CN100588663C

CN100588663C - Multiple catalyst system for olefin polymerization and polymers produced therefrom

Info

Publication number: CN100588663C
Application number: CN200380101509A
Authority: CN
Inventors: 江培军; A·德克梅日安; J·A·M·卡尼克; C·L·西姆斯; R·阿伯哈里; C·A·加西亚-佛朗哥; D·R·约翰斯拉德
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2002-10-15
Filing date: 2003-10-15
Publication date: 2010-02-10
Anticipated expiration: 2023-10-15
Also published as: CN1820034B; CN1705688A; CN1820034A

Abstract

This invention relates to a polymer comprising one or more C3 to C40 olefins, optionally one or more diolefins, and less than 15 mole % of ehtylene, where the polymer has: a) a Dot T-Peel of 1 Newtonor more; and b) a branching index (g') of 0.95 or less measured at the Mz of the polymer; c) an Mw of 100,000 or less and to a continuous process to produce a branched olefin polymer comprising 1) selecting a first catalyst component capable of producing a polymer having an Mw of 100,000 or less and a crystallinity of 5% or less under selected polymerization conditions; 2) selecting a second catalyst component capable of producing polymer having an Mw of 100,000 or less and a crystallinity of 20% or more at the selected polymerization conditions; 3) contacting the catalyst components in the presence of one or more activators with one or more C3 to C40 olefins, and, optionally one or more diolefins; 4) at a temperature of greater than 100 DEG C; 5) at a residence time of 120 minutes or less; 6) wherein the ratio of the first catalyst to the second catalyst is from 1:1 to 50:1; 7) wherein the activity of the catalyst components is at least 100 kilograms of polymer per gram of the catalyst components; and wherein at least 20% of the olefins are converted to polymer.

Description

Be used for the multi-catalyst system of olefinic polymerization and by the polymkeric substance of its production

Relevant case information

The application require the denomination of invention submitted to on October 15th, 2002 for the provisional application USSN 60/418,482 of " be used for the multi-catalyst system of olefinic polymerization and by the polymkeric substance of its production " as right of priority.The application also require with the denomination of invention submitted on April 4th, 2003 for the USSN 60/460,714 of " polyolefine adhesive composition and goods prepared therefrom " as right of priority.

The US2000000199093P of USSN 60/199,093 that the application and on April 21st, 2000 submit to and 20 submissions in April calendar year 2001 (requiring with USSN 60/199,093 as right of priority) is relevant.USSN 09/745,394 that the application also December 21 in 60/171,715,2000 mentioned with the USSN that submitted on December 21st, 1999 and the USSN09/746 that mentioned on December 21st, 2000,332 is relevant.The application is also relevant with WO 01/81493.

Technical field

The present invention relates to the method for multi-catalyst olefin polymerization with by the polymkeric substance of its production.The present invention be more particularly directed to produce the method for polyolefine binding agent and by the binding agent of its production.

Background technology

For some application such as binding agent, single polymers does not have the necessary performance combination.The mutual blend of each single polyolefine that usually will have some characteristic is with the useful property of each one-component of expectation combination.The result is generally the blend of the average behaviour of each single performance that presents these single resins.For example EP 0527589 discloses the blend of snappiness lower molecular weight amorphous polypropylene and high molecular isotatic polypropylene, obtains to have balancing machine intensity and flexible composition thus.The snappiness that these composition exhibiting are better than independent isotatic polypropylene, but still lack other physical property.Also there is the insufficient problem of compatibility in the physical blending thing.Unless choose component according to consistency, otherwise they can be separated or a small amount of component migrates to the surface.Reactor blend, be called tight blend (being included in the composition of two or more polymkeric substance that prepare in same reactor or the series reaction device) again, usually be used for head it off, yet the catalyst system that will find under identical environment operation to produce different polymkeric substance is a challenge.

Past has used the multi-catalyst system to produce the reactor blend of various polymkeric substance (being called tight blend again) and other polymer composition.Reactor blend and other still polymer composition are usually thought the physical blending thing that is better than similar polymkeric substance.For example US 6,248, and 832 disclose the polymer composition of producing in the presence of one or more Stereoselective metallocene catalyst systems and at least a non-Stereoselective metallocene catalyst system.The performance of resulting polymers is better than the performance of disclosed physical blending thing among EP 0527589 and the US 5,539,056.

Therefore to be used to produce the multi-catalyst system of new polymer composition be that this area is interested in exploitation.US5 for example, 516,848 disclose with the different purposes based on the transistion metal compound of cyclopentadienyl of two kinds of aikyiaiurnirsoxan beta or non-coordination anion activatory.Especially, embodiment discloses the combination of catalyst compound, for example uses activator such as methylaluminoxane or four (pentafluorophenyl group) boric acid N, accelerine activatory (Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And racemize-Me ₂Si (H ₄Ind) ZrCl ₂, or (Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And Me ₂Si (Ind ₂) HfMe ₂(Ind=indenyl), produce thus have bimodal molecular weight distribution (Mw/Mn), (12 to 52wt% isotactic PP in the product of

embodiment

2,3 and 4) and weight-average molecular weight that degree of isotacticity changes surpass 100,000 and sometimes even up to 1, the polypropylene of 200,000 (for as thermoplastics).Same US 6,184,327 disclose a kind of thermoplastic elastomer that comprises the branched olefin polymer with crystallization side chain and amorphous main chain, wherein at least the side chain of 90mol% be isotactic or syndiotactic polypropylene and at least the main chain of 80mol% be Atactic Polypropelene, this elastomerics is produced by the following method: a) under about 90 ℃ to about 120 ℃ of temperature propylene monomer is contacted with the catalyst composition that comprises chirality solid rigid (stereorigid) transition metal catalyst compound that can produce isotactic or syndiotactic polypropylene in solution; B) a) product and propylene and non-essential one or more copolymerisable monomers are carried out copolymerization with the achirality transition-metal catalyst that can produce Atactic Polypropelene in polymerization reactor; And c) reclaims branched olefin polymer.Similarly, US6,147,180 disclose a kind of synthetic method of thermoplastic polymer composition, and said composition is produced by the following method: polymerization single polymerization monomer production at least 40% ethenyl blocking macromonomer at first, then with this macromonomer and ethylene copolymer.In addition, US6,323,284 disclose a kind of passing through with two kinds of isolating catalyst system copolymerization alpha-olefins and α, and the ω diolefine is produced the method for thermoplastic compounds (mixture of crystallization and amorphous polyolefin multipolymer).

In addition, other people has tested with the rapid method of multistep and has produced new polymer composition.For example EP0366411 disclose by use that two step methods produce have the EPDM main chain and with its at the polyacrylic graftomer of one or more diolefinic monomer position grafted, this two steps method is used different Ziegler-Natta catalyst systems in each step.This graftomer allegedly can be used for improving the impact property of co-blend polypropylene composition.

Although disclosed each polymkeric substance has properties of interest combination in the above-mentioned document, but still need provide other that be suitable for each end-use new with different performance equilibrated novel composition.Especially, also need to find a kind of firm composition that has the binding agent characteristic simultaneously and can use adhesive techniques and device to use.

For the general information in this field, can reference:

1.DeSouza and Casagrande delivers the dual catalyst system paper in calendar year 2001: " Recent Advances in Olefin Polymerization Using Binary Catalyst Systems, Macromol.Rapid Commun.2001,22, No.16 (p1293 to 1301).At 1299 pages, they have reported the propylene system of production " gluing " product.

2. the research of being undertaken by Lieber and Brintzinger recently: " Propene Polymerization with Catalyst Mixtures ContainingDifferent Ansa-Zirconocenes:Chain Transfer to AlkylaluminumCocatalyst and Formation of Stereoblock Polymers " at the field mix thing production stereoblock polypropylene that has different stereoselective metallocene catalysts by use, Macromolecules 2000,33, No.25 (p 9192-9199).Propylene polymerization uses metallocene catalyst H ₄C ₂(Flu) ₂ZrCl ₂, racemize-Me ₂Si (2-Me-4-tBu-C ₅H ₂) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂At MAO (methylaluminoxane) or triisobutyl aluminium (Al ¹Bu ₃)/triphenylcarbenium four (perfluorophenyl borate) (trityl borate) is carried out under existing as catalyst for copolymerization.Make spent mixed catalyst H ₄C ₂(Flu) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂At MAO or AliBu ₃Propylene polymerization under/trityl borate exists generates waxy solid, and this solid can be separated into random (ether is solvable) and isotactic (insoluble) fraction fully.Each fraction does not contain any combination of isotactic and random five unit group types, shows that these catalyst mixtures do not form stereoblock polymer.

3.Aggarwal the various polymkeric substance of the production of delivering: " Structures andProperties of Block Polymers and Multiphase Polymer Systems:AnOverview of Present Status and Future Potential ", S.L.Aggarwal, Sixth Biennial Manchester Polymer Symposium (UMIST Manchester, March 1976).

4. " adopt the selectivity in the propylene polymerization that metallocene catalyst carries out " people such as Resconi, Chem Rev.2000,100,1253-1345.

None directly relates to above-mentioned reference based on the polyolefinic demand that contains the binding agent of amorphous and crystallographic component simultaneously.This type of binding agent of industrial needs is as requiring the obviously surrogate of the blend of the hydrocarbon resin tackifier of amount.

Interested other reference comprises:

1) EP patent: EP 0619325B1, EP 719802B1;

2) US patent/open source literature: 6,207,606,6,258,903,6,271,323,6,340,703,6,297,301, US 2001/0007896A 1,6,184,327,6,225,432,6,342,574,6,147,180,6,114,457,6,143,846,5,998,547,5,696,045,5,350,817, US6,569,965;

3) PCT open source literature: WO 00/37514, WO 01/81493, WO 98/49229, WO98/32784 and WO 01/09200;

4)“Metallocene-Based Branch-Block thermoplastic Elastomers”，Markel，et al.Macromolecules 2000，Volume 33，No.23.pgs.8541-8548。

Summary of the invention

A kind of polymkeric substance that the present invention relates to comprise one or more C3 to C40 alkene, non-essential one or more diolefine and be lower than 15mol% ethene, wherein this polymkeric substance has:

A) some T shape peeling force (Dot T-Peel) 1 newton or bigger; With

B) branch index (g ') 0.95 or lower is with the Mz measurement of polymkeric substance;

C) Mw 100,000 or lower.

The invention still further relates to and relate to a kind of polymkeric substance that comprises one or more C3 to C40 alkene, wherein this polymkeric substance has:

A) some T shape peeling force 1 newton on kraft paper or bigger;

C) Mw 10,000 to 100,000; With

D) melting heat 1 is to 70J/g.

A) some T shape peeling force 1 newton on kraft paper or bigger;

B) branch index (g ') 0.98 or lower is with the Mz measurement of polymkeric substance;

C) Mw 10,000 to 60,000; With

D) melting heat 1 is to 50J/g.

The invention still further relates to a kind of homo-polypropylene or propylene and the multipolymer of 5mol% ethene at the most, it has:

A) isotactic continuous length (isotactic continuous length (isotactic run length) " IRL " is defined as the per-cent of mmmm five unit groups divided by 0.5x mmmr five unit group per-cents) 1 to 30, preferred 3 to 25, more preferably 4 to 20 is measured by carbon 13NMR;

B) r diad per-cent greater than 20%, preferred 20 to 70%, measure by carbon 13NMR; With

C) melting heat 70J/g or lower, preferred 60J/g or lower, more excellent 1 to 55J/g, more preferably 4 are to 50J/g.

The invention still further relates to the polyolefinic method of a kind of production, comprising:

1) choose first catalyst component, this catalyst component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower and degree of crystallinity 5% or lower polymkeric substance;

2) choose second catalyst component, this catalyst component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower and degree of crystallinity 20% or bigger polymkeric substance;

3) these catalyst components are contacted in conversion zone under the condition of choosing with one or more C 3 to C40 alkene in the presence of one or more activators;

4) obtain polymkeric substance.

The invention further relates to the continuation method of production branched olefin polymer, comprising:

3) these catalyst components are contacted with non-essential one or more diolefine with one or more C3 to C40 alkene in the presence of one or more activators;

4) be higher than under 100 ℃ in temperature;

5) in 120 minutes residence time or shorter;

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1;

7) wherein the activity of catalyst component is 100kg polymkeric substance/g catalyst component at least; Wherein at least 20% conversion of olefines is a polymkeric substance.

The accompanying drawing summary

Fig. 1 is with variation of temperature figure for the complex viscosity of embodiment 12,22 and 49 when sample is cooled off with 10 ℃/min.

Fig. 2 is for its branch index of the polymkeric substance g ' of embodiment 4 and 31 productions and the graph of a relation of molecular weight.

Fig. 3 is from the heptane Soxhlet insolubles (top trace) of embodiment 4 extractions and the C-13NMR of the solvable fraction of hexane room temperature (bottom trace).

Fig. 4 is the C-13NMR spectrum of aPP/scPP branched block with respect to scPP and aPP comparison.Comparative sample is once produced with a kind of catalyzer; APP is synthetic with the catalyzer of regulation, and scPP produces with stereospecific catalyst.Top trace is the aPP comparative sample.Middle trace is the scPP comparative sample, and bottom trace is embodiment 4.

Fig. 5 shows from the temperature of the classification sample of embodiment 31 extractions and the relation between the complex viscosity.

Fig. 6 is the DSC trace of the polymkeric substance of embodiment 32 in the table 6.

Technology contents describes in detail

Be explanation the present invention and its claim and easily reference, when relating to the polymer that comprises alkene, the alkene that exists in the polymer is the polymerized form of alkene.

In another embodiment, the polymer that the present invention relates to comprise one or more C3 to C40 alkene (preferred propylene) and be lower than 50mol% ethene, this polymer has:

A) some T shape peeling force 1 to 10,000 newton; With

B) Mz/Mn 2 to 200; And/or

C) Mw is that X and g ' are Y (measuring with the Mz of polymer) according to following table C:

Table C

X(Mw)	Y(g′)
X(Mw)	Y(g′)	100,000 or lower, preferred 80,000 or lower, preferred 70,000 or lower, more preferably 60,000 or lower, more preferably 50,000 or lower, more preferably 40,000 or lower, more preferably 30,000 or lower, more preferably 20,000 or lower, more preferably 10,000 or lower. In some embodiments, X also is at least 7000, more preferably 10,000, more preferably at least 15,000.	0.9 or lower preferred 0.7 or lower preferred 0.5-0.9
75,000 or lower, preferred 70,000 or lower, preferred 60,000 or lower, more preferably 50,000 or lower, more preferably 40,000 or lower, more preferably 30,000 or lower, more preferably 20,000 or lower, more preferably 10,000 or lower. In some embodiments, A also is at least 1000, preferably at least 2000, more preferably at least 3,000, more preferably at least 4,000, more preferably at least 5,000, more preferably at least 7,000, more preferably at least 10,000, more preferably at least 15,000.	0.92 or lower preferred 0.6 or lower preferred 0.4-0.6		0.9 or lower preferred 0.7 or lower preferred 0.5-0.9
	0.92 or lower preferred 0.6 or lower preferred 0.4-0.6	50,000 or lower, more preferably 40,000 or lower, more preferably 30,000 or lower, more preferably 20,000 or lower, more preferably 10,000 or lower. In some embodiments, A also is at least 1000, preferably at least 2000, more preferably at least 3,000, more preferably at least 4,000, more preferably at least 5,000, more preferably at least 7,000, more preferably at least 10,000, more preferably at least 15,000.	0.95 or lower preferred 0.7 or lower preferred 0.5-0.7
30,000 or lower, more preferably 25,000 or lower, more preferably 20,000 or lower, more preferably 15,000 or lower, more preferably 10,000 or lower. In some embodiments, A also is at least 1000, preferably at least 2000, more preferably at least 3,000, more preferably at least 4,000, more preferably at least 5,000, more preferably at least 7,000, more preferably at least 10,000, more preferably at least 15,000.	0.98 or lower preferred 0.7-0.98		0.95 or lower preferred 0.7 or lower preferred 0.5-0.7

In another embodiment, when Mw is 15,000 to 100,000 o'clock, g '＜(10 then^-12Mw ²-10 ^-6Mw+1.0178)。

In some embodiments, g ' is 0.9 or lower, 0.8 or lower, 0.7 or lower, 0.6 or lower, 0.5 or lower, and with the Mz measurement of polymer.

In another embodiment, above-mentioned polymer has 40 to 250 ℃ of peak fusing points (Tm), or 60 to 190 ℃, or 60 to 150 ℃, or 60 to 130 ℃. In some embodiments, the peak fusing point is 60 to 160 ℃. In other embodiments, the peak fusing point is 124-140 ℃. In other embodiments, melting hump is 40-130 ℃.

In another embodiment, above-mentioned polymer also has viscosity (being called again Brookfield viscosity or melt viscosity) 90 under 190 ℃, 000mPasec or lower (measuring according to ASTM D3236 under 190 ℃), or 80,000 or lower, or 70,000 or lower, or 60,000 or lower, or 50,000 or lower, or 40,000 or lower, or 30,000 or lower, or 20,000 or lower, or 10,000 or lower, or 8,000 or lower, or 5000 or lower, or 4000 or lower, or 3000 or lower, or 1500 or lower, or 250 to 6000 mPasec, or 500 to 5500mPasec, or 500 to 3000mPasec, or 500 to 1500mPasec; And/or the viscosity 8000mPasec in the time of 160 ℃ or lower (under 160 ℃, measuring according to ASTM D3236); Or 7000 or lower, or 6000 or lower, or 5000 or lower, or 4000 or lower, or 3000 or lower, or 1500 or lower, or 250 to 6000mPa.sec, or 500 to 5500mPasec, or 500 to 3000mPasec, or 500 to 1500mPasec. In other embodiments, the viscosity in the time of 190 ℃ is 200,000mPasec or lower, depends on application. In other embodiments, viscosity is 50,000mPasec or lower, depends on application.

In another embodiment, above-mentioned polymer also has melting heat of 70J/g or lower, or 60J/g or lower, or 50J/g or lower, or 40J/g or lower, or 30J/g or lower, or 20J/g or lower and greater than 0, or greater than 1J/g, or greater than 10J/g, or be 20 to 50J/g.

In another embodiment, above-mentioned polymer is also had an Xiao A hardness (measuring according to ASTM 2240) 95 or lower, 70 or lower, or 60 or lower, or 50 or lower, or 40 or lower, or 30 or lower, or 20 or lower. In other embodiments, Xiao A hardness is 5 or higher, 10 or higher, or 15 or higher. In some used such as packing material, Xiao A hardness was preferably 60-70.

In another embodiment, polymer of the present invention has Mz/Mn 2 to 200, and preferred 2 to 150, preferred 10 to 100.

In another embodiment, above-mentioned polymer also has 200 ℃ or lower of shear bond fail temperatures (SAFT measures according to ASTM 4498), or 40 to 150 ℃, or 60 to 130 ℃, or 65 to 110 ℃, or 70-80 ℃. In certain embodiments, preferred SAFT 130-140 ℃.

In another embodiment, above-mentioned polymer also has T shape peeling force 1 to 10,000 newton, or 3 to 4000 newton, or 5 to 3000 newton, or 10 to 2000 newton, or 15 to 1000 newton. Point T shape peeling force is measured according to ASTM D 1876, different is that sample is produced by the following method: with 3 inches of two 1 inch x (2.54cm x 7.62cm) brown paper basic unit cut substrate and a binding agent point combination, the volume of binding agent is: occupy about 1 square inch (1 inch=2.54cm) area when when compression under the 500g load. In case after the preparation, all samples (with 2 inches of speed/min) pull open, is recorded the damage destructive power that applies with testing machine in harness test. Record that each specimen reaches the most energetically and it is average, so obtain on average the most energetically, it is recorded as a T shape peeling force.

In another embodiment, above-mentioned polymer also has a couple of days to 1 hardening time second, or 60 seconds or shorter, or 30 seconds or shorter, or 20 seconds or shorter, or 15 seconds or shorter, or 10 seconds or shorter, or 5 seconds or shorter, or 4 seconds or shorter, or 3 seconds or shorter, more or 2 seconds or shorter, or 1 second or shorter.

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

In another embodiment, above-mentioned polymer also has Mz 1,000, and 000 or lower, preferred 15,000 to 1,000,000, or 20,000 to 800,000, or 25,000 to 350,000.

In another embodiment, above-mentioned polymer also can have breaking strain (measuring according to ASTM D-1708) 50 to 1000%, preferred 80 to 200% under 25 ℃. In some of the other embodiments, breaking strain is 100 to 500%.

In another embodiment, polymer described herein has fracture tensile strength (measuring according to ASTM D-1708) 0.5MPa or higher under 25 ℃, or 0.75MPa or higher, or 1.0MPa or higher, or 1.5MPa or higher, or 2.0MPa or higher, or 2.5MPa or higher, or 3.0MPa or higher, or 3.5MPa or higher.

In another embodiment, above-mentioned polymer also has 20 to 110 ℃ of crystalline temperatures (Tc). In some embodiments, Tc is 70 to 100 ℃. In other embodiments, Tc is 30 to 80 ℃. In other embodiments, Tc is 20 to 50 ℃.

In some embodiments, above-mentioned polymer has slope-0.1 or lower in temperature Tc+10 ℃ to Tc+40 ℃ scope in as shown in Figure 1 complex viscosity and temperature trace, preferably-0.15 or lower, more preferably-0.25 or lower (under nitrogen atmosphere and 10 ℃/min of cooldown rate by the ARES dynamic mechanically spectrometer measurement with frequency 10rad/s and strain 20% operation). Slope is defined as log (complex viscosity) with respect to the derivative of temperature.

In another embodiment, the Tc of above-mentioned polymer is lower than at least 10 ℃ of Tm, preferably is lower than at least 20 ℃ of Tm, preferably is lower than at least 30 ℃ of Tm, more preferably less than at least 35 ℃ of Tm.

In another embodiment, more above-mentioned polymer have melt index (MI) than (I₁₀/I ₂) 6.5 or lower, preferred 6.0 or lower, preferred 5.5 or lower, preferred 5.0 or lower, preferred 4.5 or lower, preferred 1 to 6.0 (I₁₀And I₂Measure in that 2.16kg and 190 ℃ are lower according to ASTM 1238D).

In another embodiment, more above-mentioned polymer have melt index (MI) (measuring in that 2.16kg and 190 ℃ are lower according to ASTM 1238 D) 25dg/min or higher, preferred 50dg/min or higher, preferred 100dg/min or higher, more preferably 200dg/min or higher, more preferably 500dg/min or higher, more preferably 2000dg/min or higher.

In another embodiment, polymer has melt index (MI) 900dg/min or higher.

In another embodiment, it is wide that above-mentioned polymer has in the DSC trace 10 to 60 ℃ of crystallization ranges, and preferred 20 to 50 ℃, preferred 30 to 45 ℃. Have therein in the DSC trace at two or more non-overlapped peaks, it is wide that each peak has in the DSC trace 10 to 60 ℃ of crystallization ranges, and preferred 20 to 50 ℃, preferred 30 to 45 ℃.

In another embodiment, the polymer that the present invention produces has molecular weight distribution (Mw/Mn) at least 2, and preferably at least 5, preferably at least 10, further more preferably at least 20.

In another embodiment, the polymer of production can have single mode, bimodal or the multi-modal molecular weight distribution (Mw/Mn) of polymer material, measures by size exclusion chromatography (SEC). Bimodal or the multi-modal SEC of referring to trace have more than a peak or flex point. Flex point is that the second dervative signal of wherein curve changes the point of (for example just becoming or on the contrary from negative).

In another embodiment, above-mentioned polymer has activation energy 8 to 15cal/mol. Activation energy calculates owing to the relation in the zone of fuel factor (being assumed to similar Arrhenius relation) with complex viscosity and therein viscosity rising of temperature.

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

In another embodiment, above-mentioned polymkeric substance also can have one or more following performances:

A) the peak fusing point is 60 to 190 ℃, or 60 to 150 ℃, or 80 to 130 ℃; And/or

B) the viscosity 8000mPasec in the time of 190 ℃ or lower (under 190 ℃, measuring) according to ASTMD 3236, or 5000 or lower, or 4000 or lower, or 3000 or lower, or 1500 or lower, or 250 to 6000mPasec, or 500 to 5500mPasec, or 500 to 3000mPasec, or 500 to 1500mPasec; And/or the viscosity 8000mPasec in the time of 160 ℃ or lower (under 160 ℃, measuring) according to ASTM D3236; Or 7000 or lower, or 6000 or lower, or 5000 or lower, or 4000 or lower, or 3000 or lower, or 1500 or lower, or 250 to 6000mPa.sec, or 500 to 5500mPasec, or 500 to 3000mPasec, or 500 to 1500mPasec; And/or

C) H _f(melting heat) 70J/g or lower, or 60J/g or lower, or 50J/g or lower, or 40J/g or lower, or 30J/g or lower, or 20J/g or lower and, or greater than 1J/g, or greater than 10J/g greater than 0, or 20 to 50J/g; And/or

D) Xiao A hardness (measuring) 90 or lower according to ASTM 2240, or 80 or lower, or 70 or lower, or 60 or lower, or 50 or lower, or 40 or lower; And/or

E) shear bond fail temperature (SAFT measures according to ASTM 4498) is 40 to 150 ℃, or 60 to 130 ℃, or 65 to 110 ℃, or 70-80 ℃; And/or

F) some T shape peeling force 1 to 10,000 newton, or 3 to 4000 newton, or 5 to 3000 newton, or 10 to 2000 newton, or 15 to 1000 newton; And/or

G) a couple of days to 0.1 set time second, or 60 seconds or shorter, or 30 seconds or shorter, or 20 seconds or shorter, or 15 seconds or shorter, or 10 seconds or shorter, or 5 seconds or shorter, or 4 seconds or shorter, or 3 seconds or shorter, more or 2 seconds or shorter, or 1 second or shorter; And/or

H) Mw/Mn is greater than 1 to 75, or 2 to 60, or 2 to 50, or 3 to 20; And/or

I) Mz 1,000, and 000 or lower, preferred 15,000 to 500,000, or 20,000 to 400,000, or 25,000 to 350,000.

Useful property combination comprises aforesaidly having T shape peeling force 1 to 10,000 newton, or 3 to 4000 newton, or 5 to 3000 newton, or 10 to 2000 newton, or the polymkeric substance of 15 to 1000 newton and following performance:

1.Mw 30,000 or lower, 60 to 190 ℃ of peak fusing points, melting heat 1 to 70J/g, branch index (g ') 0.90 or lower (Mz with polymkeric substance measures) and the melt viscosity 8000mPasec in the time of 190 ℃ or lower; Or

2.Mz 20,000 to 500,000 and 60 to 150 ℃ of SAFT; Or

3.Mz/Mn 2-200 and set time 2 seconds or shorter; Or

4.H _f(melting heat) 20 to 50J/g, Mz 20,000-500,000 and Shore hardness 50 or lower; Or

5.Mw/Mn the viscosity 5000mmPasec during greater than 1 to 50,190 ℃ or lower; Or

6.Mw 50,000 or lower, 60 to 190 ℃ of peak fusing points, melting heat 2 to 70J/g, branch index (g ') 0.70 or lower (Mz with polymkeric substance measures) and the melt viscosity 8000mPas ec in the time of 190 ℃ or lower.

In preferred embodiments, polymkeric substance of the present invention comprises amorphous, crystallization and branched block structure.

In preferred embodiments, polymkeric substance comprises 50wt% propylene at least, preferably at least 60% propylene, or at least 70% propylene, or at least 80% propylene.In another embodiment, polymkeric substance comprises propylene and 15mol% ethene or lower, preferred 10mol% ethene or lower, more preferably 9mol% ethene or lower, more preferably 8mol% ethene or lower, more preferably 7mol% ethene or lower, more preferably 6mol% ethene or lower, more preferably 5mol% ethene or lower, more preferably 4mol% ethene or lower, more preferably 3mol% ethene or lower, more preferably 2mol% ethene or lower, more preferably 1mol% ethene or lower.

In another embodiment, polymkeric substance of the present invention comprises and is lower than 5mol% ethene, preferably is lower than 4.5mol% ethene, preferably be lower than 4.0mol% ethene, or be lower than 3.5mol% ethene, or be lower than 3.0mol% ethene, or be lower than 2.5mol% ethene, or be lower than 2.0mol% ethene, or be lower than 1.5mol% ethene, or be lower than 1.0mol% ethene, or be lower than 0.5mol% ethene, or be lower than 0.25mol% ethene, or be lower than 0mol% ethene.

In another embodiment, the polymkeric substance of production has 5 ℃ or lower of second-order transition temperatures (Tg), and preferred 0 ℃ or lower, preferred-5 ℃ or lower, or-5 ℃ to-40 ℃, or-5 ℃ to-15 ℃, according to ASTM E 1356 measurements

In another embodiment, polymkeric substance of the present invention has amorphous content at least 50%, or at least 60%, or at least 70%, or even 50 to 99%.Amorphous percentage composition is measured according to ASTM E 794-85 with difference formula scanning calorimetry.

In another embodiment, polymkeric substance of the present invention has percent crvstallinity 40% or lower, and perhaps 30% or lower, perhaps 20% or lower, or even 10% to 30%.Percent crvstallinity content is measured according to ASTM E 794-85 with difference formula scanning calorimetry.In another embodiment, polymkeric substance described herein has percent crvstallinity 5 to 40%, and perhaps 10 to 30%.

In another embodiment, the polymkeric substance of producing by the present invention has molecular weight distribution (Mw/Mn) at least 1.5, and preferably at least 2, preferably at least 5, preferably at least 10, or even at least 20.In other embodiments, Mw/Mn is 20 or lower, 10 or lower, even 5 or lower.Molecular weight distribution generally depends on the catalyzer of use and processing condition such as temperature, monomer concentration, catalyst ratio (if using multi-catalyst), or does not have hydrogen.The consumption of hydrogen can be 2wt% at the most, but is preferably 50 to 500ppm.

In another embodiment, find that the polymkeric substance of producing has at least two kinds of molecular weight fractions, its amount is preferably greater than 20wt% greater than 2wt%, separately by polymer weight, passes through gel permeation chromatography.These fractions can be determined by observing two kinds of different molecular weight modes on the GPC trace.An example is to be presented at 20, peak at 000Mw place and 50, and the GPC trace at another peak at 000Mw place, wherein the representative of the area under first peak is greater than the polymkeric substance of 2wt%, and the area representative under second peak is greater than the polymkeric substance of 2wt%.

In another embodiment, polymkeric substance of the present invention has the solvable fraction of hexane room temperature of 20wt% or higher (based on the weight of starting polymer), with 70wt% or lower, preferred 50wt% or lower Soxhlet ebullient heptane insolubles are based on polymer weight.The Soxhlet heptane insolubles is meant the wherein a kind of fraction that obtains during with continuous solvent extraction technology classification when with sample.This classification process carries out in two steps: a step relates to the room temperature solvent extraction, and another step is a Soxhlet extractron.In the room temperature solvent extraction, about 1g polymkeric substance is dissolved in the 50ml solvent (for example hexane) to separate amorphous or the very low molecular weight material.With this mixture stir about 12 hours at room temperature.Solvable fraction is separated from insoluble substance by filtering under vacuum.Then insoluble substance is carried out Soxhlet extractron technology.This extraction relates to based on it and has boiling point just above the solubleness isolating polymer fraction in all kinds of SOLVENTS of room temperature to 110 ℃.Will be from the solvent-extracted insoluble substance of room temperature at first with the extraction (Soxhlet) of spending the night of for example hexane and heptane; Weigh by evaporating solvent recovery extracting substance and with resistates.Then with insoluble sample with having the solvent of higher boiling temperature such as heptane extracts and carry out after the solvent evaporation it being weighed.Will from the insolubles of final step and sleeve pipe in stink cupboard dry air to evaporate most of solvent, dry in the vacuum drying oven of nitrogen purge then.Calculate the amount of insoluble substance remaining in the sleeve pipe then, condition is the tare weight of known sleeve.

In another embodiment, the polymkeric substance that the present invention produces has heptane insoluble fraction 70wt% or lower, has branch index g ' 0.9 (preferred 0.7) or lower based on the weight and the heptane insoluble fraction of starting polymer, measures with the Mz of polymkeric substance.In preferred embodiments, this composition has the solvable fraction of hexane of 20wt% at least, based on the weight of starting polymer.In another embodiment, the polymkeric substance that the present invention produces has heptane insoluble fraction 70wt% or lower, based on the weight and the heptane insoluble Mz 20,000 to 5000,000 partly of starting polymer.In preferred embodiments, this composition also has the solvable fraction of hexane of 20wt% at least, based on the weight of starting polymer.In another embodiment, the polymkeric substance of production has the hexane soluble part of 20wt% at least, based on the weight of starting polymer.

In another embodiment, polymkeric substance comprises propylene and 15mol% ethene or lower, preferred 10mol% ethene or lower, more preferably 9mol% ethene or lower, more preferably 8mol% ethene or lower, more preferably 7mol% ethene or lower, more preferably 6mol% ethene or lower, more preferably 5mol% ethene or lower, more preferably 4mol% ethene or lower, more preferably 3mol% ethene or lower, more preferably 2mol% ethene or lower, more preferably 1mol% ethene or lower.

In another embodiment, polymkeric substance of the present invention comprises the ethene that is lower than 5mol%, preferably is lower than 4.5mol% ethene, preferably be lower than 4.0mol% ethene, or be lower than 3.5mol% ethene, or be lower than 3.0mol% ethene, or be lower than 2.5mol% ethene, or be lower than 2.0mol% ethene, or be lower than 1.5mol% ethene, or be lower than 1.0mol% ethene, or be lower than 0.5mol% ethene, or be lower than 0.25mol% ethene, or 0mol% ethene.

