CN103052655B

CN103052655B - Processes for making multimodal molecular weight distribution polyolefins

Info

Publication number: CN103052655B
Application number: CN201180037911.6A
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: 2015-05-13
Anticipated expiration: 2031-10-26
Also published as: RU2579518C2; WO2012067777A3; EP2640757A4; MY165619A; EP2640757A2; CN103052655A; BR112013002457B1; BR112013002457A2; RU2013122566A; WO2012067777A2

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 state molecular weight distribution polyolefin

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

Prioity claim

This application claims the USSN12/950 submitted on November 19th, 2010,501 and the interests of EP10196508.5 submitted on December 22nd, 2010 and right of priority.

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

The polyolefine with bimodal molecular weight distribution is desirable, because they can by the combination of the processing characteristics of the improvement of the advantageous mechanical performance of high molecular weight block and low molecular weight fraction.This provide to have compared with only having the polyolefine of high molecular weight block or low molecular weight fraction useful with polyolefine that is desirable combining properties.Such as, although desirable mechanical property and stable bubble formation are given polyolefin polymer by high molecular usually, but it also suppresses to extrude processing by the counterpressure improved in forcing machine usually, promote the melt fracture defect in expanding bubble, possibly, the orientation degree in finished film is also promoted.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 state molecular weight distribution polyolefin comprising low molecular weight fraction and high molecular weight block while the forcing machine counterpressure of reduction and downtrod melt fracture is desirable.This type of polyolefine may require this kind useful and in the film of desirable combining properties and other goods, there is great applicability.

The polyolefine with multimodal state molecular weight distribution can obtain as follows: by high molecular polyolefine and low-molecular-weight polyolefin physical blending, as U.S. Patent number 4, and 461, like that open in 873.But the blend prepared of these physics is usually containing high gel level, and this causes the film outward appearance of the difference caused due to those gels.Although workability has improvement, blended costliness often, require the homogeneity completely of mixture of melts, and be the troublesome additional blending step of manufacture/manufacture craft increase.

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

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

The catalyst system comprising two kinds of different metal cyclopentadienyl catalysts is disclosed in the preparation of the bimodal molecular weight distribution polyolefin in EP0619325.EP0619325 describes the polyolefine with multimodal or at least bimodal molecular weight distribution, such as poly preparation method.The metallocenes used is, such as, dichloro two (cyclopentadienyl) closes zirconium and dichloro-ethylidene two (indenyl) closes zirconium.By the metalloscene catalyst that use two kinds in same reactor is different, obtain at least bimodal molecular weight distribution.

WO99/03899 discloses preparation in single reactor and has the application of the poly catalyst composition of wide or bimodal molecular weight distribution.Described catalyzer is by silicon oxide (in advance at 600 DEG C calcine) and dibutylmagnesium, n-butyl alcohol and titanium tetrachloride, and methylaluminoxane and dichloro-ethylidene two [1-indenyl] close the interaction preparation of the solution of zirconium.

U.S. Patent number 7,163,906 disclose a kind of catalyst composition, this catalyst composition comprises the product of contact of at least one Metallocenic compound, at least one organic chromium polymerizing catalyst, fluorided silica and at least one alkylaluminium cpd, and this catalyst composition is then in an inert atmosphere for making vinyl polymerization.U.S. Patent number 7,163, the metallocenes used in the embodiment of 906 is that dichloro two (n-butyl cyclopentadienyl) closes zirconium and the organo-chromium compound used comprises two cumene chromium and two luxuriant chromium.U.S. Patent number 7,163, metallocenes disclosed in 906-organic chromium catalyst system preparation is characterised in that the polyethylene of very wide molecular weight distribution (70.3-8.4).U.S. Patent number 7,163, the polyethylene display medium molecular weight distributions of preparation in 906, has owing to the peak, center of metallocene components with owing to the wide tail composition while chromium component on height and that side of lower molecular weight.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 to divide in the method for control the polyolefinic various molecular level with multimodal state molecular weight distribution in exploitation and still have significant challenge.Therefore, the method allowing specifically to be controlled the composition of each kurtosis of multimodal state molecular weight distribution polymer is still needed.

Summary of the invention

The present invention relates to the preparation method of multimodal state polyolefin compositions, the method comprises: (i) makes at least one first olefinic monomer and hybrid catalyst system contact under polymerization conditions at least to prepare and have 5,000g/mol-600, first polyolefin component of the Mw of 000g/mol, wherein said hybrid catalyst system comprises: (a) at least one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (b) at least one organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii), after, described first polyolefin component/hybrid catalyst system combination is contacted with molecular switch; (iii) described first polyolefin component/hybrid catalyst system combination is made can to contact under polymerization conditions by the second olefinic monomer identical or different with described first olefinic monomer with at least one; (iv) multimodal state polyolefin compositions is obtained.

The invention further relates to hybrid catalyst system, it comprises: (i) at least one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (ii) activator; (iii) at least one organic chromium polymerizing catalyst; (iv) solid support material; Wherein wherein described in comprise the activated polymerizing condition of polymerizing catalyst of the 4th race or the 5th group 4 transition metal under, described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein after contact with molecular switch and under polymerization conditions, described organic chromium polymerizing catalyst has than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

The invention further relates to the preparation method of loading type hybrid catalyst system, comprise: (i) makes described solid support material and the polymerizing catalyst and the activating agent that comprise the 4th race or the 5th group 4 transition metal, so that the reactive group on solid support material described in titration, and form supported polymerisation catalysts; (ii), after, described supported polymerisation catalysts is made to contact to form loading type hybrid catalyst system with organic chromium polymerizing catalyst; Wherein wherein described in comprise the activated polymerizing condition of polymerizing catalyst of the 4th race or the 5th group 4 transition metal under, described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein after contact with molecular switch and under polymerization conditions, described organic chromium polymerizing catalyst has than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

Accompanying drawing is sketched

Fig. 1 represents the multimodal polyethylene molecular weight distribution using catalyzer 2 (loading type dichloro two (1-methyl, 3-butyl cyclopentadienyl) closes zirconium/bis-(cyclopentadienyl) chromium hybrid catalyst system) to obtain.

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

Describe in detail:

Contriver it has surprisingly been found that working load type hybrid catalyst system and molecular switch preparation can to have the multimodal state molecular weight distribution polyolefin of control to each kurtosis." molecular weight " used herein refers to weight-average molecular weight (Mw), except as otherwise noted.

In embodiment herein, the present invention relates to the method comprised the following steps: (i) makes at least one first olefinic monomer and hybrid catalyst system contact under polymerization conditions at least to prepare and have 5,000g/mol-600, first polyolefin component of the Mw of 000g/mo l, wherein said hybrid catalyst system comprises: (a) at least one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (b) at least one organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii), after, described first polyolefin component/hybrid catalyst system combination is contacted with molecular switch; (iii) the second olefinic monomer that described first polyolefin component/hybrid catalyst system combination and at least one can be identical or different is made to contact under polymerization conditions; (iv) multimodal state polyolefin compositions is obtained.

" alkene ", or be called that " alkene " is the straight chain with at least one double bond of carbon and hydrogen, side chain or ring compound.For the object of the present invention and claim thereof, when polymkeric substance is called " comprising alkene ", the alkene be present in described polymkeric substance is 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 different from each other." terpolymer " is the polymkeric substance with three monomeric units different from each other." difference " that be used for relating to monomeric unit indicates described monomeric unit to differ at least one atom or isomery difference each other.

Term as used herein " hybrid catalyst system " is used for referring to any composition or mixture, it comprises the different catalyst compound of (i) at least two kinds, at this, namely can by the polymerizing catalyst comprising the 4th race 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 " multimodal state " being used for describing polymkeric substance or polymer composition refers to " multimodal state molecular weight distribution ", it is interpreted as referring to gel permeation chromatography (GPC) trace, be plotted as d (wt%)/d (Log [M]) and, to weight-average molecular weight (g/mol), there is more than one peak or flex point." flex point " is the point (such as, from negative to positive, vice versa) that the flection sign of wherein curve changes.Such as, the polyolefin compositions comprising the first low-molecular weight polymer component and the second high molecular weight polymer components thinks " 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 is measured by GPC.

" molecular switch " used herein is used for reducing, or cuts off, or quencher comprises the activity of the polymerizing catalyst of the 4th race 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 first component of molecular switch bag and alkylaluminium cpd.The component of molecular switch can sequentially in introduction method.In preferred embodiments, oxygen is contacted with the first polyolefin component/hybrid catalyst system, under polymerizing condition (preferentially comprising inert atmosphere), add alkylaluminium cpd afterwards.

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

" catalyst activity " be use comprise W transition metal (M) polymerizing catalyst during T hour in prepare measuring of how many grams polymkeric substance (P); And can pass through with following formula: P/ (T × W) represents.Relate to " activity " that polymerizing catalyst uses herein and refer to that described polymerizing catalyst has at least 50g (molM) ^-1hr ^-1catalyst activity, wherein M is that the activity existed in the catalyst component of hybrid catalyst system may owing to its transition metal structure division.Relate to " nonactive " that polymerizing catalyst uses herein to refer to that described polymerizing catalyst has and be less than 50g (mo lM) ^-1hr ^-1catalyst activity.For claim with herein concerning the object of the discussion of relative reactivity, activity be as mentioned above by 75mL barrel type reactor under the pressure of 200ps i (1.38MPa) and the aggregated data carrying out being polymerized with ethene and obtain calculate.Then described reactor be heated to the temperature of 85 DEG C and keep 45 minutes at these temperatures.

