CN107282112B - Ethylene oligomerization catalyst composition and application thereof - Google Patents
Ethylene oligomerization catalyst composition and application thereof Download PDFInfo
- Publication number
- CN107282112B CN107282112B CN201610195928.9A CN201610195928A CN107282112B CN 107282112 B CN107282112 B CN 107282112B CN 201610195928 A CN201610195928 A CN 201610195928A CN 107282112 B CN107282112 B CN 107282112B
- Authority
- CN
- China
- Prior art keywords
- composition
- compound
- transition metal
- aluminum
- metal compound
- 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.)
- Active
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
- B01J31/18—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
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Abstract
The application discloses a catalyst composition for ethylene oligomerization, which comprises a ligand compound shown in formula I, a transition metal compound, an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent; wherein R is1、R2、R3And R4The same or different, each independently selected from hydrogen, alkyl, alkoxy or halogen. The invention also provides an ethylene oligomerization method, which comprises the step of carrying out ethylene oligomerization reaction in the presence of the catalyst composition for ethylene oligomerization. The catalyst composition provided by the invention has the advantages of high activity and high selectivity.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process, and correspondingly relates to an ethylene oligomerization method.
Background
Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry by which inexpensive small-molecule olefins can be converted into high value-added products linear α -olefin (LAO) is an important organic chemical raw material4-C8The compound is mainly applied to the field of producing high-quality Polyethylene (PE) as an important organic raw material and a chemical intermediate. The Linear Low Density Polyethylene (LLDPE) produced by copolymerizing 1-hexene or 1-octene with ethylene can obviously improve various properties of PE, in particular can obviously improve the mechanical property, optical property, tear strength and impact strength of polyethylene, and the product is very suitable for the fields of packaging films, agricultural covering films for greenhouses, sheds and the like. LAO C10-C30Can be used as additives for preparing daily detergents, flotation agents, emulsifying agents, lubricating components of refrigerating machines and drilling fluid, plasticizers, various additives, low-viscosity synthetic oils, polymers and copolymers, petroleum and petroleum product additives, higher alkylamines, higher organoaluminum compounds, higher alkylaryl hydrocarbons, higher fatty alcohols and fatty acids, epoxides, heat carriers, and the like. In LAO C20-C30In recent years, with the increasing development of the polyolefin industry, the worldwide demand for α -olefins has increased rapidly, most of the α -olefins being produced by oligomerization of ethylene.
Since the 70's last century, the research of transition metal complexes for the polymerization and oligomerization of olefins has been receiving increasing attention from scientists, and efforts have been made to develop new catalysts and to improve the existing catalysts to increase the activity of the catalysts and the selectivity of the catalytic products among numerous explorations, the earliest, most developed and concentrated nickel-based cationic catalyst systems have been developed, such as U.S. Pat. Nos. 3686351 and 3676523, and the Shell company SHOP process based on the patent technology, in the Shell company SHOP process, O-P bridged ligands have been involved, but the catalysts have toxic organophosphorus groups and have complicated synthesis steps and poor stability, and subsequently, many patents such as O-O, P-N, P-P and N-N coordinated nickel catalysts, such as JP 17611060627, WO 9996, WO991550, CN1401666, CN 9270, etc., the catalysts obtained from the above patents have generally had disadvantages of relatively complicated preparation methods, other catalysts and aluminum catalysts, such as chromium cocatalyst, aluminum cocatalyst, Brookn-aluminum cocatalyst, Brookn aluminoxane, high cost catalyst systems have been found to be used as catalysts for the ethylene oligomerization catalyst (CO 2, CO-9-O-N cocatalyst, CO-9-N cocatalyst has been used in the large-9-N cocatalyst for the production of ethylene oligomerization catalyst systems (CO-9-NH-N cocatalyst, CO-9-N cocatalyst, CO-9-N cocatalyst has been widely used in the production of ethylene oligomerization catalyst for the high-9-N coordination catalyst for the ethylene oligomerization catalyst for the.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and the ethylene oligomerization method is strictly controlled to be carried out in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, and the reaction initiation and repeatability of the oligomerization reaction process are very poor.
