CN101018815B

CN101018815B - Olefin polymerization multi-catalyst and reactor assembly and the polymer produced

Info

Publication number: CN101018815B
Application number: CN200580019491.3A
Authority: CN
Inventors: R·艾伯哈里; C·L·西姆斯; 江培军; D·R·约翰斯拉德; J·A·M·肯尼奇
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2004-04-15
Filing date: 2005-04-13
Publication date: 2016-11-30
Anticipated expiration: 2025-04-13

Abstract

The present invention relates to produce the continuation method of branched olefin polymer, including: 1) it is selected to produce under the polymerizing condition selected have≤100, the first catalytic component of the Mw of 000 and the polymer of the degree of crystallinity of≤20%；2) it is selected to produce under the polymerizing condition selected and there is≤the second catalytic component of the Mw of 100,000 and the polymer of the degree of crystallinity of >=20% (preferably >=40%)；3) catalytic component, one or more activators are made to contact at a temperature of higher than 70 DEG C in the first reaction zone with one or more C2 C40 alkene, the time of staying≤120 minute；With 4) content of the first reaction zone is transferred to second reaction zone, make this content contact at a temperature of higher than 70 DEG C with catalytic component, activator and/or one or more C2 C40 alkene further, the time of staying≤120 minute；With 5) optionally, the content of second reaction zone is transferred to the 3rd reaction zone, make this content contact at a temperature of higher than 70 DEG C with catalyst compounds, activator and/or one or more C2 C40 alkene further, the time of staying≤120 minute；With 6) reclaim the branched olefin polymer of one or more C3 C40 alkene comprising at least 50mol%, wherein the first catalytic component is present at least one reaction zone, second catalytic component is present in second reaction zone, and wherein at least one reaction zone, C2 C40 alkene is C3 C40 alhpa olefin.

Description

Olefin polymerization multi-catalyst and reactor assembly and the polymer produced

Technical field

The present invention relates to use multi-catalyst and the method for multiple reactor olefin polymerization and the polymer thus produced.Special , not the present invention relates to the binding agent producing the method for polyolefin-based adhesive and so producing.

Background technology

For some applies such as binding agent, various polymer do not possess the combining properties of necessity.There is certain spy Property various polyolefin be usually blended together, it is desirable in combine various components advantageous attributes.Generally, result is showing The blend of the meansigma methods of each performance of various resins.Such as, EP 0 527 589 discloses the low-molecular-weight amorphous of flexibility Polypropylene and the blend of high molecular isotactic polypropylene, have the mechanical strength of balance and flexible combination with acquisition Thing.Compared with single isotactic polypropylene, these compositionss show more preferable flexibility, but still lack other physics genus Property.Physical blending thing also has the problem that compatibility is insufficient.Unless selected component to obtain the compatibility between them, they can Can be separated, or less component can potentially migrate into surface.Also referred to as intimate blending thing reactor blend (same instead Answer device or in series reactor the compositions comprising two or more polymer of preparation) be frequently utilized for solving these and ask Topic, but, finding plays a role under equivalent environment becomes a challenge with the catalyst system of the different polymer of production.

Past has used multi-catalyst system to produce reactor blend (the also known as intimate blending of various polymer Thing) and other polymer composition.Reactor blend is often regarded as being better than similar gathering with other single tank polymer composition The physical blending thing of compound.Such as, US6,248,832 disclose at one or more stereospecific metallocene catalyst systems The polymer composition of preparation in the presence of the metallocene catalyst system selected with at least one non-cubic.With EP 0 527 589 With US 5, the physical blending thing disclosed in 539,056 compares, and the polymer produced has favourable performance.

Therefore, this area is interested to produce novel polymer compositions for exploitation multi-catalyst system.Such as, US Patent 5,516,848 discloses the two kinds of different cyclopentadienyl type transition metal activated by aikyiaiurnirsoxan beta or non-coordinating anion The use of compound.Especially, embodiment, in addition to disclosing other content, discloses with activator such as MAO or N, N-bis- The catalyst compounds of the combination of monomethylaniline. four (pentafluorophenyl group) borate activatable, such as (Me₂Si(Me₄C₅)(N-c- C₁₂H₂₃)TiCl₂With raceme-Me₂Si(H₄Ind)ZrCl₂, or Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂And Me₂Si(Ind₂) HfMe₂(Ind=indenyl), has a bimodal molecular weight distribution (Mw/Mn) for preparation, different amounts of isotacticity ( In the product of embodiment 2,3 and 4,12-52wt% isotaxy PP) and have more than 100, the weight average molecular weight of 000, some are very Up to the polypropylene of the weight average molecular weight of 1,200,000 (as thermoplastic).Equally, US 6,184,327 discloses bag Containing the thermoplastic elastomer (TPE) of the branched olefin polymer with non-crystallizable side chains and amorphous skeleton, the side chain of at least a part of which 90mol% It is isotaxy or syndiotactic polypropylene, and the skeleton of at least 80mol% is atactic polypropylene, by including following step Prepared by rapid method: a) in the solution, at a temperature of about 90 to about 120 DEG C, makes propylene monomer and can produce with comprising The carbon monoxide-olefin polymeric of the chirality of isotaxy or syndiotactic polypropylene, solid rigid transition metal catalyst compound Contact；B) product a) is made to use in polymer reactor can give birth to propylene and one or more optional copolymerizable monomer Produce the achiral catalyst copolymerization of atactic polypropylene；And c) reclaim branched olefin polymer.Similarly, US 6,147,180 Disclosing the synthesis of thermoplastic polymer composition, said composition is prepared via a method which: be first polymerized monomer, is formed at least The macromonomer of 40% vinyl terminal, then by this macromonomer and ethylene copolymer.It addition, US 6,323,284 disclosure By using two kinds of independent catalyst system copolymerization alpha-olefins and α, ω-diene prepare thermoplastic compounds (crystallization and The mixture of amorphous polyolefin copolymer) method.

Equally, other people test the multistep method for producing novel polymer compositions.Such as, EP 0 366 411 Disclosing a kind of graft polymers, it has EPDM skeleton, by using two-step method to connect in one or more diene monomers sites Branch polypropylene, each step of this two-step method uses different ziegler-natta catalyst systems.This graft polymers is it is said that can For improving the erosion-resisting characteristics of co-blend polypropylene compositions.

Although polymer has significant combining properties each of above with reference to described in document, but still needs energy Enough new compositions that other the new He different performance balance being suitable for various final uses is provided.In particular, it is desirable that find A kind of firm but there is adhesion characteristic and the compositions that adhesive techniques and equipment can be used to apply.

About the general information in this field, it is referred to following:

1.DeSouza and Casagrande calendar year 2001 "Recent Advances inOlefin Polymerization Using Binary Catalyst Systems”, Macromol.Rapid Commun.2001,22, The problem proposing binary catalyst system in No.16 (the 1293-1301 page).At page 1299, they report generation " glue Viscous " the propylene system of product.

2. nearest, Lieber with Brintzinger has carried out having the most stereoselective metallocene by use and has urged The mixture on the spot of agent prepares the polyacrylic research of stereoblock, is reported in " Propene Polymerization with Catalyst Mixtures ContainingDifferent Ansa-Zirconocenes:Chain Transfer to AlkylaluminumCocatalysts and Formation of Stereoblock Polymers ", In Macromolecules 2000,33, No.25 (the 9192-9199 page).Propylene polymerization uses metalloscene catalyst H₄C₂ (Flu)₂ZrCl₂, raceme-Me₂Si(2-Me-4-tBu-C₅H₂)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂Making MAO (MAO) or triisobutyl aluminium (Al for promoterⁱBu₃)/tetra-(perfluorophenyl boric acid) (boric acid trityl Ester) carry out in the presence of triphenylcarbenium.Use the catalyst H of mixing₄C₂(Flu)₂ZrCl₂With raceme-Me₂Si(2- MeInd)₂ZrCl₂At MAO or AliBu₃Propylene polymerization in the presence of/borate creates waxy solid, and they can It is completely separated into atactic (ether is solvable) and isotaxy (insoluble) fraction.Neither one fraction contain isotaxy and Any combination of atactic five unit group (pentad) pattern, shows that these catalyst mixtures are formed without stereoblock and gather Compound.

3. at " Structures and Properties of Block Polymers andMultiphase Polymer Systems:An Overview of Present Status andFuture Potential ", S.L.Aggarwal, Sixth Biennial ManchesterPolymer Symposium (UMIST Manchester, March 1976) in, Aggarwal elaborates the various polymer produced.

4.“Selectivity in Propene Polymerization with MetalloceneCatalysts” Resconi et al., Chem Rev.2000,100,1253-1345.

Directly solve the polyolefin-type binding agent containing amorphous and crystallographic component above with reference to document neither one Demand.Industrially need this binding agent as the substitute of the blend needing a large amount of hydrocarbon resin tackifier.

Other significant list of references includes:

1) EP patent: EP 0 619 325 B1 and EP 719 802 B1.

2) US patent/disclosure: 6,207,606,6,258,903,6,271,323,6,340,703,6,297,301, US2001/0007896 A1,6,184,327,6,225,432,6,342,574,6,147,180,6,114,457,6,143, 846,5,998,547,5,696,045,5,350,817 and 6,659,965.

3) PCT Publication: WO 00/37514, WO01/81493, WO 98/49229, WO 98/32784 and WO 01/ 09200。

4) " Metallocene-Based Branch-Block thermoplasticElastomers, " Markel etc. People, Macromolecules 2000, volume 33, No.23, the 8541-8548 page.

Summary of the invention

The present invention relates to produce the continuation method of branched olefin polymer, including:

1) it is selected to produce under the polymerizing condition selected and there is≤the gathering of the degree of crystallinity of the Mw of 100,000 and≤20% First catalytic component of compound；

2) it is selected to produce under the polymerizing condition selected and there is≤Mw of 100,000 and >=20% (preferably >=40%) Second catalytic component of polymer of degree of crystallinity；

3) make catalytic component, one or more activators and one or more C2-C40 alkene in the first reaction zone Contact at a temperature of higher than 70 DEG C, the time of staying≤120 minute；With

4) content of the first reaction zone is transferred to second reaction zone, and make this content and catalyst group further Point, activator and/or one or more C2-C40 alkene contact at a temperature of higher than 70 DEG C, the time of staying≤120 minute；With

5) optionally, the content of second reaction zone is transferred to the 3rd reaction zone, and makes this content further and urge Agent compound, activator and/or one or more C2-C40 alkene contact at a temperature of higher than 70 DEG C, and the time of staying≤ 120 minutes；With

6) branched olefin polymer of one or more the C3-C40 alkene comprising at least 50mol% is reclaimed,

Wherein the first catalytic component is present at least one reaction zone, and the second catalytic component is present in the second reaction District, and wherein at least one reaction zone, C2-C40 alkene is C3-C40 alpha-olefin.

Describe in detail

And mention for convenience for the present invention and claims thereof, when mentioning that a kind of polymer comprises alkene Time, the described alkene existed in the polymer is the form of the polymerization of described alkene.

In another embodiment, the present invention relates to comprise one or more C3-C40 alkene, preferably propylene and being less than The polymer of the ethylene of 50mol%, it has:

A) the some T of 1 newton to 10,000 newton peels off；With

B) Mz/Mn of 2-200；And/or

C) according to the Mw that numerical value is X and g ' that numerical value is Y (measuring at the Mz of described polymer) of following table C:

Table C

X(Mw)	Y(g′)
		100000 or less, preferably 80000 or less, preferably 70000 or less, more preferably 60000 or less, more preferably 50000 or less, more preferably 40000 or less, more preferably 30000 or less, more preferably 20000 or less, more preferably 10000 or less.In certain embodiments, X also at least 1000, more preferably at least 2000, more preferably at least 3000, more preferably at least 4000, more preferably at least 5000, more preferably 7000, more preferably at least 10000, more preferably at least 15000.	0.9 or less, preferably 0.7 or Less；Preferably at 0.5-0.9 Between.
75000 or less, preferably 70000 or less, more preferably 60000 or less, more preferably 50000 or less, more preferably 40000 or less, more preferably 30000 or less, more preferably 20000 or less, more preferably 10000 or less.In certain embodiments, A also at least 1000, more preferably at least 2000, more preferably at least 3000, more preferably at least 4000, more preferably at least 5000, more preferably at least 7000, more preferably at least 10000, more preferably at least	0.92 or less, preferably 0.6 Or it is less；Preferably at 0.4- Between 0.6

It is 15000.
		50000 or less, more preferably 40000 or less, more preferably 30000 or less, more preferably 20000 or less, more preferably 10000 or less.In certain embodiments, A is the most at least It is 1000, more preferably at least 2000, more preferably at least 3000, more preferably at least 4000, more preferably at least 5000, more preferably at least 7000, more preferably at least 10000, More preferably at least 15000.	0.95 or less, preferably 0.7 Or it is less；Preferably at 0.5- Between 0.7
30000 or less, preferably 25000 or less, more preferably 20000 or less, more preferably 15000 or less, more preferably 10000 or less.In certain embodiments, A is also at least 1000, more preferably at least 2000, more preferably at least 3000, more preferably at least 4000, more preferably at least 5000, more preferably at least 7000, more preferably at least 10000, more More preferably at least 15000.	0.98 or less, preferably Between 0.7-0.98

In some embodiments, the g ' measured at the Mz of polymer is≤0.9 ,≤0.8 ,≤0.7 ,≤0.6 ,≤0.5, ≤ 0.4 ,≤0.3.

In another embodiment, above-mentioned polymer also has 40-250 DEG C, or 60-190 DEG C, or about 60 to 150 DEG C, or the peak melting point (Tm) of 80-130 DEG C.In some embodiments, peak melting point is 60-160 DEG C.Other embodiment party In case, peak melting point is 124-140 DEG C.In other embodiments, the highest melt temperature is 40-130 DEG C.

In another embodiment, above-mentioned polymer also has at 190 DEG C≤90, and 000mPa sec is (at 190 DEG C Under measured by ASTM D3236)；Or≤80,000, or≤70,000, or≤60,000, or≤50,000, or≤40,000, Or≤30,000, or≤20,000, or≤10,000, or≤8,000, or≤5000, or≤4000, or≤3000, or≤ 1500, or 250-6000mPa sec, or 500-5500mPa sec, or 500-3000mPa sec, or 500-1500mPa The viscosity of sec, and/or at 160 DEG C≤8000mPa sec (being measured by ASTM D3236 at 160 DEG C)；Or≤7000, Or≤6000, or≤5000, or≤4000, or≤3000, or≤1500, or 250-6000mPa sec, or 500- 5500mPa sec, or 500-3000mPa sec, or the viscosity of 500-1500mPa sec.In other embodiments, take Certainly in application, this viscosity is≤200 at 190 DEG C, 000mPa sec.In other embodiments, depending on application, this glues Degree is≤50,000mPa sec.

In another embodiment, above-mentioned polymer also has≤70J/g, or≤60J/g, or≤a 50J/g, or≤ 40J/g, or≤30J/g, or≤20J/g and more than 0, or more than 1J/g, or more than 10J/g, or the heat of fusion of 20-50J/g.

In another embodiment, above-mentioned polymer also has≤95, or≤70, or≤60, or≤50, or≤40, Or≤30, or the Xiao A hardness (being measured by ASTM 2240) of≤20.In other embodiments, Xiao A hardness is >=5, Or >=10, or >=15.In some application such as packaging, Xiao A hardness is preferably 60-70.

In another embodiment, the polymer of the present invention has 2-200, preferably 2-150, the Mz/ of preferably 10-100 Mn。

In another embodiment, above-mentioned polymer also has≤200 DEG C, or 40-150 DEG C, or 60-130 DEG C, or The shear adhesion fail temperature (SAFT-is measured by ASTM 4498) of 65-110 DEG C, or 70-80 DEG C.In some embodiment In, the SAFT of 130-140 DEG C is preferred.

In another embodiment, above-mentioned polymer also has 1-10,000 newton, or 3-4000 newton, or 5-3000 Newton, or 10-2000 newton, or the some T stripping of 15-1000 newton.Point T-peels off and determines according to ASTM D 1876, different , by taking advantage of the kraft paper substrate cut substrate of 3 inches (2.54cm × 7.62cm) to combine with some binding agents by two 1 inch Preparing sample, the volume of described binding agent is to occupy the area of about 1 square inch when by 500 grammes per square metre things compressing together (1 inch=2.54cm).After once preparing sample, will in parallel testing by recording the device of the damage power applied All of sample pulls open (speed with 2 inches per minute).Maximum, force that each sample of being tested of record is reached also is averaged Value, thus produce and be reported as the average maximum, force that a T-peels off.

In another embodiment, above-mentioned polymer also has several days to 1 second, or≤60 seconds, or≤30 seconds, or≤20 Second, or≤15 seconds, or≤10 seconds, or≤5 seconds, or≤4 seconds, or≤3 seconds, or≤2 seconds, or the setting time of≤1 second.

In another embodiment, above-mentioned polymer also has 2-75, or 4-60, or 5-50, or the Mw/Mn of 6-20.

In another embodiment, above-mentioned polymer also has≤500,000, preferably 15,000-500,000, or 20, 000-400,000, or 25,000-350, the Mz of 000.

In another embodiment, above-mentioned polymer can also have 50-1000%, preferably 80-200% fracture should Become (being measured at 25 DEG C by ASTM D-1708).In some of the other embodiments, breaking strain is 100-500%.

In another embodiment, polymer as herein described has >=0.5MPa, or >=a 0.75MPa, or >= 1.0MPa, or >=1.5MPa, or >=2.0MPa, or >=2.5MPa, or >=3.0MPa, or the fracture tensile strength of >=3.5MPa (being measured at 25 DEG C by ASTM D-1708).

In another embodiment, above-mentioned polymer also has the crystalline temperature (Tc) of 20-110 DEG C.Some embodiment party In case, Tc is 70-100 DEG C.In other embodiments, Tc is 30-80 DEG C.In other embodiments, Tc is 20-50 DEG C.

In some embodiments, above-mentioned polymer at the relation curve of complex viscosity and temperature (by 10rad/s's Under frequency run ARES dynamic mechanical spectrometer, use 20% strain, under nitrogen atmosphere, and use 10 DEG C/min cold But rate determination) within the temperature range of Tc+10 DEG C to Tc+40 DEG C, have≤-0.1, preferably≤-0.15, more preferably≤- The slope of 0.25.Seeing US patent application publication No.US 2004-0138392, on July 15th, 2004 is open.This slope is determined Justice is the log (complex viscosity) difference quotient to temperature.

In another embodiment, above-mentioned polymer has lower at least 10 DEG C than Tm, preferably low at least 20 DEG C than Tm, excellent Select lower at least 30 DEG C than Tm, more preferably than the Tc of low at least 35 DEG C of Tm.

In another embodiment, more above-mentioned polymer have≤6.5, preferably≤6.0, preferably≤5.5, preferably≤ Melt index ratio (the I of 5.0, preferably≤4.5, preferably 1-6.0₁₀/I₂)。(I₁₀And I₂According to ASTM 1238D, 2.16kg, 190 DEG C Measure).

In another embodiment, more above-mentioned polymer have >=25dg/min, a preferably >=50dg/min, preferably >= The melt index (MI) of 100dg/min, more preferably >=200dg/min, more preferably >=500dg/min, more preferably >=2000dg/min is (logical Cross ASTM 1238D, 2.16kg, 190 DEG C of mensuration).

In another embodiment, described polymer has the >=melt index (MI) of 900dg/min.

In another embodiment, above-mentioned polymer has width in DSC curve and is 10-60 DEG C, preferably 20-50 DEG C, the crystallization range of preferably 30-45 DEG C.In the DSC curve with two or more non-overlapped peaks, then in DSC curve Each peak there is 10-60 DEG C, preferably 20-50 DEG C, preferably 30-45 DEG C wide crystallization range.

In another embodiment, the present invention polymer produced has at least 2, and preferably at least 5, preferably at least The molecular weight distribution (Mw/Mn) of 10, still more preferably at least 20.

In another embodiment, the result measured according to size exclusion chromatography (SEC) (SEC), the polymer produced can To have single peak type, bimodal pattern or the molecular weight distribution of multimodal polymerization species.So-called bimodal pattern or multimodal refer to that SEC is bent Line has more than one peak or flex point.Flex point be curve quadratic derivative symbols change (the most from negative to positive, or from just to Negative) point.

In another embodiment, above-mentioned polymer has the activation energy of 8-15cal/mol.Activation energy uses in thermal effect The mutual relation of complex viscosity and temperature in the region that viscosity increases should be caused to calculate (relation assuming Arrhenius sample).

In another embodiment, the polymer of the present invention can have the degree of crystallinity of at least 5%.

In another embodiment, above-mentioned polymer can also have one or more following parameter:

A) 60-190 DEG C, or about 60 to 150 DEG C, or the peak melting point of 80-130 DEG C；And/or

B) at 190 DEG C≤8000mPa sec (being measured by ASTM D3236 at 190 DEG C), or≤5000, or≤ 4000, or≤3000, or≤1500, or 250-6000mPa sec, or 500-5500mPa sec, or 500-3000mPa Sec, or the viscosity of 500-1500mPa sec, or at 160 DEG C≤8000mPa sec (passes through ASTM at 160 DEG C D3236 measures), or≤7000, or≤6000, or≤5000, or≤4000, or≤3000, or≤1500, or 250- 6000mPa sec, or 500-5500mPa sec, or 500-3000mPa sec, or the viscosity of 500-1500mPa sec； And/or

C)≤70J/g, or≤60J/g, or≤50J/g, or≤40J/g, or≤30J/g, or≤20J/g and more than 0, or More than 1J/g, or more than 10J/g, or the Hf (heat of fusion) of 20-50J/g；And/or

The Xiao A hardness of d)≤70, or≤60, or≤50, or≤40, or≤30, or≤20 (is surveyed by ASTM 2240 Fixed)；And/or

(SAFT-leads to the shear adhesion fail temperature of e) 40-150 DEG C, or 60-130 DEG C, or 65-110 DEG C, or 70-80 DEG C Cross ASTM 4498 to measure)；And/or

F) 1-10,000 newton, or 3-4000 newton, or 5-3000 newton, or 10-2000 newton, or 15-1000 newton Some T peel off；And/or

G) several days to 0.1 second, or≤60 seconds, or≤30 seconds, or≤20 seconds, or≤15 seconds, or≤10 seconds, or≤5 seconds, or ≤ 4 seconds, or≤3 seconds, or≤2 seconds, or the setting time of≤1 second；And/or

H) 1-75, or 2-60, or 2-50, or the Mw/Mn of 3-20；And/or

I)≤500,000, preferably 15,000-500,000, or 20,000-400,000, or 25,000-350, the Mz of 000.

The combination of useful feature includes polymer as above, and it has 1-10,000 newton, or 3-4000 newton, Or the some T of 5-3000 newton, or 10-2000 newton, or 15-1000 newton peels off and following parameter:

1. the Mw of≤30,000, the peak melting point of 60-190 DEG C, the heat of fusion of 1-70J/g, measure at the Mz of polymer The branch index (g ') of≤0.90；With at 190 DEG C≤melt viscosity of 8000mPa Sec；Or

The SAFT of Mz and 60-150 DEG C of 2.20,000-500,000；Or

The Mz/Mn of 3.2-200 and the setting time of≤2 seconds；Or

The Hf (heat of fusion) of 4.20-50J/g, the Mz of 20,000-500,000 and the Shore hardness of≤50；Or

5. the Mw/Mn more than 1 to 50, at 190 DEG C≤viscosity of 5000mPa sec；Or

6. the Mw of≤50,000, the peak melting point of 60-190 DEG C, the heat of fusion of 2-70J/g, measure at the Mz of polymer The branch index (g ') of≤0.70, and at 190 DEG C≤melt viscosity of 8000mPa sec.

In a preferred embodiment, the polymer of the present invention includes amorphous, crystallization and branched block molecular structure.

In a preferred embodiment, described polymer includes at least 50wt% propylene, preferably at least 60% propylene, or Person at least 70% propylene, or at least 80% propylene.In another embodiment, described polymer include propylene and≤ 50mol% ethylene, preferably≤45mol% ethylene, more preferably≤40mol% ethylene, more preferably≤35mol% ethylene, more preferably ≤ 30mol% ethylene, more preferably≤25mol% ethylene, more preferably≤20mol% ethylene, more preferably≤15mol% ethylene, more Preferably≤10mol% ethylene, more preferably≤5mol% ethylene.

In another embodiment, the polymer produced has≤5 DEG C, preferably≤-5 DEG C, or-5 to-40 DEG C, Or the glass transition temperature (Tg) measured by ASTM E 1356 of-5 to-15 DEG C.

In another embodiment, the polymer of the present invention has≤40%, or≤30%, or≤20%, or The degree of crystallinity of person 10-30%.Percent crystallinity content uses differential scanning calorimetry measurement to determine according to ASTM D 3417-99. Percentage amorphous thing content determines by deducting degree of crystallinity % from 100.

In another embodiment, the polymer of the present invention has at least 50%, or at least 60%, or at least 70%, or the amorphous thing content of 50-95%.

In another embodiment, the polymer that the present invention is produced has at least 1.5, and preferably at least 2, preferably at least The molecular weight distribution (Mw/Mn) of 5, preferably at least 10, or at least 20.In other embodiments, Mw/Mn≤20 ,≤10, very To≤5.Molecular weight distribution be generally dependent on used catalyst and process conditions such as temperature, monomer concentration, catalyst ratio (as Fruit uses multiple catalysts) and the presence or absence of hydrogen.Hydrogen can use with the amount of up to 2wt%, but preferably with 50-500ppm Level use.

In another embodiment, according to the measurement result of gel permeation chromatography, the polymer tool produced is found There is an at least two molecular weight fraction, each to exist based on amount higher than 20wt% in terms of polymer weight.These fraction can lead to Cross in GPC curve, observe that two different molecular weight populations are identified.One example is showing at 20,000Mw One peak and 50, the GPC curve at another peak at 000Mw, wherein under first peak area account for the 20wt% of polymer with On, under second peak, area accounts for more than the 20wt% of polymer.

In another embodiment, the polymer of the present invention has >=20wt% (weight based on starting polymer) Hexane room temperature soluble fraction, and Soxhlet based on polymer weight meter≤70wt%, preferably≤50wt% boiling heptan Heptane insoluble matter.Soxhlet heptane insoluble matter refers to that the level obtained when sample uses continuous solvent extraction technology classification divides it One.Described classification is performed in two steps: one includes that ambient solvent extracts, and another is Soxhlet extractron.Molten in room temperature In agent extraction, the polymer of about 1g is dissolved in 50ml solvent (hexane), poly-with that isolate amorphous or very low molecular weight Compound kind.This mixture is stirred at room temperature about 12 hours.Vacuum is used to filter soluble fraction and insoluble thing Matter separates.Then insoluble material experiences Soxhlet extractron operation.This include based on polymer fractions boiling point for just above Room temperature separates them to the dissolubility in the various solvents of 110 DEG C.The insoluble substance obtained by ambient solvent extraction is first With hexane extracted overnight (Soxhlet)；The material of extraction is reclaimed by evaporation solvent, residue of weighing.Insoluble sample is right Afterwards with heptane extraxtion, and weigh after evaporation solvent.Derive from the insoluble matter of terminal stage and sleeve (thimble) at ventilated chamber In air-dry, to evaporate most of solvent, then nitrogen purging vacuum oven.Then calculate and stay in sleeve The amount of insoluble matter, condition be the deadweight of described sleeve be known.

In another embodiment, the polymer produced in the present invention has based on starting polymer weight meter 20- The heptane insoluble fraction of 70wt%, and heptane insoluble fraction have≤0.9 (preferably≤0.7) polymer Mz survey Fixed branch index g '.In another embodiment, the polymer produced in the present invention has based on starting polymer weight The heptane insoluble fraction of gauge 20-70wt%, the Mz of this heptane insoluble fraction is 20,000-500,000.At one preferably In embodiment, described compositions also has at least 20wt% hexane soluble fraction, on the basis of the weight of starting polymer Meter.In another embodiment, the polymer produced has hexane based on starting polymer weight meter at least 20wt% Soluble part, and this hexane soluble part has Tg but without Tm.

In another embodiment, the polymer of the present invention comprises less than 4.5mol% ethylene, preferably shorter than 4.0mol% ethylene, or less than 3.5mol% ethylene, or less than 3.0mol% ethylene, or less than 2.5mol% ethylene, Or less than 2.0mol% ethylene, or less than 1.5mol% ethylene, or less than 1.0mol% ethylene, or it is less than 0.5mol% ethylene, or less than 0.25mol ethylene, or 0mol% ethylene.

For the ease of mentioning, the polymer by the second Catalyst Production with at least 40% degree of crystallinity is also referred to as " semi-crystalline polymer ", has and can be referred to as " non-less than the polymer produced by the first catalytic component of 20% degree of crystallinity Crystalline polymer ".

In another embodiment of the present invention, the polymer produced has distinctive three district's complex viscosities-temperature Degree figure.The temperature dependency of complex viscosity uses the ARES dynamic mechanical spectrometer run under the frequency of 10rad/s, uses The strain of 20%, under nitrogen atmosphere, and uses the cooldown rate of 10 DEG C/min to measure.First by sample melted, the most gradually It is cooled to room temperature, monitors the increase of complex viscosity simultaneously.More than fusing point (this is typical polymer process temperature), plural number Viscosity is relatively low (I district), and is gradually increased along with the reduction of temperature.In II district, when the temperature decreases, complex viscosity Sharply increase.(III district) Shi Gao complex viscosity district of 3rd district, it occurs under the lower temperature being equivalent to apply temperature.At III Qu Zhong, this complex viscosity is high, and slightly changes along with reducing further of temperature.This complex viscosity curve is at hot melt Property binding agent application in provide long movement time (opening time) at processing temperatures and at a lower temperature fast The desirable combination of setting time.

In a preferred embodiment, that produced here, have and have at least less than the polymer of 1mol% ethylene 2mol%, preferably at least 4mol%, preferably at least 6mol%, more preferably at least 8mol%, more preferably at least 10mol%, more excellent Select (the CH of at least 12mol%, more preferably at least 15mol%, more preferably at least 18mol%, more preferably at least 20mol%₂)₂Single Unit, by as described below¹³C NMR measures.

In another embodiment, by as described below¹³C NMR measures, that produced here, have 1-5mol% The polymer of ethylene has at least 2+Xmol%, preferably at least 4+Xmol%, preferably at least 6+Xmol%, more preferably at least 8+ Xmol%, more preferably at least 10+Xmol%, more preferably at least 12+Xmol%, more preferably at least 15+Xmol%, more preferably at least (the CH of 18+mol%, more preferably at least 20+Xmol%₂)₂Unit, wherein X is the mol% of ethylene.

In a preferred embodiment, that produced here, have and have non-less than the polymer of 1mol% ethylene Brilliant component (it is defined as the part of the polymer composition of the degree of crystallinity less than 20%), this amorphous composition contains at least 3mol%, preferably at least 4mol%, preferably at least 6mol%, more preferably at least 8mol% more preferably at least 10mol%, more preferably (the CH of at least 12mol%, more preferably at least 15mol%, more preferably at least 18mol%, more preferably at least 20mol%₂)₂Unit, By as described below¹³C NMR measures.

In another embodiment, polymer that produced here, that have 1-5mol% ethylene has amorphous composition (it is defined as the part of the polymer composition of the degree of crystallinity less than 20%), by as described below¹³C NMR surveys Fixed, this amorphous composition contains at least 3+Xmol%, preferably at least 4+Xmol%, preferably at least 6+Xmol%, more preferably at least 8+ Xmol%, more preferably at least 10+Xmol%, more preferably at least 12+Xmol%, more preferably at least 15+Xmol%, more preferably at least (the CH of 18+mol%, more preferably at least 20+Xmol%₂)₂Unit, wherein X is the mol% of ethylene.

Monomer

In a preferred embodiment, described polymer includes olefin homo or copolymer, comprises one or more C3-C40 alpha-olefin.In a further preferred embodiment, described olefin polymer also comprises one or more alkadienes copolymerization Monomer, preferably one or more C4-C40 alkadienes.

In a preferred embodiment, described polymer includes olefin homo or copolymer, has less than 5mol% Ethylene, and comprise one or more C3-C40 alpha-olefins.In a further preferred embodiment, have less than 5mol% ethylene Olefin polymer also comprises one or more diolefin comonomers, preferably one or more C4-C40 alkadienes.

In a preferred embodiment, the polymer produced here is Noblen or copolymer.Described copolymerization list Body is preferably that C4-C20 is linear, branched or cyclic monomer, in one embodiment, is that C4-C12 is linear or branched alpha-olefins, Preferably butylene, amylene, hexene, heptene, octene, nonene, decene, dodecylene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 3,5,5-trimethyl-1-hexenes etc..Ethylene can exist with the amount of≤5mol%.

In another embodiment, the polymer produced here is can to select catalyst by Stereoselective and non-cubic One or more linear or branched C3-C30 prochiral alpha-olefin of polymerization or containing the alkene of C5-C30 ring or combinations thereof thing Copolymer." prochirality " used herein refers to advantageously form isotaxy when using stereospecific polymerization catalyst Or the monomer of syndiotactic polymer.

