CN114702530A - Imidazole bridged metallocene, catalyst, preparation and application thereof - Google Patents

Imidazole bridged metallocene, catalyst, preparation and application thereof Download PDF

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CN114702530A
CN114702530A CN202110000075.XA CN202110000075A CN114702530A CN 114702530 A CN114702530 A CN 114702530A CN 202110000075 A CN202110000075 A CN 202110000075A CN 114702530 A CN114702530 A CN 114702530A
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imidazole
alkyl
metallocene
catalyst
reaction
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CN114702530B (en
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张志智
王陶
孙潇磊
刘全杰
张喜文
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/04—Well-defined hydrocarbons aliphatic
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/024—Well-defined aliphatic compounds unsaturated

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Abstract

The invention discloses a metallocene catalyst. The catalyst comprises imidazole bridged metallocene, alkyl metal and solvent; imidazole bridged metallocene is used as a main catalyst, and alkyl metal is used as a cocatalyst; wherein the imidazole-bridged metallocene: the molar ratio of the alkyl metal is 1 (5-500), and the solvent accounts for 40-90 wt% of the catalyst. The main catalyst adopts a novel metallocene structure, effectively regulates and controls the electronic and space effects of the metallocene, and greatly improves the catalytic activity of the metallocene. The catalyst composition of the invention improves C content in butylene oligomerization products16And C20Isomerism of benzeneAlkane selectivity and yield.

Description

Imidazole bridged metallocene, catalyst, preparation and application thereof
Technical Field
The invention relates to metallocene, a catalyst, and preparation and application thereof, in particular to a metallocene catalyst for preparing high-boiling-point solvent oil by butylene oligomerization.
Background
The mixed butene is oligomerized to produce isomeric olefin C8-C20, and the isomeric alkane solvent oil may be produced through hydrogenation. The synthetic isoparaffin solvent oil is a special oil product which does not contain harmful substances such as sulfur, aromatic hydrocarbon and the like and has no peculiar smell, and can be used as a solvent for producing products such as coating, insecticide, printing ink and the like. And can be used as base oil of low-melting point lubricating oil. Wherein C is16And C20The high carbon hydrocarbon is used for ink solvent and the like, and is high-value solvent oil. A large amount of butylene can be obtained in the ethylene cracking process of petroleum refining and the olefin preparation process of coal chemical industry. The catalyst for butene oligomerization mainly comprises a Ziegler homogeneous catalyst, solid phosphoric acid, strong acid cation exchange resin, a molecular sieve, solid super acid, a supported sulfate catalyst, ionic liquid and the like.
The primary product of the early catalysts catalyzed butene oligomerization was the C8 dimer. U.S. Pat. No. 4,83305 uses nickel octoate/ethyl aluminium dichloride/halogenated acetic acid as catalyst to catalyze oligomerization of n-butene to synthesize C8Olefin, C8The selectivity to olefin was 90%.
U.S. Pat. Nos. 4,4316851, 4366087 and 4398049 use nickel salts of mixed acids of haloacetic acids and carboxylic acids [ (R) as catalyst1COO)(R2COO)Ni]Catalyst system of ethyl aluminium halide for catalyzing butene oligomerization to synthesize high-carbon olefin8Olefins predominate. The catalyst system is to C8、C12And C16The selectivity to olefin was 85%, 12% and 3%, respectively.
European patent EP0091232 utilizes NiCl2(PEt3)/EtAlCl2Catalyzing oligomerization of n-butene to synthesize high-carbon olefin, C8And C12The selectivity of olefin is 50% and 20%, and the oligomerization product contains a small amount of saturated hydrocarbon besides olefin. Using nickel octoate/EtAlCl2When it is a catalyst, C8The olefin selectivity was 90%.
U.S. Pat. No. 4,4737480 Ziegler catalysts of Ni/Al series are improved in catalyst activity by adding a third component, such as a Zn compound, but C12And C16Selectivity of higher olefins is not increased, C8The selectivity of olefin is still 85-90%.
US4225743 uses a high-carbon nickel fatty acid/water/alkyl aluminum halide catalyst system to catalyze the oligomerization of butene fraction containing 5-55 wt% of isobutene to obtain C containing a small amount of 2,2, 4-trimethylpentene8An olefin.