Be easy reference, also will be called " semi-crystalline polymer ", will be lower than 5% polymkeric substance and be called " amorphous polymer " by the degree of crystallinity that has of first kind of catalyst component production by the polymkeric substance with at least 20% degree of crystallinity of second kind of Catalyst Production.

In another embodiment of the present invention, the polymkeric substance of production has three district's complex viscosity-temperature graphs of feature, as shown in Figure 1.The temperature dependency of complex viscosity is measured under nitrogen atmosphere and 10 ℃/min of rate of cooling in order to the ARES dynamic mechanically spectrograph of frequency 10rad/s and strain 20% operation.At first, be cooled to room temperature then gradually, monitor the rising of complex viscosity simultaneously the sample fusing.When being higher than fusing point (this temperature is typical polymer processing temperature), complex viscosity low relatively (I district), it reduces rising gradually with temperature.In the II district, when temperature descended, raising suddenly appearred in complex viscosity.The 3rd district (III district) is high complex viscosity district, and it occurs under the lesser temps that is equivalent to application (the final use) temperature.In the III district, complex viscosity is high and further reduce slight the variation with temperature.This complex viscosity pattern is provided at the desirable combination that length under the processing temperature is opened wide time and fast set time at a lower temperature in the hot melts binding agent is used.

In preferred embodiments, here the polymkeric substance of producing that is lower than 1mol% ethene that has has at least 2mol%, preferred 4mol%, preferred 6mol%, more preferably 8mol%, more preferably 10mol%, more preferably 12mol%, more preferably 15mol%,, more preferably 18mol%, the more preferably (CH of 5mol% ₂) ₂The unit is measured by carbon 13NMR as described below.

In another embodiment, the polymkeric substance of producing here with 1 to 10mol% ethene has at least 2+X mol%, preferred 4+X mol%, preferred 6+X mol%, more preferably 8+X mol%, more preferably 10+X mol%, more preferably 12+X mol%, more preferably 15+X mol%, more preferably 18+X mol%, more preferably 20+X mol% (CH ₂) ₂The unit, wherein X is the mol% of ethene, (CH ₂) ₂The unit is measured by carbon 13NMR as described below.

In preferred embodiments, here the polymkeric substance of producing that is lower than 1mol% ethene that has has amorphous component (its be defined as have degree of crystallinity be lower than 5% polymer composition part), and this component comprises at least 3mol%, preferred 4mol%, preferred 6mol%, more preferably 8mol%, more preferably 10mol%, more preferably 12mol%, more preferably 15mol%, more preferably 18mol%, the more preferably (CH of 20mol% ₂) ₂The unit is measured by carbon 13NMR as described below.

In another embodiment, here the polymkeric substance with 1 to 10mol% ethene of Sheng Chaning has amorphous component (its be defined as have degree of crystallinity be lower than 20% polymer composition part), this component comprises at least 3+X mol%, preferred 4+X mol%, preferred 6+X mol%, more preferably 8+X mol%, more preferably 10+X mol%, more preferably 12+X mol%,, more preferably 15+Xmol%, more preferably 18+X mol%, more preferably 20+X mol% (CH ₂) ₂The unit, wherein X is the mol% of ethene, (CH ₂) ₂The unit is measured by carbon 13NMR as described below.

Monomer

In preferred embodiments, polymkeric substance comprises olefin homo or the multipolymer that contains one or more C3 to C40 alhpa olefins.In another preferred embodiment, olefin polymer further comprises one or more diolefine comonomers, preferably one or more C4 to C40 diolefine.

In preferred embodiments, polymkeric substance comprises olefin homo or multipolymer, and it has the 5mol% of being lower than ethene and comprises one or more C3 to C40 alhpa olefins.In another preferred embodiment, have the olefin polymer that is lower than 5mol% ethene, further comprise one or more diolefine comonomers, preferably one or more C4 to C40 diolefine.

In preferred embodiments, the polymkeric substance of producing here is alfon or multipolymer.Comonomer is preferably C4 to C20 linearity, branching or cyclic monomer, be C4 to C12 linearity or branching alhpa olefin in one embodiment, preferred butylene, amylene, hexene, heptene, octene, nonene, decene, dodecylene, 4-methyl-amylene-1,3-methylpentene-1,3,5,5-trimethylammonium-hexene-1 or the like.The amount of ethene can be 5mol% or lower.

In another embodiment, the polymkeric substance of producing here is for can or containing the alkene of C5 to C30 ring or the multipolymer of its combination by Stereoselective and non-one or more linearities of stereospecific catalyst polymeric or branching C3 to C30 prochirality alpha-olefin.Prochirality used herein is meant the monomer that helps to form isotactic or syndiotactic polymer when with the stereospecific catalyst polymerization.

The polymerizable olefinic partly can be linearity, branching or contains the mixture of ring or these structures.Preferred linear alpha-alkene comprises C3 to C8 alpha-olefin, more preferably propylene, 1-butylene, 1-hexene and 1-octene, further more preferably propylene or 1-butylene.Preferred branching alpha-olefin comprises 4-methyl-1-pentene, 3-Methyl-1-pentene, 3,5,5-trimethylammonium-1-hexene, 5-ethyl-1-nonene.Preferably contain the aromatic group monomer and comprise 30 carbon atoms at the most.Suitable contain the aromatic group monomer comprise at least one, preferred 1 to 3 aromatic structure, more preferably phenyl, indenyl, fluorenyl or naphthyl moiety.The monomer that contains aromatic group further comprises at least one polymerizable double bond, and after polymerization, aromatic structure will be the side group of auto-polymerization owner chain like this.This monomer that contains aromatic group can further be replaced by one or more alkyl (including but not limited to C1 to C10 alkyl).In addition, two adjacent substituting groups can be connected to form ring structure.The monomer that preferably contains aromatic group comprises that at least one is attached to the aromatic structure on the polymerizable olefinic part.Particularly preferred aromatic monomer bag vinylbenzene, alpha-methyl styrene, to ring-alkylated styrenes, Vinyl toluene, vinyl naphthalene, allyl benzene and indenes, particularly vinylbenzene, p-methylstyrene, 4-phenyl-Bu butylene and allyl benzene.

The monomer that contains non-aromatics cyclic group also is preferred.These monomers can comprise 30 carbon atoms at the most.The suitable monomer that contains non-aromatics cyclic group preferably has at least one polymerizable olefinic group, and this ethylenic group is the side group on the ring structure or the part of ring structure.This ring structure also can further be replaced by one or more alkyl (including but not limited to C1 to C10 alkyl).The monomer that preferably contains non-aromatics cyclic group comprises vinyl cyclohexane, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, cyclopentadiene, cyclopentenes, tetrahydrobenzene, cyclobutene, vinyl diamantane etc.

Can be used for preferred diolefinic monomer of the present invention and comprise any hydrocarbon structure with at least two unsaturated link(age)s, preferred C4 to C30, wherein at least two unsaturated link(age)s are introduced in the polymkeric substance by Stereoselective or non-stereospecific catalyst easily.Diolefinic monomer further is preferably selected from α, ω-diolefinic monomer (i.e. two-vinyl monomer).The more preferably linear two-vinyl monomer of diolefinic monomer most preferably is those that contain 4 to 30 carbon atoms.The example of preferred diolefine comprises divinyl, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, 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, the tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, particularly preferred diolefine comprises 1, the 6-heptadiene, 1, the 7-octadiene, 1, the 8-nonadiene, 1, the 9-decadiene, 1,10-11 carbon diene, 1,11-12 carbon diene, 1, the 12-oleatridecadiene, 1,13-14 carbon diene and low molecular weight polybutadiene (Mw is lower than 1000g/mol).Preferred cyclodiene is included in that each ring position has or cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, the Dicyclopentadiene (DCPD) of unsubstituted or contain the diolefine of senior ring.

In preferred embodiments, amount in the polymkeric substance that one or more diolefine are here produced for 10wt% at the most, preferred 0.00001 to 1.0wt%, preferred 0.002 to 0.5wt%, further more preferably 0.003 to 0.2wt%, by the gross weight of forming.In some embodiments, or still less, with 500pm preferred 400ppm or still less, preferred 300ppm or diolefine still less add in the polymerization.In other embodiments, will be at least 50ppm or 100ppm or more or 150ppm or more diolefine add in the polymerization.

In preferred embodiments, olefin polymer is a homo-polypropylene.In another preferred embodiment, olefin polymer comprises propylene, ethene, preferably is lower than 5mol% ethene and at least a divinyl comonomer.In another preferred embodiment, olefin polymer comprises propylene and at least a divinyl comonomer.

In another embodiment, olefin polymer comprises:

First monomer, its amount be 40 to 95mol%, preferred 50 to 90mol%, preferred 60 to 80mol% and

Comonomer, its amount be 5 to 40mol%, preferred 10 to 60mol%, more preferably 20 to 40mol% and

The 3rd monomer (termonomer), its amount are 0 to 10mol%, more preferably 0.5 to 5mol%, more preferably 1 to 3mol%.

In preferred embodiments, first monomer comprises one or more arbitrary C3 to C8 linearities, branching or ring-type alpha-olefin, comprises propylene, butylene (with its all isomer), amylene (with its all isomer), hexene (with its all isomer), heptene (with its all isomer) and octene (with its all isomer).Preferred monomer comprises propylene, 1-butylene, 1-hexene, 1-octene etc.

In preferred embodiments, comonomer comprises that (condition is if there is ethene for one or more arbitrary C2 to C40 linearities, branching or ring-type alpha-olefin, its amount is 5mol% or lower), comprise ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, cetene, vinylbenzene, 3,5,5-trimethylammonium hexene-1,3-methylpentene-1,4-methylpentene-1, norbornylene and cyclopentenes.

In preferred embodiments, the 3rd monomer comprises one or more arbitrary C2 to C40 linearities, branching or ring-type alpha-olefin (optimal ethylene, if exist, its amount is 5mol% or lower), include but not limited to ethene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, undecylene, dodecylene, cetene, divinyl, 1, the 5-hexadiene, 1, the 6-heptadiene, 1, the 4-pentadiene, 1, the 7-octadiene, 1, the 8-nonadiene, 1, the 9-decadiene, 1,11-12 carbon diene, vinylbenzene, 3,5,5-trimethylammonium hexene-1,3-methylpentene-1,4-methylpentene-1 and cyclopentadiene.

In preferred embodiments, polymkeric substance comprises propylene and 0 to 50mol% ethene, preferred 0 to 30mol% ethene, more preferably 0 to 15mol% ethene, more preferably 0 to 10mol% ethene, more preferably 0 to 5mol% ethene.

In preferred embodiments, polymkeric substance comprises propylene and 0 to 50mol% butylene, preferred 0 to 30mol% butylene, more preferably 0 to 15mol% butylene, more preferably 0 to 10mol% butylene, more preferably 0 to 5mol% butylene.

In preferred embodiments, polymkeric substance comprises propylene and 0 to 50mol% hexene, preferred 0 to 30mol% hexene, more preferably 0 to 15mol% hexene, more preferably 0 to 10mol% hexene, more preferably 0 to 5mol% hexene.

Method

The invention further relates to the method for producing above-mentioned olefin polymer, comprising:

1) choose first catalyst component, this component can be produced has Mw100, and 000 or lower and melting heat 10J/g or lower polymkeric substance;

2) choose second catalyst component, this component can be produced has Mw100, and 000 or lower and degree of crystallinity 20% or higher polymkeric substance;

3) these catalyst components are contacted in conversion zone with one or more alkene in the presence of one or more activators.

3) these catalyst components are contacted in conversion zone with one or more diolefine with one or more alkene in the presence of one or more activators.

1) choose first catalyst component, this component can be produced has Mw100, and 000 or lower and melting heat 70J/g or lower polymkeric substance, the macromonomer that can polymerization has reactive terminal;

2) choose second catalyst component, this component can be produced has reactive terminal, Mw100, and 000 or lower and degree of crystallinity 30% or higher macromonomer;

3) these catalyst components are contacted at conversion zone with non-essential diolefine with one or more alkene in the presence of one or more activators.

1) choose first catalyst component, this component can be produced has Mw30, and 000 or lower and melting heat 10J/g or lower polymkeric substance, the macromonomer that can polymerization has reactive terminal;

2) choose second catalyst component, this component can be produced has reactive terminal, Mw30, and 000 or lower and degree of crystallinity 20% or higher macromonomer;

3) these catalyst components are contacted at conversion zone with non-essential other alkene with propylene in the presence of one or more activators.

In another preferred embodiment, the present invention relates to the continuation method of production branched olefin polymer, comprising:

1) chooses first catalyst component, this component can be produced under the polymerizing condition of choosing has Mw100,000 or lower, preferred 80,000 or lower, preferred 60,000 or lower and degree of crystallinity 5% or lower, preferred 3% or lower, more preferably 2% or lower polymkeric substance;

2) choose second catalyst component, this component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower, preferred 80,000 or lower, preferred 60,000 or lower and degree of crystallinity 20% or higher, preferred 30% or higher, more preferably 40% or higher polymkeric substance;

3) under the polymerizing condition of choosing with these catalyst components in the presence of one or more activators with one or more C3 to C40 alkene, preferably one or more C3 to C 12 alkene, preferred C3 and one or more ethene with or C4 to C20 comonomer contact with non-essential one or more diolefine, preferred C4 to C20 diolefine;

4) temperature be higher than 70 ℃, preferably be higher than 100 ℃, preferably be higher than 105 ℃, more preferably be higher than 110 ℃, more preferably be higher than under 115 ℃;

5) 120 minutes residence time or shorter, preferred 60 minutes or shorter, preferred 50 minutes or shorter, preferred 40 minutes, preferred 30 minutes or shorter, preferred 25 minutes or shorter, more preferably 20 minutes or shorter, more preferably 15 minutes or shorter, more preferably at 10 minutes or shorter, more preferably 5 minutes or shorter, more preferably 3 minutes or shorter under, or the residence time can be 60 to 120 minutes;

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1, preferred 1: 1 to 20: 1, and more preferably 1: 1 to 1: 10;

7) wherein the activity of catalyst component is 3kg at least, preferably 50kg, more preferably 100kg, more preferably 200kg, more preferably 300kg, more preferably 400kg, more preferably 500kg polymkeric substance/g catalyst mixture at least at least at least; Wherein at least 80%, preferably at least 85%, more preferably at least 90%,, more preferably at least 95% conversion of olefines is a polymkeric substance.

In another embodiment, first catalyst component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower and degree of crystallinity 5% or lower polymkeric substance, second catalyst component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower and degree of crystallinity 20% or higher polymkeric substance.

In another embodiment, at least 20% more, preferred 20% or more, more preferably 60% or more, more preferably 75% or more, more preferably 85% or more, more preferably 95% or more conversion of olefines be polymkeric substance.

In preferred embodiments, aforesaid method carries out in solution phase, slurry or body phase polymerisation process.

Term is meant continuously in the system of not operating (or attempting operation) under the interrupting or stopping.For example, the continuation method of producing polymkeric substance is the reactant method that adds continuously in one or more reactors and polymeric articles is drawn off continuously wherein.

In another embodiment preferred, in aforesaid method, concentration of reactants is changing 20% or lower, preferred 15% or lower during the residence time in conversion zone, and more preferably 10% or lower.In preferred embodiments, monomeric concentration is keeping constant in conversion zone during the residence time.Monomer concentration advantageous variant 20% or lower, preferred 15% or lower, more preferably 10% or lower, more preferably 5% or lower.

In preferred embodiments, the concentration of catalyst component is keeping constant in conversion zone during the residence time.Monomeric concentration advantageous variant 20% or lower, preferred 15% or lower, more preferably 10% or lower, more preferably 5% or lower.

In preferred embodiments, the concentration of activator is keeping constant in conversion zone during the residence time.Monomeric concentration advantageous variant 20% or lower, preferred 15% or lower, more preferably 10% or lower, more preferably 5% or lower.

In another embodiment preferred, in aforesaid method, can there be the 3rd catalyzer (or more kinds of).The 3rd catalyzer can be arbitrary catalyst component of listing here.Preferred the 3rd catalyzer comprises the catalyzer that can produce wax.Other preferred the 3rd catalyzer can comprise any catalyzer described herein.Can choose the catalyzer that two or more productions have the various macromonomers of reactive terminal, use with catalyst combination that can these macromonomers of polymerization.Two or more catalyzer that can the polymerization macromonomer can be chosen and a kind of catalyzer of macromonomer can be produced with reactive terminal.Similarly, also can be chosen at three kinds of catalyzer producing different polymkeric substance under the identical reaction conditions.For example can choose the catalyzer of producing slight crystalline polymer, produce the catalyzer of highly crystalline polymkeric substance and produce the catalyzer of amorphous polymer, wherein any catalyzer can be produced the polymkeric substance that macromonomer with reactive terminal or polymerization have reactive terminal.Similarly, can choose two kinds of catalyzer, a kind of production crystalline polymer, a kind of production amorphous polymer is wherein anyly produced the polymkeric substance that macromonomer with reactive terminal or polymerization have reactive terminal.Similarly, can choose catalyzer, the catalyzer of producing wax of producing slight crystalline polymer and the catalyzer of producing amorphous polymer, wherein anyly produce the polymkeric substance that macromonomer with reactive terminal or polymerization have reactive terminal.

Conversion zone is meant the zone that wherein deactivated catalyst and monomer can react.

The macromonomer that term has a reactive terminal is meant and has 12 or more carbon atoms (preferred 20 or more, more preferably 30 or more, more preferably 12 to 8000 carbon atoms), and has a polymkeric substance that polymerizable is gone into vinyl, vinylidene base, vinylene or other end group in the polymer chain of growing.The macromonomer that term can polymerization has reactive terminal is meant and the macromonomer (it is tending towards molecular weight greater than typical single monomer such as ethene or propylene) with reactive terminal can be introduced the catalyst component in the polymer chain that grow.The ethenyl blocking chain is generally more active than vinylene or vinylidene base end-blocking chain.

In particularly preferred embodiments, the present invention relates to a kind of olefin polymer, its by in identical polymerisation medium in the presence of at least a stereospecific catalyst system and at least a other catalyst system one or more C of copolymerization ₃Or high alpha-olefin and/or one or more di-vinyl monomers and 5mol% ethylene production at the most optionally.This polymerization is preferably carried out in the presence of two kinds of catalyzer simultaneously.So the polymkeric substance of producing can comprise amorphous polymer chains section and crystalline polymer segment, and wherein at least some segments are interconnection.Amorphous and crystalline polymer segment is generally one or more alpha-olefins (optionally comprising 5mol% ethene at the most) and/or one or more have the monomeric multipolymer of at least two ethylenic unsaturated bonds.These unsaturated link(age)s of two classes all are fit to and introduce in the polymer chain of growing by the polycoordination of using first or second catalyst system independently easily, so diolefine are introduced in the polymer segment by two kinds of Catalyst Production in the hybrid catalyst system of the present invention.In preferred embodiments, these monomers with at least two ethylenic unsaturated bonds are diolefine, preferred two-vinyl monomer.At least a portion that it is believed that cross-linked polymer segment mixture is to realize by a part two-vinyl comonomer is introduced in two polymer segments between the composition polymerization period, so produces crosslinked between these segments.

In another embodiment, can in single reaction vessel, prepare and comprise amorphous and polyolefine branch-block compositions aasemi-crystalline component, produce required performance balance thus.Especially, can be in the successive soln reactor spent mixed catalyst and propylene as preferred raw material situ production aPP-g-scPP branched structure.In one embodiment, can select Stereoselective bridged bis-indenyl the 4th Catalyst Production hypocrystalline PP of family macromonomer.(all references at the periodic table of elements all are meant the News at Chemical and Engineering, the periodic table of elements of delivering in 63 (5), 27,1985).Bridging list-cyclopentadienyl heteroatoms the 4th family's catalyzer can be used for making up amorphous PP (aPP) main chain, introduces some hypocrystalline macromonomers (scPP) simultaneously.It is believed that like this and can produce the aPP-g-scPP structure that its " g-" expression polymer type is partially grafted at least.By selecting catalyst, polymeric reaction condition and/or by introducing diolefine properties-correcting agent, can be amorphous and the crystallographic component various branches of the production block structure that link together.In the chain that effectively introducing is being grown, preferably has the macromonomer of vinyl end group.Also can use the end of the chain degree of unsaturation (vinylene and vinylidene base) of other type.Be not wishing to be bound by theory down, it is believed that branch-segmented copolymer comprises the amorphous main chain that has from the crystallization side chain of scPP macromonomer, and it is believed that side chain is a polypropylene macromers, it can be by using the Preparation of Catalyst that is fit to preparation isotactic or syndiotactic polypropylene under solution polymerization condition.

The preferred reaction method that production has the polypropylene macromers of high-content terminal ethylenyl groups degree of unsaturation is described in US6, in 117,962.The catalyzer that uses be generally solid rigid, chirality or asymmetric bridge metallocenes.For example referring to US4,892,851, US5,017,714, US5,132,281, US5,296,434, US5,278,264, US 5,304, and 614, US5,510,502, WO-A-(PCT/US92/10066), WO-A-93/19103, EP-A2-0577581, EP-A1-0578838 and academic documents " The Influence of Aromatic Substituentson the Polymerization Behaavior of Bridged Zirconocene Catalyst ", Spaleck, W. wait the people, Organometallics 1994,13,954-963, with " ansa-Zirconocene Polymerization Catalysts with Annelated RingLigaands-Effects on Catalytic Activity and Polymer Chaain Lengths ", Brinzinger, people such as H., Orgaanometallics 1994,13,964-970 and the document of wherein quoting.

In some embodiments, it is luxuriant or hafnium is luxuriant that first catalyzer that comprises the solid rigid transition metal precursors catalyst compound that is used for production hypocrystalline polypropylene macromers of the present invention is selected from two (indenyl) zirconiums of racemize bridging.In another embodiment, the transition metal precursors catalyst compound is that two (indenyl) zirconiums of racemize-dimetylsilyl-bridging are luxuriant or hafnium is luxuriant.In another embodiment, the transition metal precursors catalyst compound is two (2-methyl-4-phenyl indenyl) zirconium dichlorides of racemize-dimetylsilyl or hafnium or zirconium dimethyl or hafnium.In another embodiment preferred, transition-metal catalyst is two (indenyl) the luxuriant hafniums of racemize-dimetylsilyl-bridging such as two (indenyl) dimethyl of racemize-dimetylsilyl or hafnium dichloride.

It is believed that branch-block fraction and degree of branching depend on the utilizability of the macromonomer with unsaturated end of the chain and the macromonomer introducing performance of special catalyst.For increasing the total amount of aPP-g-scPP branch-block compositions, can in helping the method scope of macromonomer production and insertion, operate usually.These conditions are described in US6,117,962 and people's such as journal of writings W.Weng Macromol.Ra pid Commun., 2000,21, among the 1103-1107 and the embodiment by wherein further specify.

The sum that it is believed that ethenyl blocking scPP macromonomer is high more, and the probability that makes it introduce the aPP main chain is high more, and therefore branch-block the sum that obtains is high more.

For further increasing the sum of macromonomer, diolefinic monomer can be introduced in the reaction medium with vinyl chain end.Products obtained therefrom is generally the branch-block species that increases sum by isotatic polypropylene segment, Atactic Polypropelene segment with because of the other coupling that brings by the diolefine linking agent and forms.

Crosslinked generally being meant by the two keys of each diolefinic monomer are introduced makes two polymer segments connect in two different polymer segments.So its degree of crystallinity of polymer segment that connects can be identical or different.Also can three or more polymer segments be connected by two or more diolefine on the polymer segment are introduced.

Selecting a kind of consideration of monomer or combination of monomers is that the catalyst system that available two or more that choose are different forms crystallization and amorphous polymer chains section simultaneously.In some embodiments, also need the degree that diolefinic monomer (if existence) is introduced in the crystallization segment is restricted to the amount that does not change its degree of crystallinity basically.It is minimum that the amount of diolefine coupling agent keeps usually, has viscosity 8000mPa.s or lower to guarantee the integrally combined thing for some binding agents application.

As mentioned above, for increasing the total amount of aPP-g-scPP branch-block compositions, can in helping the method scope of macromonomer production and insertion, operate usually.Advantageous conditions comprises:

1) high concentration catalyst is produced semi-crystalline ethylene base end-blocking macromonomer, and/or

2) regulate the Al/ metal ratio; And/or

3) High Operating Temperature; And/or

4) macromonomer is introduced the catalyst structure with high-affinity; And/or

5) residence time of growing relatively; And/or

6) high monomer transformation efficiency (monomer lacks (starvation) condition and strengthens the macromonomer introducing); And/or

7) add properties-correcting agent rate (diolefine) to strengthen the total amount of ethenyl blocking macromonomer.

The other method that strengthens aPP-g-scPP branch block compositions is to add therein vinyl is transferred to the chain-transfer agent that the polymer chain end makes the catalyzer deactivation simultaneously.These chain-transfer agents include but not limited to vinylchlorid, vinyl fluoride, bromine ethene.In the method, alkyl aluminum activator such as aikyiaiurnirsoxan beta (the be generally methylaluminoxane) reactivate of catalyzer by existing.

Similarly, fusing and crystallization property can be selected by catalyzer, comonomer adds and the variation of processing condition such as temperature and catalyst ratio (if use more than one catalyzer) is controlled.

Catalyst compound

Any catalyst compound that can produce required polymer material can be used for implementing the present invention.In the description here, transistion metal compound can be described as catalyst precursor, precursor catalyst compound or catalyst compound, and these terms can exchange use.Catalyst body is the combination of catalyst precursor and activator.

Catalyst compound and selection

Any precursor catalyst compound (catalyst precursor compound) that can produce required polymer material can be used for implementing the present invention.The precursor catalyst compound that can be used for the inventive method comprises metallocene transistion metal compound (each atoms metal comprises, two or three cyclopentadiene parts), Nonmetallocene early transition metal compound (comprising those with acid amides and/or phenates type part), Nonmetallocene rear transition metal compound (comprising those with diimine or diimine pyridyl ligands) and other transistion metal compound.

Usually, can be used for bulky ligand metallocene compound of the present invention (preceding body catalyst) and comprise half or the full lamellar compound that has with one or more bulky ligand of at least one atoms metal bonding.Typical bulky ligand metallocene compound is generally described as one or more bulky ligand and the one or more leavings group that contains with at least one atoms metal bonding.Bulky ligand generally is combined as representative with one or more openings, acyclic or condensed ring or member ring systems or its.These bulky ligand, preferably ring or member ring systems generally are made up of the periodic table of elements 13 to 16 family's atoms, and these atoms are preferably selected from carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium or its combination.The ring or member ring systems most preferably form by carbon atom, as but be not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligands structure or other similar functions ligand structure such as pentadienyl, cyclooctatetraene two bases, cyclobutadiene base or substituted allyl part.Can comprise the phenates that acid amides, phosphide, imines, phosphinimine, amidine salt (amidinates) and ortho position replace with other part that cyclopentadienyl-type ligands has a similar functions.Atoms metal is preferably selected from the periodic table of elements 3 to 15 families or group of the lanthanides or actinium series.This metal is preferably and is selected from 3 to 12 families, more preferably 4,5 and 6 group 4 transition metals, and transition metal most preferably is selected from 4 families.

In one embodiment, can be used for one or more bulky ligand metallocene catalyst compounds that catalyst composition of the present invention comprises that following general formula is represented:

L ^AL ^BMQ ^* _n (1)

Wherein M is the atoms metal of the periodic table of elements and can be 3 to 12 family's metals or be selected from the metal of the group of the lanthanides or the actinium series of the periodic table of elements, and M is preferably 4,5 or 6 group 4 transition metals, and M is 4 group 4 transition metals more preferably, and M is more preferably zirconium, hafnium or titanium further.Bulky ligand L ^AAnd L ^BFor opening, acyclic or fused rings or member ring systems and be any assistant ligand system, comprise cyclopentadienyl ligands or cyclopentadienyl-type ligands, the heteroatoms replacement that does not replace or replace and/or contain heteroatomic cyclopentadienyl-type ligands.The non-limitative example of bulky ligand comprises cyclopentadienyl ligands, ring penta phenanthryl part, indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, dibenzo [b; h] fluorenyl ligand, benzo [b] fluorenyl ligand, cyclooctatetraene two ylidene ligands, ring penta ring dodecylene part, nitrence ylidene ligands, Azulene part, pentalene part, phosphoryl (phosphoyl) part, phosphinimine (WO 99/40125), pyrryl part, pyrazolyl part, carbazyl part, boron benzene part etc.; comprise its hydrogenation variant, as the tetrahydro indenyl part.In one embodiment, L ^AAnd L ^BCan be can with any other ligand structure of M π bonding.In another embodiment, L ^AOr L ^BAtom and molecule amount (MW) surpass 60a.m.u., be preferably greater than 65a.m.u..In another embodiment, L ^AAnd L ^BCan comprise the one or more heteroatomss such as nitrogen, silicon, boron, germanium, sulphur and the phosphorus that combine open, acyclic or preferred condensed ring of formation or member ring systems (helping part) with carbon atom as heterocyclic pentylene Kiev.Other L ^AAnd L ^BBulky ligand includes but not limited to huge acid amides, phosphide, alkoxide, fragrant oxide compound, imide, carboline (carbolides), borollides, porphyrin, phthalocyanine, corrin and the big ring of other polyazo.Each L ^AAnd L ^BCan be bulky ligand independently with the identical or different type of M bonding.In an embodiment of general formula 1, only there is L ^AOr L ^BIn one.

Each L ^AAnd L ^BCan be not replace or independently by all substituent R ^*Binding substances replace.Substituent R ^*Non-limitative example comprise one or more following groups that are selected from: hydrogen or linearity or branched-alkyl, alkenyl, alkynyl group, cycloalkyl, aryl, acyl group, aroyl, alkoxyl group, aryloxy, alkylthio, dialkylamino, alkoxy carbonyl, aryloxycarbonyl, carbomoyl, alkyl-or dialkyl-7-amino formyl radical, acyloxy, amino (amido), virtue is amino or its binding substances.In preferred embodiments, substituent R ^*Have 50 non-hydrogen atoms at the most, preferred 1 to 30 carbon atom, it also can be by halogen or heteroatoms or the replacement of its analogue.Alkyl substituent R ^*Non-limitative example comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc., comprise its all isomer such as the tertiary butyl, sec.-propyls etc.Other alkyl comprises methyl fluoride, fluoro ethyl, and two fluoro ethyls, the iodine propyl group, the bromine hexyl, the organic quasi-metal group that benzyl chloride base and alkyl replace comprises trimethyl silyl, trimethylammonium germyl, methyl diethylsilane base etc.; The organic quasi-metal group that replaces with the halo alkyl comprises three (trifluoromethyl) silyl, methyl-two (difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Comprise for example dimethyl boron with dibasic boryl; Belong to (pnictogen) element group with dibasic phosphorus and comprise dimethyl amine, dimethyl phosphine, diphenylamine, aminomethyl phenyl phosphine, the chalcogen group comprises methoxyl group, oxyethyl group, propoxy-, phenoxy group, methyl sulphur and ethyl sulphur.Non-hydrogen substituent R ^*Comprise atoms carbon, silicon, boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur, germanium etc., comprise alkene, comprise the ethenyl blocking part, as fourth-3-thiazolinyl, third-2-thiazolinyl, own-5-thiazolinyl etc. such as but not limited to the unsaturated substituting group of olefinic.In addition, at least two R ^*Group, preferred two adjacent R groups are connected to form the ring structure with 3 to 30 atoms that are selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or its combination.In addition, substituent R ^*Also can and form double-basis with the carbon σ key of metal M bonding at one end and L bonding.Other part such as at least one leavings group Q ^*Can with the metal M bonding.In one embodiment, Q ^*For having and the unstable part of the single anion of the σ key of M.According to the oxidation state of metal, the numerical value of n is 0,1 or 2, the neutral bulky ligand metallocene catalyst compound of top like this general formula 1 expression.Q ^*The non-limitative example of part comprises weak base such as amine, phosphine, ether, carboxylate salt, diolefine, has alkyl, hydride or halogen etc. or its combination of 1 to 20 carbon atom.In another embodiment, two or more Q ^*Form the part of fused rings or member ring systems.Q ^*Other example of part comprises above-mentioned R ^*Those substituting groups, comprise cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, fourth support base (two Q ^*), pentamethylene base (two Q ^*), methyne (methylidene) (two Q ^*), methoxyl group, oxyethyl group, propoxy-, phenoxy group, two (N-methyl anilides), dimethylformamide, dimethyl phosphide base etc.

In another embodiment, can be used for catalyst composition of the present invention and can comprise one or more bulky ligand metallocene catalyst compounds, the L of its formula of 1 ^AAnd L ^BBy at least one bridged group A ^*Bridging mutually, represent as following general formula 2:

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

The compound of general formula 2 is called bridging bulky ligand metallocene catalyst compound.L ^A, L ^B, M, Q ^*With n be defined above.Bridged group A ^*Non-limitative example comprise the bridged group that contains at least one 13 to 16 family's atom, be commonly referred to the divalence structure division, at least a such as but not limited in carbon, oxygen, nitrogen, silicon, aluminium, boron, germanium and tin or its combination.Preferred bridged group A ^*Comprise carbon, silicon or germanium atom, A ^*Most preferably comprise at least one Siliciumatom or at least one carbon atom.Bridged group A ^*Also can comprise substituent R defined above ^*(comprising halogen and iron).Bridged group A ^*Non-limitative example can be by R ' ₂C, R ' ₂CCR ' ₂, R ' ₂Si, R ' ₂Si CR ' ₂, R ' ₂SiSiR ' ₂R ' ₂Ge, R ' P, R ' N, R ' B represent, wherein R ' is hydride, alkyl, substituted hydrocarbon radical, brine alkyl, replacement brine alkyl, alkyl replacement organic quasi-metal, brine alkyl replacement organic quasi-metal, two replacement boron, two replacement phosphorus genus, replacement chalcogen or halogen group independently, or two or more R ' can be connected to form member ring systems.In one embodiment, the bridging bulky ligand metallocene catalyst compound of general formula 2 has two or more bridged groups A ^*(EP 664301B1).In another embodiment, the bulky ligand metallocene catalyst compound is the bulky ligand L of its formula of 1 and 2 ^AAnd L ^BOn R ^*Those that substituting group is replaced by the substituting group of identical or different quantity on each bulky ligand.In another embodiment, general formula 1 and 2 bulky ligand L ^AAnd L ^BDifferent mutually.

