CN101166575A - Bimetallic catalyst, polymerization process and bimodal polyolefins obtained therefrom - Google Patents

Abstract

The present invention provides bimetallic catalysts, and methods of making bimetallic catalysts comprising a modified ziegler-natta catalyst and a metallocene, which in one embodiment comprises reacting: a ziegler-natta catalyst comprising a group 4, 5 or 6 metal halide and/or oxide, optionally including a magnesium compound, is combined with (b) a modifying compound ("modifier"), wherein the modifying compound is a group 13 alkyl compound, to form a modified ziegler-natta catalyst. The invention also provides a process for the polymerization of olefins using the bimetallic catalyst of the invention. The modified Ziegler-Natta catalyst is preferably inactive, i.e., it is unreactive toward olefin polymerization alone. In one embodiment, the molar ratio of the group 13 metal (of the modifier) to the group 4, 5 or 6 metal halide and/or oxide is less than 10: 1. The bimetallic catalysts of the invention are useful for producing bimodal polymers, especially bimodal polyethylene, having a polydispersity (Mw/Mn) of from 12 to 50. These bimodal polyolefins are useful in articles such as pipes and films.

Description

Bimetallic catalyst, polymerization and thus obtained bimodal polyolefin

Background technology

Invention field

The present invention relates to bimetallic catalyst, produce the method for these catalyst, and the method for using these bimetallic catalyst olefin polymerizations.More specifically, the present invention relates to comprise the bimetallic catalyst of modification Ziegler-Natta catalyst, and the method for thus obtained production bimodal polyolefin.

The explanation of association area

Polymerization as herein described can be a solution, gas phase, slurry phase or high pressure method.As discussed in more detail above, gas phase or slurry phase polymerisation process are preferred, comprise catalyst and olefinic monomer (at least a of them is ethene or propylene).Such as in patent documentation reflection, in order to find the improvement in these class methods, paid a large amount of effort.Some of these patents are indicated in this article.To illustrate in further detail following by improvement provided by the invention described here.

General introduction

One aspect of the present invention relates to the method for production modification Ziegler-Natta catalyst, in one embodiment, this method comprise with: (a) comprise 4,5 or 6 family's metal halide and/or oxides, choose wantonly and comprise that the Ziegler-Natta catalyst of magnesium compound combines with (b) modified compound (" modifier "), wherein modified compound is the mixture of 13 family's alkyl compounds or compound, to form the modification Ziegler-Natta catalyst.This modification Ziegler-Natta catalyst is preferably non-activated, that is to say, it is nonreactive for olefinic polymerization separately.In one embodiment, this modifier can be used general formula AlX _nR _3-nDescribe, wherein Al is an aluminium, and X is independently selected from halogen, preferred fluorine, chlorine or bromine, C ₁-C ₂₀-alkoxyl, C ₁-C ₂₀Alkyl amino and their bond; Be independently selected from C with R ₁-C ₂₀Alkyl and C ₆-C ₂₀Aryl; Wherein n is 0,1,2 or 3 in one embodiment, and in a particular, n is 1,2 or 3; In addition, wherein modifier can be blend by the described compound of this general formula.In one embodiment, 4, the 5 or 6 family's metal halides of (modifier) 13 family's metals and Ziegler-Natta catalyst and/or the mol ratio of oxide are lower than 10: 1.

Another aspect of the present invention is the method for producing bimetallic catalyst, and this method comprises that with the Ziegler-Natta catalyst and second catalytic component preferable alloy cyclopentadienyl catalyst merges, and forms bimetallic catalyst; Wherein Ziegler-Natta catalyst can modification before or after merging with second catalytic component.This method that forms bimetallic catalyst has obtained for example can support in for example inorganic oxide carrier with for example by using the bimetallic catalyst that comprises Ziegler-Natta catalyst component (" Ziegler-Natta catalyst ") and metallocene catalyst components (" metalloscene catalyst ") of aikyiaiurnirsoxan beta and/or other alkyl aluminum activation.

Bimetallic catalyst of the present invention can be used for producing bimodal polyolefin, and especially bimodal polyethylene has the polydispersity (Mw/Mn) of 12-30 in one embodiment and is higher than 1,000,000 Mz value.This bimodal polyethylene can have the density of other characteristic such as 0.94-0.98g/cc in a particular, and preferably produces in a step in single-reactor.These bimodal polyolefins can be used for following goods, such as tubing, film and blow molding applications (for example the bottle, the bucket and other container).

Describe in detail

Preface

The employed periodic table about element of this paper " family " adopts as at CRC HANDBOOK OFCHEMISTRY AND PHYSICS (David R.Lide ed., CRC Press 81 ^StEd.2000) " newly " numbering plan of the periodic table family in.

The structural formula of Shi Yonging is used according to the common sense in chemical field in this article; Line ("-") is used to be illustrated in metallic atom (" M ", 3-12 family atom) and part, part atom or atom (cyclopentadienyl group for example, nitrogen, oxygen, halide ion, alkyl etc.) association between, and phrase " with ... associate ", " being bonded in " and " combination " is not limited to represent the chemical bond of certain type, because these lines and phrase are used for representing " chemical bond "; " chemical bond " is defined as has the attraction from atom to atom that the aggregation that is enough to make combination plays the intensity of unit or " compound ".

One aspect of the present invention relates to the modification Ziegler-Natta catalyst, and the method for preparing the modification Ziegler-Natta catalyst.Another aspect of the present invention comprises the bimetallic catalyst that contains the modification Ziegler-Natta catalyst, and the method for preparing this bimetallic catalyst.Polymerization disclosed herein relates to allows olefinic type monomers contact with bimetallic catalyst of the present invention.Alkene and bimetallic catalyst can preferably contact in a reactor in one or more reactors, form polyolefin product as described herein.Term as used herein " bimetallic catalyst " is meant and comprises at least two kinds of different catalysts compounds, and they at least a is any composition, mixture or the system of so-called " modification Ziegler-Natta catalyst " as described herein.Various different catalysts may reside on the single carrier granular, make that bimetallic catalyst is a carrying bimetallic catalyst.Yet, the term as used herein bimetallic catalyst comprises that also wherein one of catalytic component (for example first catalyst compounds) is present on a collection of carrier granular, and another catalyst (for example second catalyst compounds) is present in system or mixture on another batch carrier granular.Preferably, under latter event, with these two kinds of catalyst-loaded whiles or be incorporated in the single-reactor according to the order of sequence, and, promptly carry out polymerization under two batches of catalyst-loaded existence at this bimetallic catalyst.

Though bimetallic catalyst can comprise two or more different catalysts, be convenient to discuss in the present invention, only describe these catalyst compounds in detail two kinds, i.e. " first catalytic component " and " second catalytic component ", each comfortable following argumentation.First catalytic component is that the modification Ziegler-Natta catalyst and second catalytic component are single site catalysed immunomodulator compounds, for example metallocene catalyst compound.Other single site catalysts is such as the so-called catalyst compounds that contains 15 family's elements, for example at WO 99/01460; EP A1 0 893 454; EP A1 0 894 005; US 5,318, and 935; US 5,889, and 128; US 6,333,389 B2 and US6, and those disclosed also can be used as second catalytic component among 271,325 B1.

Can in all sorts of ways one or both different catalysts are fixed or are incorporated on the carrier, form bimetallic catalyst.For example, a kind of operation of preparation carrying bimetallic catalyst can comprise providing and supports first catalytic component, allow the slurry that comprises this first catalytic component and non-polar hydrocarbon with comprise second catalytic component, can also comprise mixture (solution or the slurry) contact of activator.This operation may further include drying and comprises the products therefrom of first and second catalytic components and reclaim bimetallic catalyst.

First catalytic component

Bimetallic catalyst as herein described comprises " first catalytic component ", and it is the modification Ziegler-Natta catalyst.Ziegler-Natta catalyst is known in the art, for example is described among the ZIEGLER CATALYSTS 363-386 (eds., Springer-Verlag 1995 for G.Fink, R.Mulhaupt and H.H.Brintzinger).The example of this type of catalyst comprises those that contain 4,5 or 6 group 4 transition metal oxides, alkoxide and chloride (or their bond), optional and following material merges: magnesium compound, in and/or external electronic donor, and carrier material, for example 13 and 14 family's inorganic oxides, this is well known in the art, for example be described in POLYPROPYLENE HANDBOOK 12-44 (Edward P.Moore, Jr.ed., Hanser Publishers 1996) and for example US 5, in 258,345.

In the present invention, do not activate Ziegler-Natta catalyst and contact, form not activation modification Ziegler-Natta catalyst or " modification Ziegler-Natta catalyst " with " modifier " (following), it then with second catalytic component, preferred metallocenes merges, and bimetallic catalyst is provided.In one embodiment, Ziegler-Natta catalyst comprises 4,5 or 6 group 4 transition metals, preferentially is selected from 4 and 5 families, and more preferably titanium also more preferably derives from titanium chloride compound.In another embodiment, Ziegler-Natta catalyst further comprises organo-magnesium compound.In certain embodiments of the invention, the modification Ziegler-Natta catalyst is with before modifier contacts and keep activation afterwards, for example up to after modification Ziegler-Natta catalyst and Metallocenic compound merging, and before initiated polymerization.Ideally, the modification Ziegler-Natta catalyst component of bimetallic catalyst keeps activation, up in polymer reactor with till olefinic monomer contacts.

Term " activation " is meant " not activation ", " non-activity " or " passivity ", preferably make this catalyst can not (not have further to handle or the situation of modification under) promotion polymerization, when with monomer when in reactor, merging under the polymerizing condition.Preferably, " not activation " catalyst is not have activity; Or activity is lower than the catalyst of 10g polymer/g catalyst.In addition, in some embodiment at least, " activation " catalyst is to have the catalyst that is lower than 100g polymer/g activity of such catalysts; In other embodiments, activating catalyst is not to have the catalyst that is lower than 500g polymer/g activity of such catalysts.Those skilled in the art will appreciate that this catalyst must be with some mode " activation " before it is used to promote polymerization.As described below, activation is generally undertaken by this catalyst compounds (for example Ziegler-Natta catalyst) is merged with " activator ".Though method as herein described also comprises various activation steps, for example, with catalyst and activator such as TMA and hydration also, these activation steps should not obscured with catalyst as herein described " modification ".And the former has obtained activating catalyst, but the latter does not obtain activating catalyst, even modifier as herein described has been used as co-catalyst or activator in other composition or method.

In one embodiment, " modifier " cited herein is to comprise at least one 13 family's metal, preferred aluminium or boron, and any compound of alkyl (or alkoxyl or alkyl amino) or the blend of compound.In one embodiment, this modifier can be used general formula AlX _nR _3-nDescribe, wherein Al is an aluminium, and X is independently selected from halogen, preferred fluorine, chlorine or bromine, C ₁-C ₂₀-alkoxyl, C ₁-C ₂₀Alkyl amino and their bond; Be independently selected from C with R ₁-C ₂₀Alkyl and C ₆-C ₂₀Aryl; Wherein n is 0,1,2 or 3 in one embodiment, and in a particular, n is 1,2 or 3, and in another more specific embodiment, n is 1 or 2; And wherein modifier can be blend by described two or more compounds of this general formula.For example, as used herein modifier can comprise the diethylaluminum chloride of any ratio that caters to the need and the blend of ethylaluminium dichloride.The explanation of modifier compound is not limited to its physical form, because it can be a neat liquid, comprises the solution that is fit to diluent, the slurry in diluent, or drying solid.In a particular, this modifier comprises at least one halogen group.In another embodiment of modifier, this modifier comprises the aluminium compound of ethyl or butyl, and at least one chlorine.The limiting examples of the modifier that is fit to comprises diethylaluminum chloride (DEAC), sesquialter ethylaluminium chloride (EASC), diethylaluminum ethoxide (DEAL-E) and their mixture.