Polymerisable alkene structures part can be linear, branched, containing ring or the mixture of these structures.Preferably Linear alpha-alkene include C3-C8 alpha-olefin, more preferably propylene, 1-butylene, 1-hexene and 1-octene, more more preferably propylene or 1- Butylene.Preferably branched alpha-olefins includes 4-methyl-1-pentene, 3-Methyl-1-pentene and 3,5,5-trimethyl-1-hexenes, 5- Ethyl-1-nonene.The preferably monomer containing aromatic group contains at most 30 carbon atoms.The suitably monomer bag containing aromatic group Include at least one aromatic structure, preferably 1-3, more preferably phenyl, indenyl, fluorenyl or naphthyl moieties.Containing aromatic group Monomer comprises at least one polymerisable double bond further, the most after polymerisation, described aromatic structure by pendant in polymer Skeleton.Monomer containing aromatic group can be replaced by one or more alkyl further, and described alkyl includes but not limited to C1- C10 alkyl.It addition, two adjacent replacements can be connected as ring structure.The preferably monomer containing aromatic group contains and is connected to At least one aromatic structure of polymerizable olefinic structure division.Especially preferred aromatic monomer includes styrene, Alpha-Methyl benzene second Alkene, to ring-alkylated styrenes, vinyltoluene class, vinyl naphthalene, allyl benzene and indenes, especially styrene, p-methylstyrene, 4-phenyl-1-butylene and allyl benzene.

Monomer containing nonaromatic cyclic group is also preferred.These monomers can contain at most 30 carbon atoms.Suitably contain The monomer of nonaromatic cyclic group preferably has at least one polymerisable ethylenic group, described group pendant in described circulus, Or a part for described circulus.Described circulus can also be further by one or more alkyl, such as but not It is limited to C1-C10 alkyl to replace.The preferably monomer containing nonaromatic cyclic group includes vinyl cyclohexane, VCH, ethylene Base norborene, ethylidene norbornene, cyclopentadiene, cyclopentenes, cyclohexene, cyclobutane, vinyladamantane etc..

Can be used for the preferred diolefinic monomer of the present invention include preferred C4-C30, there is at least two unsaturated bond Any hydrocarbon structure, at least two in wherein said unsaturated bond has the catalyst selected to draw easily by Stereoselective or non-cubic Enter in polymer.It may further be preferable that diolefinic monomer is selected from α, ω-diene monomers (i.e. di-vinyl monomers).More excellent Selection of land, diolefinic monomer is linear di-vinyl monomers, most preferably those of 4-30 carbon atom.The preferably reality of diene Example includes butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, Oleatridecadiene, 14 carbon diene, 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, especially preferred diene Including 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadinene, 1,10-ten one carbon diene, 1,11-ten two carbon two Alkene, 1,12-oleatridecadiene, 1,13-ten four carbon diene, and low molecular weight polybutadiene (Mw is less than 1000g/mol).Preferably Cyclic diolefine include cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, bicyclo-penta Diene or on each ring position with or without the higher level of substituent group containing cyclodiene.

In a preferred embodiment, counting on the basis of the gross weight of compositions, one or more diene are with at most 10wt%, preferably 0.00001-1.0wt%, preferably 0.002-0.5wt%, the amount even more preferably from 0.003-0.2wt% is present in Here in the polymer produced.In some embodiments, general≤500ppm, preferably≤400ppm, preferably≤300ppm's Diene joins in polymerization.In other embodiments, by least 50ppm, or >=100ppm, or the diene addition of >=150ppm In polymerization.

In a preferred embodiment, described olefin polymer is homo-polypropylene.In a further preferred embodiment, Described olefin polymer comprises propylene, ethylene, preferably shorter than 5mol% ethylene, and at least one di-vinyl comonomer.? In another preferred embodiment, described olefin polymer comprises propylene and at least one di-vinyl comonomer.

In another embodiment, described olefin polymer comprises:

With 40-95mol%, the first monomer that the amount of preferably 50-90mol%, preferably 60-80mol% exists, and

With 5-40mol%, the comonomer that the amount of preferably 10-60mol%, more preferably 20-40mol% exists, and

With 0-10mol%, the Third monomer that the amount of more preferably 0.5-5mol%, more preferably 1-3mol% exists (termonomer)。

In a preferred embodiment, described first monomer comprises that any C3-C8 is linear, branched or in cyclic alpha-olefin One or more, including propylene, butylene (with its all isomers), amylene (with its all isomers), hexene (owns with it Isomer), heptene (with its all isomers), and octene (with its all isomers).Preferably monomer includes propylene, 1-fourth Alkene, 1-hexene, 1-octene etc..

In a preferred embodiment, described comonomer comprises that any C2-C40 is linear, branched or cyclic alpha-olefin In one or more (premise is if there is ethylene, and its amount is≤5mol%), including ethylene, propylene, butylene, penta Alkene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene, hexadecene, styrene, 3,5,5-trimethyl-1- Hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, norborene and cyclopentenes.

In a preferred embodiment, described Third monomer comprises that any C2-C40 is linear, branched or cyclic alpha-olefin In one or more (preferably, if ethylene, its amount is≤5mol%), include but not limited to ethylene, Propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene, hexadecene, butadiene, 1, 5-hexadiene, 1,6-heptadiene, Isosorbide-5-Nitrae-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadinene, 1,11-ten two carbon two Alkene, styrene, 3,5,5-trimethyl-1-hexenes, 3-Methyl-1-pentene, 4-methyl-1-pentene and cyclopentadiene.

In a preferred embodiment, described polymer includes polypropylene and 0-50mol% ethylene, preferably 0- 30mol% ethylene, more preferably 0-15mol% ethylene, more preferably 0-10mol% ethylene, more preferably 0-5mol% ethylene.

In a preferred embodiment, described polymer includes propylene and 0-50mol% butylene, preferably 0-30mol% Butylene, more preferably 0-15mol% butylene, more preferably 0-10mol% butylene, more preferably 0-5mol% butylene.

In a preferred embodiment, described polymer includes propylene and 0-50mol% hexene, preferably 0-30mol% Hexene, more preferably 0-15mol% hexene, more preferably 0-10mol% hexene, more preferably 0-5mol% hexene.

Method

The present invention relates to a kind of continuation method producing branched olefin polymer, including:

1) it is selected to produce under the polymerizing condition selected and there is≤Mw of 100,000 and≤20% (preferably≤5%) First catalytic component of polymer of degree of crystallinity；

2) it is selected to produce under the polymerizing condition selected and there is≤Mw of 100,000 and >=40% (preferably >=20%) Second catalytic component of polymer of degree of crystallinity；

3) make catalytic component, one or more activators and one or more C2-C40 alkene in the first reaction zone Contact higher than at a temperature of 70 DEG C (preferably >=100 DEG C), the time of staying≤120 minute (preferably≤60 minutes)；With

4) content of the first reaction zone is transferred to second reaction zone, and make this content and catalyst group further Point, activator and/or one or more C2-C40 alkene contacting higher than at a temperature of 70 DEG C (preferably >=100 DEG C), during stop Between≤120 minutes (preferably≤60 minutes)；With

5) optionally, the content of second reaction zone is transferred to the 3rd reaction zone, and makes this content further and urge Agent compound, activator and/or one or more C2-C40 alkene are connecing higher than at a temperature of 70 DEG C (preferably above 100 DEG C) Touch, the time of staying≤120 minute (preferably≤60 minutes)；With

Wherein said first catalytic component is present at least one reaction zone, and described second catalytic component is present in Two reaction zones, and wherein at least one reaction zone, described C2-C40 alkene is C3-C40 alpha-olefin.

The invention still further relates to a kind of continuation method producing branched olefin polymer, including:

1) it is selected to produce under the polymerizing condition selected and there is≤the Mw of 100,000 and≤70J/g (preferably≤10J/ First catalytic component of the polymer of heat of fusion g)；

2) it is selected to produce under the polymerizing condition selected and there is≤Mw of 100,000 and >=20% (preferably >=30%) Second catalytic component of polymer of degree of crystallinity；

3) make catalytic component, one or more activators and one or more C2-C40 alkene in the first reaction zone Contact higher than at a temperature of 70 DEG C (preferably above 100 DEG C), the time of staying≤120 minute (preferably≤60 minutes)；With

4) content of the first reaction zone is transferred to second reaction zone, and make this content and catalyst group further Point, activator and/or one or more C2-C40 alkene contacting higher than at a temperature of 70 DEG C (preferably above 100 DEG C), stop Time≤120 minute (preferably≤60 minutes)；With

1) be selected to produce under the polymerizing condition selected have≤Mw of 100,000 and≤70J/g (preferably≤ The polymer of heat of fusion 10J/g), the first catalytic component of the macromonomer with reactive terminal can be polymerized；

2) it is selected to produce under the polymerizing condition selected that there is the reactive terminal ,≤Mw and >=20% of 100,000 Second catalytic component of the macromonomer of the degree of crystallinity of (preferably >=30%)；

The invention still further relates to a kind of method preparing above-mentioned olefin polymer, including:

1) be selected to be polymerized the macromonomer with reactive terminal, it is possible to produce and have≤30, the Mw of 000 and≤ First catalytic component of the polymer of the heat of fusion of 70J/g (preferably≤10J/g)；

2) it is selected to produce and there is the reactive terminal ,≤Mw of 30,000 and the degree of crystallinity of >=20% (preferably >=30%) The second catalytic component of macromonomer；

In another preferred embodiment, the present invention relates to a kind of continuation method producing branched olefin polymer, Including:

1) it is selected to produce under the polymerizing condition selected have≤100,000, preferably≤80,000, preferably≤60, The Mw of 000 and≤20%, the first catalytic component of the polymer of the degree of crystallinity of preferably≤15%, more preferably≤10%；

2) it is selected to produce under the polymerizing condition selected have≤100,000, preferably≤80,000, preferably≤60, The Mw of 000 and >=20%, the second catalysis of the polymer of the degree of crystallinity of preferably >=40%, preferably >=50%, more preferably >=60% Agent component；

3) make catalytic component, one or more activators and one or more C2-C40 alkene (preferably one or more One or more in C3-C12 alkene, preferably C3 and ethylene and/or C4-C20 comonomer, and optionally one or more two Alkene, preferably C4-C20 diene) in the first reaction zone higher than 70 DEG C (preferably above 100 DEG C, more preferably higher than 105 DEG C, more Preferably above 110 DEG C, more preferably higher than 115 DEG C) at a temperature of contact, the time of staying≤120 minute (preferably≤60 minutes, more Preferably≤50 minutes, preferably 40 minutes, preferably≤30 minutes, preferably≤25 minutes, more preferably≤20 minutes, more preferably≤15 points Clock, more preferably≤10 minutes, more preferably≤5 minutes)；With

4) content of the first reaction zone is transferred to second reaction zone, and make this content and catalyst group further Point, activator and/or one or more C2-C40 alkene (preferably one or more C3-C12 alkene, preferably C3 and ethylene and/or One or more in C4-C20 comonomer, and optionally one or more alkadienes, preferably C4-C20 diene) higher than 70 Connect at a temperature of DEG C (preferably above 100 DEG C, more preferably higher than 105 DEG C, more preferably higher than 110 DEG C, more preferably higher than 115 DEG C) Touch, and the time of staying≤120 minute (preferably≤60 minutes, more preferably≤50 minutes, preferably 40 minutes, preferably≤30 minutes, preferably ≤ 25 minutes, more preferably≤20 minutes, more preferably≤15 minutes, more preferably≤10 minutes, more preferably≤5 minutes, more preferably≤3 Minute)；With

5) optionally, the content of second reaction zone is transferred to the 3rd reaction zone, and makes this content further and urge Agent compound, activator and/or one or more C2-C40 alkene (preferably one or more C3-C12 alkene, preferably C3 and One or more in ethylene and/or C4-C20 comonomer, and optionally one or more alkadienes, preferably C4-C20 bis- Alkene) higher than 70 DEG C (preferably above 100 DEG C, more preferably higher than 105 DEG C, more preferably higher than 110 DEG C, more preferably higher than 115 DEG C) At a temperature of contact, the time of staying≤120 minute (preferably≤60 minutes, more preferably≤50 minutes, preferably 40 minutes, preferably≤ 30 minutes, preferably≤25 minutes, more preferably≤20 minutes, more preferably≤15 minutes, more preferably≤10 minutes, more preferably≤5 points Clock, more preferably≤3 minutes)；With

6) branched olefin polymer of one or more the C3-C40 alkene comprising at least 50mol% is reclaimed, wherein said First catalytic component is present at least one reaction zone, and described second catalytic component is present in second (the most different) Reaction zone, and wherein at least one reaction zone, described C2-C40 alkene is C3-C40 alpha-olefin；With

A) wherein the ratio of the first catalyst and the second catalyst is 1: 1 to 50: 1, and preferably 1: 1 to 30: 1, preferably 1: 1 arrives 20: 1, more preferably 1: 1 to 1: 10；

B) activity of wherein said catalytic component is at least 3 kg of polymer/gram catalyst mixture, preferably at least 50 Kg of polymer/gram catalyst mixture, more preferably at least double centner polymer/gram catalyst mixture, more preferably at least 200 kg of polymer/gram catalyst mixture, more preferably 300 kg of polymer/gram catalyst mixture, more preferably 400 kilograms Polymer/gram catalyst mixture, more preferably 50 kg of polymer/gram catalyst mixture；With at least a part of which 80%, preferably At least 85%, more preferably at least 90%, the alkene of more preferably at least 95% is converted into polymer.

In another embodiment, at least 20% or more alkene is converted into polymer, and preferably >=20%, more excellent Choosing >=60%, the alkene of more preferably >=75%, more preferably >=85%, more preferably >=95% is converted into polymer.

In a preferred embodiment, said method is carried out in solution phase, slurry or bulk phase polymerization method.

What is called refers to run the system of (or being intended to run) continuously in the case of not having to be interrupted or do not have to stop.Such as, It is wherein reactant to be introduced continuously in one or more reactor and be continuously withdrawn for preparing the continuation method of polymer The method of polymer product.

In another preferred embodiment, in the above-mentioned methods, in time of staying inner reaction zone, reactant is dense Change≤20% of degree, preferably≤15%, more preferably≤10%.In a preferred embodiment, instead within the time of staying Monomer concentration in district is answered to keep constant.Preferably, monomer concentration change≤20%, preferably≤15%, more preferably≤10%, more excellent Choosing≤5%.

In a preferred embodiment, in time of staying inner reaction zone, the concentration of catalytic component keeps constant. Preferably, monomer concentration change≤20%, preferably≤15%, more preferably≤10%, more preferably≤5%.

In a preferred embodiment, in time of staying inner reaction zone, the concentration of activator keeps constant.Preferably Ground, monomer concentration change≤20%, preferably≤15%, more preferably≤10%, more preferably≤5%.

In a further preferred embodiment, the 3rd catalyst (or more) may reside in said method.3rd urges Agent can be any catalytic component enumerated herein.Preferred 3rd catalyst includes the catalyst that can produce wax.Especially Its preferred 3rd catalyst include can producing under the polymerizing condition selected have≤Mw of 20,000 with≤10% knot Those of the polymer of crystalline substance degree.In another embodiment, include can be poly-select for especially preferred 3rd catalyst Produce under the conditions of conjunction and have≤20, the Mw of 000 and >=10%, those of the polymer of the degree of crystallinity of preferably >=20%.

Other preferred 3rd catalyst can include any catalyst as herein described.Can select two or more Plant catalyst and produce the various macromonomer with reactive terminal, with the catalyst that can be polymerized this macromonomer It is used in combination.Two or more can be selected the catalyst of macromonomer and one can to produce and have reaction The catalyst of the macromonomer of property end.Same way, it is also possible to select to produce the three of different polymer under the same reaction conditions Plant catalyst.For example, it is possible to select to produce a kind of catalyst of the polymer somewhat crystallized, produce the one of high crystallinity polymer Catalyst and a kind of catalyst of production amorphous polymer, any described catalyst can produce has dividing greatly of reactive terminal Sub-monomer or polymerization have the polymer of reactive terminal.It is likewise possible to select two kinds of catalyst, i.e. a kind of production crystallizes The catalyst of polymer and a kind of catalyst producing amorphous polymer, any described catalyst can be prepared and has reactive end The macromonomer of end or polymerization have the polymer of reactive terminal.It is also possible to select to produce the polymerization somewhat crystallized A kind of catalyst of thing, produces a kind of catalyst of wax and produces a kind of catalyst of amorphous polymer, any described catalyst Can prepare and there is the macromonomer of reactive terminal or polymerization has the polymer of reactive terminal.

So-called reaction zone refers to the region that the catalyst of activation can react wherein with monomer.

What is called have the macromonomer of reactive terminal refer to have >=12 carbon atoms (preferably >=20, more preferably >=30, more preferably 12-8000 carbon atom) and have vinyl, ethenylidene, vinylene or other can be polymerized The polymer of the end group in the polymer chain of growth.So-called can polymerization has the macromonomer of reactive terminal and refers to one Planting catalytic component, it can have macromonomer of reactive terminal (often more than typical single monomer such as second Alkene or the molecule of propylene) it is incorporated in the polymer chain of growth.The chain of vinyl terminal is generally reactive higher than 1,2-Asia ethylene Base or the chain of ethenylidene terminal.

In a preferred embodiment, propylene is present in first, second and/or the 3rd in reaction zone, preferably in an amount of from 20-100wt%, preferably 40-99wt%, more preferably 60-95wt%, based on monomer weight present in reaction zone.

In a preferred embodiment, ethylene is present in first, second and/or the 3rd reaction zone, based in reaction zone The weight meter of monomer, its amount preferably at most 50wt%, preferably 1-40wt%, preferably 5-20wt%, preferably 5-10wt%.? In another embodiment, ethylene is not present in reaction zone, or if it exists, its amount is≤10wt%, excellent Choosing≤5wt%, preferably≤3wt%, preferably≤2wt%, preferably≤1wt%, preferably≤0.5wt%, based on the list in reaction zone The weight meter of body.

In a preferred embodiment, ethylene and propylene are present in first, second and/or the 3rd in reaction zone.

In another embodiment, propylene with the amount of 100wt% (to be present in the weight of the monomer in the first reaction zone On the basis of count) be present in the first reaction zone, and ethylene with the amount of at most 50wt% (with the monomer being present in second reaction zone Weight on the basis of count) be present in second reaction zone.

In another embodiment, ethylene with the amount of 100wt% (to be present in the weight of the monomer in the first reaction zone On the basis of count) be present in the first reaction zone.

In another embodiment, propylene with the amount of 100wt% (to be present in the weight of the monomer in the first reaction zone On the basis of count) be present in the first reaction zone and second reaction zone.

In another embodiment, propylene and ethylene are present in the first reaction zone, and anti-except being present in first Answer beyond the residual ethylene monomer in the content in district, do not have ethylene to be introduced in second reaction zone.

In another embodiment, ethylene is intermittently introduced in one or more reaction zone.

In another embodiment, propylene is present in the first reaction zone, and ethylene is present in second reaction zone, and second Catalytic component is present in the first reaction zone, and the first catalytic component is present in second reaction zone.

In another embodiment, propylene is present in the first reaction zone, and propylene and ethylene or other monomer are present in In second reaction zone, the second catalytic component is present in the first reaction zone, and the first catalytic component is present in the second reaction Qu Zhong.

In another embodiment, propylene is present in the first reaction zone, and propylene and ethylene are present in second reaction zone In, the second catalytic component is present in the first reaction zone, and the first catalytic component is present in second reaction zone.

In another embodiment, propylene and ethylene are present in the first reaction zone, and propylene is present in second reaction zone In, the first catalytic component is present in the first reaction zone, and the second catalytic component is present in second reaction zone.

In another embodiment, propylene is present in the first reaction zone, and propylene and ethylene are present in second reaction zone In, the second catalytic component is present in the first reaction zone, and the second catalytic component is present in second reaction zone.

In another embodiment, ethylene is present in the first reaction zone, and propylene and ethylene or other monomer are present in In second reaction zone, the first catalytic component is present in the first reaction zone, and the first and second catalytic components are present in second In reaction zone, and be present in the catalyst compounds in the first reaction zone can select polymerizing condition under produce Mw≤ 20,000 and the polymer of degree of crystallinity >=50%.

In another embodiment, ethylene is present in the first reaction zone, and propylene is present in second reaction zone, propylene Being present in the 3rd reaction zone, the first catalytic component is present in second reaction zone, and the second catalytic component is present in the 3rd In reaction zone, and be present in the catalyst compounds in the first reaction zone can select polymerizing condition under produce Mw≤ 20,000 and the polymer of degree of crystallinity≤10%.

In another embodiment, ethylene is present in the first reaction zone, and propylene is present in second reaction zone, propylene Being present in the 3rd reaction zone, the first catalytic component is present in second reaction zone, and the second catalytic component is present in the 3rd In reaction zone, and be present in the catalyst compounds in the first reaction zone can select polymerizing condition under produce Mw≤ 20,000 and degree of crystallinity >=10%, the polymer of preferably >=20%, preferably >=30%, preferably >=40%, preferably >=50%.

In another embodiment, all catalytic components are only incorporated in the first reaction zone, and except being present in Beyond residual catalyst component in the content of the first reaction zone, catalytic component is not had to be introduced in second reaction zone.

In another embodiment, only a kind of catalytic component is present in all reaction zones.Described catalytic component Can only be introduced in the first reaction zone, or be introduced in multiple reaction zone.

In another embodiment, two or more catalytic components is present in one or all reaction zones, at least A kind of described catalytic component can produce the polymer of degree of crystallinity≤5%, and at least one under the polymerizing condition selected Other catalytic component can produce the polymer of degree of crystallinity >=20% under the polymerizing condition selected.

In another embodiment, during diolefinic monomer is present in one or all reaction zones.

In another embodiment, during hydrogen is present in one or all reaction zones.

In a specific embodiment, the present invention relates to by making one or more C₃Or higher level alpha-olefin and/or The ethylene of one or more di-vinyl monomers and optional at most 5mol% is at least one stereospecific catalyst system The polyolefin polymer produced with copolymerization in the presence of at least one other catalyst system.The polymer so produced can contain Amorphous polymer segment and crystalline polymer segments, at least some of which segment is had to be joined together.Generally, amorphous and crystallization Polymer segment be one or more alpha-olefins (optionally including at most 5mol% ethylene) and/or one or more have at least two The copolymer of the monomer of individual ethylenic unsaturated bond.These unsaturated bonds are suitable for and easily by being used independently first or second The coordination polymerization of catalyst system and be incorporated in the polymer chain of growth so that it is mixed that alkadienes is introduced in by the present invention Close in the polymer segment that two kinds of catalyst in catalyst system are produced.In a preferred embodiment, have at least These monomers of two ethylenic unsaturated bonds are alkadienes, preferably di-vinyl monomers.It is believed that by by a part of divinyl Comonomer is incorporated in two kinds of polymer segments, so produces crosslinking between those segments, real during compositions is polymerized Show the crosslinking of at least some of polymer segment mixture.

In another embodiment, the polyolefin branched block compositions containing amorphous and aasemi-crystalline component can be two Prepared by individual or more reactor, the performance balance needed for obtaining.Especially, aPP-g-scPP branched structure can be two Individual or more successive soln reactor make spent mixed catalyst and the propylene as preferred feedstock prepare on the spot.At one In embodiment, stereospecific bridged bis-indenyl 4 race catalyst can be selected to prepare hypocrystalline PP macromonomer.( All referring at Chemical and EngineeringNews when mentioning the periodic table of elements, 63 (5), disclosed in 27,1985 Table.) the monocyclopentadienyl hetero atom 4 race catalyst of bridging can be used to build amorphous PP (aPP) skeleton, it is simultaneously introduced one A little hypocrystalline macromonomers (scPP).This it is believed that and creates aPP-g-scPP structure, and wherein "-g-" represents described polymerization species Type is at least partly grafted.By selecting catalyst, polymeric reaction condition and/or by introducing diene modified dose, can be by non- Brilliant and crystallographic component links together, and forms various branched block structure.In order to effectively be attached in the chain of growth, there is ethylene The macromonomer of cardinal extremity base is preferred.Other type of end of the chain unsaturated bond (vinylene and Asia can also be used Vinyl).While not wishing to bound by theory, it is believed that branched block copolymer includes amorphous skeleton, this amorphous skeleton has Being derived from the non-crystallizable side chains of scPP macromonomer, and described side chain is believed to be polypropylene macromers, it can be at solution Prepare with the catalyst being suitable to prepare isotaxy or syndiotactic polypropylene under polymerizing condition.

Preparation has a kind of preferably reaction method of the polypropylene macromers of high terminal ethylenyl groups unsaturated bond content It is described in US patent 6,117,962.Normally used catalyst is solid rigid, chirality or asymmetrical bridging metal Cyclopentadienyl.See for example US patent No.4,892,851, US patents No.5,017,714, US patent No.5,132,281, US patents No.5,296,434, US patents No.5,278,264, US patents No.5,304,614, US patents No.5,510,502, WO-A- (PCT/US92/10066) WO-A-93/19103, EP-A2-0 577 581, EP-A1-0 578 838 and academic documents " The Influence ofAromatic Substituents on the Polymerization Behavior of BridgedZirconocene Catalysts ", Spaleck, W. et al., Organometallics 1994,13,954-963 And " ansa-Zirconocene Polymerization Catalystswith Annelated Ring Ligands- Effects on Catalytic Activity andPolymer Chain Lengths ", Brinzinger, H. et al., Organometallics1994,13,964-970, and references cited therein.

In some embodiments, for prepare the present invention semi-crystalline polypropylene macromonomer comprise solid rigid First catalyst of transition metal procatalyst compound is selected from racemic bridging double (indenyl) zirconium cyclopentadienyl or hafnium cyclopentadienyl.At another In embodiment, described transition metal procatalyst compound is raceme-dimethylsilyl double (indenyl) zirconium cyclopentadienyl Or hafnium cyclopentadienyl.In another embodiment, described transition metal procatalyst compound is raceme-dichloro or dimethyl two Double (the 2-methyl 4-phenyl indenyl) zirconium of methyl silicane base or conjunction hafnium.In another preferred embodiment, described transition Metallic catalyst is raceme-dimethylsilyl double (indenyl) hafnium cyclopentadienyl, such as raceme-dimethyl or dichloro two Methyl silicane base double (indenyl) closes hafnium.

It is believed that the mark of branched block and branching level depend on having obtaining of the macromonomer of the unsaturated end of the chain Property and special catalyst macromonomer introduce ability.In order to increase the number of aPP-g-scPP branched block compositions (population), generally operate in the process window that beneficially macromonomer produces and inserts.Such condition is retouched State in US patent 6,117,962 and magazine article W.Weng et al., Macromol.Rapid Commun., 2000,21,1103- In 1107, and it is further illustrated by by embodiment here.

It is also believed that the number of the scPP macromonomer of vinyl terminal is the biggest, what they were introduced on aPP skeleton can Energy property is the highest, and therefore branched block number is the biggest.

In order to improve the number of the macromonomer with the vinyl end of the chain further, diolefinic monomer can be incorporated into In reaction medium.Products therefrom is typically by isotactic polypropylene segment, atactic polypropylene segment and increased number of The blend that the branched block material that the additional coupling caused by alkadienes cross-linking agent is formed forms.

Crosslinking typically refers to by each double bond of diolefinic monomer being incorporated in two different polymer segments Connect two polymer segments.The polymer segment so connected can be identical or different for degree of crystallinity.Can also pass through In a polymer segment two and more alkadienes are incorporated in two other polymer segments by three or More polymer segments connect.

One Consideration of selection monomer or combination of monomers is, by selecting two or more different catalysts bodies System, can form crystallization and both amorphous polymer segments.In some embodiments, it is also desirable to if the alkadienes that will exist Monomer introducing level in crystalline segment limits to the amount not substantially changing its degree of crystallinity.Alkadienes coupling agent generally remains At floor level, with guarantee whole compositions have some binding agent applicable application≤viscosity of 80000mPa s.

As it has been described above, for the number increasing aPP-g-scPP branched block compositions, generally at beneficially macromole list Operation in the process window that body is formed and inserts.Favourable condition includes:

1. produce the high concentration of the catalyst of the macromonomer of semi-crystalline ethylene base terminal, and/or

2. regulation Al/ metal ratio；And/or

3. High Operating Temperature；And/or

4. there is the catalyst structure of the high-affinity introduced for macromonomer；And/or

The most relatively long time of staying；And/or

6. high monomer conversion ratio (condition of monomer shortage improves the insertion of macromonomer)；And/or

7. add modifying agent (diene) to improve the number of the macromonomer of vinyl terminal.

The another kind of method improving aPP-g-scPP branched block compositions is to add chain-transferring agent, and this chain-transferring agent is by second Thiazolinyl transfers to the end catalyst deactivation simultaneously of polymer chain.This type of chain-transferring agent includes but not limited to vinyl chloride, fluorothene, Bromine ethylene.In the process, owing to there is alkyl aluminum activator such as aikyiaiurnirsoxan beta (usual MAO), described catalyst It is re-activated.

Similarly, melted and crystallization property can pass through catalyst choice, comonomer adds and process conditions such as temperature Change with catalyst ratio (if using more than one catalyst) controls.

Catalyst compounds

In the practice of the invention, it is possible to use any can produce required polymer material (i.e. Mw≤100,000 He The polymer of heat of fusion≤70J/g, or Mw≤100,000 and the polymer of degree of crystallinity≤70%) catalyst compounds.At this In description, transistion metal compound can be described as catalyst precarsor, procatalyst compound or catalyst compounds, this A little terms are used interchangeably.Catalyst system is the combination of catalyst precarsor and activator.

Catalyst compounds and selection

In the practice of the present invention, it is possible to use any can produce required polymer material (i.e. Mw≤100,000 and knot The polymer of crystalline substance degree≤5%, or Mw≤100,000 and the polymer of degree of crystallinity >=20%) procatalyst compound (catalyst Precursor compound).The procatalyst compound that can use in the method for the invention includes metallocene compounds (containing one, two or three cyclopentadienyl ligands/metallic atom), non-metallocene early transition metal compound (includes tool Have those of amino and/or phenoxy group type part), non-metallocene late transition metal compound (includes having diimine or two sub- Those of amine pyridyl ligands) and other transistion metal compound.

Generally, the bulky ligand (bulky ligand) Metallocenic compound (procatalyst) that can be used for the present invention includes tool There are half and full sandwich compound of the one or more bulky ligand being bonded at least one metallic atom.Typical bulky ligand Metallocenic compound is described generally as containing being bonded to one or more bulky ligand of at least one metallic atom and one Or multiple leaving group.Bulky ligand generally with the ring of one or more openings, acyclic or thick sum or ring system or they It is combined as representing.These bulky ligand, preferably ring or ring system are typically by the atom in the 13-16 race atom of the periodic table of elements Composition；Preferably, described atom is selected from carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron and aluminum or combinations thereof.Most preferably, described Ring or ring system are made up of carbon atom, such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligands structure or its Its similar functions ligand structure such as pentadienyl, cyclo-octatetraene diyl, cyclobutadiene base or substituted pi-allyl part.Can be similar to Other part in cyclopentadienyl-type ligands function includes ammonification species (amides), phosphatization species, imines, and phosphine is sub- Amine, amidine class (amidinates) and ortho position substituted benzene oxidatoin species.Described metallic atom is preferably selected from the periodic table of elements 3-15 race and/or group of the lanthanides or actinides.Preferably, described metal is selected from 3-12 race, the transition gold of more preferably 4,5 and 6 races Belonging to, most preferably, described transition metal is selected from 4 races.

In one embodiment, the carbon monoxide-olefin polymeric that can be used for the present invention includes what one or more were expressed from the next Bulky Ligand Metallocene catalyst compounds:

L^AL^BMQ*_n (1)

Wherein M is the metallic atom of the periodic table of elements, and can be the 3-12 race metal of the periodic table of elements or group of the lanthanides or Actinides, it is preferable that M is 4,5 or 6 group 4 transition metals, it is highly preferred that M is 4 group 4 transition metals, more it is highly preferred that M is zirconium, Hafnium or titanium.Described bulky ligand L^AAnd L^BIt is ring or the ring system of open, acyclic or thick sum, and is any assistant ligand body System, including unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, hetero atom replaces and/or containing miscellaneous former The cyclopentadienyl-type ligands of son.The limiting examples of bulky ligand includes cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, Indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, dibenzo [b, h] fluorenyl ligand, benzo [b] fluorenyl ligand, cyclo-octatetraene two Ylidene ligands, cyclopentano cyclododecene part, azenyl ligands, part, pentalene part, phosphoryl (phosphoyl) part, phosphinimine (WO99/40125), pyrrole radicals part, pyrozolyl ligands, carbazolyl ligands, bora benzene is joined Body etc., including their hydrogenated modifications thereof, such as tetrahydro indenyl part.In one embodiment, L^AAnd L^BCan be can be with π It is bonded other ligand structure any being connected to M.In still another embodiment, L^AOr L^BAtom and molecule amount (MW) exceed 60a.m.u., preferably greater than 65a.m.u..In another embodiment, L^AAnd L^BOne or more hetero atom can be included, Such as nitrogen, silicon, boron, germanium, sulfur and phosphorus, formed together with carbon atom open, acyclic or the thickest and ring or ring system, such as Heterocyclic pentylene base assistant ligand.Other L^AAnd L^BBulky ligand includes but not limited to huge ammonification species, phosphatization species, alkane Oxide-based, virtue oxide, imido species (imides), carbon compound (carbolides), borides (borollides), porphyrin, phthalocyanines, corrin class and other polyazo macro ring.Independently, each L^AAnd L^BCan be to be bonded in M The bulky ligand of identical or different type.In an embodiment of formula 1, only exist L^AOr L^BOne of.

Independently, each L^AAnd L^BCan be unsubstituted, or the combination being replaced base R* replaces.Substituent R * unrestricted Property example include the one or more groups selected from lower group: hydrogen, or linear or branched-alkyl, thiazolinyl, alkynyl, cycloalkyl, aryl, Acyl group, aroyl, alkoxyl, aryloxy group, alkylthio group, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, carbamoyl, Alkyl-or dialkyl-carbamoyl radicals, acyloxy, acylamino-, aromatic acylamino or combinations thereof.The side of being preferable to carry out In case, substituent R * has at most 50 non-hydrogen atoms, preferably 1-30 carbon atom, and it can also be by halogen or hetero atom or class Replace like thing.The limiting examples of alkyl substituent R* includes methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopenta, Cyclohexyl, benzyl or phenyl etc., including their isomers all, the such as tert-butyl group, isopropyl etc..Other alkyl includes fluorine first Base, fluoro ethyl, two fluoro ethyls, iodine propyl group, bromine hexyl, chlorobenzyl and alkyl substituted organic quasi-metal group, including trimethyl Silicyl, trimethylgermyl groups and methyl diethylsilane base etc.；Organic quasi-metal group substituted with halocarbon base, bag Include three (trifluoromethyl) silicyl, double (difluoromethyl) silicyl of methyl, bromomethyl dimethyl germyl etc.；Take with two The boron group in generation, including such as dimethyl boron；With dibasic pnicogen group, including dimethyl amine, dimethyl phosphine, hexichol Base amine, aminomethyl phenyl phosphine, chalcogen group, including methoxyl group, ethyoxyl, propoxyl group, phenoxy group, methyl mercapto and ethylmercapto group. Non-hydrogen substituent R* includes atomic carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, stannum, sulfur, and germanium etc., including alkene, such as but not limited to olefinic Unsaturated substituent group, including the part such as butyl-3-thiazolinyl of vinyl terminal, acrylate-2-thiazolinyl, hex-5-thiazolinyl etc..Further, at least Two R* groups, preferably two adjacent R group connect, formed have selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron or they Combination in the ring structure of 3-30 atom.Further, substituent R * can also is that and is at one end bonded to L and forms bonding Double-basis (diradical) in the carbon σ key of metal M.Other part can be bonded to metal M, for example, at least one leaving group Q*.In one embodiment, Q* is the single anion instability part of the σ key having and being connected to M.Depend on described metal Oxidation state, the value of n is 0,1 or 2 so that formula above (1) represents neutral Bulky Ligand Metallocene catalyst compounds.Q* joins The limiting examples of body includes weak base such as amine, phosphine class, ethers, carboxylate radical, dienes, has the hydrocarbon of 1-20 carbon atom Base, hydride ion or halogen etc., or combinations thereof.In another embodiment, two or more Q* form thick sum Ring or a part for ring system.Other example of Q* part includes those substituent groups of R* as above, including cyclobutyl, hexamethylene Base, heptyl, tolyl, trifluoromethyl, tetramethylene (two Q*), pentamethylene (two Q*), methylene (two Q*), methoxy Base, ethyoxyl, propoxyl group, phenoxy group, join (methylphenylamine), dimethylamino, dimethyl phosphino-etc..

In another embodiment, the carbon monoxide-olefin polymeric that can be used for the present invention can include that one or more use following formula The 2 Bulky Ligand Metallocene catalyst compounds represented, the L of its formula of 1^AAnd L^BMutual by least one bridged group A* Bridging:

L^AA*L^BMQ*_n (2)

The compound of formula 2 is referred to as the Bulky Ligand Metallocene catalyst compounds of bridging.L^A、L^B, M, Q* and n as more than Defined.The limiting examples of bridged group A* includes the bridged group containing at least one 13-16 race atom, is usually claimed For divalent moiety, described atom be such as but not limited at least one of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or Combinations thereof.Preferably, bridged group A* contains carbon, silicon or germanium atom, most preferably, A* contain at least one silicon atom or At least one carbon atom.Bridged group A* can be possibly together with substituent R * as defined above, including halogen and ferrum.Bridged group The limiting examples of A* can use R '₂C, R '₂CCR′₂, R '₂Si, R '₂SiCR′₂, R '₂SiSiR′₂, R '₂Ge, R ' P, R ' N, R ' B Representing, wherein R ' is a kind of group independently, and it is hydride ion, alkyl, substituted alkyl, halocarbon base, substituted halocarbon Base, the substituted organic quasi-metal of alkyl, the substituted organic quasi-metal of halocarbon base, dibasic boron, dibasic pnicogen, take The chalcogen in generation or halogen, or two or more R ' can connect cyclization or ring system.In one embodiment, formula The Bulky Ligand Metallocene catalyst compounds of the bridging of 2 has two or more bridged groups A* (EP 664 301B1).

In another embodiment, described Bulky Ligand Metallocene catalyst compounds is wherein the Pang of formula 1 and 2 Big ligand L^AAnd L^BOn R* substituent group by the identical or different number in each bulky ligand substituent group replace those. In another embodiment, bulky ligand L of formula 1 and 2^AAnd L^BDifferent from each other.

Other Bulky Ligand Metallocene catalyst compounds and the catalyst system that can be used for the present invention can be included in U.S. patent 5,064,802,5,145,819,5,149,819,5,243,001,5,239,022,5,276,208,5,296, 434,5,321,106,5,329,031,5,304,614,5,677,401,5,723,398,5,753,578,5,854,363,5, 856,547,5,858,903,5,859,158,5,900,517 and 5,939,503, and PCT Publication WO 93/08221, WO93/ 08199, WO 95/07140, WO98/11144, WO98/41530, WO98/41529, WO98/46650, WO99/02540 and WO99/14221, and European Published EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 Described in 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 748821 and EP-B1-0 757 996 Those, all full patent texts are hereby incorporated by here.

In another embodiment, the carbon monoxide-olefin polymeric that can be used for the present invention can include bridging hetero atom, single Pang Big Ligand Metallocene Compound.The catalyst of these types and catalyst system are disclosed in such as PCT Publication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO 99/20637, and U.S. patent 5,057,475,5,096,867,5,055,438,5,198,401,5,227,440 and 5,264,405, and Europe In open EP-A-0 420 436, all these full patent texts are hereby incorporated by here.

In another embodiment, the carbon monoxide-olefin polymeric that can be used for the present invention includes that one or more are by following formula 3 table The Bulky Ligand Metallocene catalyst compounds shown:

L^CA*J*MQ*_n (3)

Wherein M is 3-16 race metallic atom or the metal in the actinium series and lanthanide series of the periodic table of elements, and preferably M is 3-12 group 4 transition metal, more preferably M are 4,5 or 6 group 4 transition metals, and most preferably M is 4 group 4 transition metals of any oxidation state, especially It is titanium；L^CIt it is the substituted or unsubstituted bulky ligand being bonded in M；J* is bonded in M；A* is bonded in J* and L^C；J* is miscellaneous former Sub-assistant ligand；A* is bridged group；Q* is univalent anionic ligand；N is integer 0,1 or 2.In formula above 3, L^C、A* With the ring system that J* forms thick sum.In one embodiment, the L of formula 3^CAs above with respect to L^ADefined such.Formula 3 A*, M and Q* are as above defined in formula 1.In formula 3, J* is containing heteroatomic part, and wherein J* is element The element that ligancy is 3 of periodic chart 15 race, or the element that ligancy is 2 of the periodic table of elements 16 race.Preferably, J* contains Nitrogen, phosphorus, oxygen or sulphur atom, wherein nitrogen is most preferred.In one embodiment of the invention, described Bulky Ligand Metallocene Catalyst compounds is heterocyclic ligand complexes, wherein said bulky ligand i.e. ring or ring system include one or more hetero atom or Combinations thereof.Heteroatomic limiting examples includes 13-16 race element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and stannum. The example of these Bulky Ligand Metallocene catalyst compounds is disclosed in WO 96/33202, WO 96/34021, WO 97/ 17379, WO 98/22486, EP-A1-0 874 005 and US patent 5,637,660,5,539,124,5,554,775,5,756, 611,5,233,049,5,744,417 and 5, in 856,258, all patents are hereby incorporated by here.

In one embodiment, described Bulky Ligand Metallocene compound (procatalyst) is based on containing pyridine or quinoline Those coordination compounds of the bidentate ligand of quinoline structure division, the U.S. application serial 09/103 such as proposed on June 23rd, 1998, Those described in 620, this patent is hereby incorporated by here.In another embodiment, described bulky ligand metal Cyclopentadienyl catalyst compound is those described in PCT Publication WO99/01481 and WO98/42664, and this two patents is by drawing In full it is combined in here.

In another embodiment, described Bulky Ligand Metallocene catalyst compounds is metal (preferably transition gold Belong to), joining of bulky ligand (part of the most substituted or unsubstituted π-bonding) and one or more miscellaneous allylic structure part Compound, such as those described in US patent 5,527,752 and 5,747,406 and EP-B1-0 735 057, all these specially Profit is combined in here by reference of text.

In another embodiment, described Bulky Ligand Metallocene catalyst compounds is at PCT Publication WO 99/ Those described in 01481 and WO 98/42664, described patent is combined in here by reference of text.

6 useful race's Bulky Ligand Metallocene catalyst systems are described in US patent 5, and in 942,462, described patent is led to Cross to quote and be combined in here.

Other useful catalyst is included in those multinuclear metallocenas described in WO 99/20665 and 6,010,794 and urges Agent, these patents are hereby incorporated by here.Other metalloscene catalyst includes that described in EP 0 950 667A1 A bit, the metalloscene catalyst (EP 0 970074A1) of double cross connection, (tethered) metallocene carried the baby (EP 970 963A2) With in US patent 6, those the sulfonyl catalyst described in 008,394, these patents are hereby incorporated by here.

Further contemplating that, in one embodiment, above-mentioned Bulky Ligand Metallocene catalyst includes their structure or optics Or enantiomer (meso and racemic isomer, for example, see US patent 5,852,143, this patent is incorporated by reference Herein) and their mixture.

Being further contemplated that, any one of above-mentioned Bulky Ligand Metallocene catalyst compounds has at least one fluorion Or fluorine-containing leaving group, such as the US application serial 09/191 proposed on November 13rd, 1998, described in 916.

The metallic compound containing 15 races used in the carbon monoxide-olefin polymeric of the present invention passes through methods known in the art Preparation, such as in EP 0 893 454A1, US patent No.5,889,128 and in US patent No.5, the ginseng quoted in 889,128 Examining those methods disclosed in document, all these documents are incorporated herein.The US that on May 17th, 1999 submits to Application serial 09/312,878 disclose gas phase or slurry phase polymerisation process, the described Shen of the double amide catalyst using load Please it is incorporated herein also by quoting.About the out of Memory of the metallic compound containing 15 races, refer to Mitsui Chemicals, Inc., EP0 893 454A1, described patent discloses the transition metal amide for olefin polymerization and activation The combination of agent.

In one embodiment, before being used in the polymerization, the described metallic compound containing 15 races is allowed to ageing.? Noticing in the case of at least one, a kind of such catalyst compounds (being aged at least 48 hours) performance is better than freshly prepd Catalyst compounds.

It is further contemplated that, it is possible to use double amino-type procatalysts.Exemplary compounds includes described in patent documentation Those.International Patent Publication WO 96/23010, WO 97/48735 and Gibson et al., Chem.Comm., 849-850 (1998) diimine type ligands for 8-10 compounds of group is disclosed, its experience ion activation olefin polymerization.US patent 5, 502,124 and divisional U.S. Patent 5,504,049 describe the polymerisation catalyst system of 5-10 race metal, wherein active center is Highly oxidized and stable by the polyanionic ligand system of low ligancy.5 races referring further to US patent 5,851,945 are organic Metal catalyst compounds and the 5-10 race organo-metallic catalyst containing tridentate ligand of US patent 6,294,495.WO99/ 30822 describe available ionizing cocatalysts activates, can be used for 11 race's catalyst precarsors of alkene and vinylic polar molecules Compound.

Other available catalyst compounds be described in EP-A2-0 816 384 and US patent 5,851,945 those 5 With 6 race's metal imido complexes, these patents are incorporated herein.It addition, metalloscene catalyst include by D.H.McConville et al. is at Organometallics 1995, double (aryl ammonia of the bridging described in 14,5478-5480 Base) 4 compounds of group, described document is incorporated herein.It addition, WO96/27439 describes double (ammonia of bridging Base) catalyst compounds, described document is incorporated herein.Other available catalyst in U.S. patent 5,852, Being described as double (hydroxy aromatic nitrogen ligands) in 146, described patent is incorporated herein.Containing one or more 15 Other useful catalyst of race's atom is included in those described in WO 98/46651, and described file is hereby incorporated by Herein.

US patent 5,318,935 describes can the bridging of 4 race's metals of polymerization of Alpha-olefin and double amino of non-bridging urge Agent compound.D.H.McConville et al. at Organometallics 1995, describe in 14,5478-5480 for Double (arylamino)-4 compounds of group of the bridging of olefinic polymerization.This list of references gives synthetic method and characterization of compound. At D.H.McConville et al., Macromolecules 1996,29, the further work specification of report in 5241-5243 Double (arylamino)-4 compounds of group of bridging, they are the polymerization catalysts of 1-hexene.The transition of other applicable present invention Metallic compound is included in those described in WO 96/40805.The unexamined US application serial of JIUYUE in 1999 submission on the 29th 09/408,050 discloses cation 3 race or lanthanide series metal olefin polymerization complexes.One monoanionic bidentate ligand and two Single anion ligand stablizes these catalyst precarsors, and these precursors can be with the cocatalysts activation of the present invention.

Described document describes other suitable catalyst precursor compounds many.Chemical combination containing seizable part The compound that thing maybe can be partially alkylated or alkylated and contain seizable part is suitable for the present invention.For example, with reference to V.C.Gibson etc. People, " The Search forNew-Generation Olefin Polymerization Catalysts:Life BeyondMetallocenes ", Angew.Chem.Int.Ed., 38,428-447 (1999).

The present invention can also with the catalyst containing phenoxy ligand such as those disclosed in EP 0 874 005A1 Implementing, described patent is incorporated herein.

In another embodiment, the present invention can be implemented with the transition-metal catalyst of general type.General type Transition-metal catalyst be those traditional Z-Ns well known in the art, vanadium and Karen Phillips type catalyst.Example As, Ziegler-Natta catalyst is described inZiegler-Natta Catalysts and Polymerizations,John Boor, Academic Press, New York, in 1979.In US patent 4,115,639,4,077,904,4,482,687,4, 564,605,4,721,763,4,879,359 and 4, also discuss the reality of the transition-metal catalyst of general type in 960,741 Example, all these full patent texts are incorporated herein.The transition gold of the general type that can use in the present invention Metal catalyst compound includes the 3-17 race of the periodic table of elements, preferably 4-12 race, the transistion metal compound of more preferably 4-6 race.

The preferably transition-metal catalyst of general type can use formula M R_xRepresenting, wherein M is the gold of 3-17 race Belong to, the metal of preferably 4-6 race, the metal of more preferably 4 races, most preferably titanium；R is halogen or oxyl；It is the oxidation of metal M with x State.The limiting examples of R includes alkoxyl, phenoxy group, bromine, chlorine and fluorine.Wherein M is that the transition metal of general type of titanium is urged The limiting examples of agent includes TiCl₄, TiBr₄, Ti (OC₂H₅)₃Cl, Ti (OC₂H₅)Cl₃, Ti (OC₄H₉)₃Cl, Ti (OC₃H₇)₂Cl₂, Ti (OC₂H₅)₂Br₂, TiCl₃·1/3AlCl₃With Ti (OC₁₂H₂₅)Cl₃.Can be used for the present invention based on magnesium titanium The transition metal catalyst compound of the general type of electron-donor complexes is described in such as US patent 4,302,565 and 4, In 302,566, described full patent texts is incorporated herein.MgTiCl₆(ethyl acetate) 4 derivant is particularly preferred 's.

UK Patent Application 2,105,355 and US patent No.5,317,036 describes the vanadium catalyst of various general type Compound, described patent is incorporated herein.The limiting examples bag of the vanadium catalyst compound of general type Include three halogenation vanadyl, alkoxy vanadyl and alkoxyl vanadyl, such as VOCl₃, VOCl₂(OBu) (wherein Bu=butyl) and VO(OC₂H₅)₃；Four halogenation vanadium and alkoxy vanadium, such as VCl₄And VCl₃(OBu)；Vanadium acetylacetonate, chloracetyl acetone vanadium, Vanadyl acetylacetonate and chloracetyl acetone vanadyl, such as V (AcAc)₃And VOCl₂(AcAc), wherein (AcAc) is acetylacetone,2,4-pentanedione root. Preferably the vanadium catalyst compound of general type is VOCl₃, VCl₄And VOCl₂-OR, wherein R is alkyl, preferably C₁-C₁₀Aliphatic series Or aromatic hydrocarbyl, such as ethyl, phenyl, isopropyl, butyl, propyl group, normal-butyl, isobutyl group, the tert-butyl group, hexyl, cyclohexyl, naphthalene Base etc., and vanadium acetylacetonate.

It is applicable to chrome catalysts compound (the commonly referred to as Karen Phillips type catalyst) bag of the general type of the present invention Include CrO₃, chromium cyclopentadienyl, chromic acid silyl ester, chromium dioxychloride. (CrO₂Cl₂), 2 ethyl hexanoic acid chromium, chromium acetylacetonate (Cr (AcAc)₃) Deng.Limiting examples is disclosed in US patent 3,709,853,3,709,954,3,231,550,3,242,099 and 4,077,904 In, these full patent texts are incorporated herein.

The transition metal catalyst compound and the catalyst system that are applicable to other general type of the present invention are disclosed in US Patent 4,124,532,4,302,565,4,302,566,4,376,062,4,379,758,5,066,737,5,763,723,5, 849,655,5,852,144,5,854,164 and 5,869,585 and disclosed EP-A2 0 416 815 A2 and EP-A1 0 420 In 436, all these patents are all incorporated herein.

Other catalyst can include cationic catalyst well known in the art such as AlCl₃And other cobalt, ferrum, nickel and palladium Catalyst.See for example US patent 3,487,112,4,472,559,4,182,814 and 4,689,437, all these patents are led to Cross to quote and be incorporated herein.

Further contemplating that, other catalyst can be with the catalyst compounds group in the carbon monoxide-olefin polymeric that can be used for the present invention Close.For example, with reference to US patent 4,937,299,4,935,474,5,281,679,5,359,015,5,470,811 and 5,719, 241, all these full patent texts are incorporated herein.

Being further contemplated that, one or more of above-mentioned catalyst compounds or catalyst system can be normal with one or more Catalyst compounds or the catalyst system of rule are used in combination.The limiting examples of mixed catalyst and catalyst system is retouched State in US patent 4,159,965,4,325,837,4,701,432,5,124,418,5,077,255,5,183,867,5,391, PCT Publication WO disclosed on August 1st, 660,5,395,810,5,691,264,5,723,399 and 5,767,031 and 1996 In 96/23010, all these files are incorporated herein in full.

Preferred metalloscene catalyst for the present invention can represent more specifically with one of below general formula (all to be mentioned Race be Chemical and Engineering News, 63 (5), the new race of the periodic table of elements described in 27,1985 represents Method):

[{[(A-Cp)MX₁]⁺}_d]{[B′]^d-} (4)

[{[A-Cp)MX₁L]⁺}_d]{[B′]^d-} (5)

Wherein:

(A-Cp) it is (Cp), (Cp*) or Cp-A '-Cp*；It is " substituted identical or not that Cp with Cp* is by 0-5 substituent group S Same cyclopentadienyl rings, each substituent group S " is alkyl, substituted alkyl, halocarbon base, substituted halocarbon base, alkyl independently Substituted organic quasi-metal, the substituted organic quasi-metal of halocarbon base, dibasic boron, dibasic pnicogen, substituted sulfur Belonging to element or halogen group, or Cp and Cp* is cyclopentadienyl rings, " group connects into C to the adjacent S of any two of which₄- C₂₀Ring, to provide saturated or undersaturated multi-ring cyclopentadienyl ligands；One or two carbon atom in ring of Cp and Cp* Can also be by 15 or 16 race's elements, especially S, O, N or P replaces；

A ' is bridged group；

(C₅H_5-y-xS″_x) by individual S " the substituted cyclopentadienyl rings of group as defined above of 0-5；

X is 0-5, represents substitution value；

M is titanium, zirconium or hafnium；

X₁Being hydride, alkyl, substituted alkyl, alkyl substituted organic quasi-metal group or halocarbon base replace Organic quasi-metal group, described group can optionally be covalently attached to M and L or L ' either or both, all or any M, S " or S ', premise is X₁It it not substituted or unsubstituted cyclopentadienyl rings；

(JS′_z-1-y) be heteroatom ligand, wherein J be ligancy be the element of the periodic table of elements 15 race of 3, or ligancy It it is the element of 16 races of 2；S ' is alkyl, substituted alkyl, halocarbon base, substituted halocarbon base, the substituted organic quasi-metal of alkyl Or the substituted organic quasi-metal of halocarbon base；It is the ligancy of element J with z；

Y is 0 or 1；

L is alkene, alkadienes or aryne part.L ' is identical with L, and can be additionally that amine, phosphine, ether or sulfide are joined Body, or other neutral Lewis base any；L ' can also is that the Second Transition compound of same type so that two metals Center M and M* passes through X₁With X '₁Bridging, wherein M* has the implication identical with M, X '₁、X₂With X '₂Have and X₁Identical implication, The most this dimeric compounds (it is the precursor of cationic moiety of catalyst) represents by below general formula:

Wherein

W is the integer of 0-3；

B ' is that molecular diameter is about 4 angstroms or is more than chemically stable, the non-nucleophilic anionic complex of 4 angstroms, or by road Anion produced by the precursors reaction of the cationic moiety of Lewis acid activator and the catalyst system described in formula 1-4 Lewis acid activation agent.When B ' is Lewis acid activation agent, X₁Can also is that the alkyl given by Lewis acid activation agent； With

D is the integer of the electric charge representing B '.

Described catalyst is preferably by preparing the combination of at least two component.In a kind of method for optimizing, the first component It is by 4 race's metal compounds with second component or part that at least one part is combined such as its cationic moiety containing at least one The cyclopentadienyl derivative of thing.Second component is the ion-exchange compound comprising cation and non-coordinating anion, described Cation and at least one the part irreversible reaction contained in described 4 race's metallic compounds (the first component), and described non- Coordination anion is to comprise covalent coordinate in carrying the central metal of formal charge or metalloid atom and shielding described metal Or single coordinate complex of multiple lipophilic groups of metalloid atom, or comprise the anion of multiple boron atom, such as Polyhedral boranes, carborane and metallocarborane.

The suitable anion being commonly used for described second component can be to have any of following molecule attribute to stablize and huge Big anionic complex: 1) described anion should have the molecular diameter more than 4 angstroms；2) described anion should be formed surely Fixed ammonium salt；3) negative charge in described anion should be delocalization in anionic framework, or should be positioned at anion In-core；4) described anion should be the worst nucleophile；With 5) described anion should not be strong reducing agent or Oxidant.Fully describe in the chemical literature and met the anion of these standards-such as multinuclear borine, carborane, metal carbon Borine, many oxygen anions (polyoxoanion) and anion binding compound.

The cationic moiety of second component can include the lewis base of Bronsted acid, such as proton or protonation, Or can include lewis acid, such as ferricinum ion,, triphenylcarbenium or silver cation.

In another kind of method for optimizing, second component is Lewis acid complex, it by with at least one of the first component Ligand reaction, thus formed and there is institute among formula 4-6 that capture from the first component, presently in connection with the part in second component The ionic species stated.Aikyiaiurnirsoxan beta and especially MAO (by trimethyl aluminium aliphatic series or aromatic hydrocarbon in Chemical Calculation The water of amount reacts the product formed), it is especially preferred lewis acid second component.Modified alumoxane is also preferred.Aluminum Oxygen alkane is well known in the present art, and their preparation method is US patent 4,542,199,4,544,762,5,015,749 He It is described in 5,041,585.The technology preparing modified alumoxane is disclosed in US patent 5,041,584, EP-A-0 516 476 He In EP-A-0561 476, these files are incorporated herein.

After the first and second components being combined, one of part of second component and the first component reacts, thus produces by 4 Race's metal cation and the anion pair of above-mentioned anion composition, described anion and the 4 race's metal sun formed by the first component Ion is compatible, and is unworthy of being positioned at described 4 race's metal cations.The anion of the second compound allows for making 4 race's metal sun The ability as catalyst of ion is stable, and must be enough unstable, to allow in the course of the polymerization process by alkene, alkadienes Or acetylene series unsaturated monomer is replaced.The catalyst of the present invention can be supported.The US patent 4 that on February 28th, 1989 authorizes, 808,561, the US patent 5,057 of the US patent mandate on October 15th, 4,897,455,1991 that January 3 nineteen ninety authorizes, 475, US patent application serial numbers 459,921 (publishing as PCT International Publication WO91/09882), Canadian Patent 1,268,753, US patent 5,240,894 and WO 94 03506 discloses catalyst and the method for the described catalyst of production of such load, this A little patents are incorporated herein.

Can be used as 4 race's gold of the first compound (procatalyst) in the preparation of the preferred metalloscene catalyst of the present invention Belonging to compound, i.e. titanium, zirconium and hafnium metallocene compound is the cyclopentadienyl derivative of titanium, zirconium and hafnium.Usually, useful titanium Cyclopentadienyl, zirconium cyclopentadienyl and hafnium cyclopentadienyl can represent by below general formula:

(A-Cp)MX₁X₂ (8)

(A-Cp)ML (9)

Wherein:

(A-Cp) it is (Cp) (Cp*) or Cp-A '-Cp*；Cp and Cp* is by 0-5 substituent group S " substituted identical or different Cyclopentadienyl rings, each substituent group S " be that alkyl, substituted alkyl, halocarbon base, substituted halocarbon base, alkyl take independently The organic quasi-metal in generation, the substituted organic quasi-metal of halocarbon base, dibasic boron, dibasic pnicogen, substituted chalcogen Element or halogen group, or Cp and Cp* be cyclopentadienyl rings, the S that any two of which is adjacent " group connects into C₄-C₂₀ Ring is to provide saturated or undersaturated multi-ring cyclopentadienyl ligands；

A ' is bridged group；

Y is 0 or 1；

(C₅H_5-y-xS″_x) " the substituted cyclopentadienyl rings of group by 0-5 S as defined above；

X is 0-5, represents substitution value；

(JS′_z-1-y) be heteroatom ligand, wherein J be ligancy be the element of the periodic table of elements 15 race of 3, or ligancy It it is the element of 16 races of 2；S ' is alkyl, substituted alkyl, halocarbon base, substituted halocarbon base, the substituted organic quasi-metal of alkyl, Or the substituted organic quasi-metal of halocarbon base；It is the ligancy of element J with z；

L is alkene, alkadienes or aryne part.L ' is identical with L, and can be additionally that amine, phosphine, ether or sulfide are joined Body, or other neutral Lewis base any；L ' can also is that the Second Transition compound of same type so that two metals Center M and M* passes through X₁With X '₁Bridging, wherein M* has the implication identical with M, X '₁Have and X₁Identical implication, X '₂Have With X₂Identical implication, the most this dimeric compounds (it is the precursor of cationic moiety of catalyst) formula above 7 table Show；

W is the integer of 0-3；With

X₁And X₂Hydride independently, alkyl, substituted alkyl, halocarbon base, substituted halocarbon base, alkyl and Halocarbon base substituted organic quasi-metal group, substituted pnicogen group, or substituted chalcogen group；Or X₁And X₂ Connect, and be bonded to described metallic atom, form the becket containing about 3 to about 20 carbon atoms (metallacycle)；Or X₁And X₂Can be alkene, alkadienes or aryne part together；Or live when using lewis acid (they can be by X as above for agent such as MAO₁Part gives transition metal component) time, X₁And X₂Can be independent Ground is halogen, alkoxyl, aryloxy group, amino (amide), phosphino-(phosphide) or other univalent anionic ligand, or X₁ And X₂The two can also connect into anionic cheating ligand, and premise is X₁And X₂It it not substituted or unsubstituted cyclopentadienyl rings.

Table A describes the representative composition part of the metallocene components of formula 7-10.Described list is only for illustrating Bright purpose, it is restrictive for shall in no way be construed to.Many final components can be constituted the most to each other by arrangement is described Likely combine and formed.Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, cycloalkynyl radical is included when open in this application With aromatic group when interior alkyl, described term includes all isomers.Such as, butyl includes normal-butyl, 2-methyl-prop Base, 1-methyl-propyl, the tert-butyl group and cyclobutyl；Amyl group include n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl, neopentyl, cyclopenta and methyl-cyclobutyl；Cyclobutenyl includes 1-butylene base, crotyl, 3-cyclobutenyl, 1- Methyl-1-propylene base, 1-methyl-2-acrylic, 2-methyl-1-propylene base and the E of 2-methyl-2-acrylic and Z-shaped formula.This bag Including group bonding situation when another group, such as, propyl-cyclopentadienyl includes n-pro-pyl cyclopentadienyl group, different Propyl-cyclopentadienyl and cyclopropyl rings pentadienyl.Usually, the part shown in Table A or group include all isomery bodily forms Formula.Such as, dimethylcyclo-pentadienyl includes 1,2-dimethylcyclo-pentadienyl and 1,3-dimethylcyclo-pentadienyl；Methyl indenes Base includes 1-methylindenyl, 2-methylindenyl, 3-methylindenyl, 4-methylindenyl, 5-methylindenyl, 6-methylindenyl and 7-first Base indenyl；Methylethyl phenyl includes adjacent Methylethyl phenyl, a Methylethyl phenyl and to Methylethyl phenyl.Concrete basis The example of invention catalyst precarsor has below general formula, and some of them composition as listed is in Table A.In order to transition metal component is described Member, selects any combination of species cited in Table A.In name, for bridged group A ', word " silicyl " and " silylene " is used interchangeably, and represents divalent group kind.For bridged group A ', " ethylidene " refers to that ethylene is even Connect base, be not ethylene-1,1-diyl.Therefore, for bridged group A ', " ethylidene " and " ethylene " is used interchangeably. For having the compound of bridged group A ', the bridging position on cyclopentadienyl type ring is always considered 1-position.Therefore, example As, " 1-fluorenyl " and " fluorenyl " are used interchangeably.

The exemplary compounds of formula 8 type is: dimethyl double (cyclopentadienyl group) closes hafnium, dihydro ethylenebis (tetrahydro indenyl) zirconium, double (pentamethyl) zirconium of diethyl, dimethylsilyl (1-fluorenyl) (cyclopentadiene Base) close titanium etc..The exemplary compounds of formula 9 type is double (cyclopentadienyl group) (1,3-butadiene) zirconiums, double (cyclopentadiene Base) (2,3-dimethyl-1,3-butadiene) zirconium, double (pentamethylcyclopentadiene base) (benzene) zirconium, double (pentamethylcyclopentadiene Base) ethylene conjunction titanium etc..The exemplary compounds of formula 10 type is dimethylsilyl (tetramethyl-ring pentadiene Base) (tert-butylamino) zirconium, dimethylethylene (methyl cyclopentadienyl) (phenyl amino) closes titanium, dihydro methylbenzene Base silicyl (indenyl) (phenyl phosphino-) closes hafnium and (pentamethylcyclopentadiene base) (di-t-butyl amino) closes hafnium dimethanol Salt.

Coordination compound contains neutral Lewis base ligands such as ether or forms the condition of dimeric compounds by around metal center The spatial volume of part determines.Such as, at Me₂Si(Me₄C₅)(N-t-Bu)ZrCl₂In the space requirement of the tert-butyl group be higher than At Me₂Si(Me₄C₅)(NPh)ZrCl₂·Et₂Phenyl in O, thus previous compound does not allow ether to join in solid state Position.Similarly, due at [Me₂Si(Me₃SiC₅H₃)(N-t-Bu)ZrCl₂]₂In trimethyl silyl cyclopentadienyl group Spatial volume is less than Me₂Si(Me₄C₅)(N-t-Bu)ZrCl₂In the spatial volume of tetramethyl-ring pentadienyl, so previousization Compound is dimerization, and latter compound is not.