Disclosure of Invention
In order to overcome the defects and shortcomings of the catalyst, the inventor of the invention surprisingly finds that ethylene is oligomerized under the action of a catalyst composition comprising a catalyst ligand shown in formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide, so that the catalyst has obviously higher oligomerization activity, and the oligomerization is rapid in initiation, stable in operation and good in repeatability; the tert-butyl hydroperoxide is used as organic peroxide to promote the reaction, thereby overcoming the technical bias of the technical personnel in the field and achieving unexpected technical effect.
Accordingly, in a first embodiment of the present invention, there is provided a catalyst composition for ethylene oligomerization comprising a ligand compound represented by formula I, a transition metal compound, an aluminum-containing cocatalyst and t-butyl hydroperoxide;
wherein R is1、R2、R3And R4The same or different, each independently selected from hydrogen, alkyl, alkoxy, and halogen.
In a preferred embodiment of the present invention, the alkyl group is C1-C20Alkyl, preferably C1-C10Alkyl, more preferably C1-C6An alkyl group. The alkyl group in the present invention includes at least one of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl and isomers thereof, with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl or isohexyl being even more preferred; most preferred is methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In a preferred embodiment of the present invention, the alkoxy group is C1-C20Alkoxy, preferably C1-C10Alkoxy, more preferably C1-C6An alkoxy group. The alkoxy group in the present invention includes at least one of the following groups: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, isopentoxy, n-hexoxy, sec-hexoxy, isohexoxy, n-heptoxy and isomers thereof; still more preferably a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a sec-pentyloxy group, an isopentyloxy group, a n-hexyloxy group or an isohexyloxy group; most preferred is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy.
In a preferred embodiment of the invention, the halogen is selected from fluorine, chlorine or bromine.
In a preferred embodiment of the present invention, the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound and a nickel compound, preferably at least one selected from the group consisting of chromium trichloride, chromium acetylacetonate, chromium isooctanoate and chromium tris (tetrahydrofuran) trichloride.
In a preferred embodiment of the present invention, the cocatalyst is an organoaluminum compound; preferably an alkylaluminum compound and/or an aluminoxane compound, more preferably at least one of the following compounds: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, methylaluminoxane, ethylaluminoxane or modified methylaluminoxane; most preferably methylaluminoxane or triethylaluminium.
In a preferred embodiment of the invention, the molar ratio of the ligand, the transition metal compound and the cocatalyst is 1 (0.1-10): 1-1000, preferably 1 (0.25-2): 10-1000, such as 1 (0.25-2): 10-700, more preferably 1 (0.5-2): 50-1000, such as 1 (0.5-2): 100-500), such as 1 (0.5-2): 50-200. In a specific example, the ligand, transition metal compound and cocatalyst are present in a molar ratio of 1:1 (50-1000). Within the above range, a more active catalyst composition can be advantageously obtained.
In a preferred embodiment of the present invention, an organic solvent is further included in the composition. Wherein the weight content of the tert-butyl hydroperoxide contained in the catalyst composition is 25-1000ppm by weight based on the weight of the organic solvent; more preferably 150-750ppm, most preferably 250-500 ppm. Within the above range, higher catalytic activity can be obtained.
In a preferred embodiment of the present invention, the organic solvent is at least one selected from aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds. The aromatic hydrocarbon compound is preferably at least one selected from benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene or monochlorobenzene and derivatives thereof; the aliphatic hydrocarbon compound is preferably at least one selected from linear alkanes, branched alkanes, and cyclic alkanes, and more preferably at least one selected from pentane, heptane, cyclohexane, and hexane.
The second embodiment of the invention also provides an ethylene oligomerization method, which comprises the step of carrying out ethylene oligomerization reaction in the presence of the catalyst composition for ethylene oligomerization.
In a preferred embodiment of the present invention, the reaction temperature of the reaction is 0 to 200 ℃, preferably 0 to 100 ℃. Wherein the reaction pressure is 0.1-6.0MPa, preferably 0.5-5.0 MPa.
In a preferred embodiment of the present invention, the ligand, transition metal compound and co-catalyst are catalytic amounts. In a specific example, the transition metal compound is present in a concentration of 0.001 to 1mmol/L, based on the volume of the composition. In a specific embodiment, the concentration of the transition metal compound is 0.01 to 0.05 mmol/L.
Specifically, in the ethylene oligomerization or olefin oligomerization process of the present invention: feeding ethylene or an olefin, an optional organic solvent and the catalyst composition of the present invention into a reactor, and then controlling the ethylene pressure (i.e., the reaction pressure) to 0.1 to 6.0MPa, preferably 0.5 to 5.0 MPa; the reaction temperature is 0-200 ℃, preferably 0-100 ℃, after the reaction is finished, the reaction is cooled to room temperature, and the gas and liquid phase products are taken for chromatographic analysis. In a specific example, the concentration of the transition metal compound is from 0.001 to 1mmol metal/L based on the volume of the composition.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of the catalyst ligand shown in the formula I, the transition metal compound, the aluminum-containing cocatalyst and the tert-butyl hydroperoxide catalyst composition, so that the catalyst composition has high oligomerization reaction activity, and the oligomerization reaction is quick in initiation, stable in operation and good in repeatability. The catalytic system is simple and easy to prepare and control. When the catalyst system is used for ethylene oligomerization, the catalyst has high activity, and C in the product6-C18And the content of the components is high, and the current world pair α -C can be met6、α-C8、α-C10And the above long chain olefin products.
In the invention, especially in the pilot plant and industrial production process of ethylene oligomerization, not only does the strict control of an anhydrous oxygen-free system not need to be carried out, but also has higher oligomerization reaction activity in the presence of organic peroxide, namely tert-butyl hydroperoxide, and has the advantages of rapid reaction initiation, stable operation and good repeatability, thereby obtaining beneficial effects.
Detailed Description
The present invention will be described in detail with reference to examples, but it should be understood that the scope of the present invention is not limited to the examples.
In the examples of the present invention, NMR was detected by an AV400MHz NMR spectrometer of Bruker, Switzerland.
The gas chromatography was performed using a Hewlett packard 5890 chromatograph. The mass spectrum was detected by a gas chromatograph-mass spectrometer of TraceDSQ model, Phenix, USA.
Example 1
A stainless steel polymerizer is used. Heating a stainless steel polymerization kettle to 100 ℃, vacuumizing, replacing with nitrogen for a plurality of times, and then filling ethylene until the ethylene pressure is 2MPa, and cooling to room temperature. Then adding toluene at 70 deg.C, and simultaneously adding 5 μmol ligand compound 1 (shown as formula I, wherein R is1＝R2＝R3＝R4＝CH3) The total volume of the mixed solution is 100mL, wherein the molar ratio of the ligand to the chromium chloride to the triethyl aluminum is 1:1: 200, namely the adding amount of chromium chloride is 5 mu mol, and the adding amount of triethyl aluminum is 1 mmol; the molar ratio Al/Cr is 200. The content of t-butyl hydroperoxide was 25ppm by weight based on the weight of the organic solvent. Controlling the reaction pressure to be 2.0MPa, and introducing ethylene to carry out ethylene oligomerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The results are shown in Table 1.
Example 2
The same as in example 1 except that the content of t-butyl hydroperoxide was 150 ppm; the results are shown in Table 1.
Example 3
The same as in example 1 except that the content of t-butyl hydroperoxide was 300 ppm; the results are shown in Table 1.
Example 4
The same as in example 1 except that the tert-butyl hydroperoxide content was 500 ppm; the results are shown in Table 1.
Example 5
The same as in example 1 except that the content of t-butyl hydroperoxide was 750 ppm; the results are shown in Table 1.
Example 6
The same as in example 1 except that the tert-butyl hydroperoxide content was 1000 ppm; the results are shown in Table 1.
Example 7
The same as in example 1 except that the tert-butyl hydroperoxide content was 1500 ppm; the results are shown in Table 1.
Example 8
The triethyl aluminum was replaced by methyl aluminoxane under the same conditions as in example 6; the results are shown in Table 1.
Example 9
The Al/Cr molar ratio was changed to 50 under the same conditions as in example 6; the results are shown in Table 1.
Example 10
The Al/Cr molar ratio was changed to 1000 under the same conditions as in example 6; the results are shown in Table 1.
Comparative example 1
The same as in example 1, except that the content of t-butyl hydroperoxide was 0ppm by weight. The results are shown in Table 1.
As can be seen from the data in Table 1, according to the catalyst composition provided by the present invention, ethylene is oligomerized under the action of the catalyst composition containing tert-butyl hydroperoxide, and rather, the catalyst composition has high oligomerization activity, and as can be seen from the comparison of the activity of the catalyst composition of the comparative example 1, the activity of the catalyst composition of the present invention corresponding to the same oligomerization conditions is increased by several times, and the selectivity of α -olefin obtained in the examples of the present invention is also very high compared with the selectivity of α -olefin in the comparative example.
In addition, the oligomerization reaction of the invention has the advantages of rapid initiation, stable operation and good repeatability. Even when the Al/Cr ratio is as low as 50, the catalyst still has good oligomerization catalytic activity, so that the ethylene oligomerization cost is greatly reduced, and the catalyst has strong practicability and wide industrialization prospect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (21)
1. A catalyst composition for ethylene oligomerization comprises a ligand compound shown in formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide;
wherein R is1、R2、R3And R4The same or different, each independently selected from hydrogen, alkyl, alkoxy and halogen;
the composition further comprises an organic solvent, and the weight content of the tert-butyl hydroperoxide contained in the composition is 25-1500ppm by weight based on the weight of the organic solvent;
the ligand compound is: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.1-10) to 1-1000.
2. The composition of claim 1, wherein the alkyl group is C1-C20An alkyl group; and/or the alkoxy is C1-C20An alkoxy group.
3. The composition of claim 2, wherein the alkyl group is C1-C10Alkyl, and/or the alkoxy is C1-C10An alkoxy group.
4. The composition of claim 2, wherein the alkyl group is C1-C6Alkyl, and/or the alkoxy is C1-C6An alkoxy group.
5. The composition as claimed in any one of claims 1 to 4, wherein the composition comprises tert-butyl hydroperoxide in an amount of 150-1000ppm by weight, based on the weight of the organic solvent.
6. The composition as set forth in any one of claims 1 to 4, wherein the t-butyl hydroperoxide is contained in the composition in an amount of 250-750ppm by weight based on the weight of the organic solvent.
7. The composition of any one of claims 1 to 4, wherein the ligand compound: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.25-2) to 10-700.
8. The composition of any one of claims 1 to 4, wherein the ligand compound: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.5-2) to (100-500).
9. The composition of any one of claims 1 to 4, wherein the ligand compound: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1:1 (50-1000).
10. The composition according to any one of claims 1 to 4, wherein the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound.
11. The composition of claim 10, wherein the transition metal compound is selected from at least one of chromium trichloride, chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
12. The composition of any one of claims 1-4, wherein the aluminum-containing co-catalyst is an organoaluminum compound.
13. The composition of claim 12, wherein the aluminum-containing cocatalyst is an alkylaluminum compound and/or an aluminoxane compound.
14. The composition of claim 12, wherein the aluminum-containing co-catalyst is at least one of the following compounds: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, methylaluminoxane, ethylaluminoxane and modified methylaluminoxane.
15. The composition according to any one of claims 1 to 4, wherein the organic solvent is at least one selected from aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds.
16. The composition of claim 15, wherein the aromatic hydrocarbon compound is at least one selected from the group consisting of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorobenzene; the aliphatic hydrocarbon compound is selected from at least one of linear alkanes, branched alkanes and cyclic alkanes.
17. The composition as claimed in claim 15, wherein the organic solvent is selected from at least one of pentane, heptane, cyclohexane and hexane.
18. A process for oligomerization of ethylene, comprising carrying out the oligomerization of ethylene in the presence of the catalyst composition for oligomerization of ethylene as claimed in any one of claims 1 to 17.
19. The method of claim 18, wherein the reaction temperature of the reaction is 0-200 ℃; and/or the reaction pressure is 0.1-6.0 MPa.
20. The method of claim 19, wherein the reaction temperature of the reaction is 0-100 ℃; and/or the reaction pressure is 0.5-5.0 MPa.
21. The method of any one of claims 18 to 20, wherein the transition metal compound is present in a concentration of from 0.001 to 1mmol/L, based on the volume of the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610195928.9A CN107282112B (en) | 2016-03-31 | 2016-03-31 | Ethylene oligomerization catalyst composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610195928.9A CN107282112B (en) | 2016-03-31 | 2016-03-31 | Ethylene oligomerization catalyst composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107282112A CN107282112A (en) | 2017-10-24 |
| CN107282112B true CN107282112B (en) | 2020-05-12 |
Family
ID=60087570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610195928.9A Active CN107282112B (en) | 2016-03-31 | 2016-03-31 | Ethylene oligomerization catalyst composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107282112B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114054095B (en) * | 2020-08-10 | 2023-11-10 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst composition and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415787A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Olefin polymerization catalyst composition and application method thereof |
| CN104415788A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Olefin polymerization catalyst composition and application thereof |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
-
2016
- 2016-03-31 CN CN201610195928.9A patent/CN107282112B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415787A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Olefin polymerization catalyst composition and application method thereof |
| CN104415788A (en) * | 2013-08-23 | 2015-03-18 | 中国石油化工股份有限公司 | Olefin polymerization catalyst composition and application thereof |
| WO2015148496A1 (en) * | 2014-03-26 | 2015-10-01 | E. I. Du Pont De Nemours And Company | PROCESS FOR MANUFACTURING LINEAR α-OLEFINS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107282112A (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107282126B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN107282129B (en) | Ethylene trimerization and tetramerization catalyst composition and application thereof | |
| CN107282112B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN109701642B (en) | Catalyst composition and application thereof | |
| CN107282110B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN114054095B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN107282108B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN107282127B (en) | Catalyst composition for ethylene trimerization and tetramerization and application thereof | |
| CN109701648B (en) | Catalyst composition and application | |
| CN107282131B (en) | Catalyst composition and application thereof in ethylene tetramerization | |
| CN107282133B (en) | Ethylene tetramerization catalyst composition and application | |
| CN109701650B (en) | Preparation method and application of cocatalyst for olefin oligomerization | |
| CN107282128B (en) | Ethylene tetramerization catalyst composition and ethylene tetramerization method | |
| CN107282122B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN107149947B (en) | Catalyst for ethylene oligomerization and application thereof | |
| CN107282125B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN105498840B (en) | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method | |
| CN109701640B (en) | Catalyst composition and application thereof | |
| CN109701651B (en) | Catalyst composition and application thereof | |
| CN109701641B (en) | Catalyst composition and application thereof | |
| CN109701647B (en) | Catalyst composition and application thereof | |
| CN109701660B (en) | Catalyst composition and application thereof | |
| CN109701661B (en) | Catalyst composition and application thereof | |
| CN109701643B (en) | Catalyst composition and application thereof | |
| CN109701662B (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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |