CN113600241A - Catalyst system for selective trimerization of ethylene and preparation and application thereof - Google Patents

Catalyst system for selective trimerization of ethylene and preparation and application thereof Download PDF

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CN113600241A
CN113600241A CN202110661563.5A CN202110661563A CN113600241A CN 113600241 A CN113600241 A CN 113600241A CN 202110661563 A CN202110661563 A CN 202110661563A CN 113600241 A CN113600241 A CN 113600241A
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catalyst system
ethylene
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ligand
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CN113600241B (en
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张军
赵兴
马旭峰
刘瑶
孔维欢
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East China University of Science and Technology
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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
    • B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • 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
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    • 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
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    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a catalyst system for selective trimerization of ethylene, and a preparation method and application thereof, wherein the catalyst system comprises a ligand, a transition metal compound and an activator, wherein the chemical structural formula of the ligand is shown as the following formula (I):
Figure DDA0003115557000000011
in the formula, the group R1To R8Each independently is halogen, substituted hydrocarbyl, substituted heterohydrocarbyl, hydrogen, hydrocarbyl, or heterohydrocarbyl; radical R9And R10Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group. The catalyst provided by the inventionThe catalyst system has the advantages of simple ligand synthesis, easily obtained raw materials, stable property and low cost, and simultaneously the catalyst has high catalytic ethylene selectivity oligomerization activity, high 1-hexene selectivity and low solid polymer content, can meet the requirements of industrial departments, and has important application value.

Description

Catalyst system for selective trimerization of ethylene and preparation and application thereof
Technical Field
The invention belongs to the technical field of ethylene oligomerization, and relates to a catalyst system for selective ethylene trimerization, and preparation and application thereof.
Background
Linear alpha-olefins (LAO) are used as important chemical raw materials for preparing lubricating oil, surfactant and the like, wherein 1-hexene and 1-octene are indispensable comonomers in synthesizing Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE) (the comonomer content in LLDPE is generally 8-10%, and the comonomer content in HDPE is 1-2%). Ethylene oligomerization is used as an important method for producing linear alpha-olefin, has greatly improved product quality compared with the traditional methods such as wax cracking, coal extraction, extraction separation and the like, and is widely applied to industrial production.
The traditional ethylene oligomerization catalysis mainly uses metallic titanium system, zirconium system, iron system and the like, and the catalytic systems mainly follow a Cossee-Arlman mechanism, namely, ethylene molecules are inserted into the metal center of a catalyst to grow linear chains, the obtained linear alpha-olefin is normally distributed, and the linear alpha-olefin is separated and purified according to the requirements in industrial application. The ethylene high-selectivity oligomerization mainly follows a metal cyclization mechanism, so that the produced alpha-olefin is in Schulz-Flory distribution, the product at the peak has higher content, and the method provides an important way for producing the alpha-olefin with specific carbon number. In recent years, the increase of the demand of 1-hexene and 1-octene makes the selective oligomerization of ethylene become a hot spot for industrial and academic research.
At present, the reports of ethylene high-selectivity oligomerization mainly include dimerization, trimerization and tetramerization for preparing 1-butene, 1-hexene and 1-octene. In these catalytic systems, the structural regulation of the catalyst plays a key role in product distribution, and the regulation of the catalyst structure depends on the change of the skeleton and the substituent of the ligand. In recent years, research in the field focuses on ethylene selective oligomerization catalysis mechanism and ligand design, and some important achievements are achieved. In 2002, the company British Petroleum reported that the Cr/PNP catalytic system was used for the selective preparation of 1-hexene (chem. Commun.2002, 858). In 2003, Phillips Petroleum utilizes a developed Phillips chromium trimerization catalyst to realize the industrialization of ethylene trimerization (US5523507), and similar catalytic systems are also successively adopted in China for petrochemical (Yanshan mountain) and medium Petroleum (Daqing) to realize the industrial production of 1-hexene. In 2004, the company Sasol developed an ethylene selective tetramerisation catalytic system using Cr/PNP catalysts (WO 2004056478). However, ethylene trimerization/tetramerization catalyst systems mainly use diphosphine ligands, and other types of ligands, such as P, N-ligands, are only reported. In 2012, Sydora topic group reported the synthesis of an N-phosphinamidine ligand and its application to selective trimerization/tetramerization of ethylene (ACS cat. 2012,2,2452), with 1-hexene selectivity reaching 95%. In 2015, a group of Radcliffe subjects synthesize phosphonomethylamine ligands (ACS Catal.2015,5,7095) for the first time, the biting angle of the ligands is small when the ligands are coordinated with Cr, and the ethylene tetramerization selectivity reaches 61% by regulating and controlling substituent groups on the ligands. In conclusion, the P, N-type ligand has good effect on catalyzing ethylene trimerization/tetramerization reaction, so that the novel P, N-type ligand is designed, the framework range of the ligand is widened, and the important research significance and industrial application value are achieved.