Can be used for other bulky ligand metallocene catalyst compound of the present invention and catalyst system and comprise those that describe in the following document: US5,064,802,5,145,819,5,149,819,5,243,001,5,239,022,5,276,208,5,296,434,5,321,106,5,329,031,5,304,614,5,677,401,5,723,398,5,753,578,5,854,363,5,856,547,5,858,903,5,859,158,5,900,517 and 5,939,503, and WO93/08221, WO93/08199, WO95/07140, WO98/11144, WO98/41530, WO98/41529, WO98/46650, WO99/02540 and WO 99/14221, and EP-A-0578838, EP-A-0638595, EP-B-0513380, EP-A1-0816372, EP-A2-0839834, EP-B1-0632819, EP-B1-0748821 and EP-B1-0757996, all these documents are incorporated herein by reference here.

In another embodiment, can be used for catalyst composition of the present invention and can comprise bridging heteroatoms list bulky ligand metallocene compound.These catalyzer and catalyst system type specification are in following document: WO92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO 99/20637, and US5,057,475,5,096,867,5,055,438,5,198,401,5,227,440 and 5,264,405, and EP-A-0420436, all these documents are incorporated herein by reference here.

In another embodiment, can be used for one or more bulky ligand metallocene catalyst compounds that catalyst composition of the present invention comprises following general formula 3 expressions:

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

Wherein M is the atoms metal of the periodic table of elements 3 to 16 families or is selected from group of the lanthanides or the metal of actinium series, and M is preferably 3 to 12 group 4 transition metals, and M is 4,5 or 6 group 4 transition metals more preferably, and M most preferably is 4 group 4 transition metals that are in any oxidation state, is in particular titanium; L ^CFor with the replacement or the unsubstituted bulky ligand of M bonding, J ^*With the M bonding; A ^*With J ^*And L ^CBonding; J ^*Be the heteroatoms assistant ligand; A ^*Be bridged group; Q ^*Be the monovalent anion part; N is an integer 0,1 or 2.In above-mentioned general formula 3, L ^C, A ^*And J ^*Form the fused rings system.In one embodiment, the L of general formula 3 ^CFor top to L ^ADefinition.A in the general formula 3 ^*, M and Q ^*For what define in the top general formula 1.In general formula 3, J ^*For containing heteroatomic part, wherein J ^*For being selected from the element with three ligancies of the periodic table of elements 15 families, or be selected from the element with two ligancies of 16 families.J ^*Preferred package is nitrogenous, phosphorus, oxygen or sulphur atom, and wherein nitrogen is most preferred.In embodiments of the invention, the bulky ligand metallocene catalyst compound is the heterocyclic ligand title complex, and wherein bulky ligand is encircled or member ring systems, comprises one or more heteroatomss or its combination.Heteroatomic non-limitative example comprises 13 to 16 family's elements, preferred nitrogen, boron, sulphur, oxygen, aluminium, silicon, phosphorus and tin.The example of these bulky ligand metallocene catalyst compounds is described in the following document: WO96/33202, WO 96/34021, WO 97/17379 and WO 98/22486, and EP-A1-0874005 and US5,637,660,5,539,124,5,554,775,5,756,611,5,233,049,5,744,417 and 5,856,258, all documents are introduced as reference here.

In one embodiment, bulky ligand metallocene compound (preceding body catalyst) is those title complexs based on the bitooth ligand that contains pyridine or quinoline moiety, as describing among the US 09/103,620 (application on June 23rd, 1998) those, this application are introduced as reference here.In another embodiment, the bulky ligand metallocene catalyst compound is those that describe among WO99/01481 and the WO 98/42664, and these documents all are incorporated herein by reference here.

In another embodiment, the bulky ligand metallocene catalyst compound is metal, preferred transition metal, bulky ligand, preferably replace or unsubstituted π-ligands bound thereto, with the title complex of one or more assorted allyl group parts, US 5,527,752 and 5,747,406 and EP-B1-0735057 in describe those, all documents are here as with reference to introducing.

In another embodiment, the bulky ligand metallocene catalyst compound is those that describe among WO 99/01481 and the WO 98/42664, and these documents all are incorporated herein by reference here.

6 useful family's bulky ligand metallocene catalyst systems are described in US5, and in 942,462, the document is incorporated herein by reference here.

Other useful catalysts comprises those multinuclear metallocene catalyzer, and as WO 99/20665 and 6,010, those that describe in 794 and transition metal metaaracyle structure as describing among the EP 0969101A2, are incorporated herein by reference here.Other metallocene catalyst comprises those that describe among the EP 0950667A1, double cross connection metallocene catalyst (EP 0970074A1), mooring (tethered) metallocene (EP 970963A2) and US 6; 008; those alkylsulfonyl catalyzer of describing in 394, these documents are incorporated herein by reference here.

Consider that also in one embodiment, above-mentioned bulky ligand metallocene catalyst comprises its structure or optics or enantiomer (meso and racemic isomer for example referring to US 5,852,143, are incorporated herein by reference) and its mixture here.

Consider that also above-mentioned arbitrary bulky ligand metallocene catalyst compound has at least one fluorochemical or fluorine-containing leavings group, as what describe in the US application serial number 09/191,916 (application on November 13rd, 1998)

The compound that contains 15 family's metals that is used for catalyst composition of the present invention prepares by means known in the art, as EP 0893454A1, US5,889, in 128 and US 5, those that describe in the reference of quoting in 889,128, all these documents are incorporated herein by reference here.US application serial number 09/312,878 (application on May 17th, 1999) discloses the gas or the slurry phase polymerisation process of working load bisamide catalyzer, and the document also is incorporated herein by reference here.

Other information for the compound that contains 15 family's metals sees also Mitsui Chemicals, the EP 0893454A1 of Inc., and the document discloses the transition metal acid amides combined with activator and has been used for olefin polymerization.

In one embodiment, the compound that will contain 15 family's metals wears out before being used for polymerization.Notice that under at least a situation, the performance of this catalyst compound (aging at least 48 hours) is better than freshly prepd catalyst compound performance.

Also consider and to use bisamide based precursor catalyzer.Exemplary compound comprises those that describe in the patent documentation.People's such as WO 96/23010, WO 97/48735 and Gibson Chem.Comm., pp.849-850 (1998) discloses the part based on diimine of the 8-10 compounds of group that carries out ion activation and olefin polymerization.From the polymerisation catalyst system of 5-10 family metal, wherein the active centre is described in US5 by high oxidation and stable by low ligancy polyanionic ligand system, in 502,124 and its division US5,504,049.Also can be referring to US5,851,945 5 family's organo-metallic catalyst compound and US6,294,495 contain tridentate ligand 5-10 family organo-metallic catalyst.Can be used for being described among the WO 99/30822 of alkene and vinyl-based polar molecule with ionization promotor activatory 11 family's catalyst precursor compounds.

Other useful catalysts compound is EP-A2-0816384 and US5, those 5 and 6 family metal imino-title complexs of describing in 851,945, and described document is incorporated herein by reference here.In addition, metallocene catalyst comprises bridging two (virtue is amino) 4 compounds of group, is described in Organometallics 1995,14 by people such as D.H.McConville, and among the 5478-5480, the document is incorporated herein by reference here.In addition, two (amino) catalyst compound of bridging are described in WO96/27439, and the document is incorporated herein by reference here.Two (the hydroxyaromatic nitrogen ligand) described among other useful catalysts such as the US 5,852,146, the document is incorporated herein by reference here.Other useful catalysts that contains one or more 15 family atoms comprises those that describe among the WO 98/46651, and the document is incorporated herein by reference here.

US5,318,935 have described bridging and non-bridged two amino catalyst compound of 4 family's metals that can carry out alpha-olefine polymerizing.Bridging two (virtue is amino) 4 compounds of group that are used for olefinic polymerization are described in Organometallics1995 by people such as D.H.McConville, and 14, among the 5478-5480.The document has provided synthetic method and compound characterizes.Further work appears at people's such as D.H.McConville Macromolecules1996,29, among the 5241-5243, this job description as the bridging of 1-hexene polymerizing catalyst two (virtue is amino) 4 compounds of group.Transistion metal compound suitable of the present invention in addition comprises those that describe among the WO96/40805.Positively charged ion 3 families or lanthanide series metal olefinic polymerization title complex are disclosed in the unsettled US application serial number 09/408,050 (September 29 1999 applying date).Single anion bitooth ligand and two kinds of single anion ligands are stablized those catalyst precursors, and this precursor can activate with ion promotor of the present invention.

A lot of extra suitable catalyst precursor compounds have been described on the document.But contain and to capture part or alkylation and make it contain the compound that to capture part to be fit to the present invention.For example referring to people's such as V.C.Gibson " The Search for New-Generation OlefinPolymerization Catalysts:Life Beyond Metallocenes ", Angew.Chem.Int.Ed., 38,428-447 (1999).

The present invention can also implement as those disclosed catalyzer among the EP 0874005A1 with the catalyzer that contains the phenates part, and the document is introduced as reference here.

In another embodiment, the conventional type transition-metal catalyst can be used for implementing the present invention.The conventional type transition-metal catalyst is those conventional Ziegler-Natta well known in the art, vanadium and Phillips type catalyzer.For example Ziegler-Natta catalyst is described in Ziegler-Natta Catalysts and Polymerizations, John Boor, and AcademicPress, New York is in 1979.The example of conventional type transition-metal catalyst also is described in US4, and in 115,639,4,077,904,4,482,687,4,564,605,4,721,763,4,879,359 and 4,960,741, all documents are here as with reference to introducing.Can be used for conventional type transition metal catalyst compound of the present invention comprises and is selected from the periodic table of elements 3 to 17 families, preferred 4 to 12 families, the more preferably transistion metal compound of 4 to 6 families.

Preferred conventional type transition-metal catalyst can be used formula M R _xExpression, wherein M is selected from 3 to 17 families, preferred 4 to 6 families, the more preferably metal of 4 families, most preferably titanium; R is halogen or-oxyl; X is the oxidation state of metal M.The non-limitative example of R comprises alkoxyl group, phenoxy group, bromide, muriate and fluoride-based.Wherein M is that the limiting examples of the conventional type transition-metal catalyst of titanium comprises TiCl ₄, TiBr ₄, Ti (OC ₂H ₅) ₃Cl, Ti (OC ₂H ₅) Cl ₃, Ti (OC ₄H ₉) ₃Cl, Ti (OC ₃H ₇) ₂Cl ₂, Ti (OC ₂H ₅) ₂Br ₂, TiCl ₃1/3AlCl ₃And Ti (OC1 ₂H ₂₅) Cl ₃

Can be used for the conventional type transition metal catalyst compound based on magnesium/titanium electron donor(ED) title complex of the present invention and be described in for example US4, in 302,565 and 4,302,566, the document all is incorporated herein by reference here.Preferred especially MgTiCl ₆(ethyl acetate) ₄Derivative.

UK Patent Application 2,105,355 and US5,317,036 (being incorporated herein by reference here) have been described various conventional type vanadium catalyst compounds.The non-limitative example of conventional type vanadium catalyst compound comprises vanadyl trihalid, alkoxy halide and alkoxide such as VOCl ₃, VOCl ₂(OBu), wherein Bu=butyl, and VO (OC ₂H ₅) ₃Four halogenation vanadium and halogenated alkoxy vanadium such as VCl ₄And VCl ₃(OBu); Vanadium and vanadyl acetylacetonate and chloracetyl acetone solvate such as V (AcAc) ₃And VOCl ₂(AcAc), wherein (AcAc) is acetylacetonate.Preferred conventional type vanadium catalyst compound is VOCl ₃, VCl ₄And VOCl ₂-OR, wherein R is an alkyl, preferred C ₁To C ₁₀Aliphatic series or aromatic hydrocarbyl such as ethyl, phenyl, sec.-propyl, butyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, hexyl, cyclohexyl, naphthyl etc. and vanadium acetylacetonate.

Be applicable to conventional type chrome catalysts compound of the present invention, be commonly referred to Phillips type catalyzer and comprise CrO ₃, luxuriant, the silyl chromate of chromium, chromyl chloride (CrO ₂Cl ₂), chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr (AcAc) ₃) etc.Non-limitative example is described in US 3,709, and in 853,3,709,954,3,231,550,3,242,099 and 4,077,904, these documents all are incorporated herein by reference here.

Be applicable to that other conventional type transition metal catalyst compound of the present invention and catalyst system are disclosed in US4,124,532,4,302,565,4,302,566,4,376,062,4,379,758,5,066,737,5,763,723,5,849,655,5,852,144,5,854,164 and 5,869,585 and EP-A20416815A2 and EP-A10420436 in, these documents all are incorporated herein by reference here.

Other catalyzer can comprise cationic catalyst well known in the art such as AlCl ₃And other cobalt, iron, nickel and palladium catalyst.For example referring to US3,487,112,4,472,559,4,182,814 and 4,689,437, these documents all are incorporated herein by reference here.

Consider that also other catalyzer can combine with the catalyst compound in being applicable to catalyst composition of the present invention.For example, referring to US4,937,299,4,935,474,5,281,679,5,359,015,5,470,811 and 5,719,241, these documents all are incorporated herein by reference here.

Further contemplate, above-mentioned one or more catalyst compound or catalyst system can combine with one or more conventional catalyst compounds or catalyst system.The non-limitative example of mixed catalyst and catalyst system is described in US4, and 159,965,4,325,837,4,701,432,5,124,418,5,077,255,5,183,867,, 5,391,660,5,395,810,5,691,264,5,723,399 and 5,767,031 and WO 96/23010 (open day on August 1st, 1996), all documents are here as with reference to introducing.

Be used for the present invention's preferred metallocene catalysed agent can be more specifically by the expression of one of following general formula (all of family are with reference to being Chemical and Engineering News all, the new family mark of the periodic table of elements of describing in 63 (5), 27,1985):

[{[(A-Cp)MX ₁] ⁺} _d]{[B′] ^d-} (4)

[{[(A-Cp)MX ₁L] ⁺} _d]{B′] ^d-} (5)

Wherein (A-Cp) is (Cp), (Cp ^*) or Cp-A '-Cp ^*Cp and Cp ^*For " the identical or different cyclopentadienyl rings of replacement; each substituting group S " is alkyl, substituted hydrocarbon radical, brine alkyl, replacement brine alkyl, alkyl replacement organic quasi-metal, brine alkyl replacement organic quasi-metal, two replacement boron, two replacement phosphorus genus, replacement chalcogen or halogen group independently by 0 to 5 substituting group S, or Cp and Cp ^*Be cyclopentadienyl rings, " group is connected to form C to wherein any two adjacent S ₄To C ₂₀Ring obtains saturated or unsaturated many ring cyclopentadienyl ligands thus; Cp and Cp ^*Also can in ring, there be one or more carbon atoms to be replaced by 15 or 16 family's elements, particularly S, O, N or P;

A ' is a bridged group;

(C ₅H _5-y-xS " _x) " the cyclopentadienyl that group replaces that is by 0 to 5 S defined above;

X is 0 to 5, the expression substitution value;

M is titanium, zirconium or hafnium;

X ₁Be that hydride group, alkyl, substituted hydrocarbon radical, alkyl replace the organic quasi-metal base or brine alkyl replaces the organic quasi-metal base, these groups can be optionally and one of M and L or both or L ' or all or arbitrary M, S " or S ' covalent bonding, condition is X ₁Not for replacing or unsubstituted cyclopentadienyl rings;

(JS ' _Z-1-y) be heteroatom ligand, wherein J is the element with ligancy 2 that is selected from the element with ligancy 3 of the periodic table of elements 15 families or is selected from the periodic table of elements 16 families; S ' is following group: alkyl, substituted hydrocarbon radical, brine alkyl, replacement brine alkyl, alkyl replace organic quasi-metal or brine alkyl replaces organic quasi-metal; With z be the ligancy of element J;

Y is 0 or 1;

L is alkene, diolefine or aryne part.L ' is identical with L, and can be amine, phosphine, ether or sulfide part, or any other neutral Lewis base; L ' also can be second transistion metal compound of same type, such two metal center M and M ^*Pass through X ₁And X ' ₁Bridging, wherein M ^*Have the implication identical, X ' with M ₁, X ₂And X ' ₂Have and X ₁Identical implication, wherein these dimer compounds that can be the precursor of catalyzer cationic moiety are represented by following general formula:

Wherein w is 0 to 3 integer,

B ' is for having molecular diameter approximately or greater than the chemically stable non-nucleophilic anionic complex of 4 dusts, or from the negatively charged ion Lewis acid activation agent of the precursors reaction of the cationic moiety of the catalyst system of describing among Lewis acid activation agent and the general formula 1-4.When B ' is the Lewis acid activation agent, X ₁Also can be the alkyl that provides by the Lewis acid activation agent; With

D is the integer of expression B ' electric charge.

Catalyzer preferably passes through at least two kinds of components in conjunction with preparation.In a preferred embodiment, first kind of component be contain at least one will with the cyclopentadienyl derivative of 4 family's metallic compounds of second component or its at least a portion such as its at least one part of cationic moiety bonded.Second component is the ion-exchange compound that comprises positively charged ion and non-coordination anion, described positively charged ion will with contained at least a part irreversible reaction in described 4 family's metallic compounds (first component), described non-coordination anion or be comprise the metal or the coordination of metalloid atom covalence of a plurality of and center band forms electric charge and shield described atom lipophilic group single coordinate complex or contain the negatively charged ion of a plurality of boron atoms such as polyhedron borine, carborane and metallocarborane.

Usually, the suitable anion that is used for second component can be the anionic complex of any stable and bulkiness with following molecule attribute: 1) negatively charged ion should have molecular diameter greater than 4 dusts; 2) negatively charged ion should form stable ammonium salt; 3) negative charge on the negatively charged ion answer delocalization on the anionic framework or localization in negatively charged ion nuclear; 4) negatively charged ion should be bad relatively nucleophilic reagent; With 5) negatively charged ion should not be strong reduction or oxidising agent.Satisfy negatively charged ion such as multinuclear borine, carborane, metallocarborane (metallacarborane), polyoxy negatively charged ion and the anion binding title complex of these standards, fully be described in the chemical literature.

The cationic moiety of second component can comprise Bronsted acid such as proton or protonated Lewis base, maybe can comprise Lewis acid such as ferricinium ion,

, triphenylcarbenium or silver-colored positively charged ion.

In another preferable methods, second component is the Lewis acid complex that will react with at least one part of first component, and the part with the present and second component bonding of capturing from first component forms the ionic species of describing the general formula 4-6 thus.Aikyiaiurnirsoxan beta and special methylaluminoxane, promptly trimethyl aluminium reacts the product that forms with stoichiometric water in aliphatic series or aromatic hydrocarbon, is particularly preferred Lewis acid second component.Modified alumoxane also is preferred.Aikyiaiurnirsoxan beta is well known in the art and its preparation method is described in US4, in 542,199,4,544,762,5,015,749 and 5,041,585.The technology of preparation modified alumoxane has been described in US5, and 041,584, among EPA0516476 and the EPA 0561476, these documents are incorporated herein by reference here.

When first and second components in conjunction with the time, a part reaction of second component and first component, it is right to generate the negatively charged ion that is made of 4 family's metallic cations and above-mentioned negatively charged ion thus, this negatively charged ion and compatible and non-with it coordination of 4 family's metallic cations that is formed by first component.The negatively charged ion of second compound must be able to be stablized 4 family's metallic cation abilities and play catalyst action, and must be sufficiently unstable to allow between polymerization period by alkene, diolefine or the displacement of acetylene series unsaturated monomer.Catalyzer of the present invention can be for loading type.US 4,808,561 (authorizing day on February 28th, 1989), 4,897,455 (authorizing day January 3 nineteen ninety), 5,057,475 (mandates on October 15th, 1991), US application serial number 459,921 (being disclosed as WO 91/09882), CA1,268,753, US5,240,894 and WO 9403506 this type of supported catalyst and its production method are disclosed, these documents are incorporated herein by reference here.

Can be used as 4 family's metallic compounds of first compound (preceding body catalyst) in the preferred metallocene catalyst of preparation the present invention, promptly titanium, zirconium and hafnium metallocene compound are the cyclopentadienyl derivative of titanium, zirconium and hafnium.Usually, useful titanium is luxuriant, zirconium is luxuriant and hafnium is luxuriant is represented by following general formula:

(A-Cp)MX ₁X ₂ (8)

(A-Cp)ML (9)

Wherein (A-Cp) is (Cp) (Cp ^*) or Cp-A '-Cp ^*, Cp and Cp ^*For " the identical or different cyclopentadienyl rings of replacement; each substituting group S " is alkyl, substituted hydrocarbon radical, brine alkyl, replacement brine alkyl, alkyl replacement organic quasi-metal, brine alkyl replacement organic quasi-metal, two replacement boron, two replacement phosphorus genus, replacement chalcogen or halogen group independently by 0 to 5 substituting group S, or Cp and Cp ^*Be cyclopentadienyl rings, " group is connected to form C to wherein any two adjacent S ₄To C ₂₀Ring obtains saturated or unsaturated many ring cyclopentadienyl ligands thus;

A ' is a bridged group;

Y is 0 or 1;

X is 0 to 5, the expression substitution value;

L is alkene, diolefine or aryne part.L ' is identical with L, and can be amine, phosphine, ether or sulfide part, or any other neutral Lewis base; L ' also can be second transistion metal compound of same type, such two metal center M and M ^*Pass through X ₁And X ' ₁Bridging, wherein M ^*Have the implication identical, X ' with M ₁Have and X ₁Identical implication, X ' ₂Have and X ₂Identical implication, wherein as this dimer compound of the precursor of catalyzer cationic moiety by above-mentioned general formula 7 expressions;

W is an integer 0 to 3; With

X ₁And X ₂Be independently hydride group, alkyl, substituted hydrocarbon radical, brine alkyl, replacement brine alkyl, alkyl-and brine alkyl replace organic quasi-metal, replace phosphorus and belong to base or replace the chalcogen base; Or X ₁And X ₂Contain about 3 metallacycle rings continuously to about 20 carbon atoms together and with the formation of atoms metal bonding; Or X ₁And X ₂Can be alkene, diolefine or aryne part together; Maybe can be with above-mentioned X when using ₁Part gives the Lewis acid activation agent of transition metal component, during as methylaluminoxane, and X ₁And X ₂Can be halogen, alkoxide, fragrant oxide compound, acid amides, phosphide or other monovalent anion part independently, or X ₁And X ₂Both also can be connected to form the negatively charged ion chelating ligand, and condition is X ₁And X ₂Not for replacing or unsubstituted cyclopentadienyl rings.

Table A has been described the representative component part of the metallocenes of general formula 7-10.This is enumerated and only is used for illustration purpose and should think and limit by any way.A lot of final components can might make up by the mutual institute of conversion component part and form.When openly comprising the alkyl of alkyl, alkenyl, alkynyl group, cycloalkyl, cycloalkenyl, loop chain alkynyl and aromatic group among the application, this term comprises all isomer.For example, butyl comprises normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tertiary butyl and cyclobutyl; Amyl group comprises n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl, neo-pentyl, cyclopentyl and methyl cyclobutyl; Butenyl comprises the E and the Z-shaped formula of 1-butylene base, crotyl, 3-butenyl, 1-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl isophthalic acid-propenyl and 2-methyl-2-propenyl.This comprises the situation when alkyl and another group bonding, and for example the propyl group cyclopentadienyl comprises n-propyl cyclopentadienyl, sec.-propyl cyclopentadienyl and cyclopropyl rings pentadienyl.Usually, part in the Table A or group comprise all isomeric forms.For example, the dimethyl cyclopentadienyl comprises 1,2-dimethyl cyclopentadienyl and 1,3-dimethyl cyclopentadienyl; The methyl indenyl comprises 1-methyl indenyl, 2-methyl indenyl, 3-methyl indenyl, 4-methyl indenyl, 5-methyl indenyl, 6-methyl indenyl and 7-methyl indenyl; The methylethyl phenyl comprises adjacent methylethyl phenyl, a methylethyl phenyl and to the methylethyl phenyl.The example of concrete catalyst precursor of the present invention adopts following general formula, and the some of them component is listed in Table A.For the composition of explanation transition metal component, choose any combination of listed material in the Table A.For the name purpose, for bridged group A ', term " silyl " and " silicylene " commutative use, and expression double-basis material, to bridged group A ', " ethylidene " is meant the ethylene link and with 1, the 1-ethylidene is distinguished mutually.Therefore, for bridged group A ', " ethylidene " and " ethylene " commutative use.For the compound with bridged group A ', the bridge location on the cyclopentadienyl type ring is put and is always thought the 1-position.Therefore, for example " 1-fluorenyl " can use with " fluorenyl " exchange.

The illustrative of compounds of general formula 8 types is: two (cyclopentadienyl) dimethyl hafnium, ethylenebis (tetrahydro indenyl) dihydro (dihidryde) zirconium, two (pentamethyl-) diethyl hafnium, dimetylsilyl (1-fluorenyl) (cyclopentadienyl) titanium dichloride etc.The illustrative of compounds of general formula 9 types is two (cyclopentadienyls) (1, the 3-divinyl) zirconium, two (cyclopentadienyl) (2,3-dimethyl-1,3-butadiene) zirconium, two (pentamethyl-cyclopentadienyl) (benzene) zirconium, two (pentamethyl-cyclopentadienyl) ethylidene titanium etc.The illustrative of compounds of general formula 10 types is: dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) zirconium dichloride, ethylidene (methyl cyclopentadienyl) (phenyl amino) dimethyl titanium, aminomethyl phenyl silyl (indenyl) (phenyl phosphorus base (phosphido)) dihydro hafnium and (pentamethyl-cyclopentadienyl) (di-t-butyl amino) dimethoxy hafnium.

The condition that the conditioned disjunction that coordination contains the part of Lewis base such as ether forms dimer compound is determined by the spatial volume around the part of metal center.For example, Me ₂Si (Me ₄C ₅) (N-t-Bu) ZrCl ₂In the tertiary butyl compare Me ₂Si (Me ₄C ₅) (NPh) ZrCl ₂Et ₂Phenyl among the O has bigger space requirement, does not therefore allow the ether coordination of last compound under its solid state.Similarly, because [Me ₂Si (Me ₃SiC ₅H ₃) (N-t-Bu) ZrCl ₂] ₂In the trimethyl silyl cyclopentadienyl with respect to Me ₂Si (Me ₄C ₅) (N-t-Bu) ZrCl ₂In its spatial volume of tetramethyl-ring pentadienyl reduce, therefore last compound is a dimer, and the latter is not.

Table A

A’	Cp，Cp ^*, CpR or (C ₅H _5-y-xS″ _x)
A’	Cp，Cp ^*, CpR or (C ₅H _5-y-xS″ _x)	The dimethylated methylene silylation	Cyclopentadienyl
The diethyl silicylene	Methyl cyclopentadienyl	The dimethylated methylene silylation	Cyclopentadienyl
The diethyl silicylene	Methyl cyclopentadienyl	The dipropyl silicylene	The dimethyl cyclopentadienyl
The dibutyl silicylene	The trimethylammonium cyclopentadienyl	The dipropyl silicylene	The dimethyl cyclopentadienyl

The diamyl silicylene	The tetramethyl-ring pentadienyl
The diamyl silicylene	The tetramethyl-ring pentadienyl	The dihexyl silicylene	Pentamethyl-cyclopentadienyl (no A ')
The diheptyl silicylene	The ethyl cyclopentadienyl	The dihexyl silicylene	Pentamethyl-cyclopentadienyl (no A ')
The diheptyl silicylene	The ethyl cyclopentadienyl	The dioctyl silicylene	The diethyl cyclopentadienyl
The dinonyl silicylene	The propyl group cyclopentadienyl	The dioctyl silicylene	The diethyl cyclopentadienyl
The dinonyl silicylene	The propyl group cyclopentadienyl	The didecyl silicylene	The dipropyl cyclopentadienyl
Two-undecyl silicylene	The butyl cyclopentadienyl	The didecyl silicylene	The dipropyl cyclopentadienyl
Two-undecyl silicylene	The butyl cyclopentadienyl	Two-dodecyl silicylene	The dibutyl cyclopentadienyl
Two-tridecyl silicylene	The amyl group cyclopentadienyl	Two-dodecyl silicylene	The dibutyl cyclopentadienyl
Two-tridecyl silicylene	The amyl group cyclopentadienyl	Two-tetradecyl silicylene	The diamyl cyclopentadienyl
Two-pentadecyl silicylene	The hexyl cyclopentadienyl	Two-tetradecyl silicylene	The diamyl cyclopentadienyl
Two-pentadecyl silicylene	The hexyl cyclopentadienyl	Two-hexadecyl silicylene	The dihexyl cyclopentadienyl
Two-heptadecyl silicylene	The heptyl cyclopentadienyl	Two-hexadecyl silicylene	The dihexyl cyclopentadienyl
Two-heptadecyl silicylene	The heptyl cyclopentadienyl	Two-octadecyl silicylene	The diheptyl cyclopentadienyl
Two-nonadecyl silicylene	The octyl group cyclopentadienyl	Two-octadecyl silicylene	The diheptyl cyclopentadienyl
Two-nonadecyl silicylene	The octyl group cyclopentadienyl	Two-eicosyl silicylene	The dioctyl cyclopentadienyl
Two-heneicosyl silicylene	The nonyl cyclopentadienyl	Two-eicosyl silicylene	The dioctyl cyclopentadienyl
Two-heneicosyl silicylene	The nonyl cyclopentadienyl	Two-docosyl silicylene	The dinonyl cyclopentadienyl
Two-tricosyl silicylene	The decyl cyclopentadienyl	Two-docosyl silicylene	The dinonyl cyclopentadienyl
Two-tricosyl silicylene	The decyl cyclopentadienyl	Two-tetracosyl silicylene	The didecyl cyclopentadienyl
Two-pentacosyl silicylene	The undecyl cyclopentadienyl	Two-tetracosyl silicylene	The didecyl cyclopentadienyl
Two-pentacosyl silicylene	The undecyl cyclopentadienyl	Two-ceryl silicylene	The dodecyl cyclopentadienyl
Two-heptacosyl silicylene	The tridecyl cyclopentadienyl	Two-ceryl silicylene	The dodecyl cyclopentadienyl
Two-heptacosyl silicylene	The tridecyl cyclopentadienyl	Two-octacosyl silicylene	The tetradecyl cyclopentadienyl
Two-nonacosyl silicylene	Pentadecyl cyclopentadienyl (no A ')	Two-octacosyl silicylene	The tetradecyl cyclopentadienyl
Two-nonacosyl silicylene	Pentadecyl cyclopentadienyl (no A ')	Two-triacontyl silicylene	The hexadecyl cyclopentadienyl
The dicyclohexyl silicylene	The heptadecyl cyclopentadienyl	Two-triacontyl silicylene	The hexadecyl cyclopentadienyl
The dicyclohexyl silicylene	The heptadecyl cyclopentadienyl	Two cyclopentyl silicylene	The octadecyl cyclopentadienyl
Two suberyl silicylene	The nonadecyl cyclopentadienyl	Two cyclopentyl silicylene	The octadecyl cyclopentadienyl
Two suberyl silicylene	The nonadecyl cyclopentadienyl	Two ring octyl group silicylene	The eicosyl cyclopentadienyl
Two ring decyl silicylene	The heneicosyl cyclopentadienyl	Two ring octyl group silicylene	The eicosyl cyclopentadienyl

