CN103052655A

CN103052655A - Processes for making multimodal molecular weight distribution polyolefins

Info

Publication number: CN103052655A
Application number: CN2011800379116A
Authority: CN
Inventors: M·W·赫尔特卡普; M·S·贝多雅
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2010-11-19
Filing date: 2011-10-26
Publication date: 2013-04-17
Anticipated expiration: 2031-10-26
Also published as: MY165619A; BR112013002457B1; WO2012067777A3; RU2013122566A; RU2579518C2; EP2640757A4; BR112013002457A2; EP2640757A2; WO2012067777A2; CN103052655B

Abstract

This invention relates to a process to make a multimodal polyolefin composition comprising: (i) contacting at least one first olefin monomer with a mixed catalyst system, under polymerization conditions, to produce at least a first polyolefin component having a Mw of 5,000 g/mol to 600,000 g/mol, wherein the mixed catalyst system comprises: (a) at least one polymerization catalyst comprising a Group 4 or Group 5 transition metal; (b) at least one organochromium polymerization catalyst; (c) an activator; and (d) a support material; (ii) thereafter, contacting the first polyolefin component/mixed catalyst system combination with a molecular switch; (iii) contacting the first polyolefin component/mixed catalyst system combination with at least one second olefin monomer, which may be the same or different, under polymerization conditions; and (iv) obtaining a multimodal polyolefin composition.

Description

The preparation method of multimodal attitude molecular weight distribution polyolefin

Contriver: Mat thew W.Hol tcamp and Mat thew S.Bedoya

Prioity claim

The application requires the USSN12/950 that submits on November 19th, 2010, and 501 and interests and the right of priority of the EP10196508.5 that submits on December 22nd, 2010.

Invention field

The present invention relates to field of olefin polymerisation, especially use mixed catalyst composition to make the method for olefinic polymerization and copolymerization.

Background of invention

Polyolefine with bimodal attitude molecular weight distribution is desirable, because they can be with the combination of the improved processing characteristics of the favourable mechanical property of high molecular weight block and low molecular weight fraction.This provides to compare with the polyolefine that high molecular weight block or low molecular weight fraction are only arranged has useful and polyolefine desirable performance combination.For example, although high molecular is given polyolefin polymer with desirable mechanical property and stable bubble formation usually, but it also suppresses to extrude processing by the counterpressure that improves in the forcing machine usually, promote the melt fracture defective in the expanding bubble, possibly, also promote orientation degree in the finished film.On the other hand, low-molecular-weight polyolefin has excellent workability usually, but intensity difference.Keep desirable mechanical property, stable bubble formation, therefore the multimodal attitude molecular weight distribution polyolefin that comprises low molecular weight fraction and high molecular weight block in the time of the forcing machine counterpressure that reduces and downtrod melt fracture is desirable.This type of polyolefine may have great applicability in the film that requires the useful and desirable performance combination of this kind and other goods.

Polyolefine with multimodal attitude molecular weight distribution can followingly obtain: with high molecular polyolefine and low-molecular-weight polyolefin physical blending, such as U.S. Patent number 4,461, like that open in 873.Yet the blend of these physics preparations contains high gel level usually, and this causes because the film outward appearance of the difference that those gels cause.Although workability has improvement, blend is expensive often, requires the completely homogeneity of mixture of melts, and increases the additional blend step that bothers for manufacturings/manufacture craft.

Some commercial runs use the technological operation of multiple reaction device with the machinable bimodal attitude molecular weight distribution polyethylene product of preparation in two or more reactors.In multiple reaction device method, each reactor prepares the single component of final product.For example, as described in EP0057420, by two step method, use two tandem reactors to carry out the preparation of bimodal attitude molecular weight distribution high density polyethylene(HDPE).In described two step method, can Optimizing Technical and catalyzer in order to provide high-level efficiency and productive rate for each step in the group method.Yet, use the multiple reactor technology to increase cost and processing consideration.

Yet, being difficult to for example use, single catalyst prepares for example bimodal attitude molecular weight distribution polyethylene of bimodal attitude molecular weight distribution polyolefin, because usually need two groups of independently reaction conditionss.As an alternative, other people has attempted using in same reactor two kinds of different catalysts to prepare simultaneously two kinds of polymkeric substance in this area.

The catalyst system that comprises two kinds of different metal cyclopentadienyl catalysts is disclosed in the preparation of the bimodal attitude molecular weight distribution polyolefin among the EP0619325.EP0619325 has described the polyolefine with multimodal or bimodal at least attitude molecular weight distribution, for example poly preparation method.Employed metallocenes is that for example, dichloro two (cyclopentadienyl) closes zirconium and dichloro ethylenebis (indenyl) is closed zirconium.By in same reactor, using two kinds of different metalloscene catalysts, obtain bimodal at least molecular weight distribution.

WO99/03899 discloses the application for preparing the poly catalyst composition with wide or bimodal molecular weight distribution in single reactor.Described catalyzer is by silicon oxide (in advance 600 ℃ lower calcining) and dibutylmagnesium, n-butyl alcohol and titanium tetrachloride, and the interaction preparation of closing the solution of zirconium of methylaluminoxane and dichloro ethylenebis [1-indenyl].

U.S. Patent number 7,163,906 disclose a kind of catalyst composition, this catalyst composition comprises the product of contact of at least a Metallocenic compound, at least a organic chromium polymerizing catalyst, fluorided silica and at least a alkylaluminium cpd, and then this catalyst composition is used for making vinyl polymerization in inert atmosphere.U.S. Patent number 7,163, the metallocenes that uses among 906 the embodiment are that dichloro two (n-butyl cyclopentadienyl) closes zirconium and employed organo-chromium compound comprises two cumene chromium and two luxuriant chromium.U.S. Patent number 7,163, disclosed metallocenes in 906-organic chromium catalyst system preparation is characterised in that the very polyethylene of wide molecular weight distribution (70.3-8.4).U.S. Patent number 7,163, the polyethylene of preparation shows medium molecular weight distributions in 906, has owing to the peak, center of metallocene components and the wide tail composition on high and that side of lower molecular weight owing to the chromium component time.In addition, U.S. Patent number 7,163,906 openly do not use molecular switch to activate a kind of catalyzer and the another kind of catalyzer of passivation.

Can provide aspect the method for polyolefinic various molecular weight fractions control with multimodal attitude molecular weight distribution in exploitation and to still have significant challenge.Therefore, still need to allow to the composition of each kurtosis of the multimodal attitude molecular weight distribution polymer concrete method of control in addition.

Summary of the invention

The present invention relates to the preparation method of multimodal attitude polyolefin compositions, the method comprises: at least a the first olefinic monomer and hybrid catalyst system are contacted under polymerizing condition to prepare at least have 5,000g/mol-600, the first polyolefin component of the Mw of 000g/mol, wherein said hybrid catalyst system comprises: (a) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (b) at least a organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii) afterwards, described the first polyolefin component/hybrid catalyst system combination is contacted with molecular switch; (iii) combination of described the first polyolefin component/hybrid catalyst system can be contacted with identical or different the second olefinic monomer of described the first olefinic monomer under polymerizing condition with at least a; (iv) obtain multimodal attitude polyolefin compositions.

The invention further relates to hybrid catalyst system, it comprises: (i) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (ii) activator; (iii) at least a organic chromium polymerizing catalyst; (iv) solid support material; Wherein therein under the described activated polymerizing condition of polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein after contacting with molecular switch and under polymerizing condition, described organic chromium polymerizing catalyst has active large at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

The invention further relates to the preparation method of loading type hybrid catalyst system, comprise: described solid support material is contacted with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the reactive group on the described solid support material of titration, and form supported polymerisation catalysts; (ii) afterwards, make described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with the organic chromium polymerizing catalyst; Wherein therein under the described activated polymerizing condition of polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein after contacting with molecular switch and under polymerizing condition, described organic chromium polymerizing catalyst has active large at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

The accompanying drawing summary

The unimodal molecular weight of polyethylene that Fig. 1 represents to use catalyzer 2 (loading type dichloro two (1-methyl, 3-butyl cyclopentadienyl) closes zirconium/pair (cyclopentadienyl) chromium hybrid catalyst system) to obtain distributes.

Fig. 2 represents to use catalyzer 2 (two (the 1-methyl of loading type dichloro that activated by molecular switch, 3-butyl cyclopentadienyl) close zirconium/pair (cyclopentadienyl) chromium hybrid catalyst system, be exposed under oxygen and the triethyl aluminum) the bimodal polyethylene molecular weight distribution that obtains.

Describe in detail:

The contriver it has surprisingly been found that can working load type hybrid catalyst system and the molecular switch preparation each kurtosis is had the multimodal attitude molecular weight distribution polyolefin of control.This paper employed " molecular weight " refers to weight-average molecular weight (Mw), except as otherwise noted.

In the embodiment of this paper, the method that the present invention relates to may further comprise the steps: (i) at least a the first olefinic monomer and hybrid catalyst system are contacted to prepare at least under polymerizing condition and have 5,000g/mol-600, the first polyolefin component of the Mw of 000g/mo l, wherein said hybrid catalyst system comprises: (a) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (b) at least a organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii) afterwards, described the first polyolefin component/hybrid catalyst system combination is contacted with molecular switch; (iii) described the first polyolefin component/hybrid catalyst system combination is contacted under polymerizing condition with at least a the second olefinic monomer that can be identical or different; (iv) obtain multimodal attitude polyolefin compositions.

" alkene " perhaps is called straight chain, side chain or ring compound with at least one two key that " alkene " is carbon and hydrogen.For the purpose of the present invention and claim thereof, when polymkeric substance was called " comprising alkene ", the alkene that is present in the described polymkeric substance was the polymerized form of described alkene." polymkeric substance " has two or more identical or different monomeric units." multipolymer " is the polymkeric substance with two or more monomeric units that differ from one another." terpolymer " is the polymkeric substance with three monomeric units that differ from one another." difference " that is used for relating to monomeric unit indicates described monomeric unit to differ each other at least one atom or isomery is different.

Term as used herein " hybrid catalyst system " is used for referring to any composition or mixture, it comprises (i) at least two kinds of different catalyst compound, at this, namely can be by the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal of molecular switch quencher or passivation and the organic chromium polymerizing catalyst that can be activated by molecular switch; (ii) activator; (iii) solid support material, component as described below.

When the term that is used for describing polymkeric substance or polymer composition " multimodal attitude " refers to " multimodal attitude molecular weight distribution ", it is interpreted as referring to gel permeation chromatography (GPC) trace, being plotted as d (wt%)/d (Log[M]) to weight-average molecular weight (g/mol), has more than a peak or flex point." flex point " is the point (for example, from just bearing, vice versa) that the flection sign of wherein curve changes.For example, the polyolefin compositions that comprises the first low-molecular weight polymer component and the second high molecular weight polymer components is thought " bimodal " polyolefin compositions.Polymer composition has " molecular weight distribution " (or MWD), and this molecular weight distribution refers to ratio or the Mw/Mn of Mw and number-average molecular weight (Mn).Mw and Mn measure by GPC.

This paper employed " molecular switch " is used for reducing, or cuts off, or quencher comprises the activity of the polymerizing catalyst of the 4th family or the 5th group 4 transition metal, and improves or open the activity of organic chromium polymerizing catalyst.In preferred embodiments, the second component of oxygen containing the first component of molecular switch bag and alkylaluminium cpd.The component of molecular switch is sequentially in the introduction method.In preferred embodiments, oxygen is contacted with the first polyolefin component/hybrid catalyst system, afterwards at the lower alkylaluminium cpd that adds of polymerizing condition (preferentially comprising inert atmosphere).

Concerning the object of the invention and claim purpose thereof, the new numbering plan of each family of the periodic table of elements is according to CHEMICAL AND ENGINEERING NEWS, uses like that in 63 (5), 27 (1985).Therefore, " group-4 metal " is the element that is selected from the periodic table of elements the 4th family.

" catalyst activity " be use comprise W transition metal (M) polymerizing catalyst during T hour in preparation how much restrain measuring of polymkeric substance (P); And can pass through (the T * W) expression with following formula: P/.It is employed that this paper relates to polymerizing catalyst " activity " refers to that described polymerizing catalyst has at least 50g (molM) ^-1Hr ^-1Catalyst activity, wherein M is that the activity that exists in the catalyst component of hybrid catalyst system may be owing to its transition metal structure division.This paper relates to polymerizing catalyst employed " nonactive " and refers to that described polymerizing catalyst has less than 50g (mo lM) ^-1Hr ^-1Catalyst activity.Concerning the purpose of the discussion of relative reactivity, activity is as mentioned above by carry out polymerization and the aggregated data that obtains calculates under the pressure of 200ps i (1.38MPa) and with ethene in the 75mL barrel type reactor for claim and this paper.Then described reactor is heated to 85 ℃ temperature and remained on this temperature lower 45 minutes.

The contriver has been found that the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal and organic chromium polymerizing catalyst are different aspect the molecular switch response." molecular switch response " refers to comprising that with same catalyzer the activity under the polymerizing condition of inert atmosphere compares, catalyzer (is for example contacting with molecular switch, be exposed to oxygen lower 5 minutes), then experience under polymerizing condition with the relative reactivity after the activation of alkylaluminium cpd.Contacting, and behind the experience polymerizing condition may become passivation and lose catalyst activity (negative molecular switch response) of catalyzer with molecular switch; Keep catalyst activity (without the molecular switch response); Or become activation and/or catalyst activity raising (positive molecular switch response).Molecular switch response can be exposed under the oxygen by catalyst component, then experiences the activity (A behind the follow-up polymerizing condition (comprise with alkylaluminium cpd and activating) _O) with the active (A of the catalyst component that under polymerizing condition (preferably including inert atmosphere), is not exposed to the hybrid catalyst system in the oxygen _I) between the ratio of difference measure; And by formula: (A _O-A _I)/A _IExpression.

