CN111889142B - Catalyst system for selective oligomerization of ethylene, reaction method and application thereof - Google Patents
Catalyst system for selective oligomerization of ethylene, reaction method and application thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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, a reaction method and application thereof, belonging to the technical field of homogeneous catalysis. The catalyst system comprises: a ligand a; a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB-VIII groups; wherein, the structural general formula of the ligand a is shown as the formula (I):
R 1 、R 2 、R 3 、R 4 、R 5 may be the same or different and are each independently selected from alkyl or aryl groups. The catalyst system is used for ethylene selective oligomerization, and has the characteristics of high catalytic activity, high product linear alpha-olefin selectivity, low 1-butene content, high 1-hexene + 1-octene selectivity and few byproducts.
Description
Technical Field
The invention belongs to the technical field of homogeneous catalysis, and particularly relates to a catalyst system for selective oligomerization of ethylene, a reaction method and application thereof.
Background
With the continuous development of global economy and the demand for high performance of synthetic materials, the application of higher linear alpha-olefins such as 1-hexene and 1-octene in the fields of high performance polyolefins, high-end synthetic lubricating oils, and the like is increasing, and the demand thereof is continuously increasing. Ethylene oligomerization is the principal process for producing high purity, linear alpha-olefins such as 1-hexene, 1-octene, 1-decene and 1-dodecene, and generally involves non-selective ethylene oligomerization and selective ethylene oligomerization.
For non-selective ethylene oligomerization technology, several novel ligand-coordinated chromium metal-based homogeneous catalysts have been reported for the synthesis of linear alpha-olefins with a broad carbon number distribution. For example, the use of a PCP backbone ligand chromium catalyst system for the catalysis of non-selective oligomerization of ethylene was reported by Sasol corporation Overett et al, with a product composition that followed the Schulz-Flory distribution (. Alpha = 0.55) (J.mol. Catal. A: chem,2008,283,114). Gambarotta et al reported that pyridine-backbone ligand-derived N, P-coordinated chromium catalysts catalyze ethylene oligomerization under methylaluminoxane activation, but the product distribution is different from Schulz-Flory distribution, C 6 -C 12 The mass fraction of (A) is up to 60-75%, the linearity is high (Organometallics, 2013,32, 7107. Subsequently, danopoulos et al reported that a chromium-based catalyst of similar structure catalyzes the oligomerization of ethylene under the activation of methylaluminoxane to produce a product C 6 -C 12 A mass fraction of 71% (Organometallics, 2016,35,4044). In addition to chromium complexes, complexes of metals such as iron, cobalt, nickel, palladium, titanium, and the like, may also be used in ethylene oligomerization, such as the late transition metal iron, cobalt complex catalysts found by Brookhart, gibson, et al, which have high catalytic activity for ethylene oligomerization and also have very high selectivity for linear alpha-olefins (Brookhart, M, et al, J.Am.chem.Soc.1998,120,7143; gibson, V.C. et al, J. Chem. Commun.1998, 849), but with a high 1-butene content (>10％)、C 6 ～C 12 Low selectivity of linear alpha-olefins.
The ethylene selective oligomerization can generate high-grade linear alpha-olefin such as 1-hexene, 1-octene, 1-decene, 1-dodecene and the like with high selectivity, and has the advantages of good atom economy, simple process route and the like. The activity of the catalyst system and the selectivity of the desired product are key to the evaluation of the advancement of this technology, and the structure of the ligand in the catalyst system plays an important role in this. 2004. Researchers from Sasol corporation of south africa made minor changes based on ethylene trimerization bisphosphine (PNP) ligands developed by professor Wass (chem. Commun.,2002, 858-859), even though the original catalytic system changed from ethylene trimerization to ethylene tetramerization. Then, many chemical companies and scientists in the world carry out follow-up research, such as PNP ligand disclosed by Chinese patent CN1741850A (WO 2004/056478A 1), CN1741849A (WO 2004/056479A 1), CN101032695A, CN101351424A, CN101415494A, CN1651142A, CN101291734A and US2006/0128910A1, korean SK energy company CN201880057196.4, CN201780043063.7, CN201780032874.7, CN201380014632.7, CN201080003564.0, CN201080003564.0, CN200880002464.9, CN200880002464.9, CN200780100280.1, and the catalyst system is designed and synthesized with Cr and MAO for ethylene tetramer, and has higher catalytic activity and longer-time stability. However, the content of the byproduct methyl cyclopentane and methylene cyclopentane in the catalytic system is high, and the total selectivity of linear alpha-olefin is low.
Disclosure of Invention
The invention aims to provide high catalytic activity and high C by finely adjusting the electronic property and steric hindrance of a catalyst ligand substituent 6 ～C 8 An ethylene selective oligomerization catalyst system with linear alpha-olefin selectivity for solving the problem of C in ethylene oligomerization reaction 6 ～C 8 The total selectivity of the linear alpha-olefin is not high.
The invention provides a catalyst system for selective oligomerization of ethylene, which comprises:
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 structural general formula of the ligand a is shown as the formula (I):
R 1 、R 2 、R 3 、R 4 、R 5 may be the same or different and are each independently selected from alkyl or aryl groups.
Further, alkyl is C 1 -C 10 Alkyl groups of (a); preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl, cyclohexyl.
Further, aryl is C 6 -C 20 Aryl groups of (a) and derivatives thereof; preferably, aryl is selected from phenyl, substituted phenyl.
Further, the transition metal compound b is a compound 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-removing alkylaluminoxane compound, wherein the alkylaluminum compound is triethylaluminum, and the aluminoxane compound is volatile component-removing methylaluminoxane.
Further, the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1.
The invention provides a reaction method for selective oligomerization of ethylene, which comprises the oligomerization of ethylene 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 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 MPa.
The invention also provides the use of any of the above catalyst systems in the selective oligomerization of ethylene.
The invention has the following advantages:
the catalyst system provided by the invention has high catalytic activity, the total selectivity of the target product 1-hexene + 1-octene is high, and the selectivity of the by-products methylcyclopentane and methylene cyclopentane is low.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The catalyst system of the present invention is described below.
Note that, in this text, "C" is used 6 ～C 12 Linear alpha-olefin Total selectivity "means C 6 ～C 12 The total amount of linear alpha-olefins in the total product (all linear alpha-olefins and by-products).
The embodiment of the invention provides a catalyst system for selective oligomerization of ethylene, which comprises a ligand a, a transition metal compound b and an activator c. Wherein, the structural general formula of the ligand a is shown as a formula (I) and contains a ligand of phosphorus atoms and nitrogen atoms; the transition metal compound b is a metal compound of IVB-VIII groups, and is a central metal atom; the activator c is a compound containing a group IIIA metal;
wherein, the structural general formula of the ligand a is shown as the formula (I):
R 1 、R 2 、R 3 、R 4 、R 5 may be the same or different and are each independently selected from alkyl or aryl groups.
In one embodiment of the present invention, the alkyl group is C 1 -C 10 The alkyl group of (1). Preferably, the alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl, cyclohexyl. More preferably, the alkyl group is selected from methyl, ethyl, n-propyl, and the like.
In one embodiment of the present invention, aryl is C 6 -C 20 Aryl group of (1) and derivatives thereof. Preferably, aryl is selected from phenyl, substituted phenyl. More preferably, aryl is selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, and the like. The aryl derivative is selected from naphthyl,Substituted naphthyl and fluorenyl, and the like.
In an embodiment of the present invention, the transition metal compound b is a compound of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium. Preferably, the transition metal compound b is CrCl 3 (THF) 3 、CrCl 2 (THF) 2 、CoCl 3 、NiBr 2 One kind of (1). More preferably, the transition metal compound b is a chromium-containing transition metal compound. Alternative chromium compounds include those of the formula CrR n A compound of the formula wherein R n Being an organic negative ion or neutral molecule, R n Usually containing 1 to 10 carbon atoms, n is an integer of 0 to 6, and the valence of chromium is 0 to 6. Specific R n The 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, crCl 3 (THF) 3 、CrCl 2 (THF) 2 One of (phenyl) chromium tricarbonyl and chromium hexacarbonyl.
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.
Specifically, the activator c may be a compound containing a group IIIA metal. Such as alkylaluminum compounds, alkylaluminoxane compounds. The alkylaluminum compound can be various trialkylaluminums, such as Triethylaluminum (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) 2 Cl) and triethylaluminum trichloride (A1) 2 Et 3 Cl 3 ) (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. The activator c may be an alkylaluminum compound and an alkylaluminoxane for removing volatile componentsWherein the alkylaluminum compound is TEAL and the alkylaluminoxane compound is DMAO. Preferably, the molar ratio of TEAL to DMAO is between 0.01 and 100, preferably between 0.1 and 10.
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, and the dosage of the activating agent can be further reduced by mixing the DMAO and the catalyst.
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 triethylaluminium to methylaluminoxane for removing volatile components is from 0.01 to 100, preferably from 0.1 to 10.
Further, the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1.
Further, the molar ratio of the ligand a, the transition metal compound b, and the activator c is 1.
Further, the molar ratio of the transition metal compound b to the activator c is 1:1 to 500.
Further, the molar ratio of the transition metal compound b to the activator c is 1:1 to 200.
The preparation of the catalyst system of the present invention is further illustrated below.
In an embodiment of the present invention, the preparation method of the ligand a may include the steps of:
(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 later use. Adding a certain amount of n-BuLi into 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 reaction for about 12-24h, filtering with a sand core funnel, washing with n-hexane for 2 times, and vacuum dryingAfter drying, white Ph is obtained 2 PR 1 NLi solid.
(2) Preparation of Ph 2 PR 1 NPR 2 R 3
Taking a certain amount of Ph 2 PR 1 Adding NLi into a proper amount of normal hexane, putting the mixture into a refrigerator for later use, and taking ClPNR 2 R 3 NR 4 R 5 Adding appropriate amount of n-hexane, placing in refrigerator, taking out the above solution after 15-20 min, and adding ClPNR 2 R 3 NR 4 R 5 Slowly adding into the above solution, stirring overnight, filtering, vacuum drying to obtain white or yellow oil, adding appropriate amount of n-hexane, stirring, mixing, and recrystallizing in refrigerator. Overnight, the n-hexane solvent was filtered off and dried under vacuum to give the product as a white or pale yellow solid powder.
In one embodiment of the present invention, the preparation method of the catalyst system may include 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 in advance; or directly adding the ligand a, the transition metal compound b and the activator c into a reaction system for in-situ synthesis;
the ligand a, the transition metal compound b and the activator c in the formula (I) can be reacted in a liquid phase reaction, for example, in the presence of a solvent, and optionally in a solvent such as 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 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 one embodiment of the invention, the reaction temperature is 0-200 ℃. Preferably from 45 ℃ to 100 ℃.
In one embodiment of the present invention, the pressure of the ethylene oligomerization reaction can be performed 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. 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 N- (dimethylamino) phosphine-N- (diphenylphosphino) cyclopentylamine (L1):
taking lithium cyclopentyl (diphenylphosphine) amine (0.9019g, 3.3mmol) and adding a proper amount of n-hexane into a refrigerator for later use, then taking dimethylamino phosphonium chloride (0.51g, 3.3mmol) and adding a proper amount of n-hexane into the refrigerator, taking out the solution after 15-20 minutes, and slowly adding the dimethylamino phosphonium chloride solution into the standby solution. Stirring overnight, filtering, vacuum drying to obtain yellow oily substance, adding appropriate amount of n-hexane, stirring, mixing, and recrystallizing in refrigerator. Overnight, the n-hexane solvent was filtered off and dried under vacuum to give a white solid powder.
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 N 2 A well-replaced stirred 100mL reactor was charged with non-dehydrated methylcyclohexane (20 mL), N- (dimethylamino) phosphine-N- (diphenylphosphino) cyclopentylamine (L1) (0.98 mg) (2.53. Mu. Mol), crCl 3 ·(THF) 3 (0.9mg, 2.4. Mu. Mol), and reacting at room temperature for 5 min.
3. Oligomerization of ethylene
A100 mL low-pressure autoclave was evacuated for 20 minutes, purged with nitrogen several times, charged with ethylene, heated to a predetermined temperature, and charged with non-dehydrated methylcyclohexane (20 mL), 0.87mL of MAO and the above catalyst. Carrying out oligomerization reaction at 30 ℃ 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%. To obtain 1.01g of oligomerization product and the activity of the catalyst is 0.84 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 2
The same as in example 1. With the difference that R 2 、R 3 Is ethyl, R 4 、R 5 Is ethyl. Obtain 0.86g of oligomerization product and the activity of the catalyst is 0.72 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 3
The same as in example 1. With the difference that R 2 、R 3 Methyl, R 4 、R 5 Is ethyl. To obtain 1.24g of oligomerization product and the activity of the catalyst is 1.03 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 4
The same as in example 1. With the difference that R 2 、R 3 Is n-propyl, R 4 、R 5 Is n-propyl. The oligomerization product 0.78 g is obtained, and the catalyst activity is 0.65 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 5
The same as in example 1. With the difference that R 2 、R 3 Is isopropyl, R 4 、R 5 Is isopropyl. The oligomerization product 0.64 g is obtained, and the catalyst activity is 0.53 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 6
The same as in example 1. With the difference that R 2 、R 3 Is cyclopentyl, R 4 、R 5 Is methyl. Obtain 0.73g of oligomerization product and the activity of the catalyst is 0.61 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 7
The same as in example 1. With the difference that R 2 、R 3 Is cyclohexyl, R 4 、R 5 Is n-propyl. Obtain oligomerization product 0.36 g and catalyst activity 0.30X 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 8
The same as in example 1. With the difference that R 2 、R 3 Is phenyl, R 4 、R 5 Is phenyl. To obtain 0.37g of oligomerization product and 0.31 multiplied by 10 of catalyst activity 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 9
The same as in example 1. Except that the reaction temperature was 50 ℃. Obtain 0.76g of oligomerization product and the activity of the catalyst is 0.63 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and the catalyst activity are shown in Table 2.
Example 10
The same as in example 1. Except that the reaction temperature was 70 ℃. Obtain 0.58g of oligomerization product and the activity of the catalyst is 0.48 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Example 11
The same as in example 9. Except that the reaction temperature was 90 ℃. Obtain 0.43g of oligomerization product and the activity of catalyst is 0.36X 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 12
The same as in example 11. Except that the amount of MAO added was 0.58mL. Obtain 0.92g of oligomerization product and the activity of catalyst is 0.77X 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 13
The same as in example 1. Except that the ethylene oligomerization reaction is carried out in a 1.0L stainless steel reaction kettle, the adding amount of the methylcyclohexane is 200mL, the reaction pressure is 6.0MPa, and the hydrogen partial pressure is 0.5MPa. Obtain 47g of oligomerization product, the catalyst activity is 3.92 multiplied by 10 7 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Example 14
The same as in example 1. Except that the reaction pressure was 3.0MPa. 3.05g of oligomerization product is obtained, and the activity of the catalyst is 2.54 multiplied by 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in Table 1, and the experimental conditions and catalyst activities are shown in Table 2.
Comparative example 1
The same as in example 1. Except that the ligands differ in structure as shown in the following formula:
obtain 0.19g of oligomerization product and the activity of catalyst is 0.16X 10 6 g oligomer/mol Cr.h. The distribution of the oligomerization products is shown in table 1, and the experimental conditions and catalyst activity are shown in table 2.
Claims (7)
1. The application of a catalyst system in the selective oligomerization reaction of ethylene to produce 1-octene and 1-hexene is characterized in that,
the catalyst system comprises:
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 structural general formula of the ligand a is shown as the formula (I):
R 1 、R 2 、R 3 、R 4 、R 5 may be the same or different and are each independently selected from alkyl or aryl;
the alkyl group is C 1 -C 10 Alkyl groups of (a); the aryl group is phenyl.
2. Use according to claim 1,
the alkyl is selected from methyl, ethyl, n-propyl, isopropyl, cyclopentyl and cyclohexyl.
3. Use according to claim 1,
the transition metal compound b is a compound of chromium, molybdenum, tungsten, cobalt, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium.
4. Use according to claim 1,
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 comprises an alkylaluminoxane compound having a volatile component removed.
5. Use according to claim 1 or 4,
the activating agent 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.
6. Use according to claim 1,
the molar ratio of the ligand a to the transition metal compound b to the activator c is 1:0.5 to 100:0.1 to 5000.
7. Use according to claim 1,
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 0.1MPa to 50MPa.
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