CN102206127A - Ethylene oligomerization method - Google Patents
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- CN102206127A CN102206127A CN2010101381271A CN201010138127A CN102206127A CN 102206127 A CN102206127 A CN 102206127A CN 2010101381271 A CN2010101381271 A CN 2010101381271A CN 201010138127 A CN201010138127 A CN 201010138127A CN 102206127 A CN102206127 A CN 102206127A
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Abstract
The invention provides an ethylene oligomerization method. Chloride of Fe<2+>, Co<2+> and Ni<2+> with 2-imino-1, 10-phenanthroline coordinated is taken as a main catalyst, Triethylaluminium is taken as a cocatalyst for replacing a high-price methylaluminoxane and the like, and the mol ratio of aluminum in the cocatalyst of triethylaluminium to central metal in the main catalyst is more than 30 and less than 200 or more than 200 and less than 500, The amount of the cocatalyst is greatly reduced, therefore the cost of the ethene oligomerization reaction is greatly reduced, the invention has a broad industrialization prospect.
Description
Technical field
The present invention relates to a kind of ethylene oligomerization method, be specifically related to a kind of use chlorination 2-imido grpup-1,10-phenanthroline iron (II), cobalt (II) or nickel (II) title complex are as Primary Catalysts, the triethyl aluminum ethylene oligomerization method as promotor.
Background technology