CN108607612B - Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method - Google Patents

Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method Download PDF

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CN108607612B
CN108607612B CN201810336377.2A CN201810336377A CN108607612B CN 108607612 B CN108607612 B CN 108607612B CN 201810336377 A CN201810336377 A CN 201810336377A CN 108607612 B CN108607612 B CN 108607612B
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catalyst system
compound
transition metal
oligomerization
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CN108607612A (en
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姜涛
张乐
阿兰法赫
陈延辉
邵怀启
李健
闫冰
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Tianjin University of Science and Technology
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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
    • 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
    • B01J35/19—
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines
    • 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

Abstract

The invention provides a catalyst system for selective oligomerization of ethylene, belonging to the technical field of catalysis. The catalyst system comprises three components: a ligand a; a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups; wherein, the ligand a at least contains one group shown as a general formula I, and the general formula I is as follows:
Figure DDA0001629381480000011
the connecting group A in the general formula I is a connecting group of which the main chain comprises alkyl, alkenyl or aryl and hetero atoms, wherein the hetero atoms are one of silicon, tin, boron, phosphorus and nitrogen; the group E is a sixth main group element oxygen or sulfur; r1、R2、R3Are respectively a phosphorus atom, a nitrogen atom and a substituent group on the group E, R1、R2、R3The same or different. The catalyst system of the invention has high activity, the target products of 1-hexene and 1-octene have high selectivity, and C in the products6～C8Linear alpha-olefins in percent by mass>90 percent, simple catalyst synthesis, low cost and long service life.

Description

Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method
Technical Field
The invention belongs to the technical field of catalysis, and relates to a catalyst system for selective oligomerization of ethylene and an ethylene oligomerization reaction method.
Background
With the increasing development of global economy, the demand for high performance polyethylene has increased, and the demand for 1-hexene and 1-octene as comonomers for the production of polyethylene continues to increase at a rate of 5.4% or more per year. The industrial production method of 1-hexene and 1-octene mainly includes paraffin cracking, ethylene oligomerization and extraction separation, among which the ethylene oligomerization method is the main method for producing 1-hexene and 1-octene.
US6184428 discloses a nickel catalyst which uses a boron compound as an activator to catalyze ethylene oligomerization to obtain a mixture of linear alpha-olefins, wherein the content of 1-hexene is 22% and the content of 1-octene is 19%. In the SHOP process (US3676523, US3635937), the content of 1-hexene in the ethylene oligomerization product accounts for 21 percent, and the content of 1-octene accounts for 11 percent. In Chevron process (DE1443927) of Bay oil company and Ethyl process (BP/Amoco, US3906053), the content of 1-hexene and 1-octene is also low, generally 13-25%. In addition, Brookhart et al report that iron-based catalysts (J.Am.chem.Soc.,1998,120: 7143; chem.Commun.1998, 849; WO99/02472) are used for ethylene oligomerization, the content of 1-hexene, 1-octene is also less than 20%. In the prior art, the content of 1-hexene and 1-octene in the oligomerization product is not too high. If the high-purity 1-hexene and 1-octene are to be obtained by multi-tower rectification separation, the process route is complex and the equipment investment is huge.
In view of this, researchers are currently working primarily on ethylene selective trimerization and tetramerization catalyst systems. It is known that the ligand structure in the catalyst system plays an important role in the selective oligomerization of ethylene, and the structure of the ligand directly influences the selectivity of the ethylene selective oligomerization catalyst system. Such as: the catalytic system consisting of the PNP ligand can produce 1-octene (CA2639882A1) with higher selectivity and high activity; the catalytic system composed of SNS ligand can catalyze ethylene trimerization with high activity and high selectivity under the condition of lower dosage of activator (CN 107233919). In addition, the activating agent plays an indispensable role in most ethylene oligomerization catalytic systems, but the production cost is high due to the large using amount and high price, so that the industrial application of the activating agent is hindered.
Therefore, the high-activity high-selectivity ethylene oligomerization catalyst system is designed, the dosage of the activating agent is reduced, and the high-activity high-selectivity ethylene tetramerization catalyst is obtained, which is worth attention of the industry people.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst system for selective oligomerization of ethylene, so as to solve the technical problems of low total selectivity of 1-hexene and 1-octene and large amount of activator in the ethylene oligomerization reaction.
The technical scheme of the invention is as follows:
a catalyst system for selective oligomerization of ethylene comprises three components:
a ligand a;
a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a at least contains one group shown as a general formula I, and the general formula I is as follows:
Figure BDA0001629381470000021
the group A is a connecting group of which the main chain comprises a heteroatom and alkyl, alkenyl or aryl, wherein the heteroatom is one of silicon, tin, boron, phosphorus and nitrogen; the group E is oxygen or sulfur atom in the sixth main group element; r1、R2、R3Are respectively a phosphorus atom, a nitrogen atom and a substituent group on the group E, R1、R2、R3The same or different.
Further, the group A is- (CH)2)n-BR'-(CH2)m-、-(CH2)n-SiR”R”'-(CH2)m-wherein n is 0. ltoreq. n.ltoreq.3, m is 0. ltoreq. m.ltoreq.3; r ', R ", R'" are each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, 2, 6-diisopropylphenyl, and the like.
