CN102180997B - Metallocene catalyst and preparation method thereof - Google Patents
Metallocene catalyst and preparation method thereof Download PDFInfo
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- CN102180997B CN102180997B CN2011100307730A CN201110030773A CN102180997B CN 102180997 B CN102180997 B CN 102180997B CN 2011100307730 A CN2011100307730 A CN 2011100307730A CN 201110030773 A CN201110030773 A CN 201110030773A CN 102180997 B CN102180997 B CN 102180997B
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Abstract
The invention provides a heterobinuclear metallocene catalyst of which the structural formula is shown in the specifications, wherein M is rare earth. The invention further provides a preparation method of the catalyst. The catalyst is applied to olefinic polymerization together with alkyl aluminoxane serving as a catalyst promoter, and has high polymerization reactivity. By adopting the catalyst, an olefinic polymerization product 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 site of metallocene catalyst is single; Activity of such catalysts is high, can obtain the very high polymkeric substance of tacticity; And the polymericular weight that obtains is high, molecular weight and MWD can be controlled through changing ligand structure, therefore receive 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 MWD 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 higher than monokaryon zirconium compounds and its hafnium homologue catalytic activity.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 high than monokaryon compound activity.The bridge long thereby this is 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); MWD (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 possibly exist a more than active site.
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.One 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 one type of metallocene catalyst.This catalyzer belongs to isodigeranyl nuclear metallocene compound, has 2 different metallic atoms in the molecule simultaneously, is used for olefin polymerization catalysis, can obtain the Vilaterm of HMW and wide molecular weight distribution.Some compound also can obtain bimodal polyethylene.
The isodigeranyl nuclear compound is to contain two different metallic atoms in the same compound; Two atoms metals link to each other through part; Part is through 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 through the transmission or the spatial transmission of part between two atoms metals, thereby influence its catalytic activity.
Among the present invention; We introduce rare earth atom in the metallocene compound; There is the 4f track in rare earth atom, and lanthanon 4f track is not participate in key directly by traditional theory of chemical bonds, but the time it can be through in the localized 4f of occupying track, mixing a small amount of matches 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; Through with the track of matches 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 matches 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 said metallocene catalyst, and this preparing method's step is few, raw material is easy to get, and cost is low, is easy to industriallization.
Another object of the present invention provides a kind of polymerization method that obtains bimodal polyolefin.Use catalyzer of the present invention, cause ethene or propylene polymerization under certain condition, can obtain bimodal polyolefin.Bimodal polyolefin can satisfy material property and processing characteristics simultaneously, has very big using value.
The present invention provides a kind of binuclear metallocene catalyzer, has following structural formula:
Wherein, M=rare earth.
Preferably, M is selected from Y, Nd or Sm.
The present invention also provides the compound method of described binuclear metallocene catalyzer, comprises the following steps:
1) fluorenyl ligand is synthetic
5,6-two chloro-1-hexenes are dissolved in the organic solvent, are cooled to-90～-60 ℃, slowly drip fluorenes lithium solution, and 0.5～2 hour dropping time, progressively increasing finishes continues reaction 8～12 hours; 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is: 5, and 6-two chloro-1-hexenes: fluorenes lithium=3～10: 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; Temperature of reaction is-90 ℃～-60 ℃; 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-30～20 ℃, 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 8～15 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex midbody (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension-s of above-mentioned lithium salts, 0～40 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl moiety.CpZrCl
3The mol ratio of DME and part lithium salts is 1: 1～1.1; Temperature of reaction is-10～30 ℃, stirring reaction 15～24 hours, and reaction product is through spinning; Residual solid is used dichloromethane extraction again; The liquid that all extraction liquids and centrifugal are obtained merges, and is concentrated into solid to occur, places for-25 ℃～-15 ℃ and promptly gets catalyzer (I) in 20～30 hours:
5) the C2 bridged metallocene double-core 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, filters then, will filtrate to concentrate and then use the organic solvent recrystallization, obtains the metallocene dinuclear catalyst of formula (II):
Preferably, organic solvent is selected from methylene dichloride, toluene, THF in the step 1).Temperature of reaction is-80～-70 ℃, and the reaction times is 10～12 hours; 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is: 5, and 6-two chloro-1-hexenes: fluorenes lithium=5～8: 1;
Preferably, step 2) in, temperature of reaction is-80 ℃～-70 ℃; Reaction times is 30-48 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, 1～2 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 10～12 hours.
