CN117563670A - Ethylene oligomerization catalyst and application thereof - Google Patents

Ethylene oligomerization catalyst and application thereof Download PDF

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CN117563670A
CN117563670A CN202311306820.9A CN202311306820A CN117563670A CN 117563670 A CN117563670 A CN 117563670A CN 202311306820 A CN202311306820 A CN 202311306820A CN 117563670 A CN117563670 A CN 117563670A
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chromium
ligand
catalyst
acid
ethylene
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吕英东
李小冬
刘建峰
范天熙
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Wanhua Chemical Group Co Ltd
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    • 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
    • B01J31/1845—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 phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • 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
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides an ethylene oligomerization catalyst and application thereof, comprising a chromium source, a cocatalyst and a ligand, wherein the ligand is perfluorophenyl boron salt with the following structure:

Description

Ethylene oligomerization catalyst and application thereof
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to an ethylene oligomerization catalyst and application thereof.
Background
1-octene is mainly used for producing high-end PE and POE, and is used as a raw material for producing plasticizers, alcohols for detergents and lubricating oil additives, and is an important organic raw material and a chemical intermediate. At present, ethylene selective oligomerization is one of the main methods for industrially preparing linear 1-octene. The patent CN100548946C adopts PNP ligand, chromium source and methylaluminoxane to form a catalytic system, so that ethylene selective tetramerization is realized, the selectivity of 1-octene in the product reaches 70%, and the industrial production of 1-octene is realized.
However, in the prior art, in the production process of producing 1-octene by ethylene selective tetramerization, a large amount of methylaluminoxane is required to be used as a cocatalyst, and the Al/Cr ratio is generally 200:1-1000:1. The cost of the methylaluminoxane is higher, and reaches thousands yuan per ton of 1-octene, so that the profitability level of the 1-octene product is reduced. In addition, a small amount of ethylene high polymer is produced in the production process, equipment and meters are blocked, the equipment and the meters are stopped periodically, the blockage is removed, and the running cost of the device is increased.
In order to overcome the defects in the existing production process, a new ethylene oligomerization catalyst, a preparation method and application thereof are developed, the consumption of a cocatalyst and a high polymer byproduct are reduced, and the catalyst has very positive significance.
Disclosure of Invention
The invention aims to provide an ethylene oligomerization catalyst and application thereof, and the ligand can be matched with metal chromium to obtain a chromium catalyst, so that ethylene can be subjected to a tetramerization reaction with high selectivity to prepare 1-octene, the usage amount of the cocatalyst can be obviously reduced, the yield of the 1-octene is high, and the content of byproducts is low.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an ethylene oligomerization catalyst comprises a chromium source, a cocatalyst and a ligand, wherein the ligand is a perfluorophenyl boron salt with the following structure:
wherein n is 1-4;
in the invention, the ligand is prepared by reacting a ligand precursor with lithium tetrakis (pentafluorophenyl) borate and an acid, wherein the ligand precursor has the following structure or hydrochloride thereof:
wherein n is 1 to 4.
The acid is selected from one or more of hydrochloric acid, sulfuric acid and hydrobromic acid.
The synthetic route is as follows:
preferably, the ligand precursor is combined with lithium tetrakis (pentafluorophenyl) borate and H in an acid + The molar ratio of (2) is 1:1:1-1:1.05:1.05, and the reaction can be carried out at normal temperature and normal pressure. Further, the ligand precursor is prepared by reacting amine shown in a formula I with diphenyl phosphine chloride in the presence of an acid binding agent, wherein the structural formula of the amine shown in the formula I isWherein n is 1 to 4.
Preferably, the acid binding agent is triethylamine.
The synthetic route is as follows:
preferably, the molar ratio of the amine shown in the formula I to the diphenyl phosphine chloride is 1:1.95-1:2.05, the dosage of the acid binding agent is 4-6 times of the molar amount of the diphenyl phosphine chloride, the reaction temperature is 0-5 ℃, and the reaction pressure is normal pressure.
In the invention, the chromium source is selected from one or more of chromium acetylacetonate, chromium trichloride, chromium (III) octoate and chromium hexacarbonyl; chromium acetylacetonate or chromium octoate is preferred.
In the invention, the cocatalyst is aluminum alkyl or aluminoxane, preferably aluminum alkyl, and the aluminum alkyl is selected from one or more of trimethylaluminum, triethylaluminum or triisobutylaluminum.
In the process of ethylene oligomerization catalyzed by chromium-based catalysts, the role of the auxiliary alkyl aluminum or aluminoxane is generally considered to be as follows: (1) capturing anions on a chromium source to form a cation active center; (2) as an anionically stabilized cationic active center; (3) and removing trace water and oxygen impurities in the reaction system. In theory, no extra promoter is needed to achieve these three effects, but in practice the promoter needs to be in excess of several hundred times to achieve the desired catalytic activity. The catalyst and the cocatalyst form an anion-cation pair, and the distance between the anion-cation pair is required to be proper to generate catalytic activity. Too close a distance, is unfavorable for the coordination of ethylene and has low activity; too far distance, the catalyst cation is unstable and easy to deactivate. Sufficient promoter must be present to ensure that a sufficient amount of highly active cation-anion pair active sites are formed.
In the invention, by introducing tetra (pentafluorophenyl) boron salt into the ligand, after the ligand is coordinated with metal chromium, the appropriate distance between the active center chromium atom and the tetra (pentafluorophenyl) boron salt is kept, so that a high-activity anion-cation pair active center is just formed, and the generation of ethylene high polymer can be effectively reduced.
In the invention, the molar ratio of the ligand to Cr is 1:1-5:1; preferably 3:1 to 4:1.
In the invention, the molar ratio of Al to Cr in the cocatalyst is 5:1 to-20:1; preferably 10:1 to 15:1; the additionally added cocatalyst mainly plays a role in removing impurities such as trace water, oxygen and the like in the system, so that the cheap trialkylaluminum is used, and high-price methylaluminoxane or modified methylaluminoxane is not needed.
The invention also provides application of the catalyst in ethylene selective oligomerization.
Further, the reaction may be carried out in a stainless steel reaction vessel. Before the reaction, the reaction kettle is heated to 110-130 ℃, vacuumized, replaced by nitrogen during the period, and cooled to room temperature.
Adding a dehydrated and deoxidized reaction solvent and a cocatalyst under inert atmosphere, stirring, adding the ligand and the chromium source after the temperature is constant, introducing hydrogen to 0.1-0.8Mpa, continuously introducing ethylene, maintaining the pressure of a reaction kettle to 3-6MPaG, and reacting for 10-40 min at 30-60 ℃. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the kettle is discharged to obtain an ethylene oligomerization product.
Preferably, the molar concentration of chromium in the system is 0.25-0.85mmol/L based on the molar amount of Cr;
further, the reaction solvent is one or more of cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane and n-heptane.
Compared with the prior art, the method of the invention has the advantages that the cocatalyst can use the alkyl aluminum with lower price, the production cost is reduced, the using amount of the cocatalyst can be reduced to 5:1-20:1, and the catalytic activity is more than or equal to 1 multiplied by 10 6 g product/(molCr.h), ethylene polymer is less than or equal to 0.02%.
Detailed Description
The process according to the invention is further illustrated by the following specific examples, but the invention is not limited to the examples listed but encompasses any other known modifications within the scope of the claims.
Gas Chromatography (GC): model Agilent WAX 1701.42249; the carrier gas is high-purity nitrogen; the sample injection mode is an automatic sample injector; the nitrogen flow is 64.5ml/min; the temperature of the vaporization chamber is 280 ℃; split sample introduction, wherein the split ratio is 1:40; the sample injection amount is 0.2 mu l; the column flow rate was 1.5ml/min; the column temperature is first-order programmed temperature, the initial temperature is 50 ℃, the temperature is kept for 2 minutes, then the temperature is increased to 200 ℃ at the speed of 10 ℃/min, and the temperature is kept for 15 minutes; the detector temperature was 300 ℃; the external standard method is selected for quantification and is used for quantitative analysis of 1-octene, 1-hexene and other oligomerization short-chain products.
The raw material sources are as follows: n, N-dimethyl-1, 2-ethylenediamine (CAS 108-00-9), shanghai Michlin Biochemical technologies Co., ltd
N, N-dimethyl-1, 3-propanediamine (CAS 109-55-7), shanghai Michelin Biochemical technologies Co., ltd
N, N-dimethyl-1, 4-butanediamine hydrochloride (CAS 65592-37-2), shanghai Jizhui Biochemical technology Co., ltd
N, N-dimethyl-1, 5-pentanediamine (CAS 3209-46-9), shanghai Jizhui Biochemical technology Co., ltd
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (CAS 118612-00-3) Suzhou Binmu New Material Co., ltd
Lithium tetrakis (pentafluorophenyl) borate (CAS 2797-28-6) New Stokes materials Inc. in Suzhou
Preparation of the ligand:
ligand 1 precursor preparation: n, N-dimethyl-1, 2-ethylenediamine (0.2 mol) was added to 500mL of methylene chloride under nitrogen protection, stirred, cooled to 0 ℃, excess triethylamine (2 mol) was added, and stirred for 5 minutes to mix uniformly. To the mixture was added dropwise diphenyl phosphorus chloride (0.4 mol) while maintaining the temperature of the reaction solution at not more than 5 ℃. After the completion of the dropwise addition, the reaction was returned to room temperature and reacted for 12 hours. And after the reaction is finished, filtering, and removing the solvent from the filtrate to obtain a crude product solid. The crude product was purified by column chromatography (eluent is a mixture of methanol and ethyl acetate in a volume ratio of 1:30) to give ligand 1 precursor in 53% yield. 1 H-NMR(400MHz,CDCl 3 ,25℃):δ＝7.42-7.24ppm(m,20H),3.43(m,2H),1.96(m,8H). 31 P-NMR(162MHz,CDCl 3 ,25℃):δ＝63.7ppm(s).
Ligand 2 precursor preparation: according to the ligand 1 precursor preparation method, N-dimethyl-1, 2-ethylenediamine is replaced by N, N-dimethyl-1, 3-propylenediamine, and the ligand 2 precursor is obtained in a yield of 70%. 1 H-NMR(400MHz,CDCl 3 ,25℃):δ＝7.40-7.21ppm(m,20H),3.29(m,2H),1.84(s,6H),1.82(t,2H, 3 J HH ＝2.0Hz),1.26(m,2H). 31 P-NMR(162MHz,CDCl 3 ,25℃):δ＝63.0ppm(s).
Ligand 3 precursor preparation: according to the ligand 1 precursor preparation method, N-dimethyl-1, 2-ethylenediamine is replaced by N, N-dimethyl-1, 4-butanediamine hydrochloride to obtain ligand 3 precursor with a yield of 78%. 1 H-NMR(400MHz,CDCl 3 ,25℃):δ＝7.40-7.20ppm(m,20H),3.28(m,2H),2.04(s,6H),1.84(m,2H),1.09(m,4H). 31 P-NMR(162MHz,CDCl 3 ,25℃):δ＝62.5ppm(s).
Ligand 4 precursor preparation: according to the ligand 1 precursor preparation method, N-dimethyl-1, 2-ethylenediamine is replaced by N, N-dimethyl-1, 5-pentanediamine, to obtain ligand 4 precursor in 77% yield. 1 H-NMR(400MHz,CDCl 3 ,25℃):δ＝7.40-7.20ppm(m,20H),3.26(m,2H),2.68(m,2H),2.22(s,6H),1.88(m,2H),1.04(m,4H). 31 P-NMR(162MHz,CDCl 3 ,25℃):δ＝62.3ppm(s).
Ligand 1 preparation: to a dichloromethane solution (600 mL) of ligand 1 precursor (0.1 mol) under nitrogen atmosphere was added dropwise HCl ethyl acetate solution (0.1 mol) at room temperature, and the mixture was stirred for 10min after the completion of the addition. The reaction solution was added dropwise to a dichloromethane solution (400 mL) of lithium tetrakis (pentafluorophenyl) borate (0.1 mol), and the reaction was completed for 2 hours. After the reaction was completed, the solid was washed with 200mL of methylene chloride, and the filtrate was combined with the washing solution and concentrated to 400mL. 400mL of n-hexane was added to the concentrate, and the distillation was continued to remove residual methylene chloride, whereby a solid was precipitated. After distillation, filtration and drying of the solid at 100℃overnight under vacuum gave ligand 1 in 85% yield.
Ligand 2 preparation: ligand 2 was obtained by replacing ligand 1 precursor with ligand 2 precursor according to the preparation method of ligand 1.
Ligand 3 preparation: ligand 3 was obtained by replacing ligand 1 precursor with ligand 3 precursor according to the preparation method of ligand 1.
Ligand 4 preparation: ligand 4 was obtained by replacing ligand 1 precursor with ligand 4 precursor according to the preparation method of ligand 1.
Example 1
Oligomerization of ethylene: before the reaction, the reaction kettle is heated to 120 ℃, vacuumized for 3 hours, replaced by nitrogen for three times during the period, cooled to room temperature, added with 200mL of dehydrated and deoxidized methylcyclohexane and quantitative aluminum alkyl, stirred, and added with ligand 1 and chromium octoate after the temperature is constant. Introducing hydrogen to 0.4Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 4.5MPaG, and reacting at 45 ℃ for 60min. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the reaction product is obtained after the kettle is discharged. The amounts of ligand 1 and chromium octoate added are shown in Table 1.
Examples 2 to 7
According to example 1, the oligomerization was carried out under different conditions with the addition of different ligands, the reaction conditions being shown in Table 1.
Comparative example 1
Oligomerization was performed using ligand 1 precursor.
Oligomerization of ethylene: before the reaction, heating the reaction kettle to 120 ℃, vacuumizing for 3 hours, replacing nitrogen for three times during the reaction, cooling to room temperature, adding 200mL of dehydrated and deoxidized methylcyclohexane and quantitative aluminum alkyl, stirring, adding ligand 1 precursor and chromium octoate after the temperature is constant, introducing hydrogen to 0.4Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 4.5MPaG, and reacting at the temperature of 45 ℃ for 60 minutes. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the reaction product is obtained after the kettle is discharged.
Comparative example 2
Oligomerization was carried out using the ligand 1 precursor and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
Oligomerization of ethylene: before the reaction, heating the reaction kettle to 120 ℃, vacuumizing for 3 hours, replacing nitrogen for three times during the reaction, cooling to room temperature, adding 200mL of dehydrated and deoxidized methylcyclohexane and quantitative aluminum alkyl, stirring, after the temperature is constant, adding ligand 1 precursor, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and chromium octoate, introducing hydrogen to 0.4Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 4.5MPaG, and reacting at 45 ℃ for 30 minutes. Then, the ethylene inlet valve is closed, the temperature is quickly reduced by using a low-temperature circulating water bath, the pressure is slowly released, and the reaction product is obtained after the kettle is discharged.
TABLE 1 reaction conditions for examples 2-8 and comparative examples 1-2
TABLE 2 comparison of the reaction results for examples 1-7 and comparative examples 1-2
1-C6 represents 1-hexene, other C6 represents alkane/alkene having 6 carbon atoms except 1-C6, 1-C8 represents 1-octene, C4+C10+ represents alkane/alkene having 4 and more than 10 carbon atoms, and PE represents polymer.
All modifications and equivalent substitutions to the technical proposal of the invention are included in the protection scope of the invention without departing from the scope of the technical proposal of the invention.

