CN116174049A - Ethylene selective tetrapalladium catalyst and application thereof - Google Patents

Ethylene selective tetrapalladium catalyst and application thereof Download PDF

Info

Publication number
CN116174049A
CN116174049A CN202310263237.8A CN202310263237A CN116174049A CN 116174049 A CN116174049 A CN 116174049A CN 202310263237 A CN202310263237 A CN 202310263237A CN 116174049 A CN116174049 A CN 116174049A
Authority
CN
China
Prior art keywords
ethylene
tetrapalladium
selective
catalyst
palladium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310263237.8A
Other languages
Chinese (zh)
Inventor
张保寿
窦涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyuan Dacheng Environment And Energy Chemical Technology Co ltd
Original Assignee
Taiyuan Dacheng Environment And Energy Chemical Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyuan Dacheng Environment And Energy Chemical Technology Co ltd filed Critical Taiyuan Dacheng Environment And Energy Chemical Technology Co ltd
Priority to CN202310263237.8A priority Critical patent/CN116174049A/en
Publication of CN116174049A publication Critical patent/CN116174049A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B01J35/19—
    • 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
    • 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
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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 an ethylene selective tetrapalladium catalyst and application thereof, belonging to the technical field of ethylene oligomerization catalysis; the palladium catalyst comprises bis (dibenzylideneacetone) palladium or tris (dibenzylideneacetone) dipalladium; the palladium catalyst is used for preparing 1-octene, and after the palladium catalyst is mixed with an organic solvent, ethylene is introduced into a mixed system for oligomerization reaction to obtain 1-octene; the palladium catalyst is used for ethylene selective tetramerization reaction, and can show good ethylene oligomerization activity and high 1-octene selectivity; the palladium catalyst is used for catalyzing ethylene oligomerization reaction, and has the advantages of high reaction activity and high 1-octene yield.