Further, a substituent group R1、R2、R3Each independently selected from methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triethylphenyl, 2,4, 6-triisopropylphenyl, naphthyl, anthryl and biphenyl; preferably, the substituent group R1、R2、R3Each independently selected from methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, 2, 6-diisopropylphenyl or naphthyl.
Further, the transition metal in the transition metal compound b is selected from one of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium.
Further, the activating agent c is one or a mixture of more than two of an alkyl aluminum compound, an alkyl aluminoxane compound and an organic boron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound having a volatile component removed.
Further, the activator c is a mixture of an alkylaluminum compound and a volatile component-removed alkylaluminoxane compound, wherein the alkylaluminum compound is triethylaluminum, and the aluminoxane compound is volatile component-removed methylaluminoxane; the molar ratio of triethyl aluminum to methylaluminoxane for removing volatile components is 0.01 to 100, preferably 0.1 to 10.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-5000.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-1000.
Further, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1: 0.5-100: 0.1-200.
Further, the molar ratio of the transition metal compound b to the activator c is 1:1 to 500.
The invention also provides a preparation method of the ethylene oligomerization catalyst system, which is characterized in that the ligand a, the transition metal compound b and the activator c are mixed in advance or are respectively and directly added into the reaction system for in-situ synthesis.
The invention also provides the ethylene oligomerization reaction method, which comprises the ethylene oligomerization reaction carried out in the presence of the catalyst system.
Further, the reaction is carried out in an inert solvent, wherein the inert solvent is one or a mixture of more than two of alkane, arene, alkene or ionic liquid.
Further, the reaction temperature is 0 ℃ to 200 ℃.
Further, the pressure of the reaction is 0.1MPa to 50 MPa.
Compared with the prior art, the catalyst system for selective oligomerization of ethylene has the following advantages:
(1) the catalyst system has high catalytic activity, the total selectivity of the target products 1-hexene and 1-octene is high, 1-butene and 1-C10 +The mass percentage content is lower, wherein C in the product6～C8The mass percentage content of the linear alpha-olefin is more than 90 percent.
(2) The catalyst system has simple synthesis, low cost and long service life.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The catalyst system of the present invention is described below.
The embodiment of the invention provides a catalyst system for selective oligomerization of ethylene, which comprises three components:
a ligand a;
a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a at least contains one group shown as a general formula I, and the general formula I is as follows:
Figure BDA0001629381470000041
the group A is a connecting group with a main chain comprising alkyl, alkenyl or aryl and a heteroatom, wherein the heteroatom is one of silicon, tin, boron, phosphorus and nitrogen; the group E is an oxygen or sulfur atom of a sixth main group element; r1、R2、R3Are respectively a phosphorus atom, a nitrogen atom and a substituent group on the group E, R1、R2、R3The same or different.
The catalyst system has high catalytic activity, the total selectivity of the target products 1-hexene and 1-octene is high, and the dosage of the activating agent is small. It is to be noted that the "total selectivity of 1-hexene to 1-octene" herein means the proportion of the total amount of 1-hexene and 1-octene in all linear alpha-olefins in the product.
The embodiment of the invention provides a catalyst system for selective oligomerization of ethylene, which comprises three components, namely a ligand a, a transition metal compound b and an activator c. The ligand a is a bidentate ligand formed by at least one phosphorus atom and a sixth main group element atom shown as a general formula I; the transition metal compound b is a metal compound of IVB-VIII groups, and is a central metal atom; the activator c acts as an activator in the catalyst system.
Under the action of an activating agent c, a ligand a effectively adjusts the electronic effect and the steric hindrance effect of the ligand a on a metal active center, namely a transition metal compound b according to the interaction between a phosphine amine group formed by adjacent phosphorus atoms and nitrogen atoms and a sixth main group element O or S atom, the length of a connecting group A and the difference of abundant substituent groups on each heteroatom, so that the catalyst system disclosed by the embodiment of the invention is finally used for selective oligomerization of ethylene and has excellent total selectivity of 1-hexene and 1-octene. The phosphamidoamine coordinating groups, unlike other monoheteroatom coordinating groups, are used in combination with metallocene compounds (. eta.)5) Eta of similarity2The coordination mode has stronger coordination capacity, so that the catalyst has better chemical stability; in addition, the O or S atom of the sixth main group element has stronger electronegativity relative to power donors such as P, N and the like, so that the metal center is easier to leave to generate an oligomerization active center, the dosage of the activator c is reduced, and the dosage of the activator c is reducedThe cost of the catalyst system is reduced.
In the ligand a of the catalyst system provided by the embodiment of the invention, the group A is a connecting group of which the main chain comprises alkyl, alkenyl or aryl and a heteroatom, wherein the heteroatom is one of silicon, tin, boron, phosphorus and nitrogen; the group E is an oxygen or sulfur atom in the element of the sixth main group. In the ethylene oligomerization process, the length of the connecting group A, the difference of hetero atoms and the like can effectively adjust the coordination among phosphorus atoms, N atoms and the group E in the ligand, thereby improving the catalytic effect.
In the transition metal compound b of the catalyst system provided by the embodiment of the invention, the transition metal compound is selected from metal compounds in IVB-VIII groups. The metal atom in the transition metal compound b is a metal active center and plays an important role in the catalytic process.