Contriver has been found that the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal is different in molecular switch response with organic chromium polymerizing catalyst." molecular switch response " refers to compared with the activity with same catalyzer under the polymerizing condition comprising inert atmosphere, catalyzer is contacting (such as with molecular switch, be exposed to oxygen lower 5 minutes), then experience the relative reactivity after the activation using alkylaluminium cpd under polymerization conditions.Contacting with molecular switch, and after experiencing polymerizing condition, catalyzer may become passivation and lose catalyst activity (negative molecular switch response); Maintain catalyst activity (without molecular switch response); Or become activation and/or catalyst activity raising (positive molecular switch response).Molecular switch response can be exposed under oxygen by catalyst component, then experiences the activity (A after follow-up polymerizing condition (comprise and activating with alkylaluminium cpd) _o) with under polymerizing condition (preferably including inert atmosphere), be not exposed to the catalyst component activity (A of the hybrid catalyst system in oxygen _i) between difference ratio measure; And by formula: (A _o-A _i)/A _irepresent.

Such as, before contacting with molecular switch, under polymerization conditions, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal usually produce obtain unimodal or bimodal molecular weight distribution polymkeric substance as the first polyolefin component.Correspondingly, organic chromium polymerizing catalyst seems not produce a lot of polymkeric substance.

In embodiment herein, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal is wherein under active polymerizing condition, organic chromium polymerizing catalyst has than the described activity little at least 50% comprising the polymerizing catalyst of the 4th race or the 5th group 4 transition metal, at least 60%, at least 70%, at least 80%, at least 90%, or the activity of at least 98%.In an optional embodiment, organic chromium polymerizing catalyst has at least single order less of the activity of the polymerizing catalyst comprising the 4th race 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 comprising the 4th race or the 5th group 4 transition metal is wherein under active polymerizing condition, the described polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal has the activity large at least 50% than organic chromium polymerizing catalyst, at least 60%, at least 70%, at least 80%, at least 90%, or the activity of at least 98%.In an optional embodiment, organic chromium polymerizing catalyst has at least single order larger than the activity of the polymerizing catalyst comprising the 4th race 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.

But, after allowing loading type hybrid catalyst system contact with molecular switch, described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst usually stop producing the polymkeric substance of pronounced amount.In such embodiments, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal, by contacting and passivation or quencher with molecular switch, does not produce the first additional polyolefin component of pronounced amount.This observes as the no longer growth of the kurtosis of the first polyolefin component in GPC trace.Therefore, for the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal, A _obe less than A _i.Therefore, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal has the response of negative molecular switch.In embodiment herein, after contacting with molecular switch also under polymerization conditions, the specific activity organic chromium polymerizing catalyst comprising the polymerizing catalyst of the 4th race or the 5th group 4 transition metal is little.In some embodiments, comprise polymerizing catalyst specific activity organic chromium polymerizing catalyst little at least 50%, at least 60%, at least 70%, at least 80%, at least 90% after contacting with molecular switch of the 4th race or the 5th group 4 transition metal, or at least 98%.In an optional embodiment, the catalyzer comprising the 4th race or the 5th group 4 transition metal has at least single order less of the activity of organic chromium polymerizing catalyst, at least two rank, at least 3 rank, at least 5 rank, or the activity at least 6 rank.

Correspondingly, after allowing loading type hybrid catalyst system contact with molecular switch, described organic chromium polymerizing catalyst produces the polymkeric substance of increasing amount usually.This observes the growth into the kurtosis at the GPC trace middle-molecular-weihydroxyethyl additional polymeric component different from the first polyolefin component.Therefore, for organic chromium polymerizing catalyst, A _obe greater than A _i.Therefore, organic chromium polymerizing catalyst has the response of positive molecular switch.In embodiment herein, with molecular switch, preferably comprise after oxygen contacts with the molecular switch of alkylaluminium cpd, and under polymerization conditions, organic chromium polymerizing catalyst has more activity than the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal.In some embodiments, organic chromium polymerizing catalyst specific activity after contacting with molecular switch comprises the polymerizing catalyst large at least 50%, at least 60%, at least 70%, at least 80%, at least 90% of the 4th race or the 5th group 4 transition metal, or at least 98%.In an optional embodiment, organic chromium polymerizing catalyst has at least single order larger than the activity of the polymerizing catalyst comprising the 4th race 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.

In some embodiments herein, after contact with molecular switch, under polymerization conditions, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal has the response of negative molecular switch and organic chromium polymerizing catalyst has positive molecular switch responds.

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

In another embodiment, hybrid catalyst system of the present invention comprises: (i) at least one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (ii) activator; (iii) at least one organic chromium polymerizing catalyst; (iv) solid support material; Wherein wherein described in comprise the activated polymerizing condition of polymerizing catalyst of the 4th race or the 5th group 4 transition metal under, described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein after contacting with molecular switch, and under polymerization conditions, the specific activity of described organic chromium polymerizing catalyst comprises the polymerizing catalyst large at least 50% of the 4th race or the 5th group 4 transition metal.

The invention further relates to the preparation method of hybrid catalyst system, comprise: (i) makes solid support material and the polymerizing catalyst and the activating agent that comprise the 4th race or the 5th group 4 transition metal, so that the reactive group on solid support material described in titration, and form supported polymerisation catalysts; (ii), after, described supported polymerisation catalysts is made to contact to form loading type hybrid catalyst system with organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst and the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal differ at least 50% in molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system wherein described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be the polymerizing catalyst little at least 50% comprising the 4th race or the 5th group 4 transition metal under active polymerizing condition described in specific activity.

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

Polymerization process

In embodiment herein, the present invention relates to the method comprised the following steps: (i) makes at least one first olefinic monomer contact under polymerization conditions with hybrid catalyst system; There is 5,000g/mol-600,000g/mol at least to prepare, preferably 8,000g/mol-400,000g/mol; Or first polyolefin component of the Mw of 10,000g/mol-300,000g/mol; Wherein said hybrid catalyst system comprises: (a) at least one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (b) at least one organic chromium polymerizing catalyst; (c) activator; (d) solid support material; (ii), after, make described first polyolefin component/hybrid catalyst system combination and molecular switch, preferably comprise oxygen and contact with the molecular switch of alkylaluminium cpd; (iii) described first polyolefin component/hybrid catalyst system combination is made can to contact under polymerization conditions by the second olefinic monomer identical or different with described first olefinic monomer with at least one; (iv) multimodal state polyolefin compositions is obtained; The activity of the catalyzer in preferred wherein step (i) is greater than 2000 pounds of polymkeric substance/hour (907Kg/hr), more preferably greater than 5000 pounds/hr (2268Kg/hr), most preferably be greater than 10,000 pound/hr (4540Kg/hr); And the activity of hybrid catalyst system in step (iii) is greater than 2000 pounds of polymkeric substance/hour (907Kg/hr), more preferably greater than 5000 pounds/hr (2268Kg/hr), most preferably be greater than 10,000 pound/hr (4540Kg/hr).

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

Described method can be interval, semi-batch or continuation method.Term as used herein " continuously " refers to the system operated when not having interrupting or stopping.Such as, the continuation method preparing polymer composition by be wherein reactant imported one or more reactor continuously and polymer composition product by the method for taking out continuously.

In gas phase polymerization process, usually adopt continuous circulation, wherein in the reactor by a part for the circulation of heat of polymerization reactor heating system, i.e. recycle gas stream (or being called recycle stream or fluidizing medium).In another part of this circulation, from recirculation composition, this heat is removed by the cooling system outside reactor.Usually, for the preparation of in the gas fluidized bed process of polymkeric substance, the gaseous stream comprising one or more monomers is made under reactive conditions, to circulate through fluidized-bed continuously in the presence of a catalyst.This gaseous stream is discharged also recirculation from this fluidized-bed and returns this reactor.Meanwhile, polymer product is discharged from reactor and added fresh monomer substitute the monomer be polymerized.(see, such as, 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 that is solid-state, granulated polymer with the addition of wherein in the liquid polymerization diluent medium of ethene and comonomer and common hydrogen and catalyzer and is formed.Removed from reactor off and on or continuously by the suspension comprising thinner, in the reactor, volatile constituent is separated also recirculation (optionally, after the distillation) to reactor with polymkeric substance.Liquid diluent for polymerisation medium normally contains the alkane of 3-7 carbon atom, preferably branched alkane.The medium adopted should be liquid and comparatively inertia under polymerization conditions.When a propane medium is used, the method must be operated on reaction diluent critical temperature and pressure.Preferably, hexane or Trimethylmethane medium is used.

Particle form polymerization one class slurry process can be used, wherein keep temperature to be less than the temperature that polymkeric substance enters solution.This kind of technology is well known in the art, and at such as U.S. Patent number 3,248, is described in 179.Other slurry methods comprise adopt loop reactor those and use those of multiple 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 inner and/or outer interchanger to control excessive temperature fluctuation.

If described method is carried out in continuous flow reactor, then with unit g _mg _c ^-1h ^-1, i.e. gram raw material monomer (g _m)/gram catalyzer (g _cthe weight hourly space velocity that)/hour (h) provides will determine the relative quantity of raw material monomer with the catalyzer adopted, and the monomer residence time in the reactor.In continuous flow reactor, the weight hourly space velocity of monomer is greater than 0.04g usually _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 particular embodiments, at least one first olefinic monomer is made to contact under polymerization conditions with hybrid catalyst system; At least to produce, there is 5,000g/mol-600, first polyolefin component of the Mw of 000g/mol.In some embodiments, the temperature of polymerization process can at about 0 DEG C-about 300 DEG C, in preferably approximately 60 DEG C-about 280 DEG C or the more preferably scope of about 70 DEG C-about 150 DEG C.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 reactor at about 15 minutes-about 240 minutes, preferably approximately 30 minutes-about 210 minutes, or in the preferably approximately scope of 45 minutes-about 180 minutes.Polymerization pressure can be any pressure that can not adversely affect polyreaction, and can the about 1000ps i (0.7kPa-6.9MPa) of about 0.1-, the about 400ps i (0.14MPa-2.8MPa) of preferably approximately 20-, or in the scope of the about 250ps i (0.34MPa-1.7MPa) of preferably approximately 50-.

