool to room temperature, and a large number of crystals are produced. Filtration and recrystallization of the solid with 30 ml of ethanol solvent finally gave the ligand 3-tert-butyl salicylidene aniline with a yield of 92%. ¹ HNMR (CDCl ₃ , 500MHz) δ: 13.93 (br, 1H, D ₂ O, OH), 8.64 (s, 1H, CH=N), 7.46～6.96 (m, 8H, aroma), 1.47 (s, 9H , C(CH ₃ ) ₃ )

(2) Preparation of the lithium salt of 3-tert-butyl salicylidene cyclohexylamine:

Add 2.910g (11.5mmol) of 3-tert-butylsalicylidenecyclohexylamine and 30ml of tetrahydrofuran into a 100ml Schlenk bottle, cool the solution to -70°C, and add 5.72ml (2.0113mol·L ^-1 , 11.5 mmol) butyllithium, after the dropwise addition was completed, the solution was naturally raised to room temperature and stirred for 3 hours to obtain a tetrahydrofuran solution of lithium salt of 3-tert-butylsalicylidenecyclohexylamine.

(3) preparation catalyst:

The tetrahydrofuran solution of the above-mentioned lithium salt of 3-tert-butylsalicylidenecyclohexylamine was cooled to -70°C, and slowly added dropwise at this temperature to a 30ml tetrahydrofuran solution of 1.213g (3.4mmol) CpZrCl ₃ ·DME, Then it was allowed to rise to room temperature naturally, and stirred overnight. The reaction solution was drained under reduced pressure, 30ml of toluene was added, filtered, and the filtrate was placed at -20°C for 18 hours, and 0.62g of white crystal catalyst F was precipitated: bis(3-tert-butylsalicylidenecyclohexyl)-(cyclopentadiene Alkenyl) zirconium chloride, yield 62%. Its structure is shown in the figure below:

¹ H NMR: (CDCl ₃ , δ, ppm) analysis value: 8.22 (s, 2H, CH=N), 7.58～7.12 (m, 6H, Ar-H), 6.73 (s, 5H, C5H5), 1.38 ( s, 18H, ^tBu -H), 2.25-1.12 (m, 22H, cyclo-C ₆ H ₁₁ ). Anal. Calcd: C, 66.11; H, 7.54; N, 3.95. Found: C, 66.37; H, 7.69; N, 4.03. MS (70eV) m/z (%): 706.3 (46, [M] ⁺ ), 671.3 (9, [M-Cl] ⁺ ), 655.3 (100, [M-Cp] ⁺ ), 448.1 (50, [ M - ^t BuOC ₆ H ₄ CH = NC ₆ H ₁₁ ] ⁺ );

IR(KBr)v: 3087m, 3020m, 2965w, 2923w, 1609vs, 1585s, 1551s, 1496s, 1474vs, 1442s, 1396s, 1395s, 1231m, 1303vs, 1283vs, 1264s, 1222s, 1187m, 1174w, 1102s 1053w, 1022s, 976s, 925m, 862m, 847s, 820vs, 808s, 791m, 778m, 762s, 749s, 732s cm ^-1 .

Example 2

Synthesis of 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

Synthesis of 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%=17.5 (ICP), based on 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 in which a Value is 20), reacted for 4 hours, filtered, washed 3 times with 30ml toluene, then washed 2 times with hexane, drained to obtain a white carrier with good fluidity, Al%: ~ 14 (ICP).

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 63mg 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 with good fluidity, that is, catalyst D.

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 with good fluidity, that is, catalyst E.

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 with good fluidity, that is, catalyst F.

Example 8

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=3 (molar ratio), reacted for 30 min under stirring, filtered, washed with 30 ml of hexane, filtered, and dried to obtain a light yellow powder with good fluidity.

Example 9

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 B of 10ml certain molar ratio and C at room temperature, C/A=1 (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 10-18

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 5-9 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. The aggregation result data is shown in Table 1.

The catalysts obtained in Example 11, Example 13 and Example 17 were used for ethylene polymerization, and the GPC curve of the obtained PE is shown in Figure 1. High temperature GPC at 135°C was used, and o-dichlorobenzene was used as a solvent.

Curve 1 among the figure is the GPC curve figure of the PE that embodiment 11 uses semi-metallocene catalyst D to polymerize; Curve 2 is the GPC curve figure of the PE that embodiment 13 uses metallocene catalyst E to polymerize; GPC curve of PE obtained by catalyst B/A polymerization. As can be seen from Fig. 1, the peak of curve 3 is significantly gentler than the peak of curve 2 and curve 1, indicating that the polymer molecular weight distribution obtained by polymerization with the composite catalyst represented by curve 3 is higher than that obtained by the catalyst represented by curve 1 or curve 2. The molecular weight distribution of the polymer obtained by polymerization should be broad.