In the activator c of the catalyst system provided by the embodiment of the invention, the activator c is a compound containing IIIA group metal. When the catalyst system is used to catalyze the oligomerization of ethylene, a proper metal compound is selected according to the difference of alkylation strength so as to achieve the optimal activation effect.
Unlike the prior art, the carbon number of the linear alpha-olefin in the prior art conforms to Schulz-Flory distribution (S-F distribution for short), the content of 1-hexene and 1-octene in the oligomerization product cannot be too high due to the distribution, and the molar ratio (Al/M molar ratio) of the activating agent to the metal active center in the prior art is generally more than 500, so that the industrial production cost is high.
In the catalyst system provided by the embodiment of the invention, under the action of the activator c, the ligand a effectively adjusts the electronic effect and the steric hindrance effect of the ligand a on the metal active center, namely the transition metal compound b, according to the interaction between the adjacent phosphorus atom and nitrogen atom and the sixth main group element O or S atom, the length of the connecting group A and the difference of the abundant substituent groups on each heteroatom, and the components a, b and c act together to have important influences on the catalytic activity of ethylene selective oligomerization, the total selectivity of 1-hexene and 1-octene and the dosage of the activator.
In an embodiment of the present invention, the molar ratio of the ligand a to the transition metal compound b in the catalyst system may be 1:0.5 to 100.
In another embodiment of the present invention, the molar ratio of the ligand a to the activator c in the catalyst system may be 1:0.1 to 5000, preferably 1:1 to 1000, and more preferably 1:1 to 200.
Specifically, the molar ratio of the ligand a to the transition metal compound b to the activator c is 1: 0.5-100: 0.1-5000; preferably, the molar ratio of the ligand a to the transition metal compound b to the activator c is 1: 0.5-100: 0.1-1000; more preferably, the molar ratio of the ligand a, the transition metal compound b and the activator c is 1:0.5 to 100:0.1 to 200.
In still another embodiment of the present invention, the molar ratio of the transition metal compound b to the activator c is 1:1 to 500.
In the prior art, the mol ratio of the activating agent to the metal active center is generally more than 500, and the industrial production cost is higher. The molar ratio of the activating agent c to the transition metal compound b is 1-500, so that the industrial cost is greatly reduced, but the catalytic activity is not reduced.
In one embodiment of the present invention, the catalyst system may further include a solvent, which may be an alkane, an aromatic hydrocarbon, an alkene, or an ionic liquid, such as methylcyclohexane.
The three components of the catalyst system of the present invention are further illustrated below.
(1) Ligand a
In one embodiment of the present invention, the ligand a at least contains one group represented by formula I, wherein formula I is as follows:
Figure BDA0001629381470000061
in one embodiment of the present invention, the group E is one of the elements of the sixth main group, and may be one of oxygen, sulfur, selenium and tellurium, and preferably an oxygen atom or a sulfur atom.
The phosphine amine group formed by the group E (oxygen or sulfur atom), phosphorus atom and nitrogen atom in the ligand a is used as a coordination group to coordinate with a transition metal active center, compared with the prior art, the oxygen atom or sulfur atom of the sixth main group element has stronger electronegativity, so that the metal center is easier to leave to generate an oligomerization active center, and the dosage of an activator c can be reduced when the ethylene is catalyzed by high selectivity and high activity to selectively oligomerize, thereby reducing the cost of a catalytic system.
In one embodiment of the present invention, the group a contains a heteroatom, and the heteroatom is one of silicon, tin, boron, phosphorus, and nitrogen.
In a further embodiment of the invention, the group a is a linking group whose main chain comprises a linear alkane group, the linear alkane being methane, ethane, propane, butane, pentane or hexane.
In yet another embodiment of the present invention, the group a is a linking group whose main chain includes an aromatic hydrocarbon group, which may be benzene, toluene, ethylbenzene, xylene, or the like.
In yet another embodiment of the invention, the group a is a linking group comprising an olefinic group in the backbone, which olefin may be a mono-olefin, such as ethylene, propylene, butylene; dienes such as 1, 3-butadiene and the like may also be used.
In yet another embodiment of the present invention, the backbone of group A comprises a heteroatom and a linking group of alkyl, alkenyl or aryl groups of 1 to 8 carbon atoms. This distance is more favorable for coordination between atoms.
Preferably, the group A may be a linking group- (CH) containing a silicon atom or a boron atom2)n-SiR”R”'-(CH2)m-or- (CH)2)n-BR'-(CH2)mN is more than or equal to 0 and less than or equal to 3, and m is more than or equal to 0 and less than or equal to 3; r ', R ' and R ' are each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl.
Preferably, the group A may be- (CH)2)nSn(R4R5)(CH2)m-、-(CH2)nP(R6)(CH2)m-, where n is 0. ltoreq. n.ltoreq.4, m is 0. ltoreq. m.ltoreq.4, R4、R5、R6Can be respectively and independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, cyclopentyl, cyclohexyl, isobutyl, tert-butyl, adamantyl, vinyl, allyl, phenyl, benzyl, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl, 3, 5-di-methylphenylTolylmethyl, methoxyphenyl, ethylphenyl, thiophenyl, bisphenyl, naphthyl or anthracenyl.
In yet another embodiment of the invention, the substituent group R1、R2、R3Each independently selected from methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triethylphenyl, 2,4, 6-triisopropylphenyl, naphthyl, anthryl and biphenyl; preferably, the substituent group R1、R2、R3Each independently selected from methyl, isopropyl, cyclohexyl, phenyl, 2, 6-diisopropylphenyl or naphthyl.