In preferred embodiments, at about 0 DEG C-about 300 DEG C in reaction vessel, preferably approximately 60 DEG C-about 280 DEG C or the more preferably temperature of about 70 DEG C-about 150 DEG C, the about 1000psi of about 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 preferably approximately residence time of 45 minutes-about 180 minutes by reactant (such as, monomer, loading type mixed catalyst, optional thinner etc.) combine.

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

The diluent/solvent be applicable to for described method comprises non-coordinated inert liq.Example comprises straight chain and branched-chain hydrocarbon such as 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, methylcycloheptane and their mixture such as, comprises those (Isopar that can commercially find ^tM); Perhalogenation hydrocarbon is perfluorination C such as _4-10aromatic substance such as benzene, toluene, sym-trimethylbenzene and dimethylbenzene that alkane, chlorobenzene and aromatics and alkyl replace.The diluent/solvent be applicable to also comprises aromatic hydrocarbon, such as toluene or dimethylbenzene, and chlorinated solvent such as methylene dichloride.In a preferred embodiment, the material concentration for the monomer be polymerized is 60 volume % solvents or lower, preferably 40 volume % or lower, preferably 20 volume % or lower, based on the cumulative volume of feedstream.

The additive be applicable to of polymerization process can comprise one or more scavenging agents, activator, promotor, chain-transfer agent, chain shuttling agent (such as zinc ethyl), properties-correcting agent, reductive agent, oxygenant, hydrogen or silane.

Useful monomer comprises alkene, ethene, propylene, butylene, amylene, hexane, heptane, octene, nonene, decene, undecylene and dodecane and their isomer especially herein.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, preferably two kinds of alkene, or preferably three kinds of alkene contact with hybrid catalyst system.In particular embodiments, 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%, is less than 40wt%; Be less than 30wt%; Be less than 20wt%; Be less than 10wt%; Or be less than 5wt%, based on the gross weight of polymkeric substance.

The amount of the loading type mixed catalyst adopted in the inventive method is to provide any amount of exercisable polyreaction.Preferably, raw material monomer mole with loading type mixed catalyst mole ratio be usually greater than 10:1, be preferably greater than 100:1, 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 transition metal mole.Or the mol ratio of raw material monomer and loading type mixed catalyst is less than 10,000,000:1 usually, is preferably less than 1,000,000:1, is more preferably less than 500,000:1.

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

Can in the known manner, such as, molecular weight by using hydrogen to control polymkeric substance.When improving the mol ratio of hydrogen and monomeric olefin in reactor, molecular weight control is proved by the raising of melt index.

" reactor " is any container that chemical reaction wherein occurs.In some embodiments, the inventive method, i.e. step (i)-(iv), carries out in same reactor.In other embodiments, step (i)-(iv) carries out in the differential responses district in same reactor.In particular embodiments, step (i)-(iv) carries out in tubular reactor.In preferred embodiments, step (i)-(iv) carries 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 the several stages in transfer device interconnected at least two independently polymerization reactor, and this makes it possible to the polymkeric substance deriving from the first polymerization reactor to transfer in the second reactor.Or the polymerization in staged reactor can comprise polymkeric substance from a reactor to the artificial transfer of subsequent reactor 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 multiloop reactor, multiple gas reactor, the combination of loop and gas reactor, autoclave reactor or the combination of solution reactor and gas or loop reactor, multiple solution reactor or multiple autoclave reactor.When using staged reactor, oxygen can be imported the first reactor, then during transfer the first polymkeric substance/mixed catalyst composition being transferred to the second reactor, or transferring in the second reactor.

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

Molecular switch

Molecular switch of the present invention has the first component of oxygen and the second component of alkylaluminium cpd." molecular switch " used herein reduces, or cuts off, or quencher comprises the activity of the polymerizing catalyst of the 4th race 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 method.In preferred embodiments, oxygen is contacted with the first polyolefin component/hybrid catalyst system, under polymerizing condition (preferably including inert atmosphere), add alkylaluminium cpd afterwards.

Oxygen is the first component of molecular switch of the present invention." oxygen " used herein can be molecular oxygen or oxygen containing medium (gas, liquid, solid) form, such as oxygen containing gas, such as air.In preferred embodiments, described molecular switch comprises oxygen in the form of air.Allow the combination of described first polyolefin component/hybrid catalyst system and oxygen by comprising the polymerizing catalyst passivation of the 4th race or the 5th group 4 transition metal described in being enough to make and making the amount of described organic chromium polymerizing catalyst oxygenate contact." oxygenate " used herein refers to react with organic chromium polymerizing catalyst and produces procatalyst." procatalyst " used herein refers to the second component by molecular switch, the catalyst compound that described alkylaluminium cpd activates.

In embodiment herein, by the second component of molecular switch, described alkylaluminium cpd activates the organic chromium procatalyst of oxygenate.In embodiment herein, alkylaluminium cpd is by general formula: Al R ₃or Al R ₂h represents, wherein each R is alkyl (preferably, comprising 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 one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (b) at least one organic chromium polymerizing catalyst; (c) activator; (d) solid support material, as below discuss.In some embodiments, the first polyolefin component/hybrid catalyst system is allowed to combine and at least 1 equivalent, at least 1.5 equivalents, at least 2 equivalents, or the oxygen of at least 3 equivalents/equivalent activating agent.

Then the first polyolefin component of described oxygenate/hybrid catalyst system combination is allowed can to contact under polymerization conditions under alkylaluminium cpd exists by the second olefinic monomer identical or different with described first olefinic monomer with at least one.Described alkylaluminium cpd is the second component of molecular switch and is used for activating the organic chromium polymerization procatalyst of described oxygenate.Now, the described polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal is at least partly, being preferably inactive and described organic chromium polymerizing catalyst is substantially at least partly, be preferably active substantially, and produce the another kind of polyolefin component being different from the first polyolefin component in molecular weight.The amount of the second polyolefin component prepared by can being controlled by the amount of monomer of supplied reactor, the amount of alkylaluminium cpd and second residence time of being polymerized.Therefore, multimodal state MWD polyolefin compositions can be prepared when controlling each kurtosis of polyolefin compositions.

Multimodal state MWD polyolefin compositions

The polymer composition prepared by the inventive method and hybrid catalyst system is multimodal state, at least has the first polyolefin component different in molecular weight and another kind of polyolefin component, and preferably consequently GPC trace has more than one peak or flex point.

By such as Macromolecules, 2001, Vol.34, No.19, gel permeation chromatography (GPC) described in pg.6812 measures 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 completely, comprise use and be equipped with differential refractive index detector (DRI), the Temperature Size Exclusion chromatogram (SEC, Waters Alliance2000) of three Polymer Laboratories PLgel10mmMixed-B posts is equipped with.Use 1.0cm ³the flow velocity of/min and the volume injected of 300 μ L operate this instrument.Encapsulate various line of pipes, post and differential refractometer (DRI detector) being maintained in the baking oven of 145 DEG C.Prepare polymers soln as follows: heat under stirring continuously at 160 DEG C filtered containing the 0.75-1.5mg/mL polymkeric substance in 1,2, the 4-trichlorobenzene (TCB) of ~ 1000ppm BHT 2 hours.To GPC be injected containing the sample of the solution of described polymkeric substance and use filtered 1,2,4-trichlorobenzene (TCB) wash-out containing ~ 1000ppm BHT.By the separation efficiency of a series of narrow MWD polystyrene standard sample calibration post group, this separation efficiency reflects the MW scope of the expection of the sample analyzed and the exclusion limit of post group.Use and to obtain and kurtosis molecular weight (Mp) be ~ 580 to 10,000,000 17 individual polystyrene standard sample generation working curves from Polymer Laborator ies (Amhers t, MA).Before the retention volume measuring often kind of polystyrene standard sample, each round calibration flow velocity is thought that flowrate marker thing is given and shares peak position (be taken as and just inject peak).When the sample is analyzed, flowing marker peak position corrected flow rate is used.Following generation working curve (log (Mp) vs. retention volume): be recorded in the peak place record retention volume in the DRI signal of often kind of PS standard model, and this data set is fitted in second-order polynomial expression.Equivalent molecular weight of polyethylene is measured with the Mark-Houwink coefficients shown in following table B by using:

Table B

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

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

Fig. 2 shows from embodiment 2B (at this, polyethylene) MWD of multimodal state polyolefin compositions that obtains, described embodiment 2B comprises by use the method contacted with triethyl aluminum with oxygen that comprises that dichloro two (1-methyl, 3-butyl cyclopentadienyl) closes the hybrid catalyst system of zirconium and pair (cyclopentadienyl) chromium and obtains.Contriver is surprised to find, and observes another kind of kurtosis, and this kurtosis is different from described first polyolefin component in molecular weight.At this, viewed new polyolefin component has the molecular weight higher than the first polyolefin component and does not exist usually owing to the lower molecular weight tail composition of organo-chromium compound.Owing to there is not this lower molecular weight tail composition, (Mw/Mn is 4.24, embodiment 2B, below embodiment part) is unexpectedly narrow so the MWD of multimodal state polyolefin compositions, such as 4.24 (embodiment 2B).