Claims (8)

1. composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene is characterized in that comprising following component:

A. (1) a kind of half cyclopentadinyl compound that is used for vinyl polymerization has following general formula [1]:

R in the formula [1] ₁Be selected from hydrogen, C ₁～C ₁₂Alkyl, C ₁～C ₁₂Alkoxyl group or C ₆～C ₁₂Aryl, R ₂Be selected from C ₁～C ₈Alkyl, cycloalkyl or C ₆～C ₁₂Aryl, R ₃Be selected from hydrogen, C ₁～C ₁₂Alkyl, C ₁～C ₁₂Alkoxyl group or C ₆～C ₁₂Aryl, M is selected from Ti, Zr or Hf;

(2) a kind of metallocene-ether-inorganic salt three component adductss have following general formula:

Cp′Cp″MQ ₂·RXR′·nM′Q _2/n

In the formula, Cp ' Cp " MQ ₂" be the metallocene compound part, be selected from the cyclopentadiene derivant base, described cyclopentadiene derivant base is a cyclopentadienyl, indenyl or fluorenyl to be metallocene compound, wherein Cp ', Cp; Part is identical or different, and the hydrogen atom in the part is optional to be replaced by one or more substituting groups, and substituting group is selected from C ₁～C ₁₂Alkyl, alkoxyl group, silylation, aryl or aralkoxy; M is selected from any one in the IVB family element in the periodic table of elements; Q is selected from halogen;

RXR ' is ether or cyclic ethers, and R and R ' are identical or different, are selected from C ₁～C ₆Alkyl, X is an oxygen;

M ' Q _2/nBe inorganic salt, wherein M ' is selected from basic metal or alkaline-earth metal; N=1 or 2, when M ' is basic metal, n=2; When M ' is alkaline-earth metal, n=1;

Mol ratio is 0.01～300: 1 between half cyclopentadinyl compound (1) and the metallocene adduct (2);

B. the aikyiaiurnirsoxan beta of loading with through carrier; In the B component among aluminium and the component A mol ratio in the included active centre in (1) and (2) be 10～2000.

2. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 1 is characterized in that, is used for half cyclopentadinyl compound of vinyl polymerization among the component A (1), R in the formula [1] ₁Be selected from hydrogen or C ₁～C ₄Alkyl; R ₂Be the substituting group on the N, be C ₁～C ₈Alkyl, cycloalkyl or C ₆～C ₁₂Aryl, R ₃Be hydrogen or C ₁～C ₄Alkyl; M is Zr;

Metallocene-ether among the component A (2)-inorganic salt three component adductss, Cp ', Cp " be cyclopentadienyl; described cyclopentadienyl hydrogen atom wherein is optional to be replaced by one or more substituting groups, and substituting group is methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, and M is a zirconium; Q is a chlorine, and RXR ' is a tetrahydrofuran (THF), M ' Q _2/nIn, M ' is a lithium;

Mol ratio is 0.1～50: 1 between half cyclopentadinyl compound (1) and the metallocene adduct (2);

In the B component among aluminium and the component A mol ratio in the included active centre in (1) and (2) be 20～500.

3. according to claim 2ly be used to prepare wide or the dual-peak distributed high density polyethylene composite catalyst system, it is characterized in that, be used for half cyclopentadinyl compound of vinyl polymerization among the component A (1), R in the formula [1] ₁Be selected from methyl, ethyl, the propyl group or the tertiary butyl, R ₂Be cyclohexyl; R ₃Be hydrogen; Mol ratio is 0.1～30: 1 between half cyclopentadinyl compound (1) and the metallocene adduct (2).

4. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 1 is characterized in that, the described carrier of B component is an inorganic oxide, butter, polymkeric substance or their mixture.

5. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 4 is characterized in that, the described carrier of B component is a silicon-dioxide.

6. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 1 is characterized in that, wherein the aikyiaiurnirsoxan beta general structure is:

Or

Wherein R represents C ₁～C ₁₂Alkyl, a are represented 4～30 integer.

7. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 6 is characterized in that, R is a methyl in the aikyiaiurnirsoxan beta, and a is 10～30 integer.

8. the composite catalyst system that is used to prepare wide or dual-peak distributed high density polyethylene according to claim 1, it is characterized in that, be added with machine aluminium compound in olefin polymerization system, described organo-aluminium compound is selected from a kind of in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, aluminium diethyl monochloride, the ethyl aluminum dichloride or their mixture.

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