Description

Ethylene selective tetrapalladium catalyst and application thereof
Technical Field
The invention belongs to the technical field of ethylene oligomerization catalysis, and particularly relates to an ethylene selective tetrapalladium catalyst and application thereof.
Background
1-octene is an important linear olefin and is mainly used for producing comonomer of linear low density polyethylene, plasticizer, surfactant, synthetic lubricating oil, etc. The products obtained by the traditional 1-olefin preparation method are widely distributed 1-olefin, wherein the content of 1-octene is low. At present, a chromium catalyst is mostly adopted in a method for selectively tetramerizing ethylene into 1-octene, and the research focus is to modulate a framework structure and a substituent of a ligand.
The use of one-dimensional metallic iron organic coordination polymers for ethylene selective tetramerization has been reported with C8 selectivities of up to 94%, 1-octene accounting for about 20%, and catalytic activities of up to 10 5 g/(mol Fe h) (China science: chemistry 47 (2017) 1218;Journal of Organometallic Chemistry 956 (2021) 122128; CN 106890643A). CN 115301290A discloses a binuclear halogenated pyridine imine iron complex, and the ethylene oligomerization activity can reach 10 6 g/(mol (M) ×h×atm) or more, and 1-octene selectivity can be up to 49% or more. Three-dimensional metal organic framework material MIL-100 constructed by trimesic acid and Fe metal center is used for ethylene selective tetramerization, and the activity is as high as 1.26 multiplied by 10 5 g/(molFe.h), but more than 80% of the products are C8 alkanes (Applied Catalysis A, general 564 (2018) 183-189). However, palladium catalysts have less reported to catalyze ethylene selective tetramerization reactions than chromium catalysts and one-dimensional iron catalysts.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides an ethylene selective tetrapalladium catalyst and application thereof. When the catalyst is used for ethylene tetramerization reaction, the reaction can show good ethylene oligomerization activity and high 1-octene selectivity.
In order to achieve the above purpose, the present invention is realized by the following technical scheme.
An ethylene selective tetrapalladium catalyst comprising a palladium complex of dibenzylideneacetone, wherein the palladium complex of dibenzylideneacetone is bis (dibenzylideneacetone) palladium represented by formula I or tris (dibenzylideneacetone) dipalladium represented by formula II:
Figure SMS_1
（І）；
Figure SMS_2
（II）。
the catalyst has good ethylene oligomerization activity and high 1-octene selectivity. Wherein, BThe activity of the olefine oligomerization can reach 10 5 g/(mol (M). Times.h.times.atm) or more, and 1-octene selectivity may be up to 50% or more.
The invention is not limited to the preparation method of the dibenzylidene acetone palladium complex shown in the formula I or the formula II, and the dibenzylidene acetone palladium complex can be prepared by the conventional method in the field.
Preferably, the palladium in the palladium complex has a zero valence.
Preferably, the palladium catalyst further comprises an aluminum-containing promoter. 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 together with dibenzylidene acetone palladium complex to raise the catalytic activity.
Preferably, the aluminum-containing cocatalyst is an aluminoxane or an alkylaluminum compound or a mixture of both.
More preferably, the aluminoxane is C1-C4 alkyl aluminoxane; the general formula of the alkyl aluminum compound is AlR n X m Wherein R is selected from C1-C8 alkyl; x is halogen.
More preferably, the alkyl aluminoxane is one of methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane and isobutyl aluminoxane; further preferred is methylaluminoxane. The halogen in the alkyl aluminum compound is 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 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.
Preferably, the molar ratio of aluminum in the aluminum-containing cocatalyst to palladium metal in the palladium complex is 50-1000:1.
When the molar ratio of aluminum in the aluminum-containing cocatalyst to palladium metal in the dibenzylidene acetone palladium complex is (75-500): 1, the catalyst has better catalytic activity, and shows more excellent ethylene oligomerization activity and 1-octene selectivity.
An application of an ethylene selective tetrapalladium catalyst is disclosed, wherein the palladium catalyst is used for preparing 1-octene in ethylene oligomerization reaction.
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.
Preferably, the catalytic preparation of 1-octene is carried out by mixing palladium catalyst with organic solvent, introducing ethylene into the mixed system for oligomerization reaction to obtain 1-octene; the molar concentration of the palladium complex in the mixed system is 2-500 mu mol/L. It can be understood that the concentration of the catalyst is also an important factor affecting the reaction activity of the reaction rate, and in the invention, when the molar concentration of the dibenzylidene acetone palladium complex in the mixed system is 2-500 mu mol/L, ethylene has good oligomerization activity and 1-octene selectivity in the catalytic system.
More preferably, the organic solvent is one or any combination of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane. 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.