Table A

A′	Cp, Cp*, CpR or (C₅H_5-y-xS″_x)
		Dimethylsilylene	Cyclopentadienyl group
Diethyl silylene	Methyl cyclopentadienyl
		Dipropyl silylene	Dimethylcyclo-pentadienyl
Dibutyl silylene	Trimethyl cyclopentadienyl group
		Diamyl silylene	Tetramethyl-ring pentadienyl
Dihexyl silylene	Pentamethylcyclopentadiene base (without A ')
		Diheptyl silylene	Ethyicydopentadi etanyf group
Dioctyl silylene	Diethyl cyclopentadienyl group
		Dinonyl silylene	Propyl-cyclopentadienyl
Didecyl silylene	Dipropyl cyclopentadienyl group
		Two (undecyl) silylene	Butyl cyclopentadienyl group
Two (dodecyl) silylene	Dibutyl cyclopentadienyl group
		Two (tridecyl) silylene	Amyl group cyclopentadienyl group
Two (myristyl) silylene	Diamyl cyclopentadienyl group
		Two (pentadecyl) silylene	Hexyl cyclopentadienyl group
Two (cetyl) silylene	Dihexyl cyclopentadienyl group
		Two (heptadecyl) silylene	Heptyl cyclopentadienyl group
Two (octadecyl) silylene	Diheptyl cyclopentadienyl group

Two (nonadecyl) silylene	Octyl group cyclopentadienyl group
		Two (eicosyl) silylene	Dioctyl cyclopentadienyl group
Two (heneicosyl) silylene	Nonyl cyclopentadienyl group
		Two (docosyl) silylene	Dinonyl cyclopentadienyl group
Two (tricosyl) silylene	Decyl cyclopentadienyl group
		Two (tetracosyl) silylene	Didecyl cyclopentadienyl group
Two (pentacosyl) silylene	Undecyl cyclopentadienyl group
		Two (cerul) silylene	Dodecyl cyclopentadienyl group
Two (heptacosyl) silylene	Tridecyl cyclopentadienyl group
		Two (octacosyl) silylene	Myristyl cyclopentadienyl group
Two (nonacosyl) silylene	Pentadecyl cyclopentadienyl group (without A ')
		Two (melissyl) silylene	Cetyl cyclopentadienyl group
Dicyclohexyl silylene	Heptadecyl cyclopentadienyl group
		Bicyclopentyl silylene	Octadecyl cyclopentadienyl group
Bicycloheptyl silylene	Nonadecyl cyclopentadienyl group
		Bicyclooctyl silylene	Eicosyl cyclopentadienyl group
Bicyclo-decyl silylene	Heneicosane cyclopentadienyl group
		Two cyclo-dodecyl silylenes	Docosane cyclopentadienyl group
Dinaphthyl silylene	Tricosane cyclopentadienyl group
		Diphenylsilylene	Lignocerane cyclopentadienyl group
Xylyl silylene	Pentacosane cyclopentadienyl group
		Dibenzyl silylene	Hexacosane cyclopentadienyl group
Diphenethyl silylene	Heptacosane cyclopentadienyl group
		Two (butyl benzene ethyl) silylene	Octacosane cyclopentadienyl group
Methylethyl silylene	Nonacosane cyclopentadienyl group
		Methyl-propyl silylene	Melissyl cyclopentadienyl group
Methyl butyl silylene	Cyclohexyl ring pentadienyl
		Methylhexyl silylene	Benzyl ring pentadienyl
Aminomethyl phenyl silylene	Diphenyl cyclopentadienyl group

Ethylphenyl silylene	Triphenyl-cyclopentadiene base
		Ethyl propyl silylene	Tetraphenyl cyclopentadienyl group
Ethyl-butyl silylene	Pentaphenylcyclopentadiene base
		Propyl group phenyl silylene	Tolyl cyclopentadienyl group
Dimethylated methylene germane base	Benzyl rings pentadienyl
		Diethyl Asia germyl	Phenethyl cyclopentadienyl group
Diphenyl Asia germyl	Cyclohexyl methyl cyclopentadienyl group
		Aminomethyl phenyl Asia germyl	Naphthyl cyclopentadienyl group
Ring tetramethylene silylene	Aminomethyl phenyl cyclopentadienyl group
		Cyclopentamethylene silylene	Methyl toluene cyclopentadienyl group
Ring trimethylene silylene	Methylethyl cyclopentadienyl group
		Cyclohexyl azane diyl (azanediyl)	Methyl-propyl cyclopentadienyl group
Butyl azane diyl	Methyl butyl cyclopentadienyl group
		Methyl azane diyl	Methyl amyl cyclopentadienyl group
Phenyl azane diyl	Methylhexyl cyclopentadienyl group
		Perfluorophenyl azane diyl	Methylheptyl cyclopentadienyl group
Methyl phosphine diyl (phosphanediyl)	Methyl Octyl cyclopentadienyl group
		Ethyl phosphine diyl	Nonyl cyclopentadienyl group
Propyl group phosphine diyl	Methyldecyl cyclopentadienyl group
		Butyl phosphine diyl	Vinyl cyclopentadienyl group
Cyclohexyl phosphine diyl	Acrylic cyclopentadienyl group
		Phenyl phosphine diyl	Cyclobutenyl cyclopentadienyl group
Methyl borine diyl	Indenyl
		Phenylborinane diyl	Methylindenyl
Methylene	Dimethylindenyl
		Dimethylated methylene base	Trimethylindenyl
Diethyl methylene	Methyl-propyl indenyl
		Dibutyl methylene	Dimethyl propyl indenyl
Dipropyl methylene	Methyl dipropyl indenyl

Diphenylmethylene	Methylethyl indenyl
		Xylyl methylene	Methyl butyl indenyl
Two (butyl phenyl) methylene	Ethyl-indenyl
		Two (trimethylsilylphenyl) methylene	Propyl group indenyl
Two (triethylsilylphenyl) methylene	Butyl indenyl
		Dibenzyl methylene	Amyl group indenyl
Ring tetramethylene methylene	Hexyl indenyl
		Cyclopentamethylene methylene	Heptyl indenyl
Ethylidene	Octyl group indenyl
		Methyl ethylidene	Nonyl indenyl
Dimethylethylene	Decyl indenyl
		Trimethyl ethylidene	Phenyl indenyl
Tetramethyl ethylidene	(fluorophenyl) indenyl
		Cyclopentylene	(aminomethyl phenyl) indenyl
Cyclohexylidene	Xenyl indenyl
		Cycloheptylidene	(double (trifluoromethyl) phenyl) indenyl
Cyclooctylene	Naphthyl indenyl
		Glyceryl	Phenanthryl indenyl
Methyl-prop diyl	Benzyl indenyl
		Dimethyl propylene diyl	Benzo indenyl
Trimethyl glyceryl	Cyclohexyl indenyl
		Tetramethyl glyceryl	Aminomethyl phenyl indenyl
Pentamethyl glyceryl	Ethylphenyl indenyl
		Hexamethyl glyceryl	Propyl group phenyl indenyl
Tetramethyl Asia disilane epoxide	Methyl naphthyl indenyl
		Vinylene	Ethyl naphthyl indenyl
Ethylene-1,1-diyl	Propyl group naphthyl indenyl
		Divinyl silylene	(aminomethyl phenyl) indenyl
Diallyl silylene	(3,5-dimethylphenyl) indenyl

Dibutene base silylene	(ethylphenyl) indenyl
		Methyl ethylene silylene	(diethyl phenyl) indenyl
Methylpropenyl silylene	(propyl group phenyl) indenyl
		Methyl butene base silylene	(dipropyl phenyl) indenyl
Dimetylsilyl methylene	Methyl tetrahydro indenyl
		Diphenylsilyl group methylene	Dimethyl tetrahydro indenyl
Dimetylsilyl ethylidene	Dimethyl dihydro indenyl
		Diphenylsilyl group ethylidene	Dimethyl three hydrogen indenyl
Dimetylsilyl propylidene	Aminomethyl phenyl tetrahydro indenyl
		Diphenylsilyl group propylidene	Aminomethyl phenyl dihydro indenyl
Dimethylated methylene stannane base	Aminomethyl phenyl three hydrogen indenyl
		Diphenyl stannylene	Ethyl tetrahydro indenyl
	Propyl group tetrahydro indenyl
			Butyl tetrahydro indenyl
	Phenyl tetrahydro indenyl
			Fluorenyl
	Methylfluorenyl
			Dimethyl fluorenyl
	Trimethyl fluorenyl
			Ethylfluorenyl
	Propyl group fluorenyl
			Butyl fluorenyl
	Dibutylfluorenyl
			Amyl group fluorenyl
	Hexyl fluorenyl
			Heptyl fluorenyl
	Octyl group fluorenyl
			Nonyl fluorenyl
	Decyl fluorenyl

	Phenylfluorenyl
			Naphthyl fluorenyl
	Benzyl fluorenyl
			Aminomethyl phenyl fluorenyl
	Ethylphenyl fluorenyl
			Propyl group phenylfluorenyl
	Methyl naphthyl fluorenyl
			Ethyl naphthyl fluorenyl
	Propyl group naphthyl fluorenyl
			Octahydrofluorenyl
	Tetrahydrofluorenyl
			Prestox octahydro dibenzo [b, h] fluorenyl
	Tetramethyl tetrahydro benzo [b] fluorenyl
			Diphenylmethyl cyclopentadienyl group
	Trimethyl silyl cyclopentadienyl group
			Triethylsilyl cyclopentadienyl group
	Trimethylgermyl groups cyclopentadienyl group
			Tributylestannyl cyclopentadienyl group
	Triethyl group plumbyl cyclopentadienyl group
			Trifluoromethyl cyclopentadienyl group
	N, N-dimethylamino cyclopentadienyl group
			P, P-dimethyl phosphine cyclopentadienyl group
	N, N-diethyl amino cyclopentadienyl group
			Methoxyl group cyclopentadienyl group
	Ethyoxyl cyclopentadienyl group
			Trimethylsiloxy cyclopentadienyl group
	(N, N-dimethylaminomethyl) cyclopentadienyl group
			Methoxyl group indenyl

	Dimethoxy indenyl
			N, N-dimethylamino indenyl
	Trimethylsiloxy indenyl
			Butyldimethylsilyl epoxide indenyl
	Double (N, N-dimethylamino) indenyl
			Two (trimethylsiloxy) indenyl
	Two (butyldimethylsilyl epoxide) indenyl
			Methoxyl group fluorenyl
	Dimethoxy fluorenyl
			N, N-dimethylamino fluorenyl
	Trimethylsiloxy fluorenyl
			Butyldimethylsilyl epoxide fluorenyl
	Dimethoxy fluorenyl
			Double (N, N-dimethylamino) fluorenyl
	Two (trimethylsiloxy) fluorenyl
			Two (butyldimethylsilyl epoxide) fluorenyl

Table A (Continued)

(JS′_z-1-y) (y=1)	X₁Or X₂	M
			Methylamino	Chlorine	Titanium
Ethylamino	Bromine	Zirconium
			Propylcarbamic	Iodine	Hafnium
Butylamino	Fluorine
			Pentyl amino	Hydride ion	L or L ' (optional)
Hexylamino	Methyl	Ethylidene
			Heptyl amino	Ethyl	Propylidene
Octyl amino	Propyl group	Butylene
			Nonylamino	Butyl	Hexene
Decylamino	Amyl group	Styrene

Eicosyl amino	Hexyl	Hexadiene
			Heneicosyl amino	Heptyl	Butadiene
Docosyl amino	Octyl group	Dimethyl butadiene
			Tricosyl amino	Nonyl	Pentadiene
Tetracosyl amino	Decyl	Methyl hexadiene
			Pentacosyl amino	Undecyl	Dimethyl hexadiene
Hexacosanoylamino	Dodecyl	Acetylene
			Heptacosyl amino	Tridecyl	Allylene
Octacosyl amino	Myristyl	Ethyl acetylene
			Nonacosyl amino	Pentadecyl	Benzyne
Melissyl amino	Cetyl	Cyclopentenes
			Phenyl amino	Heptadecyl	Cyclohexene
Tolylamino	Octadecyl
			PhenethyIamino	Nonadecyl	L′(optional)
Benzylamino	Eicosyl	Diethyl ether
			Cyclobutylamino	Heneicosyl	Dimethyl ether
Clopentylamino	Docosyl	Trimethylamine
			Cyclohexylamino	Tricosyl	Triphenylamine
Cyclo-heptylamino	Tetracosyl	Triethylamine
			Ring octyl amino	Pentacosyl	Tricyclohexyl phosphine
Ring nonylamino	Cerul	Triphenylphosphine
			Ring Decylamino	Heptacosyl	Trimethyl-phosphine
Cyclo-dodecyl amino	Octacosyl	Oxolane
			Adamantylamino	Nonacosyl	Furan
Norborny amino	Melissyl	Thiophene
			Perfluorophenyl amino	Phenyl	Dimethyl sulfide
Fluorophenylamino	Benzyl	Diphenylsulfide
			Difluorophenylamino	Phenethyl
Oxygen bridge	Tolyl

Sulphur bridge (sulfido)	Methoxyl group
			Ethyoxyl
(JS′_z-1-y) (y=0)	Propoxyl group
		Methoxyl group	Butoxy
Ethyoxyl	Dimethylamino
		Phenoxy group	Diethylamino
Dimethyl phenoxy	Methylethylamine
		Dipropyl phenoxy group	Phenoxy group
Methyl mercapto	Benzyloxy
		Ethylmercapto group	Pi-allyl
Thiophenyl
		Dimethyl benzene sulfenyl
Dipropyl thiophenyl
			X₁And X₂Together
	Methylene
			1,1-ethylidene
	1,1-propylidene
			Tetramethylene
	Pentamethylene
			Hexa-methylene
	Ethylene hydroxyl
			Butadiene
	Dimethyl butadiene
			Dimethyl butadiene
	Pentadiene
			Methylpentadiene
	Dimethyl pentadiene
			Hexadiene
	Methyl hexadiene

	Dimethyl hexadiene

Other preferred catalyst is included in those described in WO 01/48034, and this patent is hereby incorporated by this Wen Zhong.Especially preferred catalyst compounds is included in page 9 the 38th row to page 25 the 42nd row, page 28 the 5 to 17th row with And those disclosed in page 30 the 37th row to page 35 the 28th row.

The activator of catalyst compounds and activation method

Above-mentioned polymerization procatalyst compound activates the most in every way, to produce the chemical combination with sky coordination site Thing, described empty coordination site will be coordinated, insert and olefin polymerization.For patent specification and appended claims, Term " promoter " and " activator " here can exchange use, and be defined as can be by by neutral catalyst Compound is converted into the catalyst compounds cation of catalysis activity and activates anyization of any above-mentioned catalyst compounds Compound.Nonrestrictive activator such as includes aikyiaiurnirsoxan beta, alkyl aluminum, and Ionizing activators, they can be neutral or from The promoter of the general type of son.Preferably activator generally includes aluminium alkoxide compound, modified alumoxane compounds, and from Sonization anion pre-cursor compounds, they are captured reactive a, metal ligand for σ keyed jointing, make described metal complex become Become cation and the noncoordinating of balancing charge or Weakly coordinating anions are provided.

Aikyiaiurnirsoxan beta and alkyl aluminum activator

In one embodiment, using alumoxane activator as activation in the carbon monoxide-olefin polymeric of the present invention Agent.Aikyiaiurnirsoxan beta is usually containing-Al (R¹) oligomeric compound of-O-subunit, wherein R¹It it is alkyl.The example of aikyiaiurnirsoxan beta includes MAO (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.Alkylaluminoxane and changing Property alkylaluminoxane is suitable as catalyst activator, especially when seizable part is halogen, alkoxyl or amino.Also may be used To use the mixture of different aluminum modified aluminoxanes.

Activator compound below general formula including Lewis acid activation agent and especially aikyiaiurnirsoxan beta represents:

(R³-Al-O)_p (11)

R⁴(R⁵-Al-O)_p-AlR⁶ ₂ (12)

(M′)^m+Q′_m (13)

The generally linear mixture with cyclic compound of aikyiaiurnirsoxan beta.In described aikyiaiurnirsoxan beta formula, R³、R⁴、R⁵And R⁶Solely It is on the spot C₁-C₃₀Alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, " p " is 1 To the integer of about 50.Most preferably, R³、R⁴、R⁵And R⁶Being individually methyl, " p " is at least 4.When use aluminum alkyl halide or When alkyl aluminum alkoxide prepares aikyiaiurnirsoxan beta, one or more R^3-6Group can be halogen or alkoxyl.M ' is metal or quasi-gold Belonging to, Q ' is the alkyl of partly or completely perfluorinate.

It has been recognized that aikyiaiurnirsoxan beta is not a kind of discrete material.Typical aikyiaiurnirsoxan beta contains three free replacements or three alkane Base aluminum, three replacements of cluster or trialkylaluminium, and the aluminoxane molecules of different oligomeric degree.Most preferably those MAOs Containing low-level trimethyl aluminium.The trimethyl aluminium of reduced levels can pass through the reaction of trimethyl aluminium and lewis base or pass through Vacuum distilling trimethyl aluminium or realized by any alternate manner known in the art.It is also to be recognized that with transition metal After compound reaction, some aluminoxane molecules in by the anionic form represented by the anion in formula 4-6, the most here by It is considered " noncoordinating " anion.

About further instruction, see US patent 4,665,208,4,952,540,5,041,584,5,091,352,5, 206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,329,032,5,248, 801,5,235,081,5,157,137,5,103,031, and EP 0 561 476A1, EP 0 279 586B1, EP 0 516 476A, EP 0 594 218A1 and WO 94/10180.

When activator is aikyiaiurnirsoxan beta (modified or non-modified), some embodiments select the maximum amount of activator, for Al/M relative to catalyst precarsor (each metal catalytic site) molar excess 5000 times.Before minimum activator and catalyst The mol ratio of body is 1: 1.

Aikyiaiurnirsoxan beta can be prepared by the hydrolysis of corresponding trialkyl aluminium compound.MMAO can by trimethyl aluminium and Prepared by the hydrolysis of higher level trialkyl aluminium compound such as triisobutyl aluminium.MMAO generally has higher molten in aliphatic solvents Xie Du, and more stable in storage process.There is the method that many kinds prepare aikyiaiurnirsoxan beta and modified alumoxane, they unrestricted Property example is described in U.S. patent 4, and 665,208,4,952,540,5,091,352,5,206,199,5,204,419,4, 874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235, 081,5,157,137,5,103,031,5,391,793,5,391,529,5,693,838,5,731,253,5,731,451,5, 744,656,5,847,177,5,854,166,5,856,256 and 5,939,346；European Published EP-A-0 561 476, EP- B1-0 279 586, EP-A-0594218 and EP-B1-0 586 665；And PCT Publication WO 94/10180 and WO99/15534 In, all these full patent texts are incorporated herein.The most transparent MAO can be preferably used.Can To filter the muddy or aikyiaiurnirsoxan beta of gel, to form clear solution, or transparent alumina can be decanted out from turbid solution Alkane.Another aikyiaiurnirsoxan beta is 3A type modified methylaluminoxane (MMAO) promoter (trade name with 3A type modified methylaluminoxane It is purchased from Akzo Chemicals, Inc., by patent No. US 5, the protection of 041,584).

The example of the alkyl aluminum or organo-aluminum compound that can serve as activator (or scavenger) includes trimethyl aluminium, three second Base aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc..

Ionizing activators

Use neutrality or the ionizing of ion-type or Stoichiometric activators, such as three normal-butyl ammonium four (pentafluorophenyl group) boron, Three perfluorophenyl boron metalloid precursors or three perfluoronapthyl boron metalloid precursors, many halogenations miscellaneous borane anion (WO 98/ 43983), boric acid (USP No.5,942,459) and their mixture are within the scope of the invention.Neutral or ion-type Activator is used alone or is used in combination the most within the scope of the present invention with aikyiaiurnirsoxan beta or modified alumoxane activators.

The example of neutral Stoichiometric activators includes trisubstituted boron, tellurium, aluminum, gallium and indium or their mixture. Three substituent groups are each independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, halogenated aryl, alkoxyl and halogen Element.Preferably, described three groups are independently selected from halogen, single or multiple ring (including halo) aryl, alkyl, and alkenylation Compound and their mixture, preferably have the alkenyl of 1-20 carbon atom, has the alkyl of 1-20 carbon atom, The alkoxyl with 1-20 carbon atom and the aryl (including substituted aryl) with 3-20 carbon atom.It is highly preferred that institute State the alkyl that three groups are 1-4 carbon atoms, phenyl, naphthyl or their mixture.It is more preferred still that described three groups It is the aryl of halogenation, the aryl of preferred fluorinated.Most preferably, described neutral stoichiometric activator is three perfluorophenyl boron or three Perfluoronapthyl boron.

Ionic stoichiometric activator compound can contain active proton, or with the residue of described ionized compound Ion association but be unworthy of some other sun being positioned at or being only loosely coordinated in the residual ion of described ionized compound from Son.These compounds and similar compound are described in European Published EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and US patent 5,153,157,5, 198,401,5,066,741,5,206,197,5,241,025,5,384,299 and 5,502,124, and carry on August 3rd, 1994 The US patent application serial number 08/285 gone out, in 380, all these files are incorporated by reference into the application in full.

Ionized catalyst can be by making transistion metal compound and some neutral lewis acids, such as B (C₆F₆)₃Instead Should prepare, described neutral lewis acid forms anion after the hydrolyzable part (X) with transistion metal compound reacts, Such as ([B (C₆F₅)₃(X)]^-), the cationic transition metal species that described anionic stabilization is produced by described reaction.Described catalysis Agent can and preferably be prepared by the activator component belonging to ionic compound or compositions.But, use neutral compound The preparation of activator be also contemplated by the invention including.

The compound that can be used as activator component in the preparation for the ionic catalyst systems of the inventive method includes Cation and compatible non-coordinating anion, described cation is preferably capable of giving the Bronsted acid of proton, described the moon Ion is relatively large (bulky), it is possible to the stable active catalyst formed when being merged by the two compound Species (4 race's cation), and described anion is the most easily by olefinic alkadienes and acetylene series unsaturation substrate or other Property lewis base such as ethers, nitrile etc. are replaced.EPA277,003 and EPA 277,004 of publication in 1998 discloses The non-coordinating anion that two classes are compatible: 1) comprise and be coordinated in central charged metal or metalloid core with covalent bond and shield Covert states the anionic co-ordination complex of multiple lipophilic groups of core, and 2) include the anion of multiple boron atom, such as Carborane class, metallo-borane class and boranes.

In a preferred embodiment, Stoichiometric activators includes cation and anionic group, and permissible Represent by below general formula:

(L-H)_d ⁺(A^d-) (14)

Wherein:

L is neutral Lewis base；

H is hydrogen；

(L-H)⁺It it is Bronsted acid；

A^d-It it is the non-coordinating anion with electric charge d-；With

D is the integer of 1-3.

Cationic components (L-H)_d ⁺May be configured to protonate or capture the transition metal containing Bulky Ligand Metallocene urge The structure division of agent precursor such as alkyl or aryl, forms the Bronsted acid such as proton or matter of cationic transition metal species Sonization lewis base or reducible lewis acid.

Activating cations (L-H)_d ⁺Can be Bronsted acid, before proton can be given transition-metal catalyst by it Body, it is thus achieved that transition-metal cation, including ammonium, oxygen, monosilane and their mixture, preferably methylamine, aniline, two Methylamine, diethylamine, methylphenylamine, diphenylamine, trimethylamine, triethylamine, DMA, methyldiphenyl base amine, pyrrole Pyridine, to bromo-DMA and the ammonium class to nitro-DMA；By triethyl phosphine, triphenylphosphine and hexichol The class that base phosphine obtains；The oxygen class obtained by ether such as dimethyl ether, diethyl ether, oxolane and dioxane；By thioether such as diethyl The sulfonium class that base thioether and Tetramethylene sulfide obtain, and their mixture.Described activating cations (L-H)_d ⁺Can also is that such as Silver,, carbon, ferrocene class and their mixture, preferably carbon and the structure division of ferrocene class.Most preferably (L-H)_d ⁺It it is triphenylcarbenium.

Anionic group A^d-Including having formula (M^k+Q_n)^d-Those, wherein k is the integer of 1-3；N is the integer of 2-6； N-k=d；M is the element in 13 races of the periodic table of elements, preferably boron or aluminum；Hydride ion independently with Q, bridging or Non-bridged dialkyl amido, halogen root, alkoxy radical, virtue oxygen root, alkyl, substituted alkyl, halocarbon base, substituted halocarbon base and halogen The substituted hydrocarbyl group of element, described Q has at most 20 carbon atoms, premise be Q be that the situation of halogen root is less than once.Preferably Ground, each Q is the fluorination alkyl with 1-20 carbon atom；It is highly preferred that each Q is fluoro aryl, with most preferably, each Q is five Fluoro aryl.Suitably A^d-Example also include as in U.S. patent No.5, two boron compounds disclosed in 447,895, this patent It is incorporated by the application and makees reference.

Can be used as in the preparation improving catalyst of the present invention active cocatalyst boron compound exemplary but Limiting examples is trisubstituted ammonium salt, such as: tetraphenylboronic acid trimethyl ammonium, tetraphenylboronic acid triethyl ammonium, tetraphenyl Boric acid tripropyl ammonium, tetraphenylboronic acid three (normal-butyl) ammonium, tetraphenylboronic acid three (tert-butyl group) ammonium, tetraphenylboronic acid N, N-diformazan Base aniline, tetraphenylboronic acid N, N-diethylaniline, tetraphenylboronic acid N, N-dimethyl-(2，4，6-trimethyl aniline ), tetraphenylboronic acid, tetraphenylboronic acid triphenylcarbenium, tetraphenylboronic acid triphenyl, tetraphenylboronic acid triethyl group Monosilane, tetraphenylboronic acid benzene (diazonium) salt, four (pentafluorophenyl group) boric acid trimethyl ammonium, four (pentafluorophenyl group) boric acid triethyl group Ammonium, four (pentafluorophenyl group) boric acid tripropyl ammonium, four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, four (pentafluorophenyl group) boric acid three (sec-butyl) ammonium, four (pentafluorophenyl group) boric acid DMA, four (pentafluorophenyl group) boric acid N, N-diethylaniline, Four (pentafluorophenyl group) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline), four (pentafluorophenyl group) boric acid, four (five fluorine Phenyl) borate, four (pentafluorophenyl group) boric acid triphenyl, four (pentafluorophenyl group) boric acid triethyl-silicane, Four (pentafluorophenyl group) boric acid benzene (diazonium) salt, four-(2,3,4,6-tetrafluoro phenyl) boric acid trimethyl ammoniums, four-(2,3,4,6-tetrafluoros Phenyl) boric acid triethyl ammonium, four-(2,3,4,6-tetrafluoro phenyl) boric acid tripropyl ammoniums, four-(2,3,4,6-tetrafluoro phenyl) boric acid Three (normal-butyl) ammonium, four-(2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (tert-butyl group) ammoniums, four-(2,3,4,6-tetrafluoro phenyl) Boric acid DMA, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, N-diethylaniline, four-(2,3,4,6-tetra- Fluorophenyl) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline), four-(2,3,4,6-tetrafluoro phenyl) boric acid, four- (2,3,4,6-tetrafluoro phenyl) borate, four-(2,3,4,6-tetrafluoro phenyl) boric acid triphenyls, four-(2,3,4, 6-tetrafluoro phenyl) boric acid triethyl-silicane, four-(2,3,4,6-tetrafluoro phenyl) boric acid benzene (diazonium) salt, four (perfluor naphthalenes Base) boric acid trimethyl ammonium, four (perfluoronapthyl) boric acid triethyl ammonium, four (perfluoronapthyl) boric acid tripropyl ammonium, four (perfluor naphthalenes Base) boric acid three normal-butyl ammonium, four (perfluoronapthyl) boric acid tri-tert ammonium, four (perfluoronapthyl) boric acid DMA , four (perfluoronapthyl) boric acid N, N-diethylaniline, four (perfluoronapthyl) boric acid N, N-dimethyl-(2,4,6-trimethyls Aniline), four (perfluoronapthyl) boric acid, four (perfluoronapthyl) borate, four (perfluoronapthyl) boric acid triphen Base, four (perfluoronapthyl) boric acid triethyl-silicane, four (perfluoronapthyl) boric acid benzene (diazonium) salt, four (perfluorinated biphenyls) Boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluor connection Phenyl) boric acid three normal-butyl ammonium, four (perfluorinated biphenyl) boric acid tri-tert ammonium, four (perfluorinated biphenyl) boric acid N, N-dimethyl Aniline, four (perfluorinated biphenyl) boric acid N, N-diethylaniline, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2,4, 6-trimethylaniline), four (perfluorinated biphenyl) boric acid, four (perfluorinated biphenyl) borate, four (perfluors Xenyl) boric acid triphenyl, four (perfluorinated biphenyl) boric acid triethyl-silicane, four (perfluorinated biphenyl) boric acid benzene (weight Nitrogen) salt, four (3,5-double (trifluoromethyl) phenyl) boric acid trimethyl ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid triethyl group Ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid tripropyl ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid three normal-butyl Ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid tri-tert ammonium, four (3,5-double (trifluoromethyl) phenyl) boric acid N, N-bis- Monomethylaniline., four (3,5-double (trifluoromethyl) phenyl) boric acid N, N-diethylaniline, four (3,5-double (trifluoromethyl) benzene Base) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline), four (3,5-double (trifluoromethyl) phenyl) boric acid, four (3,5-double (trifluoromethyl) phenyl) borate, four (3,5-double (trifluoromethyl) phenyl) boric acid triphenyl, four (3,5-double (trifluoromethyl) phenyl) boric acid triethyl-silicane, four (3,5-double (trifluoromethyl) phenyl) boric acid benzene (diazonium) Salt, and dialkyl ammonium salt, such as: four (pentafluorophenyl group) boric acid two (isopropyl) ammonium, and four (pentafluorophenyl group) boric acid two hexamethylene Base ammonium；With other three replacements salt, such as four (pentafluorophenyl group) boric acid three (o-tolyl), and four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl).

Most preferably, described ionic stoichiometric activator (L-H)_d ⁺(A^d-) it is four (perfluorophenyl) boric acid N, N-bis- Monomethylaniline., four (perfluoronapthyl) boric acid DMA, four (perfluorinated biphenyl) boric acid DMA , four (3,5-double (trifluoromethyl) phenyl) boric acid DMA, four (perfluoronapthyl) borate, four (perfluorinated biphenyl) borate, four (3,5-double (trifluoromethyl) phenyl) borate, or four (perfluor benzene Base) borate.

In one embodiment, use without active proton but Bulky Ligand Metallocene catalyst cation can be produced Also it is conceived with the activation method of the ionizing ionic compound of their non-coordinating anion, and is described in EP-A-0 426 637, EP-A-0 573 403 and US patent No.5, in 387,568, these patents are fully incorporated the application for reference.

Term " non-coordinating anion " (NCA) refers to be unworthy of being positioned at described cation or being only weakly coordinated in described sun Ion, thus keep the anion the most easily replaced by neutral Lewis base." compatible " non-coordinating anion is initially The coordination compound formed is non-degradable when decomposing is those neutral aniones.Additionally, described anion will not be by anion substituent Or fragment transfers to cation so that described cation forms neutral four-coordination Metallocenic compound and formed by described anion Neutral by-product.According to the invention, it is possible to use non-coordinating anion be those aniones, it is compatible, balance its+ Stable metal cyclopentadienyl cation in the sense that the ionic charge of 1, but keep again enough unstability being polymerized with permission During substituted by olefinic or acetylene series unsaturated monomer.The promoter of these types uses triisobutyl aluminium or trioctylphosphine sometimes Aluminum is as scavenger.

Originally the inventive method can also use is neutral lewis acid, but forms sun with the compounds of this invention after reacting Ionic metal complex and non-coordinating anion, or the cocatalyst compound of amphion coordination compound or activator compound. Such as, three (pentafluorophenyl group) boron or aluminum are used for capturing alkyl or hydride ion part, join producing the cationic metal of the present invention Compound and stabilisation non-coordinating anion, about the explanation of 4 similar race's Metallocenic compounds, see EP-A-0427 697 He EP-A-0 520 732.Further, method and the compound of EP-A-0 495 375 are seen.In order to use 4 similar compounds of group Form amphion coordination compound, see US patent 5,624,878；5,486,632；With 5,527,929.

When the cation of non-coordinating anion precursor is Bronsted acid such as proton, or protonated Lewis base (is not wrapped Include water), or reducible lewis acid such as ferrocene or silver cation, or alkali metal or alkaline earth metal cation such as sodium, magnesium Or during those cationes of lithium, catalyst precarsor can be any ratio with the mol ratio of activator.Described activator compound Combination can also be used for activation.Such as, three (perfluorophenyl) boron can be used together with MAO.

The promoter (activator) of general type

Generally, the conventional transition metal catalyst compounds in addition to the chrome catalysts compound of some general types is used The promoter activation of one or more routines, described promoter can represent with following formula:

M³M⁴ _vX² _cR² _b-c (15)

Wherein M³It is 1-3 race and the metal of 12-13 race of the periodic table of elements；M⁴It it is the metal of 1 race of the periodic table of elements；v It is the numerical value of 0-1；Each X²It it is any halogen；C is the numerical value of 0-3；Each R²It is univalence hydrocarbyl or hydrogen；B is the numerical value of 1-4；Wherein B-c is at least 1.The organic metal promoter of other general type for the transition-metal catalyst of above-mentioned general type Compound has formula M³R² _k, wherein M³IA, IIA, IIB or Group IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and Gallium；K is equal to 1,2 or 3, depends on M³Quantivalence, this quantivalence generally depends on again M³Affiliated specific race；Each R²Permissible It it is any univalence hydrocarbyl.

The organic metal promoter of the general type can being used together with the catalyst compounds of above-mentioned general type The limiting examples of compound includes lithium methide, butyl lithium, dihexyl hydrargyrum, dibutyl magnesium, diethyl cadmium, benzyl potassium, diethyl Zinc, three n-butylaluminum, diisobutyl ethyl boron, diethyl cadmium, di-n-butyl zinc and three n-pentyl boron, and especially, including alkane Base aluminum, such as three hexyl aluminum, triethyl aluminum, trimethyl aluminium, and triisobutyl aluminium.The cocatalyst compound of other general type Including single organic group halogenide and the hydride of 2 race's metals, the list-of 3 and 13 race's metals or two-organic group halogenide and hydrogenation Thing.The limiting examples of the cocatalyst compound of this type of general type includes bromination diisobutyl aluminum, isobutyl dichloride Boron, methylmagnesium-chloride, tonsilon beryllium, bromination ethyl-cadmium, diisobutylaluminium hydride, hydrogenating methyl cadmium, hydrogenate diethyl boron, hydrogen Change hexyl beryllium, hydrogenate dipropyl boron, hydrogenate octyl group magnesium, hydrobuthyl zinc, hydrogenate dichloride boron, hydrogenation aluminum dibromide and hydrogenation bromine Cadmium.The organic metal cocatalyst compound of general type is known to those skilled in the art, and about these compounds More fully discuss and can see US patent 3,221,002 and 5,093,415, described full patent texts is incorporated herein making reference.

Other activator

Other activator is included in those described in PCT Publication WO 98/07515, such as fluoaluminic acid three (2,2 ', 2 "-nine Fluorine xenyl) ester, the disclosure thing is incorporated by the application for reference.The combination of activator is also expected by the present invention, such as alumina Alkane and Ionizing activators are used in combination, and see for example EP-B1 0 573 120, PCT Publication WO 94/07928 and WO 95/ 14044 and US patents 5,153,157 and 5,453,410；All these full patent texts are incorporated herein for reference.