In one embodiment of the present invention, the ligand a contains at least one group represented by formula I. That is, the ligand a may be one or more than two units represented by the general formula I, and may be bonded together through a group, a chemical bond, or intermolecular forces to obtain a compound having a bridge, a dendrimer, or a star shape, or may be a polymer having a polymer chain bonded thereto.
In one embodiment of the present invention, ligand a may be (R)1)2PNR2AER3Wherein A is a linking group containing the above-mentioned hetero atom; e is a sixth main group element of oxygen or sulfur; r1、R2、R3Each of which is a substituent on a phosphorus atom, a nitrogen atom and an E atom, R1、R2、R3Identical or different, each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, 2, 6-diisopropylphenyl or naphthyl.
In one embodiment of the present invention, the ligand a may also be [ (R)1)2PNR2AER3]nG and n are more than or equal to 2, wherein A is a connecting group containing the heteroatom; e is a sixth main group element of oxygen or sulfur; r1、R2、R3Are respectively a substituent group on a phosphorus atom, a nitrogen atom and a B atom, R1、R2、R3The same or different, are respectively and independently selected from methyl, isopropyl, cyclohexyl, phenyl, 2, 6-diisopropyl phenyl or naphthyl; g is a linker between the general formula I, which is linked between the groups represented by the general formula I, and may be methyl, hexyl, propyl or butyl, or may be aryl or a heteroatom-containing linking group, such as: ph2P(C5H11)N(OC2H5)Si(CH3)-C3H6-(CH3)Si(OC2H5)N(C5H11)PPh2。
(2) Transition metal compound b
In an embodiment of the present invention, the transition metal in the transition metal compound b is independently selected from one of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium.
Preferably, the transition metal compound b is CrCl3(THF)3、CoCl3、PdCl2、NiBr2One kind of (1).
Preferably, the transition metal compound b is a transition metal compound containing chromium, zirconium and titanium.
More preferably, the transition metal compound b is a chromium-containing transition metal compound. Alternative chromium compounds include those of the formula CrRn mA compound of the formula wherein RnBeing an organic negative ion or neutral molecule, RnWherein the carbon atoms are usually 1-10 carbon atoms, n is an integer of 0-6, and the valence of chromium is 0-6. Specific RnThe group is an organic matter containing carboxyl, beta-diketone group and alkyl or the group thereof. From the viewpoint of easy dissolution and easy handling, more suitable chromium compounds include chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprenate, chromium diphenyloxide, CrCl3(THF)3、CrCl2(THF)2One of (phenyl) chromium tricarbonyl and chromium hexacarbonyl.
(3) Activator c
In one embodiment of the present invention, the activator c is one or a mixture of two or more of an alkylaluminum compound, an alkylaluminoxane compound and an organoboron compound, wherein the alkylaluminoxane compound includes an alkylaluminoxane which removes volatile components.
Specifically, the activator c may be a compound containing a group IIIA metal.
Specifically, the activator c may be an alkylaluminum compound or an alkylaluminoxane compound. The alkylaluminum compound can be various trialkylaluminums, such as TEAL, 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) (ii) a The alkylaluminoxane compound may be selected from Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, modified aluminoxane, methylaluminoxane DMAO from which volatile components are removed, and the like.
Specifically, the activator c may be an organoboron compound including boroxine, triethylborane, tris (pentafluorophenyl) boron, or the like.
In the present invention, the TEAL alkylation capacity is relatively weak, and is more adaptable to the catalyst system proposed by the present invention; meanwhile, DMAO can shield the influence of volatile components such as toluene on the catalyst complexing process, so that the activity of the catalyst system is improved.
Specifically, the activator c is a mixture of an alkylaluminum compound and an alkylaluminoxane for removing volatile components, wherein the alkylaluminum compound is TEAL and the alkylaluminoxane compound is DMAO.
Preferably, the molar ratio of TEAL to DMAO is 0.01-100, preferably 0.1-10.
In another embodiment of the present invention, the activator c may also be an organic salt type activator such as methyllithium, methylmagnesium bromide, etc.; inorganic acid activators such as tetrafluoroboric acid, and the like; inorganic salt activators such as tetrafluoroborate, hexafluoroantimonate, and the like; the organoboron compounds include boroxine, triethylborane, tris (pentafluorophenyl) boron, and the like.
Accordingly, in one embodiment of the present invention, a suitable catalyst system comprises three components:
a ligand a; a transition metal compound b; an activator c;
wherein, the ligand a contains at least one group shown as a general formula I, and the general formula I is as follows:
Figure BDA0001629381470000091
the group E in the ligand a is oxygen or sulfur atom in the sixth main group element;
the group A in the ligand a may be- (CH)2)n-BR'-(CH2)m-、-(CH2)n-SiR”R”'-(CH2)mN is more than or equal to 0 and less than or equal to 3, and m is more than or equal to 0 and less than or equal to 3; r ', R ", R'", R "" and R "" are each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl, or 2, 6-diisopropylphenyl;
substituent group R of ligand a1、R2、R3Each independently selected from methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, 2, 6-diisopropylphenyl or naphthyl;
the transition metal compound b may be CrCl3(THF)3、CoCl3、PdCl2、NiBr2One of (1); or chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprenate, chromium diphenyloxide, CrCl3(THF)3、CrCl2(THF)2One of (phenyl) chromium tricarbonyl and chromium hexacarbonyl;
the activating agent c is one or a mixture of more than two of alkyl aluminum compound, alkyl aluminoxane compound and organic boron compound; the activator c may be a trialkylaluminium, such as TEAL, triisobutylaluminium, tri-n-butylaluminium, tri-n-hexylaluminium or tri-n-octylaluminium; it may also be an alkylaluminum halide, alkylaluminum hydride or alkylaluminum sesquichloride, such as AlEt2Cl and A12Et3C13(ii) a It may also be an alkylaluminoxane compound such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and modified aluminoxanes (MMAO) and DMAO; the activator c can also be a mixture of one or more of the above, for example, the activator c is a mixture of TEAL and DMAO, wherein the molar ratio of TEAL to DMAO is0.01 to 100, preferably 0.1 to 10.
The preparation of the catalyst system of the present invention is further illustrated below.
In one embodiment of the present invention, ligand a comprises a group shown in formula I, and the specific synthetic steps may include the following steps:
(1) preparation R1 2PNR2H. Firstly, a certain amount of R2NH2Dissolving in THF, adding n-butyl lithium hexane solution at certain temperature, stirring at room temperature for 2 hr, and vacuum drying to obtain R2NHLi; taking a certain amount of R2Dispersing NHLi in n-hexane, and taking a certain amount of R1 2Dissolving PCl in n-hexane, slowly dripping into the above solution, stirring at room temperature overnight, filtering, vacuum-pumping volatile components, and vacuum-distilling or recrystallizing with n-hexane to obtain R1 2PNR2H。
(2) Preparation R1 2PNR2And Li. Taking a proper amount of R1 2PNR2Dissolving H in n-hexane, dripping n-butyllithium hexane solution at a certain temperature, filtering, washing and drying to obtain R1 2PNR2Li。
(3) Preparation R3ELi are provided. A certain amount of R3Dissolving EH in THF, cooling to-35 deg.C, slowly adding n-butyllithium n-hexane solution into the above solution, naturally heating to room temperature after dropwise addition, stirring for 2 hr, and filtering with sand core funnel to obtain filter cake R2ELi products.
(4) Preparation R1 2PNR2And (5) ACL. Adding a certain amount of ACI2Dissolving in toluene, and adding R at a certain concentration1 2PNR2Slowly dripping Li toluene solution into the solution, stirring at room temperature overnight, filtering with a sand core funnel, vacuum concentrating, and distilling under reduced pressure to obtain R1 2PNR2ACl。
(5) Preparation R1 2PNR2AER3. A certain amount of R1 2PNR2Dissolving ACL in toluene, and adding R at a certain concentration3ELi slowly adding toluene solution into the above solution at a certain temperature, stirring at room temperature overnight, filtering with sand core funnel, vacuum concentrating, and recrystallizing with n-hexane to obtain white or yellow solid R1 2PNR2AER3。
In one embodiment of the present invention, when the ligand a comprises two or more groups shown in formula I, the specific synthesis steps may include the following steps:
(1) preparation R1 2PNR2ACl2. Taking a proper amount of R1 2PNR2Li is dispersed in n-hexane; taking an appropriate amount of ACL3Dissolving in n-hexane, and dissolving R1 2PNR2Slowly dripping Li dispersion liquid into the solution, stirring at room temperature overnight, filtering by a sand core funnel, and distilling under reduced pressure to obtain R1 2PNR2ACl2。
(2) Preparation of (R)1)2PNR2(ER3) And (5) ACL. A certain amount of R3ELi in toluene, and adding a certain concentration of R1 2PNR2ACl2Slowly dripping the toluene solution into the solution, stirring at room temperature overnight, filtering with a sand core funnel, vacuum concentrating, and crystallizing to obtain white or light yellow solid (R)1)2PNR2P(ER3)ACl。
(3) Preparing the Grignard reagent containing the G group. Dispersing a proper amount of Mg powder in a certain amount of ether, slowly dripping ether solution of Cl-G-Cl with a certain concentration into the Mg powder dispersion, heating and refluxing for 6 hours, and filtering to obtain the Grignard reagent containing G groups.
(4) At 0 deg.C, adding (R) at a certain concentration1)2PNR2(ER3) And (3) slowly dropwise adding the Grignard reagent into a THF solution of the ACl, stirring overnight at room temperature, filtering, then vacuum-pumping the filtrate, and passing through a rapid silica gel column by using n-hexane as a elution machine to obtain the ligand a containing two groups in the general formula I.
The method of synthesis of ligands containing multiple groups of formula I is similar to the above method.
In one embodiment of the present invention, the preparation method of the catalyst system comprises the following steps:
the components a, b and c are mixed in advance or directly added into a reaction system for in-situ synthesis. That is, the catalyst is prepared by mixing the ligand a, the transition metal compound b, and the activator c linked by the heteroatom-containing linking group in advance; or directly adding the ligand a, the transition metal compound b and the activator c connected by chain-shaped groups containing hetero atoms into a reaction system for in-situ synthesis;
the reaction mode of the ligand a, the transition metal compound b and the activator c which are connected by the connecting group containing the heteroatom in the general formula I can be liquid phase reaction, such as reaction under the action of a solvent, and the optional solvent can be toluene, benzene and derivatives thereof; or by solid phase reaction; the catalyst may also be generated by an in situ reaction during the oligomerization reaction. The reaction here may be a reaction between one, two or three compounds of the above-mentioned hetero atom ligand, transition metal compound and metal organic activator. The course of this reaction is also the aging (pre-complexing) of the catalyst.
