CN107282115B - Catalyst composition for ethylene oligomerization and application thereof - Google Patents
Catalyst composition for ethylene oligomerization and application thereof Download PDFInfo
- Publication number
- CN107282115B CN107282115B CN201610196082.0A CN201610196082A CN107282115B CN 107282115 B CN107282115 B CN 107282115B CN 201610196082 A CN201610196082 A CN 201610196082A CN 107282115 B CN107282115 B CN 107282115B
- Authority
- CN
- China
- Prior art keywords
- catalyst composition
- catalyst
- ethylene
- oligomerization
- butyl hydroperoxide
- 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
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst composition for an ethylene oligomerization reaction process and application thereof, wherein the composition comprises a main catalyst chlorinated substituted-2-benzoyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process.
Background
Linear α -olefins have found widespread use in the fields of ethylene comonomers, intermediates for surfactant synthesis, alcohols for plasticizers, synthetic lubricating oils and oil additives, etc. in recent years, with the continuous development of the polyolefin industry, there is a rapidly increasing worldwide demand for α -olefins, the vast majority of α -olefins are currently prepared by ethylene oligomerization, catalysts for ethylene oligomerization are mainly nickel-, chromium-, zirconium-and aluminum-based, etc., and in recent years, the Brookhart group (Brookhart, M et al, J.Am.Chem.Soc.,1998,120,7143 + 7144; WO99/02472,1999), the Gibson group (Gibson, V.C.Commun., 1998,849 + 850; chem.Eur.J.,2000,2221 + 2231) found some tridentate pyridine complexes of Fe (II) and Co (II), respectively, which catalyze ethylene oligomerization catalysts with high selectivity, α -olefin oligomerization catalysts.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled to be performed in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, resulting in very poor reaction initiation and repeatability of the oligomerization reaction process.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor carries out extensive and intensive research in the field of catalysts for ethylene oligomerization, and surprisingly discovers that ethylene is oligomerized under the action of a catalyst composition comprising a main catalyst chlorinated substituted-2-benzoyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide (and an organic solvent), and the catalyst composition has higher oligomerization activity, and has the advantages of quick initiation of oligomerization, stable operation and good repeatability; thereby overcoming the technical bias of the technicians in the field and achieving unexpected technical effects.
According to one aspect of the present invention, there is provided a catalyst composition for ethylene oligomerization, the composition comprising a main catalyst chlorinated substituted 2-benzoyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex represented by formula (I):
in the formula (I), R1-R6Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
The catalyst composition provided by the invention contains tert-butyl hydroperoxide, but has higher ethylene oligomerization activity and high α -olefin selectivity.
In the present invention, the term "C1-C6Alkyl "refers to a saturated straight or branched chain hydrocarbon group containing 1 to 6 carbon atoms. As C1-C6Alkyl, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl and sec-hexyl; particular preference is given to methyl, ethyl, n-propyl and isopropyl.
In the present invention, the term "C1-C6Alkoxy "means C as defined above1-C6Alkyl groups are attached to an oxygen atom. As C1-C6Alkoxy, there may be mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, n-hexoxy and sec-hexoxy; methoxy and ethoxy are particularly preferred.
In the present invention, the term "halogen" means fluorine, chlorine, bromine and iodine, and fluorine, chlorine and bromine are particularly preferred.
In the present invention, said R1-R6The choice of (a) may be any combination of the substituents referred to by the above terms. Wherein, in a preferred embodiment of the present invention, R in the main catalyst1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro; wherein R is1-R6The choice of (a) may be any combination of the above groups. In one embodiment of the above composition, R in the procatalyst3And R4Is methyl, and R1、R2、R5And R6Are all hydrogen.
In a preferred embodiment of the present invention, the aluminum-containing cocatalyst is selected from at least one of aluminoxanes and alkylaluminum compounds. In the present invention, the alkyl aluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; each X is halogen, preferably chlorine or bromine; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3. Specific examples of the alkyl aluminum compound include, but are not limited to, at least one of the following compounds: trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, such as triethylaluminum. In the present invention, the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group. Examples of the aluminoxane include, but are not limited to: at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; such as methylaluminoxane.
