CN102942641B - 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, particularly relate to the bimetallic catalyst and preparation method thereof for ethene and propylene polymerization.
Background technology
The active centre of metallocene catalyst is single, the activity of catalyzer is high, can obtain the very high polymkeric substance of tacticity, and the polymericular weight obtained is high, molecular weight and molecular weight distribution can be controlled by changing ligand structure, is therefore subject to extensive concern always.But due to the polyolefin molecular weight narrowly distributing obtained, processing difficulties and limit its process of industrialization.People attempt with composite catalyzing (see KAMINSKY W, STEIGER R. Polymerization of olefins with homogeneous zirconocene/alumoxane catalysts, Polyhedron, 1988,
7(22-23): 2375-2381) or double-core multinuclear catalyzer (see 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 ion 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 used for vinyl polymerization, and activity is very high (higher than 8.5 × 10
6gPE/mol M h, mononucleated compound M [(η-C
5h
5)
2cl
2] be 3.6 × 10
6gPE/mol M h); Molecular weight distribution broadens (M
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 there is a more than active centre.
CN1428355 discloses a kind of dinuclear metallocene compounds and preparation thereof and application in olefin polymerization, discloses the binuclear compound of dimethyl-silicon bridging, and for vinyl polymerization, and most high reactivity can reach 10
6gPE/mol Cat.
Although above-mentioned document reports dinuclear catalyst, although its catalytic performance is higher than 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 there is 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 step is many, aftertreatment is loaded down with trivial details.
Summary of the invention
The object of this invention is to provide a kind of preparation method of metallocene Zr-tombarthite catalyst, this preparation method's step is few, raw material is easy to get, 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) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in organic solvent, is cooled to-30 ~ 0 DEG C, slowly drips fluorenes lithium solution, time for adding 1.5 ~ 2.5 hours, dropwises and continue reaction 12 ~ 16 hours;
The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: fluorenes lithium=1:1 ~ 1.1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil.
2) synthesis of indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 DEG C ~ 0 DEG C; Slowly drip indenes lithium solution, time for adding 1 ~ 2 hour, dropwise and continue reaction 12-18 hour, obtain indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1 ~ 1.1.
3) synthesis of part lithium salts
By step 2) part that obtains is dissolved in normal hexane, and drip n-Butyl Lithium, dropping temperature is-20 ~ 10 DEG C, and the mol ratio of part and n-Butyl Lithium is 1:2.0 ~ 2.5, dropwises, naturally rises to room temperature, reacts 10 ~ 15 hours.Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts.
4) add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3be 2 ~ 2.2:1 with the mol ratio of part lithium salts, temperature of reaction is 0 ~ 30 DEG C, stirring reaction 10 ~ 15 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, place 10 ~ 20 hours substituted bridged metallocene double-core catalysts for-25 DEG C ~-15 DEG C, structure is shown below:
。
Preferably, in step 1), organic solvent is selected from anhydrous diethyl ether or sherwood oil.Temperature of reaction is-20 ~-10 DEG C, and the reaction times is 12 ~ 14 hours; The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: fluorenes lithium=1:1.
Preferably, step 2) in, temperature of reaction is-20 DEG C ~-10 DEG C; Reaction times is 14-16 hour; The mol ratio of indenes lithium is 1:1.
Preferably, in step 3), dropping temperature is-10 ~ 0 DEG C.The mol ratio of part and n-Butyl Lithium is 1:2.0 ~ 2.2, dropwises, naturally rises to room temperature, reacts 12 ~ 15 hours.
Preferably, in step 4), temperature of reaction is 0 ~ 20 DEG C, 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 as CyclopentadienyltitaDichloride Dichloride Cp
2tiCl
2or cyclopentadienyl zirconium dichloride Cp
2zrCl
2catalytic activity high, and the molecular weight of polymkeric substance obviously increases, and molecular weight distribution broadens.
Synthetic method of the present invention, compared with the method reported in document, synthetic route is short, and productive rate is high, avoids expensive reagent and uses, have better industrial prospect.
Embodiment
The preparation method of metallocene dinuclear catalyst is as follows:
1) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in organic solvent, is cooled to-30 ~ 0 DEG C, slowly drips fluorenes lithium solution, time for adding 1.5 ~ 2.5 hours, dropwises and continue reaction 12 ~ 16 hours;
The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: 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, effectively can control the degree of reacting, and can react by the Br in the bromo-1-octene of the chloro-8-of control 7-, and Cl does not react.And select methylene dichloride, toluene or tetrahydrofuran (THF) isopolarity larger solvent time, Br and Cl can participate in reaction, and the selectivity of reaction reduces.
When using the chloro-1-octene of 7,8-bis-as reactant, fluorenes lithium solution slowly need be added drop-wise in the chloro-8-of 7-bromo-1-octene solution, and keep the chloro-8-of 7-bromo-1-octene excessive in a large number in the reaction always.Condition control is improper can produce 7,8-bis-indenyl-1-octene.Cannot there is the next step in 7,8-bis-indenyl-1-octene, need to be separated through gel column.And the present invention utilizes the reactive difference of Br and Cl, obtain object product by the selection of suitable reaction conditions.Avoid the separation of late-stage products.Temperature of reaction is-30 ~ 0 DEG C, does not need too low temperature of reaction, is easy to control.
The concentration of the bromo-1-octene of the chloro-8-of 7-does not limit, and those skilled in the art can select suitable concentration according to practical situation.Fluorenes lithium is synthesized with known method by fluorenes and butyllithium.Butyllithium can be bought and also can be prepared in sherwood oil or normal hexane solvent with chlorobutane by Li band according to known method.
React complete, after decompression steams most of solvent, be separated through chromatographic column, obtain the chloro-1-octene of 8-indenyl-7-, save backup.Also can be separated without chromatographic column, after completion of the reaction, steam to desolventize and directly carry out the next step afterwards.
2) synthesis of indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 DEG C ~ 0 DEG C; 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, obtain indenyl fluorenyl ligand;
Synthetic method is shown below:
。
The product that step 1) obtains will steam and desolventize or solvent removed in vacuo before carrying out the next step, and the solid obtained directly can carry out the next step.If the fluorenyl ligand that step 1) obtains does not steam except organic solvent directly carry out step 2) reaction, speed of response is very slow, and products collection efficiency is low.We find, use step 2) in use tetrahydrofuran (THF) for solvent time, side reaction is few, can react rapidly, and the part productive rate obtained is high.The product that step 1) obtains also can be purified by silicagel column.
Indenes lithium is synthesized with known method by indenes and butyllithium.Butyllithium can be bought and also can be prepared by chlorobutane and Li 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.
3) synthesis of part lithium salts
By step 2) part that obtains is dissolved in normal hexane, and drip n-Butyl Lithium, dropping temperature be-20 ~ 10 DEG C, preferred-10 ~ 0 DEG C.The mol ratio of part and n-Butyl Lithium is 1:2.0 ~ 2.5, dropwises, naturally rises to room temperature, reacts 10 ~ 15 hours.Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts.
The part lithium salts obtained after draining normal hexane, is easy to preserve, also easily makes various solution or suspension.Also can not drain solvent, after concentrated, directly carry out lower step synthesis.
4) add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3be 2 ~ 2.2:1 with the mol ratio of part lithium salts, temperature of reaction is 0 ~ 30 DEG C, stirring reaction 10 ~ 15 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, place 10 ~ 20 hours substituted bridged metallocene double-core catalysts for-25 DEG C ~-15 DEG C, structure is shown below:
。
In catalyst preparing of the present invention, the selection of solvent is extremely important; In different reactions steps, use different solvents, be conducive to the carrying out reacted, be also conducive to improving productive rate.We find, solvent in preparation process is selected, and not exclusively follow the principle of " similar mix ", such as, in the reaction participated in there being lithium salts, use the non-polar solvents such as sherwood oil higher than using tetrahydrofuran (THF) productive rate on the contrary.We are through a large amount of experiments, find to use solvent of the present invention, and reaction yield is the highest.The Br that the selection of solvent also determines in the bromo-1-octene of the chloro-8-of 7-reacts, or Br and Cl reacts; We find, when adopting weak polar solvent (as anhydrous diethyl ether or sherwood oil), can to react and Cl does not react by control Br atom; But the discovery of being yet taken aback, use nonpolar pentane solvent, reaction yield is not high simultaneously.
Described each reaction all needs to carry out under an inert atmosphere, and adopt shenlink technology, rare gas element is argon gas or nitrogen.
Compound provided by the invention can make the alpha-olefin homopolymerization of C2 ~ C10 or the Primary Catalysts of copolymerization.Also needing during polymerization 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 DEG C, 0.1 ~ 0.8MPa.Alkene optimal ethylene, propylene, butylene, hexene or octene is obtained for homopolymerization or copolymerization.Polymerization process can adopt mass polymerization or solution polymerization.Analytical procedure and polymkeric substance describe, and adopt the method described in 201110030833.9.
Following examples further illustrate of the present invention, but the present invention is not limited thereto.
embodiment 1:
1) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in anhydrous diethyl ether, is cooled to-10 DEG C, slowly drips fluorenes lithium solution, time for adding 2 hours, dropwises and continue reaction 14 hours; The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: fluorenes lithium=1:1.
2) synthesis of indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-10 DEG C; Slowly drip indenes lithium solution, time for adding 1.5 hours, dropwise and continue reaction 15 hours, obtain indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1.
3) synthesis of part lithium salts
0.0266mol part is dissolved in 80ml normal hexane, drips the n-Butyl Lithium of 0.0532mol under ice-water bath, dropwises the water-bath of recession deicing, naturally rises to room temperature, react 12 hours.Cross and filter solvent, vacuum is drained, and obtains white powdery solids.For part lithium salts.
Add toluene in the part lithium salts obtained, obtain white opacity liquid, be i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 2:1, temperature of reaction is 0 DEG C, stirring reaction 15 hours, reaction product is through centrifugation, and residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, be concentrated into and occur solid, namely-15 DEG C of placements obtain compound substituted bridged metallocene double-core catalyst in 20 hours, and structure is shown below, and is brown crystal.
embodiment 2
Other are with embodiment 1, and difference is:
1) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in sherwood oil, is cooled to-20 DEG C, slowly drips fluorenes lithium solution, time for adding 2.5 hours, dropwises and continue reaction 12 hours.
2) synthesis of indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-20 DEG C; Slowly drip indenes lithium solution, time for adding 2 hours, dropwise and continue reaction 12 hours, obtain indenyl fluorenyl ligand.
3) synthesis of part lithium salts
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, react 15 hours.Cross and filter solvent, vacuum is drained, and obtains white powdery solids.For part lithium salts.
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, be i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3be 2.2:1 with the mol ratio of part lithium salts, temperature of reaction is 30 DEG C, stirring reaction 12 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, place 10 hours substituted bridged metallocene double-core catalysts for-25 DEG C, structure is as embodiment 1.
embodiment 3
Other are with embodiment 1, and difference is:
1) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in anhydrous diethyl ether, is cooled to-30 DEG C, slowly drips fluorenes lithium solution, time for adding 1.5 hours, dropwises and continue reaction 16 hours.
2) synthesis of indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, be cooled to-30 DEG C; Slowly drip indenes lithium solution, time for adding 1 hour, dropwise and continue reaction 18 hours, obtain indenyl fluorenyl ligand.
3) synthesis of part lithium salts
0.0266mol part is dissolved in 80ml normal hexane, drips the n-Butyl Lithium of 0.0558mol at 10 DEG C, dropwises the water-bath of recession deicing, naturally rises to room temperature, react 10 hours.Cross and filter solvent, vacuum is drained, and obtains white powdery solids.For part lithium salts.
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, be i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3be 2.1:1 with the mol ratio of part lithium salts, temperature of reaction is 10 DEG C, stirring reaction 10 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, place 15 hours substituted bridged metallocene double-core catalysts for-20 DEG C ~-15 DEG C, structure is as embodiment 1.
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)。
Gained compound coordinates with promoter aluminium alkyl oxygen alkane and is used for catalyzed ethylene polymerization, active in 5.21 × 10
5g ethene/mmol Zr h, Mw/Mn=2.51, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzed and synthesized is wide.
embodiment 4:
Other are with embodiment 4, unlike CpZrCl
3dME is by CpTiCl
3replace, CpTiCl
3be 2.1:1 with the mol ratio of part lithium salts, temperature of reaction is 30 DEG C, stirring reaction 12 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, namely-25 DEG C ~-15 DEG C placements obtain compound metallocene dinuclear catalyst in 30 hours, are red crystals.
Gained compound coordinates with promoter aluminium alkyl oxygen alkane and is used for catalyzed ethylene polymerization, active in 1.1 × 10
5g ethene/mmol Zr h, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzed and synthesized is wide.
Claims (4)
1. a synthetic method for metallocene dinuclear catalyst, comprises the following steps:
1) synthesis of fluorenyl ligand
The bromo-1-octene of the chloro-8-of 7-is dissolved in organic solvent, is cooled to-30 ~ 0 DEG C, slowly drips fluorenes lithium solution, time for adding 1.5 ~ 2.5 hours, dropwises and continue reaction 12 ~ 16 hours;
The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: fluorenes lithium=1:1 ~ 1.1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil;
2) synthesis of indenyl fluorenyl ligand
Step 1) add solvents tetrahydrofurane in the fluorenyl ligand that obtains, be cooled to-20 DEG C ~-10 DEG C; Slowly drip indenes lithium solution, time for adding 1 ~ 2 hour, dropwise and continue reaction 14 ~ 16 hours, obtain indenyl fluorenyl ligand; The mol ratio of fluorenyl ligand and indenes lithium is 1:1;
3) synthesis of part lithium salts
By step 2) part that obtains is dissolved in normal hexane, and drip n-Butyl Lithium, dropping temperature is-20 ~ 10 DEG C, and the mol ratio of part and n-Butyl Lithium is 1:2.0 ~ 2.5, dropwises, naturally rises to room temperature, reacts 10 ~ 15 hours; Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts;
4) step 3) add toluene in the part lithium salts that obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, under room temperature, add CpZrCl
3dME or CpTiCl
3, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl; CpZrCl
3dME or CpTiCl
3be 2 ~ 2.2:1 with the mol ratio of part lithium salts, temperature of reaction is 0 ~ 30 DEG C, stirring reaction 10 ~ 15 hours, reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained is merged, is concentrated into and occurs solid, place 10 ~ 20 hours substituted bridged metallocene double-core catalysts for-25 DEG C ~-15 DEG C, structure is shown below:
2. the synthetic method of metallocene dinuclear 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 DEG C, and the reaction times is 12 ~ 14 hours; The mol ratio of the chloro-8-of 7-bromo-1-octene and fluorenes lithium is: the bromo-1-octene of the chloro-8-of 7-: fluorenes lithium=1:1.
3. the synthetic method of metallocene dinuclear catalyst as claimed in claim 1, is characterized in that, step 3) in, dropping temperature is-10 ~ 0 DEG C; The mol ratio of part and n-Butyl Lithium is 1:2.0 ~ 2.2, dropwises, naturally rises to room temperature, reacts 12 ~ 15 hours.
4. the synthetic method of metallocene dinuclear catalyst as claimed in claim 1, is characterized in that, step 4) in, temperature of reaction is 0 ~ 20 DEG C, stirring reaction 12 ~ 15 hours.
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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 |
| CN101117341A (en) * | 2007-08-07 | 2008-02-06 | 山东轻工业学院 | Substituted bridged metallocene heterobimetallic 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 |
|---|---|---|---|---|
| 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 |
| CN101117341A (en) * | 2007-08-07 | 2008-02-06 | 山东轻工业学院 | Substituted bridged metallocene heterobimetallic 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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