CN115301290A - Catalyst for selective tetramerization of ethylene and application thereof - Google Patents

Catalyst for selective tetramerization of ethylene and application thereof Download PDF

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CN115301290A
CN115301290A CN202210920804.8A CN202210920804A CN115301290A CN 115301290 A CN115301290 A CN 115301290A CN 202210920804 A CN202210920804 A CN 202210920804A CN 115301290 A CN115301290 A CN 115301290A
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catalyst
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ethylene
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CN115301290B (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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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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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    • B01J2531/84—Metals of the iron group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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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 invention provides a catalyst for selective tetramerization of ethylene and application thereof. The catalyst comprises a binuclear halogenated pyridine imine metal complex shown as a formula I or a formula II: in formula I and formula II, R is independently selected from
Figure DDA0003777466230000011
n =0,1,2,3,4,5, or
Figure DDA0003777466230000012
R 1 And R 1 ' is one independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl; r 2 ，R 3 ，R 4 ，R 5 And R 2 ’，R 3 ’，R 4 ’，R 5 ' is 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 (1); m 2 Is Fe 3+ (ii) a X is independently selected from one of halogens. The catalyst has excellent ethylene oligomerization activity and 1-octene selectivity.

Description

Catalyst for selective tetramerization of ethylene and application thereof
The present application claims priority from the chinese patent application entitled "a catalyst for selective tetramerisation of ethylene and use thereof" filed by the chinese patent office at 26.08/2021 under the application number 202110986355.2, the entire contents of which are incorporated herein by reference.
Technical Field
The invention belongs to the field of ethylene oligomerization catalysis, and relates to a catalyst for selective ethylene tetramerization and application thereof.
Background
The 1-octene is an important chemical product and an intermediate, and is mainly used in the fields of polyethylene, plasticizer, essence, perfume, 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 conforms to Schlulz-Flory distribution, and the distribution makes the 1-octene in the oligomerization product unlikely to be too high. At present, most methods for synthesizing 1-octene by ethylene oligomerization adopt chromium catalysts for catalytic synthesis, but the selectivity of 1-octene in the methods is still limited, and the cost of the catalysts is higher.
Disclosure of Invention
The invention provides a catalyst for selective ethylene tetramerization, which comprises binuclear halogenated pyridine imine metal complex shown in formula I or formula II, and when the catalyst is used in ethylene tetramerization reaction, the reaction can show good ethylene oligomerization activity and high 1-octene selectivity.
The invention also provides a preparation method of the 1-octene, and the preparation method has the advantages of high reaction activity and high yield of the 1-octene because the catalyst is used for catalyzing ethylene oligomerization reaction.
The invention provides a catalyst for selective tetramerization of ethylene, which comprises a binuclear halogenated pyridine imine metal complex shown as a formula I or a formula II:
Figure BDA0003777466220000021
in the formula I and the formula II,
r is independently selected from
Figure BDA0003777466220000022
n =0,1,2,3,4,5, or
Figure BDA0003777466220000023
R 1 And R 1 ' each is independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl;
R 2 ，R 3 ，R 4 ，R 5 and 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 (1);
M 2 is Fe 3+ ；
X is independently selected from one of halogens.
The catalyst as described above, wherein R 1 And R 1 ' each is independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl and substituted or unsubstituted phenyl;
and/or, R 2 ，R 3 ，R 4 ，R 5 And R 2 ’，R 3 ’，R 4 ’R 5 ' are respectively and independently selected from one of hydrogen, C1-C4 alkyl, fluorine, chlorine, bromine, methoxy, ethoxy or nitro.
The catalyst as described above, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituents in' are each independently at least one selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, halogen, and nitro.
The catalyst as described above, wherein R is selected from
Figure BDA0003777466220000024
n＝0,2,3。
The 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 aluminoxane and an alkyl aluminum compound.