For example, with before molecular switch contacts, under polymerizing condition, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal usually produce obtain unimodal or bimodal attitude molecular weight distribution polymkeric substance as the first polyolefin component.As if contrast, the organic chromium polymerizing catalyst does not produce a lot of polymkeric substance.

In the embodiment of this paper, the polymerizing catalyst that comprises therein the 4th family or the 5th group 4 transition metal is under the polymerizing condition of activity, the organic chromium polymerizing catalyst has than active little 50% of the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal at least, at least 60%, at least 70%, at least 80%, at least 90%, or at least 98% activity.In an optional embodiment, the organic chromium polymerizing catalyst has the active little at least single order than the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, at least two rank, at least 3 rank, at least 5 rank, or the activity at least 6 rank.Similarly, the polymerizing catalyst that comprises therein the 4th family or the 5th group 4 transition metal is under the polymerizing condition of activity, the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal has than the activity of organic chromium polymerizing catalyst greatly at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 98% activity.In an optional embodiment, the organic chromium polymerizing catalyst has than the activity of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal single order greatly at least, two rank, 3 rank, 5 rank, or the activity on 6 rank at least at least at least at least.

Yet, allowing the loading type hybrid catalyst system with after molecular switch contacts, the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal stops to produce the polymkeric substance of obvious amount usually.In such embodiments, comprise the polymerizing catalyst of the 4th family or the 5th group 4 transition metal by contacting and passivation or quencher with molecular switch, do not produce the first additional polyolefin component of obvious amount.This observes the no longer growth into the kurtosis of the first polyolefin component in the GPC trace.Therefore, for the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, A _OLess than A _ITherefore, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal has negative molecular switch response.In the embodiment of this paper, after contact with molecular switch and under polymerizing condition, the specific activity organic chromium polymerizing catalyst of polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is little.In some embodiments, the polymerizing catalyst specific activity organic chromium polymerizing catalyst after contacting with molecular switch that comprises the 4th family or the 5th group 4 transition metal is little by at least 50%, at least 60%, and at least 70%, at least 80%, at least 90%, or at least 98%.In an optional embodiment, the catalyzer that comprises the 4th family or the 5th group 4 transition metal has the active little at least single order than organic chromium polymerizing catalyst, at least two rank, at least 3 rank, at least 5 rank, or the activity at least 6 rank.

Contrast, allowing the loading type hybrid catalyst system with after molecular switch contacts, described organic chromium polymerizing catalyst produces the polymkeric substance of increasing amount usually.This observes the growth into the kurtosis of the additional polymer component different from the first polyolefin component of molecular weight in the GPC trace.Therefore, for organic chromium polymerizing catalyst, A _OGreater than A _ITherefore, the organic chromium polymerizing catalyst has positive molecular switch response.In the embodiment of this paper, with molecular switch, after the molecular switch that preferably comprises oxygen and alkylaluminium cpd contacts, and under polymerizing condition, the organic chromium polymerizing catalyst has more activity than the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal.In some embodiments, the polymerizing catalyst that organic chromium polymerizing catalyst specific activity after contact with molecular switch comprises the 4th family or the 5th group 4 transition metal greatly at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 98%.In an optional embodiment, the organic chromium polymerizing catalyst has than the activity of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal single order greatly at least, two rank, 3 rank, 5 rank, or the activity on 6 rank at least at least at least at least.

In some embodiments of this paper, with after molecular switch contacts, under polymerizing condition, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal has negative molecular switch response and the organic chromium polymerizing catalyst has positive molecular switch response.

In a preferred embodiment, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is inactive in the step (iii) of polymerization process, and organo-chromium compound is inactive in the step (i) of polymerization process.In another preferred embodiment, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active in the step (i) of polymerization process, and organo-chromium compound is active in the step (iii) of polymerization process.In still another preferred embodiment, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active in the step (i) of polymerization process and is inactive in step (iii).In another embodiment, organo-chromium compound is inactive in the step (i) of polymerization process and is active in step (iii).

In another embodiment, hybrid catalyst system of the present invention comprises: (i) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (ii) activator; (iii) at least a organic chromium polymerizing catalyst; (iv) solid support material; Wherein therein under the described activated polymerizing condition of polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein with after molecular switch contacts, and under polymerizing condition, the polymerizing catalyst that the specific activity of described organic chromium polymerizing catalyst comprises the 4th family or the 5th group 4 transition metal greatly at least 50%.

The invention further relates to the preparation method of hybrid catalyst system, comprise: solid support material is contacted with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the reactive group on the described solid support material of titration, and form supported polymerisation catalysts; (ii) afterwards, make described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with the organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst is differing at least 50% with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal aspect the molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system therein the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal be the described polymerizing catalyst little at least 50% that comprises the 4th family or the 5th group 4 transition metal of specific activity under the active polymerizing condition.

The manufacture method of the polyolefinic method of preparation multimodal attitude, load type catalyst system and described load type catalyst system is described below.

Polymerization process

In the embodiment of this paper, the method that the present invention relates to may further comprise the steps: (i) at least a the first olefinic monomer is contacted with hybrid catalyst system under polymerizing condition; Have 5,000g/mol-600 with preparation at least, 000g/mol, preferred 8,000g/mol-400,000g/mol; Or 10,000g/mol-300, the first polyolefin component of the Mw of 000g/mol; Wherein said hybrid catalyst system comprises: (a) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (b) at least a organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii) afterwards, make described the first polyolefin component/hybrid catalyst system combination and molecular switch, the molecular switch that preferably comprises oxygen and alkylaluminium cpd contacts; (iii) combination of described the first polyolefin component/hybrid catalyst system can be contacted with identical or different the second olefinic monomer of described the first olefinic monomer under polymerizing condition with at least a; (iv) obtain multimodal attitude polyolefin compositions; Preferably wherein the activity of the catalyzer in the step (i) greater than 2000 pounds of polymkeric substance/hour (907Kg/hr), more preferably greater than 5000 pounds/hr (2268Kg/hr), most preferably greater than 10,000 pounds/hr (4540Kg/hr); And the activity of the hybrid catalyst system in the step (iii) is greater than 2000 pounds of polymkeric substance/hour (907Kg/hr), more preferably greater than 5000 pounds/hr (2268Kg/hr), most preferably greater than 10,000 pounds/hr (4540Kg/hr).

The inventive method can be undertaken by any mode as known in the art.Can use any suspension as known in the art, homogeneous phase body, solution, slurry or gas phase polymerization process.Gas phase and slurry phase polymerisation process are preferred.

Described method can be intermittence, semi-batch or continuation method.Term as used herein " continuously " refers in the situation that the system that does not have interrupting or stopping to operate.For example, the continuation method of preparation polymer composition will be the reactant method that imported continuously one or more reactors and polymer composition product and taken out continuously wherein.

In gas phase polymerization process, usually adopt continuous circulation, wherein in reactor, pass through the part of the circulation of heat of polymerization reactor heating system, i.e. recycle gas stream (perhaps being called recycle stream or fluidizing medium).In another part of this circulation, from the recirculation composition, remove this heat by the cooling system outside reactor.Usually, in the gas fluidized bed process for the preparation of polymkeric substance, the gaseous stream that comprises one or more monomers is circulated under reactive conditions in the presence of catalyzer continuously pass fluidized-bed.This gaseous stream is discharged also recirculation from this fluidized-bed return this reactor.Simultaneously, with polymer product from reactor discharge and add fresh monomer substitute polymerization monomer.(referring to, for example, U.S. Patent number 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228).

In slurry polymerization, suspension solid-state, granulated polymer has added therein in the liquid polymerization diluent medium of ethene and comonomer and common hydrogen and catalyzer and has formed.The suspension that will comprise thinner is removed from reactor off and on or continuously, and in this reactor, volatile constituent is separated with polymkeric substance and reactor is arrived in recirculation (randomly, after distillation).The liquid diluent that is used for polymerisation medium normally contains the alkane of 3-7 carbon atom, preferably branched alkane.The medium that adopts should be liquid and than inertia under polymerizing condition.When using propane medium, must on reaction diluent critical temperature and pressure, operate the method.Preferably, use hexane or Trimethylmethane medium.

Can use particle form polymerization one class slurry process, wherein keep temperature to enter the temperature of solution less than polymkeric substance.This kind technology is well known in the art, and for example is being described in the U.S. Patent number 3,248,179.Other slurry methods comprise adopt loop reactor those and use those of a plurality of stirred reactors of series, parallel or its combination.The limiting examples of slurry process comprises continuous endless tube or steel basin method.In addition, other example of slurry methods is described in U.S. Patent number 4,613, in 484.

Method of the present invention can be carried out in any glass-lined stainless steel or similar type reaction equipment.Useful reaction vessel comprises reactor (comprising continuous stirred tank reactor (CSTR), batch reactor, reactive extruder, pipe or pump, continuous fixed bed reactor, slurry-phase reactor, fluidized-bed reactor and catalytic distillation reactor).Reaction zone can be equipped with one or more in and/or external heat exchanger in order to control excessive temperature fluctuation.

If described method is carried out in continuous flow reactor, then with the g of unit _mg _c ^-1h ^-1, namely restrain raw material monomer (g _m)/gram catalyzer (g _cThe weight hourly space velocity of)/hour (h) provides will be determined the relative quantity of raw material monomer and the catalyzer that adopts, and the residence time of monomer in reactor.In continuous flow reactor, the weight hourly space velocity of monomer is usually greater than 0.04g _mg _c ^-1h ^-1, be preferably greater than 0.1g _mg _c ^-1h ^-1

Typical polymerizing condition comprises temperature, pressure and the residence time.In specific embodiment, at least a the first olefinic monomer is contacted under polymerizing condition with hybrid catalyst system; Have 5,000g/mol-600, the first polyolefin component of the Mw of 000g/mol to produce at least.In some embodiments, the temperature of polymerization process can be at about 0 ℃-about 300 ℃, in the scope of 280 ℃ of 60 ℃ of preferably approximatelies-about or more preferably about 70 ℃-about 150 ℃.If described method is carried out in batch reactor, then the residence time of olefinic monomer and catalyzer can have any time length, as long as obtain required polymer product.Generally speaking, the residence time in the reactor is at about 15 minutes-about 240 minutes, and preferably approximately 30 minutes-about 210 minutes is in the scope of or preferably approximately 45 minutes-about 180 minutes.Polymerization pressure can be any pressure that can not adversely affect polyreaction, and can be at about about 1000ps i of 0.1-(0.7kPa-6.9MPa), the about 400ps i of preferably approximately 20-(0.14MPa-2.8MPa), or in the scope of the about 250ps i of preferably approximately 50-(0.34MPa-1.7MPa).

In preferred embodiments, in reaction vessel at about 0 ℃-about 300 ℃, 280 ℃ of 60 ℃ of preferably approximatelies-about or more preferably about 70 ℃-about 150 ℃ temperature, about about 1000psi of 0.1-(0.7kPa-6.9MPa), the about 400psi of preferably approximately 20-(0.14MPa-2.8MPa), or the pressure of the about 250psi of preferably approximately 50-(0.34MPa-1.7MPa) and about 15 minutes-about 240 minutes, preferably approximately 30 minutes-about 210 minutes, or under the residence time of preferably approximately 45 minutes-about 180 minutes with reactant (for example, monomer, the loading type mixed catalyst; Optional thinner etc.) combination.

In certain embodiments, when alkene was gaseous olefin, alkene pressure was greater than 5psig (34.5kPa); Be preferably greater than about 10psig (68.9kPa); More preferably greater than about 45psig (310kPa).When thinner used with gaseous olefin, above-mentioned pressure range also can be used as the total pressure of alkene and thinner suitably.Equally, when adopting liquefied olefines and carry out the method under inert atmosphere, then above-mentioned pressure range can be used for inert gas pressure suitably.

The diluent/solvent that is fit to that is used for described method comprises non-coordination inert liq.Example comprises straight chain and branched-chain hydrocarbon for example Trimethylmethane, butane, pentane, iso-pentane, hexane, dissident's alkane, heptane, octane, dodecane and their mixture; Ring-type and alicyclic hydrocarbon be hexanaphthene, suberane, methyl cyclohexanol, methyl suberane and their mixture for example, comprises those (Isopar that can commercially find ^TM); The perhalogenation hydrocarbon is perfluorination C for example _4-10The aromatic substance that alkane, chlorobenzene and aromatics and alkyl replace is benzene, toluene, sym-trimethylbenzene and dimethylbenzene for example.The diluent/solvent that is fit to also comprises aromatic hydrocarbon, for example toluene or dimethylbenzene, and chlorinated solvent methylene dichloride for example.In a preferred embodiment, the material concentration that is used for the monomer of polymerization is 60 volume % solvents or lower, preferred 40 volume % or lower, and preferred 20 volume % or lower are based on the cumulative volume of feedstream.

The additive that is fit to of polymerization process can comprise one or more scavenging agents, activator, promotor, chain-transfer agent, chain shuttling agent (for example zinc ethyl), properties-correcting agent, reductive agent, oxygenant, hydrogen or silane.