In some embodiments, context of methods preparation has 5,000g/mol-600,000g/mol; Preferably 8,000g/mol-400,000g/mo l; Or first polyolefin component of the Mw of 10,000g/mo l-300,000g/mol.In some embodiments, context of methods preparation has about 1.1-about 10, about 2-about 8, or first polyolefin component of the MWD of about 2.2-about 5.In some embodiments, context of methods preparation has a kurtosis, or has the first polyolefin component of two kurtosis.In some embodiments, in some embodiments, context of methods preparation has 5,000g/mol-600,000g/mol; Preferably 8,000g/mol-400,000g/mol; Or the Mw of 10,000g/mol-300,000g/mol; About 1.1-about 10, about 2-about 8, or the MWD of about 2.2-about 5; And there is a kurtosis, or there is the first polyolefin component of two kurtosis.

In some embodiments, context of methods preparation comprises another kind and has 500,000g/mol-5,000,000g/mol; Preferably 550,000g/mol-2,500,000g/mol; Or the multimodal state polyolefin compositions of the polyolefin component of the Mw of 600,000g/mol-1,000,000g/mol.In some embodiments, context of methods preparation comprises another kind and has about 1.1-about 10, about 2-about 9, or the multimodal state polyolefin compositions of the polyolefin component of the MWD of about 2.2-about 6.In some embodiments, context of methods preparation comprises the multimodal state polyolefin compositions that another kind has the polyolefin component of single kurtosis.In some embodiments, context of methods preparation comprises another kind and has 500,000g/mol-5,000,000g/mol; Preferably 550,000g/mol-2,500,000g/mol; Or the Mw of 600,000g/mol-1,000,000g/mol; About 1.1-about 10, about 2-about 9, or the MWD of about 2.2-about 6; And there is the multimodal state polyolefin compositions of the polyolefin component of single kurtosis.

In some embodiments, context of methods preparation comprises and is less than 5wt%, is less than 2.5wt%, or is less than 1wt% and has and be less than 300,000g/mol, is less than 350,000g/mol or is less than the multimodal state polyolefin compositions of component of molecular weight of 375,000g/mol.The percentage with the multimodal state polyolefin compositions of the molecular weight being less than 300,000g/mol can use the technical measurement separate stage of the sample of fluoropolymer resin being divided segregation.A kind of such technology is Rising Elution Fractionation (TREF), and as the J.Poly.Sci. of the people such as Wild, 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 of the multimodal state polyolefin compositions with the molecular weight being less than 300,000g/mol, the data obtained from above-mentioned TREF technology are first used 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 dissolved.From this solubleness distribution curve, the percentage of the multimodal state polyolefin compositions with the molecular weight being less than 300,000g/mo l can be measured.

In some embodiments, context of methods preparation has at least two kurtosis, or the multimodal state polyolefin compositions of at least three kurtosis.

In some embodiments, context of methods prepares multimodal state polyolefin compositions, and it comprises (i) and has 5,000g/mol-600,000g/mol; Preferably 8,000g/mol-400,000g/mol; Or the Mw of 10,000g/mol-300,000g/mol; About 1.1-about 10, about 2-about 8, or the MWD of about 2.2-about 5; And there is a kurtosis, or there is the first polyolefin component of two kurtosis; (i i) another kind has 500,000g/mol-5,000,000g/mol; Preferably 550,000g/mol-2,500,000g/mol; Or the Mw of 600,000g/mol-1,000,000g/mol; About 1.1-about 10, about 2-about 9, or the MWD of about 2.2-about 6; And there is the polyolefin component of single kurtosis; Wherein said multimodal state polyolefin compositions: (a) has about 1.1-about 15, about 2-about 12, or the MWD of about 2.2-about 7.5; B () comprises and is less than 5wt%, be less than 2.5wt%, or is less than 1wt% and has and be less than 300,000g/mol, is less than 350,000g/mol, or is less than the component of molecular weight of 375,000g/mol; (c) there is multimodal state molecular weight distribution, preferably there are at least two kurtosis, or at least three kurtosis.

Above-mentioned lower molecular weight tail composition uses organic chromium catalyzer or conventional mixed catalyst, the characteristic of the polymkeric substance that such as metallocenes/organic chromium catalyzer obtains, and normally undesirable, because described lower-molecular-weight component may cause the film outward appearance of difference, such as, there is gel.In addition, the existence of low-molecular-weight polyolefin in multimodal state polyolefin compositions may cause smoldering in die orifice-lip accumulation and on-line operation.Of the present invention do not have the multimodal state polyolefin compositions of this lower molecular weight tail composition can process film forming and pipe on existing, and in film preparation or pipe is applied to the workability shown, and the film product with low gel level (excellent FQR) can be provided.FQR is the qualitative sequence of gel level, and from 10 to 60, wherein 10FQR indicates gel-free and the gel of the unacceptable high quantity of 60FQR instruction.In embodiment herein, multimodal state polyolefin compositions of the present invention can have and is less than 20FQR, the gel level of 30FQR or 40FQR.Multimodal state polyolefin compositions of the present invention can also show reduction towards the tendency of smoldering in the accumulation of die orifice-lip and on-line operation.Therefore, multimodal state polyolefin compositions display of the present invention is better than the polyolefinic unexpected advantage of multimodal state using conventional mixed catalyst such as metallocenes/organic chromium catalyst preparing.

Mixed catalyst composition and component

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

Concerning the object of the invention and claim object thereof, when catalyst composition is described as the neutral stable form comprising component, it will be understood by those skilled in the art that the ionic species of component is to produce the form of polymkeric substance with monomer reaction.Concerning the object of the invention and claim object thereof, " alkyl replaced " is the group be made up of carbon and hydrogen, and wherein at least one hydrogen is substituted by heteroatoms.For the present invention and appended claims, " alkoxy radical " comprises 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 one comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; (ii) activator; (iii) at least one organic chromium polymerizing catalyst; (iv) solid support material; Wherein wherein described in comprise the activated polymerizing condition of polymerizing catalyst of the 4th race or the 5th group 4 transition metal under, described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein with molecular switch, preferably comprise after oxygen contacts with the molecular switch of alkylaluminium cpd, and under polymerization conditions, organic chromium polymerizing catalyst is than the active as many as few 50% of polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal.

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

I () comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal

The invention provides the loading type mixed catalyst composition comprising polymerizing catalyst, described polymerizing catalyst comprises the 4th race 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 comprising the 4th race or the 5th group 4 transition metal can be metalloscene catalyst.Metalloscene catalyst is defined as the cyclopentadienyl moiety (or the cyclopentadienyl moiety replaced) with at least one π-keyed jointing, the more generally organometallic compound of the cyclopentadienyl moiety of two π-keyed jointings or the structure division of replacement.This comprises the structure division such as indenyl or fluorenyl or derivatives thereof of other π-keyed jointing.

Metalloscene catalyst

In some embodiments, the polymerizing catalyst comprising the 4th race 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 race 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 ^bopen, acyclic or condensed ring or ring system, comprise do not replace or replace cyclopentadienyl ligands, hybrid atom MCM-41 and/or containing heteroatomic cyclopentadienyl ligands;

Each X is leavings group;

A* is bridging base; With

N is 0,1,2 or 3.

In one embodiment, L ^aand L ^bcan be can carry out any ligand structure of π-keyed jointing, such as indenes, fluorenes, phenyl, benzyl etc. with M.In another embodiment, L ^aand L ^bone or more heteroatoms can be comprised, such as, nitrogen, silicon, boron, germanium, sulphur and phosphorus, it is combined with carbon atom and forms ring that is open, acyclic or that preferably condense or ring system, such as, heterocyclic pentylene base assistant ligand.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 an only existence.

Each L ^aand L ^bcan not replace independently or replace has at least one R* substituting group, wherein replaces and refers to L ^aand/or L ^bat least one (or at least 2,3,4,5,6,7,8 or 9) hydrogen base on (such as, cyclopentadiene, indenes, fluorenes, phenyl, benzyl etc.) is replaced by R*.The limiting examples of substituent R * comprises and is selected from hydrogen, or straight or branched alkyl, thiazolinyl, alkynyl; cycloalkyl, aryl, acyl group; aryl, alkoxyl group, aryloxy; alkyl sulfenyl, dialkyl amido, alkoxy carbonyl; aryloxycarbonyl, formamyl, alkyl or dialkyl-carbamoyl radicals; acyloxy, amido, one or more in amino or their combination of virtue.In a preferred embodiment, substituent R * has 50 non-hydrogen atoms at the most, and a preferred 1-30 carbon, 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 their isomer all, the such as tertiary butyl, sec.-propyl etc.Other alkyl comprises methyl fluoride, fluoro ethyl, two fluoro ethyls, iodine propyl group, bromine hexyl, the organic quasi-metal group that chlorobenzyl and alkyl replace, and comprises trimethyl silyl, trimethylgermyl groups, methyl diethylsilane base etc.; Organic quasi-metal group with brine alkyl replaces, comprises three (trifluoromethyl)-silyls, methyl-bis-(difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Two replace boron group comprises such as dimethyl boron; Two replace pnicogen group, comprise dimethyl amine, dimethyl phosphine, pentanoic, aminomethyl phenyl phosphine; Chalcogen radicals, comprises methoxyl group, oxyethyl group, propoxy-, phenoxy group, dimethyl sulphide and diethyl sulfide.Non-hydrogen substituent R* comprises atoms carbon, silicon, 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, such as fourth-3-thiazolinyl, the third-2-thiazolinyl, oneself-5-thiazolinyl etc.In addition, in some embodiments, at least two R* groups, preferably two adjacent R group can be connected to form and have the ring structure that 3-30 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 L keyed jointing with metal M.Especially preferred R* substituting group comprises C ₁-C ₃₀alkyl, heteroatoms or containing 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, the phenyl of replacement, benzyl (comprising the benzyl of replacement), cyclohexyl, cyclo-dodecyl, norcamphyl and their all isomer.

Part (L ^aand L ^b) limiting examples comprise cyclopentadienyl ligands, ring penta phenanthryl part, indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, dibenzo [b; h] fluorenyl ligand, benzo [b] fluorenyl ligand, cyclooctatetraene ylidene ligands, cyclopentano cyclododecene part, azenyl ligands, azulene part, pentalene part, phosphoryl part, phosphinimine, pyrryl part, pyrozolyl ligands, carbazolyl ligands, boron mixes benzene (bora tobenzene) part etc.; comprise their hydrogenated version, such as 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, such as at least one leavings group X.In one embodiment, X is the single anion ligand with M keyed jointing.Depend on the oxidation state of metal, the value of n is 0,1,2 or 3, so that formula (I) and (II) represent neutral ligand metallocene catalyst compound above.The limiting examples of X leavings group comprises weak base, such as carboxylate salt, diene, containing the alkyl of 1-20 carbon atom, and hydride or halogen etc., or their combination.In another embodiment, two or more X-shapeds become a part for 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 (methylphenylamine), 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 (such as methyl, ethyl, propyl group, butyl, hexyl and octyl group).

In formula (II), bridging base A* is by L ^aand L ^bbridging.The limiting examples of bridging base A* comprises containing at least one 13-16 race 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 divalent moiety.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 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, the alkyl of replacement, halocarbyl, the halocarbyl of replacement, silyl carbon back or germyl carbon back substituting group, and two or more adjacent R' optionally can engage formed substituted 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, and such as dialkyl silyl, 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 cyclopentadienyl, the cyclopentadienyl of replacement, indenyl, the indenyl of replacement, fluorenyl or replacement;

Each X is selected from hydride; Substituted or unsubstituted C ₁-C ₃₀alkyl; Alkoxide; Virtue oxide compound; Aminate; Halogenide; Phosphide; With the single anion ligand of one of the 14th race's organic quasi-metal; Or two X can form alkylidene or cyclometallated hydrocarbyl radical or other two anion ligand together;

A* is bridging base;

M is 0 or 1; With

N is 0,1,2 or 3.

In some embodiments, L ^aand L ^bcan replace and have substituent R ", each radicals R " is C independently ₁-C ₃₀alkyl, wherein said C ₁-C ₃₀alkyl is preferably aliphatic or aromatics.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, the alkyl of replacement, halocarbyl, the halocarbyl of replacement, silyl carbon back or germyl carbon back substituting group.

In another embodiment, the metalloscene catalyst represented by formula (IV) is useful herein.

L ^AA*J*MX _n(IV)

Wherein M is zirconium, hafnium, vanadium or titanium;

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

Each X is the leavings group with M keyed jointing;

J* be with M keyed jointing containing heteroatomic part;

A* is 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 fused ring system.J* contains the heteroatoms being selected from 13-16 race, preferred nitrogen, boron, sulphur, oxygen, aluminium, silicon, phosphorus and tin.In some embodiments, J* contains the heteroatoms with ligancy 3 being selected from the 15th race or the heteroatoms with ligancy 2 being selected from the 16th race.Preferably, J* contains nitrogen, phosphorus, oxygen or sulphur atom, and nitrogen is most preferred.These examples containing heteroatomic Ligand Metallocene 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; 5,756,611 and 5,856, in 258; They are all incorporated herein for reference.

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

Wherein:

M is Zr, Hf or Ti;

Cp is cyclopentadienyl rings;

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

Each X is selected from hydride; Substituted or unsubstituted C ₁-C ₃₀alkyl; Alkoxide; Virtue oxide compound; Aminate; Halogenide or phosphide; The single anion ligand of one of the 14th race's organic quasi-metal; Or two X can form alkylidene or cyclometallated hydrocarbyl radical or other two anion ligand together;

Y is 0 or 1;

As y=1, with the bridging base of Cp and J covalency keyed jointing while that A* being;

L is optional neutral Lewis base than water, such as alkene, diene, aryne, amine, phosphine, ether or sulfide, such as amine, phosphine, ether, such as, and diethyl ether, tetrahydrofuran (THF), xylidine, aniline, three methylphosphines and n-Butyl Amine 99; With

W is the number of 0-3.

When using in formula (V), Cp comprise cyclopentadiene part and they can carry out the analogue of π-keyed jointing with M, such as, Cp comprises indenes and fluorenes.In some embodiments, when y is 0, Cp can replace 0-5 the radicals R * replaced; With when y is 1, Cp can replace 1-4 the radicals R * replaced; Comprise independently with the radicals R * of each replacement and be selected from one of following group: containing the alkyl of 1-30 carbon, silicon or germanium atom, silyl-alkyl or germyl-alkyl, the alkyl replaced, silyl-alkyl or germyl-alkyl, wherein one or more hydrogen atoms can be closed base (phosphido), alkoxyl group, aryloxy by halogen radical, amido, phosphorus or contain one or more replacement in any group of lewis acidity or basic functionality; C ₁-C ₃₀the metalloid radicals that alkyl replaces, wherein said metalloid is selected from one of the periodic table of elements the 14th race; 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 with formed together with the carbon atom be connected with them can be saturated, part is unsaturated or aromatics, and/or substituted or unsubstituted C ₄-C ₂₀ring system, one or more R* base is elected in described replacement as, as defined above.

In some embodiments, when J* is the 15th race's element, and y is 1, or when the 16th race's element and y are 0, J* can replace a R' base; Or when J* is the 15th race's element and y is 0, J* can replace two R' bases; Or when J* is the 16th race's element and y is 1, J* can be unsubstituted; Each R' base is be selected from following group independently: containing the alkyl of 1-30 carbon, silicon or germanium atom, silyl-alkyl or germyl-alkyl; The alkyl replaced, silyl-alkyl or germyl-alkyl, wherein one or more hydrogen atoms are closed base, alkoxyl group, aryloxy or boron alkyl close one or more replacement in base by halogen radical, amido, phosphorus, preferably, all R' and J* via primary, secondary or fragrant carbon atom, and not directly with silicon or germanium atom keyed jointing.

A* as defined above, in some embodiments, usually comprise at least one the 13rd, 14 or 15 race's element such as carbon, silicon, boron, germanium, nitrogen or phosphorus and additional substituent R * as defined above, so that complete the valency of described 13rd, 14 or 15 race's elements.

In a preferred embodiment, M is Ti; X is chlorine, bromine, benzyl, phenyl or C ₁-C ₁₂alkyl (such as methyl, ethyl, propyl group, butyl, hexyl and octyl group); Y is 1; A* is the bridging base comprising carbon or silicon, and such as dialkyl silyl, 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) ₄; J* is N-R', and wherein R' is C ₁-C ₃₀alkyl, such as cyclo-dodecyl, cyclohexyl, butyl (comprising the tertiary butyl and sec-butyl), benzyl (comprising the benzyl of replacement), methyl, ethyl, amyl group, hexyl, neo-pentyl, cyclopentyl, decyl, propyl group (comprising sec.-propyl, sec.-propyl), norcamphyl and phenyl (comprising the phenyl of replacement, such as 3-tert-butyl-phenyl, 2-aminomethyl phenyl); With the fluorenyl that Cp is cyclopentadienyl, the cyclopentadienyl of replacement, indenyl, the indenyl of replacement, fluorenyl or replacement.Two adjacent substituents can form monokaryon or polycyclic ring.

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

Metallocenes such as the dichloro two (cyclopentadienyl) that other preferred metallocenes comprises non-bridging closes zirconium, dimethyl two (cyclopentadienyl) closes zirconium, dichloro two (1,2-dimethylcyclo-pentadienyl) closes zirconium, dimethyl two (1,2-dimethylcyclo-pentadienyl) closes zirconium, dichloro two (1,3-dimethylcyclo-pentadienyl) closes zirconium, dimethyl two (1,3-dimethylcyclo-pentadienyl) closes zirconium, dichloro two (1-methyl, 3-butyl cyclopentadienyl) closes zirconium, dimethyl two (1-methyl, 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 (pentamethylcyclopentadiene base) closes zirconium, dimethyl two (pentamethylcyclopentadiene base) closes zirconium, dichloro two (propyl-cyclopentadienyl) closes hafnium, dimethyl two (propyl-cyclopentadienyl) closes hafnium and other analogue replaced.

(ii) activator

Use comprises the hybrid catalyst system of activator within the scope of the present invention; Preferably, the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal activates by described activator.In embodiment herein, described activator comprises aikyiaiurnirsoxan beta, comprises the aikyiaiurnirsoxan beta of modification, and non-coordinating anion (NCA).

Aikyiaiurnirsoxan beta is generally containing-A l (R ¹) 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.The mixture of different aikyiaiurnirsoxan beta and modified alumoxane can also be used.Can preferably use visually transparent aikyiaiurnirsoxan beta.Muddiness or gel aikyiaiurnirsoxan beta can be filtered to prepare clear solution or can from the transparent aikyiaiurnirsoxan beta of this turbid solution decantation.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 contained for 041,584 times.

Can be used as the aluminoxane component of activator normally by general formula (R ^x-Al-O) _nthe oligomeric aluminum compound represented, it is ring compound, or by R ^x(R ^x-Al-O) _nalR ^x ₂the oligomeric aluminum compound represented, it is straight chain compound.In described aikyiaiurnirsoxan beta general formula, R ^xc independently ₁-C ₂₀alkyl, such as, methyl, ethyl, propyl group, butyl, amyl group, their isomer etc., the integer that " n " is 1-50.Most preferably, R ^xbe methyl and " n " is at least 4.Methylaluminoxane and modified methylaluminoxane are most preferred.For further describing, see 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.