The catalyst, wherein the molar ratio of the aluminum in the aluminum-containing cocatalyst to the metal in the dinuclear halogenated pyridine imine metal complex is (200-2000): 1.
The invention also provides a preparation method of the 1-octene, which comprises the following steps: mixing the catalyst and an organic solvent, and introducing ethylene into the mixed system for oligomerization reaction to obtain the 1-octene.
The production method as described above, wherein the organic solvent is at least one selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane.
The preparation method comprises the step of preparing the binuclear halogenated pyridine imine metal complex shown as the formula I or the formula II, wherein the molar concentration of the binuclear halogenated pyridine imine metal complex in the mixed system is 2 to 500 mu mol/L.
The catalyst comprises binuclear halogenated pyridine imine metal complex shown in formula I or formula II, and when the catalyst is used in 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 invention has the advantages of high reaction activity and high yield of 1-octene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, 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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a catalyst, which comprises a binuclear halogenated pyridine imine metal complex shown as a formula I or a formula II:
Figure BDA0003777466220000031
r in the formula I and the formula II can be the same or different and can be independently selected from
Figure BDA0003777466220000032
n =0,1,2,3,4,5, or
Figure BDA0003777466220000033
R in formula I and formula II 1 And R 1 ' may be the same or different and each may be independently selected from one of hydrogen, a substituted or unsubstituted C1 to C6 alkyl group, and a substituted or unsubstituted C6 to C15 aryl group;
r in formula I and formula II 2 ，R 3 ，R 4 ，R 5 And R 2 ’，R 3 ’，R 4 ’，R 5 ' may be the same or different, and each may be independently selected from one of hydrogen, substituted or unsubstituted C1 to C6 alkyl, halogen, substituted or unsubstituted C1 to C6 alkoxy, substituted or unsubstituted C6 to C15 aryl, and nitro;
m in the formula I 1 Selected from Fe 2+ 、Co 2+ And Ni 2+ One of (a) and (b);
m in the 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 halogen.
In the present invention, 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, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, sec-hexyl, and the like can be mentioned.
In the present invention, the term "C1-C6 alkoxy group" means a group obtained by bonding a C1-C6 alkyl group to an oxygen atom, and specifically, it may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, n-hexyloxy and sec-hexyloxy; particularly preferred are methoxy group, ethoxy group and the like.
In the present invention, the term "halogen" refers to fluorine, chlorine, bromine, iodine.
In the present invention, the term "C6-C15 aryl" refers to an aromatic ring-containing group having 6 to 15 carbon atoms, and may be, for example, phenyl, naphthyl, etc.
The inventor researches and discovers that when the catalyst comprises a binuclear shown as a formula I or a formula IIWhen the pyridine imine metal complex is halogenated, 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, and the selectivity of 1-octene can reach more than 48.64%.
Further, R in formula I and formula II 1 And R 1 ' each is independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl and substituted or unsubstituted phenyl;
and/or, R 2 ，R 3 ，R 4 ，R 5 And R 2 ’，R 3 ’，R 4 ’，R 5 ' are respectively and independently selected from one of hydrogen, C1-C4 alkyl, substituted or unsubstituted phenyl, fluorine, chlorine, bromine, methoxy, ethoxy or nitro.
Exemplary C1-C4 alkyl groups can be methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, and the like.
In a specific embodiment, R in formula I or formula II 1 And R 1 ' are both methyl, R 2 ，R 3 ，R 4 ，R 5 And 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 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 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituents in' are each independently at least one selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, halogen, and nitro. The substituent here means that when R is 1 、R 2 、R 3 、R 4 、R 5 And R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 ' selected from the aforementioned groups substituted with a substituentWhen the group is a substituted C1-C6 alkyl group, a substituted C1-C6 alkoxy group, or the like, the substituent is at least one selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, halogen, and nitro. Wherein, the alkyl can be C1-C9 straight-chain alkyl or branched-chain alkyl, such as methyl, ethyl, propyl, isopropyl, etc., and the aryl can be phenyl, naphthyl, etc.