Other suitable activator is disclosed in WO 98/09996 (being incorporated herein), and this patent is retouched State and activated Bulky Ligand Metallocene catalyst compounds with perchlorate, periodate and iodate (including their hydrate) Thing.WO 98/30602 and WO98/30603 (being incorporated herein) describe use (2,2 '-xenyl-bis-front threes Base silicic acid) lithium 4THF (lithium (2,2 '-bisphenyl-ditrimethylsilicate) 4THF) joins as huge The activator of body metallocene catalyst compound.WO 99/18135 (being incorporated herein) describes organic boron-aluminum The purposes of activator.EP-B1-0 781 299 describes and is used in combination monosilane salt and noncoordinating compatible anionic.Also Have, such as, use the activation of radiation (seeing EP-B1-0 615 981, be incorporated herein), electrochemical oxidation etc. Method be also conceived be used as making neutral bulky ligand metallocene catalyst compound or precursor to become can the Pang of olefin polymerization The activation method of big ligand metallocene cation.For activate Bulky Ligand Metallocene catalyst compounds other activator or Method is described in such as US5,849,852,5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (double Double (three (pentafluorophenyl group) borine) benzimidazole of octadecyl methyl ammonium) in, these patents are incorporated herein.

The another kind of active cocatalyst suitably forming ion includes the cation oxidant represented with following formula and non-joins The salt of position compatible anionic:

(OX^e+)_d(A^d-)_e (16)

Wherein OX^e+It it is the cation oxidant of the electric charge with e+；E is the integer of 1-3；And A-and d is as above determined Justice.The example of cation oxidant includes: ferrocene, the substituted ferrocene of alkyl, Ag⁺Or Pb²⁺。A^d-The side of being preferable to carry out Case is previously for those aniones defined in the activator containing Bronsted acid, especially four (pentafluorophenyl group) boric acid Root.

It is within the scope of the invention that, catalyst compounds can be in conjunction with above-mentioned one or more activator or activation sides Method.Such as, in US patent 5,153,157 and 5,453,410, European Published EP-B1 0 573 120 and PCT Publication WO 94/ The combination of activator is described in 07928 and WO 95/14044.These files all discuss aikyiaiurnirsoxan beta and Ionizing activators with The use of Bulky Ligand Metallocene catalyst compounds.

The selection of transition metal catalyst component

The catalyst system of the present invention comprises two or more transistion metal compounds as above.At least one institute State compound and allow for producing the crystallization poly-alpha-olefin of degree of crystallinity >=40%, preferably isotactic polypropylene or syndiotaxy Polypropylene, another kind of compound allows for producing the amorphous poly-alpha-olefin of degree of crystallinity≤20%, preferably atactic poly-third Alkene.

Selection for the transition metal component of crystallisable polymer fractions is the subset of the transition metal component of formula 8-9.Institute State preferred component formula 17 to illustrate:

Wherein A ', M, X₁And X₂As defined above.Substituent group S " v is defined independently as the S in formula 8-9 ", wherein subscript " v " represents the carbon atom on the Cp ring that described substituent group is connected.

The metallocene precursors being preferred for producing the poly-alpha-olefin of the isotaxy characteristic with raising is that of formula 17 A bit, S is wherein selected independently "_vSo that metallocene framework 1) not containing the symmetrical plane of described metal center, and 2) have logical Cross the symmetrical C of described metal center₂-axle.This type of coordination compound, such as raceme-Me₂Si (indenyl)₂ZrMe₂With raceme-Me₂Si (indenyl)₂HfMe₂It is well known in the present art, and compared with slightly asymmetric chiral systems, general production has more Gao Li The isotachyte of structure regularity.Equally, can be used for the present invention can produce the another kind of excellent of isotachyte The transistion metal compound of choosing is in US patent No.5, those the monocyclopentadienyl catalyst disclosed in 026,798, this patent It is hereby incorporated by reference.

According to the invention provides outside the preferred chirality being exclusively used in the catalyst system producing the poly-alpha-olefin of isotaxy Racemization Metallocenic compound includes the racemic form of following compound:

Double (indenyl) zirconium of dimethylsilyl,

Double (indenyl) zirconium of dimethylsilyl base,

Double (indenyl) zirconium of dichloride diphenylsilyl group,

Double (indenyl) zirconium of dimethyl diphenyl silicyl,

Double (indenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (indenyl) zirconium of dimethyl methyl phenyl silyl groups,

Double (indenyl) zirconium of dichloride ethylene,

Double (indenyl) zirconium of dimethyl ethylene,

Dichloride di-2-ethylhexylphosphine oxide (indenyl) zirconium,

Double (indenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (indenyl) closes hafnium,

Dimethylsilyl base double (indenyl) closes hafnium,

Dichloride diphenylsilyl group double (indenyl) closes hafnium,

Dimethyl diphenyl silicyl double (indenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (indenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (indenyl) closes hafnium,

Dichloride ethylenebis (indenyl) closes hafnium,

Dimethylethylene double (indenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (indenyl) closes hafnium,

Dimethylated methylene base double (indenyl) closes hafnium,

Double (tetrahydro indenyl) zirconium of dimethylsilyl,

Double (tetrahydro indenyl) zirconium of dimethylsilyl base,

Double (tetrahydro indenyl) zirconium of dichloride diphenylsilyl group,

Double (tetrahydro indenyl) zirconium of dimethyl diphenyl silicyl,

Double (tetrahydro indenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (tetrahydro indenyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (tetrahydro indenyl) zirconium,

Double (tetrahydro indenyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (tetrahydro indenyl) zirconium,

Double (tetrahydro indenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (tetrahydro indenyl) closes hafnium,

Dimethylsilyl base double (tetrahydro indenyl) closes hafnium,

Dichloride diphenylsilyl group double (tetrahydro indenyl) closes hafnium,

Dimethyl diphenyl silicyl double (tetrahydro indenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (tetrahydro indenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (tetrahydro indenyl) closes hafnium,

Dichloride ethylenebis (tetrahydro indenyl) closes hafnium,

Dimethylethylene double (tetrahydro indenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (tetrahydro indenyl) closes hafnium,

Dimethylated methylene base double (tetrahydro indenyl) closes hafnium,

Double (2-methylindenyl) zirconium of dimethylsilyl,

Double (2-methylindenyl) zirconium of dimethylsilyl base,

Double (2-methylindenyl) zirconium of dichloride diphenylsilyl group,

Double (2-methylindenyl) zirconium of dimethyl diphenyl silicyl,

Double (2-methylindenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (2-methylindenyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (2-methylindenyl) zirconium,

Double (2-methylindenyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (2-methylindenyl) zirconium,

Double (2-methylindenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (2-methylindenyl) closes hafnium,

Dimethylsilyl base double (2-methylindenyl) closes hafnium,

Dichloride diphenylsilyl group double (2-methylindenyl) closes hafnium,

Dimethyl diphenyl silicyl double (2-methylindenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (2-methylindenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (2-methylindenyl) closes hafnium,

Dichloride ethylenebis (2-methylindenyl) closes hafnium,

Dimethylethylene double (2-methylindenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (2-methylindenyl) closes hafnium,

Dimethylated methylene base double (2-methylindenyl) closes hafnium,

Double (the 2-methyl 4-phenyl indenyl) zirconium of raceme-dimethylsilyl,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethyl diphenyl silicyl,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dichloride diphenylsilyl group,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethyl diphenyl silicyl,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (2-methyl 4-phenyl indenyl) zirconium,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (2-methyl 4-phenyl indenyl) zirconium,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylsilyl base double (2-methyl 4-phenyl indenyl) closes hafnium,

Dichloride diphenylsilyl group double (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethyl diphenyl silicyl double (2-methyl 4-phenyl indenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (2-methyl 4-phenyl indenyl) closes hafnium,

Dichloride ethylenebis (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylethylene double (2-methyl 4-phenyl indenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylated methylene base double (2-methyl 4-phenyl indenyl) closes hafnium,

Double (4, the 7-dimethylindenyl) zirconium of dimethylsilyl,

Double (4, the 7-dimethylindenyl) zirconium of dimethylsilyl base,

Double (4, the 7-dimethylindenyl) zirconium of dichloride diphenylsilyl group,

Double (4, the 7-dimethylindenyl) zirconium of dimethyl diphenyl silicyl,

Double (4, the 7-dimethylindenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (4, the 7-dimethylindenyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (4,7-dimethylindenyl) zirconium,

Double (4, the 7-dimethylindenyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (4,7-dimethylindenyl) zirconium,

Double (4, the 7-dimethylindenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (4,7-dimethylindenyl) closes hafnium,

Dimethylsilyl base double (4,7-dimethylindenyl) closes hafnium,

Dichloride diphenylsilyl group double (4,7-dimethylindenyl) closes hafnium,

Dimethyl diphenyl silicyl double (4,7-dimethylindenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (4,7-dimethylindenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (4,7-dimethylindenyl) closes hafnium,

Dichloride ethylenebis (4,7-dimethylindenyl) closes hafnium,

Dimethylethylene double (4,7-dimethylindenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (4,7-dimethylindenyl) closes hafnium,

Dimethylated methylene base double (4,7-dimethylindenyl) closes hafnium,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethylsilyl,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethylsilyl base,

Double (2-methyl-4-naphthyl indenyl) zirconium of dichloride diphenylsilyl group,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethyl diphenyl silicyl,

Double (2-methyl-4-naphthyl indenyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (2-methyl-4-naphthyl indenyl) zirconium,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (2-methyl-4-naphthyl indenyl) zirconium,

Double (2-methyl-4-naphthyl indenyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dimethylsilyl base double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dichloride diphenylsilyl group double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dimethyl diphenyl silicyl double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dichloride ethylenebis (2-methyl-4-naphthyl indenyl) closes hafnium,

Dimethylethylene double (2-methyl-4-naphthyl indenyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (2-methyl-4-naphthyl indenyl) closes hafnium,

Dimethylated methylene base double (2-methyl-4-naphthyl indenyl) closes hafnium,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethylsilyl,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethylsilyl base,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dichloride diphenylsilyl group,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethyl diphenyl silicyl,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dichloride aminomethyl phenyl silicyl,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (2,3-dimethylcyclo-pentadienyl) zirconium,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (2,3-dimethylcyclo-pentadienyl) zirconium,

Double (2, the 3-dimethylcyclo-pentadienyl) zirconium of dimethylated methylene base,

Dimethylsilyl double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dimethylsilyl base double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dichloride diphenylsilyl group double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dimethyl diphenyl silicyl double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dimethyl methyl phenyl silyl groups double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dichloride ethylenebis (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dimethylethylene double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Dimethylated methylene base double (2,3-dimethylcyclo-pentadienyl) closes hafnium,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethylsilyl,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethylsilyl base,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dichloride diphenylsilyl group,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethyl diphenyl silicyl,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dichloride aminomethyl phenyl silicyl,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethyl methyl phenyl silyl groups,

Dichloride ethylenebis (3-trimethyl silyl cyclopentadienyl group) zirconium,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethylethylene,

Dichloride di-2-ethylhexylphosphine oxide (3-trimethyl silyl cyclopentadienyl group) zirconium,

Double (the 3-trimethyl silyl cyclopentadienyl group) zirconium of dimethylated methylene base,

Dimethylsilyl double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dimethylsilyl base double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dichloride diphenylsilyl group double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dimethyl diphenyl silicyl double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dichloride aminomethyl phenyl silicyl double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dimethyl methyl phenyl silyl groups double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dichloride ethylenebis (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dimethylethylene double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dichloride di-2-ethylhexylphosphine oxide (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Dimethylated methylene base double (3-trimethyl silyl cyclopentadienyl group) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl,

Dimethylsilyl double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Dichloride 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylsilyl base,

Dimethylsilyl base double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Dimethyl 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl,

Dimethylsilyl double (2-methyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene (2-methyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) zirconium,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Dichloride 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylsilyl base,

Dimethylsilyl base double (2-methyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Hafnium,

Dimethylsilyl base double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethylsilyl base double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Dimethyl 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes hafnium,

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl,

Dimethylsilyl double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Dichloride 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylsilyl base,

Dimethylsilyl base double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Dimethyl 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl,

Dimethylsilyl double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride 9-sila fluorenylidene,

Dichloride 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dichloride 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylsilyl base,

Dimethylsilyl base double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethylsilyl base double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl 9-sila fluorenylidene,

Dimethyl 9-sila fluorenylidene double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Dimethyl 9-sila fluorenylidene double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes hafnium,

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride dimethyl amino borane；

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethylformamide dimethyl base amino borane；

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dichloride diisopropylaminoethyl borine；

Double (2-methyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-di-tert-butyl-phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Dimethyl diisopropylaminoethyl borine double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Dimethyl diisopropylaminoethyl borine double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Dimethyl diisopropylaminoethyl borine double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Dimethyl diisopropylaminoethyl borine double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Dimethyl diisopropylaminoethyl borine double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Dimethyl diisopropylaminoethyl borine double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) closes Zirconium；

Double (2-ethyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diisopropyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-n-pro-pyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethylbenzene Base] indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] Indenyl) zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenes Base) zirconium；Etc..

Most preferably kind is the racemic form of following compound:

Double (indenyl) zirconium of dimethylsilyl,

Double (indenyl) zirconium of dimethylsilyl base,

Dichloride ethylenebis (indenyl) zirconium,

Double (indenyl) zirconium of dimethylethylene,

Double (tetrahydro indenyl) zirconium of dimethylsilyl,

Double (tetrahydro indenyl) zirconium of dimethylsilyl base,

Dichloride ethylenebis (tetrahydro indenyl) zirconium,

Double (tetrahydro indenyl) zirconium of dimethylethylene,

Double (2-methylindenyl) zirconium of dimethylsilyl,

Double (2-methylindenyl) zirconium of dimethylsilyl base,

Dichloride ethylenebis (2-methylindenyl) zirconium,

Double (2-methylindenyl) zirconium of dimethylethylene,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylsilyl,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylsilyl base,

Dichloride ethylenebis (2-methyl 4-phenyl indenyl) zirconium,

Double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylethylene,

Double (4, the 7-dimethylindenyl) zirconium of dimethylsilyl,

Double (4, the 7-dimethylindenyl) zirconium of dimethylsilyl base,

Dichloride ethylenebis (4,7-dimethylindenyl) zirconium,

Double (4, the 7-dimethylindenyl) zirconium of dimethylethylene,

Dimethylsilyl double (indenyl) closes hafnium,

Dimethylsilyl base double (indenyl) closes hafnium,

Dichloride ethylenebis (indenyl) closes hafnium,

Dimethylethylene double (indenyl) closes hafnium,

Dimethylsilyl double (tetrahydro indenyl) closes hafnium,

Dimethylsilyl base double (tetrahydro indenyl) closes hafnium,

Dichloride ethylenebis (tetrahydro indenyl) closes hafnium,

Dimethylethylene double (tetrahydro indenyl) closes hafnium,

Dimethylsilyl double (2-methylindenyl) closes hafnium,

Dimethylsilyl base double (2-methylindenyl) closes hafnium,

Dichloride ethylenebis (2-methylindenyl) closes hafnium,

Dimethylethylene double (2-methylindenyl) closes hafnium,

Dimethylsilyl double (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylsilyl base double (2-methyl 4-phenyl indenyl) closes hafnium,

Dichloride ethylenebis (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylethylene double (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylsilyl double (4,7-dimethylindenyl) closes hafnium,

Dimethylsilyl base double (4,7-dimethylindenyl) closes hafnium,

Dichloride ethylenebis (4,7-dimethylindenyl) closes hafnium, and

Dimethylethylene double (4,7-dimethylindenyl) closes hafnium.

Similarly, exist provide steric regularity control metallocene precursors, wherein (A-Cp) is (Cp) (Cp*), Cp and Cp* all has in cyclopentadienyl rings and has the substituent group of enough steric bulk, to limit the rotation of cyclopentadienyl ligands, makes Above-mentioned symmetric condition must be met.Preferred this kind of chiral racemic metallocene includes the double (three ring [5.2.1.0 of dimethyl^2,6] Decyl-2,5-dialkylene) zirconium and close hafnium, double (1R)-9 of dimethyl, 9-dimethyl three ring [6.1.1.0^2,6] decyl-2,5-diene Base) zirconium, the double (three ring [5.2.1.0 of dimethyl^2,6] decyl-2,5,8-trialkenyl) zirconium, double (three rings of dimethyl [5.2.2.0^2,6] 11 carbon-2,5,8-trialkenyl) zirconium and close hafnium, and dimethyl double ((1R, 8R)-7,7,9,9-tetramethyls Base [6.1.1.0^2,6] decyl-2,5-dialkylene) zirconium and close hafnium.

Preferably, the metallocene precursors of the poly-alpha-olefin for preparation with the syndiotaxy characteristic of raising is also formula 17 Those, S is wherein selected independently " so that two Cp parts have the most different steric bulk.In order to same vertical between producing Structure polymer, the mode at the nuclear substituted group of Cp is important.Therefore, used herein to " stereo disparity " or " three-dimensional Different " refer to the difference between the stereospecificity of Cp and Cp* ring, this makes each be symmetrical relative to A bridged group, But being different each other, this controls the close of each monomeric unit in succession joined in polymer chain.Cp and Cp* ring it Between three-dimensional difference for stoping close monomer the most close so that described monomer joins polymer with syndiotactic configuration In chain.

It is those of formula 17 for preparing the preferred metallocene precursors of syndiotactic polymer, is wherein selected independently S " so that 1) three-dimensional difference between two Cp parts maximizes, and 2) keep by the metal center in formula 17 and Cp ring C₁And C₁The symmetrical plane of ' carbon atom.Therefore, there is this symmetric coordination compound such as Me₂C(η⁵-C₅H₄) (1-fluorenyl) MMe₂(wherein M=Ti, Zr or Hf) is preferred, and generally has the highest vertical structure than similar but more asymmetric system generation The syndiotactic polymer of regularity.It addition, in above formula, 1-fluorenyl can with 3,8-di-t-butyl fluorenyl, octahydrofluorenyl or 3,3,6,6,9,9,12,12-prestox-4,4,5,5,10,10,11,11-octahydro dibenzo [b, h] fluorenes substitute.Because before this kind of The catalyst usually ability of polymer tacticity out of hand under the conditions of pyroreaction, so in order to ensure material relatively High-crystallinity, needs to use these catalyst under relatively low temperature of reactor, preferably at a temperature of less than 80 DEG C.

The preferred catalyst that can produce low-molecular-weight isotactic polypropylene is in US patent No.5,120,867 Described those, this patent is incorporated herein by reference.Can use in the present invention can be at single-reactor or string Connection reactor configuration is used together, additionally it is possible to any of the polyacrylic catalyst (including supported catalyst) needed for production mixes Compound, to produce blend on the spot.Preferably catalyst includes being used in combination with aikyiaiurnirsoxan beta and/or compatibility non-coordinating anion Cyclopentadienyl transition metal compounds and derivant.At Chem.Rev.2000, in 100,1253-1345, discuss life Producing other preferred catalyst of crystalline polypropylene, this document is incorporated herein by reference.

For amorphous polymer fraction transition metal component preferably select be formula 10 monocyclopentadienyl transition gold Belonging to component, wherein y is equal to 1.This preferred component formula 18 illustrates:

Wherein A ', J, S ', X₁、X₂, L ', z and w as defined above, M is titanium.Substituent group S " v be defined as with in formula 10 S " identical, wherein subscript " v " represents the carbon atom in the cyclopentadienyl rings that described substituent group is connected, and wherein in institute State and in cyclopentadienyl rings, can have 0,2 or 4 substituent groups S ", premise be described cyclopentadienyl rings be symmetrical substituted.Right Substituted being defined as is claimed to refer to that described cyclopentadienyl rings is had about the same space body at 2 and 5 and/or 3 and 4 " group replaces long-pending S.Generally, " difference in size of group is in the range of 2 carbon atoms to these S.Therefore, on 2 and 5 Replaced by methyl and ethyl respectively, or the cyclopentadienyl group replaced by hexyl and octyl group respectively on 3 and 4 is considered as symmetrical 's.Equally, described cyclopentadienyl rings can be in all 4 sites by S " group replaces, and is considered as symmetrical, as long as Each Symmetric substitutions is to having similar spatial volume.It addition, two adjacent S on 3 and 4 " group can connect with Form ring, premise be described new ring be also symmetrical substituted.

Known this kind of caltalyst ties up to create 2 when introducing C3 and higher level alpha-olefin, 1-mistake.Wherein S ' is via 3 ° Carbon (such as when S ' is the tert-butyl group or 1-adamantyl) is bonded to the 2 of the procatalyst generation of nitrogen ligand (J), and 1-mistake is less than When S ' (is such as cyclo-dodecyl, cyclohexyl as S ' via 1 ° of carbon (such as when S ' is normal-butyl, methyl or benzyl) or 2 ° of carbon Or during sec-butyl) it is bonded to the situation of described nitrogen ligand (J).In polymer backbone 2,1-mistake creates can be of value to poly- (the CH of compound performance₂)₂Unit.This base polymer, the sign of this base polymer and for producing the caltalyst of this base polymer Tying up to US5, be described in 723,560, this patent is incorporated herein by reference.The modification of the low Mw of this base polymer is permissible By changing process conditions, such as, prepared by raising temperature of reactor.

According to the preferred monocycle that the invention provides the single-minded catalyst system for preparing atactic poly-alpha-olefin Pentadienyl transistion metal compound includes:

Dimethylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (s-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (n-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dichloride diethylsilane base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dichloride diethylsilane base (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dichloride diethylsilane base (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dichloride diethylsilane base (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dichloride diethylsilane base (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dichloride methylene (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dichloride methylene (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dichloride methylene (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dichloride methylene (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dichloride methylene (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dichloride ethylidene (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dichloride ethylidene (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dichloride ethylidene (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dichloride ethylidene (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dichloride ethylidene (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (s-butylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (n-butylamino) closes titanium,

Dimethylsilyl base (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethyl diethylsilane base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethyl diethylsilane base (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethyl diethylsilane base (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethyl diethylsilane base (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dimethyl diethylsilane base (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylated methylene base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylated methylene base (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylated methylene base (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylated methylene base (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dimethylated methylene base (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylethylene (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylethylene (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylethylene (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylethylene (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium,

Dimethylethylene (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (2,5-dimethylcyclo-pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (2,5-dimethylcyclo-pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl (2,5-dimethylcyclo-pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (2,5-dimethylcyclo-pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (2,5-dimethylcyclo-pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (3,4-dimethylcyclo-pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (3,4-dimethylcyclo-pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl (3,4-dimethylcyclo-pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (3,4-dimethylcyclo-pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (3,4-dimethylcyclo-pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (2-ethyl-5-methyl cyclopentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (2-ethyl-5-methyl cyclopentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl (2-ethyl-5-methyl cyclopentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (2-ethyl-5-methyl cyclopentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (2-ethyl-5-methyl cyclopentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (3-ethyl-4-methyl cyclopentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (3-ethyl-4-methyl cyclopentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl (3-ethyl-4-methyl cyclopentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (3-ethyl-4-methyl cyclopentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (3-ethyl-4-methyl cyclopentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (cyclododecane Base amino) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (outer-2-fall Bornyl amino) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (cyclohexyl ammonia Base) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (1-diamantane (obsolete) Base amino) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (tert-butyl group ammonia Base) close titanium,

Dimethylsilyl (2-tetrahydro indenyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (2,5-dimethylcyclo-pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (2,5-dimethylcyclo-pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl base (2,5-dimethylcyclo-pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (2,5-dimethylcyclo-pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (2,5-dimethylcyclo-pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (3,4-dimethylcyclo-pentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (3,4-dimethylcyclo-pentadienyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl base (3,4-dimethylcyclo-pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (3,4-dimethylcyclo-pentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (3,4-dimethylcyclo-pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (2-ethyl-5-methyl cyclopentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (2-ethyl-5-methyl cyclopentadienyl) (outer-2-norborny amino) closes Titanium,

Dimethylsilyl base (2-ethyl-5-methyl cyclopentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (2-ethyl-5-methyl cyclopentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (2-ethyl-5-methyl cyclopentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (3-ethyl-4-methyl cyclopentadienyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (3-ethyl-4-methyl cyclopentadienyl) (outer-2-norborny amino) closes Titanium,

Dimethylsilyl base (3-ethyl-4-methyl cyclopentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (3-ethyl-4-methyl cyclopentadienyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (3-ethyl-4-methyl cyclopentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (ring 12 Alkyl amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (outer-2-fall Bornyl amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (cyclohexyl Amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (1-Buddha's warrior attendant Alkyl amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group the cyclopentadienyl group) (tert-butyl group Amino) close titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (1-adamantylamino) closes titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (tert-butylamino) closes titanium etc..

Most preferably kind is:

Dimethylsilyl (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (Cyclohexylamino),

Dimethylsilyl base (tetramethyl-ring pentadienyl) (1-adamantylamino) closes titanium, and

Dimethylsilyl base (tetramethyl-ring pentadienyl) (outer-2-norborny amino) closes titanium.

It addition, in high reaction temperatures, some produce the catalyst of syndiotaxy poly-alpha-olefin at a lower temperature The most amorphous poly-alpha-olefin will be produced at relatively high temperatures.Transition metal group for described amorphous polymer fraction The selection divided is the subset of the transition metal component of formula 8-9.This kind of preferred component formula 19 illustrates:

Wherein A ', M, X₁And X₂As defined above.S that substituent group S " v and S " ' v is defined independently as in formula 8-9 ", Wherein subscript " v " represents the carbon atom on Cp ring or Flu ring (fluorenyl ring) that described substituent group connected.

Preferably, for preparing the metallocene precursors of the poly alpha olefin mainly with amorphous characteristic (when at higher reactor When being used as catalyst under temperature conditions) it is those of formula 19, S is wherein selected independently " ' v so that described metallocene framework has Containing described metal center and divide Flu-ring and the symmetrical plane of Cp-ring equally.A ' part need not be symmetrical-such as, diformazan Base silicyl or aminomethyl phenyl silicyl will not affect that the spatial chemistry of produced polymer." ' v is determined substituent group S Justice is that " identical, wherein subscript " v " represents that the carbon in the cyclopentadienyl rings that described substituent group is connected is former with the S in formula 8-9 Son, and wherein can have 0,2 or 4 substituent groups S in described cyclopentadienyl rings " ', premise is described cyclopentadienyl rings It is symmetrical substituted." symmetrical substituted " is defined as referring to that described cyclopentadienyl rings is had at 2 and 5 and/or 3 and 4 " ' group replaces the S of about the same spatial volume.Generally, " ' group difference in size each other is at 2 carbon atoms to these S In the range of.Therefore, 2 and 5 are replaced by methyl and ethyl respectively, or replaced by hexyl and octyl group respectively on 3 and 4 Cyclopentadienyl group be considered as symmetrical.Equally, described cyclopentadienyl rings can by S, " ' group takes in all 4 sites Generation, and be considered as symmetrical, as long as each Symmetric substitutions is to having similar spatial volume.It addition, on 3 and 4 Two adjacent S " ' group can connect to be formed ring, premise be described new ring be also symmetrical substituted.Due at fluorenyl ring On S " position of v substituent group is apart from each other, so these substituent groups need not be symmetrically located on fluorenyl ring.Therefore, fluorenyl Ring can be replaced by 0-7 identical or different substituent group." group can optionally connect cyclization to two or more adjacent S.

According to the invention provides the preferred of the single-minded catalyst system for preparing amorphous or low-crystallinity poly alpha olefin Metallocene compounds include:

Dichloride isopropylidene (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethylisopropylidene (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethylated methylene base (cyclopentadienyl group) (fluorenyl) zirconium,

Diphenyl methylelle (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethylsilyl (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethylsilyl base (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (fluorenyl) zirconium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (fluorenyl) zirconium,

Dichloride isopropylidene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethylisopropylidene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethylated methylene base (cyclopentadienyl group) (fluorenyl) closes hafnium,

Diphenyl methylelle (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethylsilyl (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethylsilyl base (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (fluorenyl) closes hafnium,

Dichloride isopropylidene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethylisopropylidene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dichloride methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethylated methylene base (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Diphenyl methylelle (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes Zirconium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) Zirconium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes Zirconium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) Zirconium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethylsilyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethylsilyl base (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) zirconium,

Dichloride isopropylidene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethylisopropylidene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dichloride methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethylated methylene base (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Diphenyl methylelle (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes Hafnium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) Close hafnium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes Hafnium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) Close hafnium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethylsilyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethylsilyl base (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium,

Dichloride isopropylidene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9- Octahydro dibenzyl [b, h] fluorenyl) zirconium,

Dimethylisopropylidene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9, 9-octahydro dibenzyl [b, h] fluorenyl) zirconium,

Dichloride methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-eight Hydrogen dibenzyl [b, h] fluorenyl) zirconium,

Dimethylated methylene base (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9- Octahydro dibenzyl [b, h] fluorenyl) zirconium,

Diphenyl methylelle (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8, 9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12- Prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12- Prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethylsilyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethylsilyl base (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5, 5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium,

Dichloride isopropylidene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9- Octahydro dibenzyl [b, h] fluorenyl) close hafnium,

Dimethylisopropylidene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9, 9-octahydro dibenzyl [b, h] fluorenyl) close hafnium,

Dichloride methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-eight Hydrogen dibenzyl [b, h] fluorenyl) close hafnium,

Dimethylated methylene base (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9- Octahydro dibenzyl [b, h] fluorenyl) close hafnium,

Diphenyl methylelle (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8, 9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethyl diphenyl methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dichloride two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12- Prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dichloride two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12,12- Prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethyl two (p-trimethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dichloride diphenylsilyl group (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethyl diphenyl silicyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethylsilyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8, 8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethylsilyl base (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dichloride aminomethyl phenyl silicyl (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5,5, 8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium,

Dimethyl methyl phenyl silyl groups (cyclopentadienyl group) (3,3,6,6,9,9,12,12-prestox-4,4,5, 5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium etc..

Most preferably kind is:

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) zirconium, and

Dimethyl two (p-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,3,6,6,9,9,12, 12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyls) close hafnium.

It addition, the compound of formula 20 may be used for preparing amorphous polymer fraction:

In this case, S is selected independently "_vSo that described metallocene framework has the symmetrical plane dividing M and A ' equally. Substituent group S "_vIt is defined as with the S in formula 8-9 that " identical, wherein subscript " v " represents the ring that described substituent group is connected independently Carbon atom on pentadiene basic ring, and wherein can have 0-4 substituent group S in described cyclopentadienyl rings ", premise is institute It is symmetrical substituted for stating cyclopentadienyl rings." symmetrical substituted " is defined as referring to that described cyclopentadienyl rings is in 2 and 2 ' positions And/or 3 and 3 ' had the S of about the same spatial volume on position and/or 4 and 4 ' positions and/or 5 and 5 ' positions " group replaced.Logical Often, " group difference in size each other is in the range of 2 carbon atoms to these S.Therefore, on 2 and 2 ' positions respectively by methyl and Ethyl replaces, or the cyclopentadienyl group replaced by hexyl and octyl group respectively on 3 and 3 ' positions is considered as symmetrical.Equally, institute Stating cyclopentadienyl rings can be in all 4 sites by S " group replaces, and is considered as symmetrical, if each to weighing Dai Ji is to having similar spatial volume.It addition, two adjacent S " group can connect to be formed ring, and premise is described new ring Also it is symmetrical substituted.This type of coordination compound such as meso-Me₂Si (indenyl)₂ZrMe₂, meso-CH₂CH₂(indenyl)₂ZrCl₂ It is well known in the art, and typically produces the amorphous polymer that can be used for the present invention.

