CN115301290B - Catalyst for ethylene selective tetramerization and application thereof - Google Patents

Catalyst for ethylene selective tetramerization and application thereof Download PDF

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CN115301290B
CN115301290B CN202210920804.8A CN202210920804A CN115301290B CN 115301290 B CN115301290 B CN 115301290B CN 202210920804 A CN202210920804 A CN 202210920804A CN 115301290 B CN115301290 B CN 115301290B
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aluminum
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CN115301290A (en
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张瑛
盛东海
宁尧
田淑慧
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China University of Petroleum Beijing
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    • 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
    • B01J31/1805—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 nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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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
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
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    • 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 application provides a catalyst for ethylene selective tetramerization and application thereof. The catalyst comprises binuclear halogenated pyridine imine shown in formula I or formula IIMetal complex: in formula I and formula II, R is independently selected fromn=0, 1,2,3,4,5, orR 1 And R is R 1 ' independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C15 aryl; r is R 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’，R 5 ' independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, halogen, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C15 aryl, and nitro; m is M 1 Selected from Fe 2+ 、Co 2+ And Ni 2+ One of the following; m is M 2 Is Fe 3+ The method comprises the steps of carrying out a first treatment on the surface of the X is independently selected from one of halogens. The catalyst has excellent ethylene oligomerization activity and 1-octene selectivity.

Description

Catalyst for ethylene selective tetramerization and application thereof
The present application claims priority from chinese patent application filed at 26 of 08 of 2021, application number 202110986355.2, entitled "catalyst for ethylene selective tetramerization and its use", the entire contents of which are incorporated herein by reference.
Technical Field
The application belongs to the field of ethylene oligomerization catalysis, and relates to a catalyst for ethylene selective tetramerization and application thereof.
Background
1-octene is an important chemical product and intermediate, and is mainly used in the fields of polyethylene, plasticizer, essence and spice, lubricating oil, oil additives and the like.
Although 1-octene has important application value, the carbon number distribution of the product obtained by the traditional ethylene oligomerization technology accords with the Schlulz-Flory distribution, and the distribution makes the 1-octene in the oligomerization product impossible to be too high. At present, the method for synthesizing 1-octene by oligomerization of ethylene adopts a chromium catalyst for catalytic synthesis, but the selectivity of the 1-octene in the method is still limited, and the catalyst cost is higher.
Disclosure of Invention
The application provides a catalyst for ethylene selective tetramerization, which comprises a binuclear halogenated pyridine imine metal complex shown in a formula I or a formula II, and can show good ethylene oligomerization activity and high 1-octene selectivity when being used in ethylene tetramerization reaction.
The application also provides a preparation method of the 1-octene, which has the advantages of high reaction activity and high 1-octene yield because the preparation method uses the catalyst to catalyze the ethylene oligomerization reaction.
The application provides a catalyst for ethylene selective tetramerization, which comprises a binuclear halogenated pyridine imine metal complex shown in a formula I or a formula II:
in the formulae I and II,
r is independently selected fromn=0, 1,2,3,4,5, or +.>
R 1 And R is R 1 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C15 aryl;
R 2 ，R 3 ，R 4 ，R 5 and R is R 2 ’，R 3 ’，R 4 ’，R 5 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, halogen, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C15 aryl, and nitro;
M 1 selected from Fe 2+ 、Co 2+ And Ni 2+ One of the following;
M 2 is Fe 3+ ；
X is independently selected from one of halogens.
The catalyst as described above, wherein R 1 And R is R 1 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted phenyl;
and/or R 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’R 5 ' each independently selected from one of hydrogen, C1-C4 alkyl, fluoro, chloro, bromo, methoxy, ethoxy, or nitro.
The catalyst as described above, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituent groups in' are each independently selected from at least one of hydrogen, alkyl, aryl, alkoxy, halogen, nitro.
The catalyst as described above, wherein R is selected fromn＝0,2,3。
A catalyst as described above wherein the catalyst further comprises an aluminum-containing promoter.
The catalyst as described above, wherein the aluminum-containing cocatalyst is selected from at least one of aluminoxanes and alkylaluminum compounds.
The catalyst as described above, wherein the molar ratio of aluminum in the aluminum-containing cocatalyst to metal in the binuclear pyridinimine metal halide complex is (200 to 2000): 1.
The application also provides a preparation method of the 1-octene, which comprises the following steps: after the catalyst is mixed with an organic solvent, ethylene is introduced into the mixed system for oligomerization reaction, and 1-octene is obtained.
The production method as described above, wherein the organic solvent is at least one selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and methylene chloride.
The preparation method comprises the step of preparing the binuclear halogenated pyridine imine metal complex shown in the formula I or the formula II in a mixed system, wherein the molar concentration of the binuclear halogenated pyridine imine metal complex in the mixed system is 2-500 mu mol/L.
The catalyst disclosed by the application comprises a binuclear halogenated pyridine imine metal complex shown in a formula I or a formula II, and when the catalyst is used in an ethylene tetramerization reaction, the reaction can show good ethylene oligomerization activity and high 1-octene selectivity.
The preparation method of 1-octene provided by the application has the advantages of high reaction activity and high 1-octene yield.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The first aspect of the application provides a catalyst comprising a binuclear halogenated pyridine imine metal complex represented by formula I or formula II:
r in formula I and formula II may be the same or different and each may be independently selected fromn=0, 1,2,3,4,5, or +.>
R in formula I and formula II 1 And R is R 1 ' may be the same or different, and each may be independently selected from one of hydrogen, a substituted or unsubstituted C1-C6 alkyl group, and a substituted or unsubstituted C6-C15 aryl group;
r in formula I and formula II 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’，R 5 ' may be the same or different, and each may be independently selected from one of hydrogen, a substituted or unsubstituted C1-C6 alkyl group, halogen, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C6-C15 aryl group, and a nitro group;
m in formula I 1 Selected from Fe 2+ 、Co 2+ And Ni 2+ One of the following;
m in formula II 2 Is Fe 3+ ；
X in the formula I and the formula II can be the same or different and can be independently selected from one of halogens.
In the present application, the term "C1-C6 alkyl" refers to a saturated straight-chain hydrocarbon group or a saturated branched-chain hydrocarbon group having 1 to 6 carbon atoms, and specifically may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, sec-hexyl and the like.
In the present application, the term "C1-C6 alkoxy" refers to a group obtained by linking a C1-C6 alkyl group to an oxygen atom, and specifically may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, n-hexyloxy and Zhong Ji oxy; methoxy, ethoxy, and the like are particularly preferred.
In the present application, the term "halogen" refers to fluorine, chlorine, bromine, iodine.
In the present application, the term "aryl group of C6 to C15" means an aromatic ring-containing group having 6 to 15 carbon atoms, and may be, for example, phenyl, naphthyl, or the like.
The inventor researches find that when the binuclear halogenated pyridine imine metal complex shown in the formula I or the formula II is included in the catalyst, the catalyst has good ethylene oligomerization activity and high 1-octene selectivity. Wherein the ethylene oligomerization activity can reach 10 6 g/(mol (M). H.atm) above, 1-octene selectivity can be up to above 48.64%.
Further, R in formula I and formula II 1 And R is R 1 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted phenyl;
and/or R 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’，R 5 ' each independently selected from one of hydrogen, C1-C4 alkyl, substituted or unsubstituted phenyl, fluoro, chloro, bromo, methoxy, ethoxy, or nitro.
By way of example, the C1-C4 alkyl group may be methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, etc.
In a specific embodiment, R in formula I or formula II 1 And R is R 1 ' are all methyl groups, R 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’R 5 ' are both hydrogen.
In another specific embodiment, R in formula I or formula II 1 ，R 2 ，R 3 ，R 4 ，R 5 And R is R 1 ’，R 2 ’，R 3 ’，R 4 ’，R 5 ' are both hydrogen.