In a particular embodiment, when R is selected from
Figure BDA0003777466220000051
n =0,2,3, and has higher ethylene oligomerization activity and higher 1-octene selectivity 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 reaction, wherein the 1-octene selectivity can be up to more than 65%.
Compared with Co 2+ And Ni 2+ When M in the binuclear halogenated pyridine imine metal complex of the formula I of the present invention is 1 Further selected from Fe 2+ When the catalyst is used, the ethylene oligomerization activity and the 1-octene selectivity are more excellent.
The preparation method of the binuclear halogenated pyridine imine metal complex shown in the formula I or the formula II is not limited, and the binuclear halogenated pyridine imine metal complex can be prepared by adopting a conventional method in the field.
In a specific implementation method, the binuclear halogenated pyridine imine metal complex shown in the formula I and the formula II can be prepared by the following preparation method:
Figure BDA0003777466220000052
according to the reaction formula shown above, the raw materials a, b and c are reacted to obtain the ligand d, and then the ligand d is reacted with the metal dihalide salt M 1 X 2 Reacting to obtain the binuclear halogenated pyridine imine metal complex shown in the formula I. Likewise, 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 through reaction. Wherein R in the formula a 1 、R 2 、R 3 、R 4 、R 5 With R in formula I and formula II 1 、R 2 、R 3 、R 4 、R 5 Wherein R in the formula b is the same as 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 ' with R in formula I and formula II 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 ' are as defined, and R in formula c is as defined for R in formula I and formula II.
Further, the catalyst of the present invention also comprises an aluminum-containing co-catalyst. When the catalyst is used in ethylene oligomerization, the aluminum-containing cocatalyst can eliminate residual oxygen and moisture in the reaction system, and can be used together with binuclear halogenated pyridine imine metal complex to improve catalytic activity.
Further, the aluminum-containing cocatalyst is selected from at least one of aluminoxane and an alkyl aluminum compound.
Specifically, the aluminoxane is C1 to C4 alkylaluminoxane, more preferably methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane, and 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 selected from chlorine or bromine; the sum of n and m is 3, n is an integer of 1-3, and m is an integer of 0-2.
The alkyl aluminum compound may preferably be selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, and still more preferably diethylaluminum chloride.
In a specific embodiment, when the molar ratio of aluminum in the aluminum-containing cocatalyst to the 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 invention provides a method for producing 1-octene, comprising: mixing the catalyst and the organic solvent, and introducing ethylene into the mixed system for oligomerization reaction to obtain the 1-octene.
The mixing as described in the above process means 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 systems of the components in the catalyst, or can be obtained by mixing the components in the catalyst and then mixing the components with the organic solvent. That is, the mixed system is a reaction system before ethylene is introduced.
Further, the organic solvent is at least one selected from the group consisting of 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 is favorably obtained with 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 of the reaction activity affecting the reaction rate, and in the present invention, when the molar concentration of the dinuclear halogenated pyridine 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, before obtaining the mixed system, the method further comprises the step of pretreating the reaction device for accommodating the mixed system. Specifically, the pretreatment comprises replacing the reaction device by high-temperature drying, vacuum replacement and other operations to enable the reaction device to be in a water-free and oxygen-free state, and then replacing the reaction device by using ethylene to enable the reaction device to be filled with ethylene. Subsequently, oligomerization of the mixed system and ethylene was completed in the pretreated reaction apparatus.
During the oligomerization reaction, the reaction pressure is preferably 0.1-30 MPa, the reaction temperature is-20-150 ℃, and the reaction time is 30-100 min.
The preparation method of 1-octene takes ethylene as raw material, uses the catalyst of the first aspect to catalyze the oligomerization of ethylene, and finally realizes the high-efficiency preparation of 1-octene with excellent oligomerization activity and alpha-C8 selectivity.
Hereinafter, the catalyst of the present invention and the process for producing 1-octene will be described with reference to specific examples.
The experimental procedures 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
Figure BDA0003777466220000071
1) Pyridine-2-carbaldehyde (2g, 18.67mmol) was added dropwise to stirred ethanol (30 mL), hydrazine hydrate (0.37g, wt% =80%,9.33 mmol) was slowly added dropwise to the reaction system, followed by stirring at room temperature for 30 minutes to precipitate, which was washed with methanol (10 mL), filtered and dried to give ligand L1 (1.5g, 7.14mmol, yield 76.53%) as a yellow solid.
Ligand L1 was 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 (0.65g, 0.004mol) was dissolved in ethanol (5 mL), followed by addition of a solution of L1 (0.42g, 0.002mol) in methylene chloride (5 mL), stirring at 25 ℃ for 12 hours to precipitate, filtration, washing the precipitate with diethyl ether (15 mL) three times, and vacuum drying to give catalyst C1 as a brown solid (1.02g, 0.0019mol, 95% yield).
2. Preparation of 1-octene by selective tetramerization of ethylene
1) Replacing the reaction kettle through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction kettle has no water and oxygen;
2) Continuously replacing the reaction kettle by using ethylene to ensure that the reaction kettle is in an ethylene environment;
3) Respectively adding a toluene solvent, a toluene solution (with the concentration of 1M) of diethylaluminum chloride and a toluene solution of a catalyst C1 into a reaction kettle, 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 the diethyl aluminum chloride to the main catalyst C1 is 1000:1;
4) The oligomerization reaction is carried out for 30 minutes under the conditions that the ethylene pressure is 1MPa and the reaction temperature is 20 ℃;
5) The reaction was stopped, a small amount of the reaction product was taken out and analyzed by Gas Chromatography (GC), and it was found from the analysis that the oligomerization activity was 5.28X 10 6 g/(mol (Fe) × h × atm), the oligomer selectivity is respectively C4.59%, C6.24%, C8.02% (containing alpha-C8 73.42%), not less than C10.15%. 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 avoid the phenomenon of kettle sticking in industrial production.
The method for calculating the ethylene oligomerization activity and the selectivity of olefins with different carbon numbers comprises the following steps:
the mass of each oligomerization product (P) was calculated from formula 1 with reference to the mass of the toluene solvent i )。
The ethylene oligomerization activity (A) was calculated from the amount of the product formed (equal to the amount of ethylene consumed) by equation 2 o ) The unit is g/(mol · h · atm).
Selectivity to lower olefins (S) i ) Is the ratio of the amount of a certain low carbene hydrocarbon to the total amount of the product, and is calculated by the formula 3.
Figure BDA0003777466220000091
In formula 1, A i Refers to the peak area, A, of a particular oligomerization product Toluene Refers to the peak area of toluene, P i Refers to the mass of a particular oligomerization product.
Figure BDA0003777466220000092
In formula 2, A o Is the activity of oligomerization, P 1 +P 2 +P 3 +…P n Refers to the sum of the masses of all oligomerization products, the amount of metal species (mol) in the catalyst refers to the amount of metal ion species in the catalyst, time (h) refers to the time of oligomerization, and pressure (atm) refers to the pressure of oligomerization.
Figure BDA0003777466220000093
In formula 3, S i Refers to the selectivity of a particular oligomerization product, P i Refers to the mass of a particular oligomerization product, P 1 +P 2 +P 3 +…P n Refers to the sum of the masses of all oligomerization products.
For ease of comparison, the analytical results are listed in table 1.
Example 2
1. Synthesis of catalyst C2
Figure BDA0003777466220000094
1) Pyridine-2-carbaldehyde (2g, 18.67mmol) was added dropwise to stirred ethanol (30 mL), ethylenediamine (0.56g, 9.33mmol) was slowly added dropwise to the reaction system, formic acid (0.01 mL) was then added, the mixture was heated at 80 ℃ under a nitrogen atmosphere and stirred for 30 minutes to precipitate, the reaction solution was spin-dried, and column chromatography was performed (elution gradient was dichloromethane: methanol = 50-5) gave ligand L2 as a yellow solid (1.2g, 5.04mmol, 54.05% yield).