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

In formula (X), (XI) and (XII), M is the 13rd race's atom, preferred boron or aluminium, more preferably aluminium.(JY) heterocyclic ligand be connected with M is represented.In (JY), Y represents heterocyclic ligand and J represents at least one is included in heteroatoms in part JY.M can with any atom keyed jointing be included in Y, but preferably and heteroatoms J keyed jointing.Preferably, J is the atom being selected from the 15th or 16 races, 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 alkyl that the substituent example be applicable to comprises hydrogen, halogen, straight or branched alkyl, alkenyl or alkynyl, cycloalkyl, aryl, aryl replace, acyl group, aroyl, alkoxyl group, aryloxy, alkyl sulfide, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl or dialkyl-carbamoyl radicals, acyloxy, amido, virtue amino, straight chain, side chain or cyclic alkylidene or their combination.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 their isomer all, such as, and the tertiary butyl, sec.-propyl etc.Other example substituent comprises fluoromethyl, fluoroethyl groups, two fluoro ethyls, iodo propyl group, bromine hexyl and chlorobenzyl.

Preferably, the one or more positions on heterocyclic ligand (JY) replace the group having halogen atom or halogen atom-containing, 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, such as fluorinated phenyl.

Each R' is the substituting group with 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-carbamoyl radicals, acyloxy, amido, virtue amino, straight chain, side chain or cyclic alkylidene or their combination.Each R' can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl, comprises their isomer all, the such as tertiary butyl, sec.-propyl etc.Other R' substituting group be applicable to can comprise alkyl, such as fluoromethyl, fluoroethyl groups, two fluoro ethyls, iodo propyl group, bromo hexyl, chlorobenzyl; The organic quasi-metal base that alkyl replaces, comprises trimethyl silyl, trimethylgermyl groups, methyl diethylsilane base etc.; The organic quasi-metal base that halocarbyl replaces, comprises three (trifluoromethyl)-silyls, methyl-bis-(difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Dibasic boryl, comprises such as dimethyl boron, and dibasic pnicogen base comprises dimethylamine, dimethylphosphine, pentanoic, aminomethyl phenyl phosphine; With 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, the third-2-thiazolinyl, oneself-5-thiazolinyl etc.In addition, at least two R' groups, preferably two adjacent R' groups can be connected to form and have the ring structure that 3-30 is selected from the atom in carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or their combination.In addition, substituent R ' such as 1-butane group can form carbon bond with metal M.In one embodiment, each R' is substituted or unsubstituted alkyl and/or substituted or unsubstituted aryl, and preferred each R' is the alkyl containing 1-30 carbon atom.

In a specific embodiment, at formula (X), (XI) or in (XII), M is Al or B, preferred Al, J is included in the nitrogen-atoms in heterocyclic ligand Y, preferably (JY) is substituted or unsubstituted indyl, wherein said substituting group is preferably hydrogen, 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' is substituted or unsubstituted alkyl and/or substituted or unsubstituted aryl, preferably containing 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 in heterocyclic ligand Y, and wherein said heterocyclic ligand (JY) is unsubstituted heterocyclic ligand.In another embodiment, one or more positions on heterocyclic ligand replace the group having chlorine, bromine and/or fluorine or replacement to have chloride, bromine and/or fluorine, more preferably replace and have group that is fluorine-containing or fluorine, R' is substituted or unsubstituted alkyl and/or substituted or unsubstituted aryl, preferably containing the alkyl of 1-30 carbon atom.In another embodiment, (JY) is 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 in heterocyclic ligand Y, and wherein said heterocyclic ligand (JY) is unsubstituted heterocyclic ligand.In another embodiment, the one or more positions on heterocyclic group replace halogen such as chlorine, bromine and/or fluorine atom, or replaces and have halogen atom, the group of such as 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.

The ratio of minimum activator and transition metal (comprising the polymerizing catalyst of the 4th race or the 5th group 4 transition metal) is mol ratio 1:1.Optional preferred proportion comprises the highest 5000:1, preferably the highest 500:1, preferably the highest 200:1, preferably the highest 100:1, or preferred 1:1-50:1.

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

Use ionization or Stoichiometric activators, neutral or ionic non-coordinating anion (defined in U.S. Patent Publication No. 2009-0318644) such as four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, three perfluorophenyl boron metalloid precursors or three perfluoronapthyl boron metalloid precursors, many halogenations are mixed borane anion (WO98/43983), boric acid (U.S. Patent number 5,942,459) or their combination also within the scope of the present invention.

Preferably, activator is four (perfluoronapthyl) 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 (perfluoronapthyl) borate, four (perfluorinated biphenyl) borate, four (3, two (trifluoromethyl) phenyl of 5-) borate, four (perfluorophenyl) borate 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 useful additional activator, refer to U.S. Patent Publication No. 2009-0318644 herein.The activator that metal oxide carrier combines, such as disclosed in WO/1996/004319, those also can be used for embodiment herein.

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

(iii) organic chromium polymerizing catalyst

Any organic chromium polymerizing catalyst can be used.Organic chromium polymerizing catalysts more used in the present invention have 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, wherein L _aand L _bindependently selected from the fluorenyl of the indenyl of the cyclopentadienyl of cyclopentadienyl, replacement, indenyl, replacement, fluorenyl or 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, the alkyl of replacement, aryl or replacement independently, as long as at least one R group is the aryl of aryl or replacement; Preferred each R is selected from substituted 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 group of 1,3-) chromium (II); Two (trimethylsilyl methyl) chromium (II); Two (2,5-dimethyl pentadiene base) chromium (II); ((tetramethyl-ring pentadienyl) (tert-butylamino) dimetylsilyl) (trimethyl silyl-methyl) chromium (II); Diallyl chromium (II); (pentamethylcyclopentadiene base) two (benzyl) chromium (II) pyridine adduct; Triallyl chromium (III); Three (two (trimethyl silyl) methyl) chromium (III); (pentamethylcyclopentadiene base) two (trimethylsilyl methyl) chromium (III); Tetraallyl chromium (IV); Tetramethyl-chromium (IV); Four (benzyl) chromium (IV); Four neo-pentyl chromium (IV), four (trimethylsilane ylmethyl) chromium (IV); Four (sec.-propyl) chromium (IV); Four (2-phenyl-2-methyl-propyl) chromium (IV); Or their any combination.

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

(iv) solid support material

In embodiment herein, hybrid catalyst system can comprise inert support material.Preferably, solid support material is porous carrier materials, such as, and talcum, and inorganic oxide.Other solid support material comprises zeolite, clay, organic clay or other organic or inorganic solid support material any etc., or their mixture.

Preferably, solid support material is the inorganic oxide of finely divided form.The 2nd, 4,13 and 14 family metal oxides such as silicon oxide, aluminum oxide and their mixture is comprised for the inorganic oxide material be applicable in metallocene catalyst system herein.Can individually or other inorganic oxide be combined with silicon oxide or aluminum oxide be magnesium oxide, titanium oxide, zirconium white etc.But, the solid support material that other is applicable to can be adopted, such as, the polyethylene that finely divided functionalised polyolefin is such as finely divided.The carrier be particularly useful comprises magnesium oxide, titanium oxide, zirconium white, polynite, phyllosilicate, zeolite, talcum, clay etc.In addition, the combination of these solid support materials can be used, such as, silicon oxide-chromium, silica-alumina, silica-titania 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 volume of voids of the about 4.0cc/g of about 0.1-and the mean particle size of about 500 μm of about 5-.More preferably, the surface-area of solid support material is at the about 500m of about 50- ²in the scope of/g, volume of voids in the scope of the about 3.5cc/g of about 0.5-and mean particle size in the scope of about 200 μm of about 10-.Most preferably, the surface-area of solid support material is at the about 400m of about 100- ²in the scope of/g, volume of voids in the scope of the about 3.0cc/g of about 0.8-and mean particle size in the scope of about 100 μm of about 5-.The mean pore size of solid support material used in the present invention is at 10-1000 dust, and about 500 dusts of preferred 50-, in the scope of most preferably about 350 dusts of 75-.In some embodiments, solid support material is the silicon oxide (surface-area=300m of high surface area, amorphous 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, DAVI SON948 is used.

Solid support material should be dry, namely not containing the water absorbed.The drying of solid support material can by about 100 DEG C-about 1000 DEG C, and preferably heating or calcining are carried out at least about 600 DEG C.When solid support material is silicon oxide, it is heated at least 200 DEG C, and preferably approximately 200 DEG C is to about 850 DEG C, and optimum is chosen about 600 DEG C and kept about 1 minute-about 100 hours, about 12 hours-about 72 hours, or about 24 little times up to about 60 hours.Solid support material through calcining must have at least some reactive hydroxyl (OH) to prepare invention catalyst system.Then the described solid support material through calcining and at least one is allowed to comprise polymerizing catalyst and at least one activating agent of the 4th race or the 5th group 4 transition metal, as discussed above.

The manufacture method of loading type hybrid catalyst system

The mixed catalyst composition of the product of contact comprising following material is contained in the present invention: (i) comprises the polymerizing catalyst of the 4th race or the 5th group 4 transition metal, (ii) activator, (iii) organic chromium polymerizing catalyst, (iv) solid support material, often kind of component in them as above discuss.

The invention further relates to the preparation method of loading type hybrid catalyst system, comprise: (i) makes solid support material and the polymerizing catalyst and the activating agent that comprise the 4th race or the 5th group 4 transition metal, so that the reactive group on solid support material described in titration, and form supported polymerisation catalysts; (ii), after, described supported polymerisation catalysts is made to contact to form loading type hybrid catalyst system with organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst and the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal differ at least 50% in molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system wherein described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be the polymerizing catalyst little at least 50% comprising the 4th race or the 5th group 4 transition metal under active polymerizing condition described in specific activity.