The useful monomer of this paper comprises alkene, especially ethene, propylene, butylene, amylene, hexane, heptane, octene, nonene, decene, undecylene and dodecane and their isomer.In some embodiments, single alkene is contacted, optimal ethylene or propylene with hybrid catalyst system.In other embodiments, make more than a kind of alkene, preferred two kinds of alkene, or preferred three kinds of alkene contact with hybrid catalyst system.In specific embodiment, multipolymer can be ethylene/propene, ethylene/butylene, ethylene/pentene, ethylene/hexene or ethylene/octene.In specific embodiment more, co-monomer content is less than 50wt%, less than 40wt%; Less than 30wt%; Less than 20wt%; Less than 10wt%; Or less than 5wt%, based on the gross weight of polymkeric substance.

The amount of the loading type mixed catalyst that adopts in the inventive method provides any amount of exercisable polyreaction.Preferably, the mole of raw material monomer and the ratio of the mole of loading type mixed catalyst are preferably greater than 100:1 usually greater than 10:1, be preferably greater than 1,000:1, be preferably greater than 10,000:1, be preferably greater than 25,000:1, be preferably greater than 50,000:1, be preferably greater than 100,000:1, based on the mole of transition metal.Perhaps, the mol ratio of raw material monomer and loading type mixed catalyst preferably less than 1,000,000:1, is more preferably less than 500,000:1 usually less than 10,000,000:1.

In a preferred embodiment, based on the olefinic monomer of per 3 mmole chargings, with 0.005 nmole-500 nmole, preferred 0.1-250 nmole, most preferably 1-50 nmole loading type mixed catalyst adds reactor, based on the mole of transition metal.

Can in the known manner, for example control the molecular weight of polymkeric substance by use hydrogen.During the mol ratio of hydrogen and monomer alkene, molecular weight control is proved by the raising of melt index in improving reactor.

" reactor " is any container that chemical reaction wherein occurs.In some embodiments, the inventive method, namely step (i)-(iv) is carried out in same reactor.In other embodiments, carry out in the differential responses district of step (i)-(iv) in same reactor.In specific embodiment, step (i)-(iv) in tubular reactor, carry out.In preferred embodiments, step (i)-(iv) is carried out in Gas-phase reactor.

In other embodiments, the inventive method is carried out in two or more reactors.The preparation of polymkeric substance in staged reactor can be included in by transfer device interconnected two several stages in the polymerization reactor independently at least, and this is so that can transfer to the polymkeric substance that derives from the first polymerization reactor in the second reactor.Perhaps, the polymerization in the staged reactor can comprise that the artificial transfer of polymkeric substance from a reactor to subsequent reactor is so that successive polymerization.

Polymerizing condition in one of reactor can be different from the polymerizing condition of other reactor.These reactors can comprise any combination, comprise combination, autoclave reactor or solution reactor and the combination of gas or loop reactor, multiple solution reactor or the multiple autoclave reactor of multiloop reactor, multiple gas reactor, loop and gas reactor.When using staged reactor, oxygen can be imported the first reactor, then during transfer the first polymkeric substance/mixed catalyst composition is transferred to the second reactor, or transfer in the second reactor.

Usually, in the embodiment of this paper, in reaction vessel with reactant (for example, loading type mixed catalyst; Optional thinner etc.) with olefinic monomer combination under above-mentioned polymerizing condition, to prepare the first polyolefin component.After producing the first polyolefin component of aequum, described the first polyolefin component/hybrid catalyst system combination is contacted with oxygen.Can be by any mode as known in the art with the oxygen introduction method.In some embodiments, make reaction terminating by removing alkene, described the first polyolefin component/hybrid catalyst system combination is contacted with molecular switch.

Molecular switch

Molecular switch of the present invention has the first component of oxygen and the second component of alkylaluminium cpd.This paper employed " molecular switch " reduces, or cuts off, or quencher comprises the activity of the polymerizing catalyst of the 4th family or the 5th group 4 transition metal, and improves or open the activity of organic chromium polymerizing catalyst.In preferred embodiments, molecular switch comprises the first component oxygen and second component alkylaluminium cpd.The component preferred sequence ground of molecular switch adds in the method.In preferred embodiments, oxygen is contacted with the first polyolefin component/hybrid catalyst system, afterwards at the lower alkylaluminium cpd that adds of polymerizing condition (preferably including inert atmosphere).

Oxygen is the first component of molecular switch of the present invention.This paper employed " oxygen " can be molecular oxygen or oxygen containing medium (gas, liquid, solid) form, for example oxygen containing gas, for example air.In preferred embodiments, described molecular switch comprises the oxygen with the form of air.Allow the combination of described the first polyolefin component/hybrid catalyst system and oxygen describedly comprise the polymerizing catalyst passivation of the 4th family or the 5th group 4 transition metal and the amount of described organic chromium polymerizing catalyst oxygenate is contacted by being enough to make.This paper employed " oxygenate " refers to produce procatalyst with the reaction of organic chromium polymerizing catalyst.This paper employed " procatalyst " refers to the second component by molecular switch, the catalyst compound that described alkylaluminium cpd activates.

In the embodiment of this paper, by the second component of molecular switch, described alkylaluminium cpd activates the organic chromium procatalyst of oxygenate.In the embodiment of this paper, alkylaluminium cpd is by general formula: Al R ₃Or Al R ₂H represents, wherein each R is alkyl (preferred, as to comprise the alkyl of 2-10 carbon atom) or halogen independently.Formula AlR ₃Compound be preferred.The example of useful alkylaluminium cpd comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three-n-hexyl aluminium, three-octyl aluminum, three-iso-octyl aluminium, triphenyl aluminum, tri-propyl aluminum, ethanol diethyl aluminum, tri-butyl aluminum, diisobutylaluminium hydride and diethylaluminum chloride and analogue.

Hybrid catalyst system of the present invention comprises: (a) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (b) at least a organic chromium polymerizing catalyst; (c) activator; (d) solid support material is such as following discussion.In some embodiments, allow the first polyolefin component/hybrid catalyst system make up and at least 1 equivalent, at least 1.5 equivalents, at least 2 equivalents, or the oxygen of at least 3 equivalents/equivalent activator contact.

Then allow the first polyolefin component of described oxygenate/hybrid catalyst system combination can under polymerizing condition, contact in the presence of the alkylaluminium cpd with identical or different the second olefinic monomer of described the first olefinic monomer with at least a.Described alkylaluminium cpd is the second component of molecular switch and the organic chromium polymerization procatalyst that is used for activating described oxygenate.At this moment, the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is at least part ofly to be, preferably being that inactive and described organic chromium polymerizing catalyst is at least part of basically is, preferred is active basically, and is created in the another kind of polyolefin component that the molecular weight aspect is different from the first polyolefin component.The amount of the second polyolefin component that the residence time control of the amount of monomer that can be by supplied reactor, the amount of alkylaluminium cpd and the second polymerization is prepared.Therefore, can in the situation of each kurtosis of controlling polyolefin compositions, prepare multimodal attitude MWD polyolefin compositions.

Multimodal attitude MWD polyolefin compositions

Polymer composition by the inventive method and hybrid catalyst system preparation is the multimodal attitude, has at least the first different aspect molecular weight polyolefin component and another kind of polyolefin component, and preferred so that GPC trace has more than a peak or flex point.

By such as Macromolecules, 2001, Vol.34, No.19, gel permeation chromatography described in the pg.6812 (GPC) is measured the measurement of weight-average molecular weight (Mw), number-average molecular weight (Mn) and z average molecular weight (Mz), the document is incorporated herein for reference fully, comprise using and be equipped with differential refractive index detector (DRI), the high temperature size exclusion chromatography (SEC, Waters Alliance2000) of three Polymer Laboratories PLgel10mm Mixed-B posts is equipped with.Use 1.0cm ³The volume injected of the flow velocity of/min and 300 μ L operates this instrument.Encapsulation various line of pipes, post and differential refractometer (DRI detector) in being maintained at 145 ℃ baking oven.Be prepared as follows polymers soln: under stirring continuously, heating at 1,2 of filtered containing～1000ppm BHT the 0.75-1.5mg/mL polymkeric substance in the 4-trichlorobenzene (TCB) 2 hours under 160 ℃.The sample that will contain the solution of described polymkeric substance injects GPC and use filtered containing～1000ppm BHT 1,2,4-trichlorobenzene (TCB) wash-out.With the separation efficiency of a series of narrow MWD polystyrene standard sample calibration post groups, the MW scope of the expection of the sample that this separation efficiency reflection is analyzed and the exclusion limit of post group.Use is～580 to 10,000 from Polymer Laborator ies (Amhers t, MA) acquisition and kurtosis molecular weight (Mp), and 17 individual polystyrene standard samples of 000 produce working curves.Before measuring the retention volume of every kind of polystyrene standard sample, each round calibration flow velocity is thought that the flow velocity marker gives shared peak position (get and just inject the peak).When analytic sample, use the marker peak position corrected flow rate that flows.Following generation working curve (log (Mp) vs. retention volume): be recorded in place, the peak record retention volume in the DRI signal of every kind of PS standard model, and this data set is fitted in the second-order polynomial expression.By using the Mark-Houwink coefficient determination equivalence molecular weight of polyethylene shown in the following table B:

Table B

In the method for this paper, preparation multimodal attitude polyolefin compositions, it comprises the polyolefin component that the first polyolefin component and another kind of at least molecular weight are different from described the first polyolefin component, and preferably consequently the GPC trace has more than a peak or flex point.The character of the multimodal attitude polyolefin compositions of the invention method preparation by the application is by shown in Fig. 1 and 2.

Fig. 1 shows the first polyolefin component of the embodiment 2A that is obtained by the method for using hybrid catalyst system (at this, polyethylene) with oxygen and MWD before alkylaluminium cpd contacts, described hybrid catalyst system comprises dichloro two (1-methyl, 3-butyl cyclopentadienyl) and closes zirconium and two (cyclopentadienyl) chromium.The contriver is surprised to find, although use hybrid catalyst system, only observes a kurtosis.Embodiment 2A preparation has those the first polyolefin component of feature by the metallocenes preparation, has low MWD, at this 3.1 (referring to following embodiment 2A).

Fig. 2 shows from embodiment 2B (at this, the MWD of the multimodal attitude polyolefin compositions that polyethylene) obtains, described embodiment 2B by use comprise dichloro two (1-methyl, 3-butyl cyclopentadienyls) close zirconium and two (cyclopentadienyl) chromium hybrid catalyst system comprise the method acquisition that contacts with triethyl aluminum with oxygen.The contriver is surprised to find, and observes another kind of kurtosis, and this kurtosis is different from described the first polyolefin component aspect molecular weight.At this, viewed new polyolefin component has than the higher molecular weight of the first polyolefin component and does not have usually lower molecular weight tail composition owing to organo-chromium compound.Owing to there not being this lower molecular weight tail composition, so the MWD of multimodal attitude polyolefin compositions (Mw/Mn is 4.24, embodiment 2B, below embodiment part) is unexpectedly narrow, 4.24 (embodiment 2B) for example.

In some embodiments, the preparation of this paper method has 5,000g/mol-600,000g/mol; Preferred 8,000g/mol-400,000g/mo l; Or 10,000g/mo l-300, the first polyolefin component of the Mw of 000g/mol.In some embodiments, it is about 10 that this paper method preparation has about 1.1-, and approximately 2-is about 8, or about the first polyolefin component of the MWD of 2.2-about 5.In some embodiments, the preparation of this paper method has a kurtosis, perhaps has the first polyolefin component of two kurtosis.In some embodiments, in some embodiments, the preparation of this paper method has 5,000g/mol-600,000g/mol; Preferred 8,000g/mol-400,000g/mol; Or 10,000g/mol-300, the Mw of 000g/mol; Approximately 1.1-is about 10, and approximately 2-is about 8, or the about MWD of 2.2-about 5; And have a kurtosis, perhaps have the first polyolefin component of two kurtosis.

In some embodiments, this paper method preparation comprises another kind and has 500,000g/mol-5,000,000g/mol; Preferred 550,000g/mol-2,500,000g/mol; Or 600,000g/mol-1, the multimodal attitude polyolefin compositions of the polyolefin component of the Mw of 000,000g/mol.In some embodiments, this paper method preparation comprises another kind, and to have about 1.1-about 10, and approximately 2-is about 9, or the about multimodal attitude polyolefin compositions of the polyolefin component of the MWD of 2.2-about 6.In some embodiments, the preparation of this paper method comprises the multimodal attitude polyolefin compositions that another kind has the polyolefin component of single kurtosis.In some embodiments, this paper method preparation comprises another kind and has 500,000g/mol-5,000,000g/mol; Preferred 550,000g/mol-2,500,000g/mol; Or 600,000g/mol-1, the Mw of 000,000g/mol; Approximately 1.1-is about 10, and approximately 2-is about 9, or the about MWD of 2.2-about 6; And the multimodal attitude polyolefin compositions with polyolefin component of single kurtosis.