Two cyclo-dodecyl silicylene	The docosyl cyclopentadienyl
Two cyclo-dodecyl silicylene	The docosyl cyclopentadienyl	The dinaphthyl silicylene	The tricosyl cyclopentadienyl
The phenylbenzene silicylene	The tetracosyl cyclopentadienyl	The dinaphthyl silicylene	The tricosyl cyclopentadienyl
The phenylbenzene silicylene	The tetracosyl cyclopentadienyl	The xylyl silicylene	The pentacosyl cyclopentadienyl
The dibenzyl silicylene	The ceryl cyclopentadienyl	The xylyl silicylene	The pentacosyl cyclopentadienyl
The dibenzyl silicylene	The ceryl cyclopentadienyl	Two styroyl silicylene	The heptacosyl cyclopentadienyl
Two (butylbenzene ethyl) silicylene	The octacosyl cyclopentadienyl	Two styroyl silicylene	The heptacosyl cyclopentadienyl
Two (butylbenzene ethyl) silicylene	The octacosyl cyclopentadienyl	The methylethyl silicylene	The nonacosyl cyclopentadienyl
The methyl-propyl silicylene	The triacontyl cyclopentadienyl	The methylethyl silicylene	The nonacosyl cyclopentadienyl
The methyl-propyl silicylene	The triacontyl cyclopentadienyl	The methyl butyl silicylene	The cyclohexyl ring pentadienyl
Methyl hexyl silicylene	The benzyl ring pentadienyl	The methyl butyl silicylene	The cyclohexyl ring pentadienyl
Methyl hexyl silicylene	The benzyl ring pentadienyl	The aminomethyl phenyl silicylene	The phenylbenzene cyclopentadienyl
The ethylphenyl silicylene	The triphenyl cyclopentadienyl	The aminomethyl phenyl silicylene	The phenylbenzene cyclopentadienyl
The ethylphenyl silicylene	The triphenyl cyclopentadienyl	The ethyl propyl silicylene	The tetraphenyl cyclopentadienyl
The ethyl-butyl silicylene	The pentapheneyl cyclopentadienyl	The ethyl propyl silicylene	The tetraphenyl cyclopentadienyl
The ethyl-butyl silicylene	The pentapheneyl cyclopentadienyl	Propyl group phenyl silicylene	The tolyl cyclopentadienyl
Dimethylated methylene germane base	The benzyl rings pentadienyl	Propyl group phenyl silicylene	The tolyl cyclopentadienyl
Dimethylated methylene germane base	The benzyl rings pentadienyl	Diethyl methylene germane base	The styroyl cyclopentadienyl
Phenylbenzene methylene germane base	The cyclohexyl methyl cyclopentadienyl	Diethyl methylene germane base	The styroyl cyclopentadienyl
Phenylbenzene methylene germane base	The cyclohexyl methyl cyclopentadienyl	Aminomethyl phenyl methylene germane base	The naphthyl cyclopentadienyl
Ring tetramethylene silicylene	The aminomethyl phenyl cyclopentadienyl	Aminomethyl phenyl methylene germane base	The naphthyl cyclopentadienyl
Ring tetramethylene silicylene	The aminomethyl phenyl cyclopentadienyl	The cyclopentamethylene silicylene	Methyl tolyl cyclopentadienyl
Ring trimethylene silicylene	The methylethyl cyclopentadienyl	The cyclopentamethylene silicylene	Methyl tolyl cyclopentadienyl
Ring trimethylene silicylene	The methylethyl cyclopentadienyl	Cyclohexyl azane two bases	The methyl-propyl cyclopentadienyl
Butyl azane two bases	The methyl butyl cyclopentadienyl	Cyclohexyl azane two bases	The methyl-propyl cyclopentadienyl
Butyl azane two bases	The methyl butyl cyclopentadienyl	Methyl azane two bases	The methyl amyl cyclopentadienyl
Phenyl azane two bases	Methyl hexyl cyclopentadienyl	Methyl azane two bases	The methyl amyl cyclopentadienyl
Phenyl azane two bases	Methyl hexyl cyclopentadienyl	Perfluorophenyl azane two bases	The methylheptyl cyclopentadienyl
Methyl phosphine (phosphane) two bases	The Methyl Octyl cyclopentadienyl	Perfluorophenyl azane two bases	The methylheptyl cyclopentadienyl
Methyl phosphine (phosphane) two bases	The Methyl Octyl cyclopentadienyl	Ethyl phosphine two bases	Methyl nonyl cyclopentadienyl
Propyl group phosphine two bases	Methyl decyl cyclopentadienyl	Ethyl phosphine two bases	Methyl nonyl cyclopentadienyl

Butyl phosphine two bases	The vinyl cyclopentadienyl
Butyl phosphine two bases	The vinyl cyclopentadienyl	Cyclohexyl phosphine two bases	The propenyl cyclopentadienyl
Phenyl phosphine two bases	The butenyl cyclopentadienyl	Cyclohexyl phosphine two bases	The propenyl cyclopentadienyl
Phenyl phosphine two bases	The butenyl cyclopentadienyl	Methyl borine two bases	Indenyl
Phenylborinane two bases	The methyl indenyl	Methyl borine two bases	Indenyl
Phenylborinane two bases	The methyl indenyl	Methylene radical	The dimethyl indenyl
The dimethylated methylene base	The trimethylammonium indenyl	Methylene radical	The dimethyl indenyl
The dimethylated methylene base	The trimethylammonium indenyl	The diethyl methylene radical	The methyl-propyl indenyl
The dibutyl methylene radical	The dimethyl propyl indenyl	The diethyl methylene radical	The methyl-propyl indenyl
The dibutyl methylene radical	The dimethyl propyl indenyl	The dipropyl methylene radical	Methyl dipropyl indenyl
The phenylbenzene methylene radical	The methylethyl indenyl	The dipropyl methylene radical	Methyl dipropyl indenyl
The phenylbenzene methylene radical	The methylethyl indenyl	The xylyl methylene radical	The methyl butyl indenyl
Two (butyl phenyl) methylene radical	Ethyl-indenyl	The xylyl methylene radical	The methyl butyl indenyl
Two (butyl phenyl) methylene radical	Ethyl-indenyl	Two (trimethyl silyl phenyl) methylene radical	The propyl group indenyl
Two (triethylsilyl phenyl) methylene radical	The butyl indenyl	Two (trimethyl silyl phenyl) methylene radical	The propyl group indenyl
Two (triethylsilyl phenyl) methylene radical	The butyl indenyl	The dibenzyl methylene radical	The amyl group indenyl
Ring tetramethylene methylene radical	The hexyl indenyl	The dibenzyl methylene radical	The amyl group indenyl
Ring tetramethylene methylene radical	The hexyl indenyl	The cyclopentamethylene methylene radical	The heptyl indenyl
Ethylidene	The octyl group indenyl	The cyclopentamethylene methylene radical	The heptyl indenyl
Ethylidene	The octyl group indenyl	The methyl ethylidene	The nonyl indenyl
The dimethyl ethylidene	The decyl indenyl	The methyl ethylidene	The nonyl indenyl
The dimethyl ethylidene	The decyl indenyl	The trimethylammonium ethylidene	Phenyl indenyl
The tetramethyl-ethylidene	(fluorophenyl) indenyl	The trimethylammonium ethylidene	Phenyl indenyl
The tetramethyl-ethylidene	(fluorophenyl) indenyl	The ring pentylidene	(aminomethyl phenyl) indenyl
Cyclohexylene	The xenyl indenyl	The ring pentylidene	(aminomethyl phenyl) indenyl
Cyclohexylene	The xenyl indenyl	Encircle inferior heptyl	(two (trifluoromethyl) phenyl) indenyl
Encircle octylene	The naphthyl indenyl	Encircle inferior heptyl	(two (trifluoromethyl) phenyl) indenyl
Encircle octylene	The naphthyl indenyl	Propane two bases	The phenanthryl indenyl
Methylpropane two bases	The benzyl indenyl	Propane two bases	The phenanthryl indenyl
Methylpropane two bases	The benzyl indenyl	Dimethylpropane two bases	The benzo indenyl
Trimethyl propane two bases	The cyclohexyl indenyl	Dimethylpropane two bases	The benzo indenyl

Tetramethyl-propane two bases	The aminomethyl phenyl indenyl
Tetramethyl-propane two bases	The aminomethyl phenyl indenyl	Pentamethyl propane two bases	The ethylphenyl indenyl
Hexamethyl propane two bases	The propyl group phenyl indenyl	Pentamethyl propane two bases	The ethylphenyl indenyl
Hexamethyl propane two bases	The propyl group phenyl indenyl	Tetramethyl-two inferior siloxyies	Methyl naphthyl indenyl
Vinyl	Ethyl naphthyl indenyl	Tetramethyl-two inferior siloxyies	Methyl naphthyl indenyl
Vinyl	Ethyl naphthyl indenyl	1, the 1-ethylidene	Propyl group naphthyl indenyl
The divinyl silicylene	(aminomethyl phenyl) indenyl	1, the 1-ethylidene	Propyl group naphthyl indenyl
The divinyl silicylene	(aminomethyl phenyl) indenyl	The diallyl silicylene	(3,5-dimethylphenyl) indenyl
Dibutene base silicylene	(ethylphenyl) indenyl	The diallyl silicylene	(3,5-dimethylphenyl) indenyl
Dibutene base silicylene	(ethylphenyl) indenyl	The methyl ethylene silicylene	(diethyl phenyl) indenyl
The methylpropenyl silicylene	(propyl group phenyl) indenyl	The methyl ethylene silicylene	(diethyl phenyl) indenyl
The methylpropenyl silicylene	(propyl group phenyl) indenyl	Methyl butene base silicylene	(dipropyl phenyl) indenyl
The dimetylsilyl methylene radical	The methyl tetrahydro indenyl	Methyl butene base silicylene	(dipropyl phenyl) indenyl
The dimetylsilyl methylene radical	The methyl tetrahydro indenyl	Diphenylmethyl silylation methylene radical	The dimethyl tetrahydro indenyl
The dimetylsilyl ethylidene	Dimethyl dihydro indenyl	Diphenylmethyl silylation methylene radical	The dimethyl tetrahydro indenyl
The dimetylsilyl ethylidene	Dimethyl dihydro indenyl	Diphenylmethyl silylation ethylidene	Dimethyl three hydrogen indenyls
The dimetylsilyl propylidene	The aminomethyl phenyl tetrahydro indenyl	Diphenylmethyl silylation ethylidene	Dimethyl three hydrogen indenyls
The dimetylsilyl propylidene	The aminomethyl phenyl tetrahydro indenyl	Diphenylmethyl silylation propylidene	Aminomethyl phenyl dihydro indenyl
Dimethylated methylene stannane base	Aminomethyl phenyl three hydrogen indenyls	Diphenylmethyl silylation propylidene	Aminomethyl phenyl dihydro indenyl
Dimethylated methylene stannane base	Aminomethyl phenyl three hydrogen indenyls	The phenylbenzene stannylene	The ethyl tetrahydro indenyl
	The propyl group tetrahydro indenyl	The phenylbenzene stannylene	The ethyl tetrahydro indenyl
	The propyl group tetrahydro indenyl		The butyl tetrahydro indenyl
	The phenyl tetrahydro indenyl		The butyl tetrahydro indenyl
	The phenyl tetrahydro indenyl		Fluorenyl
	Methylfluorenyl		Fluorenyl
	Methylfluorenyl		The dimethyl fluorenyl
	The trimethylammonium fluorenyl		The dimethyl fluorenyl
	The trimethylammonium fluorenyl		The ethyl fluorenyl
	The propyl group fluorenyl		The ethyl fluorenyl
	The propyl group fluorenyl		The butyl fluorenyl
	The dibutyl fluorenyl		The butyl fluorenyl

	The amyl group fluorenyl
	The amyl group fluorenyl		The hexyl fluorenyl
	The heptyl fluorenyl		The hexyl fluorenyl
	The heptyl fluorenyl		The octyl group fluorenyl
	The nonyl fluorenyl		The octyl group fluorenyl
	The nonyl fluorenyl		The decyl fluorenyl
	The phenyl fluorenyl		The decyl fluorenyl
	The phenyl fluorenyl		The naphthyl fluorenyl
	The benzyl fluorenyl		The naphthyl fluorenyl
	The benzyl fluorenyl		The aminomethyl phenyl fluorenyl
	The ethylphenyl fluorenyl		The aminomethyl phenyl fluorenyl
	The ethylphenyl fluorenyl		Propyl group phenyl fluorenyl
	Methyl naphthyl fluorenyl		Propyl group phenyl fluorenyl
	Methyl naphthyl fluorenyl		Ethyl naphthyl fluorenyl
	Propyl group naphthyl fluorenyl		Ethyl naphthyl fluorenyl
	Propyl group naphthyl fluorenyl		Octahydrofluorenyl
	Tetrahydrofluorenyl		Octahydrofluorenyl
	Tetrahydrofluorenyl		Prestox octahydro dibenzo [b, h] fluorenyl
	Tetramethyl-tetrahydro benzo [b] fluorenyl		Prestox octahydro dibenzo [b, h] fluorenyl
	Tetramethyl-tetrahydro benzo [b] fluorenyl		The diphenyl methyl cyclopentadienyl
	The trimethyl silyl cyclopentadienyl		The diphenyl methyl cyclopentadienyl
	The trimethyl silyl cyclopentadienyl		The triethylsilyl cyclopentadienyl
	Trimethylammonium germyl cyclopentadienyl		The triethylsilyl cyclopentadienyl
	Trimethylammonium germyl cyclopentadienyl		Trimethylammonium stannyl cyclopentadienyl
	Triethyl first plumbyl cyclopentadienyl		Trimethylammonium stannyl cyclopentadienyl
	Triethyl first plumbyl cyclopentadienyl		The trifluoromethyl cyclopentadienyl
	N, N-dimethylamino cyclopentadienyl		The trifluoromethyl cyclopentadienyl
	N, N-dimethylamino cyclopentadienyl		P, P-dimethyl phosphorus basic ring pentadienyl
	N, N-diethylamino cyclopentadienyl		P, P-dimethyl phosphorus basic ring pentadienyl
	N, N-diethylamino cyclopentadienyl		The methoxyl group cyclopentadienyl
	The oxyethyl group cyclopentadienyl		The methoxyl group cyclopentadienyl

	Trimethylammonium first siloxanes cyclopentadienyl
	Trimethylammonium first siloxanes cyclopentadienyl		(N, N-dimethylaminomethyl) cyclopentadienyl
	The methoxyl group indenyl		(N, N-dimethylaminomethyl) cyclopentadienyl
	The methoxyl group indenyl		The dimethoxy indenyl
	N, N-dimethylamino indenyl		The dimethoxy indenyl
	N, N-dimethylamino indenyl		Trimethylammonium first siloxanes indenyl
	Butyl dimethyl methyl siloxanes indenyl		Trimethylammonium first siloxanes indenyl
	Butyl dimethyl methyl siloxanes indenyl		Two (N, N-dimethylamino) indenyl
	Two (trimethylammonium first siloxanes) indenyl		Two (N, N-dimethylamino) indenyl
	Two (trimethylammonium first siloxanes) indenyl		Two (butyl dimethyl methyl siloxanes) indenyl
	The methoxyl group fluorenyl		Two (butyl dimethyl methyl siloxanes) indenyl
	The methoxyl group fluorenyl		The dimethoxy fluorenyl
	N, N-dimethylamino fluorenyl		The dimethoxy fluorenyl
	N, N-dimethylamino fluorenyl		Trimethylammonium first siloxanes fluorenyl
	Butyl dimethyl methyl siloxanes fluorenyl		Trimethylammonium first siloxanes fluorenyl
	Butyl dimethyl methyl siloxanes fluorenyl		The dimethoxy fluorenyl
	Two (N, N-dimethylamino) fluorenyl		The dimethoxy fluorenyl
	Two (N, N-dimethylamino) fluorenyl		Two (trimethylammonium first siloxanes) fluorenyl
	Two (butyl dimethyl methyl siloxanes) fluorenyl		Two (trimethylammonium first siloxanes) fluorenyl

Table A (continuing)

(JS′ _z-1-y)(y＝1)	X ₁Or X ₂	M
(JS′ _z-1-y)(y＝1)	X ₁Or X ₂	M	Methylamino	Muriate	Titanium
Ethylamino	Bromide	Zirconium	Methylamino	Muriate	Titanium
Ethylamino	Bromide	Zirconium	Propyl group amino	Iodide	Hafnium
Butyl amino	Fluorochemical		Propyl group amino	Iodide	Hafnium
Butyl amino	Fluorochemical		Amyl group amino	Hydride	L or L ' (non-essential)
Hexyl amino	Methyl	Ethene	Amyl group amino	Hydride	L or L ' (non-essential)
Hexyl amino	Methyl	Ethene	Heptyl amino	Ethyl	Propylene
Octyl group amino	Propyl group	Butylene	Heptyl amino	Ethyl	Propylene
Octyl group amino	Propyl group	Butylene	Nonyl amino	Butyl	Hexene
Decyl amino	Amyl group	Vinylbenzene	Nonyl amino	Butyl	Hexene
Decyl amino	Amyl group	Vinylbenzene	Eicosyl amino	Hexyl	Hexadiene
Heneicosyl amino	Heptyl	Divinyl	Eicosyl amino	Hexyl	Hexadiene
Heneicosyl amino	Heptyl	Divinyl	Docosyl amino	Octyl group	Dimethylbutadiene
Tricosyl amino	Nonyl	Pentadiene	Docosyl amino	Octyl group	Dimethylbutadiene
Tricosyl amino	Nonyl	Pentadiene	Tetracosyl amino	Decyl	The methyl hexadiene
Pentacosyl amino	Undecyl	The dimethyl hexadiene	Tetracosyl amino	Decyl	The methyl hexadiene
Pentacosyl amino	Undecyl	The dimethyl hexadiene	Ceryl amino	Dodecyl	Acetylene
Heptacosyl amino	Tridecyl	Methylacetylene	Ceryl amino	Dodecyl	Acetylene
Heptacosyl amino	Tridecyl	Methylacetylene	Octacosyl amino	Tetradecyl	Ethylacetylene
Nonacosyl amino	Pentadecyl	Benzyne	Octacosyl amino	Tetradecyl	Ethylacetylene
Nonacosyl amino	Pentadecyl	Benzyne	Triacontyl amino	Hexadecyl	Cyclopentenes
Phenyl amino	Heptadecyl	Tetrahydrobenzene	Triacontyl amino	Hexadecyl	Cyclopentenes
Phenyl amino	Heptadecyl	Tetrahydrobenzene	Tolyl amino	Octadecyl
Styroyl amino	Nonadecyl	L ' (non-essential)	Tolyl amino	Octadecyl
Styroyl amino	Nonadecyl	L ' (non-essential)	Benzylamino	Eicosyl	Anaesthetie Ether
Cyclobutyl amino	Heneicosyl	Dimethyl ether	Benzylamino	Eicosyl	Anaesthetie Ether

Cyclopentyl amino	Docosyl	Trimethylamine
Cyclopentyl amino	Docosyl	Trimethylamine	Cyclohexyl amino	Tricosyl	Triphenylamine
Suberyl amino	Tetracosyl	Triethylamine	Cyclohexyl amino	Tricosyl	Triphenylamine
Suberyl amino	Tetracosyl	Triethylamine	Ring octyl group amino	Pentacosyl	Tricyclohexyl phosphine
Ring nonyl amino	Ceryl	Triphenylphosphine	Ring octyl group amino	Pentacosyl	Tricyclohexyl phosphine
Ring nonyl amino	Ceryl	Triphenylphosphine	Ring decyl amino	Heptacosyl	Trimethyl-phosphine
Cyclo-dodecyl amino	Octacosyl	Tetrahydrofuran (THF)	Ring decyl amino	Heptacosyl	Trimethyl-phosphine
Cyclo-dodecyl amino	Octacosyl	Tetrahydrofuran (THF)	Adamantyl (adamantyl) amino	Nonacosyl	Furans
Norcamphyl (norbornyl) amino	Triacontyl	Thiophene	Adamantyl (adamantyl) amino	Nonacosyl	Furans
Norcamphyl (norbornyl) amino	Triacontyl	Thiophene	Perfluorophenyl amino	Phenyl	Dimethylsulphide
Fluorophenyl amino	Benzyl	Diphenyl sulfide	Perfluorophenyl amino	Phenyl	Dimethylsulphide
Fluorophenyl amino	Benzyl	Diphenyl sulfide	Difluorophenyl amino	Styroyl
The oxygen base	Tolyl		Difluorophenyl amino	Styroyl
The oxygen base	Tolyl		Sulfenyl (sulfido)	Methoxyl group
	Oxyethyl group		Sulfenyl (sulfido)	Methoxyl group
	Oxyethyl group		(JS′z-1-y)(y＝0)	Propoxy-
Methoxyl group	Butoxy		(JS′z-1-y)(y＝0)	Propoxy-
Methoxyl group	Butoxy		Oxyethyl group	Dimethylamino
Phenoxy group	Diethylamino		Oxyethyl group	Dimethylamino
Phenoxy group	Diethylamino		Dimethyl phenoxy	Methylethyl amino
The dipropyl phenoxy group	Phenoxy group		Dimethyl phenoxy	Methylethyl amino
The dipropyl phenoxy group	Phenoxy group		Methylthio group	Benzyloxy
Ethylmercapto group	Allyl group		Methylthio group	Benzyloxy
Ethylmercapto group	Allyl group		Thiophenyl
The dimethyl benzene sulfenyl			Thiophenyl
The dimethyl benzene sulfenyl			The dipropyl thiophenyl	X1 and X2 are together
	Methyne		The dipropyl thiophenyl	X1 and X2 are together
	Methyne			Ethidine
	The propylidene base			Ethidine

	Tetramethylene
	Tetramethylene			Pentamethylene
	Hexa-methylene			Pentamethylene
	Hexa-methylene			The ethylene hydroxyl
	Divinyl			The ethylene hydroxyl
	Divinyl			Dimethyl butadiene
	Dimethylbutadiene			Dimethyl butadiene
	Dimethylbutadiene			Pentadiene
	Methylpentadiene			Pentadiene
	Methylpentadiene			Dimethyl pentadiene
	Hexadiene			Dimethyl pentadiene
	Hexadiene			The methyl hexadiene
	The dimethyl hexadiene			The methyl hexadiene
	The dimethyl hexadiene

Other preferred catalyst comprises those that describe among the WO01/48034, and the document is incorporated herein by reference here.Particularly preferred catalyst compound is included in and walks to the 25th page of 42 row, the 28th page of the 5th to 17 row, the 30th page the 37th for the 9th page 38 and walk to those disclosed in the 35th page of the 28th row.

The activator of catalyst compound and activation method

Above-described polymerization procatalyst compound is generally by different modes activation, but obtains to have the compound of the empty coordination position of coordination, insertion and olefin polymerization thus.In patent specification and claims, term " promotor " and " activator " commutative here use, and may be defined as can be by being converted into the neutral catalyst compound any compound that catalytic activity catalyst compound positively charged ion activates above-mentioned arbitrary catalyst compound.Non-limiting activator comprises aikyiaiurnirsoxan beta, aluminum alkyls, ionization activator (it can be neutrality or ionic) and conventional type promotor.Preferred activator generally comprises aluminium alkoxide compound, modified aluminium-oxygen hydride compounds, capture the metal ligand of an active σ-bonding and make the metal complexes cationization and provide the non-coordination of balancing charge or the ionization negatively charged ion precursor compound of weakly coordinating anion.

Aikyiaiurnirsoxan beta and alkyl aluminum activator

In one embodiment, alumoxane activator is used as activator in catalyst composition of the present invention.Aikyiaiurnirsoxan beta is generally and contains-Al (R ¹The oligomeric compound of)-O-subunit, wherein R ¹Be alkyl.The example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.Alkylaluminoxane and modification alkylaluminoxane are fit to do the activator of catalyzer, particularly in the time can capturing part and be halogenide, alkoxide or acid amides.Also can use the mixture of different aikyiaiurnirsoxan beta and modified alumoxane.

The activator compound that comprises Lewis acid activation agent, particularly aikyiaiurnirsoxan beta is represented by following general formula:

(R ³-Al-O) _p (11)

R ⁴(R ⁵-Al-O) _p-AlR ⁶ ₂ (12)

(M′) ^m+Q′ _m (13)

Aikyiaiurnirsoxan beta is generally the mixture of linear and ring compound.In the aikyiaiurnirsoxan beta general formula, R ³, R ⁴, R ⁵And R ⁶Be C independently ₁-C ₃₀Alkyl is 1 to about 50 integer as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl and " p ".R ³, R ⁴, R ⁵And R ⁶The methyl of most preferably respectively doing for oneself, " p " is at least 4.When aluminum alkyl halide or alkoxide are used to prepare aikyiaiurnirsoxan beta, one or more R ^3-6Group can be halogenide or alkoxide.M ' is metal or metalloid, and Q ' is for partially or completely fluoridizing alkyl.

Have recognized that aikyiaiurnirsoxan beta is not abstract material.A kind of typical aikyiaiurnirsoxan beta will comprise three replacements freely or trialkylaluminium, three replacements of bonding or the aikyiaiurnirsoxan beta molecule of trialkylaluminium and low polymerization degree variation.Those most preferred methylaluminoxane comprise the trimethyl aluminium of low levels.The trimethyl aluminium of low levels can be by the reaction of trimethyl aluminium and Lewis base or by the vacuum distilling trimethyl aluminium or by any alternate manner realization known in the art.Recognize that also some aikyiaiurnirsoxan beta molecules are anionic form after reacting with transistion metal compound,,, be considered to " non-coordination " negatively charged ion therefore for the object of the invention as what represent by the negatively charged ion among the equation 4-6.

For further describing, referring to US4,665,208,4,952,540,5,041,584,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,329,032,5,248,801,5,235,081,5,157,137,5,103,031 and EP0561476A1, EP0279586B1, EP0516476A, EP0594218A1 and WO94/10180.

When activator was aikyiaiurnirsoxan beta (modification or unmodified), some embodiments were selected relatively and the maximum activator of 5000 times of molar excess Al/M of catalyst precursor (each metal catalytic site).Minimum activator is 1: 1 mol ratio with the ratio of catalyst precursor.

Aikyiaiurnirsoxan beta can be by the corresponding trialkyl aluminium compound production of hydrolysis.MMAO can be by hydrolysis trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium production.MMAO more is soluble in usually in the aliphatic solvents and is more stable at lay up period.Have the various methods that prepare aikyiaiurnirsoxan beta and modified alumoxane, its non-limitative example is described in US4, 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 and EP-A-0561476, EP-B1-0279586, EP-A-0594-218 and EP-B1-0586665, and among WO 94/10180 and the WO 99/15534, all documents are introduced as reference here.Can preferably make macroscopic limpid methylaluminoxane.Muddiness or agglomerative aikyiaiurnirsoxan beta the production clear solution can be filtered, maybe limpid aikyiaiurnirsoxan beta can be from turbid solution, drained.Another aikyiaiurnirsoxan beta is modified methylaluminoxane (MMAO) promotor 3A type (available from Akzo Chemicals, Inc., commodity are called modified methylaluminoxane 3A type, covered by patent US 5,041,584).

The aluminum alkyls or the organo-aluminium compound that can be used as activator (or scavenging agent) comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and tri-n-octylaluminium etc.

The ionization activator

Can use ionization or stoichiometry activator (neutrality or ionic) within the scope of the present invention, as three (normal-butyl) ammonium four (pentafluorophenyl group) boron, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, the assorted borine negatively charged ion (WO 98/43983) of many halogenations, boric acid (US5,942,459) or its combination.Neutrality or ionic compound also can use separately or be used in combination with aikyiaiurnirsoxan beta or modified alumoxane activator within the scope of the present invention.

The example of neutral stoichiometry activator comprises that three replace boron, tellurium, aluminium, gallium and indium or its mixture.Three substituting groups are selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxyl group and halogenide independently of one another.These three substituting groups preferably are independently selected from halogen, list or many rings (comprising what halogen replaced) aryl, alkyl and alkenyl compound and composition thereof, preferably have 1 to 20 carbon atom alkenyl, have 1 to 20 carbon atom alkyl, have the alkoxyl group of 1 to 20 carbon atom and have the aryl (comprising substituted aryl) of 3 to 20 carbon atoms, these three groups more preferably have alkyl, phenyl, naphthyl or its mixture of 1 to 4 carbon atom.Three groups are the aryl of halogenation more preferably, preferred fluorinated further.Neutral stoichiometry activator most preferably is three perfluorophenyl boron or three perfluor naphthyl boron.

Ion chemistry metering activator compound can comprise active proton, or associates but not coordination or some other positively charged ions of only loose coordinate with the residual ion of ionization compound.These compounds and analogue thereof be described in EP-A-0570982, EP-A-0520732,, EP-A-0495375, EP-B1-0500944, EP-A-0277003 and EP-A-0277004, and US5,153,157,5,198,401,5,066,741,5,206,197,5,241,025,5,384,299 and 5,502,124, with US patent application 08/285,380 (August 3 1994 applying date), all these documents are incorporated herein by reference here.

Ionic catalyst can be by transistion metal compound and some neutral lewis acids such as B (C ₆F ₆) ₃When prepared in reaction, this Lewis acid are reacted at the hydrolyzable part (X) with transistion metal compound, form negatively charged ion as ([B (C ₆F ₅) ₃(X)] ^-), its stable cationic transition metal material that generates by this reaction.This catalyzer can be used and preferably be the activator component preparation of ionic compound or composition with it.Yet the present invention also considers to use neutral compound to prepare activator.

The compound that is used as activator component in preparation the inventive method in the ionic catalyst system of using comprises positively charged ion and compatible non-coordination anion, described positively charged ion is preferably the Bronsted acid that can give proton, described negatively charged ion is big (huge) relatively, can be stabilized in these two kinds of compounds in conjunction with the time active catalyst species (4 family's positively charged ion) that forms, and described negatively charged ion is enough unstable, can be by the unsaturated matrix of olefinic, diolefinic and acetylene series or other Lewis base such as displacements such as ether, nitrile.The compatible non-coordination anion of two classes has been disclosed in EPA 277,003 with regard to EPA277,004 (1988 open): 1) comprise and shield the anion binding title complex and 2 of a plurality of lipophilic groups of described nuclear) comprise the negatively charged ion of a plurality of boron atoms such as carborane, metallocarborane and borine with charged metal in center or metalloid nuclear covalent coordinate.

In preferred embodiments, the stoichiometry activator comprises positively charged ion and anionic group, and can be represented by following general formula:

(L-H) ⁺ _d(A ^d-) (14)

Wherein L is a neutral Lewis base;

H is a hydrogen;

(L-H) ⁺Be Bronsted acid

A ^D-For having the non-coordination anion of electric charge d-;

D is 1 to 3 integer.

Cationic components (L-H) ⁺ _dCan comprise Bronsted acid such as proton or protonated Lewis base or reducible Lewis acid, it can be protonated or captures the structure division such as the alkyl or aryl of the transition-metal catalyst precursor that comes self-contained bulky ligand metallocene, forms the cationic transition metal material.

Activation positively charged ion (L-H) ⁺ _dCan be Bronsted acid, it can give proton the transition-metal catalyst precursor, obtain transition-metal cation thus, comprise ammonium, oxygen Phosphonium, silyl (silylium) and its mixture, preferred methylamine, aniline, dimethylamine, diethylamine, methylphenylamine, diphenylamine, Trimethylamine 99, triethylamine, N, accelerine, methyldiphenyl base amine, pyridine, to bromo-N, accelerine, to nitro-N, the ammonium of accelerine, come from triethyl phosphine, triphenylphosphine and diphenylphosphine De Phosphonium, with come from ether such as dme, diethyl ether, tetrahydrofuran (THF) is with the oxygen of diox, come from the sulfonium of thioether such as diethyl thioether and tetramethylene sulfide, and composition thereof.Activation positively charged ion (L-H) ⁺ _dFor example also can be silver,

, carbon, ferrocene and its mixture structure division, preferred carbon and ferrocene.(L-H) ⁺ _dMost preferably be triphenylcarbenium.

Anionic group A ^D-Comprise and have general formula [M ^K+Q _n] ^D-Those, wherein k is 1 to 3 integer; N is 2 to 6 integer; N-k=d; M is the element that is selected from the periodic table of elements 13 families, preferred boron or aluminium, Q is hydride, bridging or non-bridged dialkyl amido, halogenide, alkoxide, fragrant oxide compound, alkyl, substituted hydrocarbon radical, halo alkyl independently, replaces halo alkyl and halogen substituted hydrocarbon radical, described Q has 20 carbon atoms at the most, and condition is that the Q that occurs is halogenide no more than 1 time.Preferred each Q is the alkyl of fluoridizing with 1 to 20 carbon atom, and more preferably each Q is a fluoro aryl, and each Q most preferably is five fluoro aryls.Proper A ^D-Example also comprise for example US5, disclosed two boron compounds in 447,895, the document all is incorporated herein by reference here.

