CN102070731B - C2 bridged iso-dinuclear metallocene catalyst and preparation method thereof - Google Patents
C2 bridged iso-dinuclear metallocene catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a C2 bridged iso-dinuclear metallocene catalyst represented by a structural formula shown below, wherein M represents rare earth. The invention also provides a method for preparing the catalyst. When the catalyst is matched with a cocatalyst, namely alkylaluminoxane for olefin polymerization, the catalyst is high in polymerization activity, and olefin polymerization products with high molecular weight and wide molecular weight distribution can be obtained.
Description
Technical field
The invention belongs to polyolefin field, relate to the catalyzer that is used for olefinic polymerization, relate in particular to bimetallic catalyst that is used for ethene and propylene polymerization and preparation method thereof.
Background technology
The active centre of metallocene catalyst is single, the activity of such catalysts height, can obtain the very high polymkeric substance of tacticity, and the polymericular weight height, molecular weight and the molecular weight distribution that obtain can be controlled by changing ligand structure, therefore is subjected 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 olefinswith 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 has found general method (G.M.Diamond, A.N.Cherega, P.Mountford, the M.L.H.Green of synthetic carbon bound, J.Chem.Soc., Dalton Trans, 1996,921), and synthesize a series of carbon bridging dis-cyclopentadiene compoundses, be used for ethene, propylene polymerization.Find that the double-core zirconium compounds is than monokaryon zirconium compounds and its hafnium homologue catalytic activity height.This is because [M (η-C
5H
5)
2] in the rotation of metal-metal key can M=Hf be 306KJ/mol, M=Zr is 284KJ/mol.The activity of isodigeranyl nuclear compound and close with binuclear compound, and be higher than its Hf analogue.Find that simultaneously the ethylene polymerization activity of binuclear compound depends primarily on C
5H
4The metal of the metal of one side rather than indenes one side.
Noh synthesized the carbon bridging of a series of different lengthss dicyclopentadiene two titanium compounds (S.K.Noh, J.Kim, J.Jung, C.S.Ra, D.Lee, H.B.Lee, S.W.Lee, W.S.Huh, J.Organomet.Chem., 1999,580,90-97).Be used for the catalyzed ethylene polymerization reaction.Discovery is along with (CH
2)
nThe growth of bridge, polymericular weight reduces, and polymerization activity increases, and all than monokaryon compound activity height.This is because thereby long bridge can transmit higher electric density stabilizing active center, improves polymerization activity.Noh thinks that the interaction of atoms metal not only depends on the relative distance of metal center in the binuclear metallocene, and is also relevant with bridge construction.
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
3The reaction, obtain central ion and three cyclopentadiene coordinate compounds, and then with the second normal metal halide (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
n＞5.4).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 has been used for vinyl polymerization, and high reactivity can reach 10
6GPE/mol Cat.
Though above-mentioned document has been reported dinuclear catalyst,, do not obtain bimodal polymers though its catalytic performance is higher than the monokaryon catalyzer.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.
Summary of the invention
The purpose of this invention is to provide a class C2 bridged metallocene heterobimetallic catalyst.This catalyzer belongs to isodigeranyl nuclear metallocene compound, has 2 different atoms metals in the molecule simultaneously, is used for olefin polymerization catalysis, can obtain the polyethylene of high molecular and wide molecular weight distribution.Some compound also can obtain bimodal polyethylene.
The isodigeranyl nuclear compound is to contain two different atoms metals in the same compound.Two atoms metals link to each other by part, part is by the cloud density on electronic effect, inductive effect, the modulation effects atoms metal, atoms metal also produces retroaction to part simultaneously, also can produce interaction between two atoms metals, thereby influence its catalytic activity by the transmission or the spatial transmission of part.
Among the present invention, we introduce rare earth atom in the metallocene compound, there is the 4f track in rare earth atom, lanthanon 4f track is not participate in key directly by traditional theory of chemical bonds, but the time it can be by in the localized 4f of occupying track, mixing a small amount of coupling thing track or in the delocalized molecular orbital(MO), mixing a small amount of 4f composition, to becoming key to make certain contribution, this contribution meeting is along with some difference with the difference of chemical environment; By with the track of coupling thing is mixed the bond distance being shortened, bond energy increases, and generally can reach percentum; Along with the increase 4f track of group of the lanthanides ordination number reduces the contribution that becomes key; The coupling thing that electronegativity and valence state are high is stronger to the 4f rail effect, and the 4f track is to becoming the key influence bigger.Rare earth atom is introduced in the metallocene compound, can the character to the metallocene heterobimetallic compound be exerted an influence owing to the 4f track special one-tenth key effect of rare earth atom.
Another object of the present invention provides the preparation method of described C2 bridged metallocene heterobimetallic catalyst, and this preparation method's step is few, raw material is easy to get, and cost is low, is easy to industrialization.
C2 bridged metallocene heterobimetallic 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 invention provides a kind of C2 bridged metallocene heterobimetallic catalyst, have following structural formula:
Wherein, M=rare earth.
Preferably, M is selected from Y, Nd or Sm.
The present invention also provides the synthetic method of described C2 bridged metallocene heterobimetallic catalyst, comprises the following steps:
1) fluorenyl ligand is synthetic
9,10-two chloro-1-decene are dissolved in the organic solvent, are cooled to-80～-70 ℃, slowly drip fluorenes lithium solution, 1.5～2.5 hours dropping time, dropwise and continue reaction 14～16 hours;
9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is: 9, and 10-two chloro-1-decene: fluorenes lithium=4～10: 1;
2) the indenyl fluorenyl ligand is synthetic
Fluorenyl ligand that step 1) obtains and indenes lithium react, and obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1: 1～1: 1.1; Temperature of reaction is-80～-70 ℃; Reaction times is 24-48 hour;
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 rises to room temperature naturally, reacts 10～15 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex intermediate (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, 0～30 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl.CpZrCl
3The mol ratio of DME and part lithium salts is 1: (1～1.1), stirring reaction 30～48 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, place for-25 ℃～-15 ℃ and promptly got title complex intermediate (I) in 12～24 hours:
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3The cyclopentadiene muriate according to 1: 1～1.2 molar ratio reaction, temperature of reaction is 100～110 ℃, the time is 12～24 hours; Wherein M is a rare earth, and preferred, M is selected from Y, Nd or Sm;
React the filtration that finishes, remove insolubles, filtrate is concentrated the back use the organic solvent recrystallization, obtain the C2 bridged metallocene heterobimetallic catalyst shown in the formula (II):
Preferably, organic solvent is selected from methylene dichloride, toluene, tetrahydrofuran (THF) in the step 1).Temperature of reaction is-78 ℃, and the reaction times is 14～16 hours; 9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is: 9, and 10-two chloro-1-decene: fluorenes lithium=5～8: 1;
Preferably, step 2) in, temperature of reaction is-78 ℃; Reaction times is 30-45 hour; Solvent is ether, methyl ether, sherwood oil;
Preferably, step 2) in, indenes lithium drips of solution is added in the solution of fluorenyl ligand, 0.5～1 droplet/second of rate of addition.
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 rises to room temperature naturally, reacts 12～15 hours.
Preferably, in the step 4), temperature of reaction is 0～10 ℃.Stirring reaction 36～48 hours.
Preferably, the used organic solvent of recrystallization is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride in the step 5).
Under identical catalytic condition, the catalytic activity of the C2 bridged metallocene heterobimetallic catalyst that the present invention obtains than monokaryon metallocene catalyst as cyclopentadienyl titanium dichloride Cp
2TiCl
2Or cyclopentadienyl zirconium dichloride Cp
2ZrCl
2The catalytic activity height, and the molecular weight of polymkeric substance obviously increases, molecular weight distribution broadens.
Synthetic method of the present invention is compared with reported method in the document, and synthetic route is short, and the productive rate height has been avoided the expensive reagent use, has better industrial prospect.
Embodiment
The preparation method of catalyzer (II) is as follows:
1) fluorenyl ligand is synthetic
9,10-two chloro-1-decene are dissolved in the organic solvent, are cooled to-80～-70 ℃, slowly drip fluorenes lithium solution, and 1.5～2.5 hours dropping time, progressively increasing finishes continues reaction 14～16 hours;
9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is: 9, and 10-two chloro-1-decene: fluorenes lithium=4～10: 1;
Organic solvent is selected from methylene dichloride, toluene, tetrahydrofuran (THF).
Synthetic method is shown below:
Theoretically, 9,10-two chloro-1-decene and the reaction of fluorenes lithium can obtain the part of two kinds of structures shown in the structural formula A and B among the last figure, but in fact,, there is bigger steric effect because the volume of fluorenes lithium is very big, so, under low temperature of the present invention, long reaction times, the compound that obtains all is the part of structure A, the part of structure B detect substantially less than.
The proportioning of reactant, the order of addition(of ingredients) of reactant and dropping time are very important to reaction.Rate of addition generally is controlled at 0.5～1 droplet/second, 1.5～2.5 hours dropping time.The order of addition(of ingredients) of reactant is: fluorenes lithium solution slowly is added drop-wise to 9, in the 10-two chloro-1-decene solution, keeps 9 in reaction always, 10-two chloro-1-decene are excessive.If with 9,10-two chloro-1-decene are added drop-wise in the fluorenes lithium solution, perhaps fluorenes lithium drips of solution are added to 9, in the 10-two chloro-1-decene solution but rate of addition is too fast, all can produce 9,10-two indenyls-1-decene.9, the next step can't take place in 10-two indenyls-1-decene, need separate through gel column.If obtain 9,10-two indenyls-1-decene directly carries out next step reaction without separating, the part that obtains will be a mixture, the catalyzer that finally obtains also is a mixture.The catalyzer of mixture also has certain katalysis, but effect is relatively poor.By selecting appropriate reaction conditions, can be with 9, the productive rate of 10-two indenyls-1-decene drops to minimum, neither needs through loaded down with trivial details
9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is lower than at 3 o'clock, also can produce 9,10-two indenyls-1-decene, and ratio is low more, and in the product 9, the content of 10-two indenyls-1-decene is high more.9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is high more, and productive rate high more (serves as to calculate benchmark with the fluorenes lithium) is excessive 9, and 10-two chloro-1-decene can pass through Separation and Recovery, again utilization.But 9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is too high, and follow-up separation costs is increased, and is suitable 9, and the mol ratio of 10-two chloro-1-decene and fluorenes lithium is 4～10: 1, preferred 5～8: 1.
9, the concentration of 10-two chloro-1-decene 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.
Solvent has certain influence to reaction yield.Productive rate was higher when organic solvent was selected methylene dichloride, toluene or tetrahydrofuran (THF).If select ether solvent for use, also can obtain product, but productive rate is lower.
Reaction finishes, and after decompression steams most of solvent, separates through chromatographic column, obtains 10-indenyl-9-chloro-1-decene, preserves standby.Also can separate, after reaction finishes, directly carry out the next step after steaming desolventizes without chromatographic column.
2) C2 bridging indenyl fluorenyl ligand is synthetic
Add solvent in the fluorenyl ligand that step 1) obtains, react with the indenes lithium then, obtain the indenyl fluorenyl ligand of C2 bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1: 1～1: 1.1; Temperature of reaction is-80 ℃～-70 ℃; Reaction times is 24-48 hour; Solvent is ether, methyl ether, sherwood oil.
The fluorenyl ligand that step 1) obtains also can not steam except that organic solvent directly carry out step 2) reaction, but reaction is slower, the product productive rate is low.We find, use step 2) in when using ether, methyl ether or sherwood oil as solvent, side reaction is few, the part productive rate height that obtains.
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 drips of solution is added to the mode in the fluorenyl ligand.
Synthetic method is shown below:
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 rises to room temperature naturally, reacts 10～15 hours.Remove by filter normal hexane, 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 various solution or suspension easily.Also can not drain solvent, directly descend the step synthetic after concentrated.
4) title complex intermediate (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, 0～30 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl.CpZrCl
3The mol ratio of DME and part lithium salts is 1: (1～1.1), stirring reaction 30～48 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, place for-25 ℃～-15 ℃ and promptly got title complex intermediate (I) in 12～24 hours;
Intermediate (I) purity that obtains of crystallization is higher as stated above, is easy to analyze.But this intermediate product is very responsive to empty G﹠W.If not strict airtight preservation then very easily decompose.
The title complex intermediate (I) that obtains can directly be weighed, and is convenient to calculate the ingredient proportion of compound in each step.
After all extraction liquids and the centrifugal liquid merging that obtains, directly carry out the next step after also can concentrating.Do not need-25 ℃～-15 ℃ to place 12～24 hours, saved the reaction times, and the catalyzer that finally obtains, catalytic effect is also unaffected.
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3The cyclopentadiene muriate according to 1: 1～1.2 molar ratio reaction, temperature of reaction is 100～110 ℃, the time is 12～24 hours; Wherein M is a rare earth, and preferred, M is selected from Y, Nd or Sm;
React the filtration that finishes, remove insolubles, filtrate is concentrated the back use the organic solvent recrystallization, obtain the C2 bridged metallocene heterobimetallic catalyst shown in the formula (II):
Preferably, the reaction times in the step 5) is 12～16 hours, and the used organic solvent of recrystallization is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride.
We have carried out a large amount of experiments and have selected the used solvent of recrystallization, find that polarity of solvent, solvating ability and solvability counterweight crystalline effect are all influential.Adopt different solvents, the difficulty difference of the crystallisate that obtains, active solvent as tetrahydrofuran (THF), can't obtain the crystalline product at all.Use the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride, can obtain crystalline product.We find at last, and during with the mixed solvent recrystallization of toluene and methylene dichloride, effect is best, and product purity is the highest.
In the Preparation of Catalyst of the present invention, choice of Solvent is extremely important; In different reactions steps, use different solvents, help the carrying out that react, also help improving 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, non-polar solvents such as use sherwood oil are on the contrary than using tetrahydrofuran (THF) productive rate height.We find to use solvent of the present invention through a large amount of experiments, and reaction yield is the highest.
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 a 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: NMR:Jeol JNM-EX 270E, Bruker ARX 250 and Bruker DRX 500 nmr determinations; Sample dissolves in 25 ℃ CDCl3 under argon shield; Mass spectrum: Varian MAT CH7 mass spectrograph (70eV); GC/MS uses Varian 3700 gas-chromatographies and Varian MAT 312 mass spectrum logotypes.
Polymkeric substance is described: dsc (DSC): Perkin-Elmer DSC-7 calorimeter is used for the thermal properties of characterize polymers, before the measurement, and the vacuum-drying of polymkeric substance elder generation.
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
0.5mol 9,10-two chloro-1-decene are dissolved in the 200ml tetrahydrofuran (THF), are cooled to-78 ℃, slowly drip the petroleum ether solution of 0.05mol fluorenes lithium, 1.5 hours dropping time, dropwise and continue reaction 16 hours; Product is through hydrolysis, separation, purification, and productive rate is 83.9%.
2) C2 bridging indenyl fluorenyl ligand is synthetic
-78 ℃, the 100ml petroleum ether solution of 62mmol indenes lithium slowly is added drop-wise among the fluorenyl ligand 61mmol that step 1) obtains stirring reaction 24 hours; Product is through hydrolysis, separation, purification, and productive rate is 54.7%.
3) the part lithium salts is synthetic
0.0266mol part is dissolved in the 80ml normal hexane, ice-water bath drips the n-Butyl Lithium of 0.0532mol down, dropwises, and rises to room temperature naturally, reacts 12 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex intermediate (I) is synthetic
Add 150ml toluene in above-mentioned part lithium salts, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 5 ℃ of stirring reactions 30 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-20 ℃ left standstill 24 hours, must faint yellow needle-like crystal, be the title complex intermediate, productive rate 42.4%.
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
Under the argon shield, with title complex intermediate 1.35mmol and 1.35mmol CpYCl
3Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 110 ℃ of reflux temperatures, stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 25 hours, the silver gray crystalline solid.
Filtrate is concentrated the mixed solvent recrystallization of back with toluene and methylene dichloride, obtains the C2 bridged metallocene heterobimetallic catalyst of following formula:
Embodiment 2
1) fluorenyl ligand is synthetic
0.5mol 9,10-two chloro-1-decene are dissolved in the 200ml toluene, are cooled to-78 ℃, slowly drip the petroleum ether solution of 0.06mol fluorenes lithium, 2.5 hours dropping time, dropwise and continue reaction 14 hours; Product is through hydrolysis, separation, purification, and productive rate is 83.2%.
2) C2 bridging indenyl fluorenyl ligand is synthetic
-78 ℃, the 100ml petroleum ether solution of 60mmol indenes lithium slowly is added drop-wise among the fluorenyl ligand 59mmol that step 1) obtains stirring reaction 48 hours; Product is through hydrolysis, separation, purification, and productive rate is 54.1%.
3) the part lithium salts is synthetic
0.025mol part is dissolved in the 80ml ether, ice-water bath drips the n-Butyl Lithium of 0.061mol down, dropwises, and rises to room temperature naturally, reacts 10 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex intermediate (I) is synthetic
Add 150ml toluene in above-mentioned part lithium salts, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 15 ℃ of stirring reactions 48 hours, centrifugation, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs, and-25 ℃ left standstill 12 hours, must faint yellow needle-like crystal, title complex intermediate (I), productive rate 38.9%.
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
Under the argon shield, with title complex intermediate 1.35mmol and 1.35mmol CpYCl
3Put into the Schlenk bottle that prolong is housed, add 80ml benzene, be heated to 100 ℃ of reflux temperatures, stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 25 hours, the silver gray crystalline solid.
Filter then, filtrate concentrated the back use the toluene solvant recrystallization, obtain the C2 bridged metallocene heterobimetallic catalyst of following formula:
Embodiment 3
1) fluorenyl ligand is synthetic
0.5mol 9,10-two chloro-1-decene are dissolved in the 200ml toluene, are cooled to-60 ℃, slowly drip the petroleum ether solution of 0.1mol fluorenes lithium, 2 hours dropping time, dropwise and continue reaction 15 hours; Product is through hydrolysis, separation, purification, and productive rate is 79.5%.
2) C2 bridging indenyl fluorenyl ligand is synthetic
-78 ℃, the 100ml petroleum ether solution of 60mmol indenes lithium slowly is added drop-wise among the fluorenyl ligand 59mmol that step 1) obtains stirring reaction 36 hours; Product obtains 6-(9-fluorenes)-5-(1-indenes)-1-hexene through hydrolysis, separation, purification, and productive rate is 53.2%.
GC：3233s；MS：m/e?416(M
+)
1H?NMR(CDCl3，25℃)：7.46-7.13(8H)，6.98(m，2H，CH
ind)，6.62(m，4H，CH
ind)，4.22(t，1H)，4.04(m，1H)，3.86(t，2H)，3.47(d，2H)，1.62-1.29(12H，CH
2)；
13C?NMR(CDCl3，25℃)：147.8，147.5，146.6，145.0，140.9，140.7(Cq)，138.8，136.9，136.6，132.1，131.8，127.0，126.8，126.7，126.4，126.3，124.6，124.4，123.1，122.7，120.9，119.9，119.6(CH)，114.1(＝CH
2)，53.3，45.8，37.0(CH)，36.4，33.4，30.8，28.8，27.0(CH
2)；
3) the part lithium salts is synthetic
0.0261mol part is dissolved in the 80ml sherwood oil, ice-water bath drips the n-Butyl Lithium of 0.0544mol down, dropwises, and rises to room temperature naturally, reacts 15 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex intermediate (I) is synthetic
Add 150ml toluene in above-mentioned part lithium salts, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 25 ℃ of stirring reactions 35 hours, centrifugation, resistates is with 50ml dichloromethane extraction 2 times, centrifugate and extraction liquid are merged, be concentrated into solid and occur ,-15 ℃ left standstill 20 hours, get faint yellow needle-like crystalline solid, be the title complex intermediate, productive rate 39.8%.
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
Under the argon shield, with title complex intermediate 1.35mmol and 1.35mmol CpYCl
3Put into the Schlenk bottle that prolong is housed, add 80ml toluene, be heated to 100 ℃ of reflux temperatures, stirring reaction is 20 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 25 hours, the silver gray crystalline solid.Use the dichloromethane solvent recrystallization then, obtain the bridged metallocene heterobimetallic catalyst of following formula:
Because the Y ion has unpaired electron, so have paramagnetism.So
1Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:
1H?NMR(CDCl3，25℃)：7.52-7.46(C
5H
5)，7.36-7.28(C
9H
6)，6.88-6.80(C
9H
6)，6.48-6.42(C
13H
8)，6.21-6.18(C
13H
8)，5.22-5.33(＝CH-)，5.02-4.95(＝CH
2)，3.62-3.78(THF)，1.34-1.62(CH
2)，1.07-1.18(CH
2)；
Gained catalyst vinyl polymerization, slurry polymerization, solvent are toluene, methylaluminoxane is as promotor, in the methylaluminoxane in Al and the Primary Catalysts mol ratio of metal be 1000: 1, polymerizing condition is 80 ℃, 0.5MPa.
Gained catalyst vinyl polymerization, active in 1.42 * 10
5G ethene/mmol Zr h, Mw/Mn=2.51, molecular weight distribution compares Cp2ZrCl
2Catalysis synthetic polyethylene is wide.
Embodiment 4:
Other are with embodiment 1, and different is with CpSmCl
3Replaced C pYCl
3, being heated to 110 ℃ of reflux temperatures, stirring reaction is 12 hours under reflux state, stops to stir, and reduces to room temperature.Reacting liquid filtering is removed solids, then filtrate is concentrated into 1/3 of original volume, puts into refrigerator, leaves standstill 20 hours at-20 ℃, gets the silver gray crystalline solid, and its structure is shown below.Productive rate 48.2%.
Because the Sm ion has unpaired electron, so have paramagnetism.So
1Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:
1H NMR (CDCl3,25 ℃): 7.57-7.48 (C
5H
5), 7.38-7.28 (C
9H
6), 6.89-6.72 (C
9H
6), 6.49-6.52 (C
9H
6), 6.41-6.47 (C
13H
8), 6.18-6.24 (C
13H
8), 5.54-5.39 (=CH-), 5.06-4.98 (=CH
2), 3.38-3.68 (THF), 1.48-1.72 (CH
2), 1.01-1.15 (CH
2);
Gained catalyst vinyl polymerization, active in 1.07 * 10
5G ethene/mmol Zr h, Mw/Mn=2.88, molecular weight distribution compares Cp
2ZrCl
2Catalysis synthetic polyethylene is wide.
Embodiment 5:
Other are with embodiment 1, and different is with CpNdCl
3Replaced C pYCl
3, be heated to 120 ℃ of reflux temperatures, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction is 18 hours under reflux state, stops to stir, and reduces to room temperature.1/3 ,-20 ℃ that after the filtration filtrate are concentrated into original volume left standstill 20 hours, the silver gray crystalline solid, productive rate 44%.
Because the Nd ion has unpaired electron, so have paramagnetism.So
1Active change in displacement is big and be generally bigger broad peak on the H NMR spectrum, and spectrum is read in influence.Relevant spectral data is as follows:
1H?NMR(CDCl3，25℃)：7.71-7.59(C
5H
5)，7.48-7.38(C
9H
6)，6.92-6.81(C
9H
6)，6.45-6.52(C
9H
6)，6.39-6.35(C
13H
9)，6.34-6.29(C
13H
9)，5.61-5.42(＝CH-)，5.12-4.99(＝CH
2)，3.45-3.72(THF)，1.58-1.67(CH
2)，1.26-1.34(CH
2)；
Gained catalyst vinyl polymerization, active in 1.28 * 10
5G ethene/mmol Zr h, Mw/Mn=3.23, molecular weight distribution compares Cp
2ZrCl
2Catalysis synthetic polyethylene is wide.
Claims (9)
1. the synthetic method of a C2 bridged metallocene heterobimetallic catalyst comprises the following steps:
1) fluorenyl ligand is synthetic
9,10-two chloro-1-decene are dissolved in the organic solvent, are cooled to-80～-70 ℃, slowly drip fluorenes lithium solution, 1.5～2.5 hours dropping time, dropwise and continue reaction 14～16 hours;
9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is: 9, and 10-two chloro-1-decene: fluorenes lithium=4～10: 1;
2) the indenyl fluorenyl ligand is synthetic
Fluorenyl ligand that step 1) obtains and indenes lithium react, and obtain the indenyl fluorenyl ligand of C2 bridging; The mol ratio of fluorenyl ligand and indenes lithium is 1: 1～1: 1.1; Temperature of reaction is-80～-70 ℃; Reaction times is 24-48 hour;
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 rises to room temperature naturally, reacts 10～15 hours; Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts;
4) title complex intermediate (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, 0～30 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl; CpZrCl
3The mol ratio of DME and part lithium salts is 1: (1～1.1), stirring reaction 30～48 hours, reaction product is through centrifugation, residual solid is used dichloromethane extraction again, all extraction liquids and the centrifugal liquid that obtains are merged, be concentrated into and solid occurs, place for-25 ℃～-15 ℃ and promptly got title complex intermediate (I) in 12～24 hours:
5) the C2 bridged metallocene heterobimetallic catalyst is synthetic
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3The cyclopentadiene muriate according to 1: 1～1.2 molar ratio reaction, temperature of reaction is 100～110 ℃, the time is 12～24 hours; Wherein M is a rare earth,
React the filtration that finishes, remove insolubles, filtrate is concentrated the back use the organic solvent recrystallization, obtain the C2 bridged metallocene heterobimetallic catalyst shown in the formula (II):
2. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that, M is selected from Y, Nd or Sm.
3. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that, dropping temperature is-10～0 ℃ in the step 3).
4. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that, organic solvent is selected from methylene dichloride, toluene, tetrahydrofuran (THF) in the step 1); Temperature of reaction is-78 ℃, and the reaction times is 14～16 hours; 9, the mol ratio of 10-two chloro-1-decene and fluorenes lithium is: 9, and 10-two chloro-1-decene: fluorenes lithium=5～8: 1.
5. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that step 2) in, temperature of reaction is-78 ℃; Reaction times is 30-45 hour; Organic solvent is ether, methyl ether, sherwood oil.
6. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that step 2) in, indenes lithium drips of solution is added in the solution of fluorenyl ligand, 0.5～1 droplet/second of rate of addition.
7. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 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 rises to room temperature naturally, reacts 12～15 hours.
8. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that, in the step 4), temperature of reaction is 0～10 ℃; Stirring reaction 36～48 hours.
9. the synthetic method of C2 bridged metallocene heterobimetallic catalyst as claimed in claim 1 is characterized in that, the used organic solvent of recrystallization is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride in the step 5).
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| CN102977229B (en) * | 2012-12-11 | 2014-11-05 | 齐鲁工业大学 | Method for synthetizing C2 bridging fiber metallocene dikaryon catalyst |
| CN103012629B (en) * | 2012-12-11 | 2015-04-01 | 齐鲁工业大学 | Synthetic method of bridged metallocene Zr-RE (rare earth) dinuclear catalyst |
| CN102964492B (en) * | 2012-12-11 | 2014-11-05 | 齐鲁工业大学 | Synthesis method of bridged metallocene Ti-rare earth dinuclear catalyst |
| CN102977234B (en) * | 2012-12-11 | 2014-11-05 | 齐鲁工业大学 | Method for synthetizing metallocene Ti-rare earth dikaryon catalyst |
| CN102964491B (en) * | 2012-12-11 | 2014-10-15 | 齐鲁工业大学 | Synthesis method of C2 bridged metallocene Ti-rare earth dinuclear catalyst |
| CN102942641B (en) * | 2012-12-11 | 2015-02-25 | 齐鲁工业大学 | Synthesis method of metallocene binuclear catalyst |
| CN102942644B (en) * | 2012-12-11 | 2014-11-05 | 齐鲁工业大学 | Synthesis method of C2 bridging metallocene Zr-rare earth binuclear catalyst |
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| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use 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 |
| CN101121732A (en) * | 2007-08-07 | 2008-02-13 | 山东轻工业学院 | Bridging metallocene Ti-rare earth binucleated catalyst and preparation method thereof |
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| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use 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 |
| CN101121732A (en) * | 2007-08-07 | 2008-02-13 | 山东轻工业学院 | Bridging metallocene Ti-rare earth binucleated catalyst and preparation method thereof |
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| Helmut G. Alt et al..C2-bridged metallocene dichloride complexes of the types (C13H8–CH2CHR–C9H6-nR"n )ZrCl2 and (C13H8–CH2CHR–C13H8)MCl2 (n=0, 1;R=H, alkenyl;R"=alkenyl,benzyl;M=Zr, Hf) as self-immobilizing catalyst precursors for ethylene polymerization.《Journal of Organometallic Chemistry》.1999,第580卷1-16页. * |
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