U.S. Pat. No. 4,4398049 uses nickel salts of mixed carboxylic acids and halogenated carboxylic acids (R)1COO)(R2COO) Ni/alkyl aluminum halide catalyst system for catalyzing butene oligomerization, C8Olefin selectivity of 85%, C12Olefin selectivity of 12%, C16The selectivity to olefin was 3%.
European patent EP0439865 uses NiO/SiO2-Al2O3A supported catalyst. Butene conversion was over 90% and C8 olefin selectivity was 85%.
U.S. Pat. No. 5,5510555 uses aluminosilico-alumino-oxides and reacts at 60-65 ℃ with 99% conversion of isobutene and 50%, 43% and 5% selectivity for dimers, trimers and tetramers, respectively.
Sulfate supported catalyst Fe2(SO4)3(NiSO4)/γ-Al2O3Catalyzing the oligomerization of isobutene. The reaction was carried out at 50 ℃ for 5h, with an isobutene conversion of 85% and a dimer, trimer and tetramer selectivity of 50%, 40% and 5% in this order. And WOx/ZrO developed by Lee J S et al of Korean institute of chemical technology2The catalyst catalyzes the oligomerization reaction of isobutene at 70 ℃, the conversion rate can reach 100 percent, and the selectivity of the dimer, the trimer and the tetramer is 5 percent, 80 percent and 15 percent in sequence.
The Nafion resin can catalyze the oligomerization of isobutene, the conversion rate of isobutene is 90 percent at 90 ℃, and the selectivity of diisobutylene, triisobutene and tetraisobutylene is 25.3 percent, 65.2 percent and 8.8 percent respectively.
The beta-25 molecular sieve and the ferrierite molecular sieve have excellent isobutene oligomerization performance. Under the conditions of 70 ℃ and 1.5 MPa, the conversion rate of isobutene on a beta-25 molecular sieve is 100 percent, and the selectivity of diisobutylene, triisobutene and tetraisobutylene is 10 percent, 60 percent and 30 percent respectively. Under the same reaction conditions, the conversion of isobutene on the ferrierite molecular sieve was 100%, and the selectivities for diisobutylene, triisobutene and tetraisobutylene were 8%, 80% and 10%, respectively. The molecular sieve can be regenerated.
Ionic liquids such as (C)2H5)3NHCl-xFeCl3The ionic liquid catalyzes the oligomerization of isobutene, and when the reaction is carried out for 60 min at the temperature of 40 ℃, the conversion rate of isobutene reaches 86 percent, and the selectivity of diisobutylene, triisobutene, tetraisobutylene and pentaisobutylene is 21.51 percent, 53.91 percent, 19.92 percent and 4.66 percent respectively.
The prior catalyst formula and technology can not obtain high proportion of C16And C20High-carbon olefin can not produce high-value solvent oil, and the value of special solvent oil is reduced.
Disclosure of Invention
In order to solve the above existing problems, it is an object of the present invention to provide a metallocene, a catalyst composition, their preparation and use.
According to a first aspect of the present invention, there is provided an imidazole-bridged metallocene.
An imidazole-bridged metallocene, the structural formula of which is as follows:
Figure DEST_PATH_IMAGE001
wherein R1, R2 and R3 may be H, CH3、C2H5、C3H7、C6H5One of the alkyl groups, preferably H, CH3(ii) a M may be Zr, Ti, Hf, etc., preferably Zr; z can be Cl, Br, I, CH3、C2H5、C3H7、C4H9Etc., preferably Cl, Br, I, C2H5. M is the valence of M metal-3. n is CH2N is 1 to 3, preferably 1.
According to a second aspect of the invention, there is also provided a process for the preparation of an imidazole-bridged metallocene.