In a preferred embodiment of the invention, the molar ratio of aluminium in the cocatalyst to iron in the procatalyst is from 30:1 to 900:1, such as from 100:1 to 700:1, further such as from 148:1 to 196: 1. In a specific embodiment of the above composition, the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 196:1 to 500: 1. Even in the lower molar ratio range provided, the ethylene oligomerization activity is still higher.
In a preferred embodiment of the present invention, the catalyst composition comprises tert-butyl hydroperoxide in an amount of 5 to 1750ppm by weight, such as 25 to 1750ppm by weight, such as 35 to 1300ppm by weight. In a specific example, the content of the tert-butyl hydroperoxide is 100-1300 ppm by weight; under the preferable conditions, the weight content of the tert-butyl hydroperoxide is 250-1000 ppm, such as 250-500 ppm. Within the content range of the tert-butyl hydroperoxide, the catalyst composition has higher ethylene oligomerization activity.
In a preferred embodiment of the present invention, the composition further comprises an organic solvent, that is, the composition comprises a main catalyst chlorinated substituted 2-benzoyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent. In the present invention, the weight content of the t-butyl hydroperoxide is calculated based on the weight of the organic solvent. For example, the content of t-butyl hydroperoxide is 5 to 1750ppm by weight based on the weight of the organic solvent, i.e., 5 to 1750X 10 based on 1g of the organic solvent-6g of tert-butyl hydroperoxide. The organic solvent is an organic solvent commonly used in the art, and specific examples thereof include, but are not limited to: at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride, such as toluene, xylene, or a mixture of toluene and xylene.
In the case of using the composition of the present invention in production, the amounts of the main catalyst and the cocatalyst can be selected according to the production scale and the process conditions of the specific application such as production equipment. In one embodiment of the catalyst composition, the amount of the procatalyst is 2 to 500. mu. mol/L based on the volume of the composition containing the organic solvent (i.e., 2 to 500X 10 in the composition based on 1L of the composition)-6mol of main catalyst), such as 20-100 μmol/L, such as 50 μmol/L.
According to another aspect of the invention, a method for oligomerization of ethylene is also provided. The catalyst composition can be applied to oligomerization of ethylene, and the ethylene oligomerization reaction is carried out on the ethylene in the presence of the catalyst composition. One specific embodiment may include the steps of: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding a catalyst composition comprising a main catalyst, a cocatalyst and tert-butyl hydroperoxide (and an organic solvent) into a reaction system, and fully stirring; (4) the oligomerization reaction is carried out by starting the oligomerization reaction with ethylene, and may be carried out, for example, under the following conditions: maintaining the reaction pressure at 0.1 to 30MPa, the reaction temperature at-20 to 150 ℃, and the reaction time at 30 to 100 min; (5) the reaction was stopped after a certain time. The reaction product was analyzed by Gas Chromatography (GC).
In the invention, the main catalyst and the cocatalyst in the step (3) can be dissolved by an organic solvent and then added into the reaction system. In the oligomerization reaction process, the main catalyst and the cocatalyst are mixed in an ethylene atmosphere. The temperature of the oligomerization reaction is-20 to 150 ℃, for example, 0 to 80 ℃. Under preferred conditions, the temperature ranges from-20 to 40 deg.C, such as 5 to 35 deg.C. The reaction pressure is 0.1-30 MPa, and the oligomerization activity is increased along with the increase of the ethylene pressure.
The catalyst composition is used for ethylene oligomerization, and the obtained ethylene oligomerization product comprises C4、C6、C8、C10、C12、C14、C16、C18、C20、C22α -olefin selectivity can reach 96%, after the ethylene oligomerization reaction is finished, GC analysis shows that the oligomerization activity can reach 107g·mol(Fe)-1·h-1The above. In addition, the remaining reaction mixture was neutralized with a 5% diluted hydrochloric acid acidified ethanol solution, and no polymer was obtained.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a main catalyst chlorinated substituted-2-benzoyl-1, 10-phenanthroline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst, tert-butyl hydrogen peroxide and an organic solvent, and the catalyst composition has high oligomerization reaction activity, α -olefin selectivity is high, and the oligomerization reaction is quick to initiate, stable to operate and good in repeatability.
Detailed Description
The invention is further illustrated and described with reference to specific examples, which are not intended to be limiting.
Example 1
The ethylene oligomerization reaction specifically comprises the following steps: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding tert-butyl hydroperoxide and toluene solvent into a reaction kettle, adding 1.37ml of triethyl aluminum toluene solution (the concentration is 715 mu mol/ml), adding 2ml of chloro-2-benzoyl-5, 6-dimethyl-1, 10-phenanthroline condensation-2, 6-diethyl aniline iron (II) complex (R)3And R4Is methyl, and R1、R2、R5And R6Hydrogen) was added to the reaction solution, and the total amount of the composition was adjusted to 100ml, wherein the t-butyl hydroperoxide content was 25ppm by weight and the Al/Fe ratio was 196 based on the weight of the organic solvent (i.e., toluene), and after sufficient stirring, ethylene was introduced to initiate oligomerization; (4) keeping the ethylene pressure at 1MPa and the reaction temperature at 30 ℃ for reacting for 30 minutes; (7) the reaction was stopped and a small amount of the reaction product was taken out for analysis by Gas Chromatography (GC): the oligomerization activity is 0.65 multiplied by 107g·mol(Fe)-1·h-1The oligomer content is respectively C440.96%,C6~C1049.10%,C6~C1857.00% (containing linear α -olefin 97.5%), C20~C281.66 percent. The remaining mixture was neutralized with 5% hydrochloric acid acidified ethanol solution, no polymer was obtained. The analytical results are shown in Table 1.
Example 2
The same as in example 1, except that the content of t-butyl hydroperoxide was 100ppm by weight. The data are shown in Table 1.
Example 3
The same as in example 1, except that the content of t-butyl hydroperoxide was 250ppm by weight. The data are shown in Table 1.
Example 4
The same as in example 1, except that the content of t-butyl hydroperoxide was 500ppm by weight. The data are shown in Table 1.
Example 5
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 1000 ppm. The data are shown in Table 1.
Example 6
The difference from example 1 is that the t-butyl hydroperoxide content was 1300ppm by weight. The data are shown in Table 1.
Example 7
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 1750ppm by weight, the data being shown in Table 1.
Example 8
The same as in example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the reaction temperature was 0 ℃. The data are shown in Table 1.
Example 9
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-10 ℃. The data are shown in Table 1.
Example 10
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-20 ℃. The data are shown in Table 1.
Example 11
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 40 ℃. The data are shown in Table 1.
Example 12
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and that Al/Fe is 500. The data are shown in Table 1.
Comparative example 1
The same as example 1, except that t-butyl hydroperoxide was not present in the composition. The data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, according to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a composition comprising a main catalyst chlorinated substituted-2-benzoyl-1, 10-phenanthroline iron (II) -condensation complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent, and the catalyst composition has high oligomerization reaction activity, α -olefin selectivity is high, and the oligomerization reaction is initiated quickly, stably operated and has good repeatability.
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 (23)
1. A catalyst composition for ethylene oligomerization comprises a main catalyst chlorinated 2-benzoyl-1, 10-phenanthroline iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
in the formula, R1~R6Each independently selected from hydrogen and C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro.
2. The catalyst composition of claim 1, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 5-1750 ppm.
3. The catalyst composition of claim 2, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 100-1300 ppm.
4. The catalyst composition of claim 3, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 250-1000 ppm.
5. The catalyst composition as claimed in claim 4, wherein the catalyst composition contains tert-butyl hydroperoxide in an amount of 250-500ppm by weight.
6. The catalyst composition of any of claims 1-5, wherein the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 30:1 to 900: 1.
7. The catalyst composition of claim 6, wherein the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 100:1 to 700: 1.
8. The catalyst composition of claim 7, wherein the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 196:1 to 500: 1.
9. The catalyst composition of any of claims 1-5, wherein R in the procatalyst is1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro.
10. The catalyst composition of claim 9, wherein R in the procatalyst is3And R4Is methyl, and R1、R2、R5And R6Are all hydrogen.
11. The catalyst composition of any one of claims 1-5, wherein the aluminum-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminum compound.
12. The catalyst composition according to claim 11, characterized in that the alkylaluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; x is halogen; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3.
13. The catalyst composition of claim 12, wherein X is chlorine or bromine.
14. The catalyst composition of claim 13, wherein the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.
15. The catalyst composition of claim 11, wherein the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group.
16. The catalyst composition of claim 15, wherein the aluminoxane is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
17. The catalyst composition of any one of claims 1-5, further comprising an organic solvent.
18. The catalyst composition of claim 17, wherein the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride.
19. The catalyst composition of claim 17, wherein the main catalyst is present in an amount of 2 to 500 μmol/L.
20. The catalyst composition of claim 19, wherein the main catalyst is present in the catalyst composition in an amount of 20 to 100 μmol/L.
21. A method for oligomerization of ethylene, wherein ethylene is subjected to the oligomerization reaction in the presence of the catalyst composition according to any one of claims 1 to 20.
22. The process for oligomerization of ethylene according to claim 21, wherein the reaction temperature is from-20 to 150 ℃.
23. The process for oligomerization of ethylene according to claim 22, wherein the reaction temperature is from-20 to 40 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610196082.0A CN107282115B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition for ethylene oligomerization and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610196082.0A CN107282115B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition for ethylene oligomerization and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107282115A CN107282115A (en) | 2017-10-24 |
CN107282115B true CN107282115B (en) | 2020-05-12 |
Family
ID=60087200
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610196082.0A Active CN107282115B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition for ethylene oligomerization and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107282115B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102964388A (en) * | 2011-09-01 | 2013-03-13 | 中国石油化工股份有限公司 | Preparation method of benzoyl-substituted 1,10-phenanthroline complex and catalytic application in ethylene oligomerization |
CN104447161A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
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 CN201610196082.0A patent/CN107282115B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102964388A (en) * | 2011-09-01 | 2013-03-13 | 中国石油化工股份有限公司 | Preparation method of benzoyl-substituted 1,10-phenanthroline complex and catalytic application in ethylene oligomerization |
CN104447161A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
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 |
---|---|
CN107282115A (en) | 2017-10-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107282126B (en) | Ethylene tetramerization catalyst composition and application thereof | |
NL2012643C2 (en) | Catalyst composition and process for ethylene oligomerization. | |
CN107282115B (en) | Catalyst composition for ethylene oligomerization and application thereof | |
CN109701642B (en) | Catalyst composition and application thereof | |
CN107282107B (en) | Catalyst composition for ethylene oligomerization and application thereof | |
CN107282113B (en) | Catalyst composition for ethylene oligomerization and application thereof | |
CN107282111B (en) | Catalyst composition for ethylene oligomerization and ethylene oligomerization method | |
CN107282116B (en) | Catalyst composition for ethylene oligomerization and application thereof | |
CN107282117B (en) | Ethylene oligomerization catalyst composition and oligomerization method | |
CN107282119B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107282109B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107286278B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107282120B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107282118B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107282121B (en) | Catalyst composition for ethylene oligomerization and oligomerization method | |
CN107282123B (en) | Ethylene oligomerization catalyst composition and application thereof | |
CN105562087B (en) | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application | |
CN109701647B (en) | Catalyst composition and application thereof | |
CN109701651B (en) | Catalyst composition and application thereof | |
CN109701641B (en) | Catalyst composition and application thereof | |
CN109701640B (en) | Catalyst composition and application thereof | |
CN104549505B (en) | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and ethylene oligomerization method | |
CN105478166B (en) | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application | |
CN116037207A (en) | Catalyst composition for olefin oligomerization and preparation method and application thereof | |
CN109701643B (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 |