Can in preparation the present invention improved catalyzer, be used as the illustrative of boron compound of active cocatalyst but non-limitative example is three substituted ammonium salts as tetraphenyl boric acid trimethyl ammonium, tetraphenyl boric acid triethyl ammonium, tetraphenyl boric acid tripropyl ammonium, tetraphenyl boric acid three (normal-butyl) ammonium, tetraphenyl boric acid three (tertiary butyl) ammonium, tetraphenyl boric acid N, accelerine, tetraphenyl boric acid N, N-Diethyl Aniline, tetraphenyl boric acid N, N-dimethyl-(2,4,6-trimethylaniline), tetraphenyl boric acid

(tropillium), tetraphenyl boric acid triphenylcarbenium, tetraphenyl boric acid triphenyl phosphonium, tetraphenyl boric acid triethylsilyl, tetraphenyl boric acid benzene (diazonium salt), 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 N, accelerine, four (pentafluorophenyl group) boric acid N, the N-Diethyl Aniline, four (pentafluorophenyl group) boric acid N, N-dimethyl-(2,4, the 6-trimethylaniline), four (pentafluorophenyl group) boric acid

Four (pentafluorophenyl group) boric acid triphenylcarbenium, four (pentafluorophenyl group) boric acid triphenyl phosphonium, four (pentafluorophenyl group) boric acid triethylsilyl, four (pentafluorophenyl group) boric acid benzene (diazonium salt), 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 (tertiary butyl) ammonium, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, accelerine, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, the N-Diethyl Aniline, four-(2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2,4, the 6-trimethylaniline), four-(2,3,4,6-tetrafluoro phenyl) boric acid

Four-(2,3,4,6-tetrafluoro phenyl) boric acid triphenylcarbenium, four-(2,3,4,6-tetrafluoro phenyl) boric acid triphenyl phosphonium, four-(2,3,4,6-tetrafluoro phenyl) the boric acid triethylsilyl, four-(2,3,4,6-tetrafluoro phenyl) boric acid benzene (diazonium salt), four (perfluor naphthyl) boric acid trimethyl ammonium, four (perfluor naphthyl) boric acid triethyl ammonium, four (perfluor naphthyl) boric acid tripropyl ammonium, four (perfluor naphthyl) boric acid three (normal-butyl) ammoniums, four (perfluor naphthyl) boric acid three (tertiary butyl) ammoniums, four (perfluor naphthyl) boric acid N, accelerine, four (perfluor naphthyl) boric acid N, the N-Diethyl Aniline, four (perfluor naphthyl) boric acid N, N-dimethyl-(2), four (perfluor naphthyl) boric acid

Four (perfluor naphthyl) boric acid triphenylcarbenium, four (perfluor naphthyl) boric acid triphenyl phosphonium, four (perfluor naphthyl) boric acid triethylsilyl, four (perfluor naphthyl) boric acid benzene (diazonium salt), four (perfluorinated biphenyl) boric acid trimethyl ammonium, four (perfluorinated biphenyl) boric acid triethyl ammonium, four (perfluorinated biphenyl) boric acid tripropyl ammonium, four (perfluorinated biphenyl) boric acid three (normal-butyl) ammonium, four (perfluorinated biphenyl) boric acid three (tertiary butyl) ammonium, four (perfluorinated biphenyl) boric acid N, accelerine, four (perfluorinated biphenyl) boric acid N, the N-Diethyl Aniline, four (perfluorinated biphenyl) boric acid N, N-dimethyl-(2,4, the 6-trimethylaniline), four (perfluorinated biphenyl) boric acid

Four (perfluorinated biphenyl) boric acid triphenylcarbenium, four (perfluorinated biphenyl) boric acid triphenyl phosphonium, four (perfluorinated biphenyl) boric acid triethylsilyl, four (perfluorinated biphenyl) boric acid benzene (diazonium salt), four (3, two (trifluoromethyl) phenyl of 5-) boric acid trimethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triethyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid tripropyl ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (normal-butyl) ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid three (tertiary butyl) ammonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, accelerine, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, the N-Diethyl Aniline, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, N-dimethyl-(2,4, the 6-trimethylaniline), four (3, two (trifluoromethyl) phenyl of 5-) boric acid

, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenylcarbenium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenyl phosphonium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triethylsilyl, four (3, two (trifluoromethyl) phenyl of 5-) boric acid benzene (diazonium salt), with dialkyl ammonium salt as four (pentafluorophenyl group) boric acid di-isopropyl ammonium and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium, with other San Qu Dai phosphonium salt, as four (pentafluorophenyl group) boric acid three (o-tolyl) Phosphonium and four (pentafluorophenyl group) boric acid three (and 2,6-3,5-dimethylphenyl) Phosphonium.

Ion chemistry metering activator (L-H) ⁺ _d(A ^D-) most preferably be four (perfluorophenyl) boric acid N, accelerine, four (perfluor naphthyl) boric acid N, accelerine, four (perfluorinated biphenyl) boric acid N, accelerine, four (3, two (trifluoromethyl) phenyl of 5-) boric acid N, accelerine, four (perfluor naphthyl) boric acid triphenylcarbenium, four (perfluorinated biphenyl) boric acid triphenylcarbenium, four (3, two (trifluoromethyl) phenyl of 5-) boric acid triphenylcarbenium or four (perfluorophenyl) boric acid triphenylcarbenium.

In one embodiment, use and not contain active proton but can produce bulky ligand metallocene catalyst positively charged ion and the activation method of the ionization ionic compound of Qi Fei coordination anion is also considered, and be described in EP-A-0426637, EP-A-0573403 and US5,387, in 568, these documents all are incorporated herein by reference here.

Term " non-coordination anion " (NCA) be meant not with described positively charged ion coordination or only with described positively charged ion a little less than coordination so keep easily by the enough instable negatively charged ion of neutral Lewis base metathetical.The non-coordination anion of " consistency " be when the initial title complex that forms decomposes, be not degraded to neutral those.This negatively charged ion can not be passed to positively charged ion with anion substituent or segment and make it form neutral four-coordination metallocene compound and from this anionic neutral byproduct in addition.Can be used for non-coordination anion of the present invention and be compatible, stablize metallocene cation (with regard to balance its+1 attitude ionic charge with regard to) and between polymerization period, keep enough permission by olefinic or instable those negatively charged ion of acetylene series unsaturated monomer metathetical.These type promotors use triisobutyl aluminium or trioctylaluminum as scavenging agent sometimes.

The inventive method also can be used cocatalyst compound or activator compound, is Lewis acid when they begin but is forming cationic metal title complex and non-coordination anion or zwitter-ion title complex when reacting with The compounds of this invention.For example three (pentafluorophenyl group) boron or aluminium play the effect of capturing alkyl or hydride part and producing cationic metal title complex of the present invention and stable non-coordination anion, referring to EP-A-0 427 697 and EP-A-0 520 732 (for similar 4 family's metallocene compounds are described).In addition, referring to method and the compound of EP-A-0 495 375.In order to use similar 4 family's chemical combination to form the zwitter-ion title complex, referring to US5,624,878,5,486,632 and 5,527,929.

When the positively charged ion of non-coordination anion precursor was those of Bronsted acid such as proton or protonated Lewis base (not comprising water) or reductibility Lewis acid such as ferrocene or silver-colored positively charged ion or basic metal or alkaline earth metal cation such as sodium, magnesium or lithium, the mol ratio of catalyst precursor and activator can be any ratio.The composition of described activator compound also can be used for activation.For example, three (perfluorophenyl) boron can be used with methylaluminoxane.

Conventional type promotor (activator)

Usually, do not comprise the conventional transition metal catalyst compound conventional promotor activation that can represent one or more by following general formula of some conventional type chrome catalysts compounds:

M ³M ⁴ _v X ² _c R ² _b-c。(15)

M wherein ³Be the periodic table of elements 1 to 3 family and 12 to 13 family's metals; M ⁴Be the periodic table of elements 1 family's metal; V is 0 to 1 number; Each X ²Be any halogen; C is 0 to 3 number; Each R ²Be univalence hydrocarbyl or hydrogen; B is 1 to 4 number; Wherein b-c is at least 1.Other conventional type organo-metallic cocatalyst compound that is used for above-mentioned conventional type transition-metal catalyst has formula M ³R ² _k, M wherein ³For IA, IIA, IIB or IIIA family metal, as lithium, sodium, beryllium, barium, boron, aluminium, zinc, cadmium and gallium; K equals 1,2 or 3, depends on M ³Valence state, this valence state generally depends on M again ³Affiliated concrete family; Each R ²Can be any univalence hydrocarbyl.

The non-limitative example that can be used for the conventional type organo-metallic cocatalyst compound of above-mentioned conventional type catalyst compound comprises that lithium methide, butyllithium, dihexyl mercury, dibutyl magnesium, diethyl cadmium, benzyl potassium, zinc ethyl, three n-butylaluminum, diisobutyl ethyl boron, diethyl cadmium, di-n-butyl zinc and three n-pentyl boron, particularly aluminum alkyls are as three hexyl aluminium, triethyl aluminum, trimethyl aluminium and triisobutyl aluminium.Other conventional type cocatalyst compound comprises single Organohalogen compounds of 2 family's metals and the list of hydride and 3 and 13 family's metals-or two-Organohalogen compounds and hydride.The non-limitative example of these conventional type cocatalyst compounds comprises bromination diisobutyl aluminum, isobutyl dichloride boron, methylmagnesium-chloride, tonsilon beryllium, bromination ethyl calcium, diisobutylaluminium hydride, hydrogenation methyl cadmium, hydrogenation diethyl boron, hydrogenation hexyl beryllium, hydrogenation dipropyl boron, hydrogenation octyl group magnesium, hydrogenation butyl zinc, hydrogenation dichloro-boron, hydrogenation two bromo aluminium and hydrogenation bromo cadmium.Conventional type organo-metallic cocatalyst compound be well known in the art those, and the more thorough discussion of these compounds can be at US 3,221, finds in 002 and 5,093,415, these documents all are incorporated herein by reference here.

Other activator

Other activator comprises those that describe among the WO98/07515, as (2,2 ', 2 " nine fluorine xenyls) fluoaluminate, the disclosure document all is incorporated herein by reference here.The combination of activator also is that the present invention considers, for example aikyiaiurnirsoxan beta and ionization activator combination is for example referring to EP-B10573120, WO 94/07928 and WO 95/14044 and US5,153,157 and 5,453,410, all these documents all are incorporated herein by reference here.

Other suitable activator is disclosed among the WO 98/09996 (being incorporated herein by reference here), and the document is described with perchlorate, periodate and iodate (comprising its hydrate) activation bulky ligand metallocene catalyst compound.WO 98/30602 and WO98/30603 (being incorporated herein by reference here) have described the activator as the bulky ligand metallocene catalyst compound with (2,2 '-two phenyl-two trimethylammonium silicic acid) lithium 4THF.WO 99/18135 (being incorporated herein by reference here) has described and has used organic boron-aluminium activator.EP-B1-0781299 has described the compatible negatively charged ion combination with non-coordination of use silyl salt.In addition, the activation method of also considering for example to use radiation (referring to EP-B1-0615981, being incorporated herein by reference), electrochemical oxidation etc. here is as making neutral bulky ligand metallocene catalyst compound or precursor become the activation method of bulky ligand metallocene cation that can olefin polymerization.Other activator and the method for activation bulky ligand metallocene catalyst compound are described in for example US 5,849,852,5,859,653 and 5,869,723 and these documents of WO98/32775, WO 99/42467 (two-octadecyl methyl ammonium-two (three (pentafluorophenyl group) borine) benzoglyoxaline alkane (benz imi dazolide)) be incorporated herein by reference here.

Another suitable following general formula of formation ionic active cocatalyst is represented comprises the compatible anionic salt with non-coordination of cation oxidant:

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

OX wherein ^E+For having the cation oxidant of electric charge e+; E is 1 to 3 integer; And A ^-With d be previously defined.The example of cation oxidant comprises: ferrocene, Ag that ferrocene, alkyl replace ⁺Or pb ^{+ 2}A ^D-Preferred embodiment be the front at the activator that contains Bronsted acid, those negatively charged ion of four (pentafluorophenyl group) borate definition particularly.

In the scope of the invention, catalyst compound can combine with above-mentioned one or more activators or activation method.For example, a kind of combination of activator has been described in US 5,153, and 157 and 5,453,410, among EP-B10573120 and WO 94/07928 and the WO 95/14044.These documents all have been discussed by aikyiaiurnirsoxan beta and the ionization activator uses with the bulky ligand metallocene catalyst compound.

The selection of transition metal catalyst component

Catalyst system of the present invention comprises above-mentioned two or more transistion metal compounds.At least a compound must production crystallization poly-alpha-olefin, preferably have degree of crystallinity 40% or higher isotatic polypropylene or syndiotactic polypropylene.Other compound must can be produced amorphous poly-alpha-olefin, preferably has degree of crystallinity 20% or lower Atactic Polypropelene.

The transition metal component of choosing that is used for crystalline polymer level part is the subclass of the transition metal component of equation 8-9.Preferred ingredients explanation in following equation 17

Wherein A ', M, X ₁And X ₂For previously defined.Substituting group S " v is defined as the S among the equation 8-9 independently ", wherein subscript " v " is represented the carbon atom on the Cp-ring of this substituting group and its bonding.

The metallocene precursor that is used for producing the poly--alhpa olefin of the isotactic characteristic with raising is preferably those of equation 17, wherein S " _vChoose independently and make metallocene skeleton 1) symmetrical plane at no containing metal center; With 2) have a C that passes metal center ₂-symmetry axis.These title complexs such as racemize-Me ₂Si (indenyl) ₂ZrMe ₂And racemize-Me ₂Si (indenyl) ₂HfMe ₂Be known in this field, produce isotactic polymer usually with taxis higher than low symmetrical chirality system.In addition, the transistion metal compound that can produce another preferred type that is applicable to isotactic polymer of the present invention is US5, those disclosed monocyclopentadienyl catalyzer in 026,798, and the document is incorporated herein by reference here.

According to the invention provides be exclusively used in produce isotactic poly--the preferred chiral racemic metallocene compound of the catalyst system of alhpa olefin comprises the racemize modification of following material:

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Dimethylsilane two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

9-silicon heterofluorene two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Dimethylsilane two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

9-silicon heterofluorene two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂The dimethyl hafnium;

Dimethylsilane two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3 divinyl;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene; V dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1 4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1 4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The dimethylamino borine (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The dimethylamino borine (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The dimethylamino borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

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

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

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

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

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

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

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

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

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

The diisopropylaminoethyl borine (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

The diisopropylaminoethyl borine (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl; The diisopropylaminoethyl borine (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

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

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

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

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

The diisopropylaminoethyl borine (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-methyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-normal-butyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dichloride;

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

Two (trimethyl silyl) amino borane (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dichloride;

Two (trimethyl silyl) amino borane (the 2-methyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-ethyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-sec.-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-n-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-normal-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-isobutyl-, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Two (trimethyl silyl) amino borane (2-methyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-isobutyl-, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 ' two-tert-butyl-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-ethyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-sec.-propyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-trifluoromethyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-ethyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-n-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-sec.-propyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-normal-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-isobutyl-, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-sec-butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-diisopropyl phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-methyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-sec.-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-normal-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-isobutyl-, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl;

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl; With

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl; Or the like.

Most preferred material is the racemic modification of following material:

Two (indenyl) zirconium dichlorides of dimetylsilyl, two (indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, two (tetrahydro indenyl) zirconium dichlorides of dimetylsilyl, two (tetrahydro indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (tetrahydro indenyl) zirconium dichloride, ethylenebis (tetrahydro indenyl) zirconium dimethyl, two (the 2-methyl indenyl) zirconium dichlorides of dimetylsilyl, two (the 2-methyl indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (2-methyl indenyl) zirconium dichloride, ethylenebis (2-methyl indenyl) zirconium dimethyl, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of dimetylsilyl, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (2-methyl-4-phenyl indenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenyl indenyl) zirconium dimethyl, dimetylsilyl two (4,7-dimethyl indenyl) zirconium dichloride, dimetylsilyl two (4,7-dimethyl indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of dimetylsilyl, two (indenyl) dimethyl hafniums of dimetylsilyl, ethylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) dimethyl hafnium, two (tetrahydro indenyl) hafnium dichloride of dimetylsilyl, two (tetrahydro indenyl) dimethyl hafniums of dimetylsilyl, ethylenebis (tetrahydro indenyl) hafnium dichloride, ethylenebis (tetrahydro indenyl) dimethyl hafnium, two (the 2-methyl indenyl) hafnium dichloride of dimetylsilyl, two (2-methyl indenyl) the dimethyl hafniums of dimetylsilyl, ethylenebis (2-methyl indenyl) hafnium dichloride, ethylenebis (2-methyl indenyl) dimethyl hafnium, two (2-methyl-4-phenyl indenyl) hafnium dichloride of dimetylsilyl, two (2-methyl-4-phenyl indenyl) the dimethyl hafniums of dimetylsilyl, ethylenebis (2-methyl-4-phenyl indenyl) hafnium dichloride, ethylenebis (2-methyl-4-phenyl indenyl) dimethyl hafnium, dimetylsilyl two (4,7-dimethyl indenyl) hafnium dichloride, dimetylsilyl two (4,7-dimethyl indenyl) dimethyl hafnium, ethylenebis (4,7-dimethyl indenyl) hafnium dichloride and ethylenebis (4,7-dimethyl indenyl) dimethyl hafnium.

Similarly, have the metallocene precursor that tacticity control is provided, wherein (A-Cp) is (Cp) (Cp ^*), two Cp and Cp ^*On the cyclopentadienyl rings of enough spatial volumes, have the rotation of substituting group, so satisfy above-mentioned symmetric condition with the restriction cyclopentadienyl ligands.This type of preferred chiral racemic metallocene comprises couple (three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-2, the 5-dialkylene) zirconium dimethyl and-hafnium, two ((1R)-9,9-dimethyl three ring [6.1.1.0 ^2,6] last of the ten Heavenly stems-2, the 5-dialkylene) zirconium dimethyl, two (three the ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-2,5,8-trialkenyl) zirconium dimethyl, two (three ring [5.2.2.0 ^2,6] 11 carbon-2,5, the 8-trialkenyl) zirconium dimethyl and-hafnium and two ((1R, 8R)-7,7,9,9-tetramethyl-[6.1.1.0 ^2,6] last of the ten Heavenly stems-2, the 5-dialkylene) zirconium dimethyl and-hafnium.

The metallocene precursor that is used for producing the poly-alpha-olefin that has between enhanced the rule characteristic preferably also is those of equation 17, and wherein S " chooses independently and makes two Cp-parts have different spatial volumes.For producing syndiotactic polymer, the substituent pattern on the Cp-ring is important.Therefore, the difference on term space difference used herein or the space is used in reference to Cp and Cp ^*Space characteristics difference between the ring, this difference make separately with respect to A bridged group symmetry, but different mutually, and so the approach of each follow-up monomeric unit of polymer chain is introduced in control.Cp and Cp ^*Space difference between the ring plays and stops the approaching random approaching effect of monomer, and monomer is added in the polymer chain with a rule configuration.

Being used to produce the preferred metallocene precursor of syndiotactic polymer, is in the equation 17 those, wherein S " choose independently and make 1) space difference between two Cp-parts maximum and 2) C that exists in the equation 17 metal center that passes and Cp-to encircle ₁And C _{1 '}A symmetrical plane of carbon atom.Therefore, have this symmetric title complex such as Me ₂C ( ⁵-C ₅H ₄) (1-fluorenyl) MMe ₂(wherein M=Ti, Zr or Hf) is preferred, and compares the syndiotactic polymer that common production has higher taxis with similar but low symmetric system.In addition, in the superincumbent equation, the 1-fluorenyl can be by 3,8-di-t-butyl fluorenyl, octahydrofluorenyl or 3,3,6,6,9,9,12, and 12-prestox-4,4,5,5,10,10,11,11-octahydro dibenzo [b, h] fluorenes replaces.Because this type of preceding body catalyst ability of polymkeric substance taxis out of hand under the pyroreaction temperature usually, therefore for guaranteeing higher crystallinity in material, need be than the low reactor temperature, preferably be lower than 80 ℃ of these catalyzer of use down.

The preferred catalyst that can produce the lower molecular weight isotatic polypropylene is US5, those that describe in 120,867, and this patent is incorporated herein by reference here.Can one be used from any mixture (comprising supported catalyst) that in the configuration of single reaction vessel and serial reaction device, also can produce required polyacrylic catalyzer and can be used for production scene blend among the present invention.Preferred catalyzer comprises cyclopentadienyl transition metal compounds and its derivative that is used in combination with aikyiaiurnirsoxan beta and/or compatible non-coordination anion.

The in addition preferred catalyzer that can produce crystalline polypropylene is disclosed in Chem.rev.2000, and 100, among the 1253-1345, the document is incorporated herein by reference here.

The transition metal component of preferably choosing that is used for amorphous polymer level part is the list of equation 10-cyclopentadienyl transition metal component, and wherein y equals 1.Explanation in this preferred ingredients equation 18 below:

Wherein A ', J, S ', X ₁, X ₂, L ', z and w be previously defined, M is a titanium.Substituting group S " _vDefinition and equation 10 in S " identical, carbon atom on the substituent cyclopentadienyl rings of subscript " v " expression bonding wherein, wherein on cyclopentadienyl rings, can have zero, two or four substituting group S ", condition is that cyclopentadienyl rings is replaced by symmetry." group replacement that the symmetry replacement is defined as and is meant that cyclopentadienyl rings is at 2 and 5 and/or 3 and 4 S with about same space volume.Usually " size of group differs within 2 carbon atoms these S.Therefore at 2 and 5 respectively by methyl with ethyl replaces or be considered to symmetric at 3 and 4 cyclopentadienyls that replaced by hexyl and octyl group respectively.In addition, cyclopentadienyl rings can " group replaces, as long as each symmetry promptly can be considered symmetry to having similar spatial volume in all 4 positions by S.In addition, " group can be connected to form ring to two adjacent S in 3 and 4, replaces as long as this new ring also is a symmetry.

When introduce C3 or more during high alpha-olefin known this type of catalyst system give 2,1-misidentification (mistake).Wherein the preceding body catalyst of S ' by 3 ° of carbon (when for example S ' is for the tertiary butyl or 1-adamantyl) and nitrogen ligand (J) bonding with when S ' by 1 ° of carbon (when for example S ' is normal-butyl, methyl or benzyl) or 2 ° of carbon (when for example S ' is cyclo-dodecyl, cyclohexyl or sec-butyl) compare with the preceding body catalyst of nitrogen ligand (J) bonding have seldom 2, the 1-misidentification.In this main polymer chain 2,1-misidentification give can be useful to polymer performance (CH ₂) ₂The unit.The catalyst system that the sign of this base polymer, this base polymer and being used to is produced this base polymer is described in US5, and in 723,560, this patent is incorporated herein by reference here.The low Mw variant of this base polymer can be by changing processing condition, for example by improving temperature of reactor production.

Most preferred material is: dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, and dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium.

In addition, under higher reaction temperatures, some catalyzer of rule poly-alpha olefins will be produced noncrystalline in fact poly-alpha olefins between producing at a lower temperature under comparatively high temps.The transition metal component of choosing for this amorphous polymer level part is the subclass for the transition metal component of equation 8-9.Explanation in this type of preferred ingredient equation 19 below:

Wherein A ', M, X ₁And X ₂For previously defined.Substituting group S " _vAnd S " ' _vBeing S right among the equation 8-9 independently, " definition, wherein substituent Cp-ring of subscript " v " expression bonding or Flu-encircle carbon atom on (fluorenyl-ring) ring.

(when under higher temperature of reactor condition when the catalyzer) be used to produce metallocene precursor and be preferably those of equation 19 with the poly-alpha-olefin that is mainly amorphous feature, wherein " ' v chooses so that the metallocene framework has the containing metal center and Flu-and Cp-ring are divided into two-part symmetrical plane S independently.A ' part does not need dimetylsilyl of symmetry-for example or aminomethyl phenyl silyl not to influence the stereochemistry of the polymkeric substance of production.Substituting group S " ' _vDefinition and equation 8-9 in S " identical, carbon atom on the substituent cyclopentadienyl rings of subscript " v " expression bonding wherein, wherein on cyclopentadienyl rings, can have zero, two or four substituting group S " ', condition is that cyclopentadienyl rings is replaced by symmetry." ' group replacement that the symmetry replacement is defined as and is meant that cyclopentadienyl rings is at 2 and 5 and/or 3 and 4 S with about same space volume.Usually " size of ' group differs in 2 carbon atoms these S.Therefore at 2 and 5 respectively by methyl with ethyl replaces or be considered to symmetric at 3 and 4 cyclopentadienyls that replaced by hexyl and octyl group respectively.In addition, cyclopentadienyl rings can " ' group replaces, as long as each symmetry can be regarded as symmetric to having similar spatial volume in all 4 positions by S.In addition, " ' group can be connected to form ring to two adjacent S in 3 and 4, replaces as long as this new ring also is a symmetry.Because S on the fluorenyl ring " _vSubstituting group is at a distance of far away, and therefore, these substituting groups do not need symmetry to be placed on the fluorenes ring.Therefore the fluorenyl ring can be replaced by identical or different 0-7 substituting group." group can optionally be connected to form ring to the S that two or more are adjacent.

Most preferred material is: two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) zirconium dichloride, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) hafnium dichloride, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) zirconium dimethyl, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) dimethyl hafnium, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyl) zirconium dichloride, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyl) hafnium dichloride, two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyl) zirconium dimethyl, with two (right-the triethylsilyl phenyl) methylene radical (cyclopentadienyl) (3,3,6,6,9,9,12,12-prestox-4,4,5,5,8,8,9,9-octahydro dibenzyl [b, h] fluorenyl) dimethyl hafnium.

In addition, the compound of general formula 20 can be used for producing amorphous polymer level part.

In the case, S _v" choose independently, M and A ' are divided into two-part symmetrical plane so that the metallocene framework has.Substituting group S _v" be defined as independently with equation 8-9 in S " identical, wherein carbon atom on the substituent cyclopentadienyl rings of subscript " v " expression bonding wherein can have zero to four substituting group S on cyclopentadienyl rings ", condition is that cyclopentadienyl rings is replaced by symmetry.Symmetry replace be defined as be meant cyclopentadienyl rings in 2 and 2 ' position and/or 3 and 3 ' position and/or 4 and 4 ' position and/or 5 and 5 ' position is had the S of about same space volume, and " group replaces.Usually " size of group differs in 2 carbon atoms these S.Therefore in 2 and 2 ' position respectively by methyl with ethyl replaces or the cyclopentadienyl that replaced by hexyl and octyl group respectively in 3 and 3 ' position is considered to symmetric.In addition, cyclopentadienyl rings can " group replaces, as long as each symmetry then is considered to symmetric to having similar spatial volume in all 4 positions by S.In addition, " group can be connected to form ring to two adjacent S, replaces as long as this new ring also is a symmetry.These title complexs such as meso-Me ₂Si (indenyl) ₂ZrMe ₂, meso-CH ₂CH ₂(indenyl) ₂ZrCl ₂Be well known in the art, generally can be used for production amorphous polymer of the present invention.

According to the invention provides the meso variant that the preferred meso-metallocene compound that is exclusively used in the catalyst system of producing amorphous poly-alpha-olefin comprises following material: two (indenyl) zirconium dichlorides of dimetylsilyl, two (indenyl) zirconium dimethyls of dimetylsilyl, two (indenyl) zirconium dichlorides of diphenylmethyl silylation, two (indenyl) zirconium dimethyls of diphenylmethyl silylation, two (indenyl) zirconium dichlorides of aminomethyl phenyl silyl, two (indenyl) zirconium dimethyls of aminomethyl phenyl silyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, methylene-bis (indenyl) zirconium dichloride, methylene-bis (indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of dimetylsilyl, two (indenyl) dimethyl hafniums of dimetylsilyl, two (indenyl) hafnium dichloride of diphenylmethyl silylation, two (indenyl) dimethyl hafniums of diphenylmethyl silylation, two (indenyl) hafnium dichloride of aminomethyl phenyl silyl, two (indenyl) dimethyl hafniums of aminomethyl phenyl silyl, ethylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) dimethyl hafnium, methylene-bis (indenyl) hafnium dichloride, methylene-bis (indenyl) dimethyl hafnium, two (tetrahydro indenyl) zirconium dichlorides of dimetylsilyl, two (tetrahydro indenyl) zirconium dimethyls of dimetylsilyl, two (tetrahydro indenyl) zirconium dichlorides of diphenylmethyl silylation, two (tetrahydro indenyl) zirconium dimethyls of diphenylmethyl silylation, two (tetrahydro indenyl) zirconium dichlorides of aminomethyl phenyl silyl, two (tetrahydro indenyl) zirconium dimethyls of aminomethyl phenyl silyl, ethylenebis (tetrahydro indenyl) zirconium dichloride, ethylenebis (tetrahydro indenyl) zirconium dimethyl, methylene-bis (tetrahydro indenyl) zirconium dichloride, methylene-bis (tetrahydro indenyl) zirconium dimethyl, two (tetrahydro indenyl) hafnium dichloride of dimetylsilyl, two (tetrahydro indenyl) dimethyl hafniums of dimetylsilyl, two (tetrahydro indenyl) hafnium dichloride of diphenylmethyl silylation, two (tetrahydro indenyl) dimethyl hafniums of diphenylmethyl silylation, two (tetrahydro indenyl) hafnium dichloride of aminomethyl phenyl silyl, two (tetrahydro indenyl) dimethyl hafniums of aminomethyl phenyl silyl, ethylenebis (tetrahydro indenyl) hafnium dichloride, ethylenebis (tetrahydro indenyl) dimethyl hafnium, methylene-bis (tetrahydro indenyl) hafnium dichloride, methylene-bis (tetrahydro indenyl) dimethyl hafnium, two (the 2-methyl indenyl) zirconium dichlorides of dimetylsilyl, two (the 2-methyl indenyl) zirconium dimethyls of dimetylsilyl, two (the 2-methyl indenyl) zirconium dichlorides of diphenylmethyl silylation, two (the 2-methyl indenyl) zirconium dimethyls of diphenylmethyl silylation, two (the 2-methyl indenyl) zirconium dichlorides of aminomethyl phenyl silyl, two (the 2-methyl indenyl) zirconium dimethyls of aminomethyl phenyl silyl, ethylenebis (2-methyl indenyl) zirconium dichloride, ethylenebis (2-methyl indenyl) zirconium dimethyl, methylene-bis (2-methyl indenyl) zirconium dichloride, methylene-bis (2-methyl indenyl) zirconium dimethyl, two (the 2-methyl indenyl) hafnium dichloride of dimetylsilyl, two (2-methyl indenyl) the dimethyl hafniums of dimetylsilyl, two (the 2-methyl indenyl) hafnium dichloride of diphenylmethyl silylation, two (2-methyl indenyl) the dimethyl hafniums of diphenylmethyl silylation, two (the 2-methyl indenyl) hafnium dichloride of aminomethyl phenyl silyl, two (2-methyl indenyl) the dimethyl hafniums of aminomethyl phenyl silyl, ethylenebis (2-methyl indenyl) hafnium dichloride, ethylenebis (2-methyl indenyl) dimethyl hafnium, methylene-bis (2-methyl indenyl) hafnium dichloride, methylene-bis (2-methyl indenyl) dimethyl hafnium, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of dimetylsilyl, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of diphenylmethyl silylation, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of diphenylmethyl silylation, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of diphenylmethyl silylation, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of aminomethyl phenyl silyl, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of aminomethyl phenyl silyl, ethylenebis (2-methyl-4-phenyl indenyl) zirconium dichloride, ethylenebis (2-methyl-4-phenyl indenyl) zirconium dimethyl, methylene-bis (2-methyl-4-phenyl indenyl) zirconium dichloride, methylene-bis (2-methyl-4-phenyl indenyl) zirconium dimethyl, two (2-methyl-4-phenyl indenyl) hafnium dichloride of dimetylsilyl, two (2-methyl-4-phenyl indenyl) the dimethyl hafniums of dimetylsilyl, two (2-methyl-4-phenyl indenyl) hafnium dichloride of diphenylmethyl silylation, two (2-methyl-4-phenyl indenyl) the dimethyl hafniums of diphenylmethyl silylation, two (2-methyl-4-phenyl indenyl) hafnium dichloride of aminomethyl phenyl silyl, two (2-methyl-4-phenyl indenyl) the dimethyl hafniums of aminomethyl phenyl silyl, ethylenebis (2-methyl-4-phenyl indenyl) hafnium dichloride, ethylenebis (2-methyl-4-phenyl indenyl) dimethyl hafnium, methylene-bis (2-methyl-4-phenyl indenyl) hafnium dichloride, methylene-bis (2-methyl-4-phenyl indenyl) dimethyl hafnium, dimetylsilyl two (4,7-dimethyl indenyl) zirconium dichloride, dimetylsilyl two (4,7-dimethyl indenyl) zirconium dimethyl, diphenylmethyl silylation two (4,7-dimethyl indenyl) zirconium dichloride, diphenylmethyl silylation two (4,7-dimethyl indenyl) zirconium dimethyl, aminomethyl phenyl silyl two (4,7-dimethyl indenyl) zirconium dichloride, aminomethyl phenyl silyl two (4,7-dimethyl indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl indenyl) zirconium dimethyl, methylene-bis (4,7-dimethyl indenyl) zirconium dichloride, methylene-bis (4,7-dimethyl indenyl) zirconium dimethyl, dimetylsilyl two (4,7-dimethyl indenyl) hafnium dichloride, dimetylsilyl two (4,7-dimethyl indenyl) dimethyl hafnium, diphenylmethyl silylation two (4,7-dimethyl indenyl) hafnium dichloride, diphenylmethyl silylation two (4,7-dimethyl indenyl) dimethyl hafnium, aminomethyl phenyl silyl two (4,7-dimethyl indenyl) hafnium dichloride, aminomethyl phenyl silyl two (4,7-dimethyl indenyl) dimethyl hafnium, ethylenebis (4,7-dimethyl indenyl) hafnium dichloride, ethylenebis (4,7-dimethyl indenyl) dimethyl hafnium, methylene-bis (4,7-dimethyl indenyl) hafnium dichloride, methylene-bis (4,7-dimethyl indenyl) dimethyl hafnium etc.

Most preferred material is the racemic modification of following material: two (indenyl) zirconium dichlorides of dimetylsilyl, two (indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of dimetylsilyl, two (indenyl) dimethyl hafniums of dimetylsilyl, ethylenebis (indenyl) hafnium dichloride, ethylenebis (indenyl) dimethyl hafnium, two (tetrahydro indenyl) zirconium dichlorides of dimetylsilyl, two (tetrahydro indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (tetrahydro indenyl) zirconium dichloride, ethylenebis (tetrahydro indenyl) zirconium dimethyl, two (tetrahydro indenyl) hafnium dichloride of dimetylsilyl, two (tetrahydro indenyl) dimethyl hafniums of dimetylsilyl, ethylenebis (tetrahydro indenyl) hafnium dichloride, ethylenebis (tetrahydro indenyl) dimethyl hafnium, two (the 2-methyl indenyl) zirconium dichlorides of dimetylsilyl, two (the 2-methyl indenyl) zirconium dimethyls of dimetylsilyl, ethylenebis (2-methyl indenyl) zirconium dichloride, ethylenebis (2-methyl indenyl) zirconium dimethyl, two (the 2-methyl indenyl) hafnium dichloride of dimetylsilyl, two (2-methyl indenyl) the dimethyl hafniums of dimetylsilyl, ethylenebis (2-methyl indenyl) hafnium dichloride, and ethylenebis (2-methyl indenyl) dimethyl hafnium.