Other limiting examples of modifier comprises: methylaluminium dichloride, ethylaluminium dichloride, aluminium isobutyl dichloride, the dichloride octyl aluminum, sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, sesquialter bromination aluminium ethide, sesquialter chlorination aluminium isobutyl, chlorodimethylalumiu, diethylaluminum chloride, bromination diethyl aluminum, iodate diethyl aluminum, chlorination di aluminium, chlorination di-n-butyl aluminium, di-isobutyl aluminum chloride, chlorination di-n-octyl aluminium, diethylaluminum ethoxide, diisobutyl aluminum ethoxide, bis oxide (diisobutyl aluminum), methoxyl group diethyl boron, chlorination dimethyl boron, chlorination diethyl boron, chlorination di-n-butyl boron, chlorination diisobutyl boron and their mixture.

Preferably, the mol ratio of 13 family's metals and transition metal (in Ziegler-Natta catalyst) was less than 10: 1.It is envisaged that the amount of the modifier of representing with the mol ratio that is equal to or greater than 10: 1 can cause the catalyst activation, this is undesirable.The catalyst that becomes activation can not store any considerable time and do not degraded.For example, activating catalyst can just begin degraded after the storage in 1 week only.In some embodiment of this method, 13 family's metals in modifier fall into certain limit with the mol ratio of the transition metal in Ziegler-Natta catalyst, for example have 7: 1; Or 5: 1; Or 4: 1; Or 3: 1; Or even 2: 1 the upper limit and 0.01: 1, or the lower limit of 0.1: 1 or 1: 1, wherein this scope can be that above any lower limit combines with any of above any upper limit.When modifier comprised chlorine, preferably, the level of modifier had and is equal to or less than 5: 1 mol ratio, because the corrosivity of chlorine.

Select the engagement sequence of modifier wherein and/or activator and Ziegler-Natta catalyst, so that obtain the highest catalyst activity (or productivity ratio).In one embodiment, modifier does not at first contact with activating Ziegler-Natta catalyst, (separates or does not separate product) subsequently and allow the not activation Ziegler-Natta catalyst of this modification contact with activator.In another embodiment, Ziegler-Natta catalyst contacts with activator with modifier simultaneously.In the particular aspects of this back embodiment, activator is trimethyl aluminium (TMA), and in another more specific embodiment of a back embodiment, activator does not comprise TMA.In these any embodiments, Ziegler-Natta catalyst or modification ziegler natta catalyst can support on carrier material.

Phrase " separation of product " for example is meant removes the unwanted diluent that uses of final carbon monoxide-olefin polymeric (for example Ziegler-Natta catalyst) in the preparation process of product.

In another more specific embodiment, at first support Ziegler-Natta catalyst, for example be fixed in carrier such as on the inorganic oxide, in one embodiment on silica.In another embodiment, this Ziegler-Natta catalyst that supports can any desirable order and organo-magnesium compound merging.The non-activated Ziegler-Natta catalyst that supports merges with second catalyst compounds then, (separates or does not separate product) subsequently and contact with modifier.In an alternative embodiment, the non-activated Ziegler-Natta catalyst that supports at first contacts with modifier, forms modification Ziegler-Natta catalyst (separate or without separated product), contacts with this second catalytic component subsequently.This second catalytic component is activation and in another embodiment in advance in one embodiment, with support Ziegler-Natta catalyst and activate after merging.Products therefrom is a bimetallic catalyst.

In one embodiment, the gained bimetallic catalyst comprises carrier material, modification Ziegler-Natta catalyst, and the activator that is suitable for metallocene, aikyiaiurnirsoxan beta for example known in the art, triarylborane or ionic borates activator.

In an embodiment of bimetallic catalyst, be suitable for the luxuriant activator of activated metal, join in the modification Ziegler-Natta catalyst that supports with metallocene simultaneously such as aikyiaiurnirsoxan beta.In one embodiment by allow alkyl aluminum compound before entering polymer reactor or after entering polymer reactor, for example trimethyl aluminium (TMA) directly contacts with bimetallic catalyst and activates then for Ziegler-Natta catalyst or modification Ziegler-Natta catalyst.Preferably, also a certain amount of water is joined in the polymer reactor in any suitable manner, so that carry out the activation of modification Z-N component.In another embodiment, with modifier and activator, preferred TMA joins not activation simultaneously, in the Ziegler-Natta catalyst that preferably supports.In a more specific embodiment, when interpolation does not comprise the modified compound of TMA, comprise the carrying bimetallic catalyst that does not activate Ziegler-Natta catalyst and merge with the TMA of the amount that is enough to activate Ziegler-Natta catalyst before entering polymer reactor or in polymer reactor, this modifier is with less than the aluminium of 10: 1 modifier and the amount interpolation of the mol ratio of the transition metal of Ziegler-Natta catalyst.

As mentioned above, Ziegler-Natta catalyst can support on carrier.The particular that forms Ziegler-Natta catalyst comprises that with carrier material for example inorganic oxide contacts with the organo-magnesium compound that contains at least one alkyl such as aluminium oxide or silica, forms to support organo-magnesium compound; Allow this support organo-magnesium compound and 4,5 or 6 group 4 transition metal halide then, alkoxide or oxide contact form and do not activate Ziegler-Natta catalyst; Allow the aforesaid modifier that does not activate Ziegler-Natta catalyst and effective dose of such formation then, in one embodiment, modifier is such as diethylaluminum chloride (DEAC) or sesquialter ethylaluminium chloride (EASC) or diethylaluminum ethoxide (DEAL-E) or the contact of their blend, thus formation modification Ziegler-Natta catalyst.

The optional organo-magnesium compound that is present in Ziegler-Natta catalyst and/or the modification Ziegler-Natta catalyst can represent that wherein R ' and R are identical or different C with general formula R MgR ' ₂-C ₁₂Alkyl, or C ₄-C ₁₀Alkyl, or C ₄-C ₈Alkyl.In another embodiment, Ziegler-Natta catalyst is by allowing organo-magnesium compound and 4 or 5 family's oxides, alkoxide or halide, and preferred titanium chloride compound contacts and forms, and wherein organo-magnesium compound has formula M g (OR) ₂Or R ¹ _mMgR ² _nR wherein, R ¹And R ²Be C ₁-C ₈Alkyl, and m and n are 0,1 or 2.

Ziegler-Natta catalyst can in all sorts of ways before or after the modification of Ziegler-Natta catalyst and combine with carrier or carrier, placed or was fixed on carrier or the carrier.Preferably, first catalytic component was fixed on the carrier before the modification of first catalytic component.In one of these methods, carrier material mixes with nonpolar hydrocarbon solvents, forms the carrier slurry.The carrier slurry contacts with organo-magnesium compound in one embodiment, is preferably dissolved in then in the non-polar hydrocarbon of carrier slurry, forms solution, then organo-magnesium compound is deposited on the carrier.

Preferably, the amount that is included in the organo-magnesium compound in the carrier slurry only is that physics or chemical deposition are in carrier, any excessive organo-magnesium compound for example is fixed in the amount of the hydroxyl on the carrier, and is no more than this amount, because can cause undesirable side reaction in polymerization process afterwards.Conventional experiment can be used for measuring the optimised quantity of organo-magnesium compound in the carrier slurry.For example, when stirring slurry, organo-magnesium compound can be joined in the carrier slurry, up in carrier solvent, detecting organo-magnesium compound.In addition, the amount that can surpass the amount on the carrier that deposits to is added organo-magnesium compound, in this case, can remove the excessive of any not deposition by filtration and washing.The amount (mol) of organo-magnesium compound based on the amount (g) of dehydration silica is 0.2-2.0mmol/g.

In one embodiment, optional carrier slurry and the electron donor that comprises organo-magnesium compound is such as tetraethyl orthosilicate (TEOS) or have general formula R " organic alcohol contact of OH, wherein R " is C ₁-C ₁₂Alkyl, or C ₁-C ₈Alkyl, or C ₂-C ₄Alkyl, and/or ether or cyclic ethers are such as oxolane.In specific embodiments, " OH is a n-butanol to R.Organic alcohol is preferably effectively providing 0.2-1.5, or 0.4-1.2, or 0.6-1.1, or the R of 0.9-1.0, and " OH: the amount of Mg mol/mol ratio is used.

The carrier slurry that comprises organo-magnesium compound and organic alcohol can contact with transistion metal compound then, forms Ziegler-Natta catalyst.The transistion metal compound that is fit to is the compound that dissolves in 4,5 or 6 family's metals of the non-polar hydrocarbon that is used for forming the carrier slurry.The limiting examples of transistion metal compound for example comprises the halide of titanium and vanadium, and oxyhalide or alkoxy halide are such as titanium tetrachloride (TiCl ₄), vanadium tetrachloride (VCl ₄) and vanadium oxytrichloride (VOCl ₃), and titanium and vanadium alkoxide, wherein the alkoxyl structure division has 1-20 carbon atom, the branching or the non-branching alkyl of preferred 1-6 carbon atom.Can also use the mixture of this type of transistion metal compound.The consumption of non-metallocene transistion metal compound is enough to provide 0.3-1.5, or the transition metal of 0.5-0.8 and magnesium mol/mol ratio.

In one embodiment of the invention, an embodiment at first prepares the Ziegler-Natta catalyst that comprises 4,5 or 6 family's metals, contacts with modifier subsequently, not be used in the modifier contact to separate Ziegler-Natta catalyst before.This is a modifier wherein for example as described herein, alkyl aluminum and the method on the spot that also merges as the Ziegler-Natta catalyst at the slurry of the diluent that is used for preparing Ziegler-Natta catalyst simultaneously in a particular.

Second catalytic component

Second catalytic component and Z-N component merge, and form bimetallic catalyst.Modification or unmodified Ziegler-Natta catalyst and second catalytic component can use technology known to those skilled in the art to merge in numerous modes.Especially, in one embodiment, Ziegler-Natta catalyst can at first merge with second catalytic component, contacts with modifier subsequently; In addition, Ziegler-Natta catalyst can at first contact with modifier, contacts with second catalytic component subsequently; Wherein any embodiment can comprise or not comprise carrier material.For example, second catalytic component can be incorporated in the carrier slurry that comprises the modification Ziegler-Natta catalyst.Solvent in the carrier slurry then can be in normal way, for example by evaporation or remove by filter, to obtain dry carrying bimetallic catalyst component.

In a preferred embodiment, " second catalytic component " is metallocene catalyst compound as described herein.Metallocene catalyst compound is generally for example at 1﹠amp; 2METALLOCENE-BASED POLYOLEFINS (John Scheirs ﹠amp; W.Kaminsky eds., John Wiley ﹠amp; Sons, Ltd.2000); G.G.Hlatky, 181COORDINATION CHEM.REV.243-296 (1999) and especially for being used for synthesizing polyethylene has carried out describing in the whole text in 1METALLOCENE-BASED POLYOLEFINS 261-377 (2000).Comprise and to have one or more Cp parts of being bonded at least one 3-12 family metallic atom (cyclopentadienyl group and with the part of cyclopentadienyl group isomorphism (isolobal)) and " half is sandwich " and " sandwich entirely " compound of being bonded in one or more leaving groups of this at least one metallic atom as described metallocene catalyst compound in this article.Hereinafter, these compounds are called as " metallocene " or " metallocene catalyst compound ".Support on carrier material in the particular that this metallocene catalyst components is described further below, and in desirable embodiment, support with the modification Ziegler-Natta catalyst, also more preferably, this metallocene and modification Ziegler-Natta catalyst are fixing jointly with the activator compound that can activate this metallocene.

The Cp part is single or multiple rings or member ring systems, and its at least a portion comprises the system of π keyed jointing, such as cycloalkadienyl part and heterocyclic analogs.This ring or member ring systems generally comprise the atom that is selected from the 13-16 family atom, and more specifically, the atom of forming the Cp part is selected from carbon, nitrogen, and oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium and their bond, wherein carbon accounts at least 50% of annular atoms.Also more specifically, the Cp part be selected from replace or unsubstituted ring pentadienyl part and with the part of cyclopentadienyl group isomorphism, their non-limitative example comprises cyclopentadienyl group, indenyl, fluorenyl and other structure.Other non-limitative example of this type of part comprises such as cyclopentadienyl group, encircles penta phenanthryl, indenyl, benzo indenyl, fluorenyl, octahydrofluorenyl, cyclo-octatetraene base, ring penta ring dodecylene, phenanthridinyl, 3,4-benzo fluorenyl, 9-phenyl fluorenyl, 8-H-ring penta [a] acenaphthylene base, 7H-dibenzo fluorenyl, indeno [1,2-9] anthrene, the thieno indenyl, thieno fluorenyl, their hydrogenation modification (for example 4,5,6,7-tetrahydro indenyl, or " H ₄Ind "), their replacement modification, and their heterocycle modification.

Metallic atom " M " in the metallocene catalyst compound described in whole specification and claims can be selected from 3-12 family atom and group of the lanthanides atom in one embodiment; In a more specific embodiment, be selected from 3-10 family atom, in another more specific embodiment, be selected from Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir and Ni; In another more specific embodiment, be selected from 4,5 and 6 family's atoms and also be selected from Ti in a more specific embodiment, Zr, the Hf atom, and in another more specific embodiment, be Zr.The oxidation state of metallic atom " M " can be 0 to+7 in one embodiment; In a more specific embodiment be+1 ,+2 ,+3 ,+4, or+5; In another more specific embodiment be+2 ,+3 or+4.Unless otherwise prescribed, the group in conjunction with metallic atom " M " should make that following is electroneutral at the compound described in general formula and the structural formula.This Cp part and this metallic atom M form at least one chemical bond, thereby have formed " metallocene catalyst compound ".This Cp part is different from the leaving group that is bonded in catalyst compounds, is that their utmost points are not easy to replace/abstraction reaction.

In one aspect of the invention, these one or more metallocene catalyst compound are represented with general formula (I):

Cp ^ACp ^BMX _n (I)

Wherein M as mentioned above; Each X is connected to M with chemical bond-linking; Each Cp group is connected to M with chemical bond-linking; With n be 0 or the integer of 1-4, especially 1 or 2.

In general formula (I), use Cp ^AAnd Cp ^BThe part of expression can follow cyclopentadienyl ligands or identical or different with the part of cyclopentadienyl group isomorphism, they any one or the two can contain hetero atom and they any one or the two can be replaced by radicals R.In one embodiment, Cp ^AAnd Cp ^BIndependently be selected from cyclopentadienyl group, indenyl, tetrahydro indenyl, fluorenyl, their substitutive derivatives separately.

Independently, each Cp of general formula (I) ^AAnd Cp ^BCan be unsubstituted or be substituted any one or a plurality of replacement of basic R.Comprise hydrogen base, alkyl, alkenyl, alkynyl as the substituent R of use in structural formula (I) and the limiting examples of the ring substituents in structural formula (Va-d); cycloalkyl, aryl, acyl group, aroyl; alkoxyl, aryloxy group, alkyl hydrosulfide, dialkylamine; alkyl amino, alkoxy carbonyl, aryloxycarbonyl; carbamoyl, alkyl-and the dialkyl-7-amino formoxyl, acyloxy; acyl amino, aroylamino, and their bond.

More specifically, the limiting examples of the alkyl substituent R relevant with general formula (I)-(V) comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopenta, cyclohexyl, benzyl, phenyl, aminomethyl phenyl and tert-butyl-phenyl etc. comprise all their isomers, the tert-butyl group for example, isopropyl etc.Other possible group comprises substituted alkyl and aryl, methyl fluoride for example, fluoro ethyl, two fluoro ethyls, the iodine propyl group, bromine hexyl, the organic quasi-metal group that benzyl chloride base and alkyl replace, comprise trimethyl silyl, trimethyl germyl, methyl diethylsilane base etc.; Organic quasi-metal group with brine alkyl replaces comprises three (trifluoromethyl) silicyl, two (difluoromethyl) silicyls of methyl, bromomethyl dimethyl germyl etc.; And two replace boron group, comprises for example dimethyl boron; With two replacements, 15 family's groups, comprise dimethyl amine, dimethyl phosphine, diphenylamine, the aminomethyl phenyl phosphine, 16 family's groups comprise methoxyl group, ethyoxyl, propoxyl group, phenoxy group, methyl mercapto and ethylmercapto group.Other substituent R comprises alkene, for example but be not limited to the unsaturated substituting group of olefinic, comprises the part of vinyl terminal, 3-cyclobutenyl for example, 2-acrylic, 5-hexenyl etc.In one embodiment, at least two R groups and in one embodiment two adjacent R groups connect into and have the ring structure that is selected from 3-30 atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron and their bond.Also have, substituent R group such as 1-butyl can form the keyed jointing that is incorporated into element M.

Each X in above general formula (I) and following general formula/structural formula (II)-(V) independently is selected from any leaving group in one embodiment; In a more specific embodiment, be selected from halide ion, hydride ion, C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl, C ₆-C ₁₂Aryl, C ₇-C ₂₀Alkaryl, C ₁-C ₁₂Alkoxyl, C ₆-C ₁₆Aryloxy group, C ₇-C ₁₈Alkyl-aryloxy, C ₁-C ₁₂Fluoroalkyl, C ₆-C ₁₂Fluoro aryl, and C ₁-C ₁₂Contain heteroatomic hydrocarbon and their substitutive derivative; In another more specific embodiment, be selected from hydride ion, halide ion, C ₁-C ₆Alkyl, C ₂-C ₆Alkenyl, C ₇-C ₁₈Alkaryl, C ₁-C ₆Alkoxyl, C ₆-C ₁₄Aryloxy group, C ₇-C ₁₆Alkyl-aryloxy, C ₁-C ₆The alkyl carboxylic acid root, C ₁-C ₆The fluorinated alkyl carboxylate radical, C ₆-C ₁₂The aryl carboxylic acid root, C ₇-C ₁₈The alkaryl carboxylate radical, C ₁-C ₆Fluoroalkyl, C ₂-C ₆Fluorine alkenyl, and C ₇-C ₁₈The fluothane aryl; In another more specific embodiment, be selected from hydride ion, chlorine, fluorine, methyl, phenyl, phenoxy group, benzyloxy, tosyl, methyl fluoride and fluorophenyl; In another more specific embodiment, be selected from C ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl, C ₆-C ₁₂Aryl, C ₇-C ₂₀Alkaryl replaces C ₁-C ₁₂Alkyl replaces C ₆-C ₁₂Aryl replaces C ₇-C ₂₀Alkaryl and C ₁-C ₁₂Contain heteroatomic alkyl, C ₁-C ₁₂Contain heteroatomic aryl and C ₁-C ₁₂Contain heteroatomic alkaryl; In going back a more specific embodiment, be selected from chlorine, fluorine, C ₁-C ₆Alkyl, C ₂-C ₆Alkenyl, C ₇-C ₁₈Alkaryl, halogenation C ₁-C ₆Alkyl, halogenation C ₂-C ₆Alkenyl and halogenation C ₇-C ₁₈Alkaryl; In another more specific embodiment, be selected from fluorine, methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, trimethylphenyl, methyl fluoride (single, two and trifluoromethyl) and fluorophenyl (singly, two, three, four and pentafluorophenyl group); And be fluorine in the another more specific embodiment.

Other limiting examples of X group in general formula (I) comprises amine, amino-compound, phosphine, ether, carboxylate radical, diene has the alkyl of 1-20 carbon atom, fluoridize alkyl (for example-C ₆F ₅(pentafluorophenyl group)), fluorinated alkyl carboxylate radical (CF for example ₃C (O) O ^-), hydride ion and halide ion and their bonds.Other example of X part comprises alkyl such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methene base, methoxyl group, ethyoxyl, propoxyl group, phenoxy group, two (methylphenylamines), dimethylamino, dimethyl phosphorus base etc.In one embodiment, two or more X-shapeds have become the part of condensed ring or member ring systems.

In another aspect of the present invention, metallocene catalyst components comprises those of general formula (I), wherein Cp ^AAnd Cp ^BBy at least one abutment (A) bridging, make this structural formula represent each other with following general formula (II):

Cp ^A(A)Cp ^BMX _n (II)

These bridging compounds with general formula (II) expression are called as " bridged metallocene ".Cp in structural formula (II) ^A, Cp ^B, M, X and n such as above for general formula (I) definition; Wherein each Cp part is connected to M and (A) is connected to each Cp with chemical bond-linking with chemical bond-linking.The limiting examples of abutment (A) comprises and contains at least one 13-16 family atom, for example but be not limited to the bivalent hydrocarbon radical of at least one carbon, oxygen, nitrogen, silicon, aluminium, boron, germanium and tin atom and their bond; Wherein this hetero atom can also be C ₁-C ₁₂Alkyl or aryl replaces, to satisfy neutral chemical valence.Abutment (A) can also contain the substituent R (for general formula (I)) just like above definition, comprises halogen group and ion.More specifically, the limiting examples C of abutment (A) ₁-C ₆Alkylidene replaces C ₁-C ₆Alkylidene, oxygen, sulphur, R ' ₂C=, R ' ₂Si=,-Si (R ') ₂Si (R ' ₂)-, R ' ₂Ge=, R ' P=(wherein two chemical bonds of "=" expression) represents that wherein R ' independently is selected from hydride ion, alkyl, substituted hydrocarbon radical, brine alkyl (halocarbyl) replaces brine alkyl, the organic quasi-metal that alkyl replaces, the organic quasi-metal that brine alkyl replaces, two replace boron, and two replace 15 family's atoms, replace 16 family's atoms, and halogen group; Wherein two or more R ' can connect into ring or member ring systems.In one embodiment, the bridged metallocene catalytic component of general formula (II) has two or more abutments (A).

Other limiting examples of abutment (A) comprises methylene, ethylidene, ethidine, the propylidene base, isopropylidene, diphenyl methylene, 1,2-dimethyl ethylidene, 1, the 2-diphenylethylene, 1,1,2,2-tetramethyl ethylidene, dimetylsilyl, the diethylsilane base, the Methylethyl silicyl, trifluoromethyl butyl silicyl, two (trifluoromethyl) silicyl, two (normal-butyl) silicyl, two (n-pro-pyl) silicyl, two (isopropyl) silicyl, two (n-hexyl) silicyl, the dicyclohexyl silicyl, the diphenylmethyl silylation, cyclohexyl phenyl silicyl, tert-butylcyclohexyl silicyl, two (tert-butyl-phenyl) silicyl, two (p-methylphenyl) silicyls and wherein the Si atom by the corresponding construction part of Ge or C atomic substitutions; Dimetylsilyl, diethylsilane base, dimethyl germyl and diethyl germyl.

The position that abutment is bonded in each Cp is unrestricted, and under the situation of indenyl or tetrahydro indenyl Cp part, abutment can be bonded in what is called " 1 " or " 2 " position of each ring, preferably " 1 " position.Though the structure in (Vc-f) has shown the ad-hoc location that is bonded in abutment, this only is an embodiment, is not restrictive.

In another embodiment, abutment (A) can also be a ring-type, comprises for example 4-10 annular atoms, comprises 5-7 annular atoms in a more specific embodiment.These annular atomses can be selected from above-mentioned element, are selected from one or more among B, C, Si, Ge, N and the O in a particular.The limiting examples that can be used as the ring structure of bridged linkage part or its part existence is a ring fourth fork base, cyclopentylidene base, cyclohexylidene base, ring fork in heptan base encircles hot fork base and one of them or two carbon atoms by at least one Si, Ge, N and O, the especially respective rings of Si and Ge displacement.One-tenth key mode between this ring and Cp group can be a cis, trans or the two combination.

Ring-type abutment (A) can be saturated or undersaturated and/or can carry one or more substituting groups and/or condense in one or more other ring structures.If present, these one or more substituting groups be selected from one embodiment alkyl (for example alkyl, as methyl) and halogen (F for example, Cl).It can be saturated or undersaturated can choosing these one or more Cp groups that condense in above ring-type bridged linkage part wantonly, and be selected from and have 4-10, more specifically 5,6 or 7 annular atomses (in specific embodiments, be selected from C, N, O and S) in those, for example cyclopenta, cyclohexyl and phenyl.And itself can condense these ring structures, for example under the situation of naphthyl.And these (optional condensing) ring structures can carry one or more substituting groups.These substituent illustrations and limiting examples is alkyl (especially alkyl) and halogen atom.

General formula (I) and part Cp (II) ^AAnd Cp ^BDiffering from one another in one embodiment, is identical in another embodiment.

Aspect another, metallocene catalyst components comprises the single ligand metal cyclopentadinyl compound (for example monocyclopentadienyl catalytic component) of bridging of the present invention.In this embodiment, this at least a metallocene catalyst components is for example at US 5,055, in 438 with bridging " half the is sandwich " metallocene of following general formula (III) expression:

Cp ^A(A)QMX _n (III)

Cp wherein ^AAs defined above, and be bonded in M; (A) be to be bonded in Q and Cp ^AAbutment; Wherein an atomic bond from the Q group is connected to M; With n be 0 or the integer of 1-3; In a particular, be 1 or 2.In above general formula (III), Cp ^A, (A) can form the condensed ring system with Q.X group in the general formula (III) and n such as above at general formula (I) and (II) definition.In one embodiment, Cp ^ABe selected from cyclopentadienyl group, indenyl, tetrahydro indenyl, fluorenyl, their replacement modification, and their bond.

In general formula (VIII), Q contains heteroatomic part, wherein bonded atoms (with the atom of metal M keyed jointing) is selected from 15 family's atoms and 16 family's atoms in one embodiment, in a more specific embodiment, be selected from nitrogen, phosphorus, oxygen or sulphur atom, and more be selected from nitrogen and oxygen in the particular at another.The limiting examples of Q group comprises alkylamine, arylamine, sulfhydryl compound; ethoxy compound, carboxylate radical (for example neopentanoic acid root), carbamic acid root; the nitrence base, azulenes, pentalene; phosphoryl (phosphoyl), phosphinimine, pyrrole radicals; pyrazolyl; carbazyl, the boron benzene of mixing, comprise can with 15 families of M keyed jointing and other compound of 16 family's atoms.

Aspect another, this at least a metallocene catalyst components is non-bridged " half the is sandwich " metallocene with general formula (IVa) expression of the present invention:

Cp ^AMQ _qX _n (IVa)

Cp wherein ^ADefine for the Cp group in (I) as above, and be the part that is bonded in M; Each Q independent keys is connected to M; Q also is bonded in Cp in one embodiment ^AX is at the leaving group described in (I) as above; N is 0-3, is 1 or 2 in one embodiment; Q is 0-3, and is 1 or 2 in one embodiment.In one embodiment, Cp ^ABe selected from cyclopentadienyl group, indenyl, tetrahydro indenyl, fluorenyl, their replacement modification, and their bond.

In general formula (IVa), Q is selected from ROO ^-, RO-, R (O)-,-NR-,-CR ₂-,-S-,-NR ₂-,-CR ₃-,-SR ,-SiR ₃,-PR ₂,-H, and replacement or unsubstituting aromatic yl, wherein R is selected from C ₁-C ₆Alkyl, C ₆-C ₁₂Aryl, C ₁-C ₆Alkylamine, C ₆-C ₁₂Alkarylamine, C ₁-C ₆Alkoxyl, C ₆-C ₁₂Aryloxy group etc.The limiting examples of Q comprises C ₁-C ₁₂The carbamic acid root, C ₁-C ₁₂Carboxylate radical (for example neopentanoic acid root), C ₂-C ₂₀Pi-allyl, and C ₂-C ₂₀Assorted allylic structure part.

Alternatively, " half sandwich " metallocene can be as described in the general formula (IVb), for example at US 6,069, described in 213 more than:

Cp ^AM (Q ₂GZ) X _nOr

T(Cp ^AM(Q ₂GZ)X _n) _m (IVb)

M wherein, Cp ^A, X and n are as defined above;

Q ₂GZ has formed multidentate ligand unit (for example neopentanoic acid root), and wherein at least one of Q group and M have formed key, and so that each Q independently is selected from-O-,-NR-,-CR ₂-and-S-; G is carbon or silicon; Be selected from R with Z ,-OR ,-NR ₂,-CR ₃,-SR ,-SiR ₃,-PR ₂Define with the mode of hydride ion group, prerequisite be when Q be-during NR-, Z is selected from-OR so ,-NR ₂,-SR ,-SiR ₃,-PR ₂And prerequisite is that the neutral chemical valence of Q is satisfied by Z; Wherein each R independently is selected from C ₁-C ₁₀Contain heteroatomic group, C ₁-C ₁₀Alkyl, C ₆-C ₁₂Aryl, C ₆-C ₁₂Alkaryl, C ₁-C ₁₀Alkoxyl, and C ₆-C ₁₂Aryloxy group;

N is 1 or 2 in a particular;

T is selected from C ₁-C ₁₀Alkylidene, C ₆-C ₁₂Arlydene and C ₁-C ₁₀Contain heteroatomic group, and C ₆-C ₁₂Abutment in the heterocyclic radical; Adjacent " the Cp of each T group bridging wherein ^AM (Q ₂GZ) X _n" group, and be connected to this Cp with chemical bond-linking ^AGroup.

M is the integer of 1-7; M is the integer of 2-6 more particularly.

In another aspect of the present invention, this at least a metallocene catalyst components can more specifically be used structural formula (Va), (Vb), (Vc), (Vd), (Ve) He (Vf) describes:

Wherein in structural formula (Va)-(Vf), M is selected from 3-12 family atom, in a more specific embodiment, be selected from 3-10 family atom, in another more specific embodiment, be selected from 3-6 family atom, in another more specific embodiment, be selected from 4 family's atoms and in another more specific embodiment, be selected from Zr and Hf; And be Zr in the particular more at another;

Wherein the Q in (Va-ii) is selected from alkylidene, aryl, arlydene, alkoxyl, aryloxy group, amine, arylamine (for example pyridine radicals), alkylamine, phosphine, alkylphosphines, substituted alkyl, substituted aryl, substituted alkoxy, substituted aryloxy replaces amine, substituted alkylamine replaces phosphine, the substituted alkyl phosphine, the carbamic acid root, assorted pi-allyl, (the suitable carbamic acid root and the limiting examples of carboxylate radical comprise the trimethylace tonitric root to carboxylate radical, the trimethylace tonitric root, the methyl acetic acid root is to the toluene acid group, benzoate anion, diethylamino formate and dimethylamino formate), fluorinated alkyl, fluoro aryl and fluorinated alkyl carboxylate radical; The saturated group that wherein defines Q contains 1-20 carbon atom in one embodiment; Wherein aromatic group comprises 5-20 carbon atom in one embodiment;

Each R wherein ^*Be selected from alkylene independently in one embodiment and contain heteroatomic alkylene; Be selected from alkylidene in another embodiment, substituted alkylene and contain heteroatomic alkylene; In a more specific embodiment, be selected from C ₁-C ₁₂Alkylidene, C ₁-C ₁₂Substituted alkylene, and C ₁-C ₁₂Contain heteroatomic alkylene; Be selected from C in another more specific embodiment ₁-C ₄Alkylidene; Two R in structural formula (Vb-f) in another embodiment wherein ^*Group is identical;

A for as described in (A) in the structural formula (II), more specifically, is selected from chemical bond ,-O-,-S-,-SO as above in one embodiment ₂-,-NR-,=SiR ₂,=GeR ₂,=SnR ₂,-R ₂SiSiR ₂-, RP=, C ₁-C ₁₂Alkylidene replaces C ₁-C ₁₂Alkylidene, divalence C ₄-C ₁₂Cyclic hydrocar-bons and replacement and unsubstituting aromatic yl; In a more specific embodiment, be selected from C ₅-C ₈Cyclic hydrocar-bons ,-CH ₂CH ₂-,=CR ₂With=SiR ₂Wherein R is selected from alkyl in one embodiment, cycloalkyl, aryl, alkoxyl, fluoroalkyl and contain heteroatomic hydro carbons; R is selected from C in a more specific embodiment ₁-C ₆Alkyl, substituted-phenyl, phenyl, and C ₁-C ₆Alkoxyl; And in another more specific embodiment, R is selected from methoxyl group, methyl, phenoxy group and phenyl;

Wherein A can not exist in another embodiment, in this case, and each R ^*As for R ¹-R ¹³Defined such;

Each X such as above described in (I);

N is the integer of 0-4, is 1-3 in one embodiment and is 1 or 2 in another embodiment; With

R ¹-R ¹³(and R ⁴'-R ⁷' and R ¹⁰'-R ¹³') independently be selected from hydrogen base, halogen group, C in one embodiment ₁-C ₁₂Alkyl, C ₂-C ₁₂Alkenyl, C ₆-C ₁₂Aryl, C ₇-C ₂₀Alkaryl, C ₁-C ₁₂Alkoxyl, C ₁-C ₁₂Fluoroalkyl, C ₆-C ₁₂Fluoro aryl, and C ₁-C ₁₂Contain heteroatomic hydrocarbon and their substitutive derivative; In a more specific embodiment, be selected from the hydrogen base, fluorine-based, chloro, bromo, C ₁-C ₆Alkyl, C ₂-C ₆Alkenyl, C ₇-C ₁₈Alkaryl, C ₁-C ₆Fluoroalkyl, C ₂-C ₆Fluorine alkenyl, and C ₇-C ₁₈The fluothane aryl; And in another more specific embodiment, be selected from the hydrogen base, and fluorine-based, chloro, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, hexyl, phenyl, 2,6-3,5-dimethylphenyl and 4-tert-butyl-phenyl; That wherein adjacent R group can form is saturated, fractional saturation or saturated ring fully.

Can present as at US5 with the structural formula of metallocene catalyst components of (Va) expression, 026,798, US 5,703,187 and US 5,747,406 in disclosed many forms, comprise as at US 5,026,798 and US 6,069,213 in disclosed dimer or low poly structure.

In the particular of the metallocene of in (Vd), representing, R ¹And R ²Formed and to have replaced or unsubstituted conjugation six-membered carbon ring system.

The limiting examples of the metallocene catalyst components consistent with the description of this paper comprises:

X _nCyclopentadienyl group closes zirconium,

X _nIndenyl closes zirconium,

X _n(1-methyl indenyl) closes zirconium,

X _n(2-methyl indenyl) closes zirconium,

X _n(1-propyl group indenyl) closes zirconium,

X _n(2-propyl group indenyl) closes zirconium,

X _n(1-butyl indenyl) closes zirconium,

X _n(2-butyl indenyl) closes zirconium,

X _n(methyl cyclopentadienyl) closes zirconium,

X _n(tetrahydro indenyl) closes zirconium,

X _n(pentamethyl cyclopentadienyl group) closes zirconium,

X _nCyclopentadienyl group closes zirconium,

X _nThe pentamethyl cyclopentadienyl group closes titanium,

X _nThe tetramethyl-ring pentadienyl closes titanium,

X _n1,2,4-trimethyl cyclopentadienyl group closes zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-ring pentadienyl) (cyclopentadienyl group) is closed zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-ring pentadienyl) (1,2,3-trimethyl-cyclopentadienyl group) is closed zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-ring pentadienyl) (1,2-dimethyl-cyclopentadienyl group) is closed zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-cyclopentadienyl group) (2-methyl-cyclopentadienyl group) is closed zirconium,

X _nDimetylsilyl (cyclopentadienyl group) (indenyl) is closed zirconium,

X _nDimetylsilyl (2-methyl indenyl) (fluorenyl) is closed zirconium,

X _nDiphenylmethyl silylation (1,2,3,4-tetramethyl-cyclopentadienyl group) (3-propyl group-cyclopentadienyl group) closes zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-cyclopentadienyl group) (the 3-tert-butyl group-cyclopentadienyl group) is closed zirconium,

X _nDimethyl germyl (1,2-dimethyl cyclopentadienyl group) (3-isopropyl cyclopentadienyl group) closes zirconium,

X _nDimetylsilyl (1,2,3,4-tetramethyl-cyclopentadienyl group) (3-methyl-cyclopentadienyl group) is closed zirconium,

X _nDiphenyl methene base (cyclopentadienyl group) (9-fluorenyl) closes zirconium,

X _nDiphenyl methene base (cyclopentadienyl group) (indenyl) closes zirconium,

X _nIsopropylidene two (cyclopentadienyl group) closes zirconium,

X _nIsopropylidene (cyclopentadienyl group) (9-fluorenyl) closes zirconium,

X _nIsopropylidene (3-methyl cyclopentadienyl) (9-fluorenyl) closes zirconium,

X _nEthylenebis (9-fluorenyl) is closed zirconium,

Meso X _nEthylenebis (1-indenyl) is closed zirconium,

X _nEthylenebis (1-indenyl) is closed zirconium,

X _nEthylenebis (2-methyl isophthalic acid-indenyl) is closed zirconium,

X _nEthylenebis (2-methyl-4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nEthylenebis (2-propyl group-4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nEthylenebis (2-isopropyl-4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nEthylenebis (2-butyl-4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nEthylenebis (2-isobutyl group-4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nDimetylsilyl (4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nDiphenyl (4,5,6,7-tetrahydrochysene-1-indenyl) closes zirconium,

X _nEthylenebis (4,5,6,7-tetrahydrochysene-1-indenyl) is closed zirconium,

X _nDimetylsilyl two (cyclopentadienyl group) is closed zirconium,

X _nDimetylsilyl two (9-fluorenyl) is closed zirconium,

X _nDimetylsilyl two (1-indenyl) is closed zirconium,

X _nDimetylsilyl two (2-methyl indenyl) is closed zirconium,

X _nDimetylsilyl two (2-propyl group indenyl) is closed zirconium,

X _nDimetylsilyl two (2-butyl indenyl) is closed zirconium,

X _nDiphenylmethyl silylation two (2-methyl indenyl) closes zirconium,

X _nDiphenylmethyl silylation two (2-propyl group indenyl) closes zirconium,

X _nDiphenylmethyl silylation two (2-butyl indenyl) closes zirconium,

X _nDimethyl germyl two (2-methyl indenyl) closes zirconium,

X _nDimetylsilyl two (tetrahydro indenyl) is closed zirconium,

X _nDimetylsilyl two (tetramethyl-ring pentadienyl) is closed zirconium,

X _nDimetylsilyl (cyclopentadienyl group) (9-fluorenyl) is closed zirconium,

X _nDiphenylmethyl silylation (cyclopentadienyl group) (9-fluorenyl) closes zirconium,

X _nDiphenylmethyl silylation two (indenyl) closes zirconium,

X _nRing trimethylene silicyl (tetramethyl-ring pentadienyl) (cyclopentadienyl group) closes zirconium,

X _nRing tetramethylene silicyl (tetramethyl-ring pentadienyl) (cyclopentadienyl group) closes zirconium,

X _nRing trimethylene silicyl (tetramethyl-ring pentadienyl) (2-methyl indenyl) closes zirconium,

X _nRing trimethylene silicyl (tetramethyl-ring pentadienyl) (3-methyl cyclopentadienyl) closes zirconium,

X _nRing trimethylene silicyl two (2-methyl indenyl) closes zirconium,

X _nRing trimethylene silicyl (tetramethyl-ring pentadienyl) (2,3,5-trimethyl cyclopentadienyl group) closes zirconium,

X _nRing trimethylene silicyl two (tetramethyl-ring pentadienyl) closes zirconium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (N-tert-butyl group amino) is closed titanium,

X _nTwo (cyclopentadienyl groups) close chromium,

X _nTwo (cyclopentadienyl groups) close zirconium,

X _nTwo (n-butyl cyclopentadienyl) close zirconium,

X _nTwo (dodecyl cyclopentadienyl groups) close zirconium,

X _nTwo (ethyl cyclopentadienyl groups) close zirconium,

X _nTwo (isobutyl group cyclopentadienyl groups) close zirconium,

X _nTwo (isopropyl cyclopentadienyl groups) close zirconium,

X _nTwo (methyl cyclopentadienyls) close zirconium,

X _nTwo (n-octyl cyclopentadienyl groups) close zirconium,

X _nTwo (n-pentyl cyclopentadienyl groups) close zirconium,

X _nTwo (n-pro-pyl cyclopentadienyl groups) close zirconium,

X _nTwo (trimethyl silyl cyclopentadienyl groups) close zirconium,

X _nTwo (1, two (trimethyl silyl) cyclopentadienyl groups of 3-) close zirconium,

X _nTwo (1-ethyls-2-methyl cyclopentadienyl) close zirconium,

X _nTwo (1-ethyls-3-methyl cyclopentadienyl) close zirconium,

X _nTwo (pentamethyl cyclopentadienyl groups) close zirconium,

X _nTwo (pentamethyl cyclopentadienyl groups) close zirconium,

X _nTwo (1-propyl group-3-methyl cyclopentadienyl) close zirconium,

X _nTwo (1-normal-butyls-3-methyl cyclopentadienyl) close zirconium,

X _nTwo (1-isobutyl groups-3-methyl cyclopentadienyl) close zirconium,

X _nTwo (1-propyl group-3-butyl cyclopentadienyl group) close zirconium,

X _nTwo (1, the 3-n-butyl cyclopentadienyl) close zirconium,

X _nTwo (4,7-dimethyl indenyl) close zirconium,

X _nTwo (indenyls) close zirconium,

X _nTwo (2-methyl indenyls) close zirconium,

X _nThe cyclopentadienyl group indenyl closes zirconium,

X _nTwo (n-pro-pyl cyclopentadienyl groups) close hafnium,

X _nTwo (n-butyl cyclopentadienyl) close hafnium,

X _nTwo (n-pentyl cyclopentadienyl groups) close hafnium,

X _n(n-pro-pyl cyclopentadienyl group) (n-butyl cyclopentadienyl) closes hafnium,

X _nTwo [(2-trimethyl silyl ethyl) cyclopentadienyl groups] close hafnium,

X _nTwo (trimethyl silyl cyclopentadienyl groups) close hafnium,

X _nTwo (2-n-pro-pyl indenyls) close hafnium,

X _nTwo (2-normal-butyl indenyls) close hafnium,

X _nDimetylsilyl two (n-pro-pyl cyclopentadienyl group) is closed hafnium,

X _nDimetylsilyl two (n-butyl cyclopentadienyl) is closed hafnium,

X _nTwo (9-n-pro-pyl fluorenyls) close hafnium,

X _nTwo (9-normal-butyl fluorenyls) close hafnium,

X _n(9-n-pro-pyl fluorenyl) (2-n-pro-pyl indenyl) closes hafnium,

X _nTwo (1-n-pro-pyls-2-methyl cyclopentadienyl) close hafnium,

X _n(n-pro-pyl cyclopentadienyl group) (1-n-pro-pyl-3-n-butyl cyclopentadienyl) closes hafnium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (cyclopropyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (cyclobutyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (cyclopenta amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (suberyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (ring octyl group amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (ring nonyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (ring decyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (ring undecyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (sec-butyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (n-octyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (positive decyl amino) is closed titanium,

X _nDimetylsilyl (tetramethyl-ring pentadienyl) (n-octadecane base amino) is closed titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (cyclopropyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (cyclobutyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (cyclopenta amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (suberyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (ring octyl group amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (ring nonyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (ring decyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (ring undecyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (sec-butyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (n-octyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (positive decyl amino) closes titanium,

X _nAminomethyl phenyl silicyl (tetramethyl-ring pentadienyl) (n-octadecane base amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (cyclopropyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (cyclobutyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (cyclopenta amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (cyclohexyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (suberyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (ring octyl group amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (ring nonyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (ring decyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (ring undecyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (sec-butyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (n-octyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (positive decyl amino) closes titanium,

X _nDiphenylmethyl silylation (tetramethyl-ring pentadienyl) (n-octadecane base amino) closes titanium and their derivative.

So-called " its derivative " is meant as above and forms for described any replacement of structural formula (Va-f) or ring; Especially, metal " M " (Cr, Zr, Ti or Hf) is selected from Cr, Zr, and the atom among Hf and the Ti especially is selected from the atomic substitutions among Zr and the Hf; " X " group is by C ₁-C ₅Alkyl, C ₆Aryl, C ₆-C ₁₀Alkaryl, any one displacement in the fluorine or chlorine; N is 1,2, or 3.

It is contemplated that above-mentioned metallocene catalyst components comprises their structure or optics or enantiomter (racemic mixture), can be pure enantiomer in one embodiment.

The employed asymmetric substituted metal metallocene catalyst components of single bridging with racemic and/or mesoisomer of this paper itself does not constitute at least two kinds of different bridged metallocene catalytic components.In a preferred embodiment, metallocene as herein described exists with their racemic form.

Can be used for any combination thereof that " metallocene catalyst components " of the present invention can comprise any " embodiment " as herein described.

Activator and activation

In certain embodiments, method as herein described further comprises and allows any of catalytic component or the two contact with catalyst activator (this paper abbreviates " activator " as).Preferably, depend on the type of catalyst, this catalyst activator is " first activator " or " second activator ", corresponds respectively to the activation of first and second catalytic components.In addition, when the contact bimetallic catalyst, for example when Ziegler-Natta catalyst and metalloscene catalyst, this catalyst activator can be the activator composition that belongs to the mixture of " first activator " and " second activator ".Preferably, have only when having monomer, activator (especially first activator) is present in the polymer reactor with bimetallic catalyst, and polymerization is initiated, usually in case activator and bimetallic catalyst are merged, this catalyst becomes activation, has therefore suffered degraded.In one embodiment, after first catalyst is modified, this activator, preferred " first activator " contacts with this first catalyst or merges, and in another embodiment, first activator contacts with Ziegler-Natta catalyst in contact modifier.

This first activator can be any or mixture that is generally used for activating the material of Ziegler-Natta catalyst, comprise metal alkyls, hydride, alkyl hydride, alkyl halide (such as alkyl lithium compounds), dialkyl zinc compounds, the trialkylboron compound, trialkyl aluminium compound, alkyl aluminium halide and alkyl aluminium hydride and tetraalkyl germanium compound.Preferably, first activator is trimethyl aluminium (TMA).The amount of first activator preferably is enough to provide about 10: 1 to about 1000: 1, preferably approximately 15: 1 to about 300: 1, most preferably about 20: 1 mol ratios to about 100: 1 activator metal atom (for example Al) and the transition metal in the Ziegler-Natta catalyst.Preferably, first activator before being injected into reactor or simultaneously with hydration also, to contact with bimetallic catalyst; The mol ratio of the water and the first activator metal atom is 0.01 to 5 in one embodiment, is 0.1 to 2 in another embodiment and is 0.15 to 1 in another embodiment.

Be suitable for activation at second catalytic component, for example second activator in the metal site in the metalloscene catalyst is different from above-mentioned first activator.The embodiment of this type of activator comprises that lewis acid such as ring-type or oligomeric poly-(oxidation alkyl aluminium) and so-called non-coordination activator (" NCA ") (in addition, " ionization activator " or " stoichiometry activator (stoichiometricactivator) "), maybe the neutral metal metallocene catalyst components can be converted into cationic any other compound of the metallocene with olefin polymerizating activity.More specifically, within the scope of the invention be, use lewis acid such as aikyiaiurnirsoxan beta (for example " MAO "), modified alumoxane (for example " TIBAO "), with alkyl aluminum compound as activator, and/or use ionization activator (neutrality or ion) to activate desired metallocene as herein described as four (pentafluorophenyl group) boron, three (normal-butyl) ammoniums and/or three perfluorophenyl boron metalloid precursors.MAO and other aluminium type activator are known in the art.The ionization activator is known in the art, for example by Eugene You-Xian Chen﹠amp; Tobin J.Marks, Cocatalysts for Metal-Catalyzed OlefinPolymerization:Activators, Activation Processes, andStructure-Activity Relationships 100 (4) CHEMICAL REVIEWS1391-1434 (2000) carried out description.As Gregory G.Hlatky, HeterogeneousSingle-Site Catalystsfor Olefin Polymerization 100 (4) CHEMICALREVIEWS 1347-1374 (2000) are described, activator can associate with carrier or combine, or this is with catalytic component (for example metallocene), or separates with catalytic component and to carry out.

This bimetallic catalyst for example comprises that the enhancing carrier of Ziegler-Natta catalyst and metalloscene catalyst can contact in many ways with catalyst activator.Preferably, this carrying bimetallic catalyst contacts with the mixture that comprises first and second activators at least.

Carrier

In certain embodiments, the non-modification that supports of bimetallic catalyst as herein described can be used for polymerization, that is, wherein monomer contacts with the bimetallic catalyst that does not support.In other embodiments, can use the modification that supports of bimetallic catalyst.Preferably, this bimetallic catalyst is catalyst-loaded.Single site catalysts is such as the carrier of metallocene, supports, the method for modification and this carrier of activation is for example at 1METALLOCENE-BASED POLYOLEFINS 173-218 (J.Scheirs ﹠amp; W.Kaminsky eds., John Wiley ﹠amp; Sons discusses in Ltd.2000).The employed phrase of this paper " supports on carrier material " and for example is meant that use any suitable mode known in the art combines catalyst, activator etc. with " carrier material ".Term as used herein " carrier " or " carrier " can exchange use, are meant any carrier material, are meant porous carrier materials in one embodiment, comprise inorganic or organic support material.The limiting examples of carrier material comprises inorganic oxide and butter, especially as talcum, and clay, silica, aluminium oxide, magnesia, zirconia, ferriferous oxide, boron oxide, calcium oxide, zinc oxide, barium monoxide, thorium oxide, materials such as phosphaljel, and the hydroxylating polymer is such as polyvinyl chloride and substituted polystyrene, functionalized or crosslinked organic carrier is such as polystyrene divinylbenzene, polyolefin or polymerizable compound, and their mixture, and various forms of graphite.In one embodiment of the invention, if present, carrier is by at 600 ℃ at the most, or at the most under 800 ℃ the dehydration temperaturre heating carrier particle prepare.In another aspect of the present invention, carrier, preferably inorganic oxide is for example used fluorization agent, the silanizing agent preliminary treatment, or by handling preliminary treatment with heterocyclic amine such as replacement or unsubstituted benzazolyl compounds.

In one or more particular, at first prepare carrier, preferably in the following manner; Then this carrier is handled (for example combining with the composition that forms first catalyst), provide to comprise the catalyst-loaded of first catalytic component.In specific embodiments, this first catalyst that supports is handled in the presence of second catalytic component then, the bimetallic catalyst that supports is provided.

This carrier preferably inorganic material such as silica (silica) or aluminium oxide.Preferably, this carrier material is a dried powder, has the 1-500 micron in certain embodiments, 5-100 micron in another embodiment, 10-50 micron in another embodiment, the particle mean size of 5-40 micron in embodiment also.The surface area of carrier is 3-600m in one embodiment ²/ g is 100-500m in another embodiment ²/ g is 200-400m in another embodiment ²/ g.

Dehydrated carrier can merge with non-polar hydrocarbon then, forms the carrier slurry, can stir and choose wantonly in mixed process and heat this slurry.

Various non-polar hydrocarbons can be used for forming the carrier slurry, but selected any non-polar hydrocarbon should remain liquid form under all correlated response temperature, and it is preferably solvable to small part in non-polar hydrocarbon to be used for forming each composition of first catalytic component.Therefore, non-polar hydrocarbon is considered to " solvent " here, though in certain embodiments each composition only part is solvable in hydrocarbon.For example, at following organo-magnesium compound in greater detail, the transistion metal compound of pure and mild first catalyst compounds is preferably solvable to small part in hydrocarbon solvent under above-mentioned mixing temperature, more preferably dissolving fully.

The example of the non-polar hydrocarbon that is fit to comprises C ₄-C ₁₀Linearity or branched paraffin, cycloalkane and aromatic compounds, and oil ratio such as mineral oil or silicone oil.More particularly, apolar chain alkane can be isopentane, hexane, isohexane, normal heptane, octane, nonane or decane; Nonpolar cycloalkane is such as cyclohexane; Or aromatic compounds is such as benzene, toluene, or ethylo benzene.Can also use the mixture of different non-polar hydrocarbons.

The carrier slurry can heat after the mixed process neutralization of carrier granular and nonpolar hydrocarbon solvents, but when any of catalyst or two kinds and carrier slurry merge, the temperature of slurry should be fully low, and such two kinds of catalyst are not all by involuntary activation.Therefore, the temperature of carrier slurry (for example silica slurries) preferably remains below 90 ℃, for example 25-70 ℃, or even narrower, under 40-60 ℃ the temperature.

Polymerization

As shown in other place of this paper, bimetallic catalyst as herein described preferably is used for preparing bimodal polyolefin, the polyolefin that promptly has bimodal molecular weight distribution.In case the preparation carrying bimetallic catalyst as mentioned above, can use this catalyst to carry out several different methods.Belong to operable distinct methods row be included in US 5,525, the operation of setting forth in 678, wherein those methods are transformed to utilize bimetallic catalyst as herein described.Equipment, process conditions, reactant, additive and other material change in established methodology according to the polyolefinic required composition that will form and performance certainly.In one embodiment, polymerization can be carried out in two or more series of steps and the identical or different method of use in each polymerization procedure; With in a more specific embodiment, in single-reactor, use the bimodal pattern catalyst to produce polymer as herein described, Bi-modal polyethylene ideally.

Above-mentioned catalyst and catalyst system, for example bimetallic catalyst can be used for the various polymerizations under the temperature and pressure of wide region.Temperature can be in-60 ℃ to 280 ℃ scope, preferred 50-200 ℃, more preferably in 60-120 ℃ the scope; And can being 1 atmosphere, used pressure is pressed onto about 500 atmospheric pressure or higher.

" polymer reactor " mentioned in this article can be any suitable reactor that is used for olefin polymerization, and is not limited to the explanation of this paper.The example of the polymerization that is fit to comprises solution, gas phase, slurry phase and high pressure method or their combination.Especially preferred is one or more alkene, and at least a of them is the gas phase or the slurry phase polymerisation of ethene or propylene.

In certain embodiments, method of the present invention relates to and has 2-30 carbon atom, preferred 2-12 the carbon atom and the more preferably solution of one or more olefinic monomers of 2-8 carbon atom, high pressure, slurry or gas phase polymerization process; Also more preferably, polymerization of the present invention adopts the step that allows this double-peak catalyst and ethene contact with one or more olefinic monomers with 3-10 carbon atom.The present invention is particularly useful for the polymerization of two or more olefinic monomers of ethene and one or more propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.

Other useful in the method for the invention monomer comprises ethylenically unsaturated monomer, has the alkadienes of 4-18 carbon atom, conjugation or non-conjugated diene, polyenoid class, vinyl monomer and cycloolefin.Can be used for non-limiting monomer of the present invention and can comprise ENB, norbornadiene, isobutene, isoprene, vinyl benzo cyclobutane, phenylethylene, alkyl-substituted styrene, ethylidene norbornene, bicyclopentadiene and cyclopentene.

In the most preferred embodiment of method of the present invention, produce the copolymer of ethene, wherein contain and have 4-15 carbon atom, preferred 4-12 carbon atom, more preferably 3-10 carbon atom also, the most preferably comonomer of at least a alpha-olefin of 4-8 carbon atom and ethene polymerization in gas phase or slurry process.

In another embodiment of method of the present invention, ethene or propylene and at least two kinds of different copolymer monomers one of (optional its can be diene) polymerization, thus form terpolymer.

Generally, in gas phase polymerization process, use circulation continuously, wherein in a part of reactor assembly circulation, heat of polymerization heats the circulating current (being referred to as recycle stream or fluidizing agent in addition) in reactor.This heat cooling system by the reactor outside in another part of this circulation is removed from the recirculation composition.Generally, at the gas fluidized bed process that is used for producing polymer, the air communication that contains one or more monomers is crossed fluid bed circulation continuously under reaction condition in the presence of catalyst.Air-flow is discharged from fluid bed, is recycled in the reactor.Simultaneously, polymer product is discharged from reactor, and adds fresh monomer, to replace the monomer of polymerization.

Reactor pressure in gas phase process can be at about 100psig (690kPa) in about 500psig (3448kPa) scope, preferably arrive in the scope of about 400psig (2759kPa), more preferably in the scope of about 350psig (2414kPa), change at about 250psig (1724kPa) at about 200psig (1379kPa).

Temperature of reactor in the gas phase process can be at about 30 ℃ to about 120 ℃, preferably approximately 60 ℃ to about 115 ℃, in more preferably about 70 ℃ to 110 ℃ scope, most preferably about 70 ℃ change in about 95 ℃ scope, and wherein desirable scope comprises any upper limit as herein described and any lower limit.

Other contemplated gas phase process of method of the present invention is included in U.S. patent Nos.5, and 627,242,5,665,818 and 5,677,375, and european publishing thing EP-A-0794200, those described in EP-A-0 802 202 and the EP-B-634 421.

Slurry phase polymerisation process is general use about 1 to about 50 atmospheric pressure and even higher pressure and 0 to about 120 ℃ temperature.In slurry polymerization, in the liquid polymeric diluent media, form the suspension of solid particle polymer, add ethene and comonomer with catalyst again, usually also have hydrogen.From reactor discontinuous or the continuous suspension that comprises diluent of discharging, wherein volatile component is separated with polymer, chooses wantonly after distillation to be recycled in the reactor.The liquid diluent that uses in polymerisation medium generally is the alkane with 3-7 carbon atom, the preferred branched alkane.Used medium should be a liquid under polymerizing condition, and is relative inertness.When using propane medium, this method must and be operated more than the pressure in the reaction diluent critical-temperature.Preferably, use hexane or iso-butane medium.

Can use the particle form polymerization, i.e. a class slurry process, wherein temperature remains on polymer and enters below the temperature of solution.These technology are known in the art, and for example at U.S. patent No.3, description are arranged in 248,179.Other slurry process comprise use loop reactor those and utilize those of a plurality of stirred reactors of series, parallel or their combination.The limiting examples of slurry process comprises continuous loop or stirred tank method.Also have, other case description of slurry process is at U.S. patent No.4, in 613,484.

In one embodiment of the invention, slurry or gas phase process are in the presence of bimetallic catalyst of the present invention and do not having or basically without any scavenger, as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethylaluminum chloride use under the situation of dibutyl zinc etc.These class methods are described among open WO 96/08520 of PCT and the US 5,712,352 and 5,763,543.In another particular, this method is operated by being incorporated into carboxylic metallic salt in the reactor and/or allowing carboxylic metallic salt contact with metallocene catalyst system of the present invention before being incorporated into reactor.In another embodiment, as disclosed in WO 96/11960 and WO 96/11961, surface modifier may reside in the bimetallic catalyst.

The bimodal polyolefin product

Utilize bimetallic catalyst as herein described, the polymer produced with method as herein described is bimodal pattern preferably.When being used to describe polyolefin, polyolefin such as polypropylene or polyethylene for example, or other homopolymers, when copolymer or terpolymer, term " bimodal pattern " is meant " bimodal molecular weight distribution ", and this term is understood that to have the wideest definition that provides for this term as the association area personnel of being reflected in printed publication and granted patent.For example, when this term uses in this article, comprise that having at least a identifiable HMW polyolefin that distributes and the single polymers composition with at least a identifiable distribution of low molecular weight is considered to " bimodal pattern " polyolefin.These height and lower-molecular-weight component can be differentiated by deconvolution techniques known in the art, so that the GPC curve by the wide of bimodal polyolefin of the present invention or band shoulder is distinguished this two kinds of components, in another embodiment, the GPC curve of bimodal polymers of the present invention can show the clearly peak with peak valley.Ideally, bimodal polymers of the present invention is characterised in that the combination that comprises as the feature of the polydispersity value determined by the GPC curve and Mz value.

Preferably, except having different molecular weight, high molecular polyolefine and low-molecular-weight polyolefin are the polymer of same type basically, for example polypropylene or polyethylene.

Can use the polyolefin of described method preparation can have various characteristics and performance.At least one advantage of bimetallic catalyst is that method therefor can be customized, and has the polyolefin of one group of expected performance with formation.For example, it is envisaged that, can form have with at US 5,525, the polymer of the identical performance of bimodal polyolefin in 678.

Bimodal polymers, general ethylene type bimodal polymers has 0.920-0.980g/cc in one embodiment, preferred 0.925-0.975g/cc, more preferably 0.930-0.970g/cc, more preferably 0.935-0.965g/cc also, even the more preferably density of 0.940-0.960g/cc.

Bimodal polymers of the present invention, especially bimodal polyethylene can characterize by their molecular weight characteristics described herein, for example measures by GPC.Bimodal polymers of the present invention has 10,000 to 50,000 number-average molecular weight (Mn) in one embodiment, and 80,000 to 800,000 weight average molecular weight (Mw).Bimodal polyolefin of the present invention also has and is higher than 900,000 in one embodiment, is higher than 1,000,000 in one embodiment, is higher than 1,100,000 in another embodiment, is higher than 1,200,000 Mz value in another embodiment.This bimodal polymers has 10-80 in one embodiment, 12-50 in another embodiment, molecular weight distribution with 15-30 in another embodiment, weight average molecular weight is than number-average molecular weight (Mw/Mn), or " polydispersity index ", wherein desirable embodiment comprises any upper limit of narration here and any combination of any lower limit.

Bimodal polymers by described method preparation can have at 0.01dg/min in certain embodiments to 1000dg/min, more preferably approximately 0.01dg/min arrives about 50dg/min, also more preferably about 0.02dg/min arrives about 2dg/min scope interior melt index (MI) (MI or I to about 10dg/min and most preferably about 0.03dg/min ₂, measure by ASTM-D-1238-E190/2.16).The bimodal polyolefin of the inventive method has 1-40dg/min in one embodiment, 1.2-20dg/min in another embodiment, the flow index (I of 1.5-20dg/min in another embodiment ₂₁By ASTM-D-1238-F, 190/21.6 measures).

Bimodal polymers as herein described has 20-500 in certain embodiments, more preferably 40-200, also more preferably 60-150 melt index (MI) ratio (I ₂₁/ I ₂), wherein Qi Wang scope can comprise any combination of any upper limit as herein described and any lower limit.

Polymer of the present invention can with any other polyblend and/or coextrusion.The limiting examples of other polymer comprises the LLDPE of being produced by common Z-N and/or metallocene catalyst method, elastomer, plastic body, hp-ldpe, high density polyethylene (HDPE), polypropylene etc.

Polymer of producing with method of the present invention and their blend can be used for such as film, sheet material and fiber extrude with coextrusion and blowing, injection moulding and rotational forming shaping operation.Film comprises by coextrusion or by blowing or cast film that lamination forms, can be used as Food Contact and contact shrinkable film in the application, antiskid film with non-food stuff, but oriented film, sealing film, oriented film, fast food packaging material, the heavy duty sack, the grocery bag, baking and Frozen Food Packaging material, medical package material, the industry wadding, film etc.Fiber comprises the melt-spun that is used to prepare filter, diaper, medical clothes, geotextiles etc. with woven or non-woven form, solution spinning and the operation of melt jet fiber.Extruded product comprises medical pipe material, electric wire and cable coating, geomembrane and pond lining.Moulding article comprises the list and the sandwich construction of forms such as bottle, jar, large-scale hollow product, rigidity food containers and toy.

Embodiment

Embodiment 1

Present embodiment has been described and has been carried out modification, then with TMA activation be used for independent polymerisation then to produce the poly various preparations that support Ziegler-Natta catalyst of single peak type.The productivity ratio of modification Ziegler-Natta catalyst (catalyst B and C) is apparently higher than the productivity ratio of unmodified Ziegler-Natta catalyst (catalyst A).

The TMA activator is that trimethyl aluminium and the sesquialter ethylaluminium chloride (EASC) in heptane is in toluene; The two is by Aldrich Chemical Company, and Inc. supplies.Diethylaluminum chloride (DEAC) is in heptane, and diethylaluminum ethoxide (DEA1-E) is in hexane; The two is supplied by Akzo Nobel Polymer Chemicals LLC..Kaydol, paraffin oil is bought from Witco Corporation, again by at first with the nitrogen degassing 1 hour, heating was purified in 10 hours under 80 ℃ and vacuum subsequently.

Catalyst A sample (sample 1-6) is represented unmodified Ziegler-Natta catalyst (not activation).These samples prepare in the following manner.With joining in the Schenk flask at 600 ℃ of Davison-grade 955 silicas (2.00g) and heptane (60ml) of calcining 4 hours down in advance, so that silica slurries to be provided.This flask is put in the oil bath that remains under 55 ℃.Dibutylmagnesium (1.44mmol) is joined in the silica slurries (55 ℃), stirred again 1 hour.Then, add 1-butanols (1.368mmol) (under 55 ℃), again mixture was stirred other 1 hour.Then, with TiCl ₄(0.864mmol) join in the reaction medium (at 55 ℃), again the gained mixture was stirred 1 hour.Under vacuum, from slurry, remove liquid then, obtain white free-pouring catalyst fines.Each catalyst sample is used Treatment with activating agent then.The type of the activator that uses with each catalyst A sample is reported in following table 1.

Catalyst B and C represent the modification Ziegler-Natta catalyst.Catalyst B sample (sample 7-11 and 14) uses " on the spot " method to be prepared as follows, and the meaning is not comprise filtration in the preparation of modification Ziegler-Natta catalyst, washing or separation.Modified catalyst is by in Kaydol oil at room temperature simply mixing 2 hour standby with catalyst A DEAC or EASC.Therefore, in particular of the present invention, the modification Ziegler-Natta catalyst can not be used in modifier contact before separate Ziegler-Natta catalyst and prepare.

In each preparation of these samples, the hydrocarbon solution that will comprise modifier in room temperature (25 ℃) down joins in the Kaydol slurry of catalyst A (0.521g is in the Kaydol of 13.50g).For sample 7-11, modifier is DEAC.For sample 14, modifier is DEAL-E.Each gained mixture was at room temperature stirred 2 hours, be used for polymerization then.Be prepared as follows catalyst C sample (sample 12 and 13), use " separation " method, the meaning is to comprise filtration, washing and dry in Preparation of Catalyst.In the preparation of each sample, will comprise that at room temperature the hydrocarbon solution of modifier (DEAC or EASC) joins in hexane (40mL) slurry of catalyst A (5.02g).Each gained mixture was at room temperature stirred 2 hours, filter then, dry under room temperature and vacuum again with twice of hexane wash (each 20mL), obtain light brown free-pouring powder.

In each of sample 1-14, in sludge phase reactor, use at Preparation of Catalyst polyethylene explanation and in following table above.Preparation contains the Kaydol oil slurry of each catalyst (sample 1-14).For each polymerization, each slurry mixture of equal portions is joined in the stainless steel bomb form height of the 50ml that contains the 50ml hexane pressure vessel (bomb).Slurry-phase reactor is the 1L stainless steel autoclave that mechanical agitator has been installed.Before polymerization, reactor came dry in 40 minutes by flow down heating at drying nitrogen under 96 ℃.Reactor is being cooled to after 50 ℃, the hexane of 500ml and the 1-hexene of 40mL are being joined in the reactor, be added on the TMA of the 1.0ml in the heptane (2.0mol is as activator) subsequently.The temperature of reactor is elevated to 85 ℃ gradually, adds the hydrogen (except sample 1,7 and 13) of 90ml again.Then with ethene with reactor be pressurized to 200psi (1,379kPa).Under ethylene pressure, each premix catalyst slurry composition is transferred in the reactor then.Continue heating, till reaching 95 ℃ polymerization temperature.Unless otherwise prescribed, each polymerization continues 60 minutes, during this period, ethene is joined in the reactor continuously, to keep constant compression force.Keep anhydrous condition.When 60 minutes finish, emptying and open reactor.The result of each aggregation test sets forth in following table 1 and 2.The gram number of the catalyst in table is meant and does not comprise and can use to help it to join the weight of the whole carbon monoxide-olefin polymeric of oily or other diluent in the polymer reactor with catalyst.The productivity ratio of each polyethylene polymerization test is according to catalyst-loaded (whole bimetallic catalyst comprises carrier etc., but does not comprise oil or other diluent) of poly gram number/gram of being produced/hour measure.

The comparative sample 1-6 of table 1, embodiment 1

Sample	Catalyst	Activator	Catalyst dosage (g)	Activator/Ti (mol ratio)	H 2 (mL)	Output (g)	Productivity ratio (g/g)
								1	A	TMA	0.0314	177	0	90.6	2884
2	A	TMA	0.0306	182	90	49.3	1611
								3	A	TMA	0.0171	325	90	22.1	1331
4	A	DEAC	0.0373	149	90	43.7	1171
								5	A	EASC	0.0404	137	90	8.6	213
6	A	DEAL-E	0.0409	136	90	2.1	51

The sample 7-14 of the present invention of table 2, embodiment 1

Sample	Catalyst	Modifier	Modifier/Ti (mol ratio)	Activator	Catalyst dosage (g)	Activator/Ti (mol ratio)	H 2 (mL)	Output (g)	Productivity ratio (g/g)
										7	B	DEAC	1.6	TMA	0.0092	604	0	99.4	10757
8	B	DEAC	0.8	TMA	0.01846	300	90	100.2	5428
										9	B	DEAC	1.6	TMA	0.0166	335	90	107.5	6451
10	B	DEAC	4.8	TMA	0.01835	303	90	88.2	4806
										11	B	DEAC	8.0	TMA	0.0187	297	90	89.3	4775
12	C	DEAC	1.6	TMA	0.0176	316	90	97.9	5562
										13	C	EASC	0.86	TMA	0.0199	280	0	152.25	7651
14	B	DEAL-E	1.49	TMA	0.0191	291	90	69.1	3618

As above proof, modification Ziegler-Natta catalyst (catalyst B and C) has shown the improvement catalyst productivity of comparing with unmodified Ziegler-Natta catalyst (catalyst A).The productivity ratio of sample 1-6 (catalyst A) all is lower than 3,000g polymer/g catalyst, and the productivity ratio of sample 7-14 (catalyst B and C) all is higher than 3,000g polymer/g catalyst.Should also be noted that for the aluminium from the wide region of 0.8 low value (sample 8) the high value (sample 11) to 8.0: the titanium mol ratio has obtained high production rate.Yet maximum productivity is under lower ratio, i.e. 0.8 and 1.6 mol ratio (referring to sample 7-9 and 12-14), and the productivity ratio of (4.8 and 8.0) is lower more than 4 mol ratio.Also have, find that halogen-containing modifier (DEAC and EASC) is better than the modifier that contains ethyoxyl (DEAL-E) performance.

Embodiment 2

Present embodiment understands that for example how catalyst productivity can not activate non-modification Ziegler-Natta catalyst and contact simultaneously with activator with modifier by allowing, but not modified catalyst at first, activating it subsequently influences.In the present embodiment, form the Kaydol oil of equal portions and do not activate category-A catalyst (0.0191g) slurry.This catalyst slurry uses the above-mentioned operation in embodiment 1 to form.Catalyst slurry is incorporated in the stainless steel bomb form height of the 50ml that contains the 50ml hexane pressure vessel.Keep anhydrous condition.

This slurry-phase reactor is the 1L stainless steel autoclave that mechanical agitator is housed.Before polymerization, reactor came dry in 40 minutes by flow down heating at drying nitrogen under 96 ℃.Reactor is being cooled to after 50 ℃, (500ml) joins in the reactor with hexane, adds the TMA activator (2.0mol) in heptane of 1.0ml and DEAC modifier (0.04mmol) and the 1-hexene (40ml) of 0.025ml subsequently.Seal this reactor then; Temperature with reactor is elevated to 85 ℃ gradually.Reactor is pressurized to 200psi (1379kPa), again ethene is incorporated in the reactor.Under ethylene pressure, premix catalyst slurry (containing catalyst A) is transferred in the reactor then.Continue heating, till reaching 95 ℃ polymerization temperature.Polymerization continues 60 minutes, during this period, ethene is joined in the reactor continuously, to keep constant compression force.When 60 minutes finish, emptying and open reactor.The result is shown in the following table 3, productivity ratio such as above expression.

Table 3, the polymerization result when modifier and activator are merged with the ZN catalyst simultaneously

Sample	Catalyst	Modifier	Modifier/Ti (mol ratio)	Activator	Catalyst dosage (g)	Activator/Ti (mol ratio)	H 2 (mL)	Output (g)	Productivity ratio (g/g)
										15	A	DEAC	5.8	TMA	0.0191	290	90	44.47	2340

Results reported shows in table 3, as report at table 2, when modifier contacts separately with Ziegler-Natta catalyst with activator, has seen that active maximum improves.

Embodiment 3

Present embodiment has been described the preparation of two kinds of different bimetallic catalysts of reflection in table 4, is used for independent polymerisation then, and to produce bimodal polyethylene, its result is shown in the table 5.

Such as at table 4 reflection, be prepared as follows " catalyst D " (sample 16).DEAC (0.1ml or 0.16mmol) is joined the not slurry of activating catalyst A (0.265g) in the Kaydol of 13.8g oil.The gained mixture was at room temperature stirred 2 hours.Add metallocene to this slurry, specifically dichloro two (n-butyl cyclopentadienyl) closes zirconium ((BuCp) ₂ZrCl ₂)) (by Boulder Scientific Company (0.011g, 0.0272mmol) supply) and activator (be MAO, 0.85ml, 2.64mmol) and Kaydol (7.2g).Contain the merging slurry that activates bimetallic catalyst and at room temperature mix then and stirred 2 hours, obtain " catalyst D ".

What also reflect in table 4 is catalyst E (sample 17), and it is prepared as follows.Similar with the sample 12 in table 2, preparation comprises the slurry of the catalyst C (0.501g) of Kaydol oil (27.4g) and DEAC modification.This slurry also comprises metallocene, i.e. (BuCp) ₂ZrCl ₂(0.026g, 0.0643mmol) and MAO (1.2ml, 3.63mmmol).This slurry was at room temperature stirred 8 hours, obtain catalyst E (sample 17).

Bimetallic catalyst of the present invention had 10: 1 in one embodiment to 1: 1,5: 1 to 2: 1 the Z-N transition metal and the mol ratio of metal metallocene in another embodiment.The aluminium of MAO activator and the mol ratio of metal metallocene are 500: 1 to 1: 1 in one embodiment, are 200: 1 to 40: 1 in another embodiment.The occurrence of embodiment is shown in the table 4.

Table 4, bimetallic catalyst

Catalyst	The Ziegler component	Ti dosage (mmol/g catalyst)	Metallocene components	Zr dosage (mmol/g catalyst)	Ti/Zr	Al/Zr
							D	Catalyst B	0.221	(BuCp) 2ZrCl 2	0.063	3.5	100
E	Catalyst C	0.242	(BuCp) 2ZrCl 2	0.087	2.8	56

Sample 16 and 17 uses in independent aggregation test, and their result reports in following table 5.Respectively be aggregated in the sludge phase reactor and carry out, to produce polyethylene.Each sample 16 and 17 (Kaydol oil slurry) of equal portions is joined in the stainless steel bomb form height of the 50ml that contains the 50ml hexane pressure vessel.Keep anhydrous condition.The polymerization time of each test is 60 minutes.

This slurry-phase reactor is the 1L stainless steel autoclave that mechanical agitator is housed.Reactor at first came dry in 40 minutes by flow down heating at drying nitrogen under 96 ℃.Reactor is being cooled to after 50 ℃, (500ml) joins in the reactor with hexane, adds the TMA in heptane (2.0mol) of 1.0ml subsequently.Also add the distilled water of 30 microlitres and the 1-hexene of 40ml.Sealed reactor then; Temperature with reactor is elevated to 85 ℃ gradually, adds the hydrogen of 90ml again.With ethene reactor is pressurized to 200psi (1379kPa).Under ethylene pressure, premix catalyst (above-mentioned) is transferred in the reactor then.Continue heating, till reaching 95 ℃ polymerization temperature.Polymerization continues 60 minutes, during this period, ethene is joined in the reactor continuously, to keep constant compression force.When 60 minutes finish, emptying and open reactor.The result of polymerization is shown in the following table 5.

The polymerization result of table 5, bimetallic catalyst

Sample	Catalyst type	Catalyst dosage (g)	Output (g)	Productivity ratio (g/g)	FI dg/min	PDI (Mw/Mn)
							16	D	0.0137	93.9	6803	8.1	17.9
17	E	0.0137	96.3	7031	2	19.2

Term " PDI " is meant polydispersity index, and it equals molecular weight distribution mw/mn, and wherein Mw is that weight average molecular weight and Mn are number-average molecular weights, and they are by using the gel permeation chromatography of crosslinked polystyrene post; Aperture order: 1 post less than , mix

3 posts; 1,2,4-trichloro-benzenes solvent, has refractive index and detects by 140 ℃.〉=10 PDI value has shown wide and/or bimodal molecular weight distribution usually.

Referring to table 5, use each bimodal pattern naturally of sample 16 and 17 polyethylene of producing, that is, they have disclosed bimodal molecular weight distribution.The polyethylene of use sample 16 Catalyst Production has 15,597 Mn; 278,896 Mw; 1,277,917 Mz; With 17.9 PDI.The polyethylene of use sample 17 Catalyst Production has 16,682 Mn; 323,121 Mw; 1,232,261 Mz; With 19.2 PDI.

Unless otherwise prescribed, the amount of the expression composition that in specification and claim, uses, performance, all numerical value of reaction condition etc. are considered to the approximation based on desired properties of seeking to obtain by the present invention and measure error etc., and should explain according to the significant digits of being reported with by using the common technology of rounding up at least.Though illustrating the number range and the value of wide region of the present invention is approximation, as far as possible accurately reports given numerical value.

All prior art files are introduced for reference with all authorities that this introducing wherein is allowed at this paper comprehensively.In addition, the All Files that this paper quoted comprises that The test procedure introduces for reference with all authorities that this introducing wherein is allowed at this paper comprehensively.

Claims (37)

1. bimetallic catalyst, it comprises:

(a) comprise the Ziegler-Natta catalyst of 4,5 or 6 group 4 transition metals;

(c) comprise the modifier of 13 family's metals; The mol ratio of 13 family's metals and transition metal was less than 10: 1; With

(b) metallocene catalyst compound.

2. the bimetallic catalyst of claim 1, the mol ratio of 13 family's metals and transition metal is 0.5: 1 to 5: 1.

3. the bimetallic catalyst of claim 1, wherein modifier is to use general formula A1X _nR _3-nThe compound of describing or the mixture of compound, wherein Al is an aluminium, X is independently selected from halogen, C ₁-C ₂₀Alkoxyl, C ₁-C ₂₀Alkyl amino and their bond; Be independently selected from C with R ₁-C ₂₀Alkyl and C ₆-C ₂₀Aryl; Wherein n is 0,1,2 or 3.

4. the bimetallic catalyst of claim 3, wherein n is 1.

5. the bimetallic catalyst of claim 1, wherein 13 family's metals are boron or aluminium.

6. the bimetallic catalyst of claim 1, wherein 13 family's metals are aluminium.

7. the bimetallic catalyst of claim 1, wherein bimetallic catalyst comprises first activator of the amount that is enough to the activation modification Ziegler-Natta catalyst in addition.

8. the bimetallic catalyst of claim 7, wherein first activator is the alkyl aluminum that combines with water.

9. the bimetallic catalyst of claim 8, wherein the mol ratio of water and alkyl aluminum is 0.01-5.

10. the bimetallic catalyst of claim 8, wherein water and alkyl aluminum and bimetallic catalyst add in polymer reactor simultaneously.

11. the bimetallic catalyst of claim 1, wherein bimetallic catalyst comprises first activator that is used to activate Ziegler-Natta catalyst in addition, wherein first activator contain aluminium and wherein the mol ratio of the first activator aluminium and Z-N transition metal greater than 10: 1.

12. the bimetallic catalyst of claim 11, wherein the mol ratio of the first activator aluminium and Z-N transition metal was greater than 20: 1.

13. the bimetallic catalyst of claim 1, wherein bimetallic catalyst comprises second activator of the amount that is enough to activated metal cyclopentadienyl catalyst compound in addition.

14. the bimetallic catalyst of claim 15, wherein second activator is the MAO (MAO) that presents in an amount at least sufficient to activated metal cyclopentadienyl catalyst compound.

15. the bimetallic catalyst of claim 1, wherein the mol ratio of 13 family's metals of modifier and transition metal is 0.5: 1 to 7: 1.

16. the bimetallic catalyst of claim 1, wherein the mol ratio of 13 family's metals of modifier and transition metal is 0.5: 1 to 5: 1.

17. the bimetallic catalyst of claim 1, wherein the mol ratio of 13 family's metals of modifier and transition metal is 0.5: 1 to 3: 1.

18. the bimetallic catalyst of claim 1, wherein Ziegler-Natta catalyst forms by allowing the organo-magnesium compound that contains at least one alkyl contact with 4 or 5 group 4 transition metal halide or oxide.

19. the bimetallic catalyst of claim 1, wherein Ziegler-Natta catalyst forms by allowing organo-magnesium compound contact with titanium chloride compound, and wherein organo-magnesium compound has formula M g (OR) ₂Or R ¹ _mMgR ² _nR wherein, R ¹And R ²Be C ₁-C ₈Alkyl, and m and n are 0,1 or 2.

20. the bimetallic catalyst of claim 1, wherein the modification Ziegler-Natta catalyst supports on carrier material.

21. the bimetallic catalyst of claim 1, wherein bimetallic catalyst has 4 under 80-100 ℃ in gas-phase polymerization reactor, the productivity ratio of 000g polymer/g catalyst.

22. the bimetallic catalyst of claim 1, wherein bimetallic catalyst has under 80-100 ℃ in gas-phase polymerization reactor and is higher than 6, the productivity ratio of 000g polymer/g catalyst.

23. the method for the bimetallic catalyst of production claim 1 comprises allowing (a) to contact with (b), to form bimetallic catalyst:

(a) by allow (i) with (ii) contact prepared modification Ziegler-Natta catalyst:

(i) contain the Ziegler-Natta catalyst of 4,5 or 6 group 4 transition metals;

The modifier that (ii) contains 13 family's metals; The mol ratio of 13 family's metals and transition metal was less than 10: 1; With

(b) metallocene catalyst compound.

24. the bimetallic catalyst of claim 1 or 23, wherein metallocene catalyst compound activation before contact.

25. the bimetallic catalyst of claim 1 or 23 wherein at first prepares Ziegler-Natta catalyst, contacts with modifier subsequently, not be used in the modifier contact to separate Ziegler-Natta catalyst before.

26. the bimetallic catalyst of claim 1 or 23, wherein Ziegler-Natta catalyst does not activate.

27. the bimetallic catalyst of claim 1 or 23, wherein modification Ziegler-Natta catalyst.

28. the method for claim 23, wherein in the step (i) of step (a) and the component (ii) merge before entering polymer reactor.

29. the method for claim 23 does not wherein comprise trimethyl aluminium at the modifier of step in (ii).

30. produce the method for bimodal polyethylene, comprise with ethene and C ₃-C ₁₀Alpha-olefin contacts in polymer reactor with the bimetallic catalytic immunomodulator compounds of claim 8.

31. the method for claim 30, wherein water and alkyl aluminum and bimetallic catalyst join polymer reactor simultaneously.

33. unit that comprises ethylene derivative and any or multiple C with the preparation of the method for claim 30 ₃-C ₁₀The bimodal polyethylene of the unit of deriving; Wherein bimodal polyethylene has the Mw/Mn value of 12-50 and is higher than 1,000,000 Mz value.

34. comprise the unit and any or multiple C of ethylene derivative ₃-C ₁₀The bimodal polyethylene of the unit of deriving; Wherein bimodal polyethylene has the Mw/Mn value of 12-50 and is higher than 1,000,000 Mz value.

35. the bimodal polyethylene of claim 34, wherein bimodal polyethylene has the density of 0.920-0.980g/cc.

36. the bimodal polyethylene of claim 34, wherein modifier is to use general formula A1X _nR _3-nThe compound of describing or the mixture of compound, wherein Al is an aluminium, X is independently selected from halogen, C ₁-C ₂₀Alkoxyl, C ₁-C ₂₀Alkyl amino and their bond; Be independently selected from C with R ₁-C ₂₀Alkyl and C ₆-C ₂₀Aryl; Wherein n is 0,1,2 or 3.

37. the bimodal polyethylene of claim 34, wherein this bimetallic catalyst and alkene merge in slurry or gas-phase reaction.

38. the bimodal polyethylene of claim 34 is used to produce pipe material product, the purposes of film product or blow molded product.