CN102942641A - Synthesis method of metallocene binuclear catalyst - Google Patents
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Abstract
The invention provides a metallocene binuclear catalyst of which the structural formula is shown in the specification, wherein M is Ti or Zr. The invention also provides a preparation method of the catalyst. The catalyst can be used for olefin polymerization together with alkyl aluminoxane serving as a cocatalyst, has high polymerization reaction activity, and can be used for producing olefin polymerization products with 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, catalyzer active high, can obtain the very high polymkeric substance of tacticity, and the polymericular weight that obtains is high, molecular weight and molecular weight distribution can be controlled by changing ligand structure, therefore are subject to extensive concern always.But because the polyolefin molecular weight narrowly distributing that obtains, 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) improves 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 at 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, get binuclear compound.This binuclear compound is used for vinyl polymerization, and activity is very high (to be 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
n5.4).Be used for propylene polymerization, get Atactic Polypropelene (mm＜0.39, general homogeneous phase Ziegler-Natta catalyst mm〉0.90).The author thinks may exist 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 is higher than the monokaryon catalyzer, do 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 defective 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 step is many, aftertreatment is loaded down with trivial details.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of metallocene Zr-tombarthite catalyst, this preparation method's step is few, raw material is easy to get, and cost is low, is easy to industrialization.
Metallocene Zr-tombarthite catalyst of the present invention, alkylaluminoxane are promotor, catalyzed ethylene or propylene polymerization, can the polyolefine of wide molecular weight distribution.Polymerization process can adopt mass polymerization or solution polymerization.
The present invention also provides described metallocene dinuclear catalyst, and its structure is as follows:
Wherein M is Zr or Ti.
The present invention also provides the synthetic method of described metallocene dinuclear catalyst, comprises the following steps:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the organic solvent, is cooled to-30～0 ℃, slowly drips fluorenes lithium solution, and time for adding 1.5 ~ 2.5 hours dropwises and continues reaction 12 ~ 16 hours;
The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: fluorenes lithium=1:1 ~ 1.1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil.
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 ℃～0 ℃; Slowly drip indenes lithium solution, time for adding 1 ~ 2 hour dropwises and continues reaction 12-18 hour, obtains the indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1～1.1.
3) the part lithium salts is synthetic
With step 2) part that obtains is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature is-20～10 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.0～2.5, dropwises, and naturally rises to room temperature, reacts 10～15 hours.Remove by filter insolubles, the decompressing and extracting normal hexane obtains the part lithium salts.
4) add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 2～2.2:1, temperature of reaction is 0～30 ℃, stirring reaction 10～15 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place 10～20 hours substituted bridged metallocene double-core catalysts for-25 ℃～-15 ℃, structure is shown below:
Preferably, organic solvent is selected from anhydrous diethyl ether or sherwood oil in the step 1).Temperature of reaction is-20～-10 ℃, and the reaction times is 12 ~ 14 hours; The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: fluorenes lithium=1:1.
Preferably, step 2) in, temperature of reaction is-20 ℃～-10 ℃; Reaction times is 14-16 hour; The mol ratio of indenes lithium is 1:1.
Preferably, in the 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 12～15 hours.
Preferably, in the step 4), temperature of reaction is 0～20 ℃, stirring reaction 12～15 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 such 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 is compared with the method for reporting in the document, and synthetic route is short, and productive rate is high, has avoided the expensive reagent use, has better industrial prospect.
Embodiment
The preparation method of metallocene dinuclear catalyst is as follows:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the organic solvent, is cooled to-30～0 ℃, slowly drips fluorenes lithium solution, and time for adding 1.5 ~ 2.5 hours dropwises and continues reaction 12 ~ 16 hours;
The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: 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 7-chloro-8-bromo-1-octene reacts, and Cl does not react.And when selecting the larger solvent of methylene dichloride, toluene or tetrahydrofuran (THF) isopolarity, Br and Cl can participate in reaction, the elective reduction of reaction.
When using 7,8-, two chloro-1-octenes as reactant, need fluorenes lithium solution slowly is added drop-wise in the 7-chloro-8-bromo-1-octene solution, and in reaction, keep 7-chloro-8-bromo-1-octene excessive in a large number always.Condition control is improper can to produce 7,8-, two indenyls-1-octene.The next step can't occur in 7,8-, two indenyls-1-octene, need to separate through gel column.And the present invention utilizes the reactive difference of Br and Cl, and the selection by suitable reaction conditions obtains the purpose product.Avoided the separation of later stage product.Temperature of reaction is-30～0 ℃, does not need too low temperature of reaction, is easy to control.