The method further comprises the step of preprocessing a reaction device for accommodating the mixed system before the mixed system is obtained. 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.
In the oligomerization reaction, the preferable reaction pressure is 0.1-30 MPa, the reaction temperature is-20-150 ℃ and the reaction time is 10-100 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.
Compared with the prior art, the invention has the following beneficial effects:
the palladium catalyst provided by the invention can show good ethylene oligomerization activity and high 1-octene selectivity; wherein the ethylene oligomerization activity can reach 10 5 g/(mol (M). Times.h.times.atm) or more, and 1-octene selectivity may be up to 50% or more.
The preparation method of 1-octene realizes the efficient preparation of 1-octene with excellent oligomerization activity and alpha-C8 selectivity. The preparation method of the 1-octene has the advantages of high reaction activity and high 1-octene yield.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail by combining the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The following describes the technical scheme of the present invention in detail with reference to examples, but the scope of protection is not limited thereto.
Example 1
1. This example proposes an ethylene selective tetrapalladium catalyst which is tris (dibenzylideneacetone) dipalladium represented by formula II:
Figure SMS_3
（II）。
2. application of ethylene selective tetrapalladium catalyst
The 1-octene is prepared by using tris (dibenzylideneacetone) dipalladium as a catalyst, diethyl aluminum chloride as a cocatalyst and toluene as a solvent, and adopting the following steps.
(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 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 50 ml, the concentration of the catalyst is 200 mu mol/L, and the molar ratio of Al in diethyl aluminum chloride to palladium metal in the palladium catalyst is 500:1, a step of;
(4) The oligomerization reaction is carried out for 60 min at the temperature of 25 ℃ 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 1.97X10 by analysis 6 g/(mol (Pd). Times.h.times.atm), oligomer selectivity was C4.69%, C8 92.24% (containing. Alpha. -C8.71%),. Gtoreq.C 10.07%, respectively, where the proportion of. Alpha. -C8 to all oligomeric products, alpha. -C8/ΣC, was 60.61%. 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 oligomeric 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).
Figure SMS_4
（1）
In the 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.
Figure SMS_5
（2）
In the 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.
Figure SMS_6
（3）
In the 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
This example is substantially identical to example 1, except that bis (dibenzylideneacetone) palladium of formula I is used as the catalyst, and the catalyst concentration is 400. Mu. Mol/L. The results of the gas phase analysis of this example are shown in Table 1.
Figure SMS_7
（І）。
Example 3
This example is substantially identical to example 1, except that the oligomerization time is 10 minutes. The results of the gas phase analysis of this example are shown in Table 1.
Example 4
This example is substantially identical to example 1, except that the oligomerization time is 20 minutes. The results of the gas phase analysis of this example are shown in Table 1.
Example 5
This example is substantially identical to example 1, except that the oligomerization time is 30 minutes. The results of the gas phase analysis of this example are shown in Table 1.
Example 6
This example is substantially identical to example 1, except that the oligomerization time is 40 minutes. The results of the gas phase analysis of this example are shown in Table 1.
Example 7
This example is substantially identical to example 1, except that the oligomerization time is 50 minutes. The results of the gas phase analysis of this example are shown in Table 1.
Example 8
This example is substantially identical to example 1, except that the molar ratio of Al in the diethylaluminum chloride to palladium metal in the palladium catalyst is 75:1. the results of the gas phase analysis of this example are shown in Table 1.
Example 9
This example is substantially identical to example 1, except that the molar ratio of Al in diethylaluminum chloride to palladium metal in the palladium catalyst is 125:1. the results of the gas phase analysis of this example are shown in Table 1.
Example 10
This example is substantially identical to example 1, except that the molar ratio of Al in diethylaluminum chloride to palladium metal in the palladium catalyst is 250:1. the results of the gas phase analysis of this example are shown in Table 1.
Figure SMS_8
As can be seen from the data in table 1, the catalyst of the present invention 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 invention has good oligomerization activity and 1-octene selectivity when used in ethylene tetramerization reaction.
While the invention has been described in detail in connection with specific preferred embodiments thereof, it is not to be construed as limited thereto, but rather as a result of a simple deduction or substitution by a person having ordinary skill in the art to which the invention pertains without departing from the scope of the invention defined by the appended claims.