In some embodiments, this paper method preparation comprises and is less than 5wt%, is less than 2.5wt%, or is less than 1wt% and has less than 300,000g/mol, less than 350,000g/mol or less than the multimodal attitude polyolefin compositions of the component of the molecular weight of 375,000g/mol.Have percentage less than the multimodal attitude polyolefin compositions of the molecular weight of 300,000g/mol and can use the technical measurement that the separate stage of the sample of fluoropolymer resin is divided segregation.A kind of such technology is intensification elution fractionation (TREF), such as the people's such as Wild J.Poly.Sci., and Poly.Phys.Ed., vol.20, p.441 (1982) and U.S. Patent number 5,008, described in 204, the document is incorporated herein for reference.In order to measure the percentage that has less than the multimodal attitude polyolefin compositions of the molecular weight of 300,000g/mol, at first use the data that obtain from above-mentioned TREF technology to produce described structure adaptability degree distribution curve.This solubleness distribution curve is the temperature variant graphic representation of part by weight of the multipolymer of dissolving.From this solubleness distribution curve, can measure the percentage that has less than the multimodal attitude polyolefin compositions of the molecular weight of 300,000g/mo l.

In some embodiments, the preparation of this paper method has at least two kurtosis, or the multimodal attitude polyolefin compositions of at least three kurtosis.

In some embodiments, this paper method prepares multimodal attitude polyolefin compositions, and it comprises (i) and has 5,000g/mol-600,000g/mol; Preferred 8,000g/mol-400,000g/mol; Or 10,000g/mol-300, the Mw of 000g/mol; Approximately 1.1-is about 10, and approximately 2-is about 8, or the about MWD of 2.2-about 5; And have a kurtosis, perhaps have the first polyolefin component of two kurtosis; (i i) another kind has 500,000g/mol-5,000,000g/mol; Preferred 550,000g/mol-2,500,000g/mol; Or 600,000g/mol-1, the Mw of 000,000g/mol; Approximately 1.1-is about 10, and approximately 2-is about 9, or the about MWD of 2.2-about 6; And has a polyolefin component of single kurtosis; Wherein said multimodal attitude polyolefin compositions: (a) have about 1.1-about 15, approximately 2-is about 12, or the about MWD of 2.2-about 7.5; (b) comprise and be less than 5wt%, be less than 2.5wt%, or be less than 1wt% and have less than 300,000g/mol, less than 350,000g/mol, or less than the component of the molecular weight of 375,000g/mol; (c) have multimodal attitude molecular weight distribution, preferably have at least two kurtosis, or at least three kurtosis.

Above-mentioned lower molecular weight tail composition is to use organic chromium catalyzer or conventional mixed catalyst, the characteristic of the polymkeric substance that obtains of metallocenes/organic chromium catalyzer for example, and normally undesirable, because described lower-molecular-weight component may cause poor film outward appearance, for example there is gel.In addition, the existence of low-molecular-weight polyolefin in multimodal attitude polyolefin compositions may cause smoldering in die orifice-lip accumulation and the on-line operation.Of the present invention do not have the multimodal attitude polyolefin compositions of this lower molecular weight tail composition to process film forming and pipe at existing installation, and aspect film preparation or for pipe, use to show good workability, and can provide the have low gel level film product of (excellent FQR).FQR is the qualitative ordering of gel level, from 10 to 60, and wherein 10FQR indication gel-free and 60FQR indicate the gel of unacceptable high quantity.In the embodiment of this paper, multimodal attitude polyolefin compositions of the present invention can have less than 20FQR the gel level of 30FQR or 40FQR.Multimodal attitude polyolefin compositions of the present invention can also show the tendency of smoldering in the accumulation of die orifice-lip and the on-line operation that reduces.Therefore, multimodal attitude polyolefin compositions demonstration of the present invention is better than using for example polyolefinic unexpected advantage of multimodal attitude of metallocenes/organic chromium catalyzer preparation of conventional mixed catalyst.

Mixed catalyst composition and component

In the description of this paper, catalyzer can be described as catalyst precursor, procatalyst compound or transistion metal compound, and these terms use interchangeably.Polymerisation catalyst system is to make monomer polymerization become the catalyst system of polymkeric substance." catalyst system " is at least a catalyst compound, at least a activator, optional activator promotor and the combination of solid support material." anion ligand " is the electronegative part of contributing one or more electron pairs for metal ion." neutral donor part " is the part with neutral charge of contributing one or more electron pairs for metal ion.

Concerning the object of the invention and claim purpose thereof, when catalyst composition was described as comprising the indifferent equilibrium form of component, the ionic species that it will be understood by those skilled in the art that component was to produce the form of polymkeric substance with monomer reaction.Concerning the object of the invention and claim purpose thereof, " alkyl that replaces " is the group that is made of carbon and hydrogen, and wherein at least one hydrogen is substituted by heteroatoms.For the present invention and appended claims, " alkoxy radical " comprises that wherein alkyl is C ₁-C ₁₀Those of alkyl.Alkyl can be straight chain, side chain or cyclic alkyl.Alkyl can be saturated or undersaturated.In some embodiments, alkyl can comprise at least one aromatic group.

Loading type hybrid catalyst system of the present invention comprises: (i) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; (ii) activator; (iii) at least a organic chromium polymerizing catalyst; (iv) solid support material; Wherein therein under the described activated polymerizing condition of polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein with molecular switch, after the molecular switch that preferably comprises oxygen and alkylaluminium cpd contacts, and under polymerizing condition, the organic chromium polymerizing catalyst lacks 50% than the active as many as of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal.

The polymerizing catalyst that (i) comprises the 4th family or the 5th group 4 transition metal below is discussed; (ii) activator; (iii) organic chromium polymerizing catalyst; (iv) each in the solid support material.

(i) comprise the polymerizing catalyst of the 4th family or the 5th group 4 transition metal

The invention provides the loading type mixed catalyst composition that comprises polymerizing catalyst, described polymerizing catalyst comprises the 4th family or the 5th group 4 transition metal; Preferred Ti, V, Zr or Hf; Preferred Ti, Zr or Hf; Or preferred Zr or Hf.In some embodiments, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal can be metalloscene catalyst.Metalloscene catalyst is defined as the cyclopentadienyl structure division (or the cyclopentadienyl structure division that replaces) with at least one π-keyed jointing, the more generally organometallic compound of the structure division of the cyclopentadienyl structure division of two π-keyed jointings or replacement.This structure division that comprises other π-keyed jointing is indenyl or fluorenyl or derivatives thereof for example.

Metalloscene catalyst

In some embodiments, the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is expressed from the next:

L ^AL ^BMX _n (I)；

Or

L ^AA*L ^BMX ⁿ (I I)；

Wherein M is the 4th family or the 5th group 4 transition metal, and preferred M is Ti, V, Zr or Hf; Preferred Ti, Zr or Hf; Or preferred Zr or Hf;

Ligand L ^AAnd L ^BBe open, acyclic or condensed ring or ring system, comprise that the cyclopentadienyl ligands, the heteroatoms that do not replace or replace replace and/or contain heteroatomic cyclopentadienyl ligands;

Each X is leavings group;

A* is the bridging base; With

N is 0,1,2 or 3.

In one embodiment, L ^AAnd L ^BCan be any ligand structure that can carry out with M π-keyed jointing, such as indenes, fluorenes, phenyl, benzyl etc.In another embodiment, L ^AAnd L ^BCan comprise one or more heteroatomss, for example, nitrogen, silicon, boron, germanium, sulphur and phosphorus, it is combined with carbon atom and forms ring or ring system open, acyclic or that preferably condense, and for example, heterocyclic pentylene Kiev helps part.Other L ^AAnd L ^BPart includes but not limited to aminate, phosphide, alkoxide, fragrant oxide compound, imines compound, phenolate thing (carbolides), boride (borollides), porphyrin, phthalocyanine, corrin and other Polyazamacrocycle.Independently, each L ^AAnd L ^BCan be identical or different.In an embodiment of general formula (I), L ^AOr L ^BIn only existence.

Each L ^AAnd L ^BCan not replace independently or replace has at least one R* substituting group, wherein replaces to refer to L ^AAnd/or L ^BOn (for example, cyclopentadiene, indenes, fluorenes, phenyl, benzyl etc.) at least one (perhaps at least 2,3,4,5,6,7,8 or 9) hydrogen base is replaced by R*.The limiting examples of substituent R * comprises and is selected from hydrogen, or the straight or branched alkyl, thiazolinyl, alkynyl; cycloalkyl, aryl, acyl group; aryl, alkoxyl group, aryloxy; the alkyl sulfenyl, dialkyl amido, alkoxy carbonyl; aryloxycarbonyl, formamyl, alkyl or dialkyl-7-amino formyl radical; acyloxy, amido, one or more in amino or their combination of virtue.In a preferred embodiment, substituent R * has at the most 50 non-hydrogen atoms, preferred 1-30 carbon, and they can also replace halogen or heteroatoms etc.The limiting examples of alkyl substituent R* comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc., comprises all their isomer, such as the tertiary butyl, sec.-propyl etc.Other alkyl comprises methyl fluoride, fluoro ethyl, and two fluoro ethyls, the iodine propyl group, the bromine hexyl, the organic quasi-metal group that chlorobenzyl and alkyl replace comprises trimethyl silyl, trimethylammonium germyl, methyl diethylsilane base etc.; Organic quasi-metal group with brine alkyl replaces comprises three (trifluoromethyl)-silyls, methyl-two (difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Two replace boron group comprises for example dimethyl boron; Two replace the pnicogen group, comprise dimethyl amine, dimethyl phosphine, pentanoic, aminomethyl phenyl phosphine; The sulfur family group comprises methoxyl group, oxyethyl group, propoxy-, phenoxy group, dimethyl sulphide and diethyl sulfide.Non-hydrogen substituent R * comprises atoms carbon, silicon, and boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur, or germanium etc. comprise alkene, such as but not limited to the unsaturated substituting group of olefinic, comprise the part of ethenyl blocking, fourth-3-thiazolinyl for example, third-2-thiazolinyl, oneself-the 5-thiazolinyl etc.In addition, in some embodiments, at least two R* groups, preferred two adjacent R groups can be connected to form has 3-30 ring structure that is selected from the atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or their combination.In other embodiments, R* at one end forms two bases of carbon σ key with the L keyed jointing and with metal M.Especially preferred R* substituting group comprises C ₁-C ₃₀Alkyl, heteroatoms or contain phenyl, benzyl (benzyl that comprises replacement), cyclohexyl, cyclo-dodecyl, norcamphyl and their all isomer of heteroatomic group (preferable methyl, ethyl), propyl group (comprising sec.-propyl, sec.-propyl), butyl (comprising the tertiary butyl and sec-butyl), neo-pentyl, cyclopentyl, hexyl, octyl group, nonyl, decyl, phenyl, replacement.

Part (L ^AAnd L ^B) limiting examples comprise cyclopentadienyl ligands, ring penta phenanthryl part, indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, dibenzo [b; h] assorted benzene (bora tobenzene) part of fluorenyl ligand, benzo [b] fluorenyl ligand, cyclooctatetraene ylidene ligands, cyclopentano cyclododecene part, nitrence ylidene ligands, azulene part, pentalene part, phosphoryl part, phosphinimine, pyrryl part, pyrazolyl part, carbazyl part, boron etc.; the hydrogenated version that comprises them, for example tetrahydro indenyl part.Preferably, L ^AAnd L ^BCyclopentadienyl ligands, indenyl ligands, benzindene ylidene ligands and/or fluorenyl ligand.

Other part can with metal M keyed jointing, for example at least one leavings group X.In one embodiment, X is the single anion ligand with the M keyed jointing.The oxidation state that depends on metal, the value of n are 0,1,2 or 3, thus above formula (I) and (II) represent the neutral ligand metallocene catalyst compound.The limiting examples of X leavings group comprises weak base, carboxylate salt for example, and diene contains the alkyl of 1-20 carbon atom, hydride or halogen etc., or their combination.In another embodiment, two or more X-shapeds become the part of condensed ring or ring system.Other example of X part comprises those substituting groups for above-mentioned R*, and comprises cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene (two X), pentamethylene (two X), methene base (two X), methoxyl group, oxyethyl group, propoxy-, phenoxy group, two (methylphenylamines), dimethyl amine compound, dimethyl phosphorus base etc.Preferably, X is alkyl or halogenide.More preferably, X is chlorine, bromine, benzyl, phenyl or C ₁-C ₁₂Alkyl (for example methyl, ethyl, propyl group, butyl, hexyl and octyl group).