The preferred meso metal of the single-minded catalyst system for preparing amorphous poly-alpha-olefin is provided according to the present invention Cyclopentadinyl compound is the meso-form of following compound:

Double (indenyl) zirconium of dimethylsilyl, double (indenyl) zirconium of dimethylsilyl base, Double (indenyl) zirconium of dichloride diphenylsilyl group, double (indenyl) zirconium of dimethyl diphenyl silicyl, dichloride first Double (indenyl) zirconium of base phenyl silyl groups, double (indenyl) zirconium of dimethyl methyl phenyl silyl groups, dichloride ethylidene Double (indenyl) zirconium, double (indenyl) zirconium of dimethylethylene, dichloride di-2-ethylhexylphosphine oxide (indenyl) zirconium, dimethylated methylene Double (indenyl) zirconium of base, dimethylsilyl double (indenyl) closes hafnium, the double (indenes of dimethylsilyl base Base) close hafnium, dichloride diphenylsilyl group double (indenyl) closes hafnium, and dimethyl diphenyl silicyl double (indenyl) closes hafnium, Dichloride aminomethyl phenyl silicyl double (indenyl) closes hafnium, and dimethyl methyl phenyl silyl groups double (indenyl) closes hafnium, dichloro Changing ethylenebis (indenyl) and close hafnium, dimethylethylene double (indenyl) closes hafnium, and dichloride di-2-ethylhexylphosphine oxide (indenyl) closes hafnium, diformazan Methylene double (indenyl) closes hafnium, double (tetrahydro indenyl) zirconium of dimethylsilyl, dimethylformamide dimethyl Ji Jia Double (tetrahydro indenyl) zirconium of silylation, double (tetrahydro indenyl) zirconium of dichloride diphenylsilyl group, dimethyl diphenyl first Double (tetrahydro indenyl) zirconium of silylation, double (tetrahydro indenyl) zirconium of dichloride aminomethyl phenyl silicyl, dimethyl methylbenzene Double (tetrahydro indenyl) zirconium of base silicyl, dichloride ethylenebis (tetrahydro indenyl) zirconium, the double (tetrahydrochysene of dimethylethylene Indenyl) zirconium, dichloride di-2-ethylhexylphosphine oxide (tetrahydro indenyl) zirconium, double (tetrahydro indenyl) zirconium of dimethylated methylene base, dichloride Dimetylsilyl double (tetrahydro indenyl) closes hafnium, and dimethylsilyl base double (tetrahydro indenyl) closes hafnium, dichloride Diphenylsilyl group double (tetrahydro indenyl) closes hafnium, and dimethyl diphenyl silicyl double (tetrahydro indenyl) closes hafnium, dichloride Aminomethyl phenyl silicyl double (tetrahydro indenyl) closes hafnium, dimethyl methyl phenyl silyl groups double (tetrahydro indenyl) conjunction hafnium, and two Chlorination ethylenebis (tetrahydro indenyl) closes hafnium, and dimethylethylene double (tetrahydro indenyl) closes hafnium, dichloride di-2-ethylhexylphosphine oxide (tetrahydrochysene Indenyl) close hafnium, dimethylated methylene base double (tetrahydro indenyl) closes hafnium, and dimethylsilyl double (2-methylindenyl) closes Zirconium, double (2-methylindenyl) zirconium of dimethylsilyl base, double (the 2-methyl indenes of dichloride diphenylsilyl group Base) zirconium, double (2-methylindenyl) zirconium of dimethyl diphenyl silicyl, the double (2-of dichloride aminomethyl phenyl silicyl Methylindenyl) zirconium, double (2-methylindenyl) zirconium of dimethyl methyl phenyl silyl groups, dichloride ethylenebis (2-first Base indenyl) zirconium, double (2-methylindenyl) zirconium of dimethylethylene, dichloride di-2-ethylhexylphosphine oxide (2-methylindenyl) zirconium, Double (2-methylindenyl) zirconium of dimethylated methylene base, dimethylsilyl double (2-methylindenyl) closes hafnium, diformazan Base dimetylsilyl double (2-methylindenyl) closes hafnium, and dichloride diphenylsilyl group double (2-methylindenyl) closes hafnium, Dimethyl diphenyl silicyl double (2-methylindenyl) closes hafnium, and dichloride aminomethyl phenyl silicyl is double (2-methylindenyl) Closing hafnium, dimethyl methyl phenyl silyl groups double (2-methylindenyl) closes hafnium, and dichloride ethylenebis (2-methylindenyl) is closed Hafnium, dimethylethylene double (2-methylindenyl) closes hafnium, and dichloride di-2-ethylhexylphosphine oxide (2-methylindenyl) closes hafnium, and dimethyl is sub- Methyl double (2-methylindenyl) closes hafnium, double (the 2-methyl 4-phenyl indenyl) zirconium of dimethylsilyl, dimethyl Double (the 2-methyl 4-phenyl indenyl) zirconium of diphenylsilyl group, double (the 2-methyl 4-phenyl of dichloride diphenylsilyl group Indenyl) zirconium, double (the 2-methyl 4-phenyl indenyl) zirconium of dimethyl diphenyl silicyl, dichloride aminomethyl phenyl first silicon Double (the 2-methyl 4-phenyl indenyl) zirconium of alkyl, dimethyl methyl phenyl silyl groups double (2-methyl 4-phenyl indenyl) closes Zirconium, dichloride ethylenebis (2-methyl 4-phenyl indenyl) zirconium, dimethylethylene is double (2-methyl 4-phenyl indenyl) Zirconium, dichloride di-2-ethylhexylphosphine oxide (2-methyl 4-phenyl indenyl) zirconium, double (the 2-methyl 4-phenyl indenes of dimethylated methylene base Base) zirconium, dimethylsilyl double (2-methyl 4-phenyl indenyl) closes hafnium, dimethylsilyl base Double (2-methyl 4-phenyl indenyls) close hafnium, and dichloride diphenylsilyl group double (2-methyl 4-phenyl indenyl) closes hafnium, diformazan Base diphenylsilyl group double (2-methyl 4-phenyl indenyl) closes hafnium, dichloride aminomethyl phenyl silicyl pair (2-methyl- 4-phenyl indenyl) close hafnium, dimethyl methyl phenyl silyl groups double (2-methyl 4-phenyl indenyl) closes hafnium, dichloride Asia second Base double (2-methyl 4-phenyl indenyl) closes hafnium, and dimethylethylene double (2-methyl 4-phenyl indenyl) closes hafnium, and dichloride is sub- Methyl double (2-methyl 4-phenyl indenyl) closes hafnium, and dimethylated methylene base double (2-methyl 4-phenyl indenyl) closes hafnium, dichloride Double (4, the 7-dimethylindenyl) zirconium of dimetylsilyl, dimethylsilyl base is double (4,7-dimethylindenyl) Zirconium, double (4, the 7-dimethylindenyl) zirconium of dichloride diphenylsilyl group, dimethyl diphenyl silicyl double (4,7- Dimethylindenyl) zirconium, double (4, the 7-dimethylindenyl) zirconium of dichloride aminomethyl phenyl silicyl, dimethyl aminomethyl phenyl Double (4, the 7-dimethylindenyl) zirconium of silicyl, dichloride ethylenebis (4,7-dimethylindenyl) zirconium, dimethyl is sub- Double (4, the 7-dimethylindenyl) zirconium of ethyl, dichloride di-2-ethylhexylphosphine oxide (4,7-dimethylindenyl) zirconium, dimethylated methylene base Double (4,7-dimethylindenyl) zirconium, dimethylsilyl double (4,7-dimethylindenyl) closes hafnium, dimethyl two Methyl silicane base double (4,7-dimethylindenyl) closes hafnium, and dichloride diphenylsilyl group double (4,7-dimethylindenyl) closes Hafnium, dimethyl diphenyl silicyl double (4,7-dimethylindenyl) closes hafnium, dichloride aminomethyl phenyl silicyl double (4,7- Dimethylindenyl) close hafnium, dimethyl methyl phenyl silyl groups double (4,7-dimethylindenyl) closes hafnium, dichloride ethylenebis (4,7-dimethylindenyl) closes hafnium, and dimethylethylene double (4,7-dimethylindenyl) closes hafnium, dichloride di-2-ethylhexylphosphine oxide (4,7- Dimethylindenyl) close hafnium, dimethylated methylene base double (4,7-dimethylindenyl) closes hafnium etc..

Most preferably kind is the racemic form of following compound:

Double (indenyl) zirconium of dimethylsilyl, double (indenyl) zirconium of dimethylsilyl base, Dichloride ethylenebis (indenyl) zirconium, double (indenyl) zirconium of dimethylethylene, the double (indenes of dimethylsilyl Base) close hafnium, dimethylsilyl base double (indenyl) closes hafnium, and dichloride ethylenebis (indenyl) closes hafnium, dimethyl Ethylenebis (indenyl) closes hafnium, double (tetrahydro indenyl) zirconium of dimethylsilyl, dimethylsilyl Double (tetrahydro indenyl) zirconium of base, dichloride ethylenebis (tetrahydro indenyl) zirconium, dimethylethylene double (tetrahydro indenyl) closes Zirconium, dimethylsilyl double (tetrahydro indenyl) closes hafnium, and dimethylsilyl base double (tetrahydro indenyl) closes Hafnium, dichloride ethylenebis (tetrahydro indenyl) conjunction hafnium, dimethylethylene double (tetrahydro indenyl) closes hafnium, dichloride Double (2-methylindenyl) zirconium of silylation, double (2-methylindenyl) zirconium of dimethylsilyl base, dichloride Asia second Double (2-methylindenyl) zirconium of base, double (2-methylindenyl) zirconium of dimethylethylene, dimethylsilyl is double (2-methylindenyl) closes hafnium, and dimethylsilyl base double (2-methylindenyl) closes hafnium, dichloride ethylenebis (2-first Base indenyl) close hafnium, and dimethylethylene double (2-methylindenyl) closes hafnium.

When two kinds of transistion metal compound type catalyst use as hybrid catalyst system in a reactor, should This selection the two transistion metal compound so that the two is compatible.Those of ordinary skill in the art can be used known Simple screening method such as¹H or¹³C NMR determines that those transistion metal compounds are compatible.

Identical activator is used, however, it is possible to be used in combination two kinds of differences preferably for described transistion metal compound Activator, such as non-coordinating anion activator and aikyiaiurnirsoxan beta.Bear if one or more transistion metal compounds contain non-hydrogen The X of ion, alkyl or substituted hydrocarbon radical₁Or X₂Part, then described aikyiaiurnirsoxan beta should add non-coordinating anion activator it Before contact with described transistion metal compound.

The combination of especially preferred transistion metal compound includes:

(1) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅)(N-c-C₁₂H₂₃) TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂(2-Me-4-PhInd=2-methyl 4-phenyl indenyl, c- C₁₂H₂₃=cyclo-dodecyl, Me₄C₅-tetramethyl-ring pentadienyl)；

(2) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(3) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅)(N-c- C₁₂H₂₃)TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂(2-MeInd=2-methylindenyl)；

(4) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron Activation Activation₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(5) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (N-1-diamantane (obsolete) Base) TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(6) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrMe₂；

(7) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (N-1-diamantane (obsolete) Base) TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(8) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(9) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (the N-tert-butyl group) TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(10) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(11) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (the N-tert-butyl group) TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(12) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(13) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (outside N--fall ice Chip base) TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(14) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrMe₂；

(15) with the Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Me₄C₅) (outside N--fall ice Chip base) TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(16) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium The Me of four (pentafluorophenyl group) boron activation₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(17) with (p-Et of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₃SiPh)₂C (Cp) (3,8- di-t-BuFlu)HfCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂(the tertiary fourth of 3,6-di-t-BuFlu=3,8-bis- Base fluorenyl, Cp=cyclopentadienyl group)；

(18) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium (the p-Et of four (pentafluorophenyl group) boron activation₃SiPh)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrMe₂；

(19) with (p-Et of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₃SiPh)₂C (Cp) (3,8- di-t-BuFlu)HfCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(20) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium (the p-Et of four (pentafluorophenyl group) boron activation₃SiPh)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(21) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(Ind)₂ZrCl₂With raceme-Me₂Si(H₄Ind)₂ZrCl₂(Ind=indenyl, H₄Ind=tetrahydro indenyl)；

(22) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(23) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(Ind)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(24) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(25) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(H₄Ind)₂ZrCl₂；

(26) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(27) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(28) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(29) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(30) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(31) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(32) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(33) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(2- MeInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(34) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrMe₂；

(35) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(2- MeInd)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(36) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(37) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(2-Me-4- PhInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(38) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(2-Me-4-PhInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrMe₂；

(39) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(2-Me-4- PhInd)₂ZrCl₂With raceme-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂；

(40) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(2-Me-4-PhInd)₂ZrMe₂With raceme-CH₂CH₂(2-Me-4- PhInd)₂ZrMe₂；

(41) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(2- MeInd)₂ZrCl₂With raceme-CH₂CH₂(2-MeInd)₂ZrCl₂；

(42) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(2-MeInd)₂ZrMe₂；

(43) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(Ind)₂ZrCl₂With raceme-CH₂CH₂(Ind)₂ZrCl₂；

(44) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(Ind)₂ZrMe₂；

(45) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(Ind)₂ZrCl₂；

(46) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(Ind)₂ZrMe₂；

(47) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(Ind)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl)；

(48) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(49) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(Ind)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂；

(50) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(51) with the meso-CH of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂CH₂(2- MeInd)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl)；

(52) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the CH of four (pentafluorophenyl group) boron activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(53) with the meso-Me of aikyiaiurnirsoxan beta such as MAO or modified methylaluminoxane activation₂Si(2-MeInd)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂；With

(54) by non-coordinating anion activator such as DMA four (pentafluorophenyl group) boron or triphenylcarbenium Meso-the Me of four (pentafluorophenyl group) boron activation₂Si(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

The two transistion metal compound (procatalyst) can be used by any ratio.For producing amorphous polymer Transistion metal compound (A) with the preferred molar ratio of transistion metal compound (B) for producing crystalline polymer 1: 1000 to 1000: 1, or 1: 100 to 500: 1, or 1: 10 to 200: 1, or 1: 1 to 100: 1, or 1: 1 to 75: 1, or In the range of person 5: 1 to 50: 1 (A: B).Selected concrete ratio will depend upon which selected definite procatalyst, activation side Method and required end-product.In one particular embodiment, when using the two procatalyst, (A-" produces amorphous polymerization The procatalyst of thing " and B-" catalyst of production crystalline polymer ") time, in the two situation about activating with identical activator Under, the preferred mol% of Molecular weights based on described procatalyst be 10-99.9%A than 0.1-90%B, or 25-99% A is than 0.5-50%B, or 50-99%A is than 1-25%B, or 75-99%A compares 1-10%B.

Usually, the procatalyst compound and the activator that are merged close with the ratio of about 1: 10,000 to about 10: 1 And.When using aikyiaiurnirsoxan beta or alkyl aluminum activator, the procatalyst merged and activator mol ratio are 1: 5000 to 10: 1, Or 1: 1000 to 10: 1, or 1: 500 to 2: 1, or 1: 300 to 1: 1.When using Ionizing activators, merged Procatalyst and activator mol ratio are 10: 1 to 1: 10, or 5: 1 to 1: 5, or 2: 1 to 1: 2, or 1.2: 1 to 1: 1.Can make Use multiple activator, including the mixture using aikyiaiurnirsoxan beta or alkyl aluminum and Ionizing activators.

In another preferred embodiment, (procatalyst adds activation to there is the 3rd catalyst in the above-mentioned methods Agent).Described 3rd catalyst can be any procatalyst component cited herein.Preferred 3rd procatalyst includes energy Enough produce those of wax.Preferably example includes:

Raceme-dimethylsilyl double (4,7-dimethylindenyl) closes hafnium,

Raceme-dimethylsilyl base double (4,7-dimethylindenyl) closes hafnium,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dimethylsilyl,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dimethylsilyl base,

Raceme-dimethylsilyl double (indenyl) closes hafnium,

Raceme-dimethylsilyl base double (indenyl) closes hafnium,

Double (indenyl) zirconium of raceme-dimethylsilyl,

Double (indenyl) zirconium of raceme-dimethylsilyl base,

Raceme-dimethylsilyl double (tetrahydro indenyl) closes hafnium,

Raceme-dimethylsilyl base double (tetrahydro indenyl) closes hafnium,

Double (tetrahydro indenyl) zirconium of raceme-dimethylsilyl,

Double (tetrahydro indenyl) zirconium of raceme-dimethylsilyl base,

Raceme-dichloride diphenylsilyl group double (4,7-dimethylindenyl) closes hafnium,

Raceme-dimethyl diphenyl silicyl double (4,7-dimethylindenyl) closes hafnium,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dichloride diphenylsilyl group,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dimethyl diphenyl silicyl,

Raceme-dichloride diphenylsilyl group double (indenyl) closes hafnium,

Raceme-dimethyl diphenyl silicyl double (indenyl) closes hafnium,

Double (indenyl) zirconium of raceme-dichloride diphenylsilyl group,

Double (indenyl) zirconium of raceme-dimethyl diphenyl silicyl,

Raceme-dichloride diphenylsilyl group double (tetrahydro indenyl) closes hafnium,

Raceme-dimethyl diphenyl silicyl double (tetrahydro indenyl) closes hafnium,

Double (tetrahydro indenyl) zirconium of raceme-dichloride diphenylsilyl group,

Double (tetrahydro indenyl) zirconium of raceme-dimethyl diphenyl silicyl,

Raceme-dichloride aminomethyl phenyl silicyl double (4,7-dimethylindenyl) closes hafnium,

Raceme-dimethyl methyl phenyl silyl groups double (4,7-dimethylindenyl) closes hafnium,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dichloride aminomethyl phenyl silicyl,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dimethyl methyl phenyl silyl groups,

Raceme-dichloride aminomethyl phenyl silicyl double (indenyl) closes hafnium,

Raceme-dimethyl methyl phenyl silyl groups double (indenyl) closes hafnium,

Double (indenyl) zirconium of raceme-dichloride aminomethyl phenyl silicyl,

Double (indenyl) zirconium of raceme-dimethyl methyl phenyl silyl groups,

Raceme-dichloride aminomethyl phenyl silicyl double (tetrahydro indenyl) closes hafnium,

Raceme-dimethyl methyl phenyl silyl groups double (tetrahydro indenyl) closes hafnium,

Double (tetrahydro indenyl) zirconium of raceme-dichloride aminomethyl phenyl silicyl,

Double (tetrahydro indenyl) zirconium of raceme-dimethyl methyl phenyl silyl groups,

Raceme-dichloride ethylenebis (4,7-dimethylindenyl) closes hafnium,

Raceme-dimethylethylene double (4,7-dimethylindenyl) closes hafnium,

Raceme-dichloride ethylenebis (4,7-dimethylindenyl) zirconium,

Double (4, the 7-dimethylindenyl) zirconium of raceme-dimethylethylene,

Raceme-dichloride ethylenebis (indenyl) closes hafnium,

Raceme-dimethylethylene double (indenyl) closes hafnium,

Raceme-dichloride ethylenebis (indenyl) zirconium,

Double (indenyl) zirconium of raceme-dimethylethylene,

Raceme-dichloride ethylenebis (tetrahydro indenyl) closes hafnium,

Raceme-dimethylethylene double (tetrahydro indenyl) closes hafnium,

Raceme-dichloride ethylenebis (tetrahydro indenyl) zirconium, and

Double (tetrahydro indenyl) zirconium of raceme-dimethylethylene.

Three kinds of transistion metal compounds (procatalyst) can be used by any ratio.For producing the mistake of amorphous polypropylene Cross metallic compound (A) and be used for the transistion metal compound (B) producing crystalline polypropylene and the transition metal for producing wax The preferred molar ratio of compound (C) at (A: B: C) 1: 1000: 500 to 1000: 1: 1, or 1: 100: 50 to 500: 1: 1, or 1: 10: 10 to 200: 1: 1, or 1: 1: 1 to 100: 1: 50, or 1: 1: 10 to 75: 1: 50, or 5: 1: 1 to 50: 1: 50 In the range of.Selected concrete ratio will depend upon which selected definite procatalyst, activation method and required end-product.

Other preferred Catalyst And Method is described in US patent 6,376,410 and 6, and in 380,122, this patent is passed through Quote and be incorporated herein.

In another embodiment, the carbon monoxide-olefin polymeric of the present invention includes carrier material or carrier.Such as, described one Kind or multiple catalysts component and/or one or more activators can be deposited on one or more carriers or carrier, with one Kind or variety carrier or carrier contact, vaporize together with one or more carriers or carrier, be incorporated into one or more carriers or On carrier, or be incorporated in one or more carriers or carrier, be adsorbed or absorbed in one or more carriers or carrier or On one or more carriers or carrier.

Described carrier material is the carrier material of any routine.Preferably, described carrier material is porous carrier materials, example Such as Talcum, inorganic oxide and butter.Other carrier material includes resinous support material such as polystyrene, functionalization or The organic carrier such as polystyrene divinylbenzene of crosslinking, polyolefin or polymerizable compound, zeolite, clay, or any other have Machine or inorganic carrier material etc., or their mixture.

Preferably carrier material is inorganic oxide, including those 2,3,4,5,13 or 14 family metal oxides.Preferably Carrier includes silicon dioxide (it can be dehydrated or not be dehydrated), pyrogenic silica, aluminium oxide (WO 99/60033), Silica-alumina and their mixture.Other useful carrier includes magnesium oxide, titanium dioxide, zirconium dioxide, chlorination Magnesium (US patent No.5,965,477), montmorillonite (European patent EP-B10511665), phyllosilicate, zeolite, Talcum, clay (US patent No.6,034,187) etc..Also have, it is possible to use the compositions of these carrier materials, such as silicon dioxide-chromium, dioxy SiClx-aluminium oxide, silica-titania etc..Other carrier material can be included in described in EP 0 767 184 B1 Those porous propylene acid based polymers, this patent is incorporated herein.Other carrier material is included in PCT WO Nano composite material described in 99/47598, the aerosol described in WO99/48605, in U.S. patent No.5,972, Spherolite described in 510, and the polymer beads described in WO 99/50311, described file is all hereby incorporated by Herein.

Preferably, carrier material (most preferably inorganic oxide) has about 10 to about 700m²The surface area of/g, greatly The pore volume of about 0.1 to about 4.0cc/g, and the particle mean size of about 5 to about 500 μm.It is highly preferred that the table of carrier material Area is of about 50 to about 500m²/ g, pore volume is of about 0.5 and is of about 10 to big to about 3.5cc/g and particle mean size About 200 μm.Most preferably, the surface area of carrier material is about 100 to about 400m²/ g, pore volume is of about 0.8 to about 3.0cc/g and particle mean size are about 5 to about 100 μm.The average pore size of the carrier that can be used for the present invention is usuallyPreferably 50-is aboutMost preferably 75-is aboutIn the range of.

As it is known in the art, described catalyst can also be carried on a kind of inert carrier together, or described in urge Agent can be separately applied on two kinds of inert carriers and mix subsequently.In two kinds of methods, the former is preferred.

In another embodiment, described carrier can include one or more types, can be treated differently for printing Carrier material.It is, for example possible to use two kinds of different silicon dioxide, described silicon dioxide has different pore volumes or not Calcine at a temperature of Tong.With scavenger or the silicon dioxide of other additive treating and do not process it is also possible to use Silicon dioxide.

Stereospecific catalyst can be used to prepare there is≤the degree of crystallinity of the Mw of 100,000 and >=30%, preferably There is the macromonomer of vinyl end.As an object lesson, preparation have the vinyl terminal link of high percentage, The method of macromonomer based on propylene includes:

A) make propylene, the most a small amount of copolymerisable monomer with containing solid rigid, activation transition-metal catalyst The carbon monoxide-olefin polymeric of compound contacts in the solution at a temperature of about 80 DEG C to about 140 DEG C；With

B) reclaim number-average molecular weight and be of about 2,000 to about 30,000 daltonian isotaxys or syndyotactic poly- Propylene chain.

Preferably, described solution includes hydrocarbon solvent.It is highly preferred that described hydrocarbon solvent is aliphatic series or arsol.Further, third Alkene monomer preferably contacts at a temperature of 90 to 120 DEG C.It is highly preferred that use the temperature of 95-115 DEG C.Most preferably, propylene list Body contacts at a temperature of 100-110 DEG C.Reactor pressure typically air is pressed onto 345MPa, preferably up to 182MPa.Instead Should carry out by intermittently or serially mode.The condition reacted for suitable slurry-type is also suitable, and is similar to molten Liquid condition, described polymerization is generally carried out in liquid propene under suitable pressure.

Catalyst discussed above is to the standard of selection.A kind of catalyst is the most stereospecific, has production significant quantity The ability of macromonomer of vinyl terminal, another kind of be typically without specific, and reactive big point can be introduced Sub-monomer.It is generally believed that Bulky Ligand Metallocene catalyst symmetrical for C2 can produce the isotactic polypropylene of vinyl terminal Macromonomer.The catalyst being conducive to β methyl to eliminate the most usually is conducive to the formation of isotactic polypropylene macromonomer. Raceme-dimethylsilyl base double (indenyl) closes hafnium, the double (2-methyl-4-benzene of dimethylsilyl Base indenyl) to close hafnium be can to produce to can be used for this for zirconium and raceme-dimethylethylene double (4,7-dimethylindenyl) The catalyst of the bright isotactic polypropylene with the high-vinyl end of the chain.High temperature, usually above 80 DEG C, it appears that advantageously affect Vinyl terminal.Equally, Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂And Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂Production can For the amorphous polypropylene of the present invention, and it is considered to introduce the macromonomer of vinyl terminal, in order to also produce scPP Side chain graft Grafting Structure on amorphous skeleton.

In alternate embodiment, by diene such as 1,9-decadinene is incorporated in reaction zone, to promote ethylene The generation of aPP and the scPP macromonomer of base terminal, this quantity contributing to increasing branched block species.

Polymerization

Above-mentioned catalyst and catalyst system are applicable to solution, body, gas phase or slurry phase polymerisation process or combinations thereof, Preferably solution phase or bulk phase polymerization method.

In one embodiment, the present invention relates to solution, body, slurry or gas phase polymerization, including one or many Plant and there is 3-30 carbon atom, preferably 3-12 carbon atom, the polymerization of the monomer of more preferably 3-8 carbon atom.Preferably monomer Including propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 3-Methyl-1-pentene and cyclenes One or more in hydrocarbon or combinations thereof.Other monomer can include vinyl monomer, alkadienes such as diene, polyene, Norborene, norbornadiene, vinyl norbornene, ethylidene norbornene monomer.Preferably, produce Noblen or be total to Polymers.In another embodiment, the copolymers of Noblen and propylene and one or more above-mentioned monomers is produced.

Multiple reactors of a reactor or serial or parallel connection can be used in the present invention.Catalytic component and activation Agent can individually be transported to reactor, or more online activation with the form of solution or slurry, or Person preactivated and as activation solution or slurry pump are delivered in reactor.A kind of preferably operation is that two kinds of solution are lived online Change.About the more information of the method being incorporated in reactor by multiple catalysts, refer to US 6,399,722 and WO 0130862A1.Although these lists of references may highlight Gas-phase reactor, but described technology is equally applicable to other type of Reactor, including continuous stirred tank reactor, slurry loop reactor etc..It is polymerized and carries out with the form of single-reactor operation, Wherein monomer, comonomer, catalyst/activator, scavenger and optional modifying agent are continuously added in single-reactor, Or carrying out with the form of tandem reactor operation, wherein said components is added into two or more reactions being connected in series In each of device.Described catalytic component can join in first reactor of tandem reactor.Described catalyst group Dividing and can be also added to, in two reactors, wherein join in the first reactor by one component, another kind of component joins In other reactor.

In one embodiment, general≤500ppm, or≤400ppm, or the hydrogen of≤300ppm joins in polymerization.? In other embodiment, by least 50ppm, or >=100ppm, or the hydrogen of >=150ppm joins in polymerization.

Gas-phase polymerization

Usually, in the phase fluidised bed processes for preparing polymer, the air-flow containing one or more monomers exists Circulated continuously by fluid bed at reaction conditions in the presence of catalyst.Described air-flow is taken out from fluid bed, and recirculation In reactor.Meanwhile, polymer product is taken out from reactor, and adds fresh monomer to replace the monomer of polymerization (see for example USP 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, all these full patent texts are expressly incorporated herein for ginseng Examine).

Slurry phase polymerisation

Slurry phase polymerisation process typically at 1 to about 50 atmospheric pressure (15psi to 735psi, 103kPa to 5068kPa) or Operate at a temperature of higher pressure and 0 DEG C to about 120 DEG C.In slurry polymerization, with the addition of monomer and comonomer with And the liquid polymerization diluent medium of catalyst is formed the suspension of solid particle polymer.From reactor intermittently or serially Discharge the suspension including diluent, wherein volatile component is separated with polymer, and be optionally recycled to after the distillation In reactor.The liquid diluent used in polymerisation medium usually has the alkane of 3-7 carbon atom, preferred branched alkane Hydrocarbon.The medium used should be liquid under polymerization conditions, and is relative inertness.When a propane medium is used, described Method must operate more than reaction diluent critical temperature and pressure.Preferably, hexane or isobutane medium are used.

In one embodiment, can be used for a kind of preferably polymerization technique of the present invention be referred to as particle form polymerization or Slurry process, wherein temperature is maintained at polymer and enters below the temperature of solution.This technology is well known in the present art, And being described in such as USP3, in 248,179, this full patent texts is incorporated herein for reference.Excellent in particle form method Selecting temperature is in the range of about 85 to about 110 DEG C.For slurry process, two kinds of preferred polymerizations are to use endless tube Those of reactor and utilize those of multiple stirred reactors of series, parallel or combinations thereof.The non-limit of slurry process Property example processed includes continuous endless tube method or stirred tank method.Further, other example of slurry process is at US 4, in 613,484 It is described；Described full patent texts is incorporated herein for reference.

In another embodiment, described slurry process is carried out continuously in a loop reactor.Described catalyst with The form of the slurry in iso-butane or be injected in reactor loop with the regularities of form of dry free-pouring powder, institute State reactor loop itself and be filled with the polymer beads of growth in the isobutane diluent containing monomer and comonomer Circulation slurry.It is optionally possible to add the hydrogen as molecular weight regulator.(in one embodiment, interpolation≤500ppm, Or≤400ppm, or the hydrogen of≤300ppm.In other embodiments, add at least 50ppm, or >=100ppm, or >= The hydrogen of 150ppm.)

Depending on required polymer melt characteristic, described reactor is maintained at the pressure of 3620kPa to 4309kPa with big At a temperature of about 60 DEG C to about 104 DEG C.Reaction heat is removed by loop wall, because most reactor is double fastener sleeve pipe Form.Allow described slurry to discharge from reactor at regular intervals or continuously, enter into the low pressure flash of heating sequentially Container, drumdrier and nitrogen purge column, to remove isobutane diluent and all unreacted monomers and comonomer. Then the powder of the not hydrocarbonaceous formed is compounded, for various application.

In another embodiment, in the slurry process can be used for the present invention use reactor and can be used for this Bright method can produce more than 2000lbs/ hour (907kg/hr), more preferably above 5000lbs/hr (2268kg/kr), and The most preferably more than polymer of 10,000lbs/hr (4540kg/hr).In another embodiment, can be used for the present invention's The slurry-phase reactor used in method produces more than 15,000lbs/ hour (6804kg/hr), and preferably greater than 25,000lbs/hr (11,340kg/hr) arrive about 100, the polymer of 000lbs/hr (45,500kg/hr).

In another embodiment, in the slurry process that can be used for the present invention, total reactor pressure is at 400psig (2758kPa) arrive in the range of 800psig (5516kPa), preferably at 450psig (3103kPa) to about 700psig (4827kPa) in the range of, more preferably in the range of 500psig (3448kPa) to about 650psig (4482kPa), optimum It is selected in the range of about 525psig (3620kPa) to 625psig (4309kPa).

In still another embodiment, in the slurry process that can be used for the present invention, principal monomer is situated between in liquid reactor Concentration in matter is of about 1 to 10wt%, preferably approximately 2 and arrives about 7wt%, and more preferably from about 2.5 arrive about 6wt%, optimum About 6wt% is arrived in choosing about 3.

The another kind of method that can be used for the present invention is a process that, wherein said method, and preferred slurries method is not having Have or substantially there is no any scavenger, such as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethyl Base aluminum, operates in the case of dibutyl zinc etc..This method is described in PCT Publication WO 96/08520 and US patent No.5, In 712,352, described file is incorporated by the application for reference.

In another embodiment, described method is run in the case of having scavenger.Typical scavenger includes three Aluminium methyl, triisobutyl aluminium, tri-n-octylaluminium and the aikyiaiurnirsoxan beta of excess or modified alumoxane.

Homogeneously, body phase or solution phase are closed

Catalyst as herein described may be advantageously used with homogeneous phase solution method.Generally, this relates in flow reactor Polymerization, the initial monomers wherein by the polymer formed and supplied and catalyst material stirring, with reduce or avoid Concentraton gradient.Suitably method is more than the fusing point of polymer, at the high pressing operation of 1-3000 bar (10-30,000MPa), its Described in monomer be used as diluent, or use solvent polymerisation in solution in.

Temperature in reactor controls by cooling down the anti-of reactor content with by reactor jacket or cooling coil Answering device to cool down, from cooling, precool charging, the combination of liquid medium (diluent, monomer or solvent) evaporation or all three comes Equilibrium polymerization heat obtains.Can also use and use the adiabatic reactor precooling charging.Temperature of reactor depends on being used Catalyst.Usually, temperature of reactor preferably can be about 30 to about 160 DEG C, and more preferably from about 90 to about 150 DEG C, most preferably from about 100 to about 140 DEG C.Polymerization temperature can change according to catalyst choice.Such as, diimine Ni urges Agent can use at 40 DEG C, and metallocene Ti catalyst can use under 100 DEG C or higher temperature.At serial operation In, the second temperature of reactor is preferably above the first temperature of reactor.In parallel reactor operates, the temperature of said two reactor Degree is independent.Pressure can be about 1mmHg to 2500 bar (25,000MPa), preferably 0.1 bar to 1600 bars (1-16, 000MPa), most preferably 1.0 to 500 bar (10-5000MPa).

In one embodiment, general≤500DDm, or≤400ppm, or the hydrogen of≤300ppm joins in polymerization.? In other embodiment, by least 50ppm, or >=100ppm, or the hydrogen of >=150ppm joins in polymerization.

Each of these methods can also use in single-reactor, reactor configuration in parallel or series.Described Liquid processes includes making olefinic monomer tie up to above-mentioned caltalyst contact in suitable diluent or solvent, and makes described monomer Reaction enough time, the polymer needed for producing.Hydrocarbon solvent is suitable, including aliphatic series and aromatic hydrocarbon.Alkane, such as own Alkane, pentane, isopentane and octane are preferred.

Described method can be at continuous stirred tank reactor, batch reactor or plug flow reactor, or serial or parallel connection The more than one reactor run is carried out.These reactors can be with and without internal cooling or heating, and monomer Charging can be freezing or the most freezing.About general process conditions, see the general open of US patent 5,001,205.Referring further to International application WO 96/33227 and WO 97/22639.For the purpose of US, All Files is hereby incorporated by the application, To describe polymerization, metallocene selection and useful removing compound.

The invention further relates to prepare the continuation method of binding agent, the method includes:

1) monomer, optional solvent, catalyst and activator are merged in reactor assembly,

2) from described reactor assembly, polymer solution is taken out,

3) if there is solvent, from described polymer solution, at least 10% solvent is removed,

4) react described in quencher,

5) described polymer solution devolatization is sent out point, to form melted polymer,

6) described melted polymer and one or more additives (the most following those) are closed in static mixer And (in a preferred embodiment, without viscosifier, or viscosifier are with less than 30wt%, preferably shorter than 20wt%, more The preferably shorter than amount of 10wt% is added),

7) from described static mixer, polymer composition is discharged, and

8) described polymer composition pelletize or rotary drum are processed；

Wherein step 1) include any of above method.