The preparation method comprises the following steps:
(1) adding cyclopentadiene into a solvent, cooling to-40-0 ℃, then dropwise adding alkyl lithium, stirring for 2-24h, then adding dihalogenated alkane, and continuing stirring for 1-24 h; distilling and separating to obtain halogenated alkyl cyclopentadiene;
(2) adding imidazole, halogenated alkyl cyclopentadiene obtained in the step (1) and alkali into acetonitrile, and reacting at the temperature of 50-80 ℃; filtering, and separating liquid to obtain N, N-dicyclopentadienyl alkyl imidazole;
(3) dissolving N, N-dicyclopentadienyl alkyl imidazole in an organic solvent, cooling to-40-0 ℃, dropwise adding alkyl lithium while stirring, and stirring for reacting for 2-24 hours; then adding zirconium tetrachloride into the mixture, and stirring the mixture for 24 to 48 hours;
(4) and (4) draining the organic solvent in the solution obtained in the step (3), adding methyl chloride for dissolving, performing solid-liquid separation, and performing distillation and concentration to obtain the imidazole bridged metallocene.
Furthermore, the molar ratio of the cyclopentadiene to the butyl lithium to the dihalogenated alkane in the step (1) is 1 (0.8-1.2) to (0.8-1.2). The solvent is selected from organic solvents commonly used in the art, such as at least one selected from tetrahydrofuran, diethyl ether, petroleum ether, N-dimethylformamide and acetonitrile, and tetrahydrofuran is preferred.
Further, the alkyl lithium in the step (1) comprises ethyl lithium, propyl lithium and butyl lithium.
Further, the dihaloalkane described in the step (1) includes 1, 2-dihaloethane, 1, 3-dihalopropane, 1, 4-dihalobutane, 1, 5-dihalopentane and the like, and the halogen is chlorine, bromine or iodine. Preferably a dihalobutane, more preferably 1, 4-dichlorobutane.
Furthermore, in the step (2), the molar ratio of the imidazole, the halogenated alkyl cyclopentadiene and the alkali is 1 (1.8-2.4) to (1-3), and the weight ratio of the imidazole to the acetonitrile is 1 (10-50). The reaction time in the step (2) is generally 10-24 h. The separation is a well known operation in the art, such as rotary distillation may be selected.
Further, the alkali in the step (2) is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
Further, in the step (3), the molar ratio of the N, N-dicyclopentadienyl alkyl imidazole to the N-butyl lithium to the zirconium tetrachloride is 1 (2.8-3.5) to 0.8-1.2; the weight ratio of the N, N-dicyclopentadienyl alkyl imidazole to the tetrahydrofuran is 1 (10-50). The organic solvent in step (3) is selected from conventional solvents in the art, such as one of tetrahydrofuran, diethyl ether, petroleum ether, N-dimethylformamide and acetonitrile. The alkyl lithium comprises at least one of ethyl lithium, propyl lithium and butyl lithium.
Furthermore, the weight ratio of the N, N-dicyclopentadienyl alkyl imidazole to the dichloromethane in the step (4) is 1 (30-80).
Further, the chloromethane in the step (4) comprises one of dichloromethane, trichloromethane and carbon tetrachloride.
According to a third aspect of the present invention there is provided a metallocene catalyst comprising an imidazole-bridged metallocene as hereinbefore described.
A metallocene catalyst comprising an imidazole-bridged metallocene, a metal alkyl and a solvent; imidazole bridged metallocene is used as a main catalyst, and alkyl metal is used as a cocatalyst; wherein the imidazole-bridged metallocene: the molar ratio of the alkyl metal is 1 (5-500), preferably 1 (10-100), and the solvent accounts for 40-90 wt%, preferably 60-80 wt% of the catalyst (composition).
Further, the metal alkyl comprises at least one of alkyl magnesium, alkyl aluminum and alkyl zinc. The alkyl magnesium is at least one selected from diethyl magnesium, dipropyl magnesium, diisopropyl magnesium and dibutyl magnesium, the alkyl aluminum is at least one selected from trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum and triisobutyl aluminum, and the alkyl zinc is at least one selected from diethyl zinc, dipropyl zinc, diisopropyl zinc, dibutyl zinc and diisobutyl zinc, preferably the alkyl aluminum, and more preferably the triisobutyl aluminum.
Further, the solvent is tetrahydrofuran, acetonitrile, toluene, alkylated oil, and the like. Preferably an alkylate.
According to a fourth aspect of the present invention, there is also provided a process for the preparation of the above metallocene catalyst.
The method comprises the following steps: and adding imidazole bridged metallocene and alkyl aluminum into a solvent, and uniformly stirring to obtain the metallocene catalyst.