In embodiment herein, allow solid support material contact with the solution of activator with the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal, so that reactive group on solid support material is titrated, and forms supported polymerisation catalysts.Comprise the polymerizing catalyst of the 4th race or the 5th group 4 transition metal, the duration of contact between activator compound and solid support material grows to as the reactive group on titration solid support material must." titration " refers to and the available reaction-ity group reaction in surfaces of carrier materials, thus surface hydroxyl is reduced by least 80%, at least 90%, at least 95% or at least 98%.Can based on the calcining temperature of used solid support material and type determination surface reaction radical concentration.Solid support material calcining temperature affects and solid support material can be used for the number of the surface reaction group reacted with the polymerizing catalyst and activator that comprise the 4th race or the 5th group 4 transition metal: drying temperature is higher, and the number at position is lower.Such as, when solid support material be before it is for the first catalyst system synthesis step by make its fluidization with nitrogen and the silicon oxide heating at about 600 DEG C about 16 hours and dewater time, usually reach the concentration of surface hydroxyl groups of about 0.7 mmole/gram (mmol/gm).Therefore, on carrier, the Precise molar ratios of activator and surface reaction group will change.Preferably, this determines ensure only to be added to by so many activator in solution so that do not allow excessive activator in the solution by depositing on solid support material based on concrete occasion.

The amount of excessive activator in the solution is not allowed to measure in any conventional manner by settling to solid support material, such as measure as follows: activator is added in carrier slurry in a solvent, stir this slurry, such as, until by any technology as known in the art, pass through simultaneously ¹it is the solution in described solvent that H NMR detects activator.Such as, for the silica support material of heating at about 600 DEG C, the mol ratio that the amount of adding the activator in slurry to meets Al and hydroxyl (OH) on silicon oxide is the about 4:1 of about 0.5:1-, the about 3:1 of preferably approximately 0.8:1-, more preferably about about 2:1 of 0.9:1-, most preferably about 1:1.On silicon oxide, the amount of Al can measure by using ICPES (inductively coupled plasma emission spectrometry), the method is described in C.R.Brundle, C.A.Evans, Jr. the material compiled with S.Wilson characterizes " the inductively coupled plasma emission spectrometry " of J.W.Olesik in encyclopedia (Encyclopedia of Mater ia l s Character izat ion), But terworth-Heinemann, Boston, Mass., 1992, in 633-644 page.In another embodiment, the activator exceeded the amount deposited on carrier can also be added, then remove, such as, by filtering and washing, any excessive activator.

To the solid support material slurrying of reactive surfaces group (usual hydroxyl) be had and allow the slurry of gained contact with the solution of activator with the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal in non-polar solvent.Prepare solid support material slurry in a solvent by solid support material being imported solvent, and this mixture is heated to about 0 DEG C-about 70 DEG C, preferably approximately 25 DEG C-about 60 DEG C, 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 be applicable to is wherein all reactants used herein, and namely activator and the polymerizing catalyst that comprises the 4th race or the 5th group 4 transition metal are solvable at least partly and are the material of liquid at the reaction temperatures.Preferred non-polar solvent is alkane, such as iso-pentane, hexane, normal heptane, octane, nonane and decane, but also can adopt other material various, comprises naphthenic hydrocarbon, such as hexanaphthene, aromatic substance, such as benzene, toluene and ethylbenzene.

Formation supported polymerisation catalysts after, relief described in supported polymerisation catalysts contact to form 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 organic chromium catalyzer-about 24 hours, about 2 hours-about 16 hours, or about 4 hours-about 8 hours.During duration of contact, mixture can be heated to about 10 DEG C-about 200 DEG C, about 20 DEG C-about 95 DEG C, preferably during duration of contact, not heat this mixture.

The mol ratio of the polymerizing catalyst and organic chromium polymerizing catalyst that comprise the 4th race or the 5th group 4 transition metal can be the about 1:10 of the about 1:100 of about 100:1-, about 10:1-, or about about 1:5 of 5:1-.The mol ratio of the polymerizing catalyst and activator compound that comprise the 4th race or the 5th group 4 transition metal can be the about 1:10 of the about 1:5 of the about 1:1 of about 1:100-, about 1:100-, about 1:50-.

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

Previously prepared or commercially available loading type is used to comprise the polymerizing catalyst of the 4th race or the 5th group 4 transition metal and activator forms hybrid catalyst system of the present invention advantageously within the scope of the present invention, as long as the reactive group on titration solid support material.In such embodiments, previously prepared or commercially available supported polymerisation catalysts is allowed to contact to form hybrid catalyst system with the first organic chromium polymerizing catalyst.Be typically about 0.5 hour the duration of contact between described previously prepared or commercially available supported polymerisation catalysts and organic chromium catalyzer-about 24 hours, about 2 hours-about 16 hours, or about 4 hours-about 8 hours.During duration of contact, mixture can be heated to about 10 DEG C-about 200 DEG C, about 20 DEG C-about 95 DEG C, preferably during duration of contact, not heat this mixture.Use previously prepared or commercially available supported polymerisation catalysts to be favourable, because it allows more easily screening of mixed catalyst, more efficiently, and save time.

In particular embodiments, the invention further relates to the manufacture method of loading type hybrid catalyst system, comprise: (i) allow solid support material with comprise polymerizing catalyst and the activating agent of the 4th race or the 5th group 4 transition metal, so that comprise the polymerizing catalyst of the 4th race or the 5th group 4 transition metal and the weight ratio of solid carrier material at the about 0.0001:1 of about 10:1-, the about 0.001:1 of about 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 the about 100:1 of about 1:10-, the about 100:1 of about 1:1-, or in the scope of about about 10:1 of 1:1-, so that the reactive group on titration solid support material, at about 10 DEG C-about 200 DEG C, at the temperature of about 20 DEG C-about 95 DEG C, keep about 0.5 hour-about 24 hours, about 2 hours-about 16 hours, or about 4 hours-about 8 hours, preferably during the duration of contact forming supported polymerisation catalysts, do not heat this mixture; (ii) supported polymerisation catalysts described in relief and organic chromium polymerizing catalyst are at about 10 DEG C-about 200 DEG C, about 0.5 hour-about 24 hours are contacted at the temperature of about 20 DEG C-about 95 DEG C, 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 loading type hybrid catalyst system; Wherein said organic chromium polymerizing catalyst and the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal differ at least 50% in molecular switch response; With the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system wherein described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be the polymerizing catalyst little at least 50% comprising the 4th race or the 5th group 4 transition metal under active polymerizing condition described in specific activity.

In another embodiment, the present invention relates to:

1. the preparation method of multimodal state polyolefin compositions, comprising:

I () makes at least one first olefinic monomer contact under polymerization conditions with hybrid catalyst system; There is 5,000g/mol-600,000g/mol at least to prepare, preferably 8,000g/mol-400,000g/mol; Or first polyolefin component of the Mw of 10,000g/mol-300,000g/mol; Wherein said hybrid catalyst system comprises:

A () at least one comprises the 4th race or the 5th group 4 transition metal; Preferred zirconium, hafnium, titanium or vanadium; Preferred zirconium, hafnium or titanium; The polymerizing catalyst of preferred zirconium or hafnium; Or the metallocenes be more preferably expressed from the next:

(i)L ^AL ^BMX _n；

Or

(ii)L ^AA*L ^BMX _n；

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

Each X is leavings group;

A* is bridging base; With

N is 0,1,2 or 3;

B organic chromium polymerizing catalyst that () at least one 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；

Wherein L _aand L _bindependently selected from the fluorenyl of the indenyl of the cyclopentadienyl of cyclopentadienyl, replacement, indenyl, replacement, fluorenyl or 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, the alkyl of replacement, aryl or 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) after, make the combination of described 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; Oxygen preferably in air form contacts; With

(iii) the second olefinic monomer that described first polyolefin component/hybrid catalyst system combination and at least one can be identical or different is made to contact under polymerization conditions; With

(iv) obtain multimodal state polyolefin compositions, described multimodal state polyolefin compositions optionally has:

A () has 5,000g/mol-600,000g/mol, and preferably 8,000g/mol-400,000g/mol; Or the Mw of 10,000g/mol-300,000g/mol; Be greater than the Mw/Mn of 1 to about 10; And there is the first polyolefin component of at least one kurtosis; With

(b) another kind of polyolefin component; With

Wherein said multimodal state polyolefin compositions:

I () has the MWD being greater than 1 to about 15;

(ii) component with the molecular weight being less than 300,000g/mol being less than 5wt% is comprised; With

(iii) there is multimodal state molecular weight distribution, preferably there are two kurtosis, or preferred three kurtosis.

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

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

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

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

6. the method for section 1-5, wherein step (i)-(iv) carries out in single reactor.

7. the method for section 1-6, wherein sequentially adds oxygen and the aluminum alkyl component of described molecular switch.

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

9. the hybrid catalyst system of arbitrary section in the section of can be used for 1-8, wherein, under the polymerizing condition of step (i), described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be active and described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race 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 than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

10. the preparation method of loading type hybrid catalyst system of sections 9, comprising:

I () makes described solid support material and the polymerizing catalyst and the activating agent that comprise the 4th race or the 5th group 4 transition metal, so that the reactive group on solid support material described in titration, and forms supported polymerisation catalysts;

(ii), after, described supported polymerisation catalysts is made to contact to form loading type hybrid catalyst system with described organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst and the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal differ at least 50% in molecular switch response; Under the polymerizing condition of step (i), the polymerizing catalyst little at least 50% of the 4th race or the 5th group 4 transition metal described in specific activity, is comprised with the organic chromium polymerizing catalyst of wherein said loading type hybrid catalyst system.

Embodiment

Characterization of The Products

Use Waters Alliance GPC2000Ser ies analyzing polymers product.Trichlorobenzene (TCB) is used at the temperature of 140 DEG C, to obtain Mw, Mn and MWD data as the flow velocity of solvent 1mL/min.Use the BHT (BHT) pressing the concentration of 1.0g/L as the stablizer in 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 carried out as follows: heating 20 hours under mild stirring once in a while at 160 DEG C-170 DEG C.Use two Waters HT-6E posts (7.8 × 300mm).With wide straight linear polyethylene standard model (the Mar l ex determining molecular weight ^tMbHB5003 resin) calibrate this post.

