CN110586188B - 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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CN110586188B
CN110586188B CN201910000024.XA CN201910000024A CN110586188B CN 110586188 B CN110586188 B CN 110586188B CN 201910000024 A CN201910000024 A CN 201910000024A CN 110586188 B CN110586188 B CN 110586188B
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catalyst system
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ligand
activator
ethylene
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CN110586188A (en
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张乐
李斌
王光远
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Shanghai Zhiying Chemical Technology Co ltd
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Handan College
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • 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
    • 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 metal chromium compound b; an activator c, the activator c being a compound containing a group IIIA metal; wherein, the ligand a is a structure shown in a general formula I, wherein R1And R2Is a substituent on the triazolyl group; r3And R4Is a substituent on a silicon atom; r1、R2、R3And R4May be the same or different; n and m are the number of methylene groups in the linking group, which may be the same or different. The ethylene selective oligomerization catalyst system is used for ethylene oligomerization, has high catalytic activity and is a target product 1-C10And 1-C12Compared with the prior art, the total selectivity of the catalyst is obviously improved, and the catalyst is simple to synthesize, low in cost and long in 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 ethylene selective oligomerization and an ethylene oligomerization reaction method.
Background
The linear alpha-olefin has wide application in the fields of ethylene comonomer, surfactant synthetic intermediate, alcohol for plasticizer, synthetic lubricating oil, oil additive and the like. In recent years, with the continuous development of polyolefin industry, the world is wideThe demand for alpha-olefins is growing rapidly. Of linear alpha-olefins, 1-C10And 1-C12The lubricating oil base oil prepared from the high-grade lubricating oil is better in performance, and has the advantages of small evaporation loss, low condensation point, high viscosity index, good thermal oxidation stability and the like compared with the polymerized oil consisting of other alpha-olefins.
Currently, the vast majority of linear alpha-olefins are prepared by oligomerization of ethylene. But 1-C10And 1-C12The selective oligomerization technology of the method has not been overcome at present, and the main production method is obtained from non-selective oligomerization products through a complicated rectification process. Among the conventional ethylene oligomerization products, 1-C10And 1-C12Has a relatively low selectivity of, among them, 1-C10Selectivity of less than 20%, 1-C12The selectivity of (A) is less than 15%.
Thus, a 1-C was devised10And 1-C12The ethylene oligomerization catalyst system with high selectivity is worth attention of the industry.
Disclosure of Invention
The invention aims to provide a catalyst system for selective oligomerization of ethylene, which aims to solve the problem of 1-C in the prior art10And 1-C12The selectivity is not high.
A catalyst system for selective oligomerization of ethylene comprises three components:
a ligand a;
a metal chromium compound b;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a is a structure shown in a general formula I and is as follows:
Figure RE-GDA0002263873370000011
R1and R2Is a substituent on the triazolyl group; r3And R4Is a substituent on a silicon atom; r1、R2、R3And R4May be the same or different; n and mThe number of methylene groups in the linker group may be the same or different.
Further, the substituent group R1、R2、R3And R4Each independently selected from hydrogen, methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl; n 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.
Further, the metal chromium compound b is CrCl2(THF)2、CrCl3(THF)3One of chromium acetylacetonate, chromium isooctanoate or chromium carbonyl.
Further, 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 includes an alkylaluminoxane compound from which a volatile component is 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 the triethyl aluminum to the methyl aluminoxane for removing volatile components is 0.01-100, preferably 0.1-10.
Further, the molar ratio of the ligand a to the metal chromium compound b to the activator c is 1: 0.5-100: 0.1-5000; preferably, the molar ratio of the ligand a, the metal chromium compound b and the activating agent c is 1: 0.5-100: 0.1-1000; more preferably, the molar ratio of the ligand a, the metal chromium compound b and the activator c is 1: 0.5-100: 0.1-200.
Further, the ligand a, the metal chromium compound b and the activator c are mixed in advance or directly added into a reaction system for in-situ synthesis.
Further, the molar ratio of the metal chromium compound b to the activator c is 1: 1-500.
The invention also provides a preparation method of the ethylene oligomerization catalyst system, which is characterized in that the ligand a, the metal chromium 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.
The catalyst system for selective oligomerization of ethylene provided by the invention has the following advantages:
(1) the catalyst system has high catalytic activity and wide oligomerization product distribution, and compared with the prior art, the catalyst system has 1-C10And 1-C12The sum of the total selectivities of (A) is significantly increased, up to 44%, where 1-C10The selectivity can reach 28 percent, 1-C12The selectivity can reach 16%.
(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 metal chromium compound b;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a is a structure shown in a general formula I and is as follows:
Figure RE-GDA0002263873370000031
R1and R2Is a substituent on the triazolyl group; r3And R4Is a substituent on a silicon atom; r1、R2、R3And R4May be the same or different; n and m are the number of methylene groups in the linking group, which may be the same or different.
In the embodiment of the invention, the ligand a is a bis-triazole structure connected with flexible chain-like groups containing silicon, wherein R is1And R2Is a substituent group at the 3,5 position on the triazole group; r3And R4Is a substituent group on a silicon atom; r is1、R2、R3And R4May be the same or different; n and m are the number of methylene groups in the bridging group, and may be the same or different.
In the prior art, an ethylene selective oligomerization catalyst system is mainly an ethylene selective trimerization and/or tetramerization catalyst system, and most of linear alpha-olefins of products of the ethylene non-selective oligomerization catalyst system are distributed in S-F (S-F) form, wherein 1-C10Selectivity of less than 20%, 1-C12The selectivity of the catalyst is lower than 15 percent, and the catalyst can be used for producing 1-C by ethylene selective oligomerization10And 1-C12The catalyst system of (A) has not yet been overcome. At present, 1-C10And 1-C12The main production method is also obtained from the non-selective oligomerization products by a complicated rectification process, and has complicated operation and higher cost.
The catalyst system for selective oligomerization of ethylene provided by the embodiment of the invention has high catalytic activity and wide distribution of oligomerization products, mainly 1-C6，1-C8，1-C10And 1-C12Predominantly, 1-C compared to the prior art10And 1-C12The sum of the total selectivities of (A) is significantly increased, up to 44%, where 1-C10The selectivity can reach 28 percent, 1-C12The selectivity can reach 16%. Note that, in the text, "1-C" is used10And 1-C12By total selectivity is meant 1-C10And 1-C12The total amount of (a) is the proportion of all linear alpha-olefins in the product.
The embodiment of the invention provides a catalyst system for ethylene selective oligomerization, which comprises three components of a ligand a, a metal chromium compound b and an activator c. The ligand a is a bis-triazole structure connected with flexible chain-like groups containing silicon; the metal chromium compound b is a central metal atom; the activator c acts as an activator in the catalyst system.
The ligand a of the catalyst system provided by the embodiment of the invention can form stable complexation with metal chromium ions by utilizing the strong coordination property of the triazole group containing three nitrogen atoms, thereby ensuring that the catalyst has longer service life; the difference of the substituent groups on the triazole group and the silicon atom in the ligand a can effectively adjust the electronic effect and the steric effect of the ligand a on the chromium ion at the metal active center, and finally the catalyst system provided by the embodiment of the invention is used for ethylene oligomerization, has excellent catalytic activity and higher 1-C10And 1-C12And (4) selectivity.
The metal chromium compound b of the catalyst system provided by the embodiment of the invention is CrCl2(THF)2、CrCl3(THF)3One of chromium acetylacetonate, chromium isooctanoate or chromium carbonyl. The metal atom in the metal chromium 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.
In the catalyst system provided by the embodiment of the invention, under the action of the activator c, the ligand a has strong coordination according to the triazolyl group, R1、R2、R3And R4The difference of substituent group structures and the length of connecting groups, namely the difference of the number of methylene groups, effectively adjusts the electronic effect and the steric hindrance effect of the ligand a on the metal active center, and the components a, b and C have the combined action of the components a, b and C to have the catalytic activity of selective oligomerization of ethylene and have the 1-C characteristic10And 1-C12The overall selectivity and the amount of activator used have a significant impact.
Furthermore, the molar ratio of the ligand a to the metal chromium compound b in the catalyst system can be 1: 0.5-100.
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 metal chromium compound b to the activator c is 1: 0.5-100: 0.1-5000; preferably, the molar ratio of the ligand a to the metal chromium compound b to the activator c is 1: 0.5-100: 0.1-1000; more preferably, the molar ratio of the ligand a, the metal chromium compound b and the activator c is 1: 0.5-100: 0.1-200.
In yet another embodiment of the present invention, the molar ratio of the metal chromium compound b to the activator c is 1:1 to 500. The Al/M molar ratio is relatively low, and the industrial cost is reduced.
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 metal chromium 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, etc.
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 has a structure shown in formula I, as follows:
Figure RE-GDA0002263873370000051
wherein R is1And R2Is a substituent on the triazolyl group; r3And R4Is a substituent on a silicon atom; r1、R2、 R3And R4May be the same or different; n and m are the number of methylene groups in the linking group, which may be the same or different.
In one embodiment of the present invention, the substituent group R1、R2、R3And R4Each independently selected from hydrogen, methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl; n 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.
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.
(2) Metal chromium compound b
In an embodiment of the invention, the metal chromium compound b is CrCl2(THF)2、CrCl3(THF)3One of chromium acetylacetonate, chromium isooctanoate or chromium carbonyl. The above-mentioned chromium metal compounds are more suitable for the catalytic system from the viewpoint of easy dissolution and easy handling.
(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 and an alkylaluminoxane compound, wherein the alkylaluminoxane compound includes 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 IIIChlorotriethylaluminum (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.
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, thereby improving the activity of the catalyst system.
Specifically, the activator c is a mixture of an alkylaluminum compound and 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.
Accordingly, in one embodiment of the present invention, a suitable catalyst system comprises three components:
a ligand a; a metal chromium compound b; an activator c;
the ligand a has a structure shown in a general formula I, and the general formula I is as follows:
Figure RE-GDA0002263873370000061
the ligand a is a silicon-containing flexible chain group bridged bis-triazole structure, wherein R1And R2Is a substituent group at the 3,5 position on the triazole group; r3And R4Is a substituent on a silicon atom in the bridging group; r1、R2、R3And R4May be the same or different; n and m are the number of methylene groups in the bridging group, and may be the same or different.
The substituent group R1、R2、R3And R4Each independently selected from methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl; n 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.
The metal chromium compound b can be CrCl2(THF)2、CrCl3(THF)3One of chromium acetylacetonate, chromium isooctanoate or chromium carbonyl.
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 activating agent c can also be a mixture of one or more than two of the above, for example, the activating agent c is a mixture of TEAL and DMAO, wherein the molar ratio of TEAL to DMAO is 0.01-100, preferably 0.1-10.
The preparation of the catalyst system of the present invention is further illustrated below.
In an embodiment of the present invention, the specific synthesis steps of the ligand a may include the following steps:
dissolving a certain amount of triazole compound in a proper amount of anhydrous tetrahydrofuran, adding a proper amount of sodium sand, stirring at room temperature overnight, slowly dripping a proper amount of dichlorosilane into the reaction solution, heating and refluxing for 12 hours, cooling, filtering, vacuumizing to remove volatile components in the filtrate to obtain a crude product, and recrystallizing by using a normal hexane/toluene mixed solution to obtain a pure ligand a product.
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 metal chromium compound b, and the activator c linked by the heteroatom-containing linking group in advance; the ligand a, the metal chromium compound b and the activator c can also be directly added into the reaction system for in-situ synthesis.
The catalyst system of the present invention is used in the oligomerization of ethyleneAnd (5) explaining the steps.
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, aromatic hydrocarbon, 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 chromium/L to 1000. mu. mol chromium/L, preferably from 0.1. mu. mol chromium/L to 10. mu. mol chromium/L.
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 R is1And R2Are all H, R3And R4When the two are methyl, and m is 1, the ligand is bis (1H-1,2, 4-triazole-1-methyl) dimethyl silane
In the warp of N2A250 ml reactor with a stirrer was fully replaced, and dehydrated THF (100ml) and triazole (17.02g, 0.25mol) were added, stirred uniformly, added with prepared sodium sand (5.75g, 0.25mol), and stirred overnight at room temperature under nitrogen. Di (chloromethyl) dimethylsilane (19.64g, 0.125mol) was dissolved in 20mL of anhydrous tetrahydrofuran at room temperature, and the solution was slowly added dropwise to the above reaction solution, and heated under reflux for 12 hours. Cooling, filtering, vacuum drying volatile components to obtain 23.9g crude product, and adding toluene/n-hexane mixed solvent (volume ratio 1:1) to obtain the final productCrystallization gave 20.7g (yield 74.5%) of pure product.
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-replaced stirred 100mL reactor was charged with dehydrated methylcyclohexane (20mL) DMAO (0.15g, 2.6mmol), TEAL (0.08g, 0.7mmol), bis (1H-1,2, 4-triazole-1-methyl) dimethylsilane (15mg) (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, and after several nitrogen replacements, ethylene was charged, and the temperature was lowered to a predetermined temperature, and then dehydrated methylcyclohexane (200mL) and the above-mentioned catalyst were added. 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 2.81 multiplied by 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 2
The same as in example 1. With the difference that R3、R4Is 2, 6-diisopropylphenyl. The catalyst activity was 1.01X 107g of oligomer/molCr. h. The distribution of the oligomerization products is shown in Table 1.
Example 3
The same as in example 1. With the difference that R3、R4Is cyclohexyl. The catalyst activity was 1.51X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 4
The same as in example 1. With the difference that R1、R2Is methyl, R3、R4Is naphthyl. The catalyst activity was 1.27X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 5
The same as in example 1. With the difference that R1、R2Is cyclopentyl, R3、R4Is methyl. The catalyst activity was 1.85X 107g oligomer/molCr.h. The distribution of the oligomeric products is shown in Table 1.
Example 6
The same as in example 1. With the difference that R1Is phenyl, R2Is methyl, R3Is cyclohexyl, R4Is naphthyl. The catalyst activity was 1.98X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 7
The same as in example 1. The difference is that m is 2 and n is 3. The catalyst activity was 2.24X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 8
The same as in example 1. Except that the ethylene pressure was 2 MPa. The catalyst activity was 3.11X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 9
The same as in example 1. Except that the reaction temperature was 75 ℃. The catalyst activity was 2.99X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 10
The same as in example 1. 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). The catalyst activity was 2.30X 107g oligomer/molCrh. The distribution of the oligomerization products is shown in Table 1.
Example 11
The same as in example 1. Except that activator c is MAO. The catalyst activity was 3.01X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
Example 12
The same as in example 1. Except that activator c is MMAO. The catalyst activity was 1.6X 107g oligomer/molCr.h. The distribution of the oligomerization products is shown in Table 1.
The experimental conditions and catalyst activities of examples 1-12 are shown in Table 2.
The data in tables 1 and 2 show that oligomerization is shown in Table 1The carbon number distribution of the product is mainly 1-C6、1-C8、1-C10、 1-C12Mainly, wherein 1-C10And 1-C12The total selectivity is obviously higher than that of the prior art (1-C)10Selectivity of less than 20%, 1-C12Less than 15%) of the selectivity. And, as pressure increases, product selectivity and activity increases; as the temperature increases, the product selectivity and activity also increases.
Figure RE-RE-GDA0002263873370000111
Figure RE-GDA0002263873370000121
Figure RE-GDA0002263873370000131

Claims (10)

1. A catalyst system for ethylene selective oligomerization is characterized by comprising three components:
a ligand a;
a metal chromium compound b;
an activator c, the activator c being a compound containing a group IIIA metal;
wherein, the ligand a is a structure shown in a general formula I and is as follows:
Figure FDA0003642484470000011
R1and R2Is a substituent on the triazolyl group; r3And R4Is a substituent on a silicon atom; r1、R2、R3And R4May be the same or different; n and m are the number of methylene groups in the linking group, which may be the same or different;
wherein R is3And R4Each independently selected from hydrogen, methyl, isopropyl, cyclohexyl or cyclopentyl.
2. The catalyst system of claim 1, wherein: the substituent group R1And R2Each independently selected from hydrogen, methyl, isopropyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 2, 6-diisopropylphenyl; n 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.
3. The catalyst system of claim 1, wherein: the metal chromium compound b is CrCl2(THF)2、CrCl3(THF)3One of chromium acetylacetonate, chromium isooctanoate or chromium carbonyl.
4. The catalyst system of claim 1, wherein: 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.
5. The catalyst system according to claim 1 or 4, characterized in that: the activating agent c is a mixture of an alkyl aluminum compound and an alkylaluminoxane compound for removing volatile components, wherein the alkyl aluminum compound is triethylaluminum, and the alkylaluminoxane compound is methylaluminoxane for removing volatile components; the molar ratio of the triethyl aluminum to the methylaluminoxane without volatile components is 0.01-100.
6. The catalyst system according to claim 1, characterized in that: the molar ratio of the ligand a to the metal chromium compound b to the activator c is 1: 0.5-100: 0.1-5000.
7. The catalyst system according to claim 6, characterized in that: the molar ratio of the ligand a, the metal chromium compound b and the activating agent c is 1: 0.5-100: 0.1-1000.
8. The catalyst system according to claim 7, characterized in that: the molar ratio of the ligand a to the metal chromium compound b to the activator c is 1: 0.5-100: 0.1-200.
9. A process for preparing a catalyst system as claimed in any one of claims 1 to 8, characterized in that: and the ligand a, the metal chromium 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, and the reaction temperature is 0-200 ℃; the reaction pressure is 0.1 MPa-50 MPa.
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