According to a fifth aspect of the present invention, there is also provided a n-butene oligomerization reaction wherein the metallocene catalyst described above is used.
An oligomerization reaction of n-butene, comprising the following: after the reactor is deoxygenated, the butene and the catalyst composition are added into the reactor, polymerization is carried out at a certain reaction temperature and reaction pressure, and the polyolefin is obtained after the reaction product is separated.
Further, the reaction temperature is 40-100 ℃, preferably 60-80 ℃, and the reaction time is generally 1-8 hours, preferably 2-4 hours; the reaction pressure is the saturated vapor pressure of each component in the reaction system at the reaction temperature, so that the reactant butylene is kept in a liquid state without external pressure.
Further, the reactor oxygen removal is a well known operation to those skilled in the art.
Compared with the prior art, the invention has the following characteristics:
1. the main catalyst adopts a novel metallocene structure, effectively regulates and controls the electronic and space effects of the metallocene, and greatly improves the catalytic activity of the metallocene. Imidazole has an electron-rich effect on zirconium metal, stabilizes the cationic property of zirconium metal, and promotes the initiation and chain growth of olefin polymerization. Meanwhile, the weak covalent bond between the zirconium metallocene and the zirconium metallocene promotes the bond length, does not obviously limit the steric hindrance of the zirconium metallocene, and is beneficial to the polymerization of the multiolefin. Meanwhile, an imidazole ionic liquid group and a metallocene group in the novel metallocene structure have a synergistic catalytic effect, zirconium metal has a negative electron effect on imidazole, the electropositivity of imidazole cations is improved, and the initiation capability of imidazole on olefin polymerization is improved. The space distance between the two active centers is proper, the bimolecular reaction of the olefin dimer can be promoted, and the selectivity of the high polymer is improved. The catalyst provided by the inventionThe catalyst composition can obviously improve the butylene oligomerization product C16And C20Selectivity and yield of isoparaffin.
2. On the premise of keeping the catalytic effect equivalent, the catalyst of the invention has obviously reduced cost.
3. The catalyst has low toxicity, low sensitivity to water and air and environment friendliness.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The imidazole-bridged metallocenes prepared in the examples were structurally determined by elemental analysis. The catalyst was subjected to elemental detection by means of an X-ray fluorescence spectrometer model ZSX100e manufactured by Japan chemical Co.
The reagents used in the examples were derived from carbofuran and were chemically pure. All liquid solvents were purified in a solvent purification unit and then reused.
Example 1
(1) 66g of cyclopentadiene (66 g/mol) were added to tetrahydrofuran, cooled to-40 ℃ and then 64g of butyllithium (64 g/mol) were added dropwise, stirred for 6h and then 127g of 1, 4-dichlorobutane (127 g/mol) were added. Stirring was continued for 10 h.
(2) 34g of imidazole (68 g/mol), 156g of chlorobutylcyclopentadiene (156 g/mol) and 106g of sodium carbonate (106 g/mol) are added to 680g of acetonitrile, heated and stirred at 70 ℃ for 24 hours, the mixture is filtered to remove solids, and the liquid is subjected to rotary distillation separation to obtain N, N-dicyclopentadienyl butylimidazole.
(3) 86g of N, N-dicyclopentadienylbutylimidazole (345 g/mol) were dissolved in 3450g of tetrahydrofuran and cooled to-40 ℃. After stirring, 48g of n-butyllithium (64 g/mol) were added dropwise, and the reaction was stirred for 5 hours. Then, 58g of zirconium tetrachloride (233 g/mol) was added thereto, and stirred for 24 hours.
(4) And (3) pumping out tetrahydrofuran in the solution, adding 6030g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the imidazole bridged zirconocene.
The obtained product imidazole bridged zirconium metallocene is characterized by an element analysis method and has the following structural general formula:
Figure 354366DEST_PATH_IMAGE002
wherein R1, R2, R3 are H; m is Zr; z is Cl, m is 1 and n is 2.
The elemental composition of the synthesized imidazole-bridged zirconocene was N2C21ZrCl2H26 with a theoretical weight percentage composition of 5.98wt% N:53.85wt% C:19.44wt% Zr:15.17wt% Cl:5.56wt% H. From the elemental analysis in table 1, it can be seen that the elemental composition of the synthesized imidazole-bridged zirconocene conforms to the theoretical composition, indicating that zirconocene was synthesized.
Example 2
(1) 66g of cyclopentadiene (66 g/mol) were added to tetrahydrofuran, cooled to-40 ℃ and 76.8g of butyllithium (64 g/mol) were added dropwise, stirred for 3h and then 127g of 1, 4-dichlorobutane (127 g/mol) were added. Stirring was continued for 10 h. Distilling and separating to obtain the chlorobutyl cyclopentadiene.
(2) 34g of imidazole (68 g/mol), 187g of chlorobutylcyclopentadiene (156 g/mol) and 159g of sodium carbonate (106 g/mol) are added to 1700g of acetonitrile, heated and stirred at a temperature of 50 ℃ for 24 hours, the solid is removed by filtration, and the liquid is subjected to rotary distillation separation to obtain N, N-dicyclopentadienyl butylimidazole.
(3) 86g of N, N-dicyclopentadienylbutylimidazole (309 g/mol) were dissolved in 4299g of tetrahydrofuran and cooled to-40 ℃. After stirring, 56g of n-butyllithium (64 g/mol) were added dropwise, and the reaction was stirred for 5 hours. Then, 70g of zirconium tetrachloride (233 g/mol) was added thereto, and stirred for 24 hours.
(4) And (3) pumping out tetrahydrofuran in the solution, adding 6878g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the imidazole bridged zirconocene.
The obtained product imidazole bridged zirconium metallocene is characterized by an elemental analysis method and has the following structural general formula:
Figure 350135DEST_PATH_IMAGE002
wherein R1, R2, R3 are H; m is Zr; z is Cl. m is 1. n is 2.
The elemental composition of the synthesized imidazole-bridged zirconium metallocene was N2C21ZrCl2H26 with a theoretical weight percent composition of 5.98wt% N:53.85wt% C:19.44wt% Zr:15.17wt% Cl:5.56wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized imidazole-bridged zirconocenes conforms to the theoretical composition, indicating that zirconocenes were synthesized.
Example 3
(1) 66g of cyclopentadiene (66 g/mol) were added to tetrahydrofuran, cooled to-40 ℃ and 51.2g of butyllithium (64 g/mol) were added dropwise, stirred for 3h and then 101.6g of 1, 4-dichlorobutane (127 g/mol) were added. Stirring was continued for 10 h.
(2) 34g of imidazole (68 g/mol), 140g of chlorobutylcyclopentadiene (156 g/mol) and 53g of sodium carbonate (106 g/mol) are added to 340g of acetonitrile, heated and stirred at the temperature of 80 ℃ for 24 hours, solids are removed by filtration, and the liquid is subjected to rotary distillation separation to obtain N, N-dicyclopentadienyl butylimidazole.
(3) 86g of N, N-dicyclopentadienylbutylimidazole (309 g/mol) were dissolved in 860g of tetrahydrofuran and cooled to-40 ℃. After stirring, 44.8g of n-butyllithium (64 g/mol) were added dropwise and the reaction was stirred for 5 hours. Then, 46.6g of zirconium tetrachloride (233 g/mol) was added thereto, and stirred for 24 hours.
(4) And (3) pumping out tetrahydrofuran in the solution, adding 2579g of dichloromethane for dissolving, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the imidazole bridged zirconium metallocene.
The obtained product imidazole bridged zirconium metallocene is characterized by an elemental analysis method and has the following structural general formula:
Figure 926610DEST_PATH_IMAGE002
wherein R1, R2, R3 are H; m is Zr; z is Cl. m is 1 and n is 2.
The elemental composition of the synthesized imidazole-bridged zirconium metallocene was N2C21ZrCl2H26 with a theoretical weight percent composition of 5.98wt% N:53.85wt% C:19.44wt% Zr:15.17wt% Cl:5.56wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized imidazole-bridged zirconocenes conforms to the theoretical composition, indicating that zirconocenes were synthesized.
Example 4
(1) 66g of cyclopentadiene (66 g/mol) were added to tetrahydrofuran, cooled to-40 ℃ and 70g of butyllithium (64 g/mol) were added dropwise, stirred for 3h and then 114g of 1, 4-dichlorobutane (127 g/mol) were added. Stirring was continued for 10 h. Distilling and separating to obtain the chlorobutyl cyclopentadiene.
(2) 34g of imidazole (68 g/mol), 163.8g of chlorobutylcyclopentadiene (156 g/mol) and 133g of sodium carbonate (106 g/mol) were added to 1360g of acetonitrile, heated with stirring at a temperature of 80 ℃ for 24 hours, filtered to remove solids, and the liquid was subjected to rotary distillation to separate N, N-dicyclopentadienyl butylimidazole.
(3) 86g of N, N-dicyclopentadienyl butylimidazole (309 g/mol) are dissolved in 2579g of tetrahydrofuran and cooled to-40 ℃. After stirring, 49.6g of n-butyllithium (64 g/mol) were added dropwise, and the reaction was stirred for 5 hours. Then, 64g of zirconium tetrachloride (233 g/mol) was added thereto, and stirred for 24 hours.
(4) And (3) pumping out tetrahydrofuran in the solution, adding 4298g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the imidazole bridged zirconium metallocene.
The obtained product imidazole bridged zirconium metallocene is characterized by an elemental analysis method and has the following structural general formula:
Figure 898983DEST_PATH_IMAGE002
wherein R1, R2, R3 are H; m is Zr; z is Cl. m is 1. n is 2.
The elemental composition of the synthesized imidazole-bridged zirconium metallocene was N2C21ZrCl2H26 with a theoretical weight percent composition of 5.98wt% N:53.85wt% C:19.44wt% Zr:15.17wt% Cl:5.56wt% H. From the elemental analysis of table 1, it can be seen that the elemental composition of the synthesized imidazole-bridged zirconocenes conforms to the theoretical composition, indicating that zirconocenes were synthesized.
Example 5
(1) 108g of 1,2, 3-trimethyl-cyclopentadiene (108 g/mol) are added to tetrahydrofuran, cooled to-40 ℃ and 70g of butyllithium (64 g/mol) are added dropwise, stirred for 3h and then 101g of 1, 3-dichloropropane (101 g/mol) are added. Stirring was continued for 10 h. Distilling and separating to obtain the 1,2, 3-trimethyl-4-chloropropyl cyclopentadiene.
(2) 34g of imidazole (68 g/mol) and 193.1g of 1,2, 3-trimethyl-4-chloropropylcyclopentadiene (184 g/mol) and 133g of sodium carbonate (106 g/mol) were added to 1360g of acetonitrile, stirred with heating at 80 ℃ for 24 hours, the solid was removed by filtration, and the liquid was subjected to rotary distillation separation to obtain N, N-bis (1, 2, 3-trimethyl-cyclopentadienyl-butyl) imidazole.
(3) 93.8g 93.8g N, N-bis (1, 2, 3-trimethyl-cyclopentadienyl-butyl) imidazole (337 g/mol) was dissolved in 2579g tetrahydrofuran and cooled to-40 ℃. After stirring, 49.6g of n-butyllithium (64 g/mol) were added dropwise, and the reaction was stirred for 5 hours. Then, 64g of zirconium tetrachloride (233 g/mol) was added thereto, and stirred for 24 hours.
(4) And (3) pumping out tetrahydrofuran in the solution, adding 4298g of dichloromethane for dissolution, carrying out solid-liquid separation, and carrying out distillation and concentration to obtain the imidazole bridged zirconium metallocene.
The obtained product imidazole bridged zirconium metallocene is characterized by an elemental analysis method and has the following structural general formula:
Figure 978935DEST_PATH_IMAGE002
wherein R1, R2 and R3 are CH3(ii) a M is Zr; z is Cl. m is 1. n is 1.
The elemental composition of the synthesized imidazole-bridged zirconium metallocene was N2C23ZrCl2H30 with a theoretical weight percent composition of 5.64wt% N:55.66wt% C:18.35wt% Zr:14.31wt% Cl:6.05wt% H. From the elemental analysis in table 1, it can be seen that the elemental composition of the synthesized imidazole-bridged zirconocene conforms to the theoretical composition, indicating that zirconocene was synthesized.
TABLE 1 elemental analysis (wt%) of metallocene
Figure 4660DEST_PATH_IMAGE003
Example 6
4.68g of the metallocene prepared in example 1 (468 g/mol) and 39.6g of tributylaluminum (198 g/mol) were added to 103g of the alkylate and stirred until homogeneous to obtain a catalyst composition. Metallocene: the molar ratio of metal alkyl is 1: 20. The solvent accounts for 70wt% of the catalyst.
Example 7
4.68g of the metallocene prepared in example 1 (468 g/mol) and 139g of tributylaluminum (198 g/mol) were added to 574g of the alkylate, and stirred uniformly to obtain a catalyst composition. Metallocene: the molar ratio of metal alkyls is 70. The proportion of the solvent in the catalyst was 80 wt%.
Example 8
4.68g of the metallocene prepared in example 1 (468 g/mol) and 198g of tributylaluminum (198 g/mol) were added to 1824g of the alkylate and stirred well to obtain a catalyst composition. Metallocene: the molar ratio of metal alkyl is 1: 100. The solvent accounts for 90wt% of the catalyst.
Example 9
4.68g of the metallocene prepared in example 1 (468 g/mol) and 19.8g of tributylaluminum (198 g/mol) were added to 36.7g of the alkylate, and stirred uniformly to obtain a catalyst composition. Metallocene: the molar ratio of metal alkyls is 1: 10. The proportion of the solvent in the catalyst was 60% by weight.
Examples 10 to 13
The oligomerization of n-butene was carried out in an autoclave equipped with electromagnetic stirring. Before reaction, the autoclave is cleaned, heated in an oil bath at 140 ℃ and vacuumized to negative pressure, and kept for 0.5 h. The autoclave was charged with high-purity nitrogen gas and evacuated again, and this was repeated three times. The reaction kettle was cooled to the reaction temperature. High-purity nitrogen is filled into the autoclave, and the pressure is 3 MPa. Heating in oil bath, and stirring. And respectively connecting the liquid butene steel cylinder and the catalyst feeding tank with a metering pump, and introducing the butene and the catalyst into the high-pressure kettle through the metering pump.
The specific process conditions and reaction results are shown in table 2.
TABLE 2 Process conditions and results
Figure DEST_PATH_IMAGE004
Comparative example 1
The existing metallocene catalyst adopts n-butyl cyclopentadiene zirconium chloride metallocene and methyl aluminoxane to catalyze butene oligomerization, 4.06g of n-butyl cyclopentadiene zirconium chloride metallocene, 58g of methyl aluminoxane and 14L of liquid butene are respectively added into a high-pressure kettle, stirred and heated. The reaction conditions were a pressure of 3MPa, a temperature of 70 ℃ and a time of 2 hours. Conversion of butene 49%, C16+C20The overall selectivity was 38%.
By comparing the graded catalyst of the invention with the existing catalyst, the activity and the total selectivity of C16+ C20 of the catalyst composition of the invention can be found to be obviously better than the existing catalyst.

Claims (22)

1. An imidazole-bridged metallocene, the structural formula of which is as follows:
Figure 476147DEST_PATH_IMAGE002
wherein R1, R2 and R3 are H, CH3、C2H5、C3H7、C6H5Preferably H, CH, preferably3(ii) a M is Zr, Ti, H or the like, preferably Zr; z is Cl, Br, I, CH3、C2H5、C3H7、C4H9Is preferably Cl, Br, I or C2H5(ii) a M is the valence state-3 of M metal; n is CH2N is 1 to 3, preferably 1.
2. A method for preparing imidazole-bridged metallocene, comprising the following steps:
(1) adding cyclopentadiene into a solvent, cooling to-40-0 ℃, then dropwise adding alkyl lithium, stirring, then adding dihalogenated alkane, and continuing stirring; separating to obtain halogenated alkyl cyclopentadiene;
(2) adding imidazole, halogenated alkyl cyclopentadiene obtained in the step (1) and alkali into acetonitrile, and reacting at the temperature of 50-80 ℃; filtering, and separating liquid to obtain N, N-dicyclopentadienyl alkyl imidazole;
(3) dissolving N, N-dicyclopentadienyl alkyl imidazole in an organic solvent, cooling to-40-0 ℃, dropwise adding alkyl lithium while stirring, and stirring for reaction; then adding zirconium tetrachloride into the mixture, and stirring the mixture for reaction;
(4) and (4) draining the organic solvent in the product obtained in the step (3), adding methyl chloride for dissolving, performing solid-liquid separation, and performing distillation and concentration to obtain the imidazole bridged metallocene.
3. The method according to claim 2, wherein the molar ratio of cyclopentadiene, butyllithium, and dihaloalkane in the step (1) is 1 (0.8 to 1.2) to (0.8 to 1.2).
4. The method according to claim 2, wherein the solvent in step (1) or step (3) is one selected from tetrahydrofuran, diethyl ether, petroleum ether, N-dimethylformamide, and acetonitrile.
5. The method of claim 2, wherein the alkyl lithium in steps (1) and (3) comprises at least one of ethyl lithium, propyl lithium, and butyl lithium.
6. The method according to claim 2, wherein the dihaloalkane in step (1) is one selected from 1, 2-dihaloethane, 1, 3-dihalopropane, 1, 4-dihalobutane and 1, 5-dihalopentane, and the halogen is chlorine, bromine or iodine, preferably dihalobutane.
7. The method according to claim 2, wherein the molar ratio of imidazole, haloalkylcyclopentadiene and base in step (2) is 1 (1.8-2.4) to (1-3), and the weight ratio of imidazole to acetonitrile is 1 (10-50).
8. The preparation method according to claim 2, wherein the reaction time in the step (2) is 10-24 hours.
9. The method according to claim 2, wherein the base in the step (2) is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
10. The method according to claim 2, wherein the molar ratio of N, N-dicyclopentadienyl alkyl imidazole, N-butyl lithium, zirconium tetrachloride in the step (3) is 1 (2.8-3.5) to (0.8-1.2); the weight ratio of the N, N-dicyclopentadienyl alkyl imidazole to the tetrahydrofuran is 1 (10-50).
11. The method according to claim 2, wherein the weight ratio of N, N-dicyclopentadienyl alkyl imidazole to methylene chloride in step (4) is 1 (30-80).
12. The method according to claim 2, wherein the chloromethane in step (4) is selected from dichloromethane, trichloromethane and carbon tetrachloride.
13. A metallocene catalyst comprising an imidazole-bridged metallocene according to claim 1.
14. The metallocene catalyst of claim 13, wherein the metallocene catalyst comprises an imidazole-bridged metallocene, an alkyl metal, and a solvent; imidazole bridged metallocene is used as a main catalyst, and alkyl metal is used as a cocatalyst; wherein the imidazole-bridged metallocene: the molar ratio of the metal alkyl is 1 (5-500).
15. The metallocene catalyst according to claim 14, wherein the solvent is present in the catalyst in an amount of 40 to 90wt%, preferably 60 to 80 wt%.
16. The metallocene catalyst of claim 14, wherein the metal alkyl comprises at least one of a magnesium alkyl, an aluminum alkyl, and a zinc alkyl; the alkyl magnesium is selected from at least one of diethyl magnesium, dipropyl magnesium, diisopropyl magnesium and dibutyl magnesium, the alkyl aluminum is selected from at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum and triisobutyl aluminum, and the alkyl zinc is selected from at least one of diethyl zinc, dipropyl zinc, diisopropyl zinc, dibutyl zinc and diisobutyl zinc.
17. A metallocene catalyst according to claim 14, characterized in that the metal alkyl is an aluminum alkyl, preferably triisobutylaluminum.
18. The metallocene catalyst of claim 14, wherein the solvent is at least one of tetrahydrofuran, acetonitrile, toluene, and an alkylate.
19. A process for the preparation of a metallocene catalyst as claimed in any one of claims 13 to 18.
20. An oligomerization reaction of n-butene, wherein the metallocene catalyst according to any one of claims 13 to 18 is used.
21. The oligomerization of n-butene of claim 20, comprising: after the reactor is deoxygenated, the butene and the catalyst composition are added into the reactor, polymerization is carried out at a certain reaction temperature and reaction pressure, and the polyolefin is obtained after the reaction product is separated.
22. The n-butene oligomerization reaction according to claim 21, wherein the reaction temperature is 40 to 100 ℃, the reaction time is 1 to 8 hours, and the reaction pressure is the saturated vapor pressure of each component in the reaction system at the reaction temperature.
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