Except as otherwise noted, all molecular weight of report are in units of g/mol.

Material

Two (cyclopentadienyl) chromium is bought and 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 former state use from Albemarle (BatonRouge, LA).Triethyl aluminum and triisobutyl aluminium are bought and former state use from AkzoNobe l (Chicago, IL).Toluene is bought from Sigma Aldr ich (St.Loui s, MO) and is used the alumina bead calcined in advance dry.

Catalyst system synthesizes

Catalyzer 1:

In toluene slurry (10ml), two (cyclopentadienyl) chromium (10mg) is combined with 1.0 grams of silicon oxide (Grace Davi son948 is calcined to 600 DEG C in advance and keeps 72 hours).After one hour, red solution becomes colourless, because two luxuriant chromium and described silicon oxide react.The solution that will close the MAO toluene solution of zirconium and 1.6 grams of 30wt% containing 16mg dichloro two (1-methyl, 3-butyl cyclopentadienyl) adds in described slurry.Described slurry is allowed at room temperature to leave standstill two hours.After 2 hours, described loaded catalyst is filtered and drying under vacuo.

Catalyzer 2:

Will containing two (the 1-methyl of 16mg dichloro, 3-butyl cyclopentadienyl) solution that closes the MAO toluene solution of zirconium and 1.6 grams of 30wt% adds in the slurry of 1.0 grams of silicon oxide (Grace Davi son948 is calcined to 600 DEG C in advance and keeps 72 hours) in toluene.Described slurry is allowed at room temperature to leave standstill two hours.After 2 hours, two (cyclopentadienyl) chromium (8mg) is added.Allow described slurry at room temperature hold over night.Filter described loaded catalyst and drying under vacuo.

Polymerization

Embodiment 1:

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

Polyvinyl resin (250mg) after being exposed in air and 30mg triethyl aluminum (TEA1) are placed in Parr reactor and at 85 DEG C ethene with being pressurized to 200ps i.After 12h, reaction produces 620mg polyethylene, increases 0.590mg.

Embodiment 2:

Embodiment 2A:

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

Embodiment 2B:

Then, the polyethylene of 0.409g embodiment 2A is placed in vial, takes out from loft drier and expose in atmosphere.In the second vial, add 3 volumetric pipettes and drip TEA1 and this vial is placed in Parr autoclave.Vial containing described polymkeric substance is placed in above this vial containing described TEAL.Then seal this reactor and be pressurized to 200ps i (1.38MPa) with ethene, and be placed in the oil bath of 85 DEG C keep 45 minutes.Such generation 0.637g polymer beads, increases 0.228g.Polymer characterization: Mn=126,258; Mw=535,110; Mw/Mn=4.24 (the GPC trace see Fig. 2).

Described herein, the All Files comprising any priority document and/or testing sequence is combined in herein by reference, to the degree that they are not inconsistent with present disclosure, as long as but in the initial application submitted to or submit to any priority document do not enumerated in document not combine by reference.It is evident that from above-mentioned general introduction and particular, although have illustrated and described form of the present invention, various amendment can made 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 to think with regard to Australian law and " comprise " synonym with term.Equally, " comprise " and contain term " primarily of ... form ", " be " and " by ... form " and use " comprise " Anywhere can with " primarily of ... form ", " be " and " by ... form and " replace.

Claims

1. a hybrid catalyst system, comprises:

A () at least one comprises the polymerizing catalyst of the 4th race 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；

Wherein L _aand L _bindependently selected from the fluorenyl of the indenyl of the cyclopentadienyl of cyclopentadienyl, replacement, indenyl, replacement, fluorenyl or 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, the alkyl of replacement, aryl or replacement independently, as long as at least one R base is the aryl of aryl or replacement;

(c) activator;

D () comprises the molecular switch of oxygen and alkylaluminium cpd; With

(e) solid support material;

Wherein wherein described in comprise the activated polymerizing condition of polymerizing catalyst of the 4th race or the 5th group 4 transition metal under, described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein after contact with molecular switch and under polymerization conditions, described organic chromium polymerizing catalyst has than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

2. the hybrid catalyst system of claim 1, wherein the 4th race or the 5th group 4 transition metal catalyzer are expressed from the next:

(i)L ^AL ^BMX _n；

Or

(ii)L ^AA*L ^BMX _n；

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

Ligand L ^aand L ^bit is open, acyclic or condensed ring system;

Each X is leavings group;

A* is bridging base; With

N is 0,1,2 or 3.

3. the hybrid catalyst system of claim 2, wherein ligand L ^aand L ^bit is open, acyclic or condensed ring.

4. the hybrid catalyst system of claim 2, wherein ligand L ^aand L ^bit is the cyclopentadienyl ligands that do not replace or replace and/or containing heteroatomic cyclopentadienyl ligands.

5. the hybrid catalyst system of claim 2, wherein ligand L ^aand L ^bit is the cyclopentadienyl ligands of hybrid atom MCM-41.

6. the hybrid catalyst system any one of claim 1-4, wherein the 4th race or the 5th group 4 transition metal are Zr, Hf, Ti or V.

7. the hybrid catalyst system any one of claim 1-4, wherein activator is aikyiaiurnirsoxan beta.

8. the preparation method of multimodal state polyolefin compositions, comprising:

I () makes at least one first olefinic monomer contact under polymerization conditions with hybrid catalyst system; Have 5,000g/mol-600 at least to prepare, first polyolefin component of the Mw of 000g/mol, wherein said hybrid catalyst system comprises:

(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；

Or

(ii i)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

(c) activator; With

(d) solid support material;

(ii), after, the first polyolefin component/hybrid catalyst system combination is contacted with molecular switch, and wherein said molecular switch comprises oxygen and alkylaluminium cpd; With

(iii) the second olefinic monomer that the first polyolefin component/hybrid catalyst system combination and at least one can be identical or different is made to contact under polymerization conditions; With

A () has 5,000g/mol-600, the Mw of 000g/mol; Be greater than the Mw/Mn of 1 to 10 and there is the first polyolefin component of at least one kurtosis; With

(b) another kind of polyolefin component; With

Wherein said multimodal state polyolefin compositions:

I () has the MWD being greater than 1 to 15;

(iii) there is multimodal state molecular weight distribution.

9. the method for claim 8, wherein under the polymerizing condition of step (i), described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be active and described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

10. the method for claim 8, wherein after contacting with molecular switch and under the polymerizing condition of step (iii), described organic chromium polymerizing catalyst has than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

The method of 11. claims 8, the wherein said polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal, by contacting and passivation with molecular switch, does not produce the first additional polyolefin component can measuring quantity.

The method of 12. claims 8, the wherein said polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal has the response of negative molecular switch and described organic chromium polymerizing catalyst has the response of positive molecular switch.

Method any one of 13. claim 8-12, wherein step (i)-(iv) carries out in single reactor.

Method any one of 14. claim 8-12, wherein sequentially adds oxygen and the aluminum alkyl component of described molecular switch.

Method any one of 15. claim 8-12, wherein step (i)-(iv) carries out in Gas-phase reactor.

Method any one of 16. claim 8-12, wherein the 4th race or the 5th group 4 transition metal catalyzer are expressed from the next:

(i)L ^AL ^BMX _n；

Or

(ii)L ^AA*L ^BMX _n；

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

Ligand L ^aand L ^bit is open, acyclic or condensed ring system;

Each X is leavings group;

A* is bridging base; With

N is 0,1,2 or 3.

The method of 17. claims 16, wherein ligand L ^aand L ^bit is open, acyclic or condensed ring.

The method of 18. claims 16, wherein ligand L ^aand L ^bit is the cyclopentadienyl ligands that do not replace or replace and/or containing heteroatomic cyclopentadienyl ligands.

The method of 19. claims 16, wherein ligand L ^aand L ^bit is the cyclopentadienyl ligands of hybrid atom MCM-41.

Method any one of 20. claim 8-12, wherein the 4th race or the 5th group 4 transition metal are Zr, Hf, Ti or V.

Method any one of 21. claim 8-12, wherein said molecular switch comprises the oxygen of the form of air.

Method any one of 22. claim 8-12, wherein said multimodal state polyolefin compositions has 2 kurtosis.

Method any one of 23. claim 8-12, wherein said molecular switch comprises oxygen and alkylaluminium cpd.

Method any one of 24. claim 8-12, wherein said activator is aikyiaiurnirsoxan beta.

Method any one of 25. claim 8-12, wherein under the polymerizing condition of step (i), described in comprise the 4th race or the 5th group 4 transition metal polymerizing catalyst be active and described organic chromium polymerizing catalyst has than the described activity comprising the activity little at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal; Wherein after contacting with molecular switch and under the polymerizing condition of step (i i i), described organic chromium polymerizing catalyst has than the described activity comprising the activity large at least 50% of the polymerizing catalyst of the 4th race or the 5th group 4 transition metal.

The method of the hybrid catalyst system of 26. preparations any one of claim 1-7, comprising:

I () makes solid support material and the polymerizing catalyst and the activating agent that comprise the 4th race or the 5th group 4 transition metal, so that the reactive group on solid support material described in titration, and forms supported polymerisation catalysts;

(ii), after, described supported polymerisation catalysts is made to contact to form loading type hybrid catalyst system with described organic chromium polymerizing catalyst; Wherein said organic chromium polymerizing catalyst and the polymerizing catalyst comprising the 4th race or the 5th group 4 transition metal differ at least 50% in molecular switch response; With