Further, R 1 、R 2 、R 3 、R 4 、R 5 And R is R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituent groups in' are each independently selected from at least one of hydrogen, alkyl, aryl, alkoxy, halogen, nitro. The substituents herein refer to, when R 1 、R 2 、R 3 、R 4 、R 5 And R is R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 When the substituent is selected from the aforementioned groups substituted with a substituent, for example, a substituted C1-C6 alkyl group, a substituted C1-C6 alkoxy group, or the like, the substituent is selected from at least one of hydrogen, an alkyl group, an aryl group, an alkoxy group, a halogen, and a nitro group. Wherein the alkyl group may be a C1-C9 straight chain alkyl group or a branched alkyl group such as methyl, ethyl, propyl, isopropyl, etc., and the aryl group may be phenyl, naphthyl, etc.
In a specific embodiment, when R is selected fromn=0, 2,3, when the catalyst comprising the binuclear halogenated pyridine imine metal complex shown in the formula I or the formula II is used for ethylene oligomerization, the reaction has higher ethylene oligomerization activity and higher 1-octene selectivity, wherein the 1-octene selectivity can be up to 65% or more.
Compared with Co 2+ And Ni 2+ When M in the binuclear halogenated pyridine imine metal complex shown in formula I in the application 1 Further selected from Fe 2+ When the catalyst shows more excellent ethylene oligomerization activity and 1-octene selectivity.
The application is not limited to the preparation method of the binuclear halogenated pyridine imine metal complex shown in the formula I or the formula II, and the binuclear halogenated pyridine imine metal complex can be prepared by adopting a conventional method in the field.
In a specific embodiment, the dinuclear pyridinimine metal halide complexes of formula I and formula II can be prepared by the following preparation method:
according to the above reaction scheme, the starting materials a, b, c are reacted to give ligand d, which is then reacted with a metal dihalide salt M 1 X 2 The binuclear halogenated pyridine imine metal complex shown in the formula I is obtained through the reaction. Similarly, ligand d is reacted with a metal trihalide salt M 2 X 3 The binuclear halogenated pyridine imine metal complex shown in the formula II can be obtained after the reaction. Wherein R in formula a 1 、R 2 、R 3 、R 4 、R 5 And R in formula I and formula II 1 、R 2 、R 3 、R 4 、R 5 Wherein R in formula b is as defined above 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 ' and R in formula I and formula II 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The definition in' is the same, R in formula c is the same as that in formula I and formula II.
Further, the catalyst of the present application further comprises an aluminum-containing cocatalyst. When the catalyst is used in ethylene oligomerization, the aluminum-containing cocatalyst can eliminate residual oxygen and water in the reaction system and can be used in combination with binuclear halogenated pyridine imine metal complex to raise the catalytic activity.
Further, the aluminum-containing cocatalyst is selected from at least one of aluminoxane and an aluminum alkyl compound.
Specifically, the aluminoxane is a C1 to C4 alkylaluminoxane, more preferably methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane, still more preferably methylaluminoxane.
Specifically, the general formula of the alkyl aluminum compound is AlR n X m Wherein R is selected from C1-C8 alkyl; x is halogen, preferably from chlorine or bromine; the sum of n and m is 3, n is an integer from 1 to 3, and m is an integer from 0 to 2.
The alkylaluminum compound may be preferably selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, and more preferably diethylaluminum chloride.
In a specific embodiment, when the molar ratio of aluminum in the aluminum-containing cocatalyst to metal in the binuclear halogenated pyridine imine metal complex is (200-2000): 1, the catalyst has better catalytic activity, and shows more excellent ethylene oligomerization activity and 1-octene selectivity.
The second aspect of the present application provides a process for producing 1-octene, comprising: after the catalyst is mixed with an organic solvent, ethylene is introduced into the mixed system for oligomerization reaction, and 1-octene is obtained.
Mixing as described in the above procedure refers to the mixing of the organic solvent system of the catalyst and the organic solvent as the reaction solvent. The organic solvent system of the catalyst can be obtained by mixing the organic solvent system of each component in the catalyst, or can be obtained by mixing each component in the catalyst and then mixing the mixture with the organic solvent. That is, the above-mentioned mixed system means a reaction system before ethylene is introduced.
Further, the organic solvent is at least one selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and methylene chloride. The organic solvent can better dissolve the catalyst, so that the catalyst is catalyzed in a liquid phase state, and the 1-octene can be obtained in a higher yield.
Further, the above organic solvent may preferably be selected from toluene and xylene.
It is understood that the concentration of the catalyst is also an important factor affecting the reactivity of the reaction rate, and in the present application, when the molar concentration of the binuclear pyridinium halide imine metal complex in the mixed system is 2 to 500. Mu. Mol/L, ethylene has good oligomerization activity and 1-octene selectivity in the catalytic system.
In a specific embodiment, the method further comprises pretreating the reaction device containing the mixed system before obtaining the mixed system. Specifically, the pretreatment comprises the steps of replacing the reaction device through operations such as high-temperature drying, vacuum replacement and the like, so that the reaction device is in an anhydrous and anaerobic state, and then replacing the reaction device by using ethylene, so that the reaction device is filled with ethylene. Subsequently, the oligomerization reaction of the mixed system and ethylene was completed in the pretreated reaction apparatus.
When oligomerization is carried out, the reaction pressure is preferably 0.1-30 MPa, the reaction temperature is-20-150 ℃ and the reaction time is 30-100 min.
According to the preparation method of 1-octene, ethylene is used as a raw material, the catalyst of the first aspect catalyzes oligomerization of ethylene, and finally, the high-efficiency preparation of 1-octene is realized with excellent oligomerization activity and alpha-C8 selectivity.
Hereinafter, the catalyst and the process for producing 1-octene of the present application will be described with reference to specific examples.
The experimental methods used in the following examples and comparative examples are conventional in the art unless otherwise specified. Materials, reagents and the like used in the following examples and comparative examples are commercially available unless otherwise specified.
Example 1
1. Synthesis of catalyst C1
1) Pyridine-2-carbaldehyde (2 g,18.67 mmol) was added dropwise to stirred ethanol (30 mL), hydrazine hydrate (0.37 g, wt% = 80%,9.33 mmol) was added slowly dropwise to the reaction system, and then precipitated out by stirring at room temperature for 30 minutes, washed with methanol (10 mL), filtered and dried to give ligand L1 (1.5 g,7.14mmol, yield 76.53%) as a yellow solid.
Ligand L1 is characterized as follows:
LCMS 211.2[M+1] + .
1 H NMR(400MHz,DMSO-d 6 )δ8.74(ddd,J＝4.8,1.5,0.9Hz,2H),8.58(s,2H),8.13(d,J＝7.9Hz,2H),7.97(td,J＝7.7,1.5Hz,2H),7.55(ddd,J＝7.5,4.8,1.1Hz,2H).
2) FeCl is added 3 (0.65 g,0.004 mol) in ethanol (5 mL),then, a solution of L1 (0.42 g,0.002 mol) in methylene chloride (5 mL) was added, and the mixture was stirred at 25℃for 12 hours to precipitate out, filtered, and the precipitate was washed three times with diethyl ether (15 mL), and dried under vacuum to give catalyst C1 (1.02 g,0.0019mol, yield 95%).
2. Preparation of 1-octene by ethylene selective tetramerization
1) The reaction kettle is replaced through operations such as high-temperature drying, vacuum replacement and the like, so that no water and no oxygen are ensured in the reaction kettle;
2) Continuously replacing the reaction kettle by using ethylene to ensure that the reaction kettle is in an ethylene environment;
3) Adding toluene solvent, diethyl aluminum chloride toluene solution (with the concentration of 1M) and catalyst C1 toluene solution into a reaction kettle respectively, fully stirring, and introducing ethylene to start oligomerization;
wherein the total volume of the solution in the reaction system is 50ml, the concentration of the catalyst C1 is 200 mu mol/L, and the molar ratio of Al in diethyl aluminum chloride to the main catalyst C1 is 1000:1, a step of;
4) The oligomerization reaction is carried out for 30 minutes at the temperature of 20 ℃ under the ethylene pressure of 1 MPa;
5) The reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and the oligomerization activity was found to be 5.28X10 by analysis 6 g/(mol (Fe). Times.h.times.atm), oligomer selectivity was C4.59%, C6.24%, C8 89.02% (containing. Alpha. -C8 73.42%),. Gtoreq.C 10.15%, respectively. The remaining mixture was neutralized with 5% hydrochloric acid acidified ethanol solution except for a small amount of reaction product for GC analysis, and no polymer was obtained. The catalyst of the embodiment can not polymerize ethylene to generate polyethylene, and avoids the phenomenon of kettle sticking in industrial production.
The calculation method of the ethylene oligomerization activity and the selectivity of the olefins with different carbon numbers is as follows:
the mass of each oligomerization product was calculated according to formula 1 using the mass of toluene solvent as a reference (P i )。
By the formula 2, the ethylene oligomerization activity (A) is calculated from the amount of the product produced (equal to the amount of ethylene consumed) o ) The unit is g/(mol)h·atm)。
Selectivity to lower olefins (S i ) Is the proportion of a certain low-carbon olefin to the total product amount, and is calculated by a formula 3.
In formula 1, A i Refers to the peak area of a certain oligomerization product, A Toluene (toluene) Refers to the peak area of toluene, P i Refers to the quality of a certain oligomerization product.
In formula 2, A o Refers to the activity of oligomerization, P 1 +P 2 +P 3 +…P n The mass (mol) of the metal in the catalyst refers to the mass of the metal ion in the catalyst, the time (h) refers to the oligomerization time, and the pressure (atm) refers to the oligomerization pressure.
In formula 3, S i Refers to the selectivity of a certain oligomerization product, P i Refers to the quality of a certain oligomerization product, P 1 +P 2 +P 3 +…P n Refers to the sum of the mass of all oligomeric products.
For comparison, the analytical results are shown in Table 1.
Example 2
1. Synthesis of catalyst C2
1) Pyridine-2-carbaldehyde (2 g,18.67 mmol) was added dropwise to ethanol (30 mL) under stirring, ethylenediamine (0.56 g,9.33 mmol) was added dropwise slowly to the reaction system, formic acid (0.01 mL) was added, and the mixture was heated at 80℃under nitrogen atmosphere, stirred for 30 minutes to precipitate out, the reaction mixture was dried by spin-drying, and the reaction mixture was separated by column chromatography (elution gradient: dichloromethane: methanol=50 to 5:1) to give ligand L2 (1.2 g,5.04mmol, 54.05%) as a yellow solid.
Ligand L2 is characterized as follows:
LCMS 239.2[M+1] + .
1 H NMR(400MHz,CDCl 3 )δ8.61(d,J＝4.1Hz,2H),8.40(s,2H),7.96(d,J＝7.9Hz,2H),7.71(td,J＝7.7,1.8Hz,2H),7.28(ddd,J＝7.5,4.9Hz,2H),4.05(s,4H).
2) The procedure for the preparation of catalyst C2 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L2 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C2 of this example and the results of the gas phase analysis are shown in Table 1.
Example 3
1. Preparation of catalyst C3
1) Pyridine-2-carbaldehyde (2 g,18.67 mmol) was added dropwise to ethanol (20 mL) under stirring, 1, 3-propanediamine (0.69 g,9.33 mmol) was diluted with ethanol (5 mL) and then slowly added dropwise to the reaction system, and the reaction system was heated to 85℃under reflux for 10 hours. Cooled to room temperature, the reaction mixture was dried by spin-drying to give a brown oil, which was separated by column chromatography (elution gradient: dichloromethane: methanol=50 to 5:1) to give ligand L3 (1.1 g,4.36mmol, yield 46.80%) as a yellow solid.
Ligand L3 is characterized as follows:
LCMS 253.1[M+1] + .
1 H NMR(400MHz,CDCl 3 )δ8.84–8.75(m,2H),8.53–8.48(m,1H),8.46–8.41(m,1H),7.79–7.70(m,3H),7.66–7.60(m,1H),7.36–7.32(m,2H),3.79–3.56(m,4H),1.88–1.83(m,2H).
2) The procedure for the preparation of catalyst C3 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L3 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C3 of this example and the results of the gas phase analysis are shown in Table 1.
Example 4
1. Preparation of catalyst C4
1) Pyridine-2-carbaldehyde (2 g,18.67 mmol) was added dropwise to stirring ethanol (20 mL), 1, 4-dibutylamine (0.82 g,9.33 mmol) was diluted with ethanol (5 mL) and then slowly added dropwise to the reaction system, the reaction system was reacted at 25℃for 8 hours, solids were precipitated, filtered, the solid (10 mL) was washed with methanol, and after washing the crude product was recrystallized from dichloromethane and n-hexane to give ligand L4 (1.3 g,4.88mmol, 52.42%) as a brown solid.
Ligand L4 is characterized as follows:
LCMS 267.1[M+1] + .
1 H NMR(400MHz,CDCl 3 )δppm:8.61(ddd,J＝4.8,1.7,0.9Hz,2H),8.36(s,2H),7.95(dt,J＝7.9,1.0Hz,2H),7.73-7.69(m,2H),7.28(ddd,J＝7.5,4.9,1.2Hz,2H),3.71(td,J＝5.2,1.4Hz,4H),1.83-1.78(m,4H).
2) The procedure for the preparation of catalyst C4 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L4 of this example during the preparation.
3) The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C4 of this example and the results of the gas phase analysis are shown in Table 1.
Example 5
1. Preparation of catalyst C5
1) 2-Acetylpyridine (2 g,16.51 mmol) was added dropwise to stirred ethanol (20 mL), hydrazine hydrate (0.33 g, wt% = 80%,8.25 mmol) and formic acid (0.01 mL) were slowly added dropwise to the reaction system, and then precipitated by stirring at 25℃for 48 hours, washed with methanol (5 mL), filtered and dried to give yellow solid ligand L5 (1.60 g,6.71mmol, yield 81.63%).
Ligand L5 is characterized as follows:
LCMS 239.3[M+1] + .
1 H NMR(400MHz,DMSO-d 6 )δ8.67(ddd,J＝4.8,1.6,0.9Hz,2H),8.19(d,J＝8.0Hz,2H),7.91(td,J＝7.9,1.8Hz,2H),7.49(ddd,J＝7.4,4.8,1.1Hz,2H),2.30(s,6H).
2) The procedure for the preparation of catalyst C5 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L5 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C5 of this example and the results of the gas phase analysis are shown in Table 1.
Example 6
1. Preparation of catalyst C6
1) 2-Acetylpyridine (2 g,16.51 mmol) was added dropwise to stirred ethanol (20 mL), ethylenediamine (0.49 g,8.25 mmol) was added slowly to the reaction system, p-toluenesulfonic acid (0.14 g,0.82 mmol) was added, and after heating to 90℃under nitrogen, the mixture was stirred for 12 hours to precipitate out, the reaction mixture was dried by spinning, and the column was separated by chromatography (elution gradient: dichloromethane: methanol=50 to 5:1) to give ligand L6 (1.3 g,4.88mmol, 59.36%) as a yellow solid.
Ligand L6 is characterized as follows:
LCMS 267.4[M+1] + .
1 HNMR(400MHz,CDCl 3 )δ8.58(ddd,J＝4.8,1.8,0.9Hz,2H),8.06(dt,J＝8.0,1.0Hz,2H),7.71-7.66(m,2H),7.26(ddd,J＝7.4,4.8,1.2Hz,2H),3.96(s,4H),2.42(s,6H).
2) The procedure for the preparation of catalyst C6 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L6 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C6 of this example and the results of the gas phase analysis are shown in Table 1.
Example 7
1. Preparation of catalyst C7
1) 2-Acetylpyridine (2 g,16.51 mmol) was added dropwise to stirred ethanol (20 mL), propylenediamine (0.61 g,8.25 mmol) was added slowly dropwise to the reaction system, then p-toluenesulfonic acid (0.14 g,0.82 mmol) was added, and the mixture was stirred under nitrogen for 12 hours at 90℃and cooled to room temperature to precipitate out, and then yellow solid ligand L7 (1.2 g,4.28mmol, yield 51.85%) was obtained by filtration and drying.
Ligand L7 is characterized as follows:
LCMS 281.1[M+1] + .
1 H NMR(400MHz,CDCl 3 )δ8.60-8.53(m,2H),7.92-7.68(m,4H),7.60(ddd,J＝8.6,7.4,1.8Hz,2H),3.70-3.53(m,4H),2.34-2.23(m,6H),1.96-1.91(m,2H).
2) The procedure for the preparation of catalyst C7 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L7 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C7 of this example and the results of the gas phase analysis are shown in Table 1.
Example 8
1. Preparation of catalyst C8
1) 2-Acetylpyridine (2 g,16.51 mmol) was added dropwise to stirred ethanol (20 mL), and butanediamine (0.73 g,8.25 mmol) was added dropwise slowly to the reaction system, followed by p-toluenesulfonic acid (0.14 g,0.82 mmol), stirring was carried out at 90℃under nitrogen atmosphere for 12 hours, the reaction mixture was dried by spin-drying, and column chromatography separation purification (elution gradient: dichloromethane: methanol=50 to 5:1) to give ligand L8 (1.3 g,4.42mmol, yield 56.52%) as a yellow solid.
Ligand L8 is characterized as follows:
LCMS 295.3[M+1] + .
1 H NMR(400MHz,CDCl 3 )δ8.61–8.56(m,2H),7.85–7.81(m,2H),7.72(ddd,J＝8.2,7.5,1.5Hz,2H),7.61(ddd,J＝8.5,7.5,1.5Hz,2H),3.79–3.66(m,4H),2.44–2.24(m,6H),1.81–1.71(m,4H).
2) The procedure for the preparation of catalyst C8 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L8 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C8 of this example and the results of the gas phase analysis are shown in Table 1.
Example 9
1. Preparation of catalyst C9
1) 2-Acetylpyridine (2 g,16.51 mmol) was added dropwise to toluene (20 mL) under stirring, 1, 4-phenylenediamine (1.01 g,9.34 mmol) was further added to the reaction system, p-toluenesulfonic acid (0.16 g,0.93 mmol) was dissolved in toluene (5 mL), and then the mixture was added dropwise to the reaction solution, and the reaction solution was refluxed under a nitrogen atmosphere at 100℃for 10 hours. The reaction solution was cooled to room temperature, and a solid was precipitated, and washed with n-hexane to give ligand L10 (1.5 g,5.24mmol, yield 56.18%) as a yellow solid.
2) The procedure for the preparation of catalyst C9 was substantially identical to that of catalyst C1, except that ligand L1 of example 1 was replaced with ligand L9 of this example during the preparation.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C9 of this example and the results of the gas phase analysis are shown in Table 1.
Example 10
This example is substantially the same as example 6 except that during the preparation of 1-octene by ethylene selective tetramerization, the ethylene pressure is maintained at 2MPa.
The results of the gas phase analysis of this example are shown in Table 1.
Example 11
1. Preparation of catalyst C10
1) The preparation of catalyst ligand L6 of this example was identical to that of example 6;
2) FeCl is added 2 ·2H 2 O (0.65 g, 0.04 mol) and ligand L6 (0.53 g,0.002 mol) were dissolved in a mixed solvent (10 mL) of ethanol and methylene chloride, and the reaction mixture was stirred at 25℃for 5 hours to precipitate out, filtered, and the precipitate was washed three times with diethyl ether (15 mL) and dried in a vacuum oven at 60℃to give yellow solid catalyst C10.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C10 of this example and the results of the gas phase analysis are shown in Table 1.
Example 12
1. Preparation of catalyst C11
1) The preparation of catalyst ligand L6 of this example was identical to that of example 6;
2) CoCl is to be processed 2 ·6H 2 O (0.95 g,0.004 mol) and L6 (0.53 g,0.002 mol) were dissolved in a mixed solvent (10 mL) of ethanol and methylene chloride, and the reaction mixture was stirred at 25℃for 5 hours to precipitate out, filtered, and the precipitate was washed three times with diethyl ether (15 mL) and dried in a vacuum oven at 60℃to give yellow solid catalyst C11.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C11 of this example and the results of the gas phase analysis are shown in Table 1.
Example 13
1. Preparation of catalyst C12
1) The preparation of catalyst ligand L6 of this example was identical to that of example 6;
2) NiCl is added 2 ·6H 2 O (0.95 g,0.004 mol) and L6 (0.53 g,0.002 mol) were dissolved in a mixed solvent (10 mL) of ethanol and methylene chloride, and the reaction mixture was stirred at 25℃for 5 hours to precipitate out, filtered, and the precipitate was washed three times with diethyl ether (15 mL) and dried in a vacuum oven at 60℃to give yellow solid catalyst C12.
2. The procedure for the preparation of 1-octene by selective tetramerization of ethylene according to this example was essentially identical to that of example 1, except that catalyst C1 of example 1 was replaced by catalyst C12 of this example and the results of the gas phase analysis are shown in Table 1.
Example 14
This example is substantially identical to example 1, except that the amount of diethylaluminum chloride is varied so that the molar ratio of Al in diethylaluminum chloride to cocatalyst C1 is 500:1. the results of the gas phase analysis of this example are shown in Table 1.
Example 15
This example is substantially the same as example 1 except that the diethyl aluminum chloride promoter is replaced with methylaluminoxane during the ethylene selective tetramerization to prepare 1-octene. The results of the gas phase analysis of this example are shown in Table 1.
TABLE 1
As can be seen from the data in table 1, the catalyst of the present application is used in ethylene tetramerization reaction, the reaction mainly generates C8 product, wherein α -C8 (1-octene) in the C8 product is a dominant product, so that the catalyst of the present application has good oligomerization activity and 1-octene selectivity when used in ethylene tetramerization reaction.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (17)

1. A catalyst for the selective tetramerization of ethylene comprising a dinuclear pyridinimine metal halide complex of formula I or formula II:
in the formulae I and II,
r is independently selected fromn=0, 1,2,3,4,5, or +.>
R 1 And R is R 1 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C15 aryl;
R 2 ，R 3 ，R 4 ，R 5 and R is R 2 ’，R 3 ’，R 4 ’，R 5 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl, halogen, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C15 aryl, and nitro;
M 1 selected from Fe 2+ 、Co 2+ And Ni 2+ One of the following;
M 2 is Fe 3+ ；
X is independently selected from one of halogens.
2. The catalyst of claim 1 wherein R 1 And R is R 1 ' each independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted phenyl;
and/or R 2 ，R 3 ，R 4 ，R 5 And R is R 2 ’，R 3 ’，R 4 ’R 5 ' each independentlyAnd is selected from one of hydrogen, C1-C4 alkyl, fluorine, chlorine, bromine, methoxy, ethoxy or nitro.
3. The catalyst according to claim 1 or 2, characterized in that R 1 、R 2 、R 3 、R 4 、R 5 And R is R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituent groups in' are each independently selected from at least one of hydrogen, alkyl, aryl, alkoxy, halogen, nitro.
4. The catalyst according to any one of claims 1 to 2, wherein R is selected fromn＝0,2,3。
5. A catalyst according to claim 3, wherein R is selected fromn＝0,2,3。
6. The catalyst of any one of claims 1-2, further comprising an aluminum-containing promoter.
7. The catalyst of claim 3 further comprising an aluminum-containing promoter.
8. The catalyst of claim 4 further comprising an aluminum-containing promoter.
9. The catalyst of claim 5 further comprising an aluminum-containing promoter.
10. The catalyst of claim 6, wherein the aluminum-containing promoter is selected from at least one of aluminoxanes and alkylaluminum compounds.
11. The catalyst of any one of claims 7-9, wherein the aluminum-containing promoter is selected from at least one of aluminoxanes and alkylaluminum compounds.
12. The catalyst of claim 6 wherein the molar ratio of aluminum in the aluminum-containing promoter to metal in the dinuclear pyridinimine metal complex is (200-2000): 1.
13. The catalyst of any one of claims 7 to 10, wherein the molar ratio of aluminum in the aluminum-containing promoter to metal in the binuclear pyridinimine metal complex is from (200 to 2000): 1.
14. The catalyst of claim 11 wherein the molar ratio of aluminum in the aluminum-containing promoter to metal in the dinuclear pyridinimine metal complex is (200-2000): 1.
15. A process for producing 1-octene, comprising:
after mixing the catalyst of any one of claims 1-14 with an organic solvent, introducing ethylene into the mixed system to carry out oligomerization reaction, thereby obtaining 1-octene.
16. The method according to claim 15, wherein the organic solvent is at least one selected from toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and methylene chloride.
17. The process according to claim 15 or 16, wherein the molar concentration of the binuclear pyridinimine metal halide complex represented by formula I or formula II in the mixed system is 2 to 500 μmol/L.
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