Disclosure of Invention
The invention aims to provide a catalyst system for selective ethylene trimerization and preparation and application thereof, wherein the catalyst system has the advantages of simple ligand synthesis, easily obtained raw materials, stable property and low cost, and simultaneously has high activity of catalyzing selective ethylene oligomerization, high 1-hexene selectivity and low solid polymer content, can meet the requirements of industrial departments, and has important application value.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a catalyst system for selective trimerization of ethylene, which comprises a ligand, a transition metal compound and an activator, wherein the chemical structural formula of the ligand is shown as the following formula (I):
Figure BDA0003115556990000021
in the formula, the group R1To R8Each independently is halogen, substituted hydrocarbyl, substituted heterohydrocarbyl, hydrogen, hydrocarbyl, or heterohydrocarbyl; radical (I)R9And R10Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group.
Further, the group R1、R2、R3、R4、R5、R6、R7、R8Each independently is hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-methylbenzyl, m-methylbenzyl, p-tert-butylbenzyl, m-tert-butylbenzyl, o-tert-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, o-isopropylbenzyl, p-fluorophenyl, o-fluorophenyl, m-fluorophenyl, p-ethylphenyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
Further, R9、R10Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-methylbenzyl, m-methylbenzyl, p-tert-butylbenzyl, m-tert-butylbenzyl, o-tert-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, o-isopropylbenzyl, p-fluorophenyl, o-fluorophenyl, m-fluorophenyl, p-ethylphenyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylPhenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
Further, the transition metal in the transition metal compound is selected from one of iron, cobalt, nickel, copper, titanium, vanadium, chromium, manganese, molybdenum, tungsten, nickel or palladium.
Further, the activating agent is one or a mixture of more of an alkyl aluminum compound, an aluminoxane compound and an organoboron compound.
Further, the molar ratio of the ligand to the transition metal element in the transition metal compound is (0.01-100): 1.
Further, the molar ratio of the activating agent to the transition metal element in the transition metal compound is (1-10000): 1.
The second technical scheme of the invention provides a preparation method of the catalyst system for selective trimerization of ethylene, which is characterized in that the ligand, the transition metal compound and the activator are mixed in advance or directly added into a reaction system for in-situ synthesis to obtain the target product catalyst system.
The third technical scheme of the invention provides application of a catalyst system for selective trimerization of ethylene, which is characterized in that the catalyst system is used for selective trimerization of ethylene to generate 1-hexene.
Further, when the catalyst system is used in an ethylene selective trimerization reaction, the reaction is carried out in an inert solvent; the temperature of the reaction is 0 ℃ to 200 ℃; the reaction pressure is 0.1MPa to 50 MPa; the concentration of the transition metal in the transition metal compound in the inert solvent is 0.01. mu. mol/L to 10000. mu. mol/L. More preferably, the inert solvent is one or a mixture of several of alkane, aromatic hydrocarbon, alkene or ionic liquid.
Compared with the prior art, the catalytic system for selective oligomerization of ethylene has the following advantages:
(1) the catalytic system has high catalytic activity, and the total selectivity of 1-hexene and 1-octene reaches 90%, 1-butene and 1-C10 +The mass percentage content is lower;
(2) the catalyst is simple to synthesize, the raw materials are easy to obtain, the cost is low, the requirements of industrial departments can be met, and the catalyst has important application value.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The catalyst system of the present invention will be explained below.
The ligand in the catalyst system of the present invention may be represented by the following formula (I):
Figure BDA0003115556990000041
in the formula, the group R1To R8Each independently is hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl; r9And R10Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group.
In some embodiments, R1、R2、R3、R4、R5、R6、R7、R8Can be independently hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-methylbenzyl, m-methylbenzyl, p-tert-butylbenzyl, m-tert-butylbenzyl, o-tert-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, o-isopropylbenzyl, p-fluorophenyl, o-fluorophenyl, m-fluorophenyl, p-ethylphenyl, o-ethylphenylPhenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
Preferably, R1、R2、R3、R4、R5、R6、R7、R8Can be independently selected from hydrogen, chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthracenyl, biphenyl, dimethylamino, diisopropylamine, trimethylsilyl, tributylsilyl or triphenylsilyl.
More preferably, R1、R2、R3、R4、R5、R6、R7、R8Can be independently selected from hydrogen, methyl, ethyl, n-butyl, isopropyl, cyclopentyl, cyclohexyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, tert-butyloxy, benzyl, phenyl, o-methylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl or trimethylsilyl.
In some embodiments, R9、R10Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylA phenylbenzyl group, an o-methylbenzyl group, a m-methylbenzyl group, a p-t-butylbenzyl group, a m-t-butylbenzyl group, an o-t-butylbenzyl group, a p-isopropylbenzyl group, a p-fluorophenyl group, an o-fluorophenyl group, a m-fluorophenyl group, a p-ethylphenyl group, an o-ethylphenyl group, a m-ethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 4-diisopropylphenyl group, a 2, 4-di-t-butylphenyl group, a 2, 6-dimethylphenyl group, a 2, 6-diisopropylphenyl group, a 3, 5-dimethylphenyl group, a 3, 5-di-t-butylphenyl group, a 2,4, 6-trimethylphenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a dimethylamino group, a diisopropylamino group, a trimethylsilyl group, a tributylsilyl group or a triphenylsilyl group.
Preferably, R9、R10Can be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthracenyl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
More preferably, R9、R10Can be independently selected from methyl, ethyl, n-butyl, isopropyl, cyclopentyl, cyclohexyl, 2, 6-dimethyl cyclohexyl, adamantyl, methoxy, tert-butyloxy, benzyl, phenyl, o-methylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl or trimethylsilyl.
In some embodiments, the ligand compound is one of the following, but it is to be understood that the scope of the invention is not limited to these examples:
Figure BDA0003115556990000061
Figure BDA0003115556990000071
Figure BDA0003115556990000081
the transition metal in the catalyst system of the present invention may be a transition metal compound commonly used in the art, and the metal atom in the transition metal compound is a metal active center and plays an important role in the catalytic process.
In some embodiments, the transition metal in the transition metal compound is selected from one of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium. Preferably, the transition metal in the transition metal compound is selected from one of chromium, cobalt, titanium, iron, nickel or palladium. More preferably, the transition metal of the transition metal compound is selected from chromium, in particular the corresponding transition metal compound is any chromium compound which enables oligomerization, and alternative chromium compounds include those of the formula CrRnA compound of the formula wherein RnIs an organic anion or a neutral molecule, RnWherein the carbon atoms are generally 1-15, n is an integer of 0-6, and the valence of Cr is 0-6. Specific RnThe group is an organic matter containing carboxyl, beta-diketone group and alkyl or other groups. From the viewpoint of easy dissolution and easy handling, a preferable chromium compound includes one of chromium trichloride-tris (tetrahydrofuran) complex, (benzene) chromium tricarbonyl, chromium (III) octanoate, chromium hexacarbonyl, chromium (III) acetylacetonate, chromium (III) naphthenate, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) 2,2,6, 6-tetramethylheptanedionate, and chromium (III) chloride. Preferably, the chromium compound is selected from chromium trichloride-tris (tetrahydrofuran) complex, chromium (III) acetylacetonate, chromium (III) 2-ethylhexanoate.
The activator in the catalyst system of the present invention acts as an activator in the catalyst system. The activators useful in the present invention can be any compound that forms an active catalyst when mixed with the ligand and the transition metal compound. The activators may be used alone or in combination.
In some embodiments, the activator is selected from an alkylaluminum compound, an aluminoxane compound, an organoboron compound, an inorganic acid, or an inorganic salt.
In particular, the activator may be an alkylaluminum compound, which may be various trialkylaluminums, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum; the alkylaluminum compound can also be an alkylaluminum halide, alkylaluminum hydride or alkylaluminum sesquichloride, such as diethylaluminum monochloride (AlEt)2Cl) and triethylaluminum trichloride (A1)2Et3C13)。
Specifically, the activator may be an alumoxane compound, which may be generally prepared by mixing water with an alkyl aluminum compound (e.g., trimethylaluminum). The aluminoxane oligomer compound prepared may be a linear compound, a cyclic compound, a cage compound or a mixture thereof. Suitable aluminoxane compounds can be selected from Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, modified aluminoxanes and methylaluminoxane DMAO, etc., which have volatile components removed.
Specifically, suitable boron compounds may include boroxine, triethylborane, triphenylborane, tris (pentafluorophenyl) borane, and the like. The organoboron compound may be used in a form of being mixed with the organoaluminum compound.
Preferably, the activator may be selected from Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane and Modified Methylaluminoxane (MMAO).
