CN102977229B - Method for synthetizing C2 bridging fiber metallocene dikaryon catalyst - Google Patents
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Abstract
The invention provides the following structural formula which represents heterogeneous C2 bridging fiber metallocene dikaryon catalyst, wherein M is Ti or Zr. The invention also provides a preparation method of the catalyst. The catalyst and promotor of alkyl aluminoxane are matched for olefin polymerization, thus having high polymerization reaction activity, and obtaining olefin polymerization products of high molecular weight and wide molecular weight distribution.
Description
Technical field
The invention belongs to polyolefin field, relate to the catalyzer for olefinic polymerization, relate in particular to bimetallic catalyst for ethene and propylene polymerization and preparation method thereof.
Background technology
The active centre of metallocene catalyst is single, the activity of catalyzer is high, can obtain the polymkeric substance that tacticity is very high, and the polymericular weight obtaining is high, molecular weight and molecular weight distribution can be controlled by changing ligand structure, are therefore subject to extensive concern always.But due to the polyolefin molecular weight narrowly distributing obtaining, processing difficulties and limited its process of industrialization.People attempt with composite catalyzing (referring to KAMINSKY W, STEIGER R. Polymerization of olefins with homogeneous zirconocene/alumoxane catalysts, Polyhedron, 1988,
7(22-23): 2375-2381) or double-core multinuclear catalyzer (referring to Feng Zuofeng, Xie Jun, Chen Bin etc., organic chemistry, 2001,
21(1), 33-40) improve the molecular weight distribution of polymkeric substance.
Green and his colleagues have synthesized the binuclear compound (T.Ushioda, M.L.H.Green, J.Haggitt, X.Yan, J.Organomet.Chem., 1996,518,155) of Si bridging.Bridging two (cyclopentadiene) two negative ions first with the CpMCl of monovalent
3reaction, obtains the compound of central ion and three cyclopentadiene coordinations, and then with the metal halide of the second equivalent (Cp ' MCl
3or MCl
4) reaction, obtain binuclear compound.This binuclear compound is for vinyl polymerization, and activity is very high (higher than 8.5 * 10
6gPE/mol M h, monokaryon compound M[(η-C
5h
5)
2cl
2] be 3.6 * 10
6gPE/mol M h); Molecular weight distribution (the M that broadens
w/ M
n>5.4).For propylene polymerization, obtain Atactic Polypropelene (mm<0.39, general homogeneous phase Ziegler-Natta catalyst mm>0.90).Author thinks may there is a more than active centre.
CN1428355 discloses a kind of dinuclear metallocene compounds and preparation and the application in olefinic polymerization, discloses the binuclear compound of dimethyl-silicon bridging, and for vinyl polymerization, and high reactivity can reach 10
6gPE/mol Cat.
Although above-mentioned document has been reported dinuclear catalyst, although its catalytic performance, higher than monokaryon catalyzer, does not obtain bimodal polymers.Chinese patent application 200710015194.2 and 200710015193.8 discloses bridged metallocene double-core catalyst and preparation method thereof, but has the defect that step is many, cost is high, total recovery is low.201110030833.9 disclose a kind of C2 bridged metallocene Zr-tombarthite catalyst and preparation method thereof, but reaction is complicated, need a kind of reactant excessive in a large number, and aftertreatment is loaded down with trivial details.
Summary of the invention
The preparation method who the object of this invention is to provide described C2 bridged metallocene double-core catalyst, this preparation method's step is few, raw material is easy to get, and cost is low, is easy to industrialization.
C2 bridged metallocene double-core catalyst of the present invention, alkylaluminoxane are promotor, and catalyzed ethylene or propylene polymerization can obtain the polyolefine of wide molecular weight distribution.Polymerization process can adopt mass polymerization or solution polymerization.
A C2 bridged metallocene double-core catalyst, its structure is as follows:
Wherein M is Ti or Zr.