The method of the catalyst system of the present invention for oligomerization of ethylene is further described below.
The invention also provides an ethylene oligomerization reaction method, which comprises the ethylene oligomerization reaction carried out in the presence of the catalyst system.
In one embodiment of the present invention, the reaction is performed in an inert solvent, wherein the inert solvent is one or more than two of alkane, arene, alkene or ionic liquid. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, 1-octene, ionic liquids, and the like, with methylcyclohexane being preferred.
In a further embodiment of the invention, the temperature of the reaction is from 0 ℃ to 200 ℃ and preferably from 50 ℃ to 150 ℃.
In a further embodiment of the invention, the pressure of the oligomerization of ethylene can be carried out at a pressure of from 0.1MPa to 50MPa, preferably from 1.0MPa to 10 MPa.
In still another embodiment of the present invention, the concentration of the catalyst in the reaction system may be from 0.01. mu. mol of metal/L to 1000. mu. mol of metal/L, preferably from 0.1. mu. mol of metal/L to 10. mu. mol of metal/L. Note that the metal here is a transition metal in the transition metal compound b.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1
1. Preparation of the ligand:
when A is-CH2(CH3)2SiCH2-, E is a sulfur atom, R1Is isopropyl, R2Is phenyl, R3Is cyclopentyl, and the ligand is N- ((cyclopentyl mercaptomethyl) dimethyl methyl) -1, 1-diisopropyl-N-phenyl phosphine amine (C)21H38NPSSi)
(1) Preparation of anilino lithium
In the warp of N2A500 ml stirred reactor, fully replaced, was charged with dehydrated THF (200ml), aniline (9.31g, 0.1mol), stirred well and cooled to-78 ℃ with liquid nitrogen. The n-butyllithium hexane solution (41.6ml, 2.4mol/L) was taken out with a 100ml syringe, slowly added dropwise to the above solution while stirring, kept at-78 ℃ for stirring for 1 hour, then warmed to room temperature and stirred for 1 hour, then the solvent was removed in vacuo, n-hexane (100ml) was added, stirred well for dispersion and filtered, and the resulting filtrate was subjected to vacuum removal of volatile components at room temperature to give 9.97g (0.098mol, 97.8%) of the product.
(2) Preparation of 1, 1-diisopropyl-N-phenylphosphine amine (C)12H20NP)
In N2In a glovebox in the atmosphere, lithium anilino (4.95g, 0.050mol) was dissolved in dehydrated n-hexane (100mL) and added to a 250mL reactor, cooled to-35 ℃, and stirred vigorously; slowly dripping diisopropyl phosphorus chloride (7.48g, 0.049mol) into the solution, naturally heating to room temperature after the dropwise addition is finished, continuously stirring overnight, filtering, vacuum-pumping volatile components in the filtrate to obtain yellow liquid, distilling and separating, collecting 145 deg.CAbout 150 ℃ fraction, 8.79g (0.042mol, 85%) of colorless liquid product is obtained.
(3) Preparation of 1, 1-diisopropyl-N-phenylphosphinyl lithium (C)12H19NPLi)
In N2In a glove box with atmosphere, 1-diisopropyl-N-phenylphosphine (8.37g, 0.040mol) is dissolved in dehydrated N-hexane (100mL), cooled to-35 ℃, N-butyllithium N-hexane solution (17.1mL, 0.041mol, 2.4mol/L) is slowly dripped into the solution while stirring, the solution is continuously stirred overnight after the dripping is finished, the filter cake is washed twice by 20mL of N-hexane after the filtration, and the mixture is drained to obtain 8.39g (0.039mol, 98%) of 1, 1-diisopropyl-N-phenylphosphine lithium,
(4) preparation of cyclopentyl lithium mercaptan salt (C)5H9SLi)
In N2In an atmosphere glove box, cyclopentyl mercaptan (5.11g, 0.050mol) was dissolved in dehydrated THF (100mL) and added to a 250mL reactor, cooled to-35 ℃ and stirred vigorously; slowly dropwise adding n-butyllithium hexane solution (20.8mL, 2.4mol/L) into the solution, naturally heating to room temperature after the solution is finished, continuing stirring for 2h, filtering, and vacuumizing to remove volatile components in the filtrate to obtain yellow solid powder (5.08g, 0.047mol, 93%).
(5) Preparation of N- ((chloromethyl) dimethylsilyl-methyl) -1, 1-diisopropyl-N-phenylphosphine amine (C)16H29NPSiCl)
In N2In an atmosphere glove box, bis (chloromethyl) dimethylsilane (3.14g, 0.02mol) was dissolved in toluene (50mL), 1-diisopropyl-N-phenylphosphinamido lithium (4.30g, 0.02mol) was dissolved in toluene (25mL), and this was slowly added dropwise to the above solution at-35 ℃ and stirred at room temperature overnight. Filtered, drained and recrystallized from n-hexane to give a white or pale yellow solid (4.68g, 14.2mmol, 71%)
(6) Preparation of N- ((cyclopentyl mercaptomethyl) dimethylsilyl) -1, 1-diisopropyl-N-phenylphosphine amine (C)21H38NPSSi)
Dissolving cyclopentyl mercaptan lithium salt (1.54g, 14.2mmol) in toluene (20mL), dissolving the N- ((chloromethyl) dimethyl methyl) -1, 1-diisopropyl-N-phenyl phosphino amine (4.68g, 14.2mmol) in toluene (50mL), slowly dripping the solution into lithium salt toluene solution at-35 ℃, stirring overnight at room temperature, filtering, draining, and recrystallizing by using N-hexane to obtain white or light yellow solid (4.66g, 11.8mmol, 83%) which is ligand N- ((cyclopentyl mercaptomethyl) dimethyl methyl) -1, 1-diisopropyl-N-phenyl phosphino amine
The products obtained by the experiment are verified to have correct structures through nuclear magnetic spectrograms.
2. Preparation of the catalyst
In the warp of N2A well-displaced stirred 100mL reactor was charged with dehydrated methylcyclohexane (20mL) DMAO (0.15g, 2.6mmol), TEAL (0.08g, 0.7mmol), N- ((cyclopentylsulfonylmethyl) dimethylsilyl-1, 1-diisopropyl-N-phenylphosphine amine (27mg) (67.8. mu. mol), CrCl3·(THF)3(12mg, 33. mu. mol), and reacted at room temperature for 5 min.
3. Oligomerization of ethylene
A500 mL autoclave was heated to vacuum for 2 hours, purged with nitrogen several times, charged with ethylene, cooled to a predetermined temperature, and charged with dehydrated methylcyclohexane (200mL) and the above catalyst. Carrying out oligomerization reaction at 45 ℃ under the pressure of 1MPa, cooling by using ice bath after reacting for 30min, releasing pressure, and terminating the reaction by using acidified ethanol with the mass fraction of 10%. 112.1g of oligomerization product is obtained, and the catalyst activity is 6.79 multiplied by 106g oligomer/(mol)CrH). The distribution of the oligomerization products is shown in Table 1.
Example 2
The same as in example 1. With the difference that R2Is 2, 6-diisopropylphenyl. To obtain 135.7g of oligomerization product and its catalyst activity is 8.22X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 3
The same as in example 1. With the difference that R1Is phenyl, R2Is cyclopentyl. 90.6g of oligomerization product is obtained, and the activity of the catalyst is 5.49 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 4
The same as in example 1. Is not limited toWherein E is an O atom. 70.6g of oligomerization product is obtained, and the activity of the catalyst is 4.28 multiplied by 106g oligomer/(molCr. h). The distribution of the oligomerization products is shown in Table 1.
Example 5
The same as in example 4. With the difference that R2Is propyl. 75.31g of oligomerization product is obtained, and the activity of the catalyst is 4.56 multiplied by 106g oligomer/(molCr. h). The distribution of the oligomerization products is shown in Table 1.
Example 6
The same as in example 1. Except that A is- (C)6H5P) -group. 81.64g of oligomerization product is obtained, and the activity of the catalyst is 4.95 multiplied by 106g oligomer/(molCr. h). The distribution of the oligomerization products is shown in Table 1.
Example 7
The same as in example 1. Except that A is- (C)6H5B) -a group. To obtain 41.92g of oligomerization product and the catalyst activity of 2.54 multiplied by 106g oligomer/(molCr. h). The distribution of the oligomerization products is shown in Table 1.
Example 8
The same as in example 1. With the difference that R1Is naphthyl. Obtain oligomerization product 87.17g, and catalyst activity is 5.28X 106g oligomer/(molCr. h). The distribution of the oligomerization products is shown in Table 1.
Example 9
The same as in example 3. With the difference that R3Is ethyl. 88.3g of oligomerization product is obtained, and the activity of the catalyst is 5.35 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 10
The same as in example 4. Except that A is a dimethyl silicon group (-Si (CH)3)2-). 30.5g of oligomerization product is obtained, and the activity of the catalyst is 1.85 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 11
The same as in example 4. Except that A is a methylcyclohexyldimethylenesilyl group (-CH)2Si(CH3)(C6H11)CH2-). 92.6g of catalyst activity was obtainedThe sex was 5.83X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 12
The same as in example 4. Except that A is a methylphenyldimethylene silicon group (-CH)2Si(CH3)(C6H5)CH2-). 107.5g were obtained, the catalyst activity was 6.52X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 13
The same as in example 4. Except that A is a diphenyldimethylene silicon group (-CH)2Si(C6H5)2CH2-). 131.9g were obtained, the catalyst activity was 7.99X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 14
The same as in example 4. Except that the ethylene pressure was 2 MPa. 138.0g of oligomerization product is obtained, and the catalyst activity is 8.36 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 15
The same as in example 4. Except that the ethylene pressure was 4MPa, the oligomerization product was 156.3g, and the catalyst activity was 9.47X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 16
The same as in example 4. Except that the reaction temperature was 0 ℃ to obtain 51.7g of an oligomerization product and the catalyst activity was 3.13X 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 17
The same as in example 4. Except that the reaction temperature was 75 ℃. Obtain 186.3g of oligomerization product and the catalyst activity of 11.29 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 18
The same as in example 4. The difference lies in that CrCl3·(THF)3The amount used was 3. mu. mol. 52.7g of oligomerization product is obtained, and the catalyst activity is 35.13 multiplied by 106g oligomer/mol Cr.h.The distribution of the oligomerization products is shown in Table 1.
Example 19
The same as in example 10. Except that the activator is MAO. Obtain 61.8g of oligomerization product, the catalyst activity is 3.75 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 20
The same as in example 10. Except that activator c is MMAO. 139.2g of oligomerization product is obtained, and the catalyst activity is 8.44 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 21
The same as in example 10. Except that the activating agent c was DMAO in an amount of 0.08g (1.3mmol), AlEt3The amount used was 0.04g (0.4 mmol). 110.9g of oligomerization product is obtained, and the activity of the catalyst is 6.72 multiplied by 106g oligomer/mol Cr h. The distribution of the oligomerization products is shown in Table 1.
Example 22
The same as in example 10. Except that the activating agent c was DMAO in an amount of 0.30g (5.2mmol), AlEt3The amount used was 0.16g (1.4 mmol). 153.7g of oligomerization product is obtained, and the activity of the catalyst is 9.32 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
Example 23
The same as in example 10. Except that the chromium compound is CrCl2(THF)2. 36.7g of oligomerization product is obtained, and the activity of the catalyst is 2.22 multiplied by 106g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1.
The experimental conditions and catalyst activities of examples 1-23 are shown in Table 2.
From Table 1, obtained by combining the data in tables 1 and 2, the product carbon number distribution is concentrated in C6And C8，C4And C10 +Less; and, C6In 1-C6And C8In 1-C8The selectivity of the catalyst is up to more than 90 percent; and 1-C6And 1-C8Total selectivity of (1-C)6And 1-C8The sum of (a) is high in the proportion of all alpha-olefins. From Table 2, the catalystsThe system has high catalytic activity for ethylene oligomerization.
TABLE 1 comparison of carbon number distribution of oligomerization products
Figure BDA0001629381470000161
Figure BDA0001629381470000171
aIs referred to as C6In 1-C6 ＝The mass percentage of (A) is as follows.bIs referred to as C8In 1-C8 ＝The mass percentage of (A) is as follows.
Figure BDA0001629381470000181
Figure BDA0001629381470000191
Figure BDA0001629381470000201

Claims (10)

1. A catalyst system for selective oligomerization of ethylene, comprising three components:
a ligand a;
a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a at least contains one group shown as a general formula I, and the general formula I is as follows:
Figure FDA0002625895250000011
the group A is a connecting group of which the main chain comprises heteroatoms and alkyl, alkenyl or aryl, wherein the heteroatoms are silicon, tin and boronOne of phosphorus and nitrogen; the group E is oxygen or sulfur atom in the sixth main group element; r1、R2、R3Are respectively a phosphorus atom, a nitrogen atom and a substituent group on the group E, R1、R2、R3The same or different.
2. The catalyst system of claim 1, wherein: the group A is- (CH)2)n-BR'-(CH2)m-、-(CH2)n-SiR”R”'-(CH2)m-wherein n is 0. ltoreq. n.ltoreq.3, m is 0. ltoreq. m.ltoreq.3; r ', R ", R'" are each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl.
3. Catalyst system according to any of claims 1 or 2, characterized in that: the substituent group R1、R2、R3Each independently selected from methyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2, 4-dimethylphenyl, 2, 4-diethylphenyl, 2, 4-diisopropylphenyl, 2, 4-dibutylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-dibutylphenyl, 2,4, 6-trimethylphenyl, 2,4, 6-triethylphenyl, 2,4, 6-triisopropylphenyl, naphthyl, anthryl and biphenyl.
4. The catalyst system of claim 1, wherein: the transition metal in the transition metal compound b is selected from one of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium.
5. Catalyst system according to claim 1, characterized in that: the activating agent c is one or a mixture of more than two of an alkyl aluminum compound and an alkyl aluminoxane compound; wherein the alkylaluminoxane compound comprises an alkylaluminoxane compound having a volatile component removed.
6. Catalyst system according to claim 1 or 5, characterized in that: the activator c is a mixture of an alkyl aluminum compound and an alkyl aluminoxane compound for removing volatile components, wherein the alkyl aluminum compound is triethyl aluminum, and the aluminoxane compound is methylaluminoxane for removing volatile components; the molar ratio of the triethyl aluminum to the methylaluminoxane without volatile components is 0.01-100.
7. The catalyst system according to claim 1, characterized in that: the molar ratio of the ligand a to the transition metal compound b to the activator c is 1: 0.5-100: 0.1-5000.
8. The catalyst system according to claim 7, characterized in that: the molar ratio of the transition metal compound b to the activator c is 1: 1-500.
9. A process for the preparation of a catalyst system according to any one of claims 1 to 8, characterized in that: and the ligand a, the transition metal compound b and the activator c are mixed in advance or directly added into a reaction system for in-situ synthesis.
10. A process for the oligomerization of ethylene using a catalyst system according to any of claims 1 to 8, characterized in that: the reaction is carried out in an inert solvent, wherein the inert solvent is one or a mixture of more than two of alkane, arene, alkene or ionic liquid; the reaction temperature is 0-200 ℃; the reaction pressure is 0.1 MPa-50 MP a.
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