In the time will being used for a reactor as hybrid catalyst system based on the catalyzer of two kinds of transistion metal compounds, these two kinds of transistion metal compounds should be chosen compatible.Simple screening method such as those skilled in the art are known ¹H or ¹³Which transistion metal compound C NMR can be used for measuring is compatible.

It is preferred using identical activator for these transistion metal compounds, yet two kinds of different activators of use capable of being combined are as non-coordination anion activator and aikyiaiurnirsoxan beta.If one or more transistion metal compounds comprise and are not the X of hydride, alkyl or substituted hydrocarbon radical ₁Or X ₂Part then should contact aikyiaiurnirsoxan beta before adding non-coordination anion activator with transistion metal compound.

The special preferably combination of transistion metal compound comprises:

(1) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂(2-Me-4-PhInd=2-methyl-4-phenyl indenyl, c-C ₁₂H ₂₃=cyclo-dodecyl, Me ₄C ₅-tetramethyl-ring pentadienyl), with aikyiaiurnirsoxan beta such as methylaluminoxane or modified methylaluminoxane activation;

(2) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(3) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂(2-MeInd=2-methyl-indenyl) is with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(4) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(5) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(6) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(7) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(8) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(9) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(10) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(11) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) is with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(12) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(13) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(14) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(15) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(16) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(17) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂(3,8-di-t-BuFlu=3,8-two-tertiary butyl fluorenyl, Cp=cyclopentadienyl) are with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(18) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(19) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(20) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(21) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrCl ₂(Ind=indenyl, H ₄The Ind=tetrahydro indenyl), with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(22) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(23) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(24) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(25) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(26) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(27) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(28) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(29) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(30) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(31) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(32) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(33) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(34) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(35) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(36) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(37) meso-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(38) meso-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(39) meso-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(40) meso-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(41) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(2-MePhInd) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(42) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(43) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(Ind) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(44) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(45) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (Ind) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(46) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(47) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂(4,7-Me ₂Ind=4,7-dimethyl indenyl), with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(48) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(49) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(50) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(51) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂(4,7-Me ₂Ind=4,7-dimethyl indenyl), with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta;

(52) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(53) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂, with for example methylaluminoxane or modified methylaluminoxane activation of aikyiaiurnirsoxan beta; With

(54) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator such as N, accelerine four (pentafluorophenyl group) boron or the activation of triphenylcarbenium four (pentafluorophenyl group) boron.

These two kinds of transistion metal compounds (preceding body catalyst) can any ratio use.(A) transistion metal compound of production amorphous polymer falls in the following scope with the preferred molar ratio of (B) transistion metal compound of producing crystalline polymer: (A: B) 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 5: 1 to 50: 1.The specified proportion of choosing depends on concrete preceding body catalyst, activation method and the required the finished product of choosing.In specific embodiment, during body catalyst before using two kinds (A-" produces the preceding body catalyst of amorphous polymer " and B-" produces the catalyzer of crystalline polymer "), wherein activate both with identical activator, preferred molecular fraction by the molecular weight of preceding body catalyst count 10 to 99.9%A than 0.1 to 90%B, or 25 to 99%A than 0.5 to 50%B, or 50 to 99%A than 1 to 25%B, or 75 to 99%A than 1 to 10%B.

Usually, bonded precursor catalyst compound and activator bonded ratio are about 1: 10,000 to about 10: 1.When using aikyiaiurnirsoxan beta or alkyl aluminum activator, the mol ratio of body catalyst and activator is 1: 5000 to 10: 1 before the bonded, or 1: 1000 to 10: 1, or 1: 500 to 2: 1, or 1: 300 to 1: 1.When using the ionization activator, the mol ratio of bonded precursor catalyst compound and activator is 10: 1 to 1: 10; 5: 1 to 1: 5; 2: 1 to 1: 2 or 1.2: 1 to 1: 1.Can use multiple activator, comprise the mixture that uses aikyiaiurnirsoxan beta or aluminum alkyls and ionization activator.

In another embodiment preferred, the third catalyzer (preceding body catalyst adds activator) is present in the aforesaid method.The arbitrary precursor catalyst component of the third catalyzer for listing here.Preferred the third precursor catalyzer comprises can produce for which of wax.Preferred example comprises: racemize-dimetylsilyl two (4,7-dimethyl indenyl) hafnium dichloride, racemize-dimetylsilyl two (4,7-dimethyl indenyl) dimethyl hafnium, racemize-dimetylsilyl two (4,7-dimethyl indenyl) zirconium dichloride, racemize-dimetylsilyl two (4,7-dimethyl indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of racemize-dimetylsilyl, two (indenyl) dimethyl hafniums of racemize-dimetylsilyl, two (indenyl) zirconium dichlorides of racemize-dimetylsilyl, two (indenyl) zirconium dimethyls of racemize-dimetylsilyl, two (tetrahydro indenyl) hafnium dichloride of racemize-dimetylsilyl, two (tetrahydro indenyl) dimethyl hafniums of racemize-dimetylsilyl, two (tetrahydro indenyl) zirconium dichlorides of racemize-dimetylsilyl, two (the four ammonia indenyls) zirconium dimethyls of racemize-dimetylsilyl, racemize-diphenylmethyl silylation two (4,7-dimethyl indenyl) hafnium dichloride, racemize-diphenylmethyl silylation two (4,7-dimethyl indenyl) dimethyl hafnium, racemize-diphenylmethyl silylation two (4,7-dimethyl indenyl) zirconium dichloride, racemize-diphenylmethyl silylation two (4,7-dimethyl indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of racemize-diphenylmethyl silylation, two (indenyl) dimethyl hafniums of racemize-diphenylmethyl silylation, two (indenyl) zirconium dichlorides of racemize-diphenylmethyl silylation, two (indenyl) zirconium dimethyls of racemize-diphenylmethyl silylation, two (tetrahydro indenyl) hafnium dichloride of racemize-diphenylmethyl silylation, two (tetrahydro indenyl) dimethyl hafniums of racemize-diphenylmethyl silylation, two (tetrahydro indenyl) zirconium dichlorides of racemize-diphenylmethyl silylation, two (tetrahydro indenyl) zirconium dimethyls of racemize-diphenylmethyl silylation, racemize-aminomethyl phenyl silyl two (4,7-dimethyl indenyl) hafnium dichloride, racemize-aminomethyl phenyl silyl two (4,7-dimethyl indenyl) dimethyl hafnium, racemize-aminomethyl phenyl silyl two (4,7-dimethyl indenyl) zirconium dichloride, racemize-aminomethyl phenyl silyl two (4,7-dimethyl indenyl) zirconium dimethyl, two (indenyl) hafnium dichloride of racemize-aminomethyl phenyl silyl, two (indenyl) dimethyl hafniums of racemize-aminomethyl phenyl silyl, two (indenyl) zirconium dichlorides of racemize-aminomethyl phenyl silyl, two (indenyl) zirconium dimethyls of racemize-aminomethyl phenyl silyl, two (tetrahydro indenyl) hafnium dichloride of racemize-aminomethyl phenyl silyl, two (tetrahydro indenyl) dimethyl hafniums of racemize-aminomethyl phenyl silyl, two (tetrahydro indenyl) zirconium dichlorides of racemize-aminomethyl phenyl silyl, two (tetrahydro indenyl) zirconium dimethyls of racemize-aminomethyl phenyl silyl, racemize-ethylenebis (4,7-dimethyl indenyl) hafnium dichloride, racemize-ethylenebis (4,7-dimethyl indenyl) dimethyl hafnium, racemize-ethylenebis (4,7-dimethyl indenyl) zirconium dichloride, racemize-ethylenebis (4,7-dimethyl indenyl) zirconium dimethyl, racemize-ethylenebis (indenyl) hafnium dichloride, racemize-ethylenebis (indenyl) dimethyl hafnium, racemize-ethylenebis (indenyl) zirconium dichloride, racemize-ethylenebis (indenyl) zirconium dimethyl, racemize-ethylenebis (tetrahydro indenyl) hafnium dichloride, racemize-ethylenebis (tetrahydro indenyl) dimethyl hafnium, racemize-ethylenebis (tetrahydro indenyl) zirconium dichloride, and racemize-ethylenebis (tetrahydro indenyl) zirconium dimethyl.

Three kinds of transistion metal compounds (preceding body catalyst) can any ratio use.Produce (A) transistion metal compound and the preferred molar ratio (A: B: C) fall into following scope in: 1: 1000: 500 to 1000: 1: 1 of (B) transistion metal compound of producing crystalline polypropylene of amorphous polypropylene with (C) transistion metal compound of producing wax, 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.The specified proportion of choosing depends on concrete preceding body catalyst, activation method and the required the finished product of choosing.

Other preferred catalyst and method are described in US 6,376, and in 410 and 6,380,122, these patents are incorporated herein by reference here.

In another embodiment, catalyst composition of the present invention comprises support materials or carrier.For example one or more catalyst components and/or one or more activators can be deposited on one or more load materials or the carrier, or be in contact with it, therewith evaporation, with its bonding, or introduce wherein, absorption or absorb within it or on it.

Support materials is arbitrary conventional load material.Preferred support materials is the porous support materials, as talcum, inorganic oxide and butter.Other support materials comprises resin-carried material such as polystyrene, functionalized or crosslinked organic carrier such as polystyrene divinylbenzene polyolefine or aggretion type compound, zeolite, clay, or any other organic or inorganic support materials etc., or its mixture.

Preferred support materials is an inorganic oxide, comprises those metal oxides of 2,3,4,5,13 or 14 families.Preferred carrier comprises the silicon-dioxide that can be dehydration or non-dehydration, pyrogenic silica, aluminum oxide (WO99/60033), silicon-aluminum oxide and its mixture.Other useful carrier comprises magnesium oxide, titanium dioxide, zirconium white, magnesium chloride (US5,965,477), montmorillonite (EP-B 10511665), leaf silicate, zeolite, talcum, clay (US 6,034,187) etc.Can also use the composition of these support materials such as silicon-dioxide-chromium, silica-alumina, silica-titania etc.Other solid support material can comprise those porous propylene acids polymkeric substance of describing among the EP 0767184B1, and the document is incorporated herein by reference here.Other support materials comprises among the WO 99/47598 aerogel, the US5 that describes among the nano composite material described, the WO 99/48605, the polymer beads of describing among spherocrystal of describing in 972,510 and the WO 99/50311, and these documents are incorporated herein by reference here.

Support materials (most preferably inorganic oxide) is preferably has surface-area about 10 to about 700m ²/ g, pore volume about 0.1 to about 4.0cc/g and average particle size particle size about 5 are to about 500 μ m.More preferably the surface-area of support materials is about 50 to about 500m ²/ g, pore volume be about 0.5 to about 3.5cc/g and average particle size particle size be about 10 to about 200 μ m.Most preferably surfaces of carrier materials is long-pending for about 100 to about 400m ²/ g, pore volume about 0.8 to about 3.0cc/g and average particle size particle size about 5 are to about 100 μ m.The average cell size that can be used for carrier of the present invention is generally 10-1000 dust, preferred 50 to about 500 dusts with most preferably 75 to about 350 dusts.

As well known in the art, catalyzer also can load on a kind of inert support together, or catalyzer is loaded to mixing then on two kinds of inert supports independently.In these two kinds of methods, preferred last method

In another embodiment, carrier comprises that one or more types can carry out the support materials of different treatment.For example, can use and have different pore volumes or two kinds of different silicon-dioxide of incinerating under differing temps.Can use silicon-dioxide and untreated silica in addition with scavenging agent or other additive treating.

Stereospecific catalyst can be used for preparation and has a Mw100, and 000 or lower and degree of crystallinity 30% or higher and preferably have a macromonomer of vinyl end.

As an object lesson, the method based on the macromonomer of propylene that a kind of preparation has the terminal key of high per-cent vinyl relates to:

A) in solution, the catalyst composition of propylene, non-essential a small amount of copolymerisable monomer and the activatory transition metal catalyst compound that contains solid rigid is contacted under about 80 ℃ to about 140 ℃ of temperature; With

B) recovery has number-average molecular weight about 2,000 to about 30,000 daltonian isotactic or syndiotactic polypropylene chains.

Solution preferably includes hydrocarbon solvent, and this hydrocarbon solvent is aliphatic series or aromatic solvent more preferably.In addition, preferably propylene monomer is contacted down for 90 ℃ to 120 ℃ in temperature.More preferably use temperature is 95 ℃ to 115 ℃.Most preferably propylene monomer is contacted down for 100 ℃ to 110 ℃ in temperature.Reactor pressure can preferably change to 182MPa to 345MPa at normal atmosphere usually.Reaction can be undertaken by intermittence or continuous mode.Suitable slurry-type reaction conditions also is suitable and similar with solution condition, and polymerization is generally carried out in liquid propene under suitable this polymeric pressure.

The right choice criteria of catalyzer is discussed in front.A kind of catalyzer is generally the stereospecific catalyst of the ability of the ethenyl blocking macromonomer with production significant amounts, and another kind is generally specific and can introduces active macromonomer.Usually, it is believed that C ₂Symmetry bulky ligand metallocene catalyst can be produced the isotatic polypropylene macromonomer of ethenyl blocking.The catalyzer that helps the β methyl to eliminate also manifests usually and helps to form the isotatic polypropylene macromonomer.Two (indenyl) dimethyl hafniums of racemize-dimetylsilyl, two (2-methyl-4-phenyl indenyl) zirconium dichlorides of dimetylsilyl and racemize-ethylenebis (4,7-dimethyl indenyl) dimethyl hafnium are used for the catalyzer with isotatic polypropylene of high-vinyl chain end of the present invention for producing.High temperature usually above 80 ℃, shows the favourable ethenyl blocking that influences.In addition, Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂Production can be used for amorphous polypropylene of the present invention, and it is believed that introducing ethenyl blocking macromonomer, to produce the scPP side chain graft structure on amorphous main chain equally thus.

In another embodiment, as 1, the 9-decadiene is introduced conversion zone to promote producing ethenyl blocking aPP and scPP macromonomer with diolefine, and this macromonomer helps to increase the total amount of branch-block species.

Polymerization process

Above-mentioned catalyzer and catalyst system are applicable to solution, body, gas or slurry phase polymerisation process or its combination, in preferred solution phase, the body phase polymerisation process.

The present invention relates to solution, body, slurry or gas phase polymerization in one embodiment, one or more have 3 to 30 carbon atoms to relate to polymerization, preferred 3-12 carbon atom, the more preferably monomer of 3 to 8 carbon atoms.Preferred monomer comprise following one or more: propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1, decylene-1,3-methyl-amylene-1 and cycloolefin or its combination.Other monomer can comprise vinyl monomer, alkadiene such as diene, polyenoid, norbornylene, norbornadiene, vinyl norbornene, ethylidene norbornene monomer.Preferred homopolymer or the multipolymer of producing propylene.In another embodiment, one or more monomeric multipolymers of producing alfon and propylene simultaneously and listing above.

This can use one or more reactors of serial or parallel connection the present invention.It is believed that catalyst component and activator can solution or slurry form or be conveyed in the reactor respectively and online activation before just will entering reactor, or activation and form in the suction reactor with activatory solution or slurry in advance.Preferably be operating as two kinds of solution of online activatory.For the more information of multi-catalyst being introduced the method in the reactor, please join US 6,399,722 and WO0130862A1.Although these documents may be emphasized Gas-phase reactor, described technology is equally applicable to other type of reactor, comprises continuously stirring jar reactor, slurry loop reactor etc.Polymerization or in single reaction vessel operation, carry out, wherein add monomer, comonomer, catalyzer/activator, scavenging agent and non-essential properties-correcting agent in the single reaction vessel continuously, or in the operation of serial reaction device, carry out, wherein said components is added in each reactor of two or more reactors that are connected in series.Catalyst component can add in first reactor in the serial reaction device.Catalyst component also can be added in two reactors, wherein a kind of component is added in first reactor, and other component is added in other reactor.

In one embodiment, with 500ppm or still less or 400ppm or still less, or 300ppm or hydrogen still less add in the polymerization.In other embodiments, incite somebody to action 50ppm or 100ppm or more at least, or in 150ppm or the more hydrogen adding polymerization.

Vapour phase polymerization

Usually, at the gas fluidized bed process that is used for producing polymkeric substance, will contain one or more monomeric gas streams and in the presence of catalyzer, under reaction conditions, circulate continuously by fluidized-bed.Gas stream is drawn off and is recirculated into the reactor from fluidized-bed.Meanwhile, polymeric articles drawn off from reactor and add fresh monomer replace the polymeric monomer (for example referring to US4,543,399,4,588,790,5,028,670,5,317,036,5,352,749,5,405,922,5,436,304,5,453,471,5,462,999,5,616,661 and 5,668,228, all these documents all are incorporated herein by reference here.)

Slurry phase polymerisation

Slurry polymerization generally 1 to about 50 barometric pressure range (15psi to 735psi, 103kPa to 5068kPa) or even 0 ℃ to about 120 ℃ of bigger pressure and temperature under carry out.In slurry polymerization, add therein and form solid particle polymer suspension in the liquid polymeric diluent media of monomer, comonomer and catalyzer.The suspension that will comprise thinner is wherein separated volatile constituent, and optionally is recirculated in the reactor after distillation from reactor discontinuous or taking-up continuously from polymkeric substance.The liquid diluent that uses in polymerisation medium is generally alkane, the preferred branched alkane with 3 to 7 carbon atoms.The medium that uses should be liquid and relative inertness under polymeric reaction condition.When using propane medium, this method must be operated being higher than under reaction diluent critical temperature and the pressure.Preferred hexane or the Trimethylmethane medium of using.

In one embodiment, be used for the polymerization that preferred polymeric technology of the present invention relates to particle form, or slurry process, wherein temperature keeps below the temperature that polymkeric substance enters solution.This technology is well known in the art, and is described in US 3,248, and in 179, the document is incorporated herein by reference here.Preferred temperature in the particle form method is about 85 ℃ to about 110 ℃.Which of loop reactor and a plurality of stirred reactors that use series, parallel or its combination two kinds of preferred polymerization processs that are used for slurry process be to use.The non-limitative example of slurry process comprises continuous loop or stirred pot method.In addition, other example of slurry process is described in US4, and in 613,484, the document is incorporated herein by reference here.

In another embodiment, slurry process carries out in loop reactor continuously.With in slurry form in Trimethylmethane or the exsiccant free flowing powder formal rule ground injecting reactor loop, this reactor loop itself is full of the circulation slurry of polymer beads in the isobutane diluent that contains monomer and comonomer of producing with catalyzer.Can optionally add hydrogen as molecular weight regulator.(add 500ppm or lower in one embodiment, or 400ppm or still less, or 300ppm or hydrogen still less.In other embodiments, add 50ppm at least, or 100ppm or more, or 150ppm or more hydrogen.)

Reactor is remained under about 60 ℃ to about 104 ℃ of pressure 3620kPa to 4309kPa and the temperature, depend on required polymer melted feature.Reaction heat is removed by the loop wall, because the reactor many places are the double jacket form of tubes.Slurry is outflow reactor at regular intervals or continuously, and order enters in low pressure flash container, rotatory drier and the nitrogen purging tower of heating, to remove isobutane diluent and all unreacted monomer and comonomers.Then gained is not had the compounding of hydrocarbon powder and be used for various application.

In another embodiment, can produce greater than 2000 pounds of polymkeric substance/hr (907Kg/hr), more preferably greater than 5000 pounds of polymkeric substance/hr (2268Kg/hr) in the method that is used for the reactor that slurry process of the present invention uses and is used for the present invention, most preferably greater than 10,000 pounds of polymkeric substance/hr (4540Kg/hr).In another embodiment, be used for slurry-phase reactor production that method of the present invention uses greater than 15,000 pounds of polymkeric substance/hr (6804Kg/hr), be preferably greater than 25,000 pounds of polymkeric substance/hr (11,340Kg/hr) to about 100,000 pound of polymkeric substance/hr (45,500Kg/hr).

In another embodiment, be used for slurry process of the present invention, total reactor pressure is that 400psig (2758kPa) is to 800psig (5516kPa), preferred 450psig (3103kPa) is to about 700psig (4827kPa), more preferably 500psig (3448kPa) is to about 650psig (4482kPa), and most preferably from about 525psig (3620kPa) is to 625psig (4309kPa).

In an embodiment again, be used for slurry process of the present invention, principal monomer concentration in the liquid reactor medium is about 1 to 10wt%, and preferred about 2 to about 7wt%, and more preferably from about 2.5 to about 6wt%, and most preferably from about 3 to about 6wt%.

Being used for other method of the present invention is such method, this method wherein, the preferred slurries method lack or essentially no any scavenging agent such as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethylaluminum chloride, dibutyl zinc etc. in the presence of operate.This method is described in WO96/08520 and US5, and in 712,352, the document is incorporated herein by reference here.

In another embodiment, this method is carried out in the presence of scavenging agent.Typical scavenging agent comprises trimethyl aluminium and triisobutyl aluminium and excessive aikyiaiurnirsoxan beta or modified alumoxane.

Homogeneous phase, body or solution phase are closed

Catalyzer described herein can be advantageously used in the homogeneous solution polymerization.This is usually directed to polymerization in flow reactor, wherein the initial monomers of the polymkeric substance that forms and adding and catalystic material is stirred to reduce or to avoid concentration gradient.(10-30 carries out under high pressure 000MPa) suitable method, and wherein monomer plays the effect of thinner or use solvent in solution polymerization at 1 to 3000 crust being higher than under the melting point polymer.

Following acquisition is pressed in the temperature control of reactor: by reactor cooling, refrigeration automatically, precooling raw material, vaporised liquid medium (thinner, monomer or solvent) or this three kinds the array mode equilibrium polymerization heat that adopts reactor jacket or spiral coil cooling tube cooling reactor material.Also can use the adiabatic reactor that adds the precooling raw material.Temperature of reactor depends on the catalyzer of use.Usually, temperature of reactor preferably can be about 30 ℃ to about 160 ℃, more preferably from about 90 ℃ to about 150 ℃, most preferably from about 100 ℃ to about 140 ℃.Polymerization temperature can be depending on catalyzer and chooses and change.For example, diimine Ni catalyzer can 40 ℃ uses down, and the metallocene titanium catalyst can use under 100 ℃ or higher temperature.At serial operation, second temperature of reactor preferably is higher than first temperature of reactor.In the reactor operation of parallel connection, the temperature of two reactors is independently.This pressure can be about 1mm Hg to 2500 crust (25,000MPa), preferred 0.1 crust to 1600 crust (1-16,000MPa), 1.0 to 500 crust (10-5000MPa) most preferably.

In one embodiment, with 500ppm or still less, or 400ppm or still less, or 300ppm or hydrogen still less add polymerization.In other embodiments, incite somebody to action 50ppm or 100ppm or more at least, or in 150ppm or the more hydrogen adding polymerization.

Each of these methods also can be used in single reaction vessel, parallel connection or tandem reactor configuration.Liquid processes comprises olefinic monomer tied up in suitable diluent or the solvent with above-mentioned catalyst body and contacts, and makes described monomer reaction time enough, produces required polymkeric substance thus.Aliphatic series and aromatic hydrocarbon solvent all are suitable.Preferred alkane such as hexane, pentane, iso-pentane and octane.

This method can be at continuously stirring jar reactor, batch reactor or plug flow reactor, or carries out in the more than one reactor of serial or parallel connection operation.These reactors can have or can not have inner cooling or heating, and the monomer material can carry out or not freeze.The general approach condition is referring to US 5,001, and 205 generality is open.Also can be referring to WO 96/33227 and WO 97/22639.All documents as with reference to introducing, are to describe polymerization process, metallocene selection and useful removing compound for the US purpose.

The invention further relates to a kind of continuation method for preparing binding agent, comprising:

1) with monomer, non-essential solvent, catalyzer and activator combination in reactor system,

2) from this reactor system, draw off polymers soln,

3) from this polymers soln, remove at least 10% solvent (if existence),

4) quenching reaction,

5) this polymers soln devolatilization is formed molten polymer,

6) molten polymer and one or more additives (as describing below which) are combined in mixing tank such as static mixer, (in preferred embodiments, do not add tackifier, or its add-on is lower than 30wt%, preferably be lower than 20wt%, more preferably less than 10wt%)

7) from mixing tank, take out polymer conjugates and

8) with this polymer conjugates granulation or carry out rotary drum processing (drumming);

Wherein step 1) comprises above-mentioned arbitrary method.

In another embodiment, the present invention relates to a kind of continuation method for preparing binding agent, comprising:

1) monomer, non-essential solvent, catalyzer and activator are mixed in reactor system,

2) from reactor system, draw off polymers soln,

3) from polymers soln, remove at least 10% solvent (if existence),

4) quenching reaction,

5) the polymers soln devolatilization is formed molten polymer,

6) molten polymer is combined in mixing tank such as static mixer with one or more additives,

7) from mixing tank, take out polymer conjugates and

8) with this polymer conjugates granulation or carry out rotary drum processing.

In particularly preferred embodiments, the present invention relates to a kind of continuation method for preparing binding agent, comprising:

1) choose first catalyst component, this catalyst component can have Mw 100,000 or lower and degree of crystallinity 20% or lower polymkeric substance choosing under the polymeric condition to produce;

2) choose second catalyst component, this catalyst component can be produced under the polymerizing condition of choosing has Mw 100,000 or lower and degree of crystallinity 40% or bigger polymkeric substance;

3) with these catalyst components in solvent and in conversion zone, in the presence of one or more activators, contacting with non-essential one or more diolefine under the polymerizing condition of choosing with one or more C3 to C40 alkene;

4) be higher than under 100 ℃ in temperature;

5) under 120 minutes residence time or shorter (preferred 60 to 120 minutes);

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1;

7) wherein the activity of catalyst component is 50kg polymkeric substance/g catalyst component at least; Wherein at least 20% conversion of olefines is a polymkeric substance;

8) from conversion zone, draw off polymers soln;

9) from polymers soln, remove at least 10% solvent;

10) quenching reaction;

11) the polymers soln devolatilization is formed molten polymer;

12) molten polymer is combined in mixing tank such as static mixer with one or more additives,

13) from mixing tank, take out polymer conjugates and

14) with this polymer conjugates granulation or carry out rotary drum processing.

3) these catalyst components are being contacted with non-essential one or more diolefine with one or more C 3 to C40 alkene in the presence of one or more activators under the polymerizing condition of choosing in solvent and in conversion zone;

4) be higher than under 100 ℃ in temperature;

5) 120 minutes residence time or shorter under;

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1;

7) wherein the activity of catalyst component is 50kg polymkeric substance/g catalyst component at least; Wherein at least 50% conversion of olefines is a polymkeric substance;

8) from conversion zone, draw off polymers soln;

9) from polymers soln, remove at least 10% solvent;

10) quenching reaction;

11) form molten polymer;

Wherein polymkeric substance comprise one or more C3 to C40 alkene and be lower than the ethene of 50mol% and wherein polymkeric substance have:

A) some T shape peeling force 1 newton or higher; With

B) branch index (g ') 0.95 or lower is with the Mz measurement of polymkeric substance; With

C) Mw 100,000 or lower; With

13) from mixing tank, take out polymer conjugates and

3) these catalyst components are being contacted with non-essential one or more diolefine with one or more C3 to C40 alkene in the presence of one or more activators under the polymerizing condition of choosing in solvent and in conversion zone;

4) be higher than under 100 ℃ in temperature;

5) 120 minutes residence time or shorter under;

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1;

8) from conversion zone, draw off polymers soln;

9) from polymers soln, remove at least 10% solvent;

10) quenching reaction;

11) form molten polymer;

Wherein polymkeric substance comprise one or more C3 to C40 alkene (preferred propylene) and be lower than the ethene of 50mo l% and wherein polymkeric substance have:

A) some T shape peeling force 3 newton or bigger; With

B) branch index (g ') 0.90 or lower is with the Mz measurement of polymkeric substance; With

C) Mw 30,000 or lower;

D) the peak fusing point is 60 to 190 ℃,

E) melting heat 1 is to 70J/g,

F) the melt viscosity 8000mPasec in the time of 190 ℃ or lower; With

13) from mixing tank, take out polymer conjugates and

1) with the combination in reactor system of monomer, catalyzer and activator,

2) from reactor system, draw off polymkeric substance,

3) quenching reaction,

4) form molten polymer,

5) molten polymer is combined with one or more additives,

6) with this polymer conjugates granulation or carry out rotary drum processing.

Polymer blend

Here the polymkeric substance of Sheng Chaning can directly form binding agent as binding agent or with other component blend.

Polymkeric substance of the present invention does not need to use tackifier usually.Yet, if need tackifier, the tackifier that can combine with above-mentioned polymkeric substance be usually used in this field which.Example includes but not limited to aliphatic hydrocarbon resin, aromatic modified aliphatic hydrocarbon resin, hydrogenation polycyclopentadiene resin, polycyclopentadiene resin, resin (gum rosin), resin ester, wood rosin, wood rosin ester, toll oil rosin, toll oil rosin ester, polyterpene, aromatic modified polyterpene, terpene phenol, aromatic modified hydrogenation polycyclopentadiene resin, Hydrogenated aliphatic resin, Hydrogenated aliphatic aromatic resin, hydrogenation terpene and modification terpene, and hydrogenated wood rosin glycerol ester.In some embodiments, with tackifier hydrogenation.In other embodiments, tackifier are nonpolar.(the nonpolar essentially no monomer of tackifier that is meant with polar group.Preferably do not have polar group, yet if exist, they are 5wt% at the most preferably, preferably is no more than 2wt%, further more preferably no more than 0.5wt%).In some embodiments, tackifier have softening temperature (ring ﹠amp; The ball method is measured according to ASTM E-28) 80 ℃ to 150 ℃, preferred 100 ℃ to 130 ℃.

If there are tackifier, then its amount is generally extremely about 80wt% of about 1wt% by blend weight, more preferably 2wt% to 40wt%, further more preferably 3wt% to 30wt%.

Preferred hydrocarbons resin as tackifier or properties-correcting agent comprises:

1. resin such as C5/C6 terpene resin, vinylbenzene terpene, alpha-methyl styrene terpene resin, C9 terpene resin, aromatic modified C 5/C6, aromatic modified annular resin, aromatic modified dicyclopentadienyl resin or its mixture.Preferred in addition resin comprises WO 91/07472, US 5,571,867, US5,171,793 and US 4,078,132 in describe which.These resins generally contain one or more following monomer combination by cationoid polymerisation and obtain: C5 diolefine (as 1-3 pentadiene, isoprene etc.), C5 alkene (as 2-methyl butene, cyclopentenes etc.), C6 alkene (as hexene), C9 vi-ny l aromatic monomers (as vinylbenzene, alpha-methyl styrene, Vinyl toluene, indenes, methyl indenes etc.), cyclic monomer (as Dicyclopentadiene (DCPD), methyl bicyclic pentadiene etc.), and/or terpene (such as limonene, carene etc.).

2. by the thermopolymerization Dicyclopentadiene (DCPD), and/or the resin that obtains by thermopolymerization cyclopentadiene and/or methyl cycle pentadiene dimer or oligopolymer and non-essential vi-ny l aromatic monomers (as vinylbenzene, alpha-methyl styrene, Vinyl toluene, indenes, methyl indenes).

If need, in polymerization with can be after separating unreacted material with the resin hydrogenation of acquisition.The example of preferred resin comprises US 4,078,132, describe among WO 91/07472, US 4,994,516, EP 0046344A, EP 0082726A and the US 5,171,793 which.

In another embodiment, the adhesive composition that comprises polymeric articles of the present invention further comprises linking agent.Preferred cross-linking agents comprise have can with those of the functional group of acid or anhydride reaction.Preferred cross-linking agents comprises alcohol, many alcohol, amine, diamines and/or triamine.The example that can be used for linking agent of the present invention comprises polyamines such as quadrol, diethylenetriamine, hexamethylene-diamine, diethyl aniino propylamine and/or menthane diamines.

In another embodiment, comprise that the adhesive composition of polymeric articles of the present invention further comprises typical additive known in the art, as filler, oxidation inhibitor, auxiliary agent, adhesive accelerant, oil and/or softening agent.Preferred filler comprises titanium dioxide, lime carbonate, barium sulfate, silica, silicon-dioxide, carbon black, sand, granulated glass sphere, mineral aggregate, talcum, clay etc.Preferred oxidation inhibitor comprises phenolic antioxidant such as Irganox 1010, Irganox 1076, all available from Ciba-Geigy.Preferred oil comprises paraffinic oils or naphthenic oil such as Primol 352 or Primol876, available from ExxonMobil Chemical France, S.A.in Paris, France.Preferred plasticizer comprises polybutene, as Parapol 950 and Parapol 1300, available from ExxonMobil Chemical Company in Houston Texas.Other preferred additives comprises that agglomeration agent, anti-caking agent, pigment, processing aid, UV stablizer, neutralizing agent, lubricant, tensio-active agent and/or nucleator also can be present in one deck and/or multilayer in the film.Preferred additives comprises silicon-dioxide, titanium dioxide, polydimethylsiloxane, talcum, dyestuff, wax, calcium stearate, carbon black, low-molecular-weight resin and granulated glass sphere.Preferred adhesive accelerant comprises polarity acid, polyaminoamide is (as Versamid 115,125 and 140, available from Henkel), carbamate such as isocyanic ester/hydroxy-terminated polyester system, as tackiness agent TN/Mondur Cb-75 (Miles, Inc.), coupling agent is (as silicon ester (Z-6020, available from Dow Corning), titanic acid ester (as Kr-44, available from Kenrich), active acrylate's monomer is (as sarbox SB-600, available from Sartomer), metal acid-salt (as Saret 633, available from Sartomer), polyphenylene oxide, oxidized polyolefin, acid modified polyolefin and anhydride modified polyolefine.