The synthetic method of the C2 bridged metallocene double-core catalyst described in the present invention also provides, comprises the following steps:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in organic solvent, is cooled to-20～10 ℃, slowly drips fluorenes lithium solution, and time for adding 1 ~ 2 hour dropwises and continues reaction 12 ~ 16 hours;
The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1 ~ 1.1:1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil.
2) C2 bridging indenyl fluorenyl ligand is synthetic
In the fluorenyl ligand that step 1) obtains, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1～1.1; Temperature of reaction is-30 ℃～0 ℃; Reaction times is 13 ~ 16 hours.
3) part lithium salts is synthetic
By step 2) part that obtains is dissolved in normal hexane, drips n-Butyl Lithium, and dropping temperature is-20～10 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.0～2.4, dropwises, and naturally rises to room temperature, reacts 12～16 hours.Remove by filter normal hexane, decompressing and extracting normal hexane, obtains part lithium salts.
4) C2 bridged metallocene double-core catalyst is synthetic
In the part lithium salts that step 3) obtains, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at-10～20 ℃
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl.CpZrCl
3dME or CpTiCl
3with the mol ratio of part lithium salts be 2～2.3:1, temperature of reaction is-10～20 ℃, stirring reaction 10～20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtaining are merged, be concentrated into and occur solid, place for-25 ℃～-15 ℃ and within 20～30 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst.
Preferably, in step 1), organic solvent is selected from anhydrous diethyl ether or sherwood oil.Temperature of reaction is-20～-10 ℃, and the reaction times is 12 ~ 14 hours; The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1:1.
Preferably, step 2) in, temperature of reaction is-20 ℃～-10 ℃; Reaction times is 14 ~ 16 hours; The mol ratio of indenes lithium is 1:1; Solvent is tetrahydrofuran (THF).
Preferably, in step 3), dropping temperature is-10～0 ℃.The mol ratio of part and n-Butyl Lithium is 1:2.0～2.2, dropwises, and naturally rises to room temperature, reacts 12～14 hours.
Preferably, in step 4), temperature of reaction is 0～10 ℃.Stirring reaction 10～15 hours.
Under identical catalytic condition, the catalytic activity of the C2 bridged metallocene double-core catalyst that the present invention obtains than monokaryon metallocene catalyst as CyclopentadienyltitaDichloride Dichloride Cp
2tiCl
2or cyclopentadienyl zirconium dichloride Cp
2zrCl
2catalytic activity high, and the molecular weight of polymkeric substance obviously increases, molecular weight distribution broadens.
Synthetic method of the present invention, compares with the method for reporting in document, and synthetic route is short, and productive rate is high, has avoided expensive reagent use, has better industrial prospect.
Embodiment
The preparation method of C2 bridged metallocene double-core catalyst is as follows:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in organic solvent, is cooled to-20～10 ℃, slowly drips fluorenes lithium solution, and time for adding 1 ~ 2 hour dropwises and continues reaction 12 ~ 16 hours.
The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1 ~ 1.1:1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil.
Synthetic method is shown below:
。
The selection of solvent is extremely important, selects anhydrous diethyl ether or sherwood oil as solvent, can effectively control the degree of reaction, and the Br that can control in the bromo-1-decene of the chloro-10-of 9-reacts, and Cl does not react.And while selecting the larger solvent of methylene dichloride, toluene or tetrahydrofuran (THF) isopolarity, Br and Cl can participate in reaction, the elective reduction of reaction.
While using the chloro-1-decene of 9,10-bis-as reactant, fluorenes lithium solution slowly need be added drop-wise in the bromo-1-decene solution of the chloro-10-of 9-, and in reaction, keep the bromo-1-decene of the chloro-10-of 9-excessive always.Condition is controlled improper meeting and is produced 9,10-, bis-indenyls-1-decene.Cannot there is the next step in 9,10-, bis-indenyls-1-decene, need to be separated through gel column.And the present invention utilizes the reactive difference of Br and Cl, the selection by suitable reaction conditions obtains object product.Avoided the separation of later stage product.Temperature of reaction is-30～0 ℃, does not need too low temperature of reaction.