In another embodiment, the present invention relates to the continuation method for preparing binding agent, the method includes:

2) from described reactor assembly, polymer solution is taken out,

4) react described in quencher,

6) described melted polymer and one or more additives are merged in static mixer,

7) from described static mixer, polymer composition is discharged, and

8) described polymer composition pelletize or rotary drum are processed.

In an especially preferred embodiment, the present invention relates to the continuation method for preparing binding agent, the method Including:

3) under the polymerizing condition selected, described catalytic component and one or more C3-C40 alkene and optional are made Kind or multiple alkadienes in the presence of one or more activators, in the reaction region, contact in a solvent；

4) in the temperature higher than 70 DEG C (preferably above 100 DEG C)；

5) in the time of staying of≤120 minutes (preferably≤60 minutes, more preferably≤30 minutes)；

6) wherein the ratio of the first catalyst and the second catalyst is 1: 1 to 50: 1 (preferably 30: 1)；

7) activity of wherein said catalytic component is at least 50 kg of polymer/gram catalytic component；And at least a part of which The alkene of 20% is converted into polymer；

8) from described reaction zone, polymer solution is taken out,

9) from described polymer solution, remove the solvent of at least 10%,

10) react described in quencher,

11) described polymer solution devolatization is sent out point, to form melted polymer,

12) described melted polymer and one or more additives are merged in static mixer,

13) from described static mixer, polymer composition is discharged, and

14) described polymer composition pelletize or rotary drum are processed.

4) in the temperature higher than 70 DEG C (preferably above 100 DEG C)；

5) the time of staying of≤30 minutes；

7) activity of wherein said catalytic component is at least 50 kg of polymer/gram catalytic component；And at least a part of which The alkene of 50% is converted into polymer；

8) from described reaction zone, polymer solution is taken out,

9) from described polymer solution, remove the solvent of at least 10%,

10) react described in quencher,

11) forming melted polymer, wherein said polymer comprises one or more C3-C40 alkene and is less than The ethylene of 50mol%, and wherein said polymer has:

The point T of a) >=1 newton peels off；With

B) Mz at described polymer measure≤branch index (g ') of 0.95；With

The Mw of c)≤100,000；With

13) from described static mixer, polymer composition is discharged, and

14) described polymer composition pelletize or rotary drum are processed.

2) it is selected to produce under the polymerizing condition selected and there is≤the gathering of the degree of crystallinity of the Mw of 100,000 and >=40% Second catalytic component of compound；

4) in the temperature higher than 100 DEG C；

5) the time of staying of≤30 minutes；

6) wherein the ratio of the first catalyst and the second catalyst is 1: 1 to 30: 1；

8) from described reaction zone, polymer solution is taken out,

9) from described polymer solution, remove the solvent of at least 10%,

10) react described in quencher,

11) forming melted polymer, wherein said polymer comprises one or more C3-C40 alkene (preferably propylene) With the ethylene less than 50mol%, and wherein said polymer has:

The point T of a) >=3 newton peels off,

B) Mz at described polymer measure≤branch index (g ') of 0.90,

The Mw of c)≤30,000,

D) peak melting point of 60-190 DEG C,

E) heat of fusion of 1-70J/g,

F) at 190 DEG C≤melt viscosity of 8000mPa sec；With

13) from described static mixer, polymer composition is discharged, and

14) described polymer composition pelletize or rotary drum are processed.

1) monomer, catalyst and activator are merged in reactor assembly,

2) from described reactor assembly, polymer is taken out,

3) react described in quencher,

4) melted polymer is formed,

5) described melted polymer is merged with one or more additives, and

6) described polymer composition pelletize or rotary drum are processed.

The compound of polymer

Here then the polymer produced can be directly used as binding agent, or is blended with other component, to form bonding Agent.

The polymer of the present invention is not usually required to viscosifier.However, if it is desired to viscosifier, can with above-mentioned polymer altogether Mixed viscosifier are commonly used in the art those.Example includes but not limited to aliphatic hydrocarbon resin, aromatic modified aliphatic hydrocarbon resin, The polycyclopentadiene resins of hydrogenation, polycyclopentadiene resins, Colophonium, rosin ester, wood rosin, wood rosin ester, toll oil rosin, appropriate That oil rosin ester, polyterpene, aromatic modified polyterpene, terpene phenolics, the dicyclopentadiene tree of aromatic modified hydrogenation Fat, the aliphatic resin of hydrogenation, the aliphatic aromatic resins of hydrogenation, the terpenes of hydrogenation and modified terpenes, and hydrogenated wood rosin glycerol ester.One In a little embodiments, described viscosifier are hydrogenation.In other embodiments, described viscosifier are nonpolar.(nonpolar Refer to that described viscosifier are substantially free of the monomer with polar group.Preferably, polar group does not exists, if but they If existence, preferably polar group amount is less than 5wt%, preferably more than 2wt%, even more preferably from being less than 0.5wt%.) in some embodiments, viscosifier have 80-150 DEG C, the softening point of preferably 100-130 DEG C (lead to by ring and ball method Cross ASTM E-28 to measure).

If viscosifier, the amount of viscosifier is typically about 1 and arrives about 80wt%, more preferably 2- 40wt%, even more preferably from 3-30wt%, weight meter based on described blend.

Preferred hydrocarbon resin as viscosifier or modifying agent includes:

1. resin, such as C5/C6 terpene resin, styrene terpene class, α-methyl styrene terpene resin, C9 terpenes tree Fat, aromatic modified C5/C6 resin, aromatic modified cyclic resin, aromatic modified dicyclopentadiene-type resin or they Mixture.Other preferred resin is included in WO 91/07472, US 5,571,867, US 5, and 171,793 and US 4,078, Those described in 132.Generally, these resins are obtained by the cationic polymerization of the compositions containing one or more following monomers : C5 alkadienes (such as 1,3-pentadiene, isoprene etc.)；C5 alkene (such as 2-methyl butene, cyclopentenes etc.)；C6 alkene (such as hexene), C9 vinyl aromatic compounds (such as styrene, α-methyl styrene, vinyltoluene, indenes, methyl indenes Deng)；Cyclic compound (such as bicyclopentadiene, methyl dicyclopentadiene etc.)；And/or terpenes (such as alkene, carene etc.).

2. by the thermal polymerization of bicyclopentadiene, and/or cyclopentadiene and/or the dimer of methyl cyclopentadiene or oligomer And the heat of optional vinyl aromatic compounds (such as styrene, α-methyl styrene, vinyltoluene, indenes, methyl indenes) The resin that polymerization obtains.If it is required, the resin obtained after being polymerized and separating unreacted material can be hydrogenated.Preferably The example of resin be included in US 4,078,132；WO 91/07472；US 4,994,516；EP 0 046344 A；EP 0 082 726 A；With those described in US 5,171,793.

In another embodiment, the adhesive composition of the polymer product comprising the present invention comprises crosslinking further Agent.Preferably cross-linking agent includes having those of the functional group that can react with acid or anhydride group.Preferably cross-linking agent includes Alcohol, polyhydric alcohol, amine, diamidogen and/or triamine.The example of the cross-linking agent that can be used for the present invention includes polyamines, such as ethylenediamine, and two is sub- Ethyl triamine, 1,6-hexamethylene diamine, diethyl amino propylamine (diethylaniinopropylamine) and/or terpane diamidogen (menthanediamine)。

In another embodiment, the adhesive composition of the polymer product comprising the present invention comprises ability further Typical additive known to territory, such as filler, antioxidant, auxiliary agent, adhesion promoter, oil, and/or plasticizer.Preferably fill out Material includes titanium dioxide, calcium carbonate, barium sulfate, Silicon stone, silicon dioxide, carbon black, sand, bead, mineral aggregate, Talcum, clay Deng.Preferably antioxidant includes phenol antioxidant, and such as Irganox 1010, Irganox1076, both derives from Ciba-Geigy.Preferably oil includes paraffin oil or naphthenic oil, such as, derive from the ExxonMobil Chemical of Paris, FRA The Primol 352 or Primol 876 of France, S.A..Preferably plasticizer includes polybutene class, such as, derive from Texas The Parapol 950 and Parapol1300 of the ExxonMobil Chemical Company of Houston, state.Other preferably adds Add agent and include adhesion agent (block), antiblocking agent, pigment, processing aid, ultra-violet stabilizer, nertralizer, lubricant, surface Activating agent and/or nucleator can also be present in the one or more layer of thin film.Preferably additive includes dioxy SiClx, titanium dioxide, polydimethylsiloxane, Talcum, dyestuff, wax, calcium stearate, carbon black, low-molecular-weight resin and bead. Preferably adhesion promoter includes polarity acids, polyaminoamide (such as derive from the Versamid 115,125 of Henkel, 140), urethanes (the such as polyester system of isocyanates/hydroxy terminal, such as binding agent TN/Mondur Cb-75 (Miles, Inc.)), coupling agent (such as silicon ester (deriving from the Z-6020 of Dow Corning)), titanate esters (such as derives from Kenrich's Kr-44), reactive acrylate monomer (such as derives from the sarbox SB-60 of Sartomer), and metal acid-salt (such as derives from The Saret 633 of Sartomer), polyphenylene oxide, the polyolefin of oxidation, the polyolefin that acid is modified, and anhydride modified polyolefin.

In another embodiment, the polymer of the present invention, with less than 3wt% antioxidant, changes less than 3wt% flowing Enter agent, merge less than 10wt% wax and/or less than 3wt% crystallization auxiliary.

Other the optional component can being combined with the polymer product of the present invention is plasticizer or other additive, such as Oil, surfactant, filler, color masterbatch etc..Preferably plasticizer includes mineral oil, polybutene, phthalic acid ester etc..Especially Preferably plasticizer includes phthalic acid ester, such as phthalic acid two different undecyl ester (DIUP), phthalic acid two Different nonyl ester (DINP), dioctyl phthalate (DOP) etc..Especially preferred oil includes aliphatic naphthenic oils.

Other the optional component can being combined with the polymer product of the present invention is low molecular weight product, such as wax, oil Or low Mn polymer (low refer to less than 5000, preferably shorter than 4000, more preferably less than 3000, still more preferably less than 2500 Mn).Preferably wax includes polarity or nonpolar wax, the wax of functionalization, polypropylene wax, Tissuemat E and wax modifiers.Preferably Wax includes ESCOMERTM101.The wax of preferred functionalization includes those with modifications such as alcohol, acid, ketone, anhydride.Preferably example Including using methyl ketone, maleic anhydride or maleic acid modified wax.Preferably oil includes aliphatic naphthenic oils, white oil etc..The lowest Mn polymer includes the polymer of lower alpha-olefins such as propylene, butylene, amylene, hexene etc..Especially preferred polymer includes Mn Polybutene less than 1000.One example of this polymer can be with PARAPOL^TMThe trade name of 950 is from ExxonMobil Chemical Company obtains.PARAPOL^TM950 be have 950 Mn and at 100 DEG C the kinematic viscosity of 220cSt (pass through ASTM D455 measure) liquid polybutene polymer.In some embodiments, in same compositions, it is used in combination polarity With nonpolar wax.

But, in some embodiments, wax is probably undesirable, and with less than 5wt%, preferably shorter than 3wt%, The more preferably less than amount of 1wt%, more preferably less than 0.5wt% exists, and counts on the basis of the weight of compositions.

In another embodiment, the polymer of the present invention contains less than 30wt%, preferably shorter than 25wt%, preferably less than In 20wt%, the above-mentioned additive combination in any of preferably shorter than 15wt%, preferably shorter than 10wt%, preferably shorter than 5wt% total With, count on the basis of the weight of polymer and additive.

In another embodiment, the present invention polymer produced can be with elastomer blended (preferred elastomer Including all natural and synthetic rubber, it is included in those defined in ASTM D1566).In a preferred embodiment, bullet Gonosome is blended with the polymer produced by the present invention, forms rubber toughened compositions.A particularly preferred embodiment In, described rubber toughened compositions is biphase (or heterogeneous) system, and wherein said rubber is discontinuous phase, and described polymer is Continuous phase.The preferably example of elastomer includes following one or more: EP rubbers, ethylene propylene diene monomer rubber, Neoprene, styrene block copolymer rubber (includes SI, SIS, SB, SBS, SIBS etc.), butyl rubber, halobutyl rubber Glue, isobutene. and copolymer to ring-alkylated styrenes, the isobutene. of halogenation and to alkylstyrene copolymers.Described blend can To merge with viscosifier and/or other additive above-mentioned.

In another embodiment, the present invention polymer produced can be blended with impact copolymer.Crushing-resistant copolymerization Thing is defined as isotaxy PP and the blend of elastomer such as EP rubbers.In a preferred embodiment, described Blend is biphase (or heterogeneous) system, and wherein impact copolymer is discontinuous phase, and described polymer is continuous phase.

In another embodiment, the present invention polymer produced can be blended with ester polymer.At one preferably In embodiment, described blend is biphase (or heterogeneous) system, and wherein said polyester is discontinuous phase, and described polymer is even Continuous phase.

In a preferred embodiment, the polymer of the invention described above gathers with metallocene polyethylene (mPE) or metallocene Propylene (mPP) merges.MPE and mPP homopolymer or copolymer generally use single-or double-cyclopentadienyl transition metallic catalyst Prepare in solution, slurry, high pressure or gas phase with aikyiaiurnirsoxan beta and/or non-coordinating anion activator.Described catalyst and activation Agent can be load or unsupported, and cyclopentadienyl rings can be substituted or unsubstituted.With this type of catalyst/activation Several commercial products that agent combination produces can be with EXCEED^TM、ACHIEVE^TMAnd EXACT^TMTrade name from Texas The ExxonMobilChemical Company of Baytown buys.About for preparing this type of mPE homopolymer and the side of copolymer Method and the more information of catalyst/activator, see WO 94/26816；WO 94/03506；EPA 277,003；EPA 277, 004；US patent No.5,153,157；US patent No.5,198,401；US patent No.5,240,894；US patent No.5,017, 714；CA1,268,753；US patent No.5,324,800；EPA 129,368；US patent No.5,264,405；EPA 520, 732；WO 9200333；US patent No.5,096,867；US patent No.5,507,475；EPA 426 637；EPA 573 403； EPA 520 732；EPA 495 375；EPA 500 944；EPA 570 982；W091/09882；W094/03506 and US patent No.5,055,438。

In another embodiment, the polypropylene homopolymer of the olefin polymer of the present invention, the preferably present invention or copolymerization Thing can be with other homopolymer and/or copolymer blended, and other homopolymer described and/or copolymer include but not limited to homopolymerization third The ethylene of alkene, propylene and at most 50wt% or the copolymer of C4-C20 alpha-olefin, isotactic polypropylene, highly isotactic poly Propylene, syndiotactic polypropylene, propylene and ethylene and/or butylene and/or the random copolymer of hexene, polybutene, ethylene-acetate Vinyl acetate, (density 0.915 is to less than 0.935g/cm for Low Density Polyethylene³), linear low density polyethylene, the poly-second of extremely-low density (density 0.86 is to less than 0.90g/cm for alkene³), (density 0.90 is to less than 0.915g/cm for very low density polyethylene³), Midst density gathers (density 0.935 is to less than 0.945g/cm for ethylene³), high density polyethylene (HDPE) (density 0.945 to 0.98g/cm³), ethylene-acetate second Alkene ester, ethylene-methyl acrylate, acrylic acid copolymer, polymethyl methacrylate, or the polymerization of available high-pressure free radical method Other polymer any, polrvinyl chloride, poly 1-butene, isotactic polybutene, ABS resin, elastomer such as EP rubbers (EPR), EPR, EPDM, elastomer block copolymer such as SBS, nylon (polyamide), Merlon, PET resin, crosslinking are vulcanized Polyethylene, the copolymer (EVOH) of ethylene and vinyl alcohol, the polymer of aromatic monomer such as polystyrene, poly-1 ester, density is 0.94-0.98g/cm³High molecular weight polyethylene, density is 0.94-0.98g/cm³Low molecular weight polyethylene, common grafting Copolymer, polyacrylonitrile homopolymer or copolymer, polyamide thermoplastic, polyacetals, polyvinylidene fluoride and other fluorination elasticity Body, Polyethylene Glycol and polyisobutylene.

In a preferred embodiment, the polyacrylic polymer of the olefin polymer of the present invention, the preferably present invention is with 10- 99wt%, preferably 20-95wt%, still more preferably at least 30-90wt%, still more preferably at least 40-90wt%, still more preferably at least The amount of 50-90wt%, still more preferably at least 60-90wt%, still more preferably at least 70-90wt% is present in described blend, Count on the basis of the weight of the polymer in blend.

Can be by two or more polymer be mixed together, by reactors in series being linked together with preparation Reactor blend, or by use in same reactor more than one catalyst to prepare polytype polymer, Prepare blends described above.Described polymer can be mixed together before entering extruder, or can mix in extruder Close.

Any above polymer, including the polymer produced by the present invention, can be functionalization.Preferably functional group's bag Include maleic acid and maleic anhydride.So-called " functionalization " refers to that described polymer contacts with unsaturated acids or anhydride.Preferably Unsaturated acids or anhydride include any unsaturated organic compound containing at least one double bond He at least one carbonyl.Represent Property acid include carboxylic acid, anhydride, ester and their salt (slaine and non-metal salt).Preferably, described organic compound contains The ethylenic unsaturated bond being conjugated with carbonyl (-C=O).Example includes maleic acid, fumaric acid, acrylic acid, methacrylic acid, clothing health Acid .beta.-methylacrylic acid, tiglic acid, and cinnamic acid, and their anhydride, ester and salt derivative.Maleic anhydride is the most excellent Choosing.Counting on the basis of the weight of hydrocarbon resin and unsaturated acids or anhydride, unsaturated acids or anhydride preferably arrive about with about 0.1 10wt%, preferably approximately 0.5 arrives about 7wt%, and the amount of still more preferably from about 1 to about 4wt% exists.

In a preferred embodiment, described unsaturated acids or anhydride include the carboxylic acid or derivatives thereof selected from lower group: Unsaturated carboxylic acid, selected from the unsaturated acids derivant of ester, acid imide, amide, anhydride and cyclic acid anhydride, or their mixture.

Application

Then the polymer product of the present invention or its compound can be directly applied to base material, or can be sprayed on base On material, usual described polymer is melted.Spraying is defined to include atomization, such as, produce uniform point-like figure, and spiral sprays Mist such as Nordson controls fibrosis or swings the long filament of stretching (as in ITW Dynafiber/Omega head or Nordson Summit technology is realized), and melt blowing technique.Melt blowing technique is defined to include in US patent 5,145, Method described in 689 or wherein use the air stream fracture long filament of extrudate and then the long filament of described fracture be deposited on base Any method on material.Usually, melt blowing technique is to use air spinning hot-melt adhesive fiber and they are defeated Deliver to the method for bonding on base material.Fiber size can easily control as 20-200 by changing melt and air ratio Micron.Due to the inherent stability of adhesive melt injection applicator, seldom have, produce preferably without spuious fiber.At purple Under outside line, described bonding is rendered as rule, smooth, the point-like figure of stretching.Atomization is to use air by hot-melt adhesive mist Turn to the least point and the method being transported to them on base material be used for bonding.

Lamination melt coating

The binding agent of the present invention may be used for the application of any binding agent, includes but not limited to disposable product, packaging, lamination Thing, contact adhesive, tapes labels, wood bonding, paper bonds, supatex fabric, road mark, reflectance coating etc..

In a preferred embodiment, the binding agent of the present invention can be used for disposable diaper and sanitary towel's base arrangement, Elasticity connection in disposable product processing, packaging, label, bookbinding, timber processing assembles application with other.Especially preferred should With including: baby diaper leg elastic, carry before diaper, diaper upright lower limb cuff, diaper chassis structure, diaper core stabilization, urine Cloth liquid migrating layer, diaper outer cover is laminated, and diaper elastic cuff is laminated, female sanitary towel core stabilisation, and female sanitary towel bonds Band, industrial filter binding material, industrial filter material is laminated, and dust mask is laminated, and surgical gowns is laminated, and surgical drage is laminated, and Perishable farm products is packed.

Above-mentioned binding agent can be applied on any base material.Preferably base material includes timber, paper, cardboard, plastics, thermoplasticity Material, rubber, metal, metal forming (such as aluminium foil and tinfoil paper), the surface of plating, cloth, supatex fabric (the most poly-third Alkene spun-bonded fibre or supatex fabric), spun-bonded fibre, cardboard, stone, Gypsum Fibrosum, glass (includes by being evaporated to by silicon oxide thin Silicon oxide (SiO coated on film surface_x) coating), foam, rock, pottery, thin film, foam of polymers (such as polyurethane foam Foam), the base material being coated with ink, dyestuff, pigment, PVDC etc. or combinations thereof.

Other preferred base material includes polyethylene, polypropylene, polyacrylate, acrylic resin, poly terephthalic acid Glycol ester, or the listed above any polymer being suitable for blend.

The polymer of any of above base material and/or the present invention can carry out Corona discharge Treatment, flame treatment, electron beam photograph Penetrate, γ line irradiates, microwave treatment or silanization.

Here the binding agent prepared, when being coated in some way between two kinds of adherends, preferably its function reaches Making compares with the standard binders of standard specifications or similar constructions keeps together described material in sufficient mode.

The polymer product of the present invention can be used for, in any binding agent application described in WO97/33921, and wherein chatting The polymer phase stated combines or replaces the polymer wherein described.

The polymer product of the present invention can also individually or be used for forming WO together with other polymer and/or additive Hook-and-loop fastener described in 02/35956.

Characterize and test

Molecular weight (number-average molecular weight (Mn), weight average molecular weight (Mw) and Z-average molecular weight (Mz)) uses equipped with differential refraction Index-Detector (DRI), online low angle light scattering (LALLS) detector and Waters 150 Size of viscometer (VIS) Exclusion Chromatograph (size-exclusion chromatography instrument) (SEC) measures.The details of detector calibration has in other place Describe [see document: T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, volume 34, 19th phase, 6812-6820, (2001)]；Below with the brief description of these assemblies.

There is three Polymer Laboratories PLgel 10mm Mixed-B posts, nominal flow rate 0.5cm3/min It is that two kinds of detector configurations are common with the SEC of nominal injection volume 300 microlitre.Various feed-lines, pillar and differential refractometer Meter (DRI detector is mainly used in measuring eluting solution concentration) is accommodated in the baking oven being held in 135 DEG C.

LALLS detector is double angles light scattering photometer (Precision DetectorInc.) of 2040 types.Being positioned at of it Flow cell in SEC baking oven uses 690nm diode laser source, and collects two angles 15 ° and the scattered light of 90 °.At these Experiment only uses 15 ° of outputs.Its signal is transported to data acquisition board (National Instruments), the latter with The rate collection reading of 16/ second.Four minimum readings are averaged, then, the signal matched is transported to SEC- LALLS-VIS computer.After LALLS detector is arranged on SEC pillar, but before viscometer.

Viscometer is high temperature 150R type (Viscotek Corporation).It is by four arranged in Wheatstone bridge configuration Individual capillary tube and two pressure transducer compositions.One sensor measures the overall presure drop through described detector, and another is positioned at Sensor between described bridge both sides measures pressure reduction.The specific viscosity of the solution flowing through viscometer is calculated by their output.Viscosity Meter is in SEC oven interior, after being positioned at LALLS detector but before DRI detector.

For SEC experiment solvent by 6g Yoshinox BHT (BHT) antioxidant is joined 1 in 4L bottle, In 2,4-trichloro-benzenes (TCB) (Aldrich SILVER REAGENT) and wait to BHT dissolve prepare.Then with 0.7 urn glass pre-flock Device filters described TCB mixture, filters with 0.1 micron Teflon filter subsequently.Have attached between high-pressure pump and SEC pillar The online 0.7 urn glass prefilter/0.22 micron Teflon filter assembly added.Then TCB used online before entering SEC Degasser (Phenomenex, DG-4000 type) deaerates.

By putting in glass container by dry polymer, add the desired amount of TCB, the most with continuous stirring will be mixed Compound heats about 2 hours at 160 DEG C prepares polymer solution.All of amount gravimetry measures.For representing The TCB density (mass/volume unit) of polymer concentration is at room temperature 1.463g/ml, is 1.324g/ml at 135 DEG C.Note Penetrating concentration is 1.0-2.0mg/ml, and the most relatively low concentration is for the sample of higher molecular weight.

Before running each sample, DRI detector and syringe are purged.Then flow in device is increased to 0.5ml/ Min, before first sample of injection, makes DRI stablize 8-9 hour.Before running sample, argon ion laser opens 1-1.5 Hour, run 20-30 minute in idle running mode including laser instrument, then change the total power to light regulative mode.

Branch index uses the SEC (SEC-VIS) with in-line viscometer to measure, and each as in SEC curve G ' report under molecular weight.Branch index g ' is defined as:

g^{'} = \frac{η_{b}}{η_{1}}

Wherein η_bIt is intrinsic viscosity and the η of branched polymer₁It is viscosity-average molecular weight (M identical with described branched polymer_v) The intrinsic viscosity of linear polymer.η₁=KM_v ^α, K and α is the measured value of linear polymer, and should prop up with for measurement Change and obtain on the identical instrument of SEC-DRI-LS-VIS instrument of index.For the polypropylene specimen provided in the present invention, make With K=0.0002288 and α=0.705.SEC-DRI-LS-VIS method eliminates the needs of calibration polydispersity, because characteristic Viscosity and molecular weight measure under each elution volume, and described each elution volume contains narrow scattered polymer demonstrably.Quilt Linear polymer selected as contrast standard thing should have identical viscosity-average molecular weight, content of monomer and composition distribution.Contain There is the method that the linear characteristic of the polymer of C2-C10 monomer passes through C-13NMR, Randall (Rev.Macromol.Chem.Phys., C 29 (2&3), the 285-297 page) confirms.C11 and more than C11 monomer linear Characteristic confirms by using the gpc analysis of MALLS detector.Such as, for the copolymer of propylene, NMR should not indicate altogether Branched branched (if i.e., comonomer is butylene, should not exist more than 2 carbon is branched) more than comonomer of polymers. For the homopolymer of propylene, GPC should not be showed more than the branched of a carbon atom.When needs for wherein comonomer be C9 or During the linear criterion thing of the polymer of more polymeric monomer, about determining the program of the reference material for those polymer, it is referred to T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, volume 34, the 19th phase, 6812- Page 6820, (2001).In the case of syndiotactic polymer, described reference material should have by C13NMR measure suitable The degree of syndiotacticity of level.

To be used for¹³The polymer samples of C NMR spectroscopy is dissolved in d₂In-sym.-tetrachloroethane, and use 75 or The NMR spectrometer of 100MHz records sample at 125 DEG C.Polymer formant is with reference to mmmm=21.8ppm.Characterizing with NMR The calculating related in polymer is carried out according to following works: F.A.Bovey, " Polymer Conformation and Configuration " Academic Press, New York 1969 and J.Randall, " Polymer SequenceDetermination, Carbon-13NMR Method, Academic Press, New York, 1977. Bernoullianity index (B) is defined as B=4 [mm] [rr]/[mr]².The percentage rate of the methylene sequences of a length of 2 (% (CH₂)₂) it being calculated as follows: (its concentration is equal in the sequence of a length of 2 for the integration of the methyl carbon between 14-18ppm The number of methylene) divided by a length of 1 between 45-49ppm methylene sequences integration and between 14-18ppm The summation of the integration of methyl carbon, then it is multiplied by 100.This is the minimum of computation of the methylene base unit weight contained in the sequence of 2 or more than 2 Value, because the methylene sequences more than 2 has been excluded.Ownership is based on H.N.Cheng and J.A.Ewen, Macromol.Chem.1989,190,1931.

Peak melting point (Tm) and peak crystallization temperature (Tc) determine according to ASTM E 794-85.Heat of fusion and degree of crystallinity ASTM D 3417-99 is used to measure.TA Instruments2920 type instrument is used to obtain differential scanning calorimetry (DSC) data.The sample weighing about 7-10mg is sealed in aluminum specimen disc.Record DSC data as follows: first by sample Product are cooled to-50 DEG C, and then with the speed of 10 DEG C/min, sample are progressively heated at 200 DEG C.Sample is protected at 200 DEG C Hold 5 minutes, then apply second time cooling-heat cycles.The incident heat of record the first and second circulation.Measure at melting curve Under area and be used for determine heat of fusion (Δ H) and degree of crystallinity.Percent crystallinity uses equation below to calculate: [under the curve Area (J/g)/B (J/g)] * 100, wherein B is the heat of fusion of homopolymer of major monomeric compoent.These B numerical value from Polymer Handbook, fourth edition, John Wiley and Sons publishes, and NewYork 1999 obtains.Use numerical value 189J/g (B) is as the heat of fusion of 100% crystallinity polypropylene.For showing multiple fusings or the polymer of peak crystallization, take High melting peak is as peak melting point, and takes the highest peak crystallization as peak crystallization temperature.

The ethylene contents of ethylene/propene copolymer uses FTIR to measure according to techniques below.By the temperature of about 150 DEG C The thin uniform films of the polymer of lower compacting is installed on Perkin ElmerSpectrum 2000 infrared spectrophotometer.Note Record sample is from 600cm^-1To 4000cm^-1Full spectrum, and according to below equation calculate ethylene contents (wt%):

Ethylene contents (wt%)=72.698-86.495X+13.696X²

Wherein X=AR/ (AR+1).Calculate in spectrum～1165cm^-1Propylene leukorrhagia area and～732cm^-1's Area under vinyl strap.Waving band for methylene, baseline limit of integration is normally from 695cm^-1To 745-775cm^-1Between Minima.For polypropylene tape, baseline limit of integration is normally from 1195 to 1126cm^-1.AR be～1165cm^-1Peak Area with～732cm^-1The ratio of area at peak.

Glass transition temperature (Tg) uses TA Instruments 2920 type instrument to be measured by ASTME 1356.

Melt viscosity (ASTM D-3236) (also known as " viscosity ", " brookfield viscosity ")

Melt viscosity curve generally at a temperature of 120-190 DEG C use Brookfield Thermosel viscometer and No. 27 rotors measure.

Typical zolymerization program

It is aggregated in series connection double-reactor successive soln method and carries out.Two reactors are the reactions of 0.5L stainless steel autoclave Device, and it is mounted with agitator, the water-cooled/steam heating elements with temperature controller and pressure controller.First solvent, list are made Body such as ethylene and propylene and if there is comonomer (such as butylene and hexene) purified by three post purification systems.Described carry Pure lines system is made up of with follow-up 5A and 3A molecular sieve column Oxiclear post (deriving from the Model#RGP-R1-500 of Labclear). As long as having the evidence that polymerization activity reduces with regard to regular regeneration purification column.3A and 5A molecular sieve column is the most respectively 260 DEG C and the design temperature of 315 DEG C under internal regeneration.Molecular screen material is bought from Aldrich.Oxiclear post regenerates in genuine man.

Solvent feed by mass flowmenter metering feeding to reactor.One pulsed feeds pump controls solvent flux also Improve the solvent pressure entering reactor.Propylene feed that compress, liquefaction is measured by mass flowmenter, and flow passes through Speed-variable pump controls.Monomer is fed to reactor by pulse pump (＞ 5ml/min) or Eldex pump (＜ 5ml/min), and flows Amount uses Brookfield mass flowmenter or Micro-Motion Coriolis type effusion meter to measure.First by solvent, Monomer and comonomer feed are to manifold.The ethylene supplied from inside is as the solvent/monomer of the cooling being dissolved in manifold Gas conveying in mixture.Then before the mixture of solvent and monomer is fed to reactor by single pipeline, logical Cross the mixture making solvent and monomer and be cooled to about-15 DEG C through subcooler.By Brookfield quality stream The flow of amount controller metering ethylene.Mass flow controller is used to be transported in reactor by hydrogen.

The content of the first reactor is flowed in the second reactor.The outlet of the first reactor is by heat tracing pipeline even Being connected to equip the second reactor being similar to the first reactor, described second reactor has independent catalyst and promoter Adding set, additional monomer, hydrogen, solvent adding set and reaction temperature control device.In polymer solution stream from After two reactors are discharged, terminate polymerization by adding a small amount of water.

It is that raceme-dimethylsilyl base is double for producing the catalyst compounds of semi-crystalline polypropylene (2-methyl 4-phenyl indenyl) zirconium (obtaining from Albemarle) and raceme-dimethyl ethylene-bis-(4,7-bis- Methylindenyl) close hafnium (obtaining from BoulderScientific Company).

It is dimethylsilyl base (tetramethyl-ring penta 2 for producing the catalyst compounds of amorphous polypropylene Thiazolinyl) (cyclo-dodecyl amino) close titanium (obtaining from Albemarle) and dimethyl [two (p-triethylsilyl benzene Base) methylene] (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) conjunction hafnium (obtaining from Albemarle).

At least 10 minutes before polymerization, catalyst in 700ml toluene with 1: 1 to 1: 1.1 mol ratio with four (pentafluorophenyl group) boric acid DMA (obtaining from Albemarle) pre-activate.Caltalyst ties up to dilute in toluene Catalyst concn to 0.2-1.4mg/ml.All catalyst solutions are maintained in the inert atmosphere of water content ＜ 1.5ppm, and By dosing pump feeding reactor.Described catalyst solution is at all aggregation tests carried out on the same day.When in one day When consuming the catalyst solution of more than 700ml, prepare a collection of new catalyst solution.