In some embodiments, the molar ratio of the ligand to the transition metal element in the transition metal compound may be 0.01: 1 to 100: 1.
preferably, the molar ratio of the ligand to the transition metal element in the transition metal compound may be 0.1: 1 to 10: 1.
more preferably, the molar ratio of the ligand to the transition metal element in the transition metal compound may be 0.5: 1 to 2: 1.
in some embodiments, the molar ratio of activator to transition metal may be 1: 1 to 10000: 1.
preferably, the molar ratio of the activator to transition metal may be 1: 1 to 2000: 1.
the preparation of the catalyst system of the invention is described further below:
in some embodiments, the ligand of formula (I), the transition metal compound, and the activator may be mixed simultaneously or in any order, with or without a solvent, to provide an active catalyst. The mixing of the catalyst components may be carried out at-20 ℃ to 250 ℃, and the presence of the olefin during the mixing of the catalyst components generally shows a protective effect, thereby providing improved catalytic performance. Further, the mixing of the catalyst components may be carried out at a temperature in the range of about 20 ℃ to 100 ℃.
In some embodiments, the isolatable metal-ligand complex can be prepared in situ from a transition metal compound and a ligand of formula (I). The metal-ligand complex is then added to the reaction medium. Alternatively, the chromium compound and the ligand may be added separately to the reactor, thereby preparing the chromium-ligand complex in situ. Preparing the complex in situ means preparing the complex in a medium in which the catalytic reaction takes place and, finally, adding an activator.
The use of the catalyst system of the present invention in ethylene oligomerization reactions is further described below.
The invention also provides an application of the catalyst system for ethylene selective oligomerization, in particular an application of the catalyst system in preparation of 1-hexene by ethylene selective trimerization. In the specific application process, the ethylene oligomerization is carried out in an inert solvent, wherein the inert solvent can be alkane, arene, alkene or ionic liquid. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, fluorobenzene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, 1-octene, etc., preferably toluene, methylcyclohexane.
In some embodiments, the reaction temperature for ethylene oligomerization is from 0 ℃ to 200 ℃, preferably from 10 ℃ to 120 ℃, more preferably from 20 ℃ to 100 ℃.
In some embodiments, the pressure of the oligomerization of ethylene may be carried out at a pressure of from 0.1MPa to 50MPa, preferably from 1.0MPa to 10 MPa.
In some embodiments, the concentration of the catalyst in the reaction system may be from 0.01. mu. mol metal/L to 10000. mu. mol metal/L, preferably 1. mu. mol metal/L to 500. mu. mol metal/L, where the metal is a transition metal in the transition metal compound.
The invention will be better understood from the following examples which are set forth for the purpose of illustration and are not to be construed as limiting the invention.
Example 1:
preparation of Complex 1:
(1) compound (2,4, 6-Me)3-C6H2) Preparation of N ═ CMePh
2,4, 6-trimethylaniline (5.0g,37mmol) and acetophenone (5.4g,44.4mmol) were dissolved in toluene (30ml), p-toluenesulfonic acid (637.1mg,3.7mmol) was added to the solution, stirred, connected to a water separator and heated under reflux for 30 h. After the reaction, the reaction mixture was filtered, and the solvent was evaporated under reduced pressure to give an oily substance, which was separated by column chromatography (eluent ratio petroleum ether: ethyl acetate: 20: 1) to give 6.6g (27.6mmol, 75%) of a yellow oily product.
1H NMR(400MHz,CDCl3)δ＝8.05(d,J＝8Hz,2H),7.50(s,3H),6.90(s,2H),2.32(s,3H),2.10(s,3H),2.03(s,6H)；13C NMR(100MHz,CDCl3)δ＝165.54,146.57,139.38,131.98,130.47,128.93,128.47,127.16,125.66,20.86,18.02,17.53.
(2) Preparation of ligand L1
(2,4, 6-Me) was added to a dry argon-filled Schlenk reaction tube3-C6H2) N-CMePh (400mg, 1.69mmol) and diethyl ether (15ml), stirred and cooled to-50 deg.C, N-butyllithium (3.2ml, 1.6mol/L in N-hexane, 2.0mmol) was slowly added dropwise thereto, stirred at this temperature for one hour, stirred at room temperature for one hour, then cooled again to-50 deg.C, diisopropylphosphine chloride (0.27ml, 1.69mmol) was added,after half an hour the reaction was allowed to warm to room temperature overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20ml) was added to dissolve it, and the mixture was filtered through celite, and the filtrate was dried by suction to obtain 0.51g (1.44mmol, 85%) of a brown oily product, which was ligand L1.
Figure BDA0003115556990000111
1H NMR(400MHz,CDCl3)δ＝7.89–7.83(m,2H),7.45–7.41(m,3H),6.85(s,2H),2.66(s,2H),2.27(s,3H),1.66–1.03(m,22H).13C NMR(101MHz,CDCl3)δ＝168.89,145.85,140.27,132.07,129.88,128.74,128.23,127.78,126.08,33.92,29.91,28.96,27.15,26.32,20.75,18.65.31P NMR(162MHz,CDCl3)δ＝0.77(s),-4.51(s).
(3) Preparation of Complex 1
Into a dry argon-filled Schlenk reaction tube were added ligand L1(176.7mg, 0.5mmol) and CrCl3(THF)3(187.3mg, 0.5mmol), to which was added redistilled dichloromethane (10mL) and stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was filtered, and the filtrate was dried by suction to obtain a solid, which was washed with n-hexane (5 mL. times.3), and dried by suction to obtain 262.7mg (0.45mmol, 90%) of a blue powder.
Anal.Calcd for C39H64Cl3CrNO4P(％):C,58.53；H,8.06；N,1.75.Found:C,58.91；H,7.49；N,1.98.
Example 2:
preparation of complex 2:
(1) preparation of compound (2,4,6-Me3-C6H2) N ═ CMePh
The same as in example 1.
(2) Preparation of ligand L2
(2,4, 6-Me) was added to a dry argon-filled Schlenk reaction tube3-C6H2) N-CMePh (400mg, 1.69mmol) and diethyl ether (15ml), stirred and cooled to-50 ℃, to which N-butyllithium (3.2ml, 1.6mol/L in N-hexane, 2.0mmol) was slowly added dropwise, stirred at this temperature for one hour,the reaction mixture was stirred at room temperature for one hour, then cooled again to-50 ℃ and dicyclohexylphosphonium chloride (0.37ml, 1.69mmol) was added and reacted for half an hour before returning to room temperature for overnight reaction. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20ml) was added for dissolution, and the mixture was filtered through celite, and the filtrate was dried by suction to give 510mg (1.44mmol, 85%) of a yellow oily product, which was ligand L2.
Figure BDA0003115556990000121
1H NMR(400MHz,CDCl3)1H NMR(400MHz,CDCl3)δ7.91–7.80(m,2H),7.45–7.40(m,3H),6.85(s,2H),2.66(s,2H),2.27(s,3H),2.12(s,6H),1.67–0.84(m,22H).13C NMR(101MHz,CDCl3)δ167.83,144.79,139.21,131.01,128.82,127.68,127.17,126.72,125.02,32.86,28.85,27.90,26.09,25.26,19.69,17.59.31P NMR(162MHz,CDCl3)δ＝0.77(s),-4.51(s).
(3) Preparation of Complex 2
In a dry argon-filled Schlenk reaction tube, ligand L2(216.8mg, 0.5mmol) and CrCl were added3(THF)3(187.3mg, 0.5mmol), to which was added redistilled dichloromethane (10mL) and stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was filtered, and the filtrate was dried by suction to obtain a solid, which was washed with n-hexane (5 mL. times.3), and dried by suction to obtain 288.0mg (0.43mmol, 87%) of a blue powder.
Anal.Calcd for C33H50Cl3CrNO2P(％):C,58.11；H,7.39；N,2.05.Found:C,58.01；H,7.69；N,1.83.
Example 3:
(1) compound (2-Me-C)6H4) Preparation of N ═ CMePh
2-methylaniline (3.6g,33.5mmol) and acetophenone (4.8g,40.2mmol) were dissolved in toluene (30ml), p-toluenesulfonic acid (576.9mg,3.4mmol) was added to the solution, stirred, connected to a water separator and heated under reflux for 30 h. After the reaction, the reaction mixture was filtered, and the solvent was evaporated under reduced pressure to give an oily substance, which was separated by column chromatography (eluent: 20: 1 petroleum ether: ethyl acetate) to give 4.9g (23.5mmol, 70%) of a yellow oily product.
1H NMR(400MHz,CDCl3):δ＝8.05-7.98(m,2H),7.51-7.42(m,3H),7.23-7.15(m,2H),7.01(t,J＝7.3Hz,1H),6.65(d,J＝7.8Hz,1H),2.17(s,3H),2.11(s,3H).13C NMR(100MHz,CDCl3):δ＝164.9,150.2,139.4,130.4,130.3,128.3,127.1,126.3,123.2,118.4,17.7,17.4.
(2) Preparation of ligand L3
(2-Me-C) was added to a dry argon-filled Schlenk reaction tube6H4) N ═ CMePh (400mg, 1.91mmol) and diethyl ether (15ml), stirred and cooled to-50 ℃, N-butyllithium (1.43ml, 1.6mol/L in N-hexane, 2.0mmol) was slowly added dropwise thereto, stirred at this temperature for one hour, stirred at room temperature for one hour, then cooled again to-50 ℃, dicyclohexylphosphine chloride (0.42ml, 1.91mmol) was added, reacted for half an hour, and then turned to room temperature for reaction overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20ml) was added for dissolution, and the mixture was filtered through celite, and the filtrate was dried by suction to give 665.7mg (1.64mmol, 85%) as a yellow oily product, which was ligand L3.
The product contains two geometric isomers.31P NMR(162MHz,CDCl3) δ -2.17 (major isomer), δ -5.69 (minor isomer).
Figure BDA0003115556990000131
1H NMR(400MHz,CDCl3)δ7.87–7.82(m,2H),7.36(m,3H),7.13(d,J＝7.5Hz,1H),7.09(d,J＝7.3Hz,1H),6.92(t,J＝7.5Hz,1H),6.67(d,J＝7.6Hz,1H),2.82(s,2H),2.12(s,3H),1.65–0.86(m,22H).13C NMR(101MHz,CDCl3)δ166.93,148.30,138.69,129.47,129.01,127.14,126.91,126.08,125.06,122.32,118.03,32.58,28.53,27.98,26.13,25.22,17.31.31P NMR(162MHz,CDCl3)δ＝2.26(s),-5.59(s).
(3) Preparation of Complex 3
In a dry and argon-filled containerTo a Schlenk reaction tube, ligand L3(202.6mg, 0.5mmol) and CrCl were added3(THF)3(187.3mg, 0.5mmol), to which was added redistilled dichloromethane (10mL) and stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was filtered, and the filtrate was dried by suction to obtain a solid, which was washed with n-hexane (5 mL. times.3), and dried by suction to obtain 234.6mg (0.37mmol, 74%) of a blue powder.
Anal.Calcd for C35H52Cl3CrNO2P(％):C,59.37；H,7.40；N,1.98.Found:C,59.51；H,7.29；N,2.08.
Example 4:
(1) compound (3, 5-Me)2-C6H4) Preparation of N ═ CMePh
3, 5-dimethylaniline (5g,41.3mmol) and acetophenone (6.0g,49.5mmol) were dissolved in toluene (30ml), p-toluenesulfonic acid (711.2mg,4.1mmol) was added to the solution, stirred, connected to a water separator and heated under reflux for 30 h. After completion of the reaction, the reaction mixture was filtered, and the solvent was distilled off under reduced pressure to give an oil, which was separated by column chromatography (eluent ratio petroleum ether: ethyl acetate: 20: 1) to give 6.5g (29.3mmol, 71%) of a pale yellow oily product.
1H NMR(400MHz,CDCl3)7.96–8.00(m,2H),7.44–7.48(m,3H),6.75(s,1H),6.44(s,2H),2.34(s,6H),2.25(s,3H)；13C NMR(100MHz,CDCl3)165.9,152.7,140.6,139.5,131.3,129.3,128.1,125.8,117.9,22.3,18.3.
(2) Preparation of ligand L4
(3, 5-Me) was added to a dry argon-filled Schlenk reaction tube2-C6H4) N ═ CMePh (400mg, 1.79mmol) and diethyl ether (15ml), stirred and cooled to-50 ℃, N-butyllithium (1.34ml, 1.6mol/L in N-hexane, 2.1mmol) was slowly added dropwise thereto, stirred at this temperature for one hour, stirred at room temperature for one hour, then cooled again to-50 ℃, dicyclohexylphosphine chloride (0.40ml, 1.79mmol) was added, reacted for half an hour, and then turned to room temperature for reaction overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20ml) was added for dissolution, and the mixture was filtered through celite, and the filtrate was dried by suction to give 546.5mg (1.61mmol, 90%) as a pale yellow oily product, which was ligand L4.
The product contains two geometric isomers.31P NMR(162MHz,CDCl3) δ — 3.07 (major isomer), δ — 6.34 (minor isomer).
Figure BDA0003115556990000151
1H NMR(400MHz,CDCl3)7.89–7.96(m,2H),7.42–7.46(m,3H),6.55(s,1H),6.37(s,2H),2.34(s,6H),2.10(s,2H),1.65–0.86(m,22H)；13C NMR(100MHz,CDCl3)164.8,151.6,141.7,138.5,132.3,128.4,128.1,125.7,117.3,32.58,28.53,27.98,26.13,23.22,18.31.31P NMR(162MHz,CDCl3)δ＝3.07(s),-6.34(s).
(3) Preparation of Complex 4
In a dry argon-filled Schlenk reaction tube, ligand L4(169.6mg, 0.5mmol) and CrCl were added3(THF)3(187.3mg, 0.5mmol), to which was added redistilled dichloromethane (10mL) and stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was filtered, and the filtrate was dried by suction to obtain a solid, which was washed with n-hexane (5 mL. times.3), and dried by suction to obtain 295.0mg (0.46mmol, 91%) of a blue powder.
Anal.Calcd for C35H52Cl3CrNOP(％):C,59.13；H,6.97；N,2.20.Found:C,59.06；H,7.25；N,2.06.
Example 5:
(1) compound (2-Me-6-Et-C)6H3) Preparation of N ═ CMePh
2-methyl-6-ethylaniline (5g,37.0mmol) and acetophenone (5.3g,44.4mmol) were dissolved in toluene (30ml), p-toluenesulfonic acid (637.1mg,3.7mmol) was added to the solution, stirring was carried out, and the mixture was heated under reflux in a water trap for 30 h. After the reaction, the reaction mixture was filtered, and the solvent was evaporated under reduced pressure to give an oily substance, which was separated by column chromatography (eluent ratio petroleum ether: ethyl acetate: 20: 1) to give 6.5g (27.4mmol, 74%) of a yellow oily product.
1H NMR(400MHz,CDCl3)δ8.08(dt,J＝4.3,2.6Hz,1H),7.56–7.47(m,1H),7.16–7.07(m,1H),7.01(td,J＝7.5,2.5Hz,1H),2.53–2.33(m,1H),2.12(d,J＝2.7Hz,2H),2.06(d,J＝2.3Hz,2H),1.18(td,J＝7.5,2.7Hz,2H).
(2) Preparation of ligand L5
To a dry argon-filled Schlenk reaction tube was added (2-Me-6-Et-C)6H3) N ═ CMePh (400mg, 1.69mmol) and diethyl ether (15ml), stirred and cooled to-50 ℃, N-butyllithium (1.27ml, 1.6mol/L in N-hexane, 2.0mmol) was slowly added dropwise thereto, stirred at this temperature for one hour, stirred at room temperature for one hour, then cooled again to-50 ℃, dicyclohexylphosphine chloride (0.38ml, 1.69mmol) was added, reacted for half an hour, and then turned to room temperature for reaction overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20ml) was added for dissolution, and the mixture was filtered through celite, and the filtrate was dried by suction to give 637.0mg (1.47mmol, 87%) of a pale yellow oily product, which was ligand L5.
The product contains two geometric isomers.31P NMR(162MHz,CDCl3) δ — 3.07 (major isomer), δ — 6.34 (minor isomer).
Figure BDA0003115556990000161
1H NMR(400MHz,CDCl3)δ7.90–7.83(m,2H),7.45–7.42(m,3H),7.08(d,J＝7.4Hz,1H),7.04(d,J＝7.2Hz,1H),6.95(t,J＝7.5Hz,1H),2.65(s,2H),2.62–2.35(m,2H),2.15(s,3H),1.92–1.40(m,22H),1.22(t,J＝7.5Hz,3H).13C NMR(101MHz,CDCl3)δ167.47,146.79,139.10,130.92,128.88,127.19,126.97,126.74,124.89,124.73,122.02,66.94,32.68,28.89,27.88,26.05,25.25,23.91,17.80,12.42.31P NMR(162MHz,CDCl3)δ0.30(s),-4.34(s).
(3) Preparation of Complex 5
In a dry argon-filled Schlenk reaction tube, ligand L5(216.8mg, 0.5mmol) and CrCl were added3(THF)3(187.3mg, 0.5mmol), to which was added redistilled dichloromethane (10mL) and stirred at room temperature for 2 h. Filtering after the reaction is finished, and draining the filtrate to obtain solid n-hexylAlkane wash (5 mL. times.3) and pump dry to give 298.0mg (0.45mmol, 90%) of blue powder.
Example 6:
1. preparation of the catalyst
To a dry argon-filled Schlenk reaction tube, complex 1(2.32mg, 4. mu. mol) was added, and after stirring for 5 minutes in redistilled methylcyclohexane (30ml), modified methylaluminoxane MMAO-3A (3.2mmol, 1.12mol/L) was added and reacted at room temperature for 5 minutes before use.
2. Oligomerization of ethylene
A120 mL stainless steel high-pressure gas reaction kettle is vacuumized for 3 hours on an oil bath at the temperature of 120 ℃ to ensure the anhydrous and oxygen-free environment of the reaction kettle, then the reaction kettle is cooled to the reaction temperature, and the built-in air of the reaction kettle is exchanged for three times by using ethylene gas. Then immediately sucking the prepared catalyst solution by a dry glass syringe and injecting the catalyst solution into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring, introducing ethylene gas, regulating the pressure to 4.0MPa, and stirring and reacting at 60 ℃ for 30 minutes. After the reaction is finished, closing the ethylene gas supply valve, cooling to 0 ℃, decompressing, opening the reaction kettle, adding quantitative internal standard nonane, and uniformly stirring. The reaction was then quenched with about 30mL of 10% aqueous HCl, and a small amount of the organic phase was filtered and analyzed by GC. The mixture remaining in the reaction kettle was filtered to obtain a solid, which was added to 10% aqueous HCl and stirred for 2 hours, filtered, dried to constant weight and weighed, the data being shown in table 1.
Example 7:
the same as example 6 except that complex 1 was replaced with complex 2(2.66mg, 4.0. mu. mol), the data are shown in Table 1.
Example 8:
the same as in example 6, except that complex 1 used was replaced with complex 3(2.52mg, 4.0. mu. mol), the data are shown in Table 1.
Example 9:
the same as in example 6, except that complex 1 used was replaced with complex 4(2.59mg, 4.0. mu. mol), the data are shown in Table 1.
Example 10:
the same as in example 6, except that complex 1 used was replaced with complex 5(2.66mg, 4.0. mu. mol), the data are shown in Table 1.
Example 11:
the same as in example 10, except that the oligomerization of ethylene was carried out at 80 ℃ and the data are shown in Table 1.
Example 12:
the same as in example 10, except that the oligomerization of ethylene was carried out at 40 ℃ and the data are shown in Table 1.
Example 13:
the same as example 10 except that MMAO-3A was used in an amount of 2.4mmol, the data are shown in Table 1.
Example 14:
the same as example 10 except that MMAO-3A was used in an amount of 4.0mmol, the data are shown in Table 1.
Example 15:
the same as in example 10 except that the reaction pressure for the oligomerization of ethylene was 2.0MPa, the data are shown in Table 1.
Example 16:
the same as in example 10 except that the reaction pressure for the oligomerization of ethylene was 1.0MPa, the data are shown in Table 1.
Table 1 catalytic data for examples 6-16
Figure BDA0003115556990000181
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A catalyst system for selective trimerization of ethylene, comprising a ligand, a transition metal compound and an activator, wherein the ligand has the chemical formula shown in the following formula (I):
Figure FDA0003115556980000011
in the formula, the group R1To R8Each independently is halogen, substituted hydrocarbyl, substituted heterohydrocarbyl, hydrogen, hydrocarbyl, or heterohydrocarbyl; radical R9And R10Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group.
2. Catalyst system for the selective trimerization of ethylene according to claim 1, characterized in that the group R1、R2、R3、R4、R5、R6、R7、R8Each independently is hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-methylbenzyl, m-methylbenzyl, p-tert-butylbenzyl, m-tert-butylbenzyl, o-tert-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, o-isopropylbenzyl, p-fluorophenyl, o-fluorophenyl, m-fluorophenyl, p-ethylphenyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
3. The catalyst system for the selective trimerization of ethylene according to claim 1, wherein R is9、R10Each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, ethoxy, isopropoxy, tert-butyloxy, benzyl, p-methylbenzyl, o-methylbenzyl, m-methylbenzyl, p-tert-butylbenzyl, m-tert-butylbenzyl, o-tert-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, o-isopropylbenzyl, p-fluorophenyl, o-fluorophenyl, m-fluorophenyl, p-ethylphenyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
4. The catalyst system for selective trimerization of ethylene according to claim 1, wherein the transition metal of the transition metal compound is selected from one of iron, cobalt, nickel, copper, titanium, vanadium, chromium, manganese, molybdenum, tungsten, nickel or palladium.
5. The catalyst system for selective trimerization of ethylene as claimed in claim 1, wherein said activator is one or a mixture of alkylaluminum compound, aluminoxane compound and organoboron compound.
6. The catalyst system for selective trimerization of ethylene according to claim 1, wherein the molar ratio of the ligand to the transition metal element in the transition metal compound is (0.01-100): 1;
the molar ratio of the activating agent to the transition metal element in the transition metal compound is (1-10000): 1.
7. The method for preparing a catalyst system for selective trimerization of ethylene according to any of the claims 1-6, wherein the ligand, the transition metal compound and the activator are premixed or directly added to the reaction system for in situ synthesis to obtain the target product catalyst system.
8. Use of a catalyst system for the selective trimerization of ethylene according to any of claims 1-6 for the selective trimerization of ethylene to 1-hexene.
9. Use of a catalyst system for the selective trimerization of ethylene according to claim 7, wherein when the catalyst system is used in the selective trimerization of ethylene, the reaction is carried out in an inert solvent; the temperature of the reaction is 0 ℃ to 200 ℃; the reaction pressure is 0.1MPa to 50 MPa; the concentration of the transition metal in the transition metal compound in the inert solvent is 0.01. mu. mol/L to 10000. mu. mol/L.
10. Use of a catalyst system for the selective trimerization of ethylene according to claim 9, wherein said inert solvent is one or a mixture of alkanes, aromatics, alkenes or ionic liquids.
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