The concentration of the bromo-1-decene of the chloro-10-of 9-does not limit, and those skilled in the art can select suitable concentration according to practical situation.Fluorenes lithium is synthetic with known method by fluorenes and butyllithium.Butyllithium can be bought also and can by Li band, be prepared in sherwood oil or normal hexane solvent with chlorobutane according to known method.
React complete, decompression steams after most of solvent, separated through chromatographic column, obtains the chloro-1-decene of 10-indenyl-9-, saves backup.Also can be separated without chromatographic column, after completion of the reaction, steam and desolventize the rear the next step of directly carrying out.
2) C2 bridging indenyl fluorenyl ligand is synthetic
In the fluorenyl ligand that step 1) obtains, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1～1.1; Temperature of reaction is-30 ℃～0 ℃; Reaction times is 13 ~ 16 hours.
If the fluorenyl ligand that step 1) obtains does not steam, directly carry out step 2 except organic solvent) reaction, speed of response is very slow, products collection efficiency is low.We find, use step 2) in while using tetrahydrofuran (THF) for solvent, side reaction is few, can react rapidly, the part productive rate obtaining is high.
Indenes lithium is synthetic with known method by indenes and butyllithium.Butyllithium can be bought also and can by chlorobutane and Li, be prepared according to known method.The order of addition(of ingredients) of fluorenyl ligand and indenes lithium is not particularly limited, and preferably indenes lithium solution is added drop-wise to the mode in fluorenyl ligand.
Synthetic method is shown below:
。
3) part lithium salts is synthetic
By step 2) part that obtains is dissolved in normal hexane, drips n-Butyl Lithium, and dropping temperature is-20～10 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.0～2.4, dropwises, and naturally rises to room temperature, reacts 12～16 hours.Remove by filter normal hexane, decompressing and extracting normal hexane, obtains part lithium salts.
Drain the part lithium salts obtaining after normal hexane, be easy to preserve, also easily make various solution or suspension.Also can not drain solvent, after concentrating, directly carry out lower step and synthesize.
4) C2 bridged metallocene double-core catalyst is synthetic
In the part lithium salts that step 3) obtains, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at-10～20 ℃
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl.CpZrCl
3dME or CpTiCl
3with the mol ratio of part lithium salts be 2～2.3:1, temperature of reaction is-10～20 ℃, stirring reaction 10～20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtaining are merged, be concentrated into and occur solid, place for-25 ℃～-15 ℃ and within 20～30 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst.
In catalyzer preparation of the present invention, the selection of solvent is extremely important; In different reactions steps, use different solvents, be conducive to the carrying out of reaction, be also conducive to improve productive rate.We find, the solvent selection in preparation process, and not exclusively follow the principle of " similar mixing ", such as, in the reaction that has lithium salts to participate in, use the non-polar solvents such as sherwood oil higher than using tetrahydrofuran (THF) productive rate on the contrary.We find to use solvent of the present invention through a large amount of experiments, and reaction yield is the highest.The selection of solvent has also determined that the Br in the bromo-1-decene of the chloro-10-of 9-reacts, or Br and Cl react; We find, when adopting weak polar solvent (as anhydrous diethyl ether or sherwood oil), can control that Br atom reacts and Cl does not react; But simultaneously also startled discovery, is used nonpolar pentane solvent, and reaction yield is not high.
Each described reaction all need be carried out under inert atmosphere, adopts shenlink technology, and rare gas element is argon gas or nitrogen.
Compound provided by the invention can be made the alpha-olefin homopolymerization of C2～C10 or the Primary Catalysts of copolymerization.During polymerization, also needing to add alkylaluminoxane is promotor.Preferred promotor is methylaluminoxane, and during polyreaction, in promotor, in Al and Primary Catalysts, the mol ratio of metal is 250～1500:1, preferably 250～1000:1.Polymerizing condition is 30～80 ℃, 0.1～0.8MPa.For homopolymerization or copolymerization, obtain alkene optimal ethylene, propylene, butylene, hexene or octene.Polymerization process can adopt mass polymerization or solution polymerization.Analytical procedure and polymkeric substance are described, and adopt the method described in 201110030833.9.
Following examples are to further illustrate of the present invention, but the present invention is not limited thereto.
embodiment 1:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in sherwood oil, is cooled to-20 ℃, slowly drips fluorenes lithium solution, and time for adding 2 hours dropwises and continues reaction 12 hours; The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1:1.
2) C2 bridging indenyl fluorenyl ligand is synthetic
In the fluorenyl ligand that step 1) obtains, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-20 ℃; Reaction times is 16 hours.
3) part lithium salts is synthetic
By step 2) part that obtains is dissolved in normal hexane, drips n-Butyl Lithium, and dropping temperature is-20 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.2, dropwises, and naturally rises to room temperature, reacts 14 hours.Remove by filter normal hexane, decompressing and extracting normal hexane, obtains part lithium salts.
4) in the part lithium salts that step 3) obtains, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at-10 ℃
3dME, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 2:1, temperature of reaction is-10 ℃, stirring reaction 15 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtaining are merged, be concentrated into and occur solid, place for-20 ℃ and within 20 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst.
embodiment 2
Other are with embodiment 1, and difference is:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in sherwood oil, is cooled to-10 ℃, slowly drips fluorenes lithium solution, and time for adding 1.5 hours dropwises and continues reaction 16 hours; The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1.1:1.
2) C2 bridging indenyl fluorenyl ligand is synthetic
In the fluorenyl ligand that step 1) obtains, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-10 ℃; Reaction times is 14 hours.
3) part lithium salts is synthetic
By step 2) part that obtains is dissolved in normal hexane, drips n-Butyl Lithium, and dropping temperature is 0 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.4, dropwises, and naturally rises to room temperature, reacts 12 hours.Remove by filter normal hexane, decompressing and extracting normal hexane, obtains part lithium salts.
4) in the part lithium salts that step 3) obtains, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at 0 ℃
3dME, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 2.1:1, temperature of reaction is 0 ℃, stirring reaction 10 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtaining are merged, be concentrated into and occur solid, place for-15 ℃ and within 30 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst.
embodiment 3
Other are with embodiment 1, and difference is:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in anhydrous diethyl ether, is cooled to 0 ℃, slowly drips fluorenes lithium solution, and time for adding 1 hour dropwises and continues reaction 14 hours; The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1:1.
2) C2 bridging indenyl fluorenyl ligand is synthetic
In the fluorenyl ligand that step 1) obtains, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-5 ℃; Reaction times is 13 hours.
3) 0.0266mol part is dissolved in 80ml normal hexane, drips the n-Butyl Lithium of 0.0585mol under ice-water bath, dropwises the water-bath of recession deicing, naturally rises to room temperature, reacts 12 hours.Remove by filter solvent, vacuum is drained, and obtains white powder solid.For part lithium salts.
In the part lithium salts obtaining, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at 20 ℃
3dME, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 2.3:1, temperature of reaction is 20 ℃, stirring reaction 18 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid obtaining are merged, and is concentrated into and occurs solid,-25 placements obtain Compound C Bridge 2 connection metallocene dinuclear catalyst for 20 hours, are brown crystal.
NMR data are as follows:
1H?NMR（CDCl3，25℃）：7.98(d,J=8.4Hz,1H),?7.82(d,J=8.4Hz,1H),?7.74(d,J=8.5Hz,1H),?7.65(2H),?7.51(6H),?7.10(2H),?6.51(t,2H,C
5H
5,?a,?J
H-H=2.63Hz),?6.44(d,8H,C
5H
5,a,?J
H-H=5.04Hz),?5.92(s,1H,CH
ind),?5.72(m,1H,=CH),?4.93(m,1H,=CH
2),?4.35(m,1H,CH
2),?4.15(2H,?CH
2),?3.85(m,1H,?CH
2),?2.63(m,1H,?CH
2),?2.52(m,1H,?CH
2),?1.96(m,2H,?CH
2),?1.40-1.29(4H,?CH
2),
13C?NMR（CDCl3，25℃）：138.2(=CH),?128.7,?128.2(CH),?127.2,?127.1(Cq),?126.1,?125.7(CH),?125.5,?125.4(Cq),?125.3,?125.1,?124.9,?124.7,?123.9(CH),?123.4,?123.3,?122.6(Cq),?122.5,?122.4(CH),?121.4(Cq),?120.9(CH),?115.8,?115.6,?115.5,?115.4,?115.2,?115.0,?114.9,?114.7,?114.6,?114.5,?114.3(=CH
2),?113.5(CH
ind),?103.6(Cq
ind),?33.5,?30.1,?29.8,?29.3,?28.8,?28.2(CH
2)。
Gained compound coordinates with promoter aluminium alkyl oxygen alkane for catalyzed ethylene polymerization, active in 3.15 * 10
5g ethene/mmol Zr h, Mw/Mn=3.23, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzing and synthesizing is wide.
embodiment 4:
Other are with embodiment 3, and that different is CpZrCl
3dME is by CpTiCl
3replace CpTiCl
3with the mol ratio of part lithium salts be 2.1:1, temperature of reaction is 30 ℃, stirring reaction 12 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid obtaining are merged, and is concentrated into and occurs solid, placing for-25 ℃～-15 ℃ and within 30 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst, is red crystals.
Gained compound coordinates with promoter aluminium alkyl oxygen alkane for catalyzed ethylene polymerization, active in 1.2 * 10
5g ethene/mmol Zr h, Mw/Mn=3.42, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzing and synthesizing is wide.
Claims (4)
1. a synthetic method for C2 bridged metallocene double-core catalyst, comprises the following steps:
1) fluorenyl ligand is synthetic
The bromo-1-decene of the chloro-10-of 9-is dissolved in organic solvent, is cooled to-20～10 ℃, slowly drips fluorenes lithium solution, and time for adding 1～2 hour dropwises and continues reaction 12～16 hours;
The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1～1.1:1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil;
2) C2 bridging indenyl fluorenyl ligand is synthetic
Step 1) in the fluorenyl ligand obtaining, add solvents tetrahydrofurane, then react with indenes lithium, obtain the indenyl fluorenyl ligand of C2 bridging; The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-20 ℃～-10 ℃; Reaction times is 14～16 hours;
3) part lithium salts is synthetic
By step 2) part that obtains is dissolved in normal hexane, drips n-Butyl Lithium, and dropping temperature is-20～10 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.0～2.4, dropwises, and naturally rises to room temperature, reacts 12～16 hours; Remove by filter normal hexane, decompressing and extracting normal hexane, obtains part lithium salts;
4) C2 bridged metallocene double-core catalyst is synthetic
Step 3) in the part lithium salts obtaining, add toluene, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, adds CpZrCl at-10～20 ℃
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3with the mol ratio of part lithium salts be 2～2.3:1, temperature of reaction is-10～20 ℃, stirring reaction 10～20 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtaining are merged, are concentrated into and occur solid, place for-25 ℃～-15 ℃ and within 20～30 hours, obtain Compound C Bridge 2 connection metallocene dinuclear catalyst:
m is Ti or Zr.
2. the synthetic method of C2 bridged metallocene double-core catalyst as claimed in claim 1, is characterized in that step 1) in organic solvent be selected from anhydrous diethyl ether or sherwood oil; Temperature of reaction is-20～-10 ℃, and the reaction times is 12～14 hours; The mol ratio of the bromo-1-decene of the chloro-10-of 9-and fluorenes lithium is: the bromo-1-decene of the chloro-10-of 9-: fluorenes lithium=1:1.
3. the synthetic method of C2 bridged metallocene double-core catalyst as claimed in claim 1, is characterized in that step 3) in, dropping temperature is-10～0 ℃; The mol ratio of part and n-Butyl Lithium is 1:2.0～2.2, dropwises, and naturally rises to room temperature, reacts 12～14 hours.
4. the synthetic method of C2 bridged metallocene double-core catalyst as claimed in claim 1, is characterized in that step 4) in, temperature of reaction is 0～10 ℃; Stirring reaction 10～15 hours.
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