CN104415789A - Catalyst composition for ethylene oligomerization and ethylene oligomerization method - Google Patents
Catalyst composition for ethylene oligomerization and ethylene oligomerization method Download PDFInfo
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- CN104415789A CN104415789A CN201310376576.3A CN201310376576A CN104415789A CN 104415789 A CN104415789 A CN 104415789A CN 201310376576 A CN201310376576 A CN 201310376576A CN 104415789 A CN104415789 A CN 104415789A
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Abstract
The invention provides a catalyst composition for ethylene oligomerization, which comprises a main catalyst of chlorinated 2-formyl-1,10-phenanthroline aminal iron (II) complex as shown in formula I, an aluminium-containing cocatalyst, water, and an organic solvent. When the catalyst composition of the invention is used in ethylene oligomerization reaction process, the catalyst compoeition has very high oligomerization reactivity, the selectivity for alpha-olefins is high, and the oligomerization reaction is rapid in initiation, stable in operation, and good in repeatability; even if the aluminium/iron ratio is low, the oligomerization reactivity is very good, so the cost of the ethylene oligomerization is greatly reduced, and the catalyst composition is strong in practicality, and wide in industrialization prospects.
Description
Technical field
The present invention relates to ethylene oligomerization field, be specifically related to a kind of carbon monoxide-olefin polymeric for ethylene oligomerization reaction process, the present invention is also corresponding relates to a kind of ethylene oligomerization method.
Background technology
Linear alpha-alkene has a wide range of applications in fields such as ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and oil dopes.In recent years, along with the development of polyolefin industry, the demand rapid development to alpha-olefin in world wide.The alpha-olefin of the current overwhelming majority is obtained by ethylene oligomerization preparation.Ethylene oligomerization method catalyst used mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (people such as Brookhart, M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (people such as Gibson, V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find that the trident pyridinimine complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation respectively, not only the catalytic activity of catalyst is very high, and alpha-olefin is selective also very high.
The open CN1850339A of the Chinese patent application of Institute of Chemistry, Academia Sinica reports a kind of catalyst for ethylene oligomerization and polymerization, and this catalyst is the Fe of 2-imido grpup-1,10-phenanthroline coordination
2+, Co
2+and Ni
2+chloride, under the effect of co-catalyst triethyl aluminum, this catalyst has good ethylene oligomerization and polymerization catalyzed performance as major catalyst, wherein iron (II) complex shows very high oligomerisation and polymerization activity to ethene, when the mol ratio of the metallic aluminium in co-catalyst and the central metal in major catalyst is 500, reaction temperature is 40 DEG C, and when reaction pressure is 1MPa, oligomerisation and polymerization activity reach 10
5gmol (Fe)
-1h
-1; Under the effect of co-catalyst MAO, when the mol ratio of the metallic aluminium in co-catalyst and the central metal in major catalyst is 200 ~ 2000, and when reaction temperature is 20 ~ 60 DEG C, oligomerisation and polymerization activity have been up to 10
7gmol (Fe)
-1h
-1; When reaction temperature is 20 ~ 50 DEG C, oligomerisation and polymerization activity raise with the rising of reaction temperature, arrival 50 DEG C of following reaction temperature rising and reduce; And oligomerisation and polymerization activity comparatively obvious with the rising increase of pressure; Oligomerization product comprises C
4, C
6, C
8, C
10, C
12, C
14, C
16, C
18, C
20, C
22selective up to more than 99.5% Deng, alpha-olefin; Polymer is low-molecular-weight polyolefin and wax-like polyolefin.And no matter be MAO, or modified methylaluminoxane is as co-catalyst, all there is high cost, the problem that consumption is excessive, and as co-catalyst large-scale application when the ethylene oligomerization, it certainly will cause production cost high.
At present, it has been generally acknowledged that water is very disadvantageous to ethylene oligomerization reaction process, CN200810111717.8 discloses a kind of method of ethylene oligomerization, carry out under being strict controlled in the environment of anhydrous and oxygen-free, therefore current ethylene oligomerization reaction is very harsh to technological requirement, causes the reaction initiation of oligomerisation reaction technique and all non-constant of repeatability.
Summary of the invention
For deficiency of the prior art, inventor has carried out research extensively and profoundly in ethylene oligomerization catalyst field, be surprised to find, ethene is comprising the major catalyst chlorination 2-formoxyl-1 shown in formula I, 10-phenanthroline contracting amine closes iron (II) complex, carries out oligomerisation reaction containing under the carbon monoxide-olefin polymeric effect of aluminum cocatalyst and organic solvent, there is obviously higher oligomerisation reaction on the contrary active, and oligomerisation reaction cause rapidly, operate steadily, reproducible; Thus overcome the technology prejudice of those skilled in the art, achieve unforeseeable technique effect.
Therefore, the invention provides a kind of ethylene oligomerization carbon monoxide-olefin polymeric, comprise major catalyst chlorination 2-formoxyl-1, the 10-phenanthroline contracting amine shown in formula I and close iron (II) complex, containing aluminum cocatalyst and organic solvent; In formula I, R
1~ R
5be selected from hydrogen, C independently of one another
1~ C
6alkyl, halogen, C
1~ C
6alkoxyl and nitro.
(Ⅰ)
In the present invention, especially in the pilot scale of ethylene oligomerization and industrial processes, not only do not need to remove the moisture in organic solvent, on the contrary, also need to add a certain amount of moisture content in organic solvent to complete the present invention.Different according to temperature, the saturation moisture content that can carry in organic solvent is different, can moisture about 450ppm in such as room temperature 30 DEG C of Toluenes.
Preferably, with the weight of organic solvent for Calculation Basis, the weight content of water is 5 ~ 350ppm; Be more preferably 20 ~ 260ppm, most preferably be 50 ~ 200ppm.
In the present invention, term " C
1-C
6alkyl " refer to saturated straight chain containing 1-6 carbon atom or branched hydrocarbyl.As C
1-C
6alkyl, can mention methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl; Particularly preferably methyl, ethyl, n-pro-pyl and isopropyl.
In the present invention, term " C
1-C
6alkoxyl " refer to above-mentioned C
1-C
6alkyl is connected with an oxygen atom group obtained.As C
1-C
6alkoxyl, can mention methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, just own oxygen base and the second month in a season own oxygen base; Particularly preferably methoxyl group and ethyoxyl.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
In a particular embodiment, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, preferred toluene and dimethylbenzene.
In the present invention, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.The general formula of such as described alkyl aluminum compound is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; X is halogen separately, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferably, described alkyl aluminum compound is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In the present invention, described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; More preferably MAO.
In preferred described carbon monoxide-olefin polymeric, with the volume of organic solvent for Calculation Basis, the content of described major catalyst is 2 ~ 500 μm of ol/L, preferably 20 ~ 100 μm of ol/L.Preferably, in co-catalyst of the present invention in aluminium and major catalyst the mol ratio of iron be 30 ~ be less than 900: 1, preferably 100 ~ 700: 1, be more preferably 148 ~ 196: 1.
In major catalyst of the present invention, preferably, R
1-R
5be selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro independently of one another; Preferred R
1and R
5for ethyl, and R
2~ R
4be hydrogen.
The present invention also provides a kind of method of ethylene oligomerization, is included in and closes iron (II) complex such as formula major catalyst chlorination 2-formoxyl-1, the 10-phenanthroline contracting amine shown in I, carry out ethylene oligomerization containing under aluminum cocatalyst and organic solvent existence; In formula I, R
1~ R
5be selected from hydrogen, C independently of one another
1~ C
6alkyl, halogen, C
1~ C
6alkoxyl and nitro.
In oligomerization of the present invention, preferably, in the weight of organic solvent for benchmark, the weight content of water is 5 ~ 350ppm, preferably 20 ~ 260ppm, is more preferably 50 ~ 120ppm.
In a specific embodiment, described major catalyst and co-catalyst be blended in ethene atmosphere under carry out.In a particular embodiment, the temperature of described reaction is-20 ~ 150 DEG C, is preferably 0 ~ 80 DEG C, is more preferably 5 ~ 35 DEG C.In the present invention, the pressure of described reaction is 0.1 ~ 30MPa, generally speaking, raises along with ethylene pressure raises oligomerization activity.
In ethylene oligomerization method of the present invention, about the kind of organic solvent kind, co-catalyst, major catalyst based on organic solvent content, help major catalyst mol ratio and R
1~ R
5substituent preferable range is all identical with the preferable range in ethylene oligomerization carbon monoxide-olefin polymeric in the present invention.
One of them concrete ethylene oligomerization embodiment can comprise the steps: that (1) is replaced reaction system by the operation such as hyperthermia drying, vacuum displacement, guarantees anhydrous and oxygen-free in reaction system; (2) use ethene to replace reaction system, make reaction system be in ethene environment; (3) in reaction system, add carbon monoxide-olefin polymeric, comprise major catalyst, co-catalyst, water and organic solvent, fully stir; (4) pass into ethene and start oligomerisation reaction, maintenance reaction pressure is 0.1 ~ 30MPa and reaction temperature is react 30 ~ 100min at-20 ~ 150 DEG C; (5) stop reaction, get product gas-chromatography and carry out (GC) analysis.In the present invention, the major catalyst described in step (3) and co-catalyst first can add reaction system with after organic solvent dissolution again.
Use carbon monoxide-olefin polymeric of the present invention to carry out ethylene oligomerization, the ethylene oligomerization product of acquisition comprises C
4, C
6, C
8, C
10, C
12, C
14, C
16, C
18, C
20, C
22deng; The selective of alpha-olefin can reach more than 96%.After ethylene oligomerization reaction terminates, carry out GC analysis.Result shows, oligomerization activity can reach 10
7gmol (Fe)
-1h
-1above.In addition, the remaining reactant mixture ethanolic solution of the watery hydrochloric acid acidifying of 5% neutralizes, and does not obtain polymer.
According to carbon monoxide-olefin polymeric provided by the invention; ethene is comprising the major catalyst chlorination 2-formoxyl-1 shown in formula I; 10-phenanthroline contracting amine closes iron (II) complex, carries out oligomerisation reaction containing under the composition effect of aluminum cocatalyst and organic solvent; compared with anhydrous catalyst composition system; there is higher oligomerisation reaction on the contrary active, and oligomerisation reaction cause rapidly, operate steadily, reproducible.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated and illustrate, but embodiment does not form any limitation of the invention.
Embodiment 1
Carbon monoxide-olefin polymeric is used for ethylene oligomerization reaction, specifically comprises the steps: that (1) is replaced reaction system by the operation such as hyperthermia drying, vacuum displacement, guarantees anhydrous and oxygen-free in reaction system; (2) use ethene to replace reaction system, make reaction system be in ethene environment; (3) add in a kettle. a certain amount of containing water-toluene, add 1.37ml triethyl aluminum toluene solution (concentration is 715 μm of ol/ml), add 2ml chlorination 2-formoxyl-1,10-phenanthroline contracting 2, after 6-diethylaniline closes the toluene solution (concentration is 2.5 μm of ol/ml) of iron (II), total composition is made to be 100ml, by changing used making containing the toluene of saturation water and the proportioning of dry toluene in the weight of the organic solvent weight content that is benchmark water as 5ppm, Al/Fe=196, after abundant stirring, pass into ethene and start oligomerisation reaction; (4) keep ethylene pressure be 1MPa and reaction temperature be at 30 DEG C react 30 minutes; (5) stop reaction, take out a small amount of product gas-chromatography and carry out (GC) analysis.
In the present embodiment, the activity of catalyst ethylene oligomerization is 0.51 × 10
7gmol (Fe)
-1h
-1, oligomer content is respectively C
422.3%, C
6~ C
1046.22%, C
6~ C
1870.32% (wherein containing linear alpha-alkene 97.8%), C
20~ C
287.38%.The remaining mixture ethanolic solution of the hcl acidifying of 5% neutralizes, and does not obtain polymer.Analysis result is in table 1.