In another embodiment, with polymkeric substance of the present invention be lower than 3wt% oxidation inhibitor, be lower than 3wt% FLOW IMPROVERS, be lower than 10wt% wax and/or be lower than 3wt% crystallization auxiliary combination.

Can be that softening agent or other additive are as oil, tensio-active agent, filler, color concentrate etc. with other non-essential component of polymeric articles combination of the present invention.Preferred plasticizer comprises mineral oil, polybutene, phthalic ester etc.Particularly preferred softening agent comprises phthalic ester such as phthalic acid two different undecyl esters (DIUP), diisononyl phthalate (DINP), dioctyl phthalate (DOP) (DOP) etc.Particularly preferred oil comprises aliphatic naphthenic oil.

Can be with other inessential component of polymeric articles of the present invention combination low molecular weight product such as wax, oil or low Mn polymkeric substance (low be meant Mn be lower than 5000, preferably be lower than 4000, more preferably less than 3000, further more preferably less than 2500).Preferred wax comprises polarity or nonpolar wax, functionalized waxes, Poly Propylene Wax, polyethylene wax and wax modifiers.Preferred wax comprises ESCOMER ^TM101.Preferred functionalized waxes comprises the wax with modifications such as alcohol, acid, ketone, acid anhydrides.Preferred example comprises the wax with methyl ketone, maleic anhydride or toxilic acid modification.Preferred oil comprises aliphatic naphthenic oil, white oil etc.Preferred low Mn polymkeric substance comprises the polymkeric substance of low alpha-olefin such as propylene, butylene, amylene, hexene etc.Particularly preferred polymkeric substance comprises that having Mn is lower than 1000 polybutene.Another example of this polymkeric substance is available from the commodity of ExxonMobi1 Chemical Company PARAPOL by name ^TM950 product.PARAPOL ^TM950 are the liquid polybutene that has Mn 950 and dynamic viscosity is 220cSt (measuring by ASTM D 445) in the time of 100 ℃.In some embodiments, polarity is used from the identical composition with nonpolar wax one.

Yet in some embodiments, wax may be unwanted, and its amount be lower than 5wt%, preferably be lower than 3wt%, more preferably less than 1wt%, more preferably less than 0.5wt%, based on the weight of polymkeric substance.

In another embodiment, polymkeric substance of the present invention has and is lower than 30 wt%, preferably is lower than 25 wt%, preferably be lower than 20wt%, preferably be lower than 15wt%, preferably be lower than 10 wt%, preferably be lower than any total combination of the above-mentioned additive of 5 wt%, based on the weight of polymkeric substance and additive.

In another embodiment, the polymkeric substance that the present invention produces can with elastomer blended (preferred elastomerics comprises all natural and synthetic rubber, comprises those that define among the ASTM D1566).In preferred embodiments, the polymer blending with elastomerics and the present invention's production forms rubber toughened composition.In particularly preferred embodiments, this rubber toughened composition is two (or heterogeneous) system, and wherein this rubber is discontinuous phase, and polymkeric substance is an external phase.Preferred elastomeric example comprises one or more in the following material: ethylene propylene rubber, propylene diene hydrocarbon monomer rubber, chloroprene rubber, styrene block copolymer rubber (comprising SI, SIS, SB, SBS, SIBS etc.), isoprene-isobutylene rubber, halobutyl rubber, iso-butylene and to the multipolymer of ring-alkylated styrenes, iso-butylene and to the halogenated copolymers of ring-alkylated styrenes.This blend can combine with above-mentioned tackifier and/or other additive.

In another embodiment, the polymkeric substance produced of the present invention can with impact-resistant copolymerized thing blend.Impact-resistant copolymerized thing is defined as the blend of isotactic PP and elastomerics such as ethylene-propylene rubber.In preferred embodiments, this blend is two (or heterogeneous) system, and wherein this impact-resistant copolymerized thing is a discontinuous phase, and polymkeric substance is an external phase.

In another embodiment, the polymkeric substance produced of the present invention can with the ester polymer blend.In preferred embodiments, this blend is two (or heterogeneous) system, and wherein this polyester is a discontinuous phase, and polymkeric substance is an external phase.

In preferred embodiments, the polymkeric substance of the invention described above can with metallocene PE (mPE ' s) or metallocene polypropylene (mPP ' s) combine.This mPE and mPP homopolymer or multipolymer generally with single-or two-cyclopentadienyl transition-metal catalyst and being combined in solution, slurry, high pressure or the gas phase of aikyiaiurnirsoxan beta and/or non-coordination anion activator produce.Catalyzer and activator can be load or unsupported, and cyclopentadienyl rings can be replacement or unsubstituted.Can be with several commercial product that this catalyzer/activator composition is produced from ExxonMobil Chemical Companyin Baytown, Texas buys, and its commodity are called EXCEED ^TM, ACHIEVES ^TMAnd EXACT ^TMFor producing this mPE homopolymer and the method for multipolymer and the more information of catalyzer/activator, referring to WO94/26816; WO94/03506; EPA277,003; EPA 277,004; US5,153,157; US5,198,401; US 5,240, and 894; US 5,017, and 714; CA 1,268, and 753; US5,324,800; EPA 129,368; US5,264,405; EPA 520,732; WO 9200333; US5,096,867; US5,507,475; EPA 426637; EPA 573403; EPA 520732; EPA 495375; EPA 500944; EPA 570982; WO91/09882; WO94/03506 and US5,055,438.

In another embodiment, olefin polymer of the present invention, preferred homopolymer polypropylene of the present invention or multipolymer can with another homopolymer and/or copolymer blended, include but not limited to homo-polypropylene, propylene and at the most 50wt% ethene or multipolymer, isotatic polypropylene, high isotatic polypropylene, syndiotactic polypropylene, propylene and the ethene of C4 to C20 alpha-olefin and/or random copolymers, polybutene, ethylene vinyl acetate, the new LDPE (film grade) of butylene and/or hexene (density 0.915 is to being lower than 0.935g/cm ³), linear low density polyethylene, (density 0.86 is to being lower than 0.90g/cm for ultra-low density polyethylene ³), (density 0.90 is to being lower than 0.915g/cm for very low density polyethylene ³), (density 0.935 is to being lower than 0.945g/cm for medium-density polyethylene ³), (density 0.945 is to 0.98g/cm for high density polyethylene(HDPE) ³), ethylene vinyl acetate, ethylene methyl acrylate, acrylic copolymer, polymethylmethacrylate maybe can pass through any other polymkeric substance of high-pressure free radical method polymeric, polyvinyl chloride, polybutene-1, the isotactic polybutene, ABS resin, elastomerics such as ethylene-propylene rubber (EPR), sulfuration EPR, EPDM, elastomer block copolymer such as SBS, nylon (polymeric amide), polycarbonate, the PET resin, crosslinked polyethylene, the multipolymer of ethene and vinyl alcohol (EVOH), aromatic monomer polymkeric substance such as polystyrene, poly--1 ester, has density 0.94 to 0.98g/cm ³High molecular weight polyethylene, have density 0.94 to 0.98g/cm ³Low molecular weight polyethylene, general graft copolymer, polyacrylonitrile homopolymer or multipolymer, polyamide thermoplastic, polyacetal, fluorinated ethylene propylene and other fluorinated elastomer, polyoxyethylene glycol and polyisobutene.

In preferred embodiments, olefin polymer of the present invention, the amount of preferred polyacrylic polymer of the present invention in blend based on the polymer weight in the blend, is 10 to 99wt%, preferred 20 to 95wt%, further more preferably at least 30 to 90wt%, further more preferably at least 40 to 90wt%, further more preferably at least 50 to 90wt%, further more preferably at least 60 to 90wt%, further more preferably at least 70 to 90wt%.

Above-mentioned blend can be produced by the following method: two or more polymkeric substance are mixed together, by the reactor made reactor blend that is cascaded or by using more than a kind of Catalyst Production multiple polymers in same reactor.These polymkeric substance can be mixed together before adding forcing machine or can mix in forcing machine.

Can above-mentioned arbitrary polymkeric substance (comprising the polymkeric substance that the present invention produces) is functionalized.Preferred functional group comprises toxilic acid and maleic anhydride.The functionalized polymkeric substance that is meant contacts with unsaturated acid or acid anhydrides.Preferred unsaturated acid or acid anhydrides comprise any unsaturated organic compound that contains at least one two key and at least one carbonyl.Representational acid comprises carboxylic acid, acid anhydrides, ester and its metal and non-metal salt.Organic compound preferably comprises and carbonyl (C=O) conjugated olefinic degree of unsaturation.Example comprises toxilic acid, fumaric acid, vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, tiglic acid and styracin extremely acid anhydrides, ester and salt derivative.Preferred especially maleic anhydride.The amount of unsaturated acid or acid anhydrides is preferably about 0.1wt% to about 10wt%, and preferably about 0.5wt% is about 7wt% extremely, further more preferably from about 1 to about 4wt%, based on the weight of hydrocarbon resin and unsaturated acid or acid anhydrides.

Unsaturated acid or acid anhydrides comprise the olefinically unsaturated carboxylic acid derivatives that is selected from unsaturated carboxylic acid and is selected from ester, imide, acid amides, acid anhydrides and cyclic acid anhydride in preferred embodiments, or the carboxylic acid or derivatives thereof of its mixture.

Use

In the present invention and its claim, use following test, except as otherwise noted.

Tensile strength

Fracture tensile strength and extension at break are measured according to ASTM D 1708.Extension at break is called breaking strain or percentage elongation again.

Stripping strength-ASTM D-1876 (be called again in the peel off cohesive force, 180 ° stripping strength, 180 ° of 180 degree under the peel angles and peel off cohesive force, T shape-stripping strength, T shape-peeling force).

Dynamic storage modulus (being called storage modulus again) is G '.

Creep resistant ASTM D-2293

Rolling ball viscosity (Rolling Ball Tack) PSTC 6

Hot shearing intensity hangs the 1000g weight by the 25mm broadband from the MYLAR polyester film and measures, and this polyester film scribbles polymkeric substance or binder formulation, and it adheres to contact area 12.5mm x 25mm and stainless steel plate.Sample is put into 40 ℃ draft furnace, and writing time is till presenting stress rupture.

Probe tack (being called the Polyken probe tack again) ASTM D 2979

Clinging power (holding power)-PSTC 7 is called shear bond power or shearing resistance again.

Density-ASTM D792 is measured down at 25 ℃.

Gardner's colour ASTM D 1544-68.

SAFT is called thermotolerance again.

Tensile strength modulus and Young's modulus when 100% elongation are measured according to ASTM E-1876.

Luminous intensity is that reflectance " Y " (measuring by ASTM D 1925) in the CIE color coordinates is divided by 100.

Polymeric articles of the present invention or its batching can directly impose on the base material and maybe can spray thereon, generally with polymer melted.Spraying is defined as and comprises atomizing, as produce even dot pattern, spiral spraying as Nordson Controlled Fiberization or the elongate filaments of vibrating, as in ITWDynafiber/Omega head or Summit technology (from Nordson), carrying out, and molten blowing technology.Molten blowing technology is defined as and comprises US 5,145, the method for describing in 689, or wherein airflow is used to make the fracture of extrudate fibril, any method on the fibril deposited base material that will rupture then.Usually, molten blowing technology is for using air spinning hot-melt adhesive fiber and being transported to method on the adherent base material.Can easily fiber size be controlled to 20 to 200 microns by the ratio that changes melt and air.Because the molten inherent stability of blowing spreader of binding agent, producing seldom, does not preferably have stray fiber.Under UV light, present the bonding of rule, smooth, tensile dot pattern form.Atomizing is delivered to the method wanted adherent base material on the hot-melt adhesive atomizing for very little point and with it for using air.

The coating of lamination melt

Binding agent of the present invention can be used for including but not limited to disposable products, packing material, laminated product, pressure sensitive adhesives, adhesive tape label, wood bonding, paper bonding, non-woven fabrics, road sign, reflective coating etc. in any binding agent application.

In preferred embodiments, binding agent of the present invention can be used for disposable diaper and sanitary towel infrastructure, in the processing of disposable, pack, label, bookbinding, carpenter's processing or other assembling elasticity in using links.Particularly preferred application comprises: stand leg cuffs, diaper infrastructure, diaper cores stabilization, diaper liquid transfer layer, diaper of adhesive tape, diaper covers outward that lamination, diaper elastic tape flange lamination, sanitary napkin core stabilization, sanitary napkin bonding strip, industry filter bonding, industrial filter material lamination, strainer is sheltered lamination, surgical operation coat lamination, surgery valance lamination and perishable prod packing before the baby diaper leg elastic tape, diaper.

Above-mentioned binding agent can impose on any base material.Preferred substrate comprises that timber, paper, card board kai, plastics, thermoplastic material, rubber, metal, tinsel (as aluminium foil and tinfoil paper), metalized surface, cloth, non-woven fabrics (particularly polypropylene spunbond fibers or non-woven fabrics), spun-bonded fibre, card board kai, stone, gypsum, glass (comprise the silicon oxide (SiO that is coated with on the film surface by silicon oxide is evaporated to _x) coating), foam, rock, pottery, film, foam of polymers (as polyurethane foam) and be coated with base material or its combination of printing ink, dyestuff, pigment, PVDC etc.

Preferred substrate comprises that polyethylene, polypropylene, polyacrylic ester, acrylic acid or the like, polyethylene terephthalate or above-mentioned polymkeric substance are suitable as any combination of blend in addition.

Arbitrary above-mentioned base material and/or polymkeric substance of the present invention can carry out corona treatment, flame treating, electron beam irradiation, gamma-radiation, microwave irradiation or silanization to be handled.

Here the binding agent of Sheng Chaning preferably carries out when being applied between two adherends according to some pattern in such a way, promptly compares with the standard declaration of like configurations or standard binding agent these materials are kept together with enough patterns.

Any binding agent that polymeric articles of the present invention can be used for wherein describing with the polymkeric substance that the combination of polymers or the replacement of description among the WO 97/33921 are wherein described is used.

Polymeric articles of the present invention also can be used for forming hook and the ring-type fastener of describing among the WO 02/35956 (fasteners) separately or with other polymkeric substance and/or additive combination.

Characterize and test

Molecular weight (number-average molecular weight (Mn), weight-average molecular weight (Mw) and z-average molecular weight (Mz)) is measured with the Waters150 size exclusion chromatography (SEC) that differential refraction rate detector (DRI), online low angle light scattering (LALLS) detector and viscosity apparatus (VIS) are housed.The details of detector calibration has been described [Volume 34 for reference: T.Sun, P.Brant, R.R.Chance and W.W.Graessley, Macromolecules, Number19,6812-6820, (2001)] in other document; Following note is the concise and to the point description to its assembly.

Have three Polymer Laboratories PLgel 10mm Mixed-B posts, nominal flow rate 0.5cm ³The SEC that volume 300 microlitres are injected in/min and nominal is common to two kinds of detector configurations.Various transfer lines, pillar and differential refractometer (the DRI detector is mainly used in and measures elute soln concentration) are put into the baking oven of 135 ℃ of maintenances.

The LALLS detector is the two angular light light scattering photometers (PrecisionDetector Inc.) of 2040 types.Its fluid chamber that is positioned on the SEC baking oven uses 690nm diode laser light source and collects the scattered light at 15 and 90 ° of two angle places.Only 15 ° of work outpuies are used for these experiments.Its signal is sent into data gathering plate (National Instruments), and this collecting board is collected reading with 16/second speed.Four minimum readings are average, then a scaling signal is sent into the SEC-LALLS-VIS computer.The LALLS detector is arranged on after the SEC post, but before viscosity apparatus.

Viscosity apparatus is high temperature 150R type (Viscotek Corporation).It is made of four kapillaries and two pressure transmitters of arranging with the comparison bridge configuration.Sensor measurement is along the total pressure drop of detector, and another measures differential pressure between the bridge both sides.Calculate the specific viscosity of the solution that flows through viscometer by its work output.Viscosity apparatus is positioned at after the LALLS detector in the SEC baking oven, but before the DRI detector.

The solvent that is used for SEC experiment be equipped with 1,2 by adding as the 6g Yoshinox BHT (BHT) of antioxidant, and 4 litre flasks of 4-trichlorobenzene (TCB) (Aldrich SILVER REAGENT) are also waited for BHT to dissolve and prepared.Then this TCB mixture is filtered through 0.7 μ m glass prefilter, filter by 0.1 μ m polytetrafluoroethylene filter then.Between high-pressure pump and SEC post, there is another online 0.7 micron glass prefilter/0.22 micron polytetrafluoroethylene filter assembly.Then (Phenomenex, ModelDG-4000) degassing enters SEC then with online degasser with TCB.

Prepare polymers soln by the following method: the exsiccant polymkeric substance is dropped in the Glass Containers, add the TCB of aequum, this mixture was heated the while continuously stirring down about 2 hours at 160 ℃.All amounts are carried out gravimetric analysis.Be used to represent that the TCB density (mass/volume) of polymer concentration at room temperature is 1.463g/ml, be 1.324g/ml down at 135 ℃.The injection concentration scope is 1.0 to 2.0mg/ml, and wherein low concentration is used for the higher molecular weight sample.

Before each sample of operation, DRI detector and syringe are purged.Then the flow velocity in the instrument is increased to 0.5ml/min, before injecting the 1st sample, DRI was stablized 8-9 hour.Argon ion laser was opened 1 to 1.5 hour, promptly before the operation sample by with idle mode running laser apparatus 20-30 minute, switch to full power with light adjusting pattern then.

Branch index is measured with the SEC (SEC-VIS) that in-line viscometer is housed, and the g ' under each molecular weight in the record SEC trace.This branch index g ' is defined as;

g′＝η _b/η ₁

η wherein _bBe the limiting viscosity of branched polymer, η ₁Be identical viscosity-average molecular weight (M with this branched polymer _v) the limiting viscosity of linear polymer.η ₁=KM _v ^α, wherein K and α are the observed value of linear polymer, and Ying Zaiyu is used for obtaining on the identical SEC-DRI-LS-VIS instrument that branch index measures.For the polypropylene specimen for preparing among the present invention, use K=0.0002288 and α=0.705.The SEC-DRI-LS-VIS method does not need to carry out polymolecularity proofreaies and correct, because limiting viscosity and molecular weight are measured under elution volume separately, can think that it comprises narrow dispersed polymeres.The linear polymer of the standard substance of choosing as a comparison should have identical viscosity-average molecular weight and co-monomer content.Contain Ca rbon-13NMR method confirmation (Rev.Macromol.Chem.Phys., the C29 (2﹠amp of the linear feature of C2 to C10 polymer of monomers by Randa ll; 3), p.285-297).

C11 and above-mentioned monomeric linear feature confirm by the gpc analysis that uses the MALLS detector.For example, for propylene copolymer, NMR should not show the degree of branching (even comonomer is a butylene, then should not have the side chain greater than 2 carbon atoms) greater than comonomer.For alfon, GPC should not show the side chain greater than a carbon atom.When comonomer wherein is that C9 or higher polymkeric substance are when needing linear standard, can be with reference to T.Sun, P.Brant, R.R.Chance, and W.W.Graessley, Macromolecules, Volume 34, Number 19,6812-6820, the scheme of relevant those polymer determination standards in (2001).For syndiotactic polymer, this standard should have can correlated normality amount, measures by Carbon 13NMR.

In another embodiment, the polymkeric substance that the present invention produces has molecular weight distribution (Mw/Mn) at least 2, and preferably at least 5, preferably at least 10, further more preferably at least 20.

In another embodiment, the polymkeric substance of production can have single mode, bimodal or the multi-modal molecular weight distribution (Mw/Mn) of polymer material, measures by size exclusion chromatography (SEC).Bimodal or the multi-modal SEC of being meant trace have more than one peak or flex point.Flex point is that the second derivative signal of wherein curve changes the point of (for example just becoming or on the contrary from negative).

Peak fusing point (Tm), peak Tc (Tc), melting heat and degree of crystallinity are according to the following program determination of ASTM E 794-85.Difference formula scanning calorimetric (DSC) data obtain with 2920 type machines of TA Instruments company.The sample of weighing for about 7-10mg is sealed in the aluminium sample disc.The DSC data are record by the following method; At first sample is cooled to-50 ℃, then it is heated to 200 ℃ gradually with 10 ℃/min of speed.This sample was kept 5 minutes down at 200 ℃, apply cooling-heating cycle for the second time then.Write down first and second times the cycling hot process.Measure this area under a curve and be used to measure melting heat and degree of crystallinity.Percent crvstallinity is calculated with formula [area below the curve (J/g)/B (J/g)] * 100, and wherein B is the melting heat of the homopolymer of principal monomer component.These B values are from Polymer Handbook, and the 4th edition, John Wiley and Sons publishes, and obtains among the New York 1999.Numerical value 189J/g (B) is as the melting heat of 100% crystalline polypropylene.For the polymkeric substance that shows a plurality of fusings or peak crystallization, as the peak fusing point, the highest peak crystallization is as the peak Tc with the highest melting hump.

Second-order transition temperature (Tg) is measured by 2920 type machines of ASTM E 1356 usefulness TA Instruments companies.

To be used for ¹³C NMR spectrographic polymer samples is dissolved in d ₂In-the sym.-tetrachloroethane, and with 75 or the NMR spectrograph of 100MHz at 125 ℃ of record samples down.The polymkeric substance resonance peak relates to mmmm=21.8ppm.The calculating that relates in the polymer characterization that is undertaken by NMR is followed F.A.Bovey at " Polymer Conformation and Configuration ", AcademicPress, New York 1969 and J.Randall exist " Polymer SequenceDetermination; Carbon-13NMR Method ", Academic Press, NewYork, the work in 1977.The length sequences per-cent of two methylene radical, % (CH ₂) ₂, according to following calculating: multiply by 100 again divided by the integration of the length sequences of a methylene radical between the 45-49ppm and the summation of the methine carbon atom integration between the 14-18ppm at the methine carbon atom integration between the 14-18ppm (equaling the length sequences number of two methylene radical on the concentration).This is the minimum of computation of methylene base unit weight contained in the sequence to two or more methylene radical, because get rid of greater than the methylene sequences of two methylene radical.This explanation is based on H.N.Cheng and J.A.Ewen, Makromol.Chem.1989,190,1931.

The ethylene content of polymkeric substance can followingly be determined.At temperature about 150 ℃ or the thin uniform thin film of relative superiority or inferiority compacting more, then it is placed on Perkin Elmer PE 1760 infrared spectrometers.The record sample is from 600cm ^-1To 4000cm ^-1Full spectrum, and calculate vinyl monomer wt% content: ethene wt%=82.585-111.987X+30.045X according to following formula ², wherein X is 1155cm ^-1The peak height and the 722cm at place ^-1Place or 732cm ^-1The ratio of the peak height (choosing peak higher among both) at place.The also available this method of the concentration of other monomer in polymkeric substance is calculated.

The binding agent test

The performance of the temperature that rises with 10 (5.5 ℃)/15min is born in SAFT (D4498 of modification) measurement bonding part under the constant force of drawing back the bonding part with shear mode.The bonding part forms (1 inch 3 inches of x (2.5cm x 7.6cm) (on kraft paper) in a manner described.Will be in baking oven at room temperature at the sample vertical hanging of its bottom-loaded 500g load.Temperature when the record weight falls (when idol has sample to reach to be higher than baking oven to hold on the fair temperature (＞265 (129 ℃)), stop, and with other sample average under this final temperature).

Be defined as that compacting bonding substrates structure enough fixedly secures together set time so that cause substrate fiber to be torn separately the time, therefore this bonding is enough by force down to the time that can remove compacting.Bonding also can strengthen by further cooling off, yet, no longer need compacting.Measure these set times in the following way; The fluxing point of binding agent placed be fixed on the folder base material that lies on the flat surface.(1 inch x 3 inches (2.5cm x 7.6cm) also uses the compacting of 500g weight to place folder intermediate plate (file folder tab) after 3 seconds on adhesive dot.This weight was stopped about 0.5 to about 10 seconds.The structure that so forms is drawn back, to such an extent as to check the enough good bonding degree that substrate fiber is torn that produces.Record produces the required shortest time of this good bonding as set time.Calibrate this method with standard substance.

After making structure, it is carried out various damages with the assessment bond effect.When to the bond damage of paper base material, quantitatively a plain mode of bond effect is that estimation is retained in the adhesive dot area in the paper fiber when along the tack line structure deteriorate.This assessment is called substrate fiber tears per-cent.An example of good fiber is when sample being nursed one's health 15 hours under-12 ℃ and attempt to destroy bonding, will have the 80-100% substrate fiber to tear estimated value.To tear may be the signal of cohesive force forfeiture to 0% substrate fiber under these conditions.

Xiao A hardness is measured according to ASTM 2240.The air cooling point of binding agent is carried out acupuncture, and by the calibration summary deflection.

Point T shape peeling force is pressed ASTM D 1876 and is measured, except sample is produced as follows: 3 inches (2.54cm x 7.62cm) base materials of two 1 inch x that will cut out combine by adhesive dot, and the volume of binding agent is for it occupies about 1 square inch (1 inch=2.54cm) area when suppressing under about 500g weight.After sample was made, the instrument of the destructive force that the damage that all samples are applied by record produces carried out the in harness test (speed is 2 inch per minute clocks) of drawing back.Write down maximum, force that each specimen reaches and it is average, so produce average maximum, force, with its record as putting T shape peeling force.

Binding agent melt viscosity (ASTM D-3236): the melt viscosity pattern is generally measured with Brookfield Thermosel viscosity apparatus and No. 27 axles down for 120 ℃ to 190 ℃ in temperature.

Stripping strength (ASTMD1876 of modification): base material (1x 3 inches (25x 76mm)) is sealed 1 to 2 second with adhensive membrane (5mil (130 μ m) is thick) under 135 ℃ and 40psi (0.28MPa) pressure.This bonding sample is oppositely peeled off with constant pinblock speed 2in/min (51mm/min) on tester for elongation.Record will bond (5 samples) peel away required mean force.

The ability of the temperature that rises with 10 (5.5 ℃)/15min is born in shear bond fail temperature (SAFT) (the ASTM D4498 of modification) measurement bonding part under the constant force of drawing back the bonding part with shear mode.1 inch (25mmx25mm) (kraft paper) of 1 inch x of adhesive is formed by the heat-sealing 1.5s according to above-mentioned operation " (b) " by binding agent.Will be in 32 ℃ baking oven at the sample vertical hanging of its bottom-loaded 500g load.Temperature when the record weight falls.Binding agent with high fail temperature is necessary for will often experience pyritous connection with wrapping of piece assembly between storage and delivery period.

Peeling off bond damage temperature (PAFT) measures with the following operation of revising according to TAPPI T814PM-77 operation.With a fusion bonding agent bar that is heated to 177 ℃ two 6 " x 12 " layers of kraft paper are forced together.With this laminate deburring and be cut into the wide bar of 1-inch.To have with these that peel off 100-g weight that mode hangs and put into baking oven.Temperature of oven raises with 30 ℃/hr of speed.Sample is hung on the switch, and this switch can trip when sample destroys with the record fail temperature.

Low temperature substrates fiber tearing: according to above-mentioned operation " (b) " preparation kraft paper adhesive.The adhesive sample is put into icebox or the required probe temperature of refrigerator acquisition.This adhesive is separated with hand, and observe the destruction type of measuring.The matrix fiber amount of tearing is represented with per-cent." SF " represents wood destruction.

By the binding agent blend being heated to 121 ℃ and fusion bonding agent beads (about 1g) is applied on the ASTM thermometer bulb measures cloud point.Note the temperature of this fusion bonding agent muddiness then.These observed values of cloud point provide the overall compatibility of hot melts, i.e. the mutual consistency indication of each component.

Compression moulding: compacting is fit to the plate of physicals test on the Carver hydropress.The 6.5g polymkeric substance is being lined with Teflon ^TMMolding between the copper coin (0.05 " thick) of the aluminium foil of coating.To have the square perforate in 4 " x 4 " 0.033 " thick sheet frame (chase) is used to control thickness of sample.Under minimum pressure 170 ℃ or 180 ℃ of following preheatings after 1 minute, the hydraulic pressure load is risen to gradually about 10,000-15,0001b keeps them 3 minutes under this pressure.Subsequently with sample and molded plate about 10,000 to 15, cooling 3 minutes between the water-cooled pressing plate of press under the 000lb load.With the at room temperature minimum balance of this plate 2 days, carry out the physicals test then.

One directional tensile test: from holoplast, cut out the dog-bone that is used for tension test with mallet handle die.Sample is of a size of those that stipulate among the ASTM D 1708.Tensile property is at Instron ^TM4502 type Elongation test airborne measurements, this test machine are equipped with a 22.48lb. loading compartment and the pneumatic pawl (pneumatic jaws) of spination anchor clamps face are housed.Be out of shape under constant pinblock speed 5.0in/min, wherein data sampling speed is 25 point/seconds.The test fore paw separates 0.876 ", under the supposition affine deformation, calculate strain by it.Calculate initial modulus, surrender (when obvious) stress and strain, peak stress, fracture tensile strength and breaking strain.Test is from minimum 5 samples of each plate, and the result who provides is a mean value.All stress of quoting all calculate based on the original cross-sectional area of sample, and the cross section that is not considered as rising strained function reduces.

Rheological property (G ', G ") measures on the ARES instrument, and this instrument is by RheometricScientific, Piscataway, New Jersey makes.At first, cool off with 1 ℃/min then this polymer melted.Begin to drop to about 80 ℃ cooling period record dynamic modulus at least 30 ℃ being higher than material melting point certainly.Therefore test result is the evolution (evolution) of storage modulus G ', out-of-phase modulus G the ratio tan δ=G of temperature function " and as "/G '.Measure and under constant frequency 10rad/s and 20% strain, carry out with the plate fishplate bar geometrical shape (plate-and-plate geometry) of 12.5mm diameter.

Embodiment

The general introduction

All polymerizations are all carried out with the mixed metallocene catalyst system in the single phase of full of liquid flow reactor.Reactor is 0.5 liter of stainless steel autoclave reactor, and the water cooling/steam heating element and the pressure controller of agitator, band temperature regulator is housed.At first by passing through three column purification systems with solvent, propylene and comonomer (as butylene and hexene) (if existence) purifying.Purification system is made up of Oxiclear post (Model#RGP-R1-500 is available from Labclear), the 5A that is connected on its back and 3A molecular sieve column.When having polymerization low activity sign, with the purification column regular regeneration.3A and 5A molecular sieve are all dividing 260 ℃ of other design temperatures and 315 ℃ of regeneration down in inside under nitrogen.Molecular screen material is available from Aldrich.The regeneration in initial manufacturing of Oxiclear post.To add in the manifold from the purifying ethene of internal material-feeding, then reactor be passed through Brookfield streams controller.Ethene is carried with the gas form that is dissolved in cold solvent/monomer mixture.Then with the solvent of purifying and monomer by be cooled to-15 ℃ approximately by refrigerator, add in the reactor through manifold then.With solvent with monomer mixes in manifold and add in the reactor through single pipe.The all liquid flow velocity is all used Brooksfield mass flow meter or Micro-Motion Coriolis type flowmeter survey

Except as otherwise noted, catalyst compound is bought by Albemarle.

Being used to produce the polyacrylic catalyst compound of hypocrystalline is two (2-methyl-4-phenyl indenyl) zirconium dichlorides of racemize-dimetylsilyl, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl, two (the 2-methyl indenyl) zirconium dimethyls of racemize-dimetylsilyl, two (indenyl) the dimethyl hafniums of racemize-dimetylsilyl and racemize-1,2-ethylidene-two (4,7-dimethyl indenyl) dimethyl hafnium (available from Boulder ScientificCompany).

The catalyst compound that is used to produce amorphous polypropylene is dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (tertiary butyl amino) (tetramethyl-ring pentadienyl) dimethyl titanium (available from Boulder Scientific Company), [two (right-the triethylsilyl phenyl) methylene radical] (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) the dimethyl hafnium (is pressed US 6,528, embodiment production in 670) and dimetylsilyl (tetramethyl-ring pentadienyl) (N-1-adamantyl) dimethyl titanium (according to US5, embodiment production in 955,625).

Dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride is according to US5, the embodiment production in 057,475.This dimethyl variant obtains by dimethyl dichloride variant.

Two (2-methyl-4-phenyl indenyl) zirconium dichlorides of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride activate with MAO (methylaluminoxane).Two (4,7-dimethyl indenyl) the dimethyl hafniums of racemize-ethylene (available from Single-Site Catalysts, LLC) activate in advance with trityl four (pentafluorophenyl group) borate.All the other catalyzer activate in advance with four (pentafluorophenyl group) boric acid N, accelerine (available from Albemarle).For preactivated catalyst system, before polyreaction, this catalyzer was activated at least 10 minutes in 1: 1 in molar ratio to 1: 1.1 with promotor in 700ml toluene.Then this catalyst body is tied up to the catalyst concn that is diluted to concentration 0.2 to 1.4mg/ml in the toluene.This catalyst solution is used for all polymerization experiment of carrying out on the same day.When the catalyst solution that consumed more than the 700ml milliliter in one day, prepare new catalyst solution batch of material.With each catalyst solution through independent pipeline suction.Catalyzer is mixed in manifold, add in the reactor through single pipeline then.In methylaluminoxane activatory system, (MAO, 10wt.% in toluene is available from Albemarle) dilutes in 1000ml toluene with the 280ml methylaluminoxane, and this solution is stored in 5 liters of stainless steel cylinders.This catalyzer is diluted to concentration 0.2 to 1.4mg/ml in toluene.With each catalyst solution and methylaluminoxane solution through dividing other pipeline suction.Catalyzer and MAO are mixed in manifold, add in the reactor through single pipeline then.Pipe connecting between catalyzer manifold and the reactor inlet is long for about 1m.