In formula (II), bridging base A* is with L ^AAnd L ^BBridging.The limiting examples of bridging base A* comprises and contains at least one 13-16 family atom, such as but not limited at least one bridging base in carbon, oxygen, nitrogen, silicon, aluminium, boron, germanium and tin atom or its combination, is commonly referred to the divalence structure division.Preferably, bridging base A* contains carbon, silicon or germanium atom, and most preferably, A* contains at least one Siliciumatom or at least one carbon atom.Bridging base A* can also contain above-mentioned substituent R *, comprises halogen and iron.The limiting examples of bridging base A* can be by following expression: R' ₂C, R' ₂Si, R' ₂Ge, R' ₂CCR' ₂, R' ₂CCR' ₂CR' ₂, R' ₂CCR' ₂CR' ₂CR' ₂, R'C=CR', R'C=CR'CR' ₂, R' ₂CCR'=CR'CR' ₂, R'C=CR'CR'=CR', R'C=CR'CR' ₂CR' ₂, R' ₂CSiR' ₂, R' ₂SiSiR' ₂, R ₂CSiR' ₂CR' ₂, R' ₂SiCR' ₂SiR' ₂, R'C=CR'SiR' ₂, R' ₂CGeR' ₂, R' ₂GeGeR' ₂, R' ₂CGeR' ₂CR' ₂, R' ₂GeCR' ₂GeR' ₂, R' ₂SiGeR' ₂, R'C=CR'GeR' ₂, R'B, R' ₂C-BR', R' ₂C-BR'-CR' ₂, R' ₂C-O-CR' ₂, R' ₂CR' ₂C-O-CR' ₂CR' ₂, R' ₂C-O-CR' ₂CR' ₂, R' ₂C-O-CR'=CR', R' ₂C-S-CR' ₂, R' ₂CR' ₂C-S-CR' ₂CR' ₂, R' ₂C-S-CR' ₂CR' ₂, R' ₂C-S-CR'=CR', R' ₂C-Se-CR' ₂, R' ₂CR' ₂C-Se-CR' ₂CR' ₂, R' ₂C-Se-CR ₂CR' ₂, R' ₂C-Se-CR'=CR', R' ₂C-N=CR', R' ₂C-NR'-CR' ₂, R' ₂C-NR'-CR' ₂CR' ₂, R' ₂C-NR'-CR'=CR', R' ₂CR' ₂C-NR'-CR' ₂CR' ₂, R' ₂C-P=CR' and R' ₂C-PR'-CR' ₂, wherein R' is hydrogen or contains C ₁-C ₂₀Alkyl, halo carbon back, halo carbon back, silyl carbon back or the germyl carbon back substituting group of replacement of alkyl, replacement, and two or more adjacent R' randomly can engage form replace or unsubstituted, saturated, part is unsaturated or aromatics, ring-type or many ring substituents.In one embodiment, the bridged metallocene catalyst compound of formula (I I) has two or more bridging bases A* (EP664301B1).Preferably, A* is the bridging base of carbon containing or silicon, dialkyl group silyl for example, and preferred A* is selected from CH ₂, CH ₂CH ₂, CH (CH ₃) ₂, SiMe ₂, SiPh ₂, SiMePh, Si (CH ₂) ₃, (Ph) ₂CH, (p-(Et) ₃SiPh) ₂CH and Si (CH ₂) ₄

In a preferred embodiment, catalyst compound is represented by following formula (III):

L ^A(A*) _mL ^BMX _n (I I I)；

Wherein M is zirconium, hafnium, vanadium or titanium;

Ligand L ^AAnd L ^BIt is the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement;

Each X is selected from hydride; Replace or unsubstituted C ₁-C ₃₀Alkyl; Alkoxide; The virtue oxide compound; Aminate; Halogenide; Phosphide; Single anion ligand with one of the 14th family's organic quasi-metal; Or two X can form alkylidene or Cyclometalated alkyl or other two anion ligand together;

A* is the bridging base;

M is 0 or 1; With

N is 0,1,2 or 3.

In some embodiments, L ^AAnd L ^BCan replace has substituent R ", each radicals R " is C independently ₁-C ₃₀Alkyl, wherein said C ₁-C ₃₀Alkyl is aliphatic series or aromatics preferably.In some embodiments, R " is C ₁-C ₂₀Alkyl, C ₁-C ₁₅Alkyl, C ₄-C ₃₀Alkyl, C ₄-C ₃₀Alkyl, C ₁-C ₈Alkyl and C ₄-C ₈Alkyl.R " limiting examples comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc.

In some embodiments, when m is 1, A* bridging L ^AAnd L ^B, and be selected from R' ₂C, R' ₂Si, R' ₂Ge, R' ₂CCR' ₂, R' ₂CCR' ₂CR' ₂, R' ₂CCR' ₂CR' ₂CR' ₂, R'C=CR', R'C=CR'CR' ₂, R' ₂CCR'=CR'CR' ₂, R'C=CR'CR'=CR', R'C=CR'CR' ₂CR' ₂, R' ₂CSiR' ₂, R' ₂SiSiR' ₂, R ₂CSiR' ₂CR' ₂, R' ₂SiCR' ₂SiR' ₂, R'C=CR'SiR' ₂, R' ₂CGeR' ₂, R' ₂GeGeR' ₂, R' ₂CGeR' ₂CR' ₂, R' ₂GeCR' ₂GeR' ₂, R' ₂S i GeR' ₂, R'C=CR'GeR' ₂, R'B, R' ₂C-BR', R' ₂C-BR'-CR' ₂, R' ₂C-O-CR' ₂, R' ₂CR' ₂C-O-CR' ₂CR' ₂, R' ₂C-O-CR' ₂CR' ₂, R' ₂C-O-CR'=CR', R' ₂C-S-CR' ₂, R' ₂CR' ₂C-S-CR' ₂CR' ₂, R' ₂C-S-CR' ₂CR' ₂, R' ₂C-S-CR'=CR', R' ₂C-Se-CR' ₂, R' ₂CR' ₂C-Se-CR' ₂CR' ₂, R' ₂C-Se-CR ₂CR' ₂, R' ₂C-Se-CR'=CR', R' ₂C-N=CR', R' ₂C-NR'-CR' ₂, R' ₂C-NR'-CR' ₂CR' ₂, R' ₂C-NR'-CR'=CR', R' ₂CR' ₂C-NR'-CR' ₂CR' ₂, R' ₂C-P=CR' and R' ₂C-PR'-CR' ₂, wherein R' is hydrogen or contains C ₁-C ₆Alkyl, halo carbon back, halo carbon back, silyl carbon back or the germyl carbon back substituting group of replacement of alkyl, replacement.

In another embodiment, the metalloscene catalyst by formula (IV) expression is useful at this paper.

L ^AA*J*MX _n (IV)

Wherein M is zirconium, hafnium, vanadium or titanium;

L ^AReplacement or the unsubstituted part with the M keyed jointing; L ^AIt preferentially is the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement;

Each X is the leavings group with the M keyed jointing;

J* is and containing of M keyed jointing of heteroatomic part;

A* is the bridging base;

A* and J* and L ^AKeyed jointing; With

N is 0,1,2 or 3.

In formula (IV), L ^A, A* and J* form the condensed ring system.J* contains the heteroatoms that is selected from 13-16 family, preferred nitrogen, boron, sulphur, oxygen, aluminium, silicon, phosphorus and tin.In some embodiments, J* contains the heteroatoms with ligancy 3 that is selected from the 15th family or the heteroatoms with ligancy 2 that is selected from the 16th family.Preferably, J* contains nitrogen, phosphorus, oxygen or sulphur atom, and nitrogen is most preferred.These examples that contain heteroatomic ligand metal cyclopentadienyl catalyst compound are described in WO96/33202; WO96/34021; WO97/17379; WO98/22486; EP-A1-0874005; U.S. Patent number 5,233,049; 5,539,124; 5,554,775; 5,637,660; 5,744,417; In 5,756,611 and 5,856,258; They all are incorporated herein for reference.

In a preferred embodiment, catalyst compound is by representing with following formula (V):

Wherein:

M is Zr, Hf or Ti;

Cp is cyclopentadienyl rings;

J* is the 15th or 16 family's heteroatomss of the 15th or 16 family's heteroatomss or replacement;

Each X is selected from hydride; Replace or unsubstituted C ₁-C ₃₀Alkyl; Alkoxide; The virtue oxide compound; Aminate; Halogenide or phosphide; The single anion ligand of one of the 14th family's organic quasi-metal; Or two X can form alkylidene or Cyclometalated alkyl or other two anion ligand together;

Y is 0 or 1;

When y=1, A* be simultaneously with the bridging base of Cp and J covalency keyed jointing;

L is the optional neutral Lewis base beyond dewatering, for example alkene, diene, aryne, amine, phosphine, ether or sulfide, and for example amine, phosphine, ether, for example, diethyl ether, tetrahydrofuran (THF), xylidine, aniline, three methylphosphines and n-Butyl Amine 99; With

W is the number of 0-3.

When using in the formula (V), Cp comprises cyclopentadiene part and their analogue that can carry out with M π-keyed jointing, and for example, Cp comprises indenes and fluorenes.In some embodiments, when y was 0, Cp can replace the radicals R * that has 0-5 to replace; With when y is 1, Cp can replace the radicals R * that has 1-4 to replace; Comprise independently with the radicals R * of each replacement and to be selected from one of following group: the alkyl, silyl-alkyl or the germyl-alkyl that contain 1-30 carbon, silicon or germanium atom, the alkyl that replaces, silyl-alkyl or germyl-alkyl, wherein one or more hydrogen atoms can be closed base (phosphido), alkoxyl group, aryloxy by halogen radical, amido, phosphorus contain lewis acidity or any group of basic functionality in one or more replacements; C ₁-C ₃₀The metalloid radicals that alkyl replaces, wherein said metalloid is selected from one of the periodic table of elements the 14th family; Halogen radical; Amido; Phosphorus closes base; Alkoxyl group or boron alkyl close base (alkylborido); Or Cp is cyclopentadienyl rings, wherein at least two adjacent R* bases can in conjunction be connected the carbon atom that is connected with them form can be saturated, part is unsaturated or aromatics, and/or replacement or unsubstituted C ₄-C ₂₀Ring system, described replacement are elected one or more R* bases as, as surface defined.

In some embodiments, when J* is the 15th family's element, and y is 1, or the 16th family's element and y are 0 o'clock, and J* can replace a R' base; Or when J* be the 15th family's element and y when being 0, J* can replace two R' bases; Or when J* be the 16th family's element and y when being 1, J* can be unsubstituted; Each R' base is to be selected from following group independently: the alkyl, silyl-alkyl or the germyl-alkyl that contain 1-30 carbon, silicon or germanium atom; The alkyl that replaces, silyl-alkyl or germyl-alkyl, wherein one or more hydrogen atoms are closed base, alkoxyl group, aryloxy or boron alkyl by halogen radical, amido, phosphorus and close one or more replacements in the base, preferably, all R' and J* via primary, the second month in a season or aromatic carbon atom keyed jointing, and not directly with silicon or germanium atom keyed jointing.

A* as surface defined, in some embodiments, usually comprise at least a the 13rd, 14 or 15 family's elements for example carbon, silicon, boron, germanium, nitrogen or phosphorus and additional substituent R * as surface defined, so that finish the valency of described the 13rd, 14 or 15 family's elements.

In a preferred embodiment, M is Ti; X is chlorine, bromine, benzyl, phenyl or C ₁-C ₁₂Alkyl (for example methyl, ethyl, propyl group, butyl, hexyl and octyl group); Y is 1; A* is the bridging base that comprises carbon or silicon, dialkyl group silyl for example, and preferred A* is selected from CH ₂, CH ₂CH ₂, CH (CH ₃) ₂, S iMe ₂, S iPh2, S iMePh, S i (CH ₂) ₃, (Ph) ₂CH, (p-(Et) ₃S iPh) ₂CH and Si (CH ₂) ₄J* is N-R', and wherein R' is C ₁-C ₃₀Alkyl, for example cyclo-dodecyl, cyclohexyl, butyl (comprising the tertiary butyl and sec-butyl), benzyl (benzyl that comprises replacement), methyl, ethyl, amyl group, hexyl, neo-pentyl, cyclopentyl, decyl, propyl group (comprising sec.-propyl, sec.-propyl), norcamphyl and phenyl (phenyl that comprises replacement, for example 3-tert-butyl-phenyl, 2-aminomethyl phenyl); With Cp be the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement.Two adjacent substituents can form monokaryon or polycyclic ring.

The polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal that other is particularly useful comprises: dichloro racemize-dimethyl-silyl-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium or dimethyl racemize-dimethyl-silyl-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium, dichloro racemize-dimethyl-silyl-two (indenyl) closes zirconium or dimethyl racemize-dimethyl-silyl-two (indenyls) close zirconium, dichloro racemize-ethidine-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium or dimethyl racemize-ethidine-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium, dichloro racemize-ethidine-two (indenyl) closes zirconium or dimethyl racemize-ethidine-two (indenyls) close zirconium, dichloro meso-dimethyl-silyl-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium or dimethyl meso-dimethyl-silyl-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium, dichloro meso-dimethyl-silyl-two (indenyl) closes zirconium or dimethyl meso-dimethyl-silyl-two (indenyls) close zirconium, dichloro meso-ethidine-two (4,5,6, the 7-tetrahydro indenyl) closes zirconium or dimethyl meso-ethidine-two (4,5,6,7-tetrahydro indenyl) closes zirconium, dichloro meso-ethidine-two (indenyl) closes zirconium or dimethyl meso-ethidine-two (indenyls) close zirconium.Other preferred single-site catalysts comprises above-mentioned racemize or the meso catalyzer of the indenyl ligands with replacement in various degree.

The metallocenes that other preferred metallocenes comprises bridging not for example dichloro two (cyclopentadienyl) closes zirconium, dimethyl two (cyclopentadienyl) closes zirconium, dichloro two (1,2-dimethyl cyclopentadienyl) closes zirconium, dimethyl two (1,2-dimethyl cyclopentadienyl) closes zirconium, dichloro two (1,3-dimethyl cyclopentadienyl) closes zirconium, dimethyl two (1,3-dimethyl cyclopentadienyl) closes zirconium, two (the 1-methyl of dichloro, 3-butyl cyclopentadienyl) closes zirconium, two (the 1-methyl of dimethyl, 3-butyl cyclopentadienyl) closes zirconium, dichloro two (1,2,3-trimethylammonium cyclopentadienyl) closes zirconium, dimethyl two (1,2,3-trimethylammonium cyclopentadienyl) closes zirconium, dichloro two (1,2,4-trimethylammonium cyclopentadienyl) closes zirconium, dimethyl two (1,2,4-trimethylammonium cyclopentadienyl) closes zirconium, dichloro two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium, dimethyl two (1,2,3,4-tetramethyl-ring pentadienyl) closes zirconium, dichloro two (pentamethyl-cyclopentadienyl) closes zirconium, dimethyl two (pentamethyl-cyclopentadienyl) closes zirconium, dichloro two (propyl group cyclopentadienyl) closes hafnium, dimethyl two (propyl group cyclopentadienyl) closes the analogue of hafnium and other replacement.