Claims (10)

1. An ethylene selective tetrapalladium catalyst, comprising a palladium complex of dibenzylideneacetone, wherein the palladium complex of dibenzylideneacetone is bis (dibenzylideneacetone) palladium represented by formula I or tris (dibenzylideneacetone) dipalladium represented by formula II:
Figure QLYQS_1
（І）；
Figure QLYQS_2
（II）。
2. an ethylene-selective tetrapalladium catalyst according to claim 1, wherein the palladium in the palladium complex is in a zero valence state.
3. An ethylene-selective tetrapalladium catalyst according to claim 1, wherein said palladium catalyst further comprises an aluminum-containing cocatalyst.
4. An ethylene-selective tetrapalladium catalyst according to claim 3, wherein the aluminum-containing cocatalyst is an alumoxane or an alkyl aluminum compound or a mixture of both.
5. The ethylene selective tetrapalladium catalyst according to claim 4, wherein said aluminoxane is a C1 to C4 alkylaluminoxane; the general formula of the alkyl aluminum compound is AlR n X m Wherein R is selected from C1-C8 alkyl; x is halogen.
6. The ethylene selective tetrapalladium catalyst according to claim 5, wherein said alkylaluminoxane is one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane; the halogen in the alkyl aluminum compound is 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.
7. The ethylene-selective tetrapalladium catalyst according to claim 1, wherein the molar ratio of aluminum in the aluminum-containing cocatalyst to palladium metal in the palladium complex is 50-1000:1.
8. Use of an ethylene-selective tetrapalladium catalyst according to any of claims 1 to 7 for the catalytic preparation of 1-octene in ethylene oligomerization reactions.
9. The use of an ethylene selective tetrapalladium catalyst according to claim 8, wherein the catalytic preparation of 1-octene is to mix the palladium catalyst with an organic solvent, and then introduce ethylene into the mixed system to perform oligomerization reaction to obtain 1-octene; the molar concentration of the palladium complex in the mixed system is 2-500 mu mol/L.
10. The use of an ethylene-selective tetrapalladium catalyst according to claim 9, wherein the organic solvent is one or any combination of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene and methylene chloride.
CN202310263237.8A 2023-03-17 2023-03-17 Ethylene selective tetrapalladium catalyst and application thereof Pending CN116174049A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310263237.8A CN116174049A (en) 2023-03-17 2023-03-17 Ethylene selective tetrapalladium catalyst and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310263237.8A CN116174049A (en) 2023-03-17 2023-03-17 Ethylene selective tetrapalladium catalyst and application thereof

Publications (1)

Publication Number Publication Date
CN116174049A true CN116174049A (en) 2023-05-30

Family

ID=86448866

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310263237.8A Pending CN116174049A (en) 2023-03-17 2023-03-17 Ethylene selective tetrapalladium catalyst and application thereof

Country Status (1)

Country Link
CN (1) CN116174049A (en)

Similar Documents

Publication Publication Date Title
NL2023317B1 (en) Method and catalyst for selective oligomerization of ethylene
CN113372389B (en) Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application
CN101569865B (en) Ethylene oligomerization catalysis system
CN112742483B (en) Catalyst system for ethylene selective oligomerization and preparation and application thereof
CN106800494B (en) Catalyst for liquid-phase ethylene oligomerization and method for catalyzing liquid-phase ethylene oligomerization
CN101117366B (en) Method for catalyzing copolymerization of ethylene and norbornene
CN103374084A (en) Magnesium chloride/silicon dioxide/tetrahydrofuran loaded late transition metal catalyst and preparation method and application thereof
CN114988980B (en) Method for producing 1-octene by high-activity oligomerization of ethylene
CN116174049A (en) Ethylene selective tetrapalladium catalyst and application thereof
CN101190928A (en) Ni metal complex and its preparation method and using method in ethene oligomerization
CN114054095B (en) Ethylene oligomerization catalyst composition and application thereof
Zhang et al. Preparation of Aryloxy-aluminoxanes and Their Use as Activators in the Bis (imino) pyridyl Iron-catalyzed Oligomerization of Ethylene
CN116510779A (en) Iron catalyst for ethylene selective tetramerization and preparation method of 1-octene
CN111196824A (en) Preparation of anthracene skeleton phosphorus-nitrogen coordination bimetallic compound and ethylene selective oligomerization catalysis thereof
CN107149947B (en) Catalyst for ethylene oligomerization and application thereof
Song et al. 2, 9-disubstituted 1, 10-phenanthroline nickel complexes: Syntheses, characterization, and their ethylene oligomerization
CN113600241B (en) Catalyst system for selective trimerization of ethylene and preparation and application thereof
CN107597191B (en) Catalyst for preparing 1-hexene by ethylene trimerization
CN106673935A (en) Dimerization method of 1-butylene
CN116037206A (en) C (C) 2 -C 3 Catalyst component for olefin oligomerization, preparation method and application thereof
CN113583052A (en) Fluorine-containing metal complex and catalyst for ethylene oligomerization
CN109701661B (en) Catalyst composition and application thereof
CN109701660B (en) Catalyst composition and application thereof
CN109701641B (en) Catalyst composition and application thereof
CN109701663B (en) Catalyst composition and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination