CN114160199B - Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof - Google Patents

Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof Download PDF

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CN114160199B
CN114160199B CN202111286522.9A CN202111286522A CN114160199B CN 114160199 B CN114160199 B CN 114160199B CN 202111286522 A CN202111286522 A CN 202111286522A CN 114160199 B CN114160199 B CN 114160199B
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CN114160199A (en
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薛宽荣
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Zhejiang Zhiying Petrochemical Technology Co ltd
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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
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B01J31/1855—Triamide derivatives thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
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    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium

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Abstract

The invention provides a catalytic system for selectively trimerizing and tetramering ethylene and application thereof, belonging to the technical field of transition metal homogeneous catalysis. The catalytic system comprises: a transition metal complex a, wherein the transition metal complex a is an organometallic compound of IVB-VIII groups; a cocatalyst b, which is an organic compound containing a group IIIA element; wherein the transition metal complex a has a structure represented by formula (I):wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 May be the same or different and are each independently selected from alkyl, aryl, acetylacetonate, carbonyl, tetrahydrofuranyl or halogen; m is a transition metal including chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium. The catalyst system is used for ethylene selective oligomerization, and has the characteristics of high catalytic activity, high selectivity of 1-hexene+1-octene and few byproducts.

Description

Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof
Technical Field
The invention belongs to the technical field of transition metal homogeneous catalysis, and particularly relates to a catalytic system for preparing 1-hexene and 1-octene by ethylene selective trimerization and tetramerization and application thereof.
Background
In recent years, polymer synthetic materials are continuously innovated, and the market demands of high-end high-performance synthetic materials are increasing year by year. The use of higher linear alpha-olefins such as 1-hexene, 1-octene and 1-decene in high performance polyolefin materials, synthetic lubricating base oils and oil additives, detergents and the like continues to increase, with demand continuing to increase at a rate of 4.2%. Ethylene selective oligomerization is a main method for producing high-purity 1-hexene, 1-octene, 1-decene, 1-dodecene and other high-grade linear alpha-olefins, and particularly, the selective trimerization of ethylene for producing 1-hexene and the tetramerization of ethylene for producing 1-octene are hot spots of research in academic circles and industry circles at home and abroad in recent years.
A technology for preparing linear alpha-olefin by oligomerization of ethylene includes non-selective oligomerization and selective oligomerization of ethylene. The non-selective ethylene oligomerization technique has the disadvantages of high byproduct content (1-butene >10%, polymer > 1.0%), low selectivity of 1-hexene, 1-octene, 1-decene and 1-dodecene. In contrast, ethylene selective trimerization and tetramerization can generate high-grade linear alpha-olefin such as 1-hexene, 1-octene and the like with high selectivity, has the advantages of good atomic economy, mild reaction conditions, simple process route and the like, and is a hot spot and a technical development direction of research in the field in recent years.
The activity of the catalyst system and the selectivity of the target product are key to evaluate the technical advancement, and the structure of the complex active center in the catalyst system is a key factor influencing the activity of the catalyst and the selectivity of the product.
In 2002, bisphosphonamines (PNP) developed by the Wass professor of the Imperial university of London, UK OMe ) The ligand (chem. Commun.,2002, 858-859) is used for synthesizing 1-hexene by ethylene trimerization, and has the characteristics of high catalytic activity and high selectivity of the target product 1-hexene. Bisphosphonamines (PNPs) developed by researchers in the Wass professor of Sasol company in south Africa 2004 OMe ) The ligand is slightly modified on the basis of the ligand, and the fact that the original catalytic system can be changed from ethylene trimerization to ethylene tetramerization by removing methoxy on PNP ligand is found, which shows that the structure of the ligand/complex in the catalytic system is the key for influencing the catalytic activity of the catalytic system and the selectivity of target products, and mainly depends on the steric hindrance and the electronic effect of the catalytic active center.
The research results of Sasol corporation report that many chemical companies and scientists internationally carry out tracking research, such as China patent CN1741850A (WO 2004/056478A 1), CN1741849A (WO 2004/056479A 1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A, CN202110525366.0, CN202110284855.1, CN202110285611.5, CN202010717943.1, CN202010718125.3 and PNP ligand disclosed in US 2006/012899A 1, korean SK energy company CN201880057196.4, CN201780043063.7, CN201780032874.7, CN201380014632.7, CN201080003564.0, CN201080003564.0, CN200880002464.9, CN200880002464.9 and CN200780100280.1 design and synthesize chiral PCCP type ligand, and the catalytic system is composed of Cr and MAO for ethylene tetramerization, so that the chiral PCCP type ligand has higher catalytic activity and longer-time stability.
In general, the idea of research and development of selective trimerization and tetramerization of ethylene is to design complexes with novel structures and different steric hindrance and electronic properties, and the steric hindrance and electronic properties of a catalytic activity center are key to influencing catalytic activity and product selectivity. In view of this, the design synthesis of novel complexes has been a hotspot of research in the art.
The reported ethylene trimerization and tetramerization catalyst system still has the defects of high content of byproduct methylcyclopentane and methylenecyclopentane, poor polymerization activity and the like, so that the key of developing the ethylene trimerization and tetramerization catalyst is to reduce the content of the byproduct and improve the selectivity of the target product.
Disclosure of Invention
The invention aims to effectively control the stability of the active center of ethylene selective oligomerization and control the chain growth reaction and the carbon number distribution of the product by finely adjusting the steric hindrance of the active center of the complex in the catalytic system, thereby obtaining the ethylene selective oligomerization catalyst system with high catalytic activity and high 1-hexene and 1-octene selectivity so as to solve the problem of C in the ethylene oligomerization 6 ～C 8 The total selectivity of linear alpha-olefin is not high.
The invention provides a catalytic system for selectively trimerizing and tetramerizing ethylene, which comprises the following components:
a transition metal complex a, wherein the transition metal complex a is an organometallic compound of IVB-VIII groups;
a cocatalyst b, which is an organic compound containing a group IIIA element;
wherein the transition metal complex a has a structure represented by formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 May be the same or different and are each independently selected from alkyl, aryl, acetylacetonate, carbonyl, tetrahydrofuranyl or halogen; m is a transition metal including chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium.
Further, the alkyl group is C 1 -C 10 Alkyl of (a); preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl or cyclohexyl.
Further, the aryl group is C 6 -C 20 Aryl groups of (a) and derivatives thereof; preferably, the aryl is selected from phenyl, substituted phenyl.
Further, the cocatalyst b is at least one of an alkyl aluminum compound, an alkyl aluminoxane compound and an organoboron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound from which volatile components are removed.
Further, the mol ratio of the transition metal complex a to the cocatalyst b is 1:0.1-5000.
The invention also provides a reaction method for ethylene selective oligomerization, which comprises ethylene oligomerization reaction carried out in the presence of any one of the catalyst systems.
Further, the reaction is carried out in an inert solvent, wherein the inert solvent is at least one of alkane, aromatic hydrocarbon, alkene or ionic liquid.
Further, the reaction temperature is 0-200 ℃; the pressure of the reaction is 0.1 MPa-50 MPa.
The invention also provides the application of the catalyst system in the selective oligomerization of ethylene.
The invention has the following advantages:
the catalyst system provided by the invention effectively adjusts the steric hindrance of the ethylene selective oligomerization catalytic active center by fine adjustment of the structure of the catalyst system complex, so that the obtained catalytic active center has the characteristics of high catalytic activity, high total selectivity of the target product 1-hexene+1-octene, low selectivity of byproducts methylcyclopentane and methylenecyclopentane and low content of byproduct polymers.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. Embodiments of the invention and features of the embodiments may be combined with each other without conflict.
The catalyst system of the present invention is described below.
Embodiments of the present invention provide a catalyst system for the selective oligomerization of ethylene comprising:
a transition metal complex a, wherein the transition metal complex a is an organometallic compound of IVB-VIII groups;
a cocatalyst b, which is a metal organic compound containing a group IIIA metal;
wherein the transition metal complex a has a structure represented by formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 May be the same or different and are each independently selected from alkyl, aryl, acetylacetonate, carbonyl, tetrahydrofuranyl or halogen; m is a transition metal including chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium. It is noted that in formula (I), ph represents phenyl, P represents phosphorus, and N represents nitrogen.
In one embodiment of the present invention, the transition metal complex a is an organometallic compound of groups IVB to VIII and has a structure represented by formula (I), wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、 R 8 、R 9 May be the same or different and are each independently selected from alkyl, aryl, acetylacetonate, carbonyl, tetrahydrofuranyl or halogen. It should be noted that groups IVB to VIII include groups IVB, VB, VIB, VIIB and VIII.
In one embodiment of the invention, the alkyl group is C 1 -C 10 Is a hydrocarbon group. Preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropylCyclopentyl, cyclohexyl. More preferably, the alkyl group is selected from methyl, ethyl, n-propyl, and the like.
In one embodiment of the invention, aryl is C 6 -C 20 Aryl groups of (a) and derivatives thereof. Preferably, the aryl group is selected from phenyl, substituted phenyl. More preferably, the aryl group is selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, and the like. The aryl derivative may be selected from naphthyl, substituted naphthyl, fluorenyl, and the like.
In one embodiment of the invention, R 6 、R 7 、R 8 、R 9 Selected from the group consisting of acetylacetonate, carbonyl, tetrahydrofuranyl, halogen, and the like. Preferably, R 6 、R 7 、R 8 、R 9 Selected from the group consisting of acetylacetonate, tetrahydrofuranyl, halogen. More preferably, R 6 、R 7 、R 8 、 R 9 Selected from the group consisting of acetylacetonate or tetrahydrofuranyl and halogen.
In one embodiment of the invention, M is independently selected from chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium. Preferably, M is one of chromium (Cr), cobalt (Co), molybdenum (Mo) and nickel (Ni).
In one embodiment of the present invention, the cocatalyst b is an organic compound containing a group IIIA element.
Specifically, the cocatalyst b may be a compound containing a group IIIA metal. Such as alkylaluminum compounds and alkylaluminoxane compounds. The alkylaluminum compound may be various trialkylaluminums such as Triethylaluminum (TEAL), triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum; the alkylaluminum compound may also be an alkylaluminum halide, alkylaluminum hydride or alkylaluminum sesquichloride, such as diethylaluminum chloride (AlEt) 2 Cl) and triethylaluminum (A1) 2 Et 3 Cl 3 ). 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 cocatalyst b may also be a group IIIA non-metal-containing compound, such as an organoboron compound, and the like.
In particular, the cocatalyst b can also be a mixture. For example, the cocatalyst b may be 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 from 0.01 to 100, preferably from 0.1 to 10.
Further, the cocatalyst b is at least one of an alkyl aluminum compound, an alkyl aluminoxane compound and an organoboron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound from which volatile components are removed.
In the invention, the TEAL alkylation capacity is relatively weak, so that the catalyst system provided by the invention can be more suitable; meanwhile, the DMAO can shield the influence of volatile components such as toluene and the like on the catalyst complexing process, so that the activity of a catalyst system is improved, and the consumption of a cocatalyst can be further reduced by mixing the volatile components with the toluene and the DMAO.
Further, the cocatalyst b is a mixture of an alkyl aluminum compound and an alkyl aluminoxane compound for removing volatile components, wherein the alkyl aluminum compound is triethylaluminum and the aluminoxane compound is methylaluminoxane for removing volatile components; the molar ratio of triethylaluminum to methylaluminoxane from which volatile components are removed is from 0.01 to 100, preferably from 0.1 to 10.
Further, the mol ratio of the transition metal complex a to the cocatalyst b is 1:0.1-5000.
Further, the mol ratio of the transition metal complex a to the cocatalyst b is 1:0.1-200.
Further, the mol ratio of the transition metal complex a to the cocatalyst b is 1:1-500.
Further, the mol ratio of the transition metal complex a to the cocatalyst b is 1:1-200.
The preparation of the catalyst system according to the invention is carried out in the following mannerStep (c) description.
In an embodiment of the present invention, the preparation method of the transition metal complex a may include the following steps:
(1) Preparation of Ph 2 PR 1 NLi
Taking a certain amount of Ph 2 PR 1 NH, adding a small amount of n-hexane, and cooling in a refrigerator for 10-20 minutes for standby. Taking a certain amount of n-BuLi, adding a small amount of n-hexane, cooling in a refrigerator for 10-15 min, taking out the two medicines, slowly dripping n-BuLi into the standby solution, naturally heating to room temperature, stirring for reacting for about 12-24h, filtering with a sand core funnel, washing with n-hexane for 2 times, and vacuum drying to obtain white solid Ph 2 PR 1 NLi①。
(2) Preparation of clodronamine
Respectively dissolving a certain amount of N, N-dimethyl ethylenediamine, triethylamine and phosphorus trichloride in a proper amount of dichloromethane for later use; at the temperature of minus 30 ℃, the dichloromethane solution of triethylamine and phosphorus trichloride is added into the dichloromethane solution of N, N-dimethyl ethylenediamine in sequence in a dropwise manner. The temperature is raised to the room temperature, a certain amount of dichloromethane solution of triethylamine is added dropwise again, and stirring is carried out for more than 7 hours. After the reaction, the methylene dichloride is removed by vacuum drying, diethyl ether is added for washing and the light yellow liquid is obtained by filtration; the diethyl ether was removed by vacuum drying to give the crude product, which was distilled under reduced pressure to give the pure product, clodronamine (2), as a colorless clear liquid.
(3) Preparation of asymmetric PNP ligands
Taking a certain amount of normal hexane solution of intermediate chlorophosphine (2), and dripping the normal hexane solution into a lithium compound Ph at the temperature of minus 30 DEG C 2 PR 1 In n-hexane mixture of NLi (1), after reaction overnight under strong stirring, filtration and vacuum drying of the liquid gave a white solid. Purification was performed by washing 3 times with acetonitrile to give the pure white solid product PNP ligand (3).
(4) Preparation of asymmetric PNP/M complexes
Dichloromethane is used as a solvent, the molar ratio of PNP ligand (3) to metal M is 1.05:1, and the reaction is stirred for 2 hours at room temperature. Filtering, washing and drying after the reaction is finished to obtain the PNP/M complex (4).
In one embodiment of the present invention, the method for preparing the catalyst system may comprise the steps of:
the transition metal complex a and the cocatalyst b are premixed or directly added into a reaction system to carry out in-situ synthesis. That is, the catalyst is prepared by mixing the transition metal complex a and the cocatalyst b in advance; or directly adding the transition metal complex a and the cocatalyst b into a reaction system for in-situ synthesis;
the reaction mode of the transition metal complex a and the cocatalyst b in the formula (I) can be liquid phase reaction, such as reaction under the action of a solvent, and the solvent can be selected from toluene, benzene, derivatives thereof and the like; or by solid phase reaction; the catalyst may also be formed by in situ reactions during oligomerization. The reaction may be between one, two or three compounds of the above-mentioned transition metal complex and metal organic cocatalyst. The course of this reaction is also the ageing (pre-complexation) of the catalyst.
The process of the catalyst system of the present invention in the 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 invention, the reaction is carried out 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 one embodiment of the invention, the reaction temperature is 0 ℃ to 200 ℃. Preferably 45℃to 100 ℃.
In one embodiment of the present invention, the ethylene oligomerization reaction may be carried out at a pressure of 0.1MPa to 50MPa, preferably 1.0MPa to 10MPa.
In one embodiment of the present invention, the concentration of the catalyst in the reaction system may be from 0.01. Mu. Mol metal/L to 1000. Mu. Mol metal/L, preferably from 0.1. Mu. Mol metal/L to 10. Mu. Mol metal/L. It is noted that the metal here is a transition metal in the transition metal complex a.
The following further illustrates the present invention in connection with specific examples, but the present invention is not limited to the following examples.
Example 1
1. Preparation of N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine/Cr complexes
(1) Preparation of lithium cyclopentyl (diphenylphosphine) amine (1)
Diphenylphosphine chloride (1.05 g,0.01 mol), cyclopentylamine (0.79 g,0.01 mol) and triethylamine (1.41 g,0.015 mol) were placed in a bottle, and an appropriate amount of THF was added thereto for dissolution. The triethylamine, diphenyl phosphorus chloride in THF was added dropwise to the cyclopentylamine in THF sequentially with vigorous stirring, and allowed to react overnight. The mixture was filtered and the liquid product was dried in vacuo to give a white transparent oil as intermediate N-cyclopentyl-1, 1-diphenylphosphinamine.
A solution of n-butyllithium (3.3 mL, 0.0070. Mu. Mol, -30 ℃) in n-hexane was added dropwise to a solution of intermediate b (1.94 g, 0.0070. Mu. Mol, -30 ℃) in n-hexane under vigorous stirring and reacted overnight. After the reaction, the mixture is filtered to obtain a white solid, and the white solid is dried to obtain a lithium compound lithium cyclopentyl (diphenyl phosphine) amine.
(2) Preparation of Poly (2-chloro-1, 3-dimethyl-1, 3, 2-diazaphosphane) (2)
N, N-dimethylethylenediamine (1.73 g,0.02 mol), triethylamine (2.98 g,0.03 mol) and phosphorus trichloride (3.24 g,0.024 mol) were dissolved in a proper amount of dichloromethane, respectively, for use; at the temperature of minus 30 ℃, the dichloromethane solution of triethylamine and phosphorus trichloride is added into the dichloromethane solution of N, N-dimethyl ethylenediamine in sequence in a dropwise manner. After the reaction mixture was warmed to room temperature, a dichloromethane solution of triethylamine (2.98 g,0.03 mol) was added dropwise thereto, and the mixture was stirred for 7 hours or more. After the reaction, the methylene dichloride is removed by vacuum drying, diethyl ether is added for washing and the light yellow liquid is obtained by filtration; the diethyl ether was removed by vacuum drying to give the crude product, which was distilled under reduced pressure to give the pure product 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphosphane as a colorless transparent liquid.
(3) Preparation of N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine
A solution of intermediate (1) (1.11 g, 0.0070 mol) in n-hexane was taken and added dropwise to a mixture of lithium compound (2) (2.02 g,0.007 mol) in n-hexane at-30℃and reacted overnight with vigorous stirring, followed by filtration and vacuum drying of the liquid to give a white solid. The pure white solid product N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine is obtained after 3 times of purification by washing with acetonitrile. 1 H NMR(400MHz,CDCl 3 )δ7.54-7.51(t,4H), 7.35-7.30(m,6H),3.53(s,2H),3.01-2.99(d,2H),2.53-2.50(d,6H),1.76-1.59(m,8H),1.35-1.34(m,1H). 31 P NMR(162MHz,CDCl 3 )δ111.67-111.60.
(4) Preparation of N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine/Cr complexes
Dehydrated dichloromethane (20 mL), N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine) (0.975 g,2.53 mmol), crCl was charged to a stirred 100mL reactor thoroughly replaced with N2 3 ·(THF) 3 (0.899 g, 2.4. Mu. Mol) and allowing the reaction mixture to react at room temperature for 50 minutes, and then draining the solvent to obtain the N-cyclopentyl-N- (diphenylphosphino) -N-2, 5-dimethyl-2, 4-diazacyclophosphine/Cr complex. Elemental analysis results: theoretical values, C,48.83; the gas phase is taken as H,5.90; n,6.83. Actual measurement value: c,48.75; h,5.96; n,6.92.
2. Oligomerization of ethylene
After heating and vacuumizing a 2.0L stainless steel reaction kettle for 20 minutes, filling nitrogen for replacing for a plurality of times, filling ethylene, heating to a preset temperature, and adding dehydrated methylcyclohexane (1.0L), 0.87mL MAO and 2.4 mu mol of the catalyst. Ethylene tetramerization reaction is carried out at 50 ℃ and 5.0MPa, the temperature and pressure of the reaction are reduced by an ice bath after 60min, and the reaction is stopped by acidified ethanol with the mass fraction of 10 percent. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 2
As in example 1. Except that R is 2 、R 5 Is ethyl. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 3
As in example 1. Except that R is 2 、R 5 Is isopropyl. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 4
As in example 1. Except that the reaction temperature was 30 ℃. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 5
As in example 1. Except that the reaction temperature was 70 ℃. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 6
Same as in example 9. Except that the reaction temperature was 90 ℃. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 7
As in example 1. Except that MAO was added in an amount of 0.58mL. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 8
As in example 1. Except that the ethylene oligomerization was carried out in a 2.0L stainless steel reaction vessel with an addition of methylcyclohexane of 200mL and a reaction pressure of 6.0MPa, wherein the hydrogen partial pressure was 0.5MPa. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 9
As in example 1. Except that the reaction pressure was 3.0MPa. The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
Example 10
The catalyst structure was the same as in example 1. Ethylene oligomerization was evaluated as follows: the 100mL autoclave was evacuated for 20 minutes, replaced with nitrogen several times, then charged with ethylene, warmed to a predetermined temperature, and methylcyclohexane (20 mL) which had not been dehydrated, 0.87mL of MAO, and 2.4. Mu. Mol of the above catalyst were added. The tetramerization reaction is carried out at 30 ℃ and 1MPa, the temperature and pressure of the reaction are reduced by an ice bath after 30min, and the reaction is stopped by acidified ethanol with the mass fraction of 10 percent.
Comparative example 1
The catalyst described in example 1 of Chinese patent 202010717943.1 has the structure shown in the following formula. The ethylene oligomerization evaluation operating conditions were as in example 10.
The catalyst activity, the product yield and the product selectivity results are shown in Table 1.
The ethylene selective oligomerization result shown in Table 1 can be obtained, and the catalyst system provided by the invention has the characteristics of high catalytic activity, high selectivity of the target product 1-hexene+1-octene, low content of 1-butene and low content of byproducts methylcyclopentane and methylenecyclopentane. Compared with comparative example 1, the catalyst activity of the catalyst is obviously higher than that of comparative example 1, the total selectivity of the target product 1-hexene+1-octene of the catalyst is higher, the selectivity of byproducts of methylcyclopentane and methylenecyclopentane is lower, and the content of byproduct polymers is lower. It can be seen that minor changes in the catalyst structure can have a significant impact on catalyst performance.

Claims (7)

1. A catalytic system for the selective trimerization and tetramerization of ethylene, comprising:
a transition metal complex a, wherein the transition metal complex a is an organometallic compound of IVB-VIII groups;
a cocatalyst b, which is an organic compound containing a group IIIA element;
wherein the transition metal complex a has a structure represented by formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 May be the same or different and are each independently selected from alkyl, aryl, acetylacetonate, carbonyl, tetrahydrofuranyl or halogen; the alkyl is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl or cyclohexyl; the aryl is selected from phenyl and substituted phenyl;
m is a transition metal including chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel, or palladium.
2. The catalyst system of claim 1, wherein the catalyst system comprises,
the cocatalyst b is at least one of an alkyl aluminum compound, an alkyl aluminoxane compound and an organoboron compound; wherein the alkylaluminoxane compound includes an alkylaluminoxane compound from which volatile components are removed.
3. The catalyst system of claim 1, wherein the catalyst system comprises,
the mol ratio of the transition metal complex a to the cocatalyst b is 1:0.1-5000.
4. A reaction method for ethylene selective oligomerization is characterized in that,
comprising oligomerization of ethylene in the presence of the catalyst system of any of claims 1-3.
5. A reaction process according to claim 4, wherein,
the reaction is carried out in an inert solvent, wherein the inert solvent is at least one of alkane, aromatic hydrocarbon, alkene or ionic liquid.
6. A reaction process according to claim 4, wherein,
the reaction temperature is 0-200 ℃;
the pressure of the reaction is 0.1 MPa-50 MPa.
7. Use of a catalyst system according to any of claims 1-3 in the selective oligomerization of ethylene.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013168103A1 (en) * 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Oligomerisation of olefinic compounds with reduced polymer formation
CN105722846A (en) * 2013-11-18 2016-06-29 Lg化学株式会社 Ligand compound, catalyst system for olefin oligomerization, and olefin oligomerization method using same
WO2020147372A1 (en) * 2019-01-15 2020-07-23 中国石油化工股份有限公司 Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization
CN111889142A (en) * 2020-07-23 2020-11-06 天津科技大学 A catalyst system, reaction method and application for selective oligomerization of ethylene
CN113019461A (en) * 2021-03-17 2021-06-25 天津科技大学 Catalyst system for selective oligomerization of ethylene, reaction method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013168103A1 (en) * 2012-05-09 2013-11-14 Sasol Technology (Proprietary) Limited Oligomerisation of olefinic compounds with reduced polymer formation
CN105722846A (en) * 2013-11-18 2016-06-29 Lg化学株式会社 Ligand compound, catalyst system for olefin oligomerization, and olefin oligomerization method using same
WO2020147372A1 (en) * 2019-01-15 2020-07-23 中国石油化工股份有限公司 Halogen-containing compound and use thereof as catalyst ligand in ethylene oligomerization
CN111889142A (en) * 2020-07-23 2020-11-06 天津科技大学 A catalyst system, reaction method and application for selective oligomerization of ethylene
CN113019461A (en) * 2021-03-17 2021-06-25 天津科技大学 Catalyst system for selective oligomerization of ethylene, reaction method and application thereof

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