The concentration of 7-chloro-8-bromo-1-octene is unqualified, and those skilled in the art can select suitable concentration according to practical situation.The fluorenes lithium is synthetic with known method by fluorenes and butyllithium.Butyllithium can be bought also and can be prepared in sherwood oil or normal hexane solvent with chlorobutane by the Li band according to known method.
React complete, after decompression steams most of solvent, separate through chromatographic column, obtain 8-indenyl-7-chloro-1-octene, save backup.Also can separate without chromatographic column, react complete after, steam and to desolventize the rear the next step of directly carrying out.
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 ℃～0 ℃; Slowly drip indenes lithium solution, the mol ratio of fluorenyl ligand and indenes lithium is 1:1～1.1; Time for adding 1 ~ 2 hour dropwises and continues reaction 12-18 hour, obtains the indenyl fluorenyl ligand;
Synthetic method is shown below:
The product that step 1) obtains will steam before carrying out the next step and desolventize or solvent removed in vacuo, and the solid that obtains can directly carry out the next step.Directly carry out step 2 if the fluorenyl ligand that step 1) obtains does not steam except organic solvent) reaction, speed of response is very slow, products collection efficiency is low.We find, use step 2) in when using tetrahydrofuran (THF) as solvent, side reaction is few, can react rapidly, the part productive rate height that obtains.The product that step 1) obtains also can be purified by silicagel column.
The indenes lithium is synthetic with known method by indenes and butyllithium.Butyllithium can be bought also can be according to known method by chlorobutane and Li preparation.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 the fluorenyl ligand.
3) the part lithium salts is synthetic
With step 2) part that obtains is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature be-20～10 ℃, preferably-10～0 ℃.The mol ratio of part and n-Butyl Lithium is 1:2.0～2.5, dropwises, and naturally rises to room temperature, reacts 10～15 hours.Remove by filter insolubles, the decompressing and extracting normal hexane obtains the part lithium salts.
Drain the part lithium salts that obtains behind the normal hexane, be easy to preserve, also make easily various solution or suspension.Also can not drain solvent, directly carry out the lower step after concentrating and synthesize.
4) add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 2～2.2:1, temperature of reaction is 0～30 ℃, stirring reaction 10～15 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place 10～20 hours substituted bridged metallocene double-core catalysts for-25 ℃～-15 ℃, structure is shown below:
。
In the 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 that react, also be conducive to improve productive rate.We find that the solvent in the preparation process is selected, and not exclusively follows the principle of " similar mixing ", such as, in the reaction that has lithium salts to participate in, the non-polar solvents such as use sherwood oil are higher than using the 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 determined that also the Br in the 7-chloro-8-bromo-1-octene reacts, or Br and Cl react; We find, when adopting weak polar solvent (such as anhydrous diethyl ether or sherwood oil), can control that the Br atom reacts and Cl does not react; But nonpolar pentane solvent is used in the discovery of also being taken aback simultaneously, and reaction yield is not high.
Described each reaction all needs to carry out under inert atmosphere, adopts the 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.Also need add alkylaluminoxane during polymerization is promotor.Preferred promotor is methylaluminoxane, during polyreaction, in the promotor in Al and the Primary Catalysts mol ratio of metal be 250～1500:1, preferred 250～1000:1.Polymerizing condition is 30～80 ℃, 0.1～0.8MPa.Be used for homopolymerization or copolymerization and get 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 201110030833.9 described methods.
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Embodiment 1:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the anhydrous diethyl ether, is cooled to-10 ℃, slowly drips fluorenes lithium solution, and time for adding 2 hours dropwises and continues reaction 14 hours; The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: fluorenes lithium=1:1.
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-10 ℃; Slowly drip indenes lithium solution, time for adding 1.5 hours dropwises and continues reaction 15 hours, obtains the indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1.
3) the part lithium salts is synthetic
0.0266mol part is dissolved in the 80ml normal hexane, drips the n-Butyl Lithium of 0.0532mol under the 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 gets the white powder solid.Be the part lithium salts.
Add toluene in the part lithium salts that obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 0 ℃, stirring reaction 15 hours, reaction product is through centrifugation, and residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, place for-15 ℃ and namely got the compound substituted bridged metallocene double-core catalyst in 20 hours, structure is shown below, and is brown crystal.
Embodiment 2
Other are with embodiment 1, and difference is:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the sherwood oil, is cooled to-20 ℃, slowly drips fluorenes lithium solution, and time for adding 2.5 hours dropwises and continues reaction 12 hours.
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-20 ℃; Slowly drip indenes lithium solution, time for adding 2 hours dropwises and continues reaction 12 hours, obtains the indenyl fluorenyl ligand.
3) the part lithium salts is synthetic
0.0266mol part is dissolved in the 80ml normal hexane, drips the n-Butyl Lithium of 0.0585mol under the ice-water bath, dropwises the water-bath of recession deicing, naturally rises to room temperature, reacts 15 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 2.2:1, 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 that obtains are merged, and is concentrated into solid to occur, place 10 hours substituted bridged metallocene double-core catalysts, structure such as embodiment 1 for-25 ℃.
Embodiment 3
Other are with embodiment 1, and difference is:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the anhydrous diethyl ether, is cooled to-30 ℃, slowly drips fluorenes lithium solution, and time for adding 1.5 hours dropwises and continues reaction 16 hours.
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 ℃; Slowly drip indenes lithium solution, time for adding 1 hour dropwises and continues reaction 18 hours, obtains the indenyl fluorenyl ligand.
3) the part lithium salts is synthetic
0.0266mol part is dissolved in the 80ml normal hexane, 10 ℃ of lower n-Butyl Lithiums that drip 0.0558mol dropwise the water-bath of recession deicing, naturally rise to room temperature, react 10 hours.Remove by filter solvent, vacuum is drained, and gets the white powder solid.Be the part lithium salts.
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 2.1:1, temperature of reaction is 10 ℃, stirring reaction 10 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place 15 hours substituted bridged metallocene double-core catalysts, structure such as embodiment 1 for-20 ℃～-15 ℃.
The Correlated Spectroscopy diagram data is as follows:
1H?NMR（CDCl3，25℃）：7.95(d,?J=8.4Hz,?1h),?7.87(d,J=8.2Hz,?1H),?7.77-7.63(3H),?7.56(t,J=6.9Hz,1H),?7.41-7.23(4H),?7.11-6.98(2H),?6.56(t,?2H,?C
5H
5,?a,?J
H-H=2.63Hz),?6.47(d,?8H,?C
5H
5,?a,?J
H-H=5.04Hz),?5.95(s,1H,CH
ind),?5.73(m.1H,=CH),?4.96(m,1H,CH
2),?4.93(m,1H,CH
2),?4.37(m,1H,CH
2),?4.19-3.97(2H,CH
2),?3.87(m,1H,CH
2),?2.65(m,2H,?CH
2),?1.96(m,2H,?CH
2),?1.50(m,2H,?CH
2);
13C?NMR（CDCl3，25℃）：138.3(=CH),?128.6,?128.5(GH),?127.7,?127.1(Cq),?126.0,?125.6(CH),?125.5,?125.4(Cq),?125.2,?125.1,?124.9,?124.5,?123.8(CH),?123.7,?123.2,?122.6(Cq),?122.5,?122.4(CH),?121.4(Cq),?120.7(CH),?115.8,?115.7,?115.6,?115.4,?115.3,?115.0,?114.9,?114.8,?114.6,?114.5,?114.6(=CH
2),?113.5(CH
ind),?103.7(Cq
ind),?33.4,?29.7,?29.4,?29.3,?27.5(CH
2)。
The gained compound cooperates with promoter aluminium alkyl oxygen alkane and is used for catalyzed ethylene polymerization, and is active in 5.21 * 10
5G ethene/mmol Zr h, Mw/Mn=2.51, molecular weight distribution compares Cp
2ZrCl
2The polyethylene that catalyzes and synthesizes is wide.
Embodiment 4:
Other are with embodiment 4, 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 that obtains are merged, and is concentrated into solid to occur, place for-25 ℃～-15 ℃ and namely got the compound metallocene dinuclear catalyst in 30 hours, be red crystals.
The gained compound cooperates with promoter aluminium alkyl oxygen alkane and is used for catalyzed ethylene polymerization, and is active in 1.1 * 10
5G ethene/mmol Zr h, molecular weight distribution compares Cp
2ZrCl
2The polyethylene that catalyzes and synthesizes is wide.
Claims (6)
1. metallocene dinuclear catalyst, its structure is as follows:
Wherein M is Zr or Ti.
2. the synthetic method of metallocene dinuclear catalyst as claimed in claim 1 comprises the following steps:
1) fluorenyl ligand is synthetic
7-chloro-8-bromo-1-octene is dissolved in the organic solvent, is cooled to-30～0 ℃, slowly drips fluorenes lithium solution, and time for adding 1.5 ~ 2.5 hours dropwises and continues reaction 12 ~ 16 hours;
The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: fluorenes lithium=1:1 ~ 1.1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil;
2) the indenyl fluorenyl ligand is synthetic
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 ℃～0 ℃; Slowly drip indenes lithium solution, time for adding 1 ~ 2 hour dropwises and continues reaction 12 ~ 18 hours, obtains the indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1～1.1;
3) the part lithium salts is synthetic
With step 2) part that obtains is dissolved in the normal hexane, drips n-Butyl Lithium, and dropping temperature is-20～10 ℃, and the mol ratio of part and n-Butyl Lithium is 1:2.0～2.5, dropwises, and naturally rises to room temperature, reacts 10～15 hours; Remove by filter insolubles, the decompressing and extracting normal hexane obtains the part lithium salts;
4) add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, namely the suspension of above-mentioned lithium salts adds CpZrCl under the room temperature
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 2～2.2:1, temperature of reaction is 0～30 ℃, stirring reaction 10～15 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, and all extraction liquids and the centrifugal liquid that obtains are merged, and is concentrated into solid to occur, place 10～20 hours substituted bridged metallocene double-core catalysts for-25 ℃～-15 ℃, structure is shown below:
。
3. the synthetic method of metallocene dinuclear catalyst as claimed in claim 2 is characterized in that, organic solvent is selected from anhydrous diethyl ether or sherwood oil in the step 1); Temperature of reaction is-20～-10 ℃, and the reaction times is 12 ~ 14 hours; The mol ratio of 7-chloro-8-bromo-1-octene and fluorenes lithium is: 7-chloro-8-bromo-1-octene: fluorenes lithium=1:1.
4. the synthetic method of metallocene dinuclear catalyst as claimed in claim 2 is characterized in that step 2) in, temperature of reaction is-20 ℃～-10 ℃; Reaction times is 14 ~ 16 hours; The mol ratio of indenes lithium is 1:1.
5. the synthetic method of metallocene dinuclear catalyst as claimed in claim 2 is characterized in that, in the 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 12～15 hours.
6. the synthetic method of metallocene dinuclear catalyst as claimed in claim 2 is characterized in that, in the step 4), temperature of reaction is 0～20 ℃, stirring reaction 12～15 hours.
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| KR20150017308A (en) * | 2013-08-06 | 2015-02-16 | 주식회사 엘지화학 | Dinuclear metallocene compound, catalyst composition and method for preparing polyolefin using the same |
| US11802170B2 (en) | 2021-04-29 | 2023-10-31 | Exxonmobil Chemical Patents Inc. | Polyolefins prepared with binuclear metallocene catalysts |
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| CN101117343A (en) * | 2007-08-07 | 2008-02-06 | 山东轻工业学院 | Substituted bridged metallocene double-core catalyst and preparation method thereof |
| CN102070731A (en) * | 2011-01-28 | 2011-05-25 | 山东轻工业学院 | C2 bridged iso-dinuclear metallocene catalyst and preparation method thereof |
| CN102174130A (en) * | 2011-01-28 | 2011-09-07 | 山东轻工业学院 | Zr-rare earth binuclear catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150017308A (en) * | 2013-08-06 | 2015-02-16 | 주식회사 엘지화학 | Dinuclear metallocene compound, catalyst composition and method for preparing polyolefin using the same |
| KR101601935B1 (en) | 2013-08-06 | 2016-03-09 | 주식회사 엘지화학 | Dinuclear metallocene compound, catalyst composition and method for preparing polyolefin using the same |
| US11802170B2 (en) | 2021-04-29 | 2023-10-31 | Exxonmobil Chemical Patents Inc. | Polyolefins prepared with binuclear metallocene catalysts |
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