Embodiment 2
With embodiment 1, difference is, the weight content of water is 20ppm.Data are in table 1.
Embodiment 3
With embodiment 1, difference is, the weight content of water is 50ppm.Data are in table 1.
Embodiment 4
With embodiment 1, difference is, the weight content of water is 120ppm.Data are in table 1.
Embodiment 5
With embodiment 1, difference is, the weight content of water is 200ppm.Data are in table 1.
Embodiment 6
With embodiment 1, difference is, the weight content of water is 260ppm.Data are in table 1.
Embodiment 7
With embodiment 1, difference is, the weight content of water is 350ppm, and data are in table 1.
Embodiment 8
With embodiment 1, difference is, the weight content of water is 200ppm and reaction temperature is 0 DEG C.Data are in table 1.
Embodiment 9
With embodiment 1, difference is, the weight content of water is 200ppm and reaction temperature is-10 DEG C.Data are in table 1.
Embodiment 10
With embodiment 1, difference is, the weight content of water is 200ppm and reaction temperature is-20 DEG C.Data are in table 1.
Embodiment 11
With embodiment 1, difference is, the weight content of water is 200ppm and reaction temperature is 50 DEG C.Data are in table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 200ppm, and makes Al/Fe=500 by the consumption adjusting co-catalyst.Data are in table 1.
Comparative example 1
With embodiment 1, difference is, water content is 0ppm.Data are in table 1.
Table 1
Data as can be seen from table 1, according to carbon monoxide-olefin polymeric provided by the invention, ethene carries out oligomerisation reaction under moisture carbon monoxide-olefin polymeric effect, there is higher oligomerisation reaction on the contrary active, specifically contrast from the catalyst activity of embodiment 1 ~ 7 and comparative example 1, under identical oligomerisation condition, in the present invention, the corresponding catalyst activity of carbon monoxide-olefin polymeric is 2.5 ~ 6 times of catalyst activity in comparative example.And the selective and alpha-olefin in comparative example of alpha-olefin that obtains of the embodiment of the present invention selective compared with equally all very high.Especially it is worthy of note, in embodiment 3 ~ 5, when water content is 50 ~ 200ppm, the activity of ethylene oligomerization is more than 1 × 10
7gmol (Fe)
-1h
-1, illustrate that the catalyst of this scope water content is particularly suitable for catalyzed ethylene oligomerisation in industrial production.In addition, in the present invention oligomerisation reaction cause rapidly, operate steadily, reproducible.
In addition, as seen from Table 1, even if when ferro-aluminum ratio is low to moderate 196, in the present invention, catalyst still has good oligomerisation reaction catalytic activity, and ethylene oligomerization reaction cost is declined to a great extent, and it is practical, and industrial prospect is wide.And from embodiment 5,8,9 and 10, react when carrying out at a lower temperature in the present invention, still there is high oligomerisation reaction active.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (17)
1. an ethylene oligomerization carbon monoxide-olefin polymeric, comprises major catalyst chlorination 2-formoxyl-1, the 10-phenanthroline contracting amine shown in formula I and closes iron (II) complex, containing aluminum cocatalyst and organic solvent;
(Ⅰ)
In formula I, R
1~ R
5be selected from hydrogen, C independently of one another
1~ C
6alkyl, halogen, C
1~ C
6alkoxyl and nitro.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, with the weight of organic solvent for Calculation Basis, the weight content of water is 5 ~ 350ppm.
3. carbon monoxide-olefin polymeric according to claim 2, is characterized in that, with the weight of organic solvent for Calculation Basis, the weight content of water is 20 ~ 260ppm, is preferably 50 ~ 200ppm.
4. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, preferred toluene and dimethylbenzene.
5. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound; The general formula of preferred described alkyl aluminum compound is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; X is halogen, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferred described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described alkyl aluminum compound is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride; More preferably triethyl aluminum; Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; Be more preferably MAO.
6. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, in described carbon monoxide-olefin polymeric, with the volume of organic solvent for Calculation Basis, the content of described major catalyst is 2 ~ 500 μm of ol/L, preferably 20 ~ 100 μm of ol/L.
7., according to the carbon monoxide-olefin polymeric in claim 1 ~ 6 described in any one, it is characterized in that, in described co-catalyst in aluminium and major catalyst the mol ratio of iron be 30 ~ be less than 900: 1, preferably 100 ~ 700: 1, be more preferably 148 ~ 196: 1.
8. according to the carbon monoxide-olefin polymeric in claim 1 ~ 6 described in any one, it is characterized in that, R
1-R
5be selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro independently of one another; Preferred R
1and R
5for ethyl, and R
2~ R
4be hydrogen.
9. a method for ethylene oligomerization, is included in and closes iron (II) complex such as formula major catalyst chlorination 2-formoxyl-1, the 10-phenanthroline contracting amine shown in I, carry out ethylene oligomerization containing under aluminum cocatalyst and organic solvent existence; In formula I, R
1~ R
5be selected from hydrogen, C independently of one another
1~ C
6alkyl, halogen, C
1~ C
6alkoxyl and nitro.
(Ⅰ)
10. method according to claim 9, is characterized in that, in the weight of organic solvent for benchmark, the weight content of water is 5 ~ 350ppm, preferably 20 ~ 260ppm, is more preferably 50 ~ 200ppm.
11. methods according to claim 9, is characterized in that, described major catalyst and co-catalyst be blended in ethene atmosphere under carry out.
12. methods according to claim 9, is characterized in that, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, preferred toluene and dimethylbenzene.
13. methods according to claim 9, is characterized in that, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound; The general formula of preferred described alkyl aluminum compound is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; X is halogen, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferred described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described alkyl aluminum compound is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride; More preferably triethyl aluminum; Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; Be more preferably MAO.
14. methods according to claim 9, is characterized in that, with the volume of organic solvent for Calculation Basis, the content of described major catalyst is 2 ~ 500 μm of ol/L, preferably 20 ~ 100 μm of ol/L.
15. methods according to claim 9, is characterized in that, in described co-catalyst in aluminium and major catalyst the mol ratio of iron be 30 ~ be less than 900: 1, preferably 100 ~ 700: 1, be more preferably 148 ~ 196: 1.
16., according to the method in claim 9 ~ 15 described in any one, is characterized in that, R
1-R
5be selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro independently of one another; Preferred R
1and R
5for ethyl, and R
2~ R
4be hydrogen.
17., according to the method in claim 9 ~ 15 described in any one, is characterized in that, the temperature of described reaction is-20 ~ 150 DEG C, are preferably 0 ~ 80 DEG C, are more preferably 5 ~ 35 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310376576.3A CN104415789B (en) | 2013-08-26 | 2013-08-26 | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and ethylene oligomerization method |
| JP2014084516A JP6466652B2 (en) | 2013-04-17 | 2014-04-16 | Catalyst composition and process for ethylene oligomerization |
| US14/254,277 US9266983B2 (en) | 2013-04-17 | 2014-04-16 | Catalyst composition and process for ethylene oligomerization |
| ZA2014/02828A ZA201402828B (en) | 2013-04-17 | 2014-04-16 | Catalyst compositions and process for ethylene oligomerization |
| KR1020140046144A KR102167323B1 (en) | 2013-04-17 | 2014-04-17 | Catalyst composition and process for ethylene oligomerization |
| BE2014/0272A BE1021842B1 (en) | 2013-04-17 | 2014-04-17 | CATALYST COMPOSITION AND METHOD FOR THE OLIGOMERIZATION OF ETHENE |
| NL2012643A NL2012643C2 (en) | 2013-04-17 | 2014-04-17 | Catalyst composition and process for ethylene oligomerization. |
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| CN107282118A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and oligomerization |
| CN107282119A (en) * | 2016-03-31 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and oligomerization |
| CN107282119B (en) * | 2016-03-31 | 2019-12-20 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization and oligomerization method |
| CN107282118B (en) * | 2016-03-31 | 2019-12-20 | 中国石油化工股份有限公司 | Catalyst composition for ethylene oligomerization and oligomerization method |
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