Preferably, in the step 4), temperature of reaction is-10～0 ℃; Stirring reaction 18～22 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).
The present invention also provides a kind of polymerization method that obtains bimodal polyolefin, and the metallocene catalyst that obtains with the present invention is a Primary Catalysts, and alkylaluminoxane (MAO) is a promotor, catalyzed ethylene or propylene polymerization; In the promotor in Al and the Primary Catalysts mol ratio of Zr be 250～1500: 1, preferred 250～1000: 1.Polymerizing condition is 30～80 ℃, 0.1～0.8Mpa; Polymerization method adopts mass polymerization or solution polymerization.
Under identical catalytic condition, the catalytic activity of the binuclear metallocene catalyzer that the present invention obtains than monokaryon metallocene catalyst like cyclopentadienyl moiety titanium dichloride Cp
2TiCl
2Or cyclopentadienyl zirconium dichloride Cp
2ZrCl
2Catalytic activity high, and the molecular weight of polymkeric substance obviously increases, MWD broadens, and can obtain bimodal polyolefin, like bimodal polyethylene.
Compound method of the present invention is compared with reported method in the document, and synthetic route is short, and productive rate is high, has avoided the expensive reagent use, has better industrial prospect.
Description of drawings
Fig. 1 is the DSC figure of embodiment 4.
Embodiment
The preparation method of catalyzer (II) is following:
1) fluorenyl ligand is synthetic
5,6-two chloro-1-hexenes are dissolved in the organic solvent, are cooled to-90～-60 ℃, slowly drip fluorenes lithium solution, and 0.5～1 hour dropping time, progressively increasing finishes continues reaction 8～12 hours; 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is: 5, and 6-two chloro-1-hexenes: fluorenes lithium=3～10: 1
Organic solvent is selected from methylene dichloride, toluene, THF.
Compound method is shown below:
Theoretically, 5,6-two chloro-1-hexenes and the reaction of fluorenes lithium can obtain the part of two kinds of structures shown in the structural formula A and B in the following formula; 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 basically 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 1～2 droplet/second, 0.5～2 hour dropping time.The order of addition(of ingredients) of reactant is: fluorenes lithium solution slowly is added drop-wise to 5, in the 6-two chloro-1-hexene solution, in reaction, keeps 5 always, 6-two chloro-1-hexenes are excessive.If with 5,6-two chloro-1-hexenes are added drop-wise in the fluorenes lithium solution, perhaps fluorenes lithium drips of solution are added to 5, in the 6-two chloro-1-hexene solution but rate of addition is too fast, all can produce 5,6-two indenyls-1-hexene.5, step reaction down can't take place in 6-two indenyls-1-hexene, need separate through gel column.
5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is lower than at 3 o'clock, also can produce 5,6-two indenyls-1-hexene, and ratio is low more, and in the product 5, the content of 6-two indenyls-1-hexene is high more.5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is high more, and productive rate high more (serves as to calculate benchmark with the fluorenes lithium) is excessive 5, and 6-two chloro-1-hexenes can pass through Separation and Recovery, utilize again.But 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is too high, and follow-up separation costs is increased, and is suitable 5, and the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is 3～10: 1, preferred 5～8: 1.
5, the concentration of 6-two chloro-1-hexenes 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 in sherwood oil or normal hexane solvent, be prepared 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 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 fluorenyl ligand 6-indenyl-5-chloro-1-hexene, preserves subsequent use.Also can separate, after reaction finishes, directly descend the step reaction 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-90 ℃～-60 ℃; 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.The order of addition(of ingredients) of fluorenyl ligand and indenes lithium is not special to be limited, and preferably indenes lithium drips of solution is added to the mode in the fluorenyl ligand.
Compound 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-30～20 ℃, and preferably temperature is-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 8～15 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 process various solution or suspension-s easily.Also can not drain solvent, directly descend the step synthetic after concentrated.
4) title complex midbody (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension-s of above-mentioned lithium salts, 0～40 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl moiety.CpZrCl
3The mol ratio of DME and part lithium salts is 1: (1～1.1); Temperature of reaction is-10～30 ℃, stirring reaction 15～24 hours, and reaction product is through spinning; Residual solid is used dichloromethane extraction again; The liquid that all extraction liquids and centrifugal are obtained merges, and is concentrated into solid to occur, places for-25 ℃～-15 ℃ and promptly gets compound (I) in 20～30 hours.
Midbody (I) purity that obtains of crystallization is higher as stated above, is easy to analyze.The solid that obtains can directly be weighed, and is convenient to calculate the ingredient proportion of compound in each step.In actual production, after all extraction liquids and the centrifugal liquid merging that obtains, directly descend the step reaction after also can concentrating.If directly descend to go on foot reaction after concentrated, the reaction times is shortened greatly, but CpMCl in needing to go on foot under the estimation according to circumstances
3Add-on.
5) the C2 bridged metallocene double-core catalyst is synthetic
In benzene or toluene, the compound of formula (I) and expression formula are CpMCl
3The cyclopentadiene muriate according to 1: the molar ratio reaction of (1～1.2), temperature of reaction are 100～110 ℃, and the time is 12～24 hours, filter then, will filtrates to concentrate and then use the organic solvent recrystallization, obtain metallocene dinuclear catalyst (II):
Preferably, the reaction times in the step 5) is 15～20 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 of the crystallisate that obtains is different, and active solvent like 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 step, 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 higher than using the 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.
Described each reaction all needs under inert atmosphere, to carry out, and adopts the shenlink technology, and rare gas element is argon gas or nitrogen.
Compound provided by the invention can be made the terminal olefin homopolymerization of C2～C10 or the Primary Catalysts of copolymerization.Also need add alkylaluminoxane during polymerization is promotor.Preferred promotor is a MAO, during polyreaction, in the promotor in A1 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 method 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 gies 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 5,6-two chloro-1-hexenes are dissolved in the 200ml THF, are cooled to-78 ℃, the petroleum ether solution of the 0.05mol fluorenes lithium that slowly progressively increases, dropwises and continues reaction 12 hours at 1 hour dropping time; Product is through hydrolysis, separation, purification, and productive rate is 80.1%.
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 52.3%.
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 10 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex midbody (I) is synthetic
In above-mentioned part lithium salts, add 150ml toluene, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 5 ℃ of stirring reactions 24 hours, spinning, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs ,-20 ℃ left standstill 24 hours, faint yellow needle-like crystal, be the title complex midbody, productive rate 39.4%.
5) the C2 bridged metallocene double-core catalyst is synthetic
Under the argon shield, with title complex midbody 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.After the filtration filtrating is concentrated into 1/3 ,-20 ℃ of original volume and left standstill 25 hours, the silver gray crystal.Filtrating is concentrated the mixed solvent recrystallization of back with toluene and methylene dichloride, obtains the bridged metallocene double-core catalyst of following formula:
Embodiment 2
1) fluorenyl ligand is synthetic
0.5mol 5,6-two chloro-1-hexenes are dissolved in the 200ml toluene, are cooled to-90 ℃, the petroleum ether solution of the 0.10mol fluorenes lithium that slowly progressively increases, dropwises and continues reaction 10 hours at 1.5 hours dropping time; Product is through hydrolysis, separation, purification, and productive rate is 83.2%.
2) C2 bridging indenyl fluorenyl ligand is synthetic
-90 ℃, 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 8 hours.Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts.
4) title complex midbody (I) is synthetic
In above-mentioned part lithium salts, add 150ml toluene, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 15 ℃ of stirring reactions 20 hours, spinning, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs ,-20 ℃ left standstill 24 hours, faint yellow needle-like crystal, be the title complex midbody, productive rate 38.9%.
5) the C2 bridged metallocene double-core catalyst is synthetic
Under the argon shield, with title complex midbody 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.After the filtration filtrating is concentrated into 1/3 ,-20 ℃ of original volume and left standstill 25 hours, the silver gray crystal.Filter then, the toluene solvant recrystallization is used in the concentrated back of will filtrating, and obtains the bridged metallocene double-core catalyst of following formula:
Embodiment 3
1) fluorenyl ligand is synthetic
0.5mol 5,6-two chloro-1-hexenes are dissolved in the 200ml toluene, are cooled to-60 ℃, the petroleum ether solution of the 0.15mol fluorenes lithium that slowly progressively increases, dropwises and continues reaction 8 hours at 2 hours dropping time; Product is through hydrolysis, separation, purification, and productive rate is 79.5%.
2) C2 bridging indenyl fluorenyl ligand is synthetic
-60 ℃, 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:2844s; MS:m/e 360 (M
+); Its NMR data are following:
1H NMR (CDCl
3, 25 ℃): 7.71-7.23 (8H), 6.95 (m, 4H), 6.55 (m, 2H), 5.65 (m, 1H ,=CH), 4.91 (m, 1H ,=CH
2), 4.90 (m, 1H ,=CH
2), 2.44 (m, 1H, CH), 2.13 (m, 2H, CH
2), 1.85 (m, 2H, CH
2), 1.51 (m, 2H, CH
2);
13C?NMR(CDCl
3，25℃)：147.8，147.7，146.8，145.0，141.1(Cq)，138.5，138.3，136.5，136.4，132.2，127.1，127.0，126.9，126.8，126.7，126.6，126.5，124.6，124.5，123.2，122.8，121.0，119.7(CH)，114.4(＝CH
2)，53.2，45.6，36.4(CH)，33.8；
3) the part lithium salts is synthetic
0.026lmol 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 midbody (I) is synthetic
In above-mentioned part lithium salts, add 150ml toluene, obtain white opacity liquid, room temperature adds 9.36 gram cyclopentadiene tri-chlorination zirconium glycol dimethyl ether (CpZrCl
3DME), 25 ℃ of stirring reactions 15 hours, spinning, resistates merges centrifugate and extraction liquid with 50ml dichloromethane extraction 2 times, is concentrated into solid and occurs ,-15 ℃ left standstill 30 hours, faint yellow needle-like crystal, be the title complex midbody, productive rate 39.8%.
5) the C2 bridged metallocene double-core catalyst is synthetic
Under the argon shield, with title complex midbody 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.After the filtration filtrating is concentrated into 1/3 ,-20 ℃ of original volume and left standstill 25 hours, the silver gray crystal.Use the dichloromethane solvent recrystallization then, obtain the bridged metallocene double-core 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 following:
1H?NMR(CDCl3，25℃)：7.45-7.40(C
5H
5)，7.26-7.20(C
9H
6)，6.86-6.74(C
9H
6)，6.48-6.56(C
9H
6)，6.35-6.42(C
13H
8)，6.13-6.19(C
13H
8)，5.57-5.33(＝CH-)，5.04-4.99(＝CH
2)，3.42-3.76(THF)，1.29-1.86(CH
2)，1.02-1.12(CH
2)；
Gained catalyst vinyl polymerization, slurry polymerization, solvent are toluene, MAO is as promotor, in the MAO 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 1.71 * 10
5G ethene/mmol Zr h, Mw/Mn=2.63, MWD compares Cp
2ZrCl
2Catalysis synthetic Vilaterm 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 filtrating is concentrated into 1/3 of original volume, puts into refrigerator, leaves standstill 20 hours at-20 ℃, gets the silver gray crystal, and its structure is shown below.Productive rate 48.8%
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 HNMR spectrum, and spectrum is read in influence.Relevant spectral data is following:
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, slurry polymerization, solvent are toluene, MAO is as promotor, in the MAO 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 0.95 * 10
5G ethene/mmol Zr h, Mw/Mn=2.92, MWD compares Cp
2ZrCl
2Catalysis synthetic Vilaterm is wide.Dsc analysis is found unexpectedly, has obtained bimodal polyethylene.
Embodiment 5:
Other are with embodiment 1, and different is with CpNdCl
3Replaced C pYCl
3, being heated to 120 ℃ of reflux temperatures, stirring reaction is 18 hours under reflux state, stops to stir, and reduces to room temperature.After the filtration filtrating is concentrated into 1/3 ,-20 ℃ of original volume and left standstill 20 hours, the silver gray crystal, productive rate 49%.
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 following:
1H?NMR(CDCl3，25℃)：7.55-7.48(C
5H
5)，7.39-7.29(C
9H
6)，6.81-6.72(C
9H
6)，6.44-6.54(C
9H
6)，6.42-6.38(C
13H
8)，6.17-6.22(C
13H
8)，5.58-5.44(＝CH-)，5.05-4.94(＝CH
2)，3.38-3.58(THF)，1.49-1.70(CH
2)，1.01-1.13(CH
2)；
Gained catalyst vinyl polymerization, slurry polymerization, solvent are toluene, MAO is as promotor, in the MAO 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 1.65 * 10
5G ethene/mmol Zr h, Mw/Mn=3.13, MWD compares Cp
2ZrCl
2Catalysis synthetic Vilaterm is wide.
Claims (8)
1. the compound method of a binuclear metallocene catalyzer comprises the following steps:
1) fluorenyl ligand is synthetic
5,6-two chloro-1-hexenes are dissolved in the organic solvent, are cooled to-90～-60 ℃, slowly drip fluorenes lithium solution, 0.5～2 hour dropping time, dropwise and continue reaction 8～12 hours; 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is: 5, and 6-two chloro-1-hexenes: fluorenes lithium=3～10: 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-90 ℃～-60 ℃; 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-30～20 ℃, and the mol ratio of part and n-Butyl Lithium is 1: 2.0～2.5, dropwises, and rises to room temperature naturally, reacts 8～15 hours; Remove by filter normal hexane, the decompressing and extracting normal hexane obtains the part lithium salts;
4) title complex midbody (I) is synthetic
Add toluene in the part lithium salts that step 3) obtains, obtain white opacity liquid, i.e. the suspension-s of above-mentioned lithium salts, 0～40 ℃ adds CpZrCl down
3DME, wherein DME is a glycol dimethyl ether, Cp is a cyclopentadienyl moiety; CpZrCl
3The mol ratio of DME and part lithium salts is 1: 1～1.1; Temperature of reaction is-10～30 ℃, stirring reaction 15～24 hours, and reaction product is through spinning; Residual solid is used dichloromethane extraction again; The liquid that all extraction liquids and centrifugal are obtained merges, and is concentrated into solid to occur, places for-25 ℃～-15 ℃ and promptly gets catalyzer (I) in 20～30 hours:
5) the C2 bridged metallocene double-core catalyst is synthetic
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3The cyclopentadiene muriate according to 1: 1～12 molar ratio reaction, temperature of reaction is 100～110 ℃, the time is 12～24 hours; Filter then, the organic solvent recrystallization is used in the concentrated back of will filtrating, and obtains the bridged metallocene double-core catalyst of formula (II); Wherein, M=rare earth:
2. the compound method of binuclear metallocene catalyzer as claimed in claim 1 is characterized in that, M is selected from Y, Nd or Sm.
3. the compound method of binuclear metallocene catalyzer as claimed in claim 1 is characterized in that, organic solvent is selected from methylene dichloride, toluene, THF in the step 1); Temperature of reaction is-80～-70 ℃, and the reaction times is 10～12 hours; 5, the mol ratio of 6-two chloro-1-hexenes and fluorenes lithium is: 5, and 6-two chloro-1-hexenes: fluorenes lithium=5～8: 1.
4. the compound method of binuclear metallocene catalyzer as claimed in claim 1 is characterized in that step 2) in, temperature of reaction is-80 ℃～-70 ℃; Reaction times is 30-48 hour; Solvent is ether, methyl ether, sherwood oil.
5. the compound method of binuclear metallocene catalyzer 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, 1～2 droplet/second of rate of addition.
6. the compound method of binuclear metallocene catalyzer 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: 2.0～22, dropwises, and rises to room temperature naturally, reacts 10～12 hours.
7. the compound method of binuclear metallocene catalyzer as claimed in claim 1 is characterized in that, in the step 4), temperature of reaction is-10～0 ℃; Stirring reaction 18～22 hours.
8. the compound method of binuclear metallocene catalyzer as claimed in claim 1 is characterized in that, in the step 5), the used organic solvent of recrystallization is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride.
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