When using multiple catalysts in a reactor, each catalyst solution is pumped by single pipeline, so After mix in manifold, then by single pipeline feeding reactor.Connection pipeline between catalyst manifold and Reactor inlet Long about 1 meter.The contact of catalyst, solvent and monomer is carried out in the reactor.Catalyst pump uses toluene as calibration medium Periodic calibration.Catalyst concn in raw material is molten by changing the catalyst concn in catalyst solution and/or change catalyst The feed rate of liquid controls.The feed rate of catalyst solution changes in the range of 0.2-5ml/min.

As impurity scavenger, 250ml tri-n-octylaluminium (TNOA) (25wt%, in toluene, Akzo Nobel) is existed 22.83 kilograms of hexanes dilute.The TNOA solution of dilution is stored under nitrogen protection in 37.9L graduated cylinder.This solution is used for All aggregation tests, until about 90% consumes, then prepare a new batch of material.This tri-n-octylaluminium (TNOA) solution Feed rate change in the range of 0 (without scavenger) to 4ml/min in different polyreactions, in order to optimize total catalysis Agent efficiency.

For relating to α, the polyreaction of ω-diene, 1,9-decadinene is diluted to 4.8-9.5vol.%'s in toluene Concentration.Then dosing pump is passed through through comonomer pipeline by the solution feeding reactor of this dilution.1,9-decadinene is from Adlrich Obtain, and first pass through the aluminium oxide through the most at high temperature activating, then pass through and the most at high temperature activate Molecular sieve carry out purification.

First pass through and under maximum permissible temperature (about 150 DEG C), solvent (such as hexane) and scavenger uninterrupted pumping are led to Cross reactor assembly 1 hour up to less, carry out cleaning reactor.After the cleaning, by reactor with flow through the water of reactor jacket/ Vapour mixture is heating/cooling to temperature required, and controls at the pressure set with the solvent flux controlled.Then, by monomer With catalyst solution feeding reactor.Use automatic temperature-adjusting control system by reactor control and the temperature that is maintained at setting. Beginning through of polymerization activity observes that the lower temperature of sticky product and water-steam mixture determines.Once set up activity And system reaches stable state, the system that operates continuously under conditions of setting up reaches a period of time of mean residence time at least 5 times, Then collect sample, then disable described reactor.That obtained by the second reactor, mainly contain solvent, polymer and the most anti- The mixture of the monomer answered is collected in collecting box.First the sample collected air-dries in fume hood, to evaporate great majority Solvent, is then dried about 12 hours in vacuum drying oven at a temperature of about 90 DEG C.The sample that vacuum drying oven of weighing is dried, To obtain productivity.Responded and carried out at a temperature of the pressure of about 2.41MPag and 70-130 DEG C.

Embodiment 1a-1i

These embodiments illustrate series connection double-reactor successive soln method, outside described method uses in the first reactor Double (2-methyl 4-phenyl indenyl) the zirconium catalyst (catalyst A) of racemization-dimethylsilyl base (from Albemarle obtains) produce isotactic polypropylene, the second reactor uses dimethyl [two (p-silicohetanes Alkyl phenyl) methylene] (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) close hafnium catalyst (catalyst B) (from Albemarle Obtain) produce amorphous polypropylene.The molecular weight of described isotactic polypropylene uses reaction temperature to control, described amorphous poly-third The molecular weight of alkene regulates as molecular weight regulator by adding hydrogen.Propylene, solvent, catalyst solution A and scavenger are entered To the first reactor.The content of the first reactor is flowed into the second reactor.Catalyst B solution and hydrogen feeding second are reacted Device.In accordance with above-mentioned general program, and detailed reaction condition and polymer performance are listed in Table 1.Urging in embodiment li Agent A is that raceme-dimethylsilyl base double (indenyl) closes hafnium (being obtained by Albemarle).

Embodiment 2a-2f

These embodiments illustrate series connection double-reactor successive soln method, outside described method uses in the first reactor Racemization-dimethylsilyl base double (2-methyl 4-phenyl indenyl) zirconium catalyst (catalyst A) produces complete with vertical Structure polypropylene, uses dimethyl [two (p-triethylsilylphenyl) methylene] (cyclopentadiene in the second reactor Base) (3,8-di-t-butyl fluorenyl) conjunction hafnium catalyst (catalyst B) production propylene/ethylene copolymer.By propylene, solvent, catalysis Agent solution A and scavenger feeding the first reactor.The content of the first reactor is flowed into the second reactor.By ethylene and catalysis Agent B solution feeding the second reactor.The degree of crystallinity of ethylene/propene copolymer is by the propylene conversion in the first reactor and enters Regulate to the ethylene volume of the second reactor.In order to produce amorphous ethylene/propene copolymer, need enough ethylene feed speed Rate.In accordance with above-mentioned general program, and detailed reaction condition and polymer performance are listed in table 2.

Embodiment 3a-3e

These embodiments illustrate series connection double-reactor successive soln method, outside described method uses in the first reactor Racemization-dimethylsilyl base double (2-methyl 4-phenyl indenyl) zirconium catalyst (catalyst A) produces complete with vertical Structure polypropylene, uses dimethyl [two (p-triethylsilylphenyl) methylene] (cyclopentadiene in the second reactor Base) (3,8-di-t-butyl fluorenyl) conjunction hafnium catalyst (catalyst B) production propylene/octene copolymer.By propylene, solvent, catalysis Agent solution A and scavenger feeding the first reactor.The content of the first reactor is flowed into the second reactor.By octene and catalysis Agent B solution feeding the second reactor.The degree of crystallinity of propylene/hexene copolymer by the propylene conversion in the first reactor and The hexene amount of feeding the second reactor regulates.For most of samples, described propylene/hexene copolymer is amorphous.In accordance with Above-mentioned general program, and detailed reaction condition and polymer performance are listed in table 3.

Embodiment 4a-4e

These embodiments illustrate series connection double-reactor successive soln method, and described method uses two in the first reactor Methyl [two (p-triethylsilylphenyl) methylene] (cyclopentadienyl group) (3,8-di-t-butyl fluorenyl) closes hafnium catalysis Agent (catalyst B) produces ethylene/propene copolymer, uses raceme-dimethylsilyl in the second reactor Base double (2-methyl 4-phenyl indenyl) zirconium catalyst (catalyst A) produces isotactic polypropylene.It is anti-that regulation is fed to first Answer the cocatalyst feed rate of device, to guarantee in the first reactor the propylene conversion more than 50%.At this propylene conversion Under, conversion of ethylene is about more than 90%.High conversion of ethylene in first reactor allows to prepare in the second reactor The product of more high-crystallinity.By propylene, ethylene, solvent, catalyst solution A and scavenger feeding the first reactor.First reaction The content of device is flowed into the second reactor.By Catalyst B solution feeding the second reactor.In accordance with above-mentioned general program, and detailed Thin reaction condition and polymer performance are listed in table 4.

Embodiment 5a-5c

These embodiments illustrate series connection double-reactor successive soln method, and described method uses raceme-dimethyl Dimetylsilyl double (2-methyl 4-phenyl indenyl) zirconium catalyst (catalyst A) produces complete same in the first reactor Vertical structure polypropylene, and in the second reactor, produce propylene/ethylene copolymer.By propylene, solvent, catalyst solution A and removing Agent feeding the first reactor.The content of the first reactor is flowed into the second reactor.By ethylene feeding the second reactor.Second The degree of crystallinity of alkene/propylene copolymer is adjusted by the ethylene volume of the propylene conversion in the first reactor and feeding the second reactor Joint.In order to produce amorphous ethylene/propene copolymer in the second reactor, it is desirable to enough ethylene feed rate.In accordance with above-mentioned General program, and detailed reaction condition and polymer performance are listed in table 5.

Embodiment 6a-6c

These embodiments illustrate series connection double-reactor successive soln method, and described method uses raceme-dimethyl Dimetylsilyl double (2-methyl 4-phenyl indenyl) zirconium catalyst (catalyst A) produces low point in the first reactor Sub-weight northylen, and use double (2-methyl 4-phenyl indenyl) the zirconium catalyst of raceme-dimethylsilyl base (catalyst A) and dimethyl [two (p-triethylsilylphenyl) methylene] (cyclopentadienyl group) (3,8-di-t-butyls Fluorenyl) mixture that closes hafnium catalyst (catalyst B) produces atactic polypropylene (aPP) in the second reactor and entirely the most together stands Structure polypropylene (iPP) and aPP/iPP branched block thing.By anti-to ethylene, solvent, catalyst solution A and scavenger feeding first Answer device.The content of the first reactor is flowed into the second reactor.By propylene and Catalyst B solution feeding the second reactor.Urge The feed rate of agent A is sufficiently high so that in the first reactor, the ethylene of more than 90% is converted.Regulation catalyst A With the ratio of catalyst B, to control the aPP/iPP ratio in the second reactor.In accordance with above-mentioned general program, and detailed reaction Condition and polymer performance are listed in table 6.

Binding agent is tested

Many hot-melt adhesives are by using straight polymer or passing through under low shear mixing effect in the temperature raised Lower by straight polymer, functionalized, viscosifier, wax, antioxidant and other composition be blended with formed flowing melt system Standby.Mixing temperature is of about 130 to about 190 DEG C.Bonding test sample is by being bonded in base material with some hot-melt adhesives Oppress described adherend together and with 500g counterweight until being cooled to room temperature and being formed.The size of described point passes through binding agent volume Controlling so that in most of the cases, the pan of the compacting formed creates just uniform in the size of base material Annulus.

Once it is made for a kind of structure, it is carried out various infringement to evaluate bonding effect.For paper base material, once glue Closing and destroy, a kind of straightforward procedure quantifying described adhesion efficiency is that estimation keeps paper fine when described structure ruptures along bonding wire The area of the adhesive spots of dimension.This estimated value is referred to as the tear of percentage substrate fiber.Sample is nursed one's health 15 hours at-12 DEG C And after attempting destroying bonding, the example of good fiber will have the estimated value of 80-100% substrate fiber tear.It is likely to Ground, 0% substrate fiber tear represents not bonding under those circumstances.

Substrate fiber tears: use program same as described above to prepare sample.For low temperature fiber tear test, will be viscous Conjunction sample is placed in fridge or refrigerator and obtains required test temperature.Substrate fiber at room temperature is torn, by institute State sample the most aging.With hands, adherend is separated, and determine viewed Failure type.Substrate fiber tears Amount as a percentage.

Point T-peels off and determines according to ASTM D 1876, except for the difference that, by taking advantage of 3 with some binding agents by two 1 inch The base material cut substrate of inch (2.54cm × 7.62cm) comes together to prepare sample, and the volume of described binding agent is for when being subject to The area (1 inch=2.54cm) of about 1 square inch is occupied during 500 grammes per square metre thing compressing.After once preparing sample, by record institute All of sample is pulled open (speed with 2 inches per minute) in parallel testing by the device of the damage power applied.Record Maximum, force that each sample tested is reached also is averaged, thus produces and be reported as the average maximum, force that a T-peels off.

Peel strength (the ASTM D1876 of amendment): by base material (1 × 3 inch (25 × 76mm)) binder film (5mils (130 μm) thickness) heat seal 1 to 2 second under 135 DEG C and 40psi (0.28MPa) pressure.On tensile testing machine with 2 inches/ Bonding sample is peeled off by the constant cross head speed of minute (51mm/ minute).Needed for adherend (5 samples) peeled away in record Mean force.

Setting time is defined as the binding agent base material structure of pressurization and is fixed together and be enough to when pulling open occur base Material fiber tearing and the most described bonding reach sufficiently strong and can remove the time required for pressure.Described it is bonded in into one May strengthen further during step cooling, but it is no longer necessary to pressure.These setting times are by by melted binding agent point-like Thing is placed on the file base material being bonded on flat table and measures.After 3 seconds by folder tabs (1 inch take advantage of 3 inches (2.5cm × 7.6cm)) it is placed in described pointing object and pressurizes with 500 grams of counterweights.Described counterweight is made to stop about 0.5 to about 10 second.Will be so The structure formed pulls open, to check the level of adhesion that be enough to produce substrate fiber tear.Needed for there is this excellent bonds Minimum time is recorded as setting time.Reference material is used to calibrate this process.

SAFT (the ASTM D4498-00 of amendment) tolerance adherend tolerates under the constant force drawing adherend with cut mode The ability of the temperature of the raising raised with the speed of 10 °F (5.5 DEG C)/15 minutes.Adherend is in the above described manner at kraft paper (1 English Very little take advantage of 3 inches (2.5cm × 7.6cm)) upper formed.Test sample is hung vertically in the baking oven of room temperature, and connecting bottom sample has 500 grams of load.The temperature that record weight falls is (when accidental sample reaches the temperature of more than baking oven ability ＞ 265 °F (129 DEG C) Time, terminate this sample test and under final temperature with other sample average).

Xiao A hardness is measured according to ASTM D 2240.Air cooled binding agent pointing object is made to stand the effect of pin, and Record deflection (deflection) from scale.

Embodiment

Following material is used in binder performance testing example:

As an example, following table lists adhesive formula and the binding agent of the polymer for the selection produced by the present invention Performance.

Although describing the present invention with reference to exemplary, but it will be understood by those skilled in the art that without departing from this In the case of the scope of invention, various change can be made and its key element can be substituted with equivalent.It addition, without departing from this In the case of invention scope, many change so that particular case and material adapt to the teachings of the present invention can be made.Therefore, this Bright it is not limited to as particular disclosed in preferred embodiment of the present invention, but the present invention includes falling into appended right All embodiments in the range of claim.

Claims

1. producing the continuation method of branched olefin polymer, the method includes:

1) be selected to produce under the polymerizing condition selected have≤Mw of 100,000 with≤20% the polymer of degree of crystallinity The first catalytic component, this first catalytic component includes that non-cubic has the metallocene catalyst compound selected；

2) be selected to produce under the polymerizing condition selected have≤Mw of 100,000 with >=20% the polymer of degree of crystallinity The second catalytic component, this second catalytic component includes stereospecific metallocene catalyst compound；

3) catalytic component, one or more activators and one or more C2-C12 alkene is made to be higher than in the first reaction zone Contact at a temperature of 70 DEG C, the time of staying≤120 minute；With

4) content of the first reaction zone is transferred to second reaction zone, and make this content and catalytic component, work further Agent and/or one or more C2-C12 alkene contact at a temperature of higher than 70 DEG C, the time of staying≤120 minute；With

5) branched olefin polymer of one or more the C3-C12 alkene comprising at least 50mol% is reclaimed,

Wherein the first catalytic component is present at least one reaction zone, and the second catalytic component is present in second reaction zone, And wherein at least one reaction zone, C2-C12 alkene is C3-C12 alpha-olefin.

2. the method described in claim 1, wherein said olefin polymer includes the propylene of 50-100mol%.

3. the method described in claim 1 or 2, wherein said olefin polymer is homo-polypropylene.

4. the method described in claim 1 or 2, during wherein propylene is present in described first reaction zone.

5. the method described in claim 1 or 2, during wherein propylene is present in described second reaction zone.

6. the method described in claim 1 or 2, during wherein ethylene is present in described first reaction zone.

7. the method described in claim 1 or 2, during wherein ethylene is present in described second reaction zone.

8. the method described in claim 1 or 2, during wherein propylene and ethylene are present in described first reaction zone.

9. the method described in claim 1 or 2, during wherein propylene and ethylene are present in described second reaction zone.

10. the method described in claim 1 or 2, wherein propylene is present in described first reaction zone with the amount of 100wt%, with Count on the basis of the weight of existing monomer.

Method described in 11. claim 1 or 2, wherein propylene is present in described second reaction zone with the amount of 100wt%, with Count on the basis of the weight of existing monomer.

Method described in 12. claim 1 or 2, wherein counts, third on the basis of the weight being present in the monomer in the first reaction zone Alkene is present in described first reaction zone with the amount of 100wt%, and the weight of the monomer to be present in second reaction zone is Benchmark meter, ethylene is present in described second reaction zone with the amount of at most 50wt%.

Method described in 13. claim 1 or 2, during wherein propylene and ethylene are present in described first reaction zone, and except depositing It is, beyond the residual ethylene monomer in the content of the first reaction zone, not to be incorporated in described second reaction zone by ethylene.

14. the method described in claim 1 or 2, wherein ethylene is intermittently introduced in one or more reaction zone.

Method described in 15. claim 1 or 2, wherein ethylene is present in reaction zone with the amount less than 10wt%, with this reaction Count on the basis of the weight of the monomer in district.

Method described in 16. claim 1 or 2, during wherein propylene and ethylene are present in described first reaction zone, propylene is present in In described second reaction zone, described first catalytic component is present in described first reaction zone, described second catalytic component It is present in described second reaction zone.

Method described in 17. claim 1, wherein:

1) described first reaction zone is the reaction comprising solvent, monomer, catalyst compounds and activator that temperature is higher than 70 DEG C Device；With

2) described second reaction zone is the reaction comprising solvent, monomer, catalyst compounds and activator that temperature is higher than 70 DEG C Device.

18. the method described in claim 1 or 2, wherein said first catalytic component includes one of the following or multiple:

Dimethylsilyl (tetramethyl-ring pentadienyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (tert-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (s-butylamino) closes titanium,

Dimethylsilyl (tetramethyl-ring pentadienyl) (n-butylamino) closes titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (cyclo-dodecyl ammonia Base) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (outer-2-norborny Amino) close titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (Cyclohexylamino) closes Titanium,

Dimethylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (1-adamantyl ammonia Base) close titanium,

Dimethylsilyl (2-tetrahydro indenyl) (cyclo-dodecyl amino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (1-adamantylamino) closes titanium,

Dimethylsilyl (2-tetrahydro indenyl) (outer-2-norborny amino) closes titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (cyclo-dodecyl Amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (outer-2-norborneol Base amino) close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (Cyclohexylamino) Close titanium,

Dimethylsilyl base (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl group) (1-adamantyl Amino) close titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (Cyclohexylamino) closes titanium,

Dimethylsilyl base (2-tetrahydro indenyl) (1-adamantylamino) closes titanium, and

Dimethylsilyl base (2-tetrahydro indenyl) (outer-2-norborny amino) closes titanium.

Method described in 19. claim 1 or 2, wherein said second catalytic component includes one of the following or multiple:

The racemic form of following compound:

Dimethylsilyl (2-methyl 4-phenyl indenyl) zirconium,

Dimethylsilyl base (2-methyl 4-phenyl indenyl) zirconium,

Dimethylsilyl (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylsilyl base (2-methyl 4-phenyl indenyl) closes hafnium,

Dimethylsilyl base double (indenyl) closes hafnium,

Dimethylsilyl double (indenyl) closes hafnium,

Double (indenyl) zirconium of dimethylsilyl base,

Double (indenyl) zirconium of dimethylsilyl,

The racemic isomer of following compound:

Double (2-methyl) alloy of dichloride dimethylsilane diyl belongs to；

Double (indenyl) alloy of dichloride dimethylsilane diyl belongs to；

Double (indenyl) alloy of dimethylformamide dimethyl base silane diyl belongs to；

Double (tetrahydro indenyl) alloy of dichloride dimethylsilane diyl belongs to；

Double (tetrahydro indenyl) alloy of dimethylformamide dimethyl base silane diyl belongs to；

Double (indenyl) alloy of diethyl-dimethyl silane diyl belongs to；With

Double (indenyl) alloy of dimethyl dibenzyl silane diyl belongs to；

Wherein said metal can be selected from Zr, Hf or Ti.

Method described in 20. claim 1 or 2, wherein said first catalytic component comprises dimethyl 1,1 '-bis-(4-tri- Ethyl silicane base phenyl) methylene (cyclopentadienyl group) (2,7-di-t-butyl-9-fluorenyl) closes hafnium and/or dimethyl 1, 1 '-bis-(4-triethylsilylphenyl) methylene (cyclopentadienyl group) (3,8-di-t-butyls-fluorenyl) closes hafnium.

Method described in 21. claim 1 or 2, wherein said second catalytic component comprises dimethylsilyl Double (2-methyl-5-phenyl indenyl) zirconium of base and/or dimethylsilyl base double (2-methyl 4-phenyl indenyl) close Zirconium.

Method described in 22. claim 1 or 2, wherein said activator includes four (pentafluorophenyl group) borate amine And/or four (pentafluorophenyl group) borateSalt.

Method described in 23. claim 1 or 2, wherein said activator includes aikyiaiurnirsoxan beta.

Method described in 24. claim 1 or 2, wherein said activator includes ionized compound.

Method described in 25. claim 24, wherein said activator comprises non-coordinating anion.

Method described in 26. claim 1 or 2, wherein said activator comprises one or more following compounds:

MAO,

Tetraphenylboronic acid trimethyl ammonium,

Tetraphenylboronic acid triethyl ammonium,

Tetraphenylboronic acid tripropyl ammonium,

Tetraphenylboronic acid three (normal-butyl) ammonium,

Tetraphenylboronic acid three (tert-butyl group) ammonium,

Tetraphenylboronic acid DMA

Tetraphenylboronic acid N, N-diethylaniline

Tetraphenylboronic acid N, N-dimethyl-(2，4，6-trimethyl aniline),

Four (pentafluorophenyl group) boric acid trimethyl ammonium,

Four (pentafluorophenyl group) boric acid triethyl ammonium,

Four (pentafluorophenyl group) boric acid tripropyl ammonium,

Four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium,

Four (pentafluorophenyl group) boric acid three (sec-butyl) ammonium,

Four (pentafluorophenyl group) boric acid DMA

Four (pentafluorophenyl group) boric acid N, N-diethylaniline

Four (pentafluorophenyl group) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline),

Four (2,3,4,6-tetrafluoro phenyl) boric acid trimethyl ammonium,

Four (2,3,4,6-tetrafluoro phenyl) boric acid triethyl ammonium,

Four (2,3,4,6-tetrafluoro phenyl) boric acid tripropyl ammonium,

Four (2,3,4,6-tetrafluoro phenyl) boric acid three (normal-butyl) ammonium,

Four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (tert-butyl group) ammonium,

Four (2,3,4,6-tetrafluoro phenyl) boric acid DMA

Four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-diethylanilineWith

Four (2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2，4，6-trimethyl aniline),

Four (pentafluorophenyl group) boric acid two (isopropyl) ammonium,

Four (pentafluorophenyl group) boric acid dicyclohexyl ammonium；

Four (pentafluorophenyl group) boric acid three (o-tolyl)With

Four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl)

Method described in 27. claim 1 or 2, wherein said first catalytic component can be polymerized and has reactive terminal Macromonomer, and described second catalytic component can produce the macromonomer with reactive terminal.

Method described in 28. claim 1 or 2, wherein one or more reaction zones comprise alkadienes further.

Method described in 29. claim 1 or 2, wherein one or more reaction zones comprise one or more C4-C40 further Alkadienes.

Method described in 30. claim 1 or 2, wherein one or more reaction zones comprise one or more further and are selected from down The diene of group: 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadinene, 1,10-ten one carbon diene, 1,11-ten Two carbon diene, 1,12-oleatridecadiene, 1,13-ten four carbon diene, cyclopentadiene, vinyl norbornene, norbornadiene, Ethylidene norbornene, divinylbenzene, bicyclopentadiene, the Mw polybutadiene less than 1000g/mol, or combinations thereof.

Method described in 31. claim 1 or 2, at least one of which reaction zone is Gas-phase reactor.

Method described in 32. claim 1 or 2, at least one of which reaction zone is solution-phase reaction device.

Method described in 33. claim 1 or 2, at least one of which reaction zone is sludge phase reactor.

Method described in 34. claim 1 or 2, the most all reaction zones are solution-phase reaction devices.

Method described in 35. claim 1 or 2, wherein said first catalytic component, described second catalytic component and described Activator includes one or more in following combination:

(1) with alumoxane activated Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(2) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrMe₂；

(2a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(3) with alumoxane activated Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(4) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(4a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅)(N-c-C₁₂H₂₃)TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(5) with alumoxane activated Me₂Si(Me₄C₅) (N-1-adamantyl) TiCl₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrCl₂；

(6) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si (2-Me-4-PhInd)₂ZrMe₂；

(6a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(7) with alumoxane activated Me₂Si(Me₄C₅) (N-1-adamantyl) TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(8) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si (2-MeInd)₂ZrMe₂；

(8a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (N-1-adamantyl) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(9) with alumoxane activated Me₂Si(Me₄C₅) (the N-tert-butyl group) TiCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(10) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrMe₂；

(10a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(12) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(12a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (the N-tert-butyl group) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(13) with alumoxane activated Me₂Si(Me₄C₅) (outside N--norborny) TiCl₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrCl₂；

(14) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme- Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(14a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(15) with alumoxane activated Me₂Si(Me₄C₅) (outside N--norborny) TiCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(16) with the Me of non-coordinating anion activator activation₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme- Me₂Si(2-MeInd)₂ZrMe₂；

(16a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Me₂Si(Me₄C₅) (outside N--norborny) TiMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(17) with alumoxane activated (p-(Et₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfCl₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrCl₂；

(18) with (p-(Et of non-coordinating anion activator activation₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂Outward Racemization-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(18a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation (p-(Et₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(19) with alumoxane activated (p-(Et₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfCl₂With raceme-Me₂Si(2- MeInd)₂ZrCl₂；

(20) with (p-(Et of non-coordinating anion activator activation₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂Outward Racemization-Me₂Si(2-MeInd)₂ZrMe₂；

(20a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation (p-(Et₃Si)Ph)₂C (Cp) (3,8-di-t-BuFlu) HfMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(21) with alumoxane activated meso-CH₂CH₂(Ind)₂ZrCl₂With raceme-Me₂Si(H₄Ind)₂ZrCl₂；

(22) with the meso-CH of non-coordinating anion activator activation₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(22a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(23) with alumoxane activated meso-CH₂CH₂(Ind)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(24) with the meso-CH of non-coordinating anion activator activation₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(24a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(Ind)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(25) with alumoxane activated meso-Me₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(H₄Ind)₂ZrCl₂；

(26) with the meso-Me of non-coordinating anion activator activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(26a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(H₄Ind)₂ZrMe₂；

(27) with alumoxane activated meso-Me₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(28) with the meso-Me of non-coordinating anion activator activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(28a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(29) with alumoxane activated meso-Me₂Si(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(30) with the meso-Me of non-coordinating anion activator activation₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrMe₂；

(30a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(31) with alumoxane activated meso-Me₂Si(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(32) with the meso-Me of non-coordinating anion activator activation₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(32a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(33) with alumoxane activated meso-CH₂CH₂(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrCl₂；

(34) with the meso-CH of non-coordinating anion activator activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2- Me-4-PhInd)₂ZrMe₂；

(34a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(35) with alumoxane activated meso-CH₂CH₂(2-MeInd)₂ZrCl₂With raceme-Me₂Si(2-MeInd)₂ZrCl₂；

(36) with the meso-CH of non-coordinating anion activator activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2- MeInd)₂ZrMe₂；

(36a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(2-MeInd)₂ZrMe₂With raceme-Me₂Si(2-MeInd)₂ZrMe₂；

(37) with alumoxane activated meso-Me₂Si(2-Me-4-PhInd)₂ZrCl₂With raceme-Me₂Si(2-Me-4- PhInd)₂ZrCl₂；

(38) with the meso-Me of non-coordinating anion activator activation₂Si(2-Me-4-PhInd)₂ZrMe₂With raceme- Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(38a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(2-Me-4-PhInd)₂ZrMe₂With raceme-Me₂Si(2-Me-4-PhInd)₂ZrMe₂；

(39) with alumoxane activated meso-CH₂CH₂(2-Me-4-PhInd)₂ZrCl₂With raceme-CH₂CH₂(2-Me-4- PhInd)₂ZrCl₂；

(40) with the meso-CH of non-coordinating anion activator activation₂CH₂(2-Me-4-PhInd)₂ZrMe₂With raceme- CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂；

(40a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂With raceme-CH₂CH₂(2-Me-4-PhInd)₂ZrMe₂；

(41) with alumoxane activated meso-CH₂CH₂(2-MeInd)₂ZrCl₂With raceme-CH₂CH₂(2-MePhInd)₂ZrCl₂；

(42) with the meso-CH of non-coordinating anion activator activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂ (2-MeInd)₂ZrMe₂；

(42a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(2-MeInd)₂ZrMe₂；

(43) with alumoxane activated meso-CH₂CH₂(Ind)₂ZrCl₂With raceme-CH₂CH₂(Ind)₂ZrCl₂；

(44) with the meso-CH of non-coordinating anion activator activation₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(Ind)₂ZrMe₂；

(44a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(Ind)₂ZrMe₂；

(45) with alumoxane activated meso-Me₂Si(Ind)₂ZrCl₂With raceme-Me₂Si(Ind)₂ZrCl₂；

(46) with the meso-Me of non-coordinating anion activator activation₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(Ind)₂ZrMe₂；

(46a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(Ind)₂ZrMe₂With raceme-Me₂Si(Ind)₂ZrMe₂；

(47) with alumoxane activated meso-CH₂CH₂(Ind)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂ (4,7-Me₂Ind=4,7-dimethylindenyl)；

(48) with the meso-CH of non-coordinating anion activator activation₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7- Me₂Ind)₂ZrMe₂；

(48a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(49) with alumoxane activated meso-Me₂Si(Ind)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂；

(50) with the meso-Me of non-coordinating anion activator activation₂Si(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7- Me₂Ind)₂ZrMe₂；

(50a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(Ind)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(51) with alumoxane activated meso-CH₂CH₂(2-MeInd)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂(4,7-Me₂Ind=4,7-dimethylindenyl)；

(52) with the meso-CH of non-coordinating anion activator activation₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂ (4,7-Me₂Ind)₂ZrMe₂；

(52a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-CH₂CH₂(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂；

(53) with alumoxane activated meso-Me₂Si(2-MeInd)₂ZrCl₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrCl₂；

(54) with the meso-Me of non-coordinating anion activator activation₂Si(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(4, 7-Me₂Ind)₂ZrMe₂；Or

(54a) with four (pentafluorophenyl group) boron DMAAnd/or four (pentafluorophenyl group) boron triphenylcarbeniumActivation Meso-Me₂Si(2-MeInd)₂ZrMe₂With raceme-CH₂CH₂(4,7-Me₂Ind)₂ZrMe₂,

Wherein Me is equal to methyl, and Ph is equal to phenyl, and Et is equal to ethyl, and Cp is equal to cyclopentadienyl group, and 3,8-di-t-BuFlu are equal to 3,8-di-t-butyl fluorenyls, 2-Me-4-PhInd is equal to 2-methyl 4-phenyl indenyl, and 2-MeInd refers to 2-methylindenyl, c- C₁₂H₂₃Equal to cyclo-dodecyl, Me₄C₅Refer to tetramethyl-ring pentadienyl, H₄Ind is equal to tetrahydro indenyl, and Ind is equal to indenyl.

Method described in 36. claim 1 or 2, wherein:

1) the first catalytic component can produce Mw≤80,000 and the polymerization of degree of crystallinity≤15% under the polymerizing condition selected Thing；

2) the second catalytic component can produce Mw≤80,000 and the polymerization of degree of crystallinity >=50% under the polymerizing condition selected Thing；

3) temperature of reaction zone is higher than 105 DEG C；

4) time of staying≤10 minute in reaction zone；

5) ratio of the first catalyst and the second catalyst is 1: 1 to 20: 1；

6) activity of wherein said catalytic component is at least double centner polymer/gram catalyst compounds；And at least a part of which The alkene of 80% is converted into polymer.

Method described in 37. claim 1 or 2, wherein said recovery comprises one or more C3-C12 alkene of at least 50mol% The step of the branched olefin polymer of hydrocarbon includes:

1) from described reaction zone, polymer solution is taken out；

2) from described polymer solution, at least 10% solvent is removed；

3) react described in quencher；

4) described polymer solution devolatization is sent out point, to form melted polymer；

5) described melted polymer and one or more additives are merged in static mixer；

6) from described static mixer, polymer composition is discharged, and

7) described polymer composition pelletize or rotary drum are processed.

Method described in 38. claim 37, wherein step 5) in additive include nucleator.

Method described in 39. claim 1 or 2, wherein said second catalytic component includes one of the following or multiple:

Dimetylsilyl double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes hafnium,

Double (2-n-pro-pyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isopropyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-normal-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-isobutyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (2-sec-butyl, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Double (the 2-tert-butyl group, 4-[3 ', the 5 '-bis--trifluoromethyl] indenyl) zirconium of dimethyl diisopropylaminoethyl borine；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane is double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenyl) Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Double (2-methyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of molybdenyl dichloride (trimethyl silyl) amino borane；

Double (2-ethyl, 4-[3 ', the 5 '-diphenyl phenyl] indenyl) zirconium of molybdenyl dichloride (trimethyl silyl) amino borane；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Molybdenyl dichloride (trimethyl silyl) amino borane double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-n-pro-pyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-isopropyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-isobutyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (the 2-tert-butyl group, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-bis--trifluoromethyl] indenes Base) zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-n-pro-pyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-isopropyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-isobutyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl is double (the 2-tert-butyl group, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-methyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-ethyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-n-pro-pyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isopropyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-normal-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-isobutyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；

Double (trimethyl silyl) amino borane of dimethyl double (2-sec-butyl, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium；Or

Double (trimethyl silyl) amino borane of dimethyl double (the 2-tert-butyl group, 4-[3 ', 5 '-diphenyl phenyl] indenyl) closes Zirconium.

Method described in 40. claim 1, wherein said first catalytic component is also present in described second reaction zone.

Method described in 41. claim 1, one of which catalytic component is present at least one reaction zone, and another kind is urged Agent component is present in second reaction zone.

Method described in 42. claim 1, wherein the 3% or more of total catalyst component is not injected in the first reaction zone.

Method described in 43. claim 1, wherein introduces the hydrogen in reaction zone.

Method described in 44. claim 1, the temperature of the most each reaction zone is different.

Method described in 45. claim 1, wherein the temperature in reaction zone is changed.