(ii) activator

The hybrid catalyst system that use comprises activator within the scope of the present invention; Preferably, described activator will comprise the polymerizing catalyst activation of the 4th family or the 5th group 4 transition metal.In the embodiment of this paper, described activator comprises aikyiaiurnirsoxan beta, comprises the aikyiaiurnirsoxan beta of modification, and non-coordination anion (NCA).

Aikyiaiurnirsoxan beta generally is to contain-A l (R ¹The oligomeric compound of)-O-subelement, wherein R ¹It is alkyl; Preferred R ¹Methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-; Or more preferably R ¹It is methyl.The example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.Can also use the mixture of different aikyiaiurnirsoxan beta and modified alumoxane.Can preferably use visually transparent aikyiaiurnirsoxan beta.Can filter muddiness or gel aikyiaiurnirsoxan beta maybe can be from the transparent aikyiaiurnirsoxan beta of this turbid solution decantation with the preparation clear solution.Another kind of aikyiaiurnirsoxan beta is can trade(brand)name Modified Methyla lumoxane type 3A (Akzo Chemicals, Inc., Chicago, IL) be purchased at U.S. Patent number 5, modified methylaluminoxane (MMAO) the promotor type 3A of containing for 041,584 time.

Can be used as the aikyiaiurnirsoxan beta component of activator normally by general formula (R ^x-Al-O) _nThe oligomeric aluminum compound of expression, it is ring compound, or by R ^x(R ^x-Al-O) _nAlR ^x ₂The oligomeric aluminum compound of expression, it is straight chain compound.In described aikyiaiurnirsoxan beta general formula, R ^xC independently ₁-C ₂₀Alkyl, for example, methyl, ethyl, propyl group, butyl, amyl group, their isomer etc., " n " is the integer of 1-50.Most preferably, R ^xThat methyl and " n " are at least 4.Methylaluminoxane and modified methylaluminoxane are most preferred.For further describing, referring to EP0279586; EP0594218; EP0561476; WO94/10180; With U.S. Patent number 4,665,208; 4,874,734; 4,908,463; 4,924,018; 4,952,540; 4,968,827; 5,041,584; 5,091,352; 5,103,031; 5,157,137; 5,204,419; 5,206,199; 5,235,081; 5,248,801; 5,329,032; 5,391,793 and 5,416,229.

The activator that use is expressed from the next is within the scope of the present invention:

(R' _xM(JY) _y) _n (X)

Or

[((JY) _yR' _x) _nM-O-M((R' _x(JY) _y) _n] _m (XI)

Or

(OMR' _x(JY) _y) _n (XI I)

In formula (X), n is 1 or 2.In formula (XI), n is that 2, m is the number of 1-10.In formula (XII), n is 1-1000, preferred 1-100, and more preferably 5-50 is more preferably the number of 5-25.(x+y)=formula (X) in the valency of M.(x+y)=formula (XI) in the valency-1 of M.(x+y)=formula (XII) in the valency-2 of M.

In formula (X), (XI) with (XII), M is the 13rd family's atom, preferred boron or aluminium, more preferably aluminium.(JY) represent the heterocyclic ligand that is connected with M.In (JY), Y represents heterocyclic ligand and J and represents at least one and be included in heteroatoms among the part JY.M can with any atom keyed jointing that is included among the Y, but preferred and heteroatoms J keyed jointing.Preferably, J is the atom that is selected from the 15th or 16 families, and more preferably J is nitrogen, oxygen or sulphur, and most preferably J is nitrogen.(JY) limiting examples comprises pyrryl, imidazolinyl, pyrazolyl, pyrrolidyl, purine radicals, carbazyl and indyl.

Heterocyclic ligand (JY) can not replace or replaces a substituting group or substituent combination.The substituent example that is fit to comprises alkyl, acyl group, aroyl, alkoxyl group, aryloxy, alkyl sulfide, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl or dialkyl-7-amino formyl radical, acyloxy, amido, virtue amino, straight chain, side chain or cyclic alkylidene or their combination that hydrogen, halogen, straight or branched alkyl, alkenyl or alkynyl, cycloalkyl, aryl, aryl replace.Described substituting group also can replace halogen, especially fluorine, or heteroatoms etc.

Substituent limiting examples comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc., comprises all their isomer, for example, and the tertiary butyl, sec.-propyl etc.Substituent other example comprises fluoro methyl, fluoro ethyl, two fluoro ethyls, iodo propyl group, bromine hexyl and chloro benzyl.

Preferably, the one or more positions on the heterocyclic ligand (JY) replace the group that halogen atom or halogen atom-containing are arranged, and preferred halogen is chlorine, bromine or fluorine, more preferably, and bromine or fluorine, most preferably fluorine.Be more preferably, substituting group is fluorine atom or fluoro aryl, for example fluoridizes phenyl.

Each R' is the substituting group with the M keyed jointing independently.Substituent R ' the limiting examples of base comprises hydrogen, straight or branched alkyl or alkenyl, alkynyl, cycloalkyl, aryl, acyl group, aroyl, alkoxyl group, aryloxy, alkyl sulfide, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl or dialkyl-7-amino formyl radical, acyloxy, amido, virtue amino, straight chain, side chain or cyclic alkylidene or their combination.Each R' can be methyl, ethyl, and propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl comprise all their isomer, the tertiary butyl for example, sec.-propyl etc.Other R' substituting group that is fit to can comprise alkyl, for example fluoro methyl, fluoro ethyl, two fluoro ethyls, iodo propyl group, bromo hexyl, chloro benzyl; The organic quasi-metal base that alkyl replaces comprises trimethyl silyl, trimethylammonium germyl, methyl diethylsilane base etc.; The organic quasi-metal base that the halo carbon back replaces comprises three (trifluoromethyl)-silyls, methyl-two (difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Dibasic boryl comprises for example dimethyl boron, and dibasic pnicogen base comprises dimethylamine, dimethylphosphine, pentanoic, aminomethyl phenyl phosphine; With the chalcogen base, comprise methoxyl group, oxyethyl group, propoxy-, phenoxy group, methyl-sulfide and diethyl sulfide.

Other R' substituting group can comprise atoms carbon, silicon, boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur or germanium etc.Substituent R ' base also comprises alkene, such as but not limited to, the unsaturated substituting group of olefinic, comprises the part of vinyl-end-blocking, such as fourth-3-thiazolinyl, third-2-thiazolinyl, oneself-5-thiazolinyl etc.In addition, at least two R' groups, preferred two adjacent R' groups can be connected to form and have 3-30 ring structure that is selected from the atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or their combination.In addition, substituent R ' for example the 1-butane group can form carbon bond with metal M.In one embodiment, each R' replaces or unsubstituted alkyl and/or replacement or unsubstituted aryl, and preferably each R' is the alkyl that contains 1-30 carbon atom.

In a specific embodiment, at formula (X), (XI) or (XII), M is Al or B, preferred Al, J is included in the nitrogen-atoms among the heterocyclic ligand Y, preferably (JY) replaces or unsubstituted indyl, wherein said substituting group is hydrogen preferably, halogen, alkyl, halogenation or partially halogenated alkyl, aryl, halogenation or partially halogenated aryl, the alkyl that aryl replaces, the alkyl that halogenation or partially halogenated aryl replace or their combination, preferred J and M keyed jointing, R' replaces or unsubstituted alkyl and/or replacement or unsubstituted aryl, preferably contains the alkyl of 1-30 carbon atom.

In another specific embodiment, in formula (X), (XI) or (XII), M is Al or B, preferred Al, J is with the nitrogen-atoms of M keyed jointing and is included among the heterocyclic ligand Y, and wherein said heterocyclic ligand (JY) is unsubstituted heterocyclic ligand.In another embodiment, one or more positions on the heterocyclic ligand replace the group that has chlorine, bromine and/or fluorine or replacement that chloride, bromine and/or fluorine are arranged, more preferably replace the group that fluorine-containing or fluorine are arranged, R' replaces or unsubstituted alkyl and/or replacement or unsubstituted aryl, preferably contains the alkyl of 1-30 carbon atom.In another embodiment, (JY) be the perhalogenation part.

In another specific embodiment, in formula (X), (XI) or (XI I), M is Al or B, preferred Al, J is with the nitrogen-atoms of M keyed jointing and is included among the heterocyclic ligand Y, and wherein said heterocyclic ligand (JY) is unsubstituted heterocyclic ligand.In another embodiment, the one or more positions on the heterocyclic group replace halogen for example chlorine, bromine and/or fluorine atom, or replaces halogen atom is arranged, for example the group of chloride, bromine and/or fluorine.More preferably, described heterocyclic group replaces fluorine or fluoro-containing group.In another embodiment, at least one R' and solid support material, preferential oxidation silicon carrier material keyed jointing.

Minimum activator and the ratio of transition metal (polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal) are mol ratio 1:1.Optional preferred proportion comprises the highest 5000:1, preferred the highest 500:1, preferred the highest 200:1, preferably the highest 100:1, or preferred 1:1-50:1.

Other preferred activator is the NCA activator.For the present invention and appended claims, " non-coordination anion " (NCA) limits the negatively charged ion that refers to not to be coordinated in the catalyst metal positively charged ion or only faintly be coordinated in described metallic cation.NCA is the coordination of weak ground so that neutral Lewis base enough, and for example olefinic or acetylene series unsaturated monomer can be replaced it from catalyst center.Can use or be included in this non-coordination anion with any metal or the metalloid that the catalyst metal positively charged ion forms the complex compound of compatible, weak coordination.Suitable metal includes, but are not limited to aluminium, gold and platinum.The metalloid that is fit to includes, but not limited to boron, aluminium, phosphorus and silicon.The subclass of NCA comprises stoichiometric activator, and they can be neutrality or ionic.Term " ion activation agent " and " agent of stoichiometry ion activation " can be used interchangeably.Equally, term " neutral stoichiometry activator " and " Lewis acid activation agent " also can be used interchangeably.

Use ionization or stoichiometry activator, the non-coordination anion of neutrality or ionic (defined in U.S. Patent Publication No. 2009-0318644) is four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, the assorted borine negatively charged ion (WO98/43983) of many halogenations, boric acid (U.S. Patent number 5 for example, 942,459) or their combination also within the scope of the present invention.

Preferably, activator is four (perfluor naphthyl) boric acid N, N-dimethyl puratized agricultural spray, four (perfluorinated biphenyl) boric acid N, N-dimethyl puratized agricultural spray, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dimethyl puratized agricultural spray, four (perfluor naphthyl) boric acid triphenylcarbenium, four (perfluorinated biphenyl) boric acid triphenylcarbenium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenylcarbenium, four (perfluorophenyl) boric acid triphenylcarbenium or four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray.Preferred activator is four (pentafluorophenyl group) boric acid N, N-dimethyl puratized agricultural spray.For the useful additional activator of this paper, see also U.S. Patent Publication No. 2009-0318644.The activator of metal oxide carrier combination, for example those disclosed also can be used for the embodiment of this paper among the WO/1996/004319.

The ratio of typical NCA activator and transition metal (total mole of transition metal, i.e. the mole number sum of the 4th family or the 5th group 4 transition metal and chromium in the hybrid catalyst system) is mol ratio 1:1.Optional preferable range comprises 0.1:1-100:1, perhaps 0.5:1-200:1, perhaps 1:1-500:1, perhaps 1:1-1000:1.The scope that is particularly useful is 0.5:1-10:1, and preferred 1:1 is to 5:1.

(iii) organic chromium polymerizing catalyst

Can use any organic chromium polymerizing catalyst.Can be used for organic chromium polymerizing catalysts more of the present invention has with one of following formula:

(i) CrR _n, wherein R is C ₁-C ₂₀Alkyl; Wherein n is selected from 2,3 and 4; Or

(ii) CrL _AL _B, L wherein _AAnd L _BBe independently selected from the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement; Or

(iii) Cr (XR _n) _m, wherein each X is N, O, P or S independently, preferred N; Each n is 1 or 2 independently; M is 1 or 2; Each R is the aryl of alkyl, aryl or the replacement of alkyl, replacement independently, as long as at least one R group is the aryl of aryl or replacement; Preferred each R is selected from and replaces or unsubstituted phenyl, naphthyl, xenyl, phenyl ether, tolyl or benzophenone phenyl; More preferably each R group is selected from naphthyl, phenyl, xenyl, fluorophenyl and tolyl.

The example of useful organic chromium polymerizing catalyst comprises: two benzene chromium (0); Two cumene chromium (0); Two (sym-trimethylbenzene) chromium (0); Bicyclic pentadiene chromium (two luxuriant chromium); Two (methyl cyclopentadienyl) chromium (II); Two (two (trimethyl silyl) allyl groups of 1,3-) chromium (II); Two (trimethyl silyl methyl) chromium (II); Two (2,5-dimethyl pentadiene base) chromium (II); ((tetramethyl-ring pentadienyl) (tertiary butyl is amino) dimetylsilyl) (trimethyl silyl-methyl) chromium (II); Diallyl chromium (II); (pentamethyl-cyclopentadienyl) two (benzyl) chromium (II) pyridine adduct; Triallyl chromium (III); Three (two (trimethyl silyl) methyl) chromium (III); (pentamethyl-cyclopentadienyl) two (trimethyl silyl methyl) chromium (III); Tetraallyl chromium (IV); Tetramethyl-chromium (IV); Four (benzyl) chromium (IV); "four news" (new ideas amyl group chromium (IV), four (three silyl methyl) chromium (IV); Four (sec.-propyl) chromium (IV); Four (2-phenyl-2-methyl-propyl) chromium (IV); Or their any combination.

Can be used for exemplary organic chromium polymerizing catalyst of the present invention and comprise following compound: (η ⁶-C ₆H ₆) Cr (CO) ₃; [(η ⁵-C ₅H ₅) Cr (CO) ₃] ₂Cr (tertiary butyl) ₄Cr (CH ₂CPh ₃) ₄(wherein Ph=phenyl); Cr (MeC ₆H ₅) ₂(wherein Me=methyl); Cr (Me ₂C ₆H ₄) ₂Cr (Me ₃C ₆Η ₃) ₂Cr (C ₆Me ₆) ₂Cr (η ⁶-naphthalene) ₂Their regional isomer and steric isomer; Or their any combination.In one aspect of the invention, the organic chromium polymerizing catalyst comprises, two cumene chromium (0), two benzene chromium (0) and two luxuriant chromium.In another aspect of the present invention, the organic chromium polymerizing catalyst comprises Cr (III) (N (SiMe ₃) ₂) ₃, Cr (III) (NPh ₂) ₃And Cr (III) (N (SiMe ₃) ₂) ₂

(iv) solid support material

In the embodiment of this paper, hybrid catalyst system can comprise inert support material.Preferably, solid support material is porous carrier materials, for example, and talcum, and inorganic oxide.Other solid support material comprises zeolite, clay, organic clay or any other organic or inorganic solid support material etc., or their mixture.

Preferably, solid support material is the inorganic oxide of finely divided form.The inorganic oxide material that is fit to that is used for the metallocene catalyst system of this paper comprises the 2nd, 4,13 and 14 family metal oxides for example silicon oxide, aluminum oxide and their mixture.Can be individually or other inorganic oxide that is combined with silicon oxide or aluminum oxide be magnesium oxide, titanium oxide, zirconium white etc.Yet, can adopt other solid support material that is fit to, for example, finely divided functionalised polyolefin is finely divided polyethylene for example.The carrier that is particularly useful comprises magnesium oxide, titanium oxide, zirconium white, polynite, phyllosilicate, zeolite, talcum, clay etc.In addition, can use the combination of these solid support materials, for example, silicon oxide-chromium, silica-alumina, silicon oxide-titanium oxide etc.Preferred solid support material comprises Al ₂O ₃, ZrO ₂, SiO ₂, and their combination, more preferably SiO ₂, Al ₂O ₃Or SiO ₂/ Al ₂O ₃

Preferably, solid support material, most preferably inorganic oxide has the about 700m of about 10- ²The surface-area of/g, the approximately volume of voids of the about 4.0cc/g of 0.1-and the approximately mean particle size of the about 500 μ m of 5-.More preferably, the surface-area of solid support material is at about about 500m of 50- ²In the scope of/g, volume of voids in the scope of the about about 3.5cc/g of 0.5-and mean particle size in the scope of about about 200 μ m of 10-.Most preferably, the surface-area of solid support material is at about about 400m of 100- ²In the scope of/g, volume of voids in the scope of the about about 3.0cc/g of 0.8-and mean particle size in the scope of about about 100 μ m of 5-.Can be used for the mean pore size of solid support material of the present invention at the 10-1000 dust, preferred about 500 dusts of 50-are most preferably in the scope of about 350 dusts of 75-.In some embodiments, solid support material is the unbodied silicon oxide (surface-area=300m of high surface area ²/ gm; Volume of voids is 1.65cm ³/ gm), and with trade name DAVISON952 or DAVISON955 by Davi son Chemical branch, W.R.Grace and Company sells.In other embodiments, use DAVI SON948.

Solid support material should be done, and does not namely contain the water of absorption.The drying of solid support material can be passed through at about 100 ℃-about 1000 ℃, and preferably about at least 600 ℃ of lower heating or calcining are carried out.When solid support material is silicon oxide, it is heated at least 200 ℃, and 200 ℃ to about 850 ℃ of preferably approximatelies, optimum are chosen about 600 ℃ and were kept about 1 minute-about 100 hours, about 12 hours-about 72 hours, or about 24 hours to about 60 hours time.Solid support material through calcining must have at least some reactive hydroxyls (OH) with preparation catalyst system of the present invention.Then allow described solid support material through calcining contact with at least a activator with at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, as discussed above such.

The manufacture method of loading type hybrid catalyst system

The mixed catalyst composition of the product of contact that comprises following material is contained in the present invention: the polymerizing catalyst that (i) comprises the 4th family or the 5th group 4 transition metal, (ii) activator, (iii) organic chromium polymerizing catalyst, (iv) solid support material, every kind of component in them is such as top discussion.

The invention further relates to the preparation method of loading type hybrid catalyst system, comprise: solid support material is contacted with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the reactive group on the described solid support material of titration, and form supported polymerisation catalysts; (ii) afterwards, make described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with the organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst is differing at least 50% with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal aspect the molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system therein the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal be the described polymerizing catalyst little at least 50% that comprises the 4th family or the 5th group 4 transition metal of specific activity under the active polymerizing condition.

In the embodiment of this paper, allow solid support material contact with the solution of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal and activator, so that the reactive group on the solid support material is titrated, and forms supported polymerisation catalysts.The duration of contact that comprises between polymerizing catalyst, activator compound and the solid support material of the 4th family or the 5th group 4 transition metal is long to must getting final product for the reactive group on the titration solid support material." titration " refer to surfaces of carrier materials on available reaction-ity group reaction, thereby surface hydroxyl is reduced by at least 80%, at least 90%, at least 95% or at least 98%.Can determine the surface reaction radical concentration based on calcining temperature and the type of employed solid support material.The solid support material calcining temperature affects the number that can be used on the solid support material with the surface reaction group of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal and activator reaction: drying temperature is higher, and the number at position is lower.For example, when solid support material is by making its fluidization with nitrogen and when heating about silicon oxide that dewatered in 16 hours down for about 600 ℃, usually reaching the concentration of surface hydroxyl groups of about 0.7 mmole/gram (mmol/gm) before it is used for the first catalyst system synthesis step.Therefore, the accurate mol ratio of activator and surface reaction group will change on the carrier.Preferably, this determines to guarantee only so many activator to be added in the solution based on concrete occasion so that will deposit on the solid support material and do not allow excessive activator in solution.

With settling to solid support material and do not allow the amount of excessive activator in solution measure in any conventional manner, following mensuration for example: activator is added in the slurry of carrier in solvent, stir simultaneously this slurry, until by any technology as known in the art, for example pass through ¹H NMR detection activator is the solution in described solvent.For example, for the silica support material in about 600 ℃ of lower heating, the amount of adding the activator in the slurry to satisfies that the mol ratio of Al and hydroxyl (OH) is the about 4:1 of about 0.5:1-on the silicon oxide, the about 3:1 of preferably approximately 0.8:1-, the more preferably about about 2:1 of 0.9:1-, most preferably about 1:1.The amount of Al can be measured by using ICPES (inductively coupled plasma emission spectrometry) on the silicon oxide, the method is described in C.R.Brundle, C.A.Evans, Jr. the material of compiling with S.Wilson characterizes " the inductively coupled plasma emission spectrometry " of J.W.Olesik in the encyclopedia (Encyclopedia of Mater ia l s Character izat ion), But terworth-Heinemann, Boston, Mass., in 1992, the 633-644 pages or leaves.In another embodiment, can also add above the activator that will deposit to the amount on the carrier, then remove, for example by filtering and washing any excessive activator.

In non-polar solvent, will have the solid support material slurrying of reactive surfaces group (usually hydroxyl) and allow the slurry of gained contact with the solution of the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal and activator.Prepare the slurry of solid support material in solvent by solid support material being imported solvent, and this mixture heating up is arrived about 0 ℃-about 70 ℃, 25 ℃-about 60 ℃ of preferably approximatelies, preferably at room temperature.Be typically about 0.5 hour duration of contact-about 24 hours, about 2 hours-about 16 hours, or about 4 hours-about 8 hours.

The non-polar solvent that is fit to is the employed reactant of all this paper wherein, and namely activator and the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal are at least part of solvable and be the material of liquid under temperature of reaction.Preferred non-polar solvent is alkane, and for example iso-pentane, hexane, normal heptane, octane, nonane and decane still also can adopt various other materials, comprise naphthenic hydrocarbon, for example hexanaphthene, aromatic substance, for example benzene, toluene and ethylbenzene.

After forming supported polymerisation catalysts, allow afterwards described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with the first organic chromium polymerizing catalyst.Be typically about 0.5 hour the duration of contact between supported polymerisation catalysts and the organic chromium catalyzer-about 24 hours, about 2 hours-about 16 hours, or about 4 hours-about 8 hours.During duration of contact, can with mixture heating up to about 10 ℃-about 200 ℃, about 20 ℃-about 95 ℃, preferably during duration of contact, not heat this mixture.

Comprising the polymerizing catalyst of the 4th family or the 5th group 4 transition metal and the mol ratio of organic chromium polymerizing catalyst can be about about 1:100 of 100:1-, the approximately about 1:10 of 10:1-, or about about 1:5 of 5:1-.Comprise the polymerizing catalyst of the 4th family or the 5th group 4 transition metal and the mol ratio of activator compound and can be about about 1:1 of 1:100-, the approximately about 1:5 of 1:100-, the approximately about 1:10 of 1:50-.

In some embodiments, comprising the polymerizing catalyst of the 4th family or the 5th group 4 transition metal and the weight ratio of solid carrier material can be about about 0.0001:1 of 10:1-, the approximately about 0.001:1 of 1:1-, or about about 0.001:1 of 0.1:1-.The weight ratio of solid support material and activator compound can be about about 100:1 of 1:10-, the approximately about 100:1 of 1:1-, or about about 10:1 of 1:1-.

The polymerizing catalyst and the activator that use in advance preparation or commercially available loading type to comprise the 4th family or the 5th group 4 transition metal form hybrid catalyst system of the present invention advantageously within the scope of the present invention, as long as the reactive group on the titration solid support material.In such embodiments, allow in advance preparation or commercially available supported polymerisation catalysts contact to form hybrid catalyst system with the first organic chromium polymerizing catalyst.Described in advance preparation or be typically about 0.5 hour-about 24 hours commercially available supported polymerisation catalysts and the duration of contact between the organic chromium catalyzer, about 2 hours-about 16 hours, or about 4 hours-about 8 hours.During duration of contact, can with mixture heating up to about 10 ℃-about 200 ℃, about 20 ℃-about 95 ℃, preferably during duration of contact, not heat this mixture.It is favourable using in advance preparation or commercially available supported polymerisation catalysts, more efficient because it allows the more easily screening of mixed catalyst, and saves time.

In specific embodiment, the invention further relates to the manufacture method of loading type hybrid catalyst system, comprise: (i) allow solid support material contact with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal and the weight ratio of solid carrier material are at about about 0.0001:1 of 10:1-, about about 0.001:1 of 1:1-, or in the scope of about about 0.001:1 of 0.1:1-; The weight ratio of solid support material and activator compound is at about about 100:1 of 1:10-, about about 100:1 of 1:1-, or in the scope of about about 10:1 of 1:1-, so that the reactive group on the titration solid support material, at about 10 ℃-about 200 ℃, kept about 0.5 hour-about 24 hours about 2 hours-about 16 hours under the about 20 ℃-about 95 ℃ temperature, or about 4 hours-about 8 hours, preferably during the duration of contact that forms supported polymerisation catalysts, do not heat this mixture; (ii) allow afterwards described supported polymerisation catalysts and organic chromium polymerizing catalyst at about 10 ℃-about 200 ℃, contact is about 0.5 hour-about 24 hours under the about 20 ℃-about 95 ℃ temperature, about 2 hours-about 16 hours, or about 4 hours-about 8 hours, preferably during duration of contact, do not heat this mixture, to form the loading type hybrid catalyst system; Wherein said organic chromium polymerizing catalyst is differing at least 50% with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal aspect the molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system therein the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal be the described polymerizing catalyst little at least 50% that comprises the 4th family or the 5th group 4 transition metal of specific activity under the active polymerizing condition.

