CN103012629B - Synthetic method of bridged metallocene Zr-RE (rare earth) dinuclear catalyst - Google Patents
Synthetic method of bridged metallocene Zr-RE (rare earth) dinuclear catalyst Download PDFInfo
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Abstract
The invention provides a bridged metallocene Zr-RE (rare earth) dinuclear catalyst expressed by the structural formula as follows, wherein M represents rare earth. The invention further provides a preparation method of the catalyst. When the catalyst is used for olefinic polymerization in coordination with a catalyst promoter (alkylaluminoxane), high polymerization reactivity is achieved, and an olefinic polymerization product with high molecular weight and high molecular weight distribution can be obtained.
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's trial composite catalyzing or double-core multinuclear catalyzer 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 the preparation method of bridged metallocene Zr-tombarthite catalyst, this preparation method's step is few, raw material is easy to get, cost is low, is easy to industrialization.
Bridged metallocene Zr-tombarthite catalyst of the present invention, alkylaluminoxane are promotor, and catalyzed ethylene or propylene polymerization can obtain the polyolefine of wide molecular weight distribution.Polymerization process can adopt mass polymerization or solution polymerization.
The invention provides a kind of bridged metallocene Zr-tombarthite catalyst, its structure is as follows:
Wherein M is rare earth, and preferably, M is selected from Y, Nd or Sm.
The invention provides the synthetic method of described bridged metallocene Zr-tombarthite catalyst, comprise the following steps:
1) synthesis of fluorenyl ligand
The bromo-1-hexene of the chloro-6-of 5-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 8 ~ 12 hours;
The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1 ~ 1.1:1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil.
2) synthesis of bridging indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1 ~ 1:1.1; Temperature of reaction is-30 DEG C ~ 0 DEG C; Reaction times is 12-18 hour;
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) synthesis of title complex intermediate (I)
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, at 0 ~ 30 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is 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 uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely-25 DEG C ~-15 DEG C placements obtain title complex intermediate (I) for 12 ~ 24 hours;
5) synthesis of bridged metallocene Zr-tombarthite catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3cyclopentadiene muriate according to the molar ratio reaction of 1:1 ~ 1.2, temperature of reaction is 100 ~ 110 DEG C, and the time is 12 ~ 24 hours; Wherein M is rare earth, and preferably, M is selected from Y, Nd or Sm;
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain the bridged metallocene Zr-tombarthite catalyst shown in formula (II):
Preferably, the reaction times in step 5) is 12 ~ 16 hours, and recrystallization organic solvent used is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride.In the mixed solvent of toluene and methylene dichloride, the ratio of toluene and methylene dichloride is 1:2 volume ratio.
Preferably, in step 1), organic solvent is selected from sherwood oil.Temperature of reaction is-20 ~-10 DEG C, and the reaction times is 10 ~ 12 hours; The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: 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 ~ 2.1, dropwises, naturally rises to room temperature, reacts 12 ~ 15 hours.
Preferably, in step 4), temperature of reaction is 0 ~ 10 DEG C.Stirring reaction 36 ~ 42 hours.
Under identical catalytic condition, the catalytic activity of the bridged combined metal ZR-rare earth dinuclear 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 bridged metallocene Zr-tombarthite catalyst is as follows:
1) synthesis of fluorenyl ligand
The bromo-1-hexene of the chloro-6-of 5-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 10 ~ 12 hours;
The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: 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-hexene of the chloro-6-of control 5-, 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-hexene of 5,6-bis-as reactant, fluorenes lithium solution slowly need be added drop-wise in the chloro-6-of 5-bromo-1-hexene solution, and keep the chloro-6-of 5-bromo-1-hexene excessive in the reaction always.Condition control is improper can produce 9,10-, bis-indenyls-1-decene.Cannot there is the next step in 9,10-, bis-indenyls-1-decene, need to be separated through gel column.And the present invention utilizes the reactive difference of Br and Cl, 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.
The concentration of the bromo-1-hexene of the chloro-6-of 5-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-hexene of 6-indenyl-5-, 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 bridging indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1 ~ 1:1.1; Temperature of reaction is-30 DEG C ~ 0 DEG C; Reaction times is 12-18 hour.
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.
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.
Synthetic method is shown below:
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) synthesis of title complex intermediate (I)
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, at 0 ~ 30 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is 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 uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely-25 DEG C ~-15 DEG C placements obtain title complex intermediate (I) for 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, very easily decomposes.
The title complex intermediate (I) obtained can directly be weighed, and is convenient to the ingredient proportion calculating compound in each step.
After all extraction liquids and the centrifugal liquid obtained being merged, after also can concentrating, directly carry out the next step.Do not need-25 DEG C ~-15 DEG C to place 12 ~ 24 hours, save the reaction times, and the catalyzer finally obtained, catalytic effect is also unaffected.5) synthesis of bridged metallocene Zr-tombarthite catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3cyclopentadiene muriate according to the molar ratio reaction of 1:1 ~ 1.2, temperature of reaction is 100 ~ 110 DEG C, and the time is 12 ~ 24 hours; Wherein M is rare earth, and preferably, M is selected from Y, Nd or Sm;
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain the bridged metallocene Zr-tombarthite catalyst shown in formula (II):
Preferably, the reaction times in step 5) is 12 ~ 16 hours, and recrystallization organic solvent used is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride.
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-hexene of the chloro-6-of 5-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-hexene of the chloro-6-of 5-is dissolved in sherwood oil, is cooled to-30 DEG C, slowly drips fluorenes lithium solution, time for adding 2 hours, dropwises and continue reaction 10 hours; The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1:1;
2) synthesis of bridging indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-20 DEG C; Reaction times is 18 hours;
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 DEG C, and the mol ratio of part and n-Butyl Lithium is 1:2.2, dropwises, naturally rises to room temperature, reacts 15 hours.Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts.
4) synthesis of title complex intermediate (I)
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, at 0 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 1:1, stirring reaction 36 hours, and reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely-25 DEG C of placements obtain title complex intermediate in 12 hours;
5) synthesis of bridged metallocene Zr-tombarthite catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpYCl
3cyclopentadiene muriate according to the molar ratio reaction of 1:1 ~ 1.2, temperature of reaction is 100 DEG C, and the time is 14 hours;
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain bridged metallocene Zr-tombarthite catalyst:
。
Embodiment 2
1) synthesis of fluorenyl ligand
The bromo-1-hexene of the chloro-6-of 5-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 8 hours; The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1.1:1;
2) synthesis of bridging indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-10 DEG C; Reaction times is 14 hours;
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 0 DEG C, and the mol ratio of part and n-Butyl Lithium is 1:2.5, dropwises, naturally rises to room temperature, reacts 12 hours.Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts.
4) synthesis of title complex intermediate (I)
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, at 10 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 1:1, stirring reaction 40 hours, and reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely-20 DEG C of placements obtain title complex intermediate in 18 hours;
5) synthesis of bridged combined metal ZR-rare earth dinuclear catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpYCl
3cyclopentadiene muriate according to 1.2 molar ratio reaction, temperature of reaction is 110 DEG C, and the time is 12 hours;
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain bridged metallocene Zr-tombarthite catalyst:
Embodiment 3
1) synthesis of fluorenyl ligand
The bromo-1-hexene of the chloro-6-of 5-is dissolved in anhydrous diethyl ether, is cooled to-10 DEG C, slowly drips fluorenes lithium solution, time for adding 1.5 hours, dropwises and continue reaction 12 hours; The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1:1;
2) synthesis of bridging indenyl fluorenyl ligand
Add solvents tetrahydrofurane in the fluorenyl ligand that step 1) obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging.The mol ratio of fluorenyl ligand and indenes lithium is 1:1; Temperature of reaction is-5 DEG C; Reaction times is 12 hours;
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 10 DEG C, and the mol ratio of part and n-Butyl Lithium is 1:2.0, dropwises, naturally rises to room temperature, reacts 10 hours.Cross and filter insolubles, decompressing and extracting normal hexane, obtain part lithium salts.
4) synthesis of title complex intermediate (I)
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, at 30 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is cyclopentadienyl.CpZrCl
3the mol ratio of DME and part lithium salts is 1:1.1, stirring reaction 30 hours, and reaction product is through centrifugation, residual solid uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely 15 DEG C of placements obtain title complex intermediate in 22 hours;
5) synthesis of bridged metallocene Zr-tombarthite catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpYCl
3cyclopentadiene muriate according to the molar ratio reaction of 1:1, temperature of reaction is 100 DEG C, and the time is 18 hours;
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain bridged metallocene Zr-tombarthite catalyst:
Because Y ion has unpaired electron, so have paramagnetism.Therefore
1in H NMR spectrum, active displacement changes greatly and is generally larger broad peak, and spectrum is read in impact.NMR data are 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 is toluene, and methylaluminoxane is as promotor, and in methylaluminoxane, in Al and Primary Catalysts, the mol ratio of metal is 1000:1, and polymerizing condition is 80 DEG C, 0.5MPa.
Gained compound for catalysis vinyl polymerization, active in 0.77 × 10
5g ethene/mmol Zr h, Mw/Mn=2.53, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzed and synthesized is wide.
Embodiment 4:
Other are with embodiment 1, unlike with CpSmCl
3replace CpYCl
3, be heated to reflux temperature 110 DEG C, at reflux stirring reaction 12 hours, stop stirring, be down to room temperature.Reacting liquid filtering removing solids, then filtrate is concentrated into 1/3 of original volume, puts into refrigerator, leave standstill 20 hours at-20 DEG C, obtain silver gray crystalline solid, its structure is shown below.Productive rate 48.2%.
Because Sm ion has unpaired electron, so have paramagnetism.Therefore
1in H NMR spectrum, active displacement changes greatly and is generally larger broad peak, and spectrum is read in impact.NMR data are as follows:
1h NMR(CDCl3,25 DEG C): 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
9), 6.18-6.24 (C
13h
9), 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 compound for catalysis vinyl polymerization, active in 0.85 × 10
5g ethene/mmol Zr h, Mw/Mn=2.98, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzed and synthesized is wide.
Embodiment 5:
Other are with embodiment 1, unlike with CpNdCl
3replace CpYCl
3, be heated to reflux temperature 120 DEG C, along with the rising of temperature of reaction, reaction solution changes into orange red by yellow gradually.Stirring reaction 18 hours at reflux, stops stirring, is down to room temperature.After filtration, filtrate is concentrated into 1/3 of original volume ,-20 DEG C leave standstill 20 hours, obtain silver gray crystalline solid, productive rate 44%.
Because Nd ion has unpaired electron, so have paramagnetism.Therefore
1in H NMR spectrum, active displacement changes greatly and is generally larger broad peak, and spectrum is read in impact.NMR data are as follows:
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
9), 6.17-6.22(C
13H
9), 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, active in 1.28 × 10
5g ethene/mmol Zr h, Mw/Mn=3.23, molecular weight distribution compares Cp
2zrCl
2the polyethylene catalyzed and synthesized is wide.
Claims (7)
1. a synthetic method for bridged metallocene Zr-tombarthite catalyst, comprises the following steps:
1) synthesis of fluorenyl ligand
The bromo-1-hexene of the chloro-6-of 5-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 8 ~ 12 hours;
The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1 ~ 1.1:1; Organic solvent is selected from anhydrous diethyl ether or sherwood oil;
2) synthesis of bridging indenyl fluorenyl ligand
Step 1) add solvents tetrahydrofurane in the fluorenyl ligand that obtains, then react with indenes lithium, obtain the indenyl fluorenyl ligand of bridging; The mol ratio of fluorenyl ligand and indenes lithium is 1:1 ~ 1:1.1; Temperature of reaction is-30 DEG C ~ 0 DEG C; Reaction times is 12-18 hour;
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) synthesis of title complex intermediate (I)
Step 3) add toluene in the part lithium salts that obtains, obtain white opacity liquid, i.e. the suspension of above-mentioned lithium salts, at 0 ~ 30 DEG C, add CpZrCl
3dME, wherein DME is glycol dimethyl ether, and Cp is 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 uses dichloromethane extraction again, all extraction liquids and the centrifugal liquid obtained are merged, be concentrated into and occur solid, namely-25 DEG C ~-15 DEG C placements obtain title complex intermediate (I) for 12 ~ 24 hours;
5) synthesis of bridged metallocene Zr-tombarthite catalyst
In benzene or toluene, the catalyzer of formula (I) and expression formula are CpMCl
3cyclopentadiene muriate according to the molar ratio reaction of 1:1 ~ 1.2, temperature of reaction is 100 ~ 110 DEG C, and the time is 12 ~ 24 hours; Wherein M is rare earth,
React complete filtration, removing insolubles, use organic solvent recrystallization after filtrate is concentrated, obtain the bridged metallocene Zr-tombarthite catalyst shown in formula (II):
2. the synthetic method of bridged metallocene Zr-tombarthite catalyst as claimed in claim 1, it is characterized in that, M is selected from Y, Nd or Sm.
3. the synthetic method of bridged metallocene Zr-tombarthite catalyst as claimed in claim 1, it is characterized in that, step 5) in reaction times be 12 ~ 16 hours, recrystallization organic solvent used is selected from the mixed solvent of toluene, methylene dichloride or toluene and methylene dichloride; In the mixed solvent of toluene and methylene dichloride, the ratio of toluene and methylene dichloride is 1:2 volume ratio.
4. the synthetic method of bridged metallocene Zr-tombarthite catalyst as claimed in claim 1, is characterized in that, step 1) in organic solvent be selected from sherwood oil; Temperature of reaction is-20 ~-10 DEG C, and the reaction times is 10 ~ 12 hours; The mol ratio of the chloro-6-of 5-bromo-1-hexene and fluorenes lithium is: the bromo-1-hexene of the chloro-6-of 5-: fluorenes lithium=1:1.
5. the synthetic method of bridged metallocene Zr-tombarthite catalyst as claimed in claim 1, is characterized in that, step 2) in, temperature of reaction is-20 DEG C ~-10 DEG C; Reaction times is 14-16 hour; The mol ratio of fluorenyl ligand and indenes lithium is 1:1.
6. the synthetic method of bridged metallocene Zr-tombarthite 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 ~ 2.1, dropwises, naturally rises to room temperature, reacts 12 ~ 15 hours.
7. the synthetic method of bridged metallocene Zr-tombarthite catalyst as claimed in claim 1, is characterized in that, step 4) in, temperature of reaction is 0 ~ 10 DEG C; Stirring reaction 36 ~ 42 hours.
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