Ligand L2 was 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 preparation procedure of the catalyst C2 was substantially identical to that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L2 of this example in the preparation process.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example is substantially the same as in example 1, except that catalyst C1 in example 1 is replaced by catalyst C2 in this example and the results of the gas phase analysis are shown in Table 1.
Example 3
1. Preparation of catalyst C3
Figure BDA0003777466220000101
1) Pyridine-2-carbaldehyde (2g, 18.67mmol) was added dropwise to stirred ethanol (20 mL), 1, 3-propanediamine (0.69g, 9.33mmol) was diluted with ethanol (5 mL) and slowly added dropwise to the reaction system, and the reaction system was heated to 85 ℃ and refluxed for 10 hours. Cooled to room temperature, the reaction was spin-dried to give a brown oil, which was isolated by column chromatography (elution gradient dichloromethane: methanol = 50-5.
Ligand L3 was 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 preparation procedure of the catalyst C3 was substantially identical to that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L3 of this example in the preparation process.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example is substantially identical to that of example 1, except that catalyst C1 of example 1 is 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
Figure BDA0003777466220000111
1) Pyridine-2-carbaldehyde (2g, 18.67mmol) is added dropwise to stirred ethanol (20 mL), 1, 4-dibutylamine (0.82g, 9.33mmol) is diluted by ethanol (5 mL) and slowly added dropwise to the reaction system, the reaction system reacts at 25 ℃ for 8 hours, a solid precipitates, the solid is filtered, the solid is washed by methanol (10 mL), and after washing, the crude product is recrystallized by dichloromethane and n-hexane to obtain a brown solid ligand L4 (1.3g, 4.88mmol, 52.42% yield).
Ligand L4 was 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 preparation procedure of the catalyst C4 was substantially identical to that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L4 of this example in the preparation process.
3) The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was identical to that of example 1, except that catalyst C1 of example 1 was replaced with 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
Figure BDA0003777466220000112
1) 2-acetylpyridine (2g, 16.51mmol) was added dropwise to stirred ethanol (20 mL), hydrazine hydrate (0.33g, wt% =80%,8.25 mmol) and formic acid (0.01 mL) were slowly added dropwise to the reaction system, followed by stirring at 25 ℃ for 48 hours to precipitate, washing with methanol (5 mL), and filtration and drying to give ligand L5 (1.60g, 6.71mmol, yield 81.63%) as a yellow solid.
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 preparation procedure of the catalyst C5 substantially coincided with that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L5 of this example during the preparation.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example is substantially identical to that of example 1, except that catalyst C1 of example 1 is 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
Figure BDA0003777466220000121
1) 2-acetylpyridine (2g, 16.51mmol) was added dropwise to stirred ethanol (20 mL), ethylenediamine (0.49g, 8.25mmol) was then added slowly dropwise to the reaction system, p-toluenesulfonic acid (0.14g, 0.82mmol) was then added, the reaction solution was stirred for 12 hours under nitrogen atmosphere and precipitated, the reaction solution was dried by spinning, and column chromatography was performed (elution gradient was dichloromethane: methanol = 50-5) gave ligand L6 (1.3g, 4.88mmol, 59.36% yield) as a yellow solid.
Ligand L6 was 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 preparation procedure of the catalyst C6 was substantially identical to that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L6 of this example in the preparation process.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C6 in this example and the results of the gas phase analysis are shown in Table 1.
Example 7
1. Preparation of catalyst C7
Figure BDA0003777466220000131
1) 2-acetylpyridine (2g, 16.51mmol) is added dropwise to stirred ethanol (20 mL), propanediamine (0.61g, 8.25mmol) is slowly added dropwise to the reaction system, then p-toluenesulfonic acid (0.14g, 0.82mmol) is added, the reaction system is heated to 90 ℃ in a nitrogen atmosphere and stirred for 12 hours to be cooled to room temperature for precipitation, and the ligand L7 is filtered and dried to obtain yellow solid ligand L7 (1.2g, 4.28mmol, yield 51.85%).
Ligand L7 was 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 preparation procedure of catalyst C7 was substantially identical to that of catalyst C1, except that the ligand L1 of example 1 was replaced with the ligand L7 of this example during the preparation.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C7 in this example and the results of the gas phase analysis are shown in Table 1.
Example 8
1. Preparation of catalyst C8
Figure BDA0003777466220000132
1) 2-acetylpyridine (2g, 16.51mmol) is added dropwise to stirred ethanol (20 mL), butanediamine (0.73g, 8.25mmol) is slowly added dropwise to the reaction system, then p-toluenesulfonic acid (0.14g, 0.82mmol) is added, the reaction solution is heated to 90 ℃ in a nitrogen atmosphere and stirred for 12 hours, and the reaction solution is dried by spinning, separated and purified by column chromatography (elution gradient is dichloromethane: methanol = 50-5) to give ligand L8 (1.3g, 4.42mmol, 56.52% yield) as a yellow solid.
Ligand L8 was 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 preparation procedure of the catalyst C8 was substantially identical to that of the catalyst C1 except that the ligand L1 of example 1 was replaced with the ligand L8 of this example in the preparation process.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C8 in this example and the results of the gas phase analysis are shown in Table 1.
Example 9
1. Preparation of catalyst C9
Figure BDA0003777466220000141
1) 2-acetylpyridine (2g, 16.51mmol) was added dropwise to stirred toluene (20 mL), 1, 4-phenylenediamine (1.01g, 9.34mmol) was added to the reaction system, p-toluenesulfonic acid (0.16g, 0.93mmol) was dissolved in toluene (5 mL), and the solution was added dropwise to the reaction mixture, and the reaction mixture was refluxed at 100 ℃ for 10 hours in a nitrogen atmosphere. The reaction mixture was cooled to room temperature, and a solid precipitated, which was washed with n-hexane to give ligand L10 (1.5g, 5.24mmol, 56.18% yield) as a yellow solid.
2) The preparation procedure of catalyst C9 was substantially identical to that of catalyst C1, except that the ligand L1 of example 1 was replaced with the ligand L9 of this example during the preparation.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example is substantially identical to that of example 1, except that catalyst C1 of example 1 is 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 essentially the same as example 6 except that during the selective tetramerisation of ethylene to produce 1-octene, an ethylene pressure of 2MPa is maintained.
The results of the gas phase analysis of this example are shown in Table 1.
Example 11
1. Preparation of catalyst C10
Figure BDA0003777466220000151
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 (0.65g, 0.004mol) and ligand L6 (0.53g, 0.002mol) were dissolved in a mixed solvent of ethanol and dichloromethane (10 mL), the reaction mixture was stirred at 25 ℃ for 5 hours to precipitate out, filtered, the precipitate was washed three times with diethyl ether (15 mL), and dried in a vacuum oven at 60 ℃ to give catalyst C10 as a yellow solid.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C10 in this example and the results of the gas phase analysis are shown in Table 1.
Example 12
1. Preparation of catalyst C11
Figure BDA0003777466220000152
1) The preparation of catalyst ligand L6 of this example was identical to that of example 6;
2) Adding CoCl 2 ·6H 2 O (0.95g, 0.004mol) and L6 (0.53g, 0.002mol) were dissolved in a mixed solvent of ethanol and dichloromethane (10 mL), and the reaction mixture was stirred at 25 ℃ for 5 hours to precipitate out, filtered, washed with diethyl ether (15 mL) three times, and dried in a vacuum oven at 60 ℃ to give catalyst C11 as a yellow solid.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C11 in this example and the results of the gas phase analysis are shown in Table 1.