All catalyst solutions are remained in the inert atmosphere of water content＜1.5ppm and and add in the reactor by volume pump.Catalyzer carries out with monomeric the contact in reactor.Adopt toluene regularly catalyst pump to be calibrated as calibrate medium.Catalyst concn in the raw material is by the suction rate-controlling of catalyst concn in the change catalyst solution and/or change catalyst solution.The suction speed of catalyst solution changes in 0.2 to 5ml/min scope.

As the impurity scavenging agent, (25wt.% in toluene, AkzoNoble) dilutes in the 22.83kg hexane with the 55ml triisobutyl aluminium.The triisobutyl aluminum solutions of dilution under covering, nitrogen is stored in 37.9 litre flasks.It is about 90% until consuming that this solution is used for all polymerization experiment, prepares new batch of material then.The suction speed of triisobutyl aluminum solutions changes with polyreaction is different, can be from 0 (no scavenging agent) to 4ml/min.

For relating to α, the polyreaction of ω-diolefine, with 1, the 9-decadiene is diluted to concentration 4.8 to 9.5vol.% in toluene.Then this diluting soln is added in the reactor through the comonomer pipeline by volume pump.(this 1, the 9-decadiene is available from Aldrich, and by by at high temperature activatory aluminum oxide under the nitrogen, then by at high temperature under nitrogen the activatory molecular sieve carry out purifying.)

At first came cleaning reactor at least one hour by under maximum permissible temperature (about 150 ℃), reactor assembly being crossed in solvent (for example hexane) and scavenging agent uninterrupted pumping.After the cleaning, with this reactor use through water/vapour mixture that reactor jacket flows through heat/be cooled to temperature required and by control the solvent streams controlling reactor under setting pressure.When reaching the steady state of operation, monomer and catalyst solution are added in the reactor then.The automatic temp Controlling System is used for reactor control and remains under the design temperature.Determine that by the reduction temperature of observing viscous product and water-steam mixture polymerization activity begins.In case after the activity of foundation and system reach balance, before collecting sample,, reactor is marked (lined out) by 5 times the time of mean residence time at least of this system of operate continuously under the condition of setting up.After system reached the stable state operation, collection mainly contained solvent, polymkeric substance and unreacted monomeric gained mixture in collection box.With the sample collected at first in stink cupboard dry air to evaporate most of solvent, then in vacuum drying oven temperature about 90 ℃ dry about 12 hours down.This vacuum drying oven exsiccant samples weighing is obtained yield.Institute responds all and to carry out under 45 to 130 ℃ of 2.41MPa-g pressure and temperatures.

Embodiment 1-4

With two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium under 115 ℃ of temperature in the catalyst ratio scope 4 samples of preparation.Polyreaction is carried out according to above-mentioned general operation.Detailed experiments condition and result provide in table 1.

Embodiment 5-8

With two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) dimethyl titanium under 100 ℃ of temperature in the catalyst ratio scope 4 samples of preparation.Polyreaction is carried out according to above-mentioned general operation.Detailed experiments condition and result provide in table 2.

Embodiment 9-15

Under the about 80.0mol% of catalyst ratio, in certain temperature range, prepare 7 samples with two (indenyl) dimethyl hafniums of dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium.Polyreaction is carried out according to above-mentioned general operation.Detailed experiments condition and result provide in table 3.These data presentation temperature have a significant effect to degree of crystallinity, Mw, Mw/Mn and branching measurer.Total amount can be controlled by temperature of reaction, and this is because the reaction kinetics of each catalyzer has unique response to polymerization temperature.

Embodiment 16-19

With two (indenyl) the dimethyl hafniums of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium under 100 ℃ of temperature under various catalyst ratios 4 samples of preparation.Polyreaction is carried out according to above-mentioned general operation.Detailed experiments condition and result provide in table 4.These data presentation catalyst ratios have a significant effect to degree of crystallinity, Mw, Mw/Mn and branching measurer.Total amount can be controlled by temperature of reaction, and this is because the reaction kinetics of each catalyzer has unique response to polymerization temperature.

Embodiment 20-34

Prepare 15 samples with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium catalyst according to above-mentioned general operation, different is will be a small amount of as 1 of diolefinic monomer, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers.Detailed experiments condition and result provide in table 5 and 6.

Embodiment 35-39

With two (indenyl) the dimethyl hafniums of dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium catalyst under the catalyst ratio 75mol% and in 85 to 105 ℃ of temperature ranges according to 5 samples of above-mentioned general operation preparation, different is will be a small amount of as 1 of diolefinic monomer, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers.Detailed experiments condition and result provide in table 7.

Embodiment 40-43

Prepare 4 samples with two (indenyl) dimethyl hafniums of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is will be a small amount of as 1 of diolefinic monomer, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers.Detailed experiments condition and result provide in table 8.

Embodiment 44-47

4 samples of preparation in 110 ℃ of temperature and certain catalyst ratio scope with racemize-ethylene-two (4,7-dimethyl indenyl) dimethyl hafniums and dimetylsilyl-(tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium.The condition that embodiment 44 to 47 uses (comprising that diolefine adds) is according to above-mentioned general operation, and different is will be a small amount of as 1 of diolefinic monomer, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers.Detailed experiments condition and result provide in table 9.

Embodiment 48-51

In 80 ℃ of temperature and catalyst ratio 74 to 84mo l% scopes, prepare 4 samples with two (2-methyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is will be a small amount of as 1 of diolefinic monomer, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers.Detailed experiments condition and result provide in table 10.

Embodiment 52-57

Under 80 to 95 ℃ of temperature and the about 87mol% of catalyst ratio, prepare 6 samples with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is (1) will be a small amount of as 1 of diolefine raw material, 9-decadiene and add together as the propylene of 'alpha '-olefin monomers; (2) small quantity of hydrogen is also added in the reactor.Detailed experiments condition and result provide in table 11.Embodiment 52-57 shows: except the control that obtains by selecting catalyst and processing condition such as temperature, the adding of hydrogen can be handled Mw effectively, Mw/Mn, degree of crystallinity, the ratio of crystallization phases and amorphous phase.

Embodiment 58-60

In 115 ℃ of temperature and the about 87mol% scope of catalyst ratio, prepare 3 samples with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is (1) adds on a small quantity 1, and the 9-decadiene is as diolefinic monomer; (2) two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium catalyst carry out premix and dilute in toluene, are not adding in the catalyzer manifold under the activation in advance then; (3) with four (pentafluorophenyl group) boric acid N, accelerine dilutes in toluene, adds then in the catalyzer manifold; (4) in the catalyzer manifold, begin catalyst activation.Detailed experiments condition and result provide in table 12.Embodiment 58-60 show catalyzer can be before just will adding reactor online activation and in reactor, activating.

Embodiment 61-66

Under 105 to 130 ℃ of temperature and the about 84.6mo l% of catalyst ratio, prepare 6 samples with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is (1) adds on a small quantity 1, and the 9-decadiene is as diolefinic monomer; (2) ethene is added in the reactor.Detailed experiments condition and result provide in table 13.Ethylene content in the polymkeric substance obtains by fourier transform infrared analysis (FTIR).

Embodiment 67-71

Under 105 to 115 ℃ of temperature (except that embodiment 69) prepares all these samples according to above-mentioned general operation with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of dimetylsilyl and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, different is (1) uses a small amount of Dicyclopentadiene (DCPD) (this Dicyclopentadiene (DCPD) is available from aldrich in embodiment 67,, at first it is dissolved in the toluene.Then with this solution through under the nitrogen at high temperature the activatory aluminum oxide, then through under nitrogen at high temperature the activatory molecular sieve carry out purifying); (2) in embodiment 68 and 70, use 1-butylene; (3) add 1 in embodiment 71,9-decadiene and 1-hexene are respectively as diolefinic monomer and comonomer.Two (2-methyl indenyl) the zirconium dimethyl catalyzer of embodiment 69 usefulness dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium and racemize-dimetylsilyl carry out.Detailed experiments condition and result provide in table 14.

Embodiment 72

Embodiment 72 carries out in 500-ml autoclave batch reactor.At first 125ml purifying toluene is added in the stainless steel autoclave reactor, then add 0.1ml triisobutyl aluminium (TIBAL) solution (25wt.%TIBAL dilutes) in 5ml toluene.Then this mixture is stirred and be heated to 120 ℃ until pressure-stabilisation.This reactor is remained under the slight positive pressure.Then under agitation add 125ml prepurification propylene.Reaction mixture is heated to 120 ℃.Under this temperature of reactor, 1.5ml pre-mixing and preactivated catalyst solution are added in the reactor by the sleeve pipe that inserts with nitrogen.This catalyst solution is made up of 32mg dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, two (2-methyl-4-phenyl indenyl) zirconium dimethyls of 1.9mg racemize-dimetylsilyl and two (indenyl) dimethyl hafniums of 1.6mg dimetylsilyl, and with 62.1mg four (pentafluorophenyl group) boric acid N, accelerine is dissolved in the 50ml toluene.This polymerization was carried out 15 minutes.Then with reactor cooling and to atmosphere emptying.In collection box, collect the gained mixture mainly contain solvent, polymkeric substance and unreacted monomer, and with this mixture at first in stink cupboard dry air to evaporate most of solvent, then in vacuum drying oven about 90 ℃ dry about 12 hours down.Resulting polymers (12.79g) shows 102.9 ℃ of peak Tcs (measuring by DSC), second-order transition temperature (Tg)-8.7 ℃ and melting heat 51.9J/g.Average molecular mass Mn/Mw/Mz is 33825/66387/267680.

Embodiment 73-75 (Comparative Examples)

Prepare 3 samples with two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl or dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium according to above-mentioned general operation, different is only to use a kind of catalyzer.Two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl are used to prepare isotatic polypropylene, and dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium is used to prepare amorphous polypropylene.The experiment condition and the viscosity of polymer samples provide in table 15.

To analyze to measure its degree of branching from several samples of front embodiment.In the present invention, degree of crystallinity is measured under branched polymer molecular weight Mz with the value of branch index g '.The result provides in to 13 at table 1.

The sample solvent extraction classification of describing among embodiment 4 and the embodiment 31-34.The result provides in table 16.The classification fraction of choosing GPC-DRI-VIS-LS and dsc analysis.Result from these analyses also provides in table 17.Complex viscosity scope from the classification fraction of the sample of description among the embodiment 31 is measured in 80 to 130 ℃ of scopes of temperature, provides in Fig. 5.

The sample of describing among the embodiment 4 and its fraction that extracts from solvent extraction are used ¹³C NMR analyzes.

Mm triad per-cent is directly measured by C-13NMR spectrum; The amount of supposing the mm triad in this mixture only depends on the aPP in the sample and the amount of scPP (" being respectively Atactic Polypropelene and hypocrystalline polypropylene ") component.By knowing tacticity (mm) amount of pure aPP and scPP component, can calculate the ratio of each component, it is equivalent to mm amount in the observed mixture.Value given below shows the per-cent of isotactic triad based on whole not classification polymkeric substance and three kinds of fractions.The data of calculating use following supposition to generate: isotactic and random be the sign of the regularity in the bulk polymer segment with reference to polymkeric substance.Use methyl triad district, calculate isotactic and have 94.7%mm, randomly contain 13.6% with reference to polymkeric substance with reference to polymkeric substance.

The isotactic polymer that sample %mm % calculates

Unassorted polymkeric substance 68 66

Hexane soluble rank part 16 about 2%

Heptane soluble rank part 76 76

Heptane insoluble level part 89 93

The viscosity of embodiment 12,22 and 49 product is measured in 80 to 130 ℃ of temperature ranges.This complex viscosity profile provides in Fig. 1.The above-mentioned three sections features of these digital proofs.

With the sample of choosing and its blend test binding agent performance.With straight polymer and tackifier, oil or wax and stablizer compounding formation hot melts binding agent blend.The performance of these polymkeric substance and its blend is with respect to typical EVA blend test available from Henkel and Chief.Blend is at high temperature carried out to form the fluid melt under low the shearing.Mixing temperature can be about 130 to 190 ℃.

EscorezTM 5637 is the aromatic modified resin of hydrogenation with 1 30 ℃ of ring and ball softening points by the Dicyclopentadiene (DCPD) raw material production, available from ExxonMob i l Chemi ca 1 Company i nHous ton, and Texas.

Parafl int H-1 is a Fi sher-Tropsch wax, shows melt viscosity 10 mpasec down at 250 °F, available from Moore and Munger.

Ar i s t owax 165 is the refining paraffin wax, available from Frank B Ro s s Co in Jer s eyC i t y New Jer sey.It is separated from oil, has 158 to 165 of fusing points.

Henke l Hot Me l t 8 0-8 36 8 are commercial hot melts, are made by the blend of EVA, tackifier and wax, available from Henkel CoRp.

MAPP 40 is maleic anhydride modified polypropylene, has 1 49 ℃ of acid number 50, viscosity 300 cp in the time of 190 ℃ and softening temperatures, available from Chus e i, USA.

Chief Hot Mel t 268 is commercial hot melts, is made by EVA, tackifier and wax, available from Ch i ef Adhes i ves.

Be high refining white mineral oil, form to have pour point-2 0 ℃, in the time of 40 ℃, have dynamic viscosity 64 to 70 cS t, available from Wi t co by radical of saturated aliphatic and cyclic aliphatic non-polar hydrocarbon.

Licomont AR 504 is a maleic anhydride inoculated polypropylene wax, has 156 ℃ of acid number 41, the 37 3 mPa s of the viscosity in the time of 190 ℃ and softening temperatures, available from C l a r i ent.

AC 540 is an ethylene acrylic acid co polymer, has 1 05 ℃ of acid number 40, the viscosity 575 in the time of 140 ℃ and dropping points, available from Honeywe l l.

Po l ywax 2000 is a polyethylene wax, and available from Bake r Pe t r o l i t e P l a i n BOPP (biaxially oriented polypropylene film), the film of 28 micron thickness is available from Mob i l F i lms.

The BOPP of corona treatment (biaxially oriented polypropylene film), the film of 28 micron thickness is available from Mobil Films.

Cardboard 84A has the cardboard that the grey Poster Board 20pt waste paper of 20% regenerated fibre is made, available from Huckster Packaging and supply, Inc.in Houston, Texas.

Cardboard 84B is common placard cardboard clay coated newsprinting paper (poster board claycoated news print), available from Huckster packaging and supply, Inc.inHouston, Texas.

Card board kai 84C is common ripple card board kai 200# blank, available from Huckster packagingand supply, Inc.in Houston, Texas.

REXTAC RT 2730 is the multipolymer of propylene, butylene and ethene, has about 67.5mol% propylene, about 30.5mol% butylene and about 2mol% ethene, and by Hunt sman, Company produces.This multipolymer has about 15mol%BB diad, about 43mol%PB diad and about 43mol%PP diad.Fusing point is 70 ℃ (having 25 to 116 ℃ of melting ranges), and Tg is-25 ℃, and degree of crystallinity is that about 7%, enthalpy is 10J/g (passing through dsc measurement).Mn is 8260, Mw be 59100 and Mz be 187900 (passing through gpc measurement).Mw/Mn is 7.15.

REXTAC RT 2715 is the multipolymer of propylene, butylene and ethene, has about 67.5mol% propylene, about 30.5mol% butylene and about 2mol% ethene, and by Hunt sman, Company produces.This multipolymer has about 11mol%BB diad, about 40mol%PB diad and about 49mol%PP diad.Fusing point is 76 ℃ (having 23 to 124 ℃ of melting ranges), and Tg is-22 ℃, and degree of crystallinity is that about 7%, enthalpy is 11J/g (passing through dsc measurement).Mn is 6630, Mw be 51200 and Mz be 166,700 (passing through gpc measurement).Mw/Mn is 7.7.

All binder formulation are all by wt%, unless in the composition that table 18 is listed to the table 50 explanation is arranged in addition.

C3/C2 is a Comparative Examples.This polymkeric substance is the ethylene/propene copolymer with the about 10wt% of ethylene content.This polymkeric substance uses the general operation preparation according to the foregoing description 1 under 70 ℃ of polymerization temperatures of two (2-methyl-4-phenyl indenyl) zirconium dimethyls of racemize-dimetylsilyl, and different is only to use a kind of catalyzer.Viscosity 1368cps when this polymkeric substance has 95 ℃ of peak temperature of fusion and 190 ℃.

There is not table 24.

Embodiment E X1-EX13

Below sample under 70 to 125 ℃ of temperature according to above-mentioned general operation preparation, different is: (1) adds a small amount of 1 in embodiment E X1-EX3, EX5 and EX9, and the 9-decadiene is as diolefinic monomer; (2) in embodiment E X13-EX17, use ethene.Detailed experiments condition and result provide in table 30,31 and 32.

Polymerizing condition

To merge the reactor feedstocks solution that forms 25l b/hr with speed 8lb/hr propylene material that adds and the hexane that adds with 17lb/hr.The tri-n-octylaluminium (TNOA) (available from Albema rle) of 3wt.% solution form that will be in hexane is introduced in this logistics with speed 0.0006lb/hr.

Catalyzer and activator add the reactor from independent inlet.This catalyst solution is by two (right-the triethylsilyl phenyl) methylene radical] (cyclopentadienyl) (3,8-di-t-butyl fluorenyl) mixture of two (2-methyl-4-phenyl indenyl) zirconium dimethyls (catalyst B) of dimethyl hafnium (catalyzer G) and racemize-dimetylsilyl is formed, and wherein has 97mol% catalyzer G.Formation 0.5wt% solution prepares catalyst solution in the toluene by this catalyst mixture is dissolved in.The activator feedstream is by four (pentafluorophenyl group) boric acid N, and the 0.2wt% solution of accelerine in toluene constitutes.Catalyzer and activator are all available from Albemarle.It is mixed at once catalyzer and traditional thread binding being made into of activator materail tube in the reactor upstream in pipeline, estimate that wherein be 2-4 minute duration of contact.Catalyzer and activator feeding rate are respectively 0.04g/hr and 0.1g/hr.

Reactor feedstocks is converted into polymkeric substance through two placed in-line continuously stirring jar reactors.The temperature of two reactors is controlled under 135 ℃.These two reactors are full liquid operation under 530psig pressure.The residence time of raw material in each reactor is 45 minutes.The transformation efficiency that propylene is converted into polymeric articles is about 91%.

From solution, reclaim molten polymer through two flash stage (all there is preheater in per stage).Fs (20psig) polymkeric substance comprises about 2% solvent, and second rank (50 torr vacuum) introduces about 800ppm volatile matter.Water is injected subordinate phase flash distillation (devolatilizer) material with the cancellation remainder catalyst and be aided with the solvent stripping.The performance of polymkeric substance and final binding agent is generally listed in the table 33.

All documents described herein comprise that any priority document and/or testing process are incorporated herein by reference.As from above-mentioned general describe and specific embodiments conspicuous, although form of the present invention is illustrated and describes, can carry out various improvement under the spirit and scope of the invention not leaving.Therefore.The present invention is not limited by these forms.

Claims

1. continuation method of producing polymkeric substance, this polymkeric substance comprises one or more C3 to C12 alkene of 50mol% at least, wherein this polymkeric substance has:

A) some T shape peeling force 1 newton on kraft paper or bigger;

C) Mw 100,000 or lower; With

D) melting heat 1 is to 70J/g.

Wherein this method steps comprises:

1) choose first catalyst component, this catalyst component can under the polymerizing condition of choosing, produce Mw be 100,000 or lower and degree of crystallinity be 5% or lower polymkeric substance;

2) choose second catalyst component, this catalyst component can under the polymerizing condition of choosing, produce Mw be 100,000 or lower and degree of crystallinity be 20% or bigger polymkeric substance;

3) these catalyst components are contacted with one or more C3 to C12 alkene in the presence of one or more activators; With

4) be higher than under 100 ℃ in temperature;

5) the residence time be 120 minutes or shorter under;

6) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 50: 1;

7) wherein the activity of catalyst component is 50kg polymkeric substance/g catalyst compound at least; Wherein at least 80% conversion of olefines is a polymkeric substance.

2. the process of claim 1 wherein that first catalyst component comprises the Stereoselective metallocene catalyst compound.

3. the process of claim 1 wherein that first catalyst component comprises non-Stereoselective metallocene catalyst compound.

4. claim 1,2 or 3 method, wherein second catalyst component comprises the Stereoselective metallocene catalyst compound.

5. the method for claim 1, wherein first catalyst component comprises following one or more materials: dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (sec-butyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (normal-butyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) titanium dichloride, diethylsilane base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride, diethylsilane base (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) titanium dichloride, diethylsilane base (tetramethyl-ring pentadienyl) (cyclohexyl amino) titanium dichloride, diethylsilane base (tetramethyl-ring pentadienyl) (1-adamantyl amino) titanium dichloride, methylene radical (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) titanium dichloride, methylene radical (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) titanium dichloride, methylene radical (tetramethyl-ring pentadienyl) (cyclohexyl amino) titanium dichloride, methylene radical (tetramethyl-ring pentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (2-tetrahydro indenyl) (cyclo-dodecyl amino) titanium dichloride, dimetylsilyl (2-tetrahydro indenyl) (cyclohexyl amino) titanium dichloride, dimetylsilyl (2-tetrahydro indenyl) (1-adamantyl amino) titanium dichloride, dimetylsilyl (2-tetrahydro indenyl) (outer-2-norcamphyl amino) titanium dichloride, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (tertiary butyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (sec-butyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (normal-butyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, diethylsilane base (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, diethylsilane base (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, diethylsilane base (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, diethylsilane base (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, methylene radical (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, methylene radical (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, methylene radical (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, methylene radical (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (tetramethyl-ring pentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (2,5-dimethyl cyclopentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (3,4-dimethyl cyclopentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-5-methyl cyclopentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (3-ethyl-4-methyl cyclopentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (outer-2-norcamphyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (2-ethyl-3-hexyl-5-methyl-4-octyl group cyclopentadienyl) (1-adamantyl amino) dimethyl titanium, dimetylsilyl (2-tetrahydro indenyl) (cyclo-dodecyl amino) dimethyl titanium, dimetylsilyl (2-tetrahydro indenyl) (cyclohexyl amino) dimethyl titanium, dimetylsilyl (2-tetrahydro indenyl) (1-adamantyl amino) dimethyl titanium and dimetylsilyl (2-tetrahydro indenyl) (outer-2-norcamphyl amino) dimethyl titanium.

6. the process of claim 1 wherein that second catalyst component comprises the racemic modification of one or more following materials:

Dimetylsilyl (2-methyl-4-phenyl indenyl) zirconium dichloride,

Dimetylsilyl (2-methyl-4-phenyl indenyl) zirconium dimethyl,

Dimetylsilyl (2-methyl-4-phenyl indenyl) hafnium dichloride,

Dimetylsilyl (2-methyl-4-phenyl indenyl) dimethyl hafnium,

Two (indenyl) dimethyl hafniums of dimetylsilyl,

Two (indenyl) hafnium dichloride of dimetylsilyl,

Two (indenyl) zirconium dimethyls of dimetylsilyl,

Two (indenyl) zirconium dichlorides of dimetylsilyl;

The racemic isomer of following material:

Two (2-methyl) the metal dichloride of dimethylsilane two bases;

Two (indenyl) metal dichloride of dimethylsilane two bases;

Two (indenyl) dimethyl metals of dimethylsilane two bases;

Two (tetrahydro indenyl) metal dichloride of dimethylsilane two bases;

Two (tetrahydro indenyl) dimethyl metals of dimethylsilane two bases;

Two (indenyl) diethyl metals of dimethylsilane two bases; With

Two (indenyl) dimethyl metals of dibenzyl silane two bases;

Wherein metal is selected from Zr, Hf or Ti.

7. the process of claim 1 wherein that activator comprises aikyiaiurnirsoxan beta.

8. the process of claim 1 wherein that activator comprises the ionization compound.

9. the process of claim 1 wherein that activator comprises non-coordination anion.

10. the process of claim 1 wherein that activator comprises one or more in the following material:

Methylaluminoxane,

Tetraphenyl boric acid trimethyl ammonium,

Tetraphenyl boric acid triethyl ammonium,

Tetraphenyl boric acid tripropyl ammonium,

Tetraphenyl boric acid three (normal-butyl) ammonium,

Tetraphenyl boric acid three (tertiary butyl) ammonium,

Tetraphenyl boric acid N, accelerine,

Tetraphenyl boric acid N, the N-Diethyl Aniline,

Tetraphenyl boric acid N, N-dimethyl-(2),

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 N, accelerine,

Four (pentafluorophenyl group) boric acid N, the N-Diethyl Aniline,

Four (pentafluorophenyl group) boric acid N, N-dimethyl-(2),

Four-(2,3,4,6-tetrafluoro phenyl) boric acid trimethyl ammoniums,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid triethyl ammoniums,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid tripropyl ammoniums,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid three (normal-butyl) ammoniums,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (tertiary butyl) ammoniums,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid N, accelerine,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid N, the N-Diethyl Aniline,

Four-(2,3,4,6-tetrafluoro phenyl) boric acid N, N-dimethyl-(2),

Four (pentafluorophenyl group) boric acid di-isopropyl ammonium,

Four (pentafluorophenyl group) boric acid dicyclohexyl ammonium,

Four (pentafluorophenyl group) boric acid triphenyl phosphonium,

Four (pentafluorophenyl group) boric acid three (o-tolyl) Phosphonium and

Four (pentafluorophenyl group) boric acid three (2,6-3,5-dimethylphenyl) Phosphonium.

11. the process of claim 1 wherein the macromonomer that first catalyst component can polymerization has reactive terminal; Second component can be produced the macromonomer with reactive terminal.

12. the method for claim 1 further comprises diolefine.

13. the method for claim 1 further comprises one or more C4 to C40 diene.

14. the method for claim 1, further comprise and be selected from one or more following diene: 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-11 carbon diene, 1,11-12 carbon diene, 1,12-oleatridecadiene, 1,13-14 carbon diene, cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, Dicyclopentadiene (DCPD) and Mw are lower than polyhutadiene or its combination of 1000g/mol.

15. the method for claim 1, further comprise and be selected from one or more following diene: 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-11 carbon diene, 1,11-12 carbon diene, 1,12-oleatridecadiene, 1,13-14 carbon diene, cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, Dicyclopentadiene (DCPD) and Mw are lower than polyhutadiene or its combination of 1000g/mol.

16. the process of claim 1 wherein that conversion zone is a Gas-phase reactor, wherein conversion zone is meant the zone that wherein deactivated catalyst and monomer can react.

17. the process of claim 1 wherein that conversion zone is the solution-phase reaction device, wherein conversion zone is meant the zone that wherein deactivated catalyst and monomer can react.

18. the process of claim 1 wherein that conversion zone is a sludge phase reactor, wherein conversion zone is meant the zone that wherein deactivated catalyst and monomer can react.

19. the process of claim 1 wherein that conversion zone is the solution-phase reaction device, wherein conversion zone is meant the zone that wherein deactivated catalyst and monomer can react.

20. the method for claim 1, wherein catalyzer comprises one or more in the following combination, wherein Me equals methyl, Ph equals that phenyl, Et equal ethyl, Cp equals cyclopentadienyl, 3,8-di-t-BuFlu equals 3, and 8-di-t-butyl fluorenyl, 2-Me-4-PhInd equal 2-methyl-4-phenyl indenyl, 2-MeInd equals 2-methyl indenyl, c-C ₁₂H ₂₃Equal cyclo-dodecyl, Me ₄C ₅Equal tetramethyl-ring pentadienyl, H ₄Ind equals tetrahydro indenyl and Ind equals indenyl:

(1) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(2) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(2a) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(3) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(4) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(4a) Me ₂Si (Me ₄C ₅) (N-c-C ₁₂H ₂₃) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(5) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(6) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(6a) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(7) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(8) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(8a) Me ₂Si (Me ₄C ₅) (N-1-adamantyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(9) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(10) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(10a) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(11) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) activates with aikyiaiurnirsoxan beta;

(12) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(12a) Me ₂Si (Me ₄C ₅) (the N-tertiary butyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(13) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(14) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(14a) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(15) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(16) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(16a) Me ₂Si (Me ₄C ₅) (outside the N--and norcamphyl) TiMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(17) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(18) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(18a) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(19) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(20) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(20a) (p-Et ₃SiPh) ₂C (Cp) (3,8-di-t-BuFlu) HfMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(21) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(22) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(22a) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(23) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(24) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(24a) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(25) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(26) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(26a) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (H ₄Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(27) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(28) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(28a) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂Use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(29) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(30) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(30a) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(31) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(32) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(32a) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(33) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(34) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(34a) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(35) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-Me ₂Si (2-MeInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(36) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(36a) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-Me ₂Si (2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(37) meso-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(38) meso-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(38a) meso-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂And racemize-Me ₂Si (2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(39) meso-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(40) meso-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(40a) meso-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-Me-4-PhInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(41) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(2-MePhInd) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(42) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂, with non-coordination anion activator activation;

(42a) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(43) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(44) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(44a) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(45) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-Me ₂Si (Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(46) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(46a) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-Me ₂Si (Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(47) meso-CH ₂CH ₂(Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂(4,7-Me ₂Ind=4,7-dimethyl indenyl), activate with aikyiaiurnirsoxan beta;

(48) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(48a) meso-CH ₂CH ₂(Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(49) meso-Me ₂Si (Ind) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(50) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(50a) meso-Me ₂Si (Ind) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(51) meso-CH ₂CH ₂(2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂(4,7-Me ₂Ind=4,7-dimethyl indenyl), activate with aikyiaiurnirsoxan beta;

(52) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(52a) meso-CH ₂CH ₂(2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron;

(53) meso-Me ₂Si (2-MeInd) ₂ZrCl ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrCl ₂, activate with aikyiaiurnirsoxan beta;

(54) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, with non-coordination anion activator activation;

(54a) meso-Me ₂Si (2-MeInd) ₂ZrMe ₂And racemize-CH ₂CH ₂(4,7-Me ₂Ind) ₂ZrMe ₂, use N, accelerine four (pentafluorophenyl group) boron and/or the activation of triphenylcarbenium four (pentafluorophenyl group) boron.

21. the process of claim 1 wherein that second kind of catalyst component comprises one or more in the following material:

Dimethylsilane two bases (the 2-n-propyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂Hafnium dichloride;

Dimethylsilane two bases (2-sec-butyl, 4-[3 ', 5 '-two-isopropyl phenyl] indenyl) ₂η 4-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-ethyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

Dimethylsilane two bases (2-n-propyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

9-silicon heterofluorene two bases (the 2-sec-butyl, 4-[3 ', 5 '-di-tert-butyl-phenyl] indenyl) ₂η ⁴-1,4-phenylbenzene-1,3-butadiene;

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

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

Two (trimethyl silyl) amino borane (2-sec-butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl; Or

Two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl.

22. the process of claim 1 wherein second catalyst component comprise-kind or multiple two (trimethyl silyl) amino borane (the 2-tertiary butyl, 4-[3 ', 5 '-two-phenyl] indenyl) ₂Zirconium dimethyl.

23. the continuation method of claim 1 further comprises:

1) with one or more C3 to C12 alkene, solvent, first catalyst component, second catalyst component and the combination in reactor system of one or more activators,

2) from this reactor system, draw off polymers soln,

3) from this polymers soln, remove at least 10% solvent,

4) quenching reaction,

5) this polymers soln devolatilization is formed molten polymer,

6) this molten polymer is combined in static mixer with one or more additives,

7) from this static mixer, take out this polymer conjugates and

24. the process of claim 1 wherein:

1) described first catalyst component can under the polymerizing condition of choosing, produce Mw be 80,000 or lower and degree of crystallinity be 5% or lower polymkeric substance;

2) described second catalyst component can under the polymerizing condition of choosing, produce Mw be 80,000 or lower and degree of crystallinity be 20% or bigger polymkeric substance;

3) these catalyst components are contacted with non-essential one or more C4 to C20 diolefine with one or more C4 to C20 alkene with propylene in the presence of one or more activators;

4) be higher than under 100 ℃ in temperature;

5) wherein the ratio of first catalyzer and second catalyzer is 1: 1 to 20: 1;

6) wherein the activity of catalyst component is 100kg polymkeric substance/g catalyst compound at least; Wherein at least 80% conversion of olefines is a polymkeric substance.

25. the method for claim 24, wherein

A) alkene comprises one or more in propylene and butylene, amylene, hexene, heptene, octene, nonene, decene, the dodecylene; With

B) temperature is higher than 110 ℃; With

C) residence time is 60 to 120 minutes.

26. the method for claim 24 or 25, wherein there is diolefine and is selected from 1, the 6-heptadiene, 1, the 7-octadiene, 1, the 8-nonadiene, 1, the 9-decadiene, 1,10-11 carbon diene, 1,11-12 carbon diene, 1, the 12-oleatridecadiene, 1,13-14 carbon diene, cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, Dicyclopentadiene (DCPD), Mw is lower than the polyhutadiene of 1000g/mol, divinyl, pentadiene, hexadiene, 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 20-carbon diene, 22 carbon diene, two oleatridecadienes, the tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, Dicyclopentadiene (DCPD) or its combination.

27. the process of claim 1 wherein that alkene comprises propylene and butylene, amylene, hexene, heptene, octene, nonene, decene, dodecylene, 4-methyl-amylene-1,3-methyl-amylene-1 and 3,5, one or more in 5-trimethylammonium-hexene-1.

28. the method for claim 1 is further comprising the steps of:

8) from this conversion zone, draw off polymers soln;

9) from this polymers soln, remove at least 10% solvent;

10) quenching reaction;

11) devolatilization forms molten polymer from this polymers soln;

12) this molten polymer is combined in static mixer with one or more additives;

13) from this static mixer, take out this polymer conjugates; With