In another embodiment, the present invention relates to:

1. the preparation method of multimodal attitude polyolefin compositions comprises:

(i) at least a the first olefinic monomer is contacted under polymerizing condition with hybrid catalyst system; Have 5,000g/mol-600 with preparation at least, 000g/mol, preferred 8,000g/mol-400,000g/mol; Or 10,000g/mol-300, the first polyolefin component of the Mw of 000g/mol; Wherein said hybrid catalyst system comprises:

(a) at least a the 4th family or the 5th group 4 transition metal of comprising; Preferred zirconium, hafnium, titanium or vanadium; Preferred zirconium, hafnium or titanium; The polymerizing catalyst of preferred zirconium or hafnium; Or the metallocenes that more preferably is expressed from the next:

(i)L ^AL ^BMX _n；

Or

(ii)L ^AA*L ^BMX _n；

Wherein M is the 4th family or the 5th group 4 transition metal;

Each X is leavings group;

A* is the bridging base; With

N is 0,1,2 or 3;

(b) at least a organic chromium polymerizing catalyst that is expressed from the next:

(i)CrR _n；

Wherein R is C ₁-C ₂₀Alkyl; With

Wherein n is selected from 2,3 and 4;

Or

(ii)CrL _AL _B；

L wherein _AAnd L _BBe independently selected from the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement; Or

(iii)Cr(XR _n) _m；

Wherein each X is N, O, P or S independently, preferred N;

Each n is 1 or 2 independently;

M is 1 or 2; With

Each R is the aryl of alkyl, aryl or the replacement of alkyl, replacement independently, as long as at least one R base is the aryl of aryl or replacement;

(c) activator, preferred aikyiaiurnirsoxan beta; With

(d) solid support material;

(ii) afterwards, make the combination of described the first polyolefin component/hybrid catalyst system and molecular switch, preferably comprise oxygen and by formula Al R ₃Or Al R ₂The molecular switch of the alkylaluminium cpd that H represents; Preferably be the oxygen contact of air form; With

(iii) described the first polyolefin component/hybrid catalyst system combination is contacted under polymerizing condition with at least a the second olefinic monomer that can be identical or different; With

(iv) obtain multimodal attitude polyolefin compositions, described multimodal attitude polyolefin compositions randomly has:

(a) have 5,000g/mol-600,000g/mol, preferred 8,000g/mol-400,000g/mol; Or 10,000g/mol-300, the Mw of 000g/mol; Mw/Mn greater than 1 to about 10; And has the first polyolefin component of at least one kurtosis; With

(b) another kind of polyolefin component; With

Wherein said multimodal attitude polyolefin compositions:

(i) has MWD greater than 1 to about 15;

(ii) comprise the component less than the molecular weight of 300,000g/mol of having that is less than 5wt%; With

(iii) have multimodal attitude molecular weight distribution, preferably have two kurtosis, or preferred three kurtosis.

2. section 1 method, wherein under the polymerizing condition of step (i), the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active and described organic chromium polymerizing catalyst has active little at least 50% activity than the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal.

3. section 1 and 2 method, wherein after contact with molecular switch and under the polymerizing condition of step (iii), described organic chromium polymerizing catalyst has active greatly at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

4. the method for section 1-3 wherein comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal by contacting and passivation with molecular switch, does not produce the first additional polyolefin component that can measure quantity.

5. the method for section 1-4, the wherein said polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal has the response of negative molecular switch and described organic chromium polymerizing catalyst has positive molecular switch response.

The section 1-5 method, wherein step (i)-(iv) is carried out in single reactor.

The section 1-6 method, oxygen and the aluminum alkyls component of wherein sequentially adding described molecular switch.

8. the method for section 1-7, wherein step (i)-(iv) in Gas-phase reactor, carry out.

9. arbitrary section hybrid catalyst system among the section of the can be used for 1-8, wherein, under the polymerizing condition of step (i), the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active and described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein, after contacting with molecular switch (preferred described molecular switch comprises oxygen and alkylaluminium cpd) and under the polymerizing condition of step (iii), described organic chromium polymerizing catalyst has active large at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

10. the preparation method of section 9 loading type hybrid catalyst system comprises:

(i) described solid support material is contacted with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the reactive group on the described solid support material of titration, and form supported polymerisation catalysts;

(ii) afterwards, make described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with described organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst is differing at least 50% with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal aspect the molecular switch response; The described polymerizing catalyst little at least 50% that comprises the 4th family or the 5th group 4 transition metal of organic chromium polymerizing catalyst specific activity under the polymerizing condition of step (i) with wherein said loading type hybrid catalyst system.

Embodiment

Characterization of The Products

Use Waters Alliance GPC2000Ser ies analyzing polymers product.Use trichlorobenzene (TCB) under 140 ℃ temperature, to obtain Mw, Mn and MWD data as solvent with the flow velocity of 1mL/min.Use the BHT (BHT) of the concentration of pressing 1.0g/L as the stablizer among the TCB.Use the volume injected of 220L and the nominal polymer concentration (at room temperature) of 0.3g/L.The dissolving of sample in stabilization TCB is following to be carried out: heating 20 hours under the mild stirring once in a while under 160 ℃-170 ℃.Use two Waters HT-6E posts (7.8 * 300mm).With after measured wide straight linear polyethylene standard model (the Mar l ex of molecular weight ^TMThe BHB5003 resin) calibrates this post.

Except as otherwise noted, all molecular weight of report are take g/mol as unit.

Material

Two (cyclopentadienyl) chromium is bought and the former state use from Strem Chemical s (Newburyport, MA).30wt% methylaluminoxane (MAO) in toluene solution and dichloro two (1-methyl, 3-butyl cyclopentadienyl) close zirconium and buy and the former state use from Albemarle (BatonRouge, LA).(Chicago IL) is bought and former state is used from AkzoNobe l for triethyl aluminum and triisobutyl aluminium.Toluene is from Sigma Aldr ich (St.Loui s, MO) purchase and dry with the alumina bead of in advance calcining.

Catalyst system is synthetic

Catalyzer 1:

Will two (cyclopentadienyl) chromium (10mg) and 1.0 gram silicon oxide (Grace Davi son948 is calcined in advance 600 ℃ and kept 72 hours) combination in toluene slurry (10ml).After one hour, red solution becomes colourless, because two luxuriant chromium and the reaction of described silicon oxide.To contain the solution that 16mg dichloro two (1-methyl, 3-butyl cyclopentadienyls) closes the MAO toluene solution of zirconium and 1.6 gram 30wt% adds in the described slurry.Allow described slurry at room temperature to leave standstill two hours.After two hours, filter described loaded catalyst and drying under vacuum.

Catalyzer 2:

To contain two (the 1-methyl of 16mg dichloro, 3-butyl cyclopentadienyl) solution that closes the MAO toluene solution of zirconium and 1.6 gram 30wt% adds in the slurry of 1.0 gram silicon oxide (Grace Davi son948 is calcined in advance 600 ℃ and kept 72 hours) in toluene.Allow described slurry at room temperature to leave standstill two hours.After two hours, add two (cyclopentadienyl) chromium (8mg).Allow at room temperature standing over night of described slurry.Filter described loaded catalyst and drying under vacuum.

Polymerization

Embodiment 1:

In the glove box of nitrogen purging, 17mg catalyzer 1 (top) and 4.0 gram pentanes are placed 75mL Parr4740 stainless steel autoclave.Triisobutyl aluminium (TIBAL, 20mg) is added in the described reactor.With ethene described reactor is forced into 200ps i, places 85 ℃ of oil baths, and stirred 35 minutes.Polymerization produces 1.1 gram polyvinyl resins, and its 250mg is exposed under the air.

Polyvinyl resin (250mg) after will being exposed in the air place the Parr reactor with 30mg triethyl aluminum (TEA1) and at 85 ℃ of lower ethene with being pressurized to 200ps i.After 12 hours, reaction produces the 620mg polyethylene, increases 0.590mg.

Embodiment 2:

Embodiment 2A:

In the glove box of nitrogen purging, the solution of 20mg catalyzer 2 in the 5mL pentane is added in the 75mL Parr4740 stainless steel autoclave.Then two TIBAL that add that volumetric pipette inhales and sealed reactor also are pressurized to 200ps i (1.38MPa) with ethene.Then reactor is placed the oil bath that is heated to 85 ℃ to keep 45 minutes.After opening reactor, obtain the tiny white polyethylene particle of 0.875g.Polymer characterization: Mn=127,692; Mw=395,957; Mw/Mn=3.1 (referring to the GPC trace of Fig. 1).

Embodiment 2B:

Then, the polyethylene of 0.409g embodiment 2A is placed vial, from loft drier, take out and be exposed in the air.In the second vial, add 3 volumetric pipettes and drip TEA1 and place the Parr autoclave inner this vial.The vial that will contain described polymkeric substance places above this vial that contains described TEAL.Then seal this reactor and be pressurized to 200ps i (1.38MPa) with ethene, and be placed in 85 ℃ the oil bath and kept 45 minutes.Produce like this 0.637g polymer beads, increase 0.228g.Polymer characterization: Mn=126,258; Mw=535,110; Mw/Mn=4.24 (referring to the GPC trace of Fig. 2).

Describe herein, the All Files that comprises any priority document and/or testing sequence is combined in herein by reference, to they not with the inconsistent degree of this paper content, yet as long as in the initial application of submitting to or submit the not by reference combination of any priority document of not enumerating in the document to.It is evident that from above-mentioned general introduction and particular, although have illustrated and described form of the present invention, can make various modifications without departing from the spirit and scope of the present invention.Therefore, do not wish that the present invention is so limited.Similarly, term " comprises " and thinks with regard to Australian law and " comprise " synonym with term.Equally, " comprise " and contain term " mainly by ... consist of ", " be " and " by ... consist of " and use " comprise " Anywhere can with " mainly by ... consist of ", " be " and " by ... consist of and " replace.

Claims

(i) at least a the first olefinic monomer is contacted under polymerizing condition with hybrid catalyst system; Have 5,000g/mol-600 to prepare at least, the first polyolefin component of the Mw of 000g/mol, wherein said hybrid catalyst system comprises:

(a) at least a polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal;

(i)CrR _n；

Wherein R is C ₁-C ₂₀Alkyl; With

Wherein n is selected from 2,3 and 4;

Or

(ii)CrL _AL _B；

L wherein _AAnd L _BBe independently selected from the fluorenyl of indenyl, fluorenyl or replacement of cyclopentadienyl, indenyl, the replacement of cyclopentadienyl, replacement;

Or

(iii)Cr(XR* _z) _m；

Wherein each X is N, O, P or S independently;

Each z is 1 or 2 independently;

M is 1 or 2; With

Each R* is the aryl of alkyl, aryl or the replacement of alkyl, replacement independently, as long as at least one R base is the aryl of aryl or replacement;

(c) activator; With

(d) solid support material;

(ii) afterwards, the first polyolefin component/hybrid catalyst system combination is contacted with molecular switch; With

(iii) the first polyolefin component/hybrid catalyst system combination is contacted under polymerizing condition with at least a the second olefinic monomer that can be identical or different; With

(a) has 5,000g/mol-600, the Mw of 000g/mol; Mw/Mn greater than 1 to about 10 also has the first polyolefin component of at least one kurtosis; With

(b) another kind of polyolefin component; With

Wherein said multimodal attitude polyolefin compositions:

(i) has MWD greater than 1 to about 15;

(iii) has multimodal attitude molecular weight distribution.

2. the method for claim 1, wherein under the polymerizing condition of step (i), the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active and described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal.

3. claim 1 or 2 method, wherein after contacting with molecular switch and under the polymerizing condition of step (iii), described organic chromium polymerizing catalyst has active large at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

4. each method among the claim 1-3, the wherein said polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal do not produce the first additional polyolefin component that can measure quantity by contacting and passivation with molecular switch.

5. each method among the claim 1-4, the wherein said polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal have negative molecular switch response and described organic chromium polymerizing catalyst has positive molecular switch response.

6. each method among the claim 1-5, wherein step (i)-(iv) is carried out in single reactor.

7. each method among the claim 1-6, oxygen and the aluminum alkyls component of wherein sequentially adding described molecular switch.

8. each method among the claim 1-7, wherein step (i)-(iv) in Gas-phase reactor, carry out.

9. each method among the claim 1-8, wherein the 4th family or the 5th group 4 transition metal catalyzer are expressed from the next:

(i)L ^AL ^BMX _n；

Or

(i i)L ^AA*L ^BMX _n；

Wherein M is the 4th family or the 5th group 4 transition metal;

Each X is leavings group;

A* is the bridging base; With

N is 0,1,2 or 3;

10. each method among the claim 1-9, wherein the 4th family or the 5th group 4 transition metal are Zr, Hf, Ti or V.

11. each method among the claim 1-10, wherein said molecular switch comprises the oxygen with the form of air.

12. each method among the claim 1-11, wherein said multimodal attitude polyolefin compositions has 2 kurtosis.

13. each method among the claim 1-12, wherein said molecular switch comprises oxygen and alkylaluminium cpd.

14. each method among the claim 1-13, wherein said activator is aikyiaiurnirsoxan beta.

15. can be used among the claim 1-14 each hybrid catalyst system, wherein under the polymerizing condition of step (i), the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal is active and described organic chromium polymerizing catalyst has active little at least 50% activity than the described polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal; Wherein after contacting with molecular switch and under the polymerizing condition of step (iii), described organic chromium polymerizing catalyst has active large at least 50% the activity that comprises the polymerizing catalyst of the 4th family or the 5th group 4 transition metal than described.

16. the method for the loading type hybrid catalyst system of preparation claim 15 comprises:

(i) solid support material is contacted with activator with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal, so that the reactive group on the described solid support material of titration, and form supported polymerisation catalysts;

(ii) afterwards, make described supported polymerisation catalysts contact to form the loading type hybrid catalyst system with described organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst is differing at least 50% with the polymerizing catalyst that comprises the 4th family or the 5th group 4 transition metal aspect the molecular switch response; With

The described polymerizing catalyst little at least 50% that comprises the 4th family or the 5th group 4 transition metal of the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system specific activity under the polymerizing condition of step (i).