Example 13
1. Preparation of catalyst C12
Figure BDA0003777466220000161
1) The preparation of catalyst ligand L6 of this example was identical to that of example 6;
2) Mixing NiCl 2 ·6H 2 O (0.95g, 0.004mol) and L6 (0.53g, 0.002mol) were dissolved in a mixed solvent of ethanol and dichloromethane (10 mL), and the reaction mixture was stirred at 25 ℃ for 5 hours to precipitate out, filtered, washed with diethyl ether (15 mL) three times, and dried in a vacuum oven at 60 ℃ to give catalyst C12 as a yellow solid.
2. The procedure for the selective tetramerisation of ethylene to produce 1-octene in this example was substantially the same as that used in example 1, except that catalyst C1 in example 1 was replaced with catalyst C12 in this example and the results of the gas phase analysis are shown in Table 1.
Example 14
This example is essentially identical to example 1, except that the amount of diethylaluminum chloride used was varied so that the molar ratio of Al in diethylaluminum chloride to co-catalyst C1 was 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 diethylaluminum chloride was replaced with methylalumoxane as a cocatalyst in the selective tetramerisation of ethylene to produce 1-octene. The results of the gas phase analysis of this example are shown in Table 1.
TABLE 1
Figure BDA0003777466220000162
Figure BDA0003777466220000171
As can be seen from the data in Table 1, when the catalyst of the present invention is used in ethylene tetramerization reaction, the reaction is mainly generated into C8 product, wherein, the alpha-C8 (1-octene) in the C8 product is the dominant product, thereby indicating that the catalyst of the present invention 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 used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A catalyst for selective tetramerization of ethylene, comprising a binuclear halogenated pyridinimine metal complex represented by formula I or formula II:
Figure FDA0003777466210000011
in the formula I and the formula II,
r is independently selected from
Figure FDA0003777466210000012
n =0,1,2,3,4,5, or
Figure FDA0003777466210000013
R 1 And R 1 ' each is independently selected from one of hydrogen, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C6-C15 aryl;
R 2 ，R 3 ，R 4 ，R 5 and 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 (1);
M 2 is Fe 3+ ；
X is independently selected from one of halogens.
2. The catalyst of claim 1, wherein R is 1 And R 1 ' each is independently selected from one of hydrogen, substituted or unsubstituted C1-C4 alkyl and substituted or unsubstituted phenyl;
and/or, R 2 ，R 3 ，R 4 ，R 5 And R 2 ’，R 3 ’，R 4 ’R 5 ' are respectively and independently selected from one of hydrogen, C1-C4 alkyl, fluorine, chlorine, bromine, methoxy, ethoxy or nitro.
3. The catalyst of claim 1 or 2, wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R 1 ’、R 2 ’、R 3 ’、R 4 ’、R 5 The substituents in' are each independently at least one selected from the group consisting of hydrogen, alkyl, aryl, alkoxy, halogen, and nitro.
4. The catalyst of any one of claims 1 to 3, wherein R is selected from the group consisting of
Figure FDA0003777466210000014
n＝0,2,3。
5. The catalyst of any one of claims 1 to 4, further comprising an aluminum-containing cocatalyst.
6. The catalyst of claim 5, wherein the aluminum-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminum compound.
7. The catalyst of claim 5 or 6, wherein the molar ratio of the aluminum in the aluminum-containing cocatalyst to the metal in the dinuclear halogenated pyridine imine metal complex is (200-2000): 1.
8. A method for producing 1-octene, characterized by comprising:
mixing the catalyst of any one of claims 1 to 7 with an organic solvent, and introducing ethylene into the mixed system to perform oligomerization reaction to obtain 1-octene.
9. The method according to claim 8, wherein the organic solvent is at least one selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride.
10. The method according to claim 8 or 9, wherein the molar concentration of the binuclear halogenated pyridinimine metal complex represented by formula I or formula II in the mixed system is 2 to 500 μmol/L.
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