CN113600241B - 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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CN113600241B
CN113600241B CN202110661563.5A CN202110661563A CN113600241B CN 113600241 B CN113600241 B CN 113600241B CN 202110661563 A CN202110661563 A CN 202110661563A CN 113600241 B CN113600241 B CN 113600241B
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ethylene
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CN113600241A (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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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts 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
    • B01J31/189Catalysts 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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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/32Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20Olefin oligomerisation or telomerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62Chromium
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    • Y02P20/52Improvements 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 R 1 To R 8 Each independently is halogen, substituted hydrocarbyl, substituted heterohydrocarbyl, hydrogen, hydrocarbyl, or heterohydrocarbyl; radical R 9 And R 10 Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group. The catalyst system provided by the invention has the advantages of simple ligand synthesis, easily obtained raw materials, stable property and low cost, and simultaneously has high activity of catalyzing ethylene selective oligomerization, 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, 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 substituents 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 company utilizes the developed Phillips chromium trimerization catalyst to realize the industrialization of ethylene trimerization (US 5523507), and China medium petrochemical industry (Yanshan mountain) and medium Petroleum (Daqing) also adopt similar catalytic systems successively 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 of 95%. In 2015, a Radcliffe subject group synthesizes a phosphonyl formamide ligand (ACS Catal.2015,5, 7095) for the first time, the biting angle of the ligand and Cr is small when the ligand is coordinated, and the ethylene tetramerization selectivity reaches 61% by regulating and controlling substituent groups on the ligand. In conclusion, the P, N-type ligand has a 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 R 1 To R 8 Each independently is halogen, substituted hydrocarbyl, substituted heterohydrocarbyl, hydrogen, hydrocarbyl, or heterohydrocarbyl; radical R 9 And R 10 Each independently is a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl group.
Further, the group R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each 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-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethylamino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
Further, R 9 、R 10 Each 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-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, anthracenyl, biphenyl, dimethylamino, diisopropylamine, trimethylsilyl, or trisilyl.
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 50MPa; 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, the total selectivity of 1-hexene and 1-octene reaches 90 percent, and 1-butene and 1-C 10 + 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 R 1 To R 8 Each independently hydrogen, halogen, hydrocarbonA substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group; r 9 And R 10 Each independently a hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl group.
In some embodiments, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 And may be each 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-t-butylbenzyl, p-isopropylbenzyl, m-isopropylbenzyl, 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, dimethylsilyl, trimethylsilyl, or trimethylsilyl.
Preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Each of which is independently selected from the group consisting of hydrogen, chloro, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-dimethylcyclohexyl, adamantyl, methoxy, isopropoxy, t-butyloxy, benzyl, p-methylbenzyl, o-ethylphenyl, m-ethylphenyl, 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-t-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-t-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthryl, biphenyl, dimethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclopentyl, 2-methylcyclopentyl, 2, 6-diisopropylphenyl, 2, 4-di-t-butylphenyl, 2, 5-dimethylphenyl, 3, 5-di-t-butylphenyl, naphthyl, anthryl, biphenyl, dimethyl, and the likeAmino, diisopropylamino, trimethylsilyl, tributylsilyl or triphenylsilyl.
More preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Can 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, R 9 、R 10 Each 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-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, anthracenyl, biphenyl, dimethylamino, diisopropylamine, trimethylsilyl, or trisilyl.
Preferably, R 9 、R 10 Can 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-dimethylphenyl2, 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, R 9 、R 10 Can be independently selected from 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, 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 CrR n A compound of the formula wherein R n Is an organic anion or a neutral molecule, R n Wherein the carbon atoms are 1-15, n is an integer of 0-6, and the valence of Cr is 0-6. Specific R n The 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, 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 combined 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 aluminum alkyl compound which may be a variety of 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) 2 Cl) and triethylaluminum trichloride (A1) 2 Et 3 C1 3 )。
Specifically, the activator may be an alumoxane compound, which may generally be 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 may be selected from Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, modified aluminoxanes and methylaluminoxane DMAO or the like to remove volatile components.
Specifically, suitable boron compounds may include boroxine, triethylborane, triphenylborane, tris (pentafluorophenyl) borane, and the like. The organoboron compound may be used in a form 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 application of the catalyst system of the present invention in the oligomerization of ethylene is further described below.
The invention also provides an application of the catalyst system for ethylene selective oligomerization, in particular to an application of the catalyst system in the preparation of 1-hexene through 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 reaction of ethylene may be carried out at a pressure of from 0.1MPa to 50MPa, preferably from 1.0MPa to 10MPa.
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 -C 6 H 2 ) Preparation of N = CMePh
2,4, 6-trimethylaniline (5.0 g, 37mmol) and acetophenone (5.4 g,44.4 mmol) were dissolved in toluene (30 ml), p-toluenesulfonic acid (637.1mg, 3.7 mmol) was added to the solution, stirred, and heated under reflux in a water trap for 30 hours. 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 subjected to column chromatography (eluent ratio petroleum ether: ethyl acetate: 20: 1) to separate 6.6g (27.6 mmol, 75%) of a yellow oily product.
1 H NMR(400MHz,CDCl 3 )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); 13 C 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 tube 3 -C 6 H 2 ) N = CMePh (400mg, 1.69mmol) and diethyl ether (15 ml), stirred and cooled to-50 deg.C, N-butyllithium (3.2ml, 1.6mol/L in N-hexane, 2.0 mmol) 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, reacted for half an hour, and then turned to room temperature for overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20 ml) was added for dissolution, followed by filtration 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
1 H NMR(400MHz,CDCl 3 )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). 13 C NMR(101MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )δ=0.77(s),-4.51(s).
(3) Preparation of Complex 1
Into a dry argon-filled Schlenk reaction tube, ligand L1 (176.7 mg,0.5 mmol) and CrCl were added 3 (THF) 3 (187.3mg, 0.5mmol), to which was addedThe dichloromethane (10 mL) was added and stirred at room temperature for 2h. 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 C 39 H 64 Cl 3 CrNO 4 P(%):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-Me 3-C6H 2) 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 tube 3 -C 6 H 2 ) N = CMePh (400mg, 1.69mmol) and diethyl ether (15 ml), stirred and cooled to-50 ℃, N-butyllithium (3.2 ml,1.6mol/L N-hexane solution, 2.0 mmol) 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 (0.37ml, 1.69mmol) was added, reacted for half an hour, and then turned to room temperature for overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20 ml) 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
1 H NMR(400MHz,CDCl 3 ) 1 H NMR(400MHz,CDCl 3 )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). 13 C NMR(101MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )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 added 3 (THF) 3 (187.3mg, 0.5mmol), and redistilled dichloromethane (10 mL) was added thereto and stirred at room temperature for 2 hours. After completion of the reaction, filtration was carried out, 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 C 33 H 50 Cl 3 CrNO 2 P(%):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) 6 H 4 ) Preparation of N = CMePh
2-methylaniline (3.6 g,33.5 mmol) and acetophenone (4.8g, 40.2mmol) were dissolved in toluene (30 ml), p-toluenesulfonic acid (576.9mg, 3.4 mmol) was added to the solution, and the mixture was stirred, connected to a water separator, and heated under reflux for 30 hours. After the completion of the reaction, filtration was carried out, and the solvent was distilled off under reduced pressure to obtain an oil, which was isolated by column chromatography (eluent ratio petroleum ether: ethyl acetate 20: 1) to obtain 4.9g (23.5mmol, 70%) of a yellow oily product.
1 H NMR(400MHz,CDCl 3 ):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). 13 C NMR(100MHz,CDCl 3 ):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
To a dry argon-filled Schlenk reaction tube was added (2-Me-C) 6 H 4 ) N = CMePh (400mg, 1.91mmol) and diethyl ether (15 ml), stirred and cooled to-50 deg.C, N-butyllithium (1.43ml, 1.6mol/L in N-hexane, 2.0 mmol) was slowly added dropwise thereto, stirred at this temperature for one hour, stirred to room temperature for one hour, then cooled again to-50 deg.C, dicyclohexylphosphonium chloride (0.42ml, 1.91mmol) was added, reacted for half an hour, and then allowed to react overnight to room temperature. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20 ml) was added to dissolve it, and the mixture was filtered through Celite, and the filtrate was dried by suction to obtain 665.7mg (1.6 mg) of a yellow oily product4mmol, 85%) to obtain ligand L3.
The product contains two geometric isomers. 31 P NMR(162MHz,CDCl 3 ) δ =2.17 (major isomer), δ = -5.69 (minor isomer).
Figure BDA0003115556990000131
1 H NMR(400MHz,CDCl 3 )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). 13 C NMR(101MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )δ=2.26(s),-5.59(s).
(3) Preparation of Complex 3
Into a dry argon-filled Schlenk reaction tube, ligand L3 (202.6 mg,0.5 mmol) and CrCl were added 3 (THF) 3 (187.3mg, 0.5mmol), and redistilled dichloromethane (10 mL) was added thereto and stirred at room temperature for 2 hours. 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 C 35 H 52 Cl 3 CrNO 2 P(%):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 -C 6 H 4 ) Preparation of N = CMePh
3, 5-dimethylaniline (5g, 41.3mmol) and acetophenone (6.0 g, 49.5mmol) were dissolved in toluene (30 ml), p-toluenesulfonic acid (711.2mg, 4.1mmol) was added to the solution, and the mixture was stirred, connected to a water separator, and heated under reflux for 30 hours. After completion of the reaction, filtration was carried out, and the solvent was distilled off under reduced pressure to give an oil, which was isolated by column chromatography (eluent: petroleum ether: ethyl acetate 20: 1) to give 6.5g (29.3mmol, 71%) of a pale yellow oily product.
1 H NMR(400MHz,CDCl 3 )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); 13 C NMR(100MHz,CDCl 3 )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 tube 2 -C 6 H 4 ) N = CMePh (400mg, 1.79mmol) and diethyl ether (15 ml), stirred and cooled to-50 deg.C, to which N-butyllithium (1.34ml, 1.6mol/L in N-hexane, 2.1 mmol) was slowly added dropwise, stirred at this temperature for one hour, turned to room temperature for one hour, then cooled again to-50 deg.C, dicyclohexylphosphonium chloride (0.40ml, 1.79mmol) was added, reacted for half an hour, and then turned to room temperature for overnight. After the reaction, the solvent was removed in vacuo, n-hexane (20 ml) was added for dissolution, celite was filtered, and the filtrate was dried to give 546.5mg (1.61mmol, 90%) of a pale yellow oily product, which was ligand L4.
The product contains two geometric isomers. 31 P NMR(162MHz,CDCl 3 ) δ =3.07 (major isomer), δ = -6.34 (minor isomer).
Figure BDA0003115556990000151
1 H NMR(400MHz,CDCl 3 )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); 13 C NMR(100MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )δ=3.07(s),-6.34(s).
(3) Preparation of Complex 4
In a dry argon-filled Schlenk reaction tube, ligand L4 (169.6 mg,0.5 mmol) and CrCl were added 3 (THF) 3 (187.3mg, 0.5mmol), and redistilled dichloromethane (10 mL) was added thereto and stirred at room temperature for 2 hours. The reaction is finishedAfter the filtration, 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 C 35 H 52 Cl 3 CrNOP(%):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) 6 H 3 ) Preparation of N = CMePh
2-methyl-6-ethylaniline (5g, 37.0 mmol) and acetophenone (5.3g, 44.4 mmol) were dissolved in toluene (30 ml), p-toluenesulfonic acid (637.1mg, 3.7 mmol) was added to the solution, stirred, and heated under reflux in a water trap for 30 hours. 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 isolated by column chromatography (eluent ratio petroleum ether: ethyl acetate: 20: 1) to give 6.5g (27.4 mmol, 74%) of a yellow oily product.
1 H NMR(400MHz,CDCl 3 )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) 6 H 3 ) N = CMePh (400mg, 1.69mmol) and diethyl ether (15 ml), stirred and cooled to-50 ℃, N-butyllithium (1.27ml, 1.6mol/L N-hexane solution, 2.0 mmol) 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 overnight. After the reaction was completed, the solvent was removed in vacuo, and n-hexane (20 ml) was added for dissolution, and the solution 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. 31 P NMR(162MHz,CDCl 3 ) δ =3.07 (major isomer), δ = -6.34 (minor isomer).
Figure BDA0003115556990000161
1 H NMR(400MHz,CDCl 3 )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). 13 C NMR(101MHz,CDCl 3 )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. 31 P NMR(162MHz,CDCl 3 )δ0.30(s),-4.34(s).
(3) Preparation of Complex 5
Into a dry argon-filled Schlenk reaction tube, ligand L5 (216.8mg, 0.5mmol) and CrCl were added 3 (THF) 3 (187.3mg, 0.5mmol), and redistilled dichloromethane (10 mL) was added thereto and stirred at room temperature for 2 hours. After completion of the reaction, filtration was carried out, and the filtrate was drained to obtain a solid, which was washed with n-hexane (5 mL. Times.3) and drained to obtain 298.0mg (0.45mmol, 90%) of a blue powder.
Example 6:
1. preparation of the catalyst
To a dry, argon-filled Schlenk reaction tube was added complex 1 (2.32mg, 4. Mu. Mol), and after stirring for 5 minutes, the redistilled methylcyclohexane (30 ml) was added modified methylaluminoxane MMAO-3A (3.2mmol, 1.12mol/L), 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 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 inside of the reaction kettle is ventilated with ethylene gas for three times. Then immediately sucking the prepared catalyst solution by a dry glass syringe, 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 remaining mixture in the reactor 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, as 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 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 by 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 (5)

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:
Figure DEST_PATH_IMAGE001
Figure 399929DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE003
or
Figure 785911DEST_PATH_IMAGE004
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;
the activating agent is one or a mixture of more of an alkyl aluminum compound, an aluminoxane compound and an organoboron compound;
the molar ratio of the ligand to the transition metal element in the transition metal compound is (0.01 to 100) 1;
the molar ratio of the activating agent to the transition metal element in the transition metal compound is (1-10000): 1.
2. The method of claim 1, wherein the ligand, the transition metal compound and the activator are premixed or directly added into a reaction system for in situ synthesis to obtain the target product catalyst system.
3. Use of a catalyst system for the selective trimerization of ethylene according to claim 1 for the selective trimerization of ethylene to 1-hexene.
4. Use of a catalyst system for the selective trimerization of ethylene according to claim 3, 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 50MPa; 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.
5. Use of a catalyst system for the selective trimerization of ethylene according to claim 4, characterized in that said inert solvent is one or a mixture of several of alkanes, aromatics, alkenes or ionic liquids.
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