Claims (8)

1. The ethylene oligomerization catalyst is characterized by comprising a chromium source, a cocatalyst and a ligand, wherein the ligand is a perfluorophenyl boron salt with the following structure:
wherein n is 1 to 4.
2. The catalyst of claim 1, wherein the ligand is prepared by reacting a ligand precursor with lithium tetrakis (pentafluorophenyl) borate and an acid, the ligand precursor having the structure:
wherein n is 1-4;
preferably, the acid is selected from one or more of hydrochloric acid, sulfuric acid and hydrobromic acid;
preferably, the ligand precursor, lithium tetrakis (pentafluorophenyl) borate and H in the acid + The molar ratio of (2) is 1:1:1-1:1.05:1.05.
3. The catalyst of claim 2 wherein the ligand precursor is prepared by reacting an amine of formula i with diphenyl phosphine chloride in the presence of an acid binding agent, wherein the amine of formula i has the formula
Wherein n is 1 to 4.
4. A catalyst according to claim 3, wherein the acid binding agent is triethylamine;
preferably, the molar ratio of the amine shown in the formula I to the diphenyl phosphine chloride is 1:1.95-1:2.05;
preferably, the dosage of the acid binding agent is 4-6 times of the molar quantity of diphenyl phosphorus chloride;
preferably, the reaction temperature of the amine shown in the formula I and diphenyl phosphine chloride is 0-5 ℃, and the reaction pressure is normal pressure.
5. The catalyst according to any one of claims 1 to 4, wherein the chromium source is selected from one or more of chromium acetylacetonate, chromium trichloride, chromium tris (tetrahydrofuran) trichloride, chromium (III) octoate, chromium hexacarbonyl; chromium acetylacetonate or chromium octoate is preferred;
preferably, the cocatalyst is an aluminum alkyl or an aluminoxane, preferably an aluminum alkyl;
preferably, the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
6. The catalyst of any one of claims 1 to 5, wherein the molar ratio of ligand to chromium is from 1:1 to 5:1; preferably 3:1 to 4:1;
preferably, the molar ratio of Al to chromium in the cocatalyst is 5:1:20:1; preferably 10:1 to 15:1.
7. Use of a catalyst according to any one of claims 1 to 6 in the selective oligomerization of ethylene.
8. The use according to claim 7, characterized by the steps of: adding a dehydrated and deoxidized reaction solvent and a cocatalyst under inert atmosphere, stirring, adding the ligand and the chromium source according to any one of claims 1-7, introducing hydrogen to 0.1-0.8Mpa, continuously introducing ethylene, maintaining the pressure of the reaction kettle to 3-6Mpa, and reacting at 30-60 ℃ for 10-40 min;
preferably, the molar concentration of chromium in the system is 0.25-0.85mmol/L based on the molar amount of Cr;
preferably, the reaction solvent is one or more of cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane and n-heptane.
CN202311306820.9A 2023-10-10 2023-10-10 Ethylene oligomerization catalyst and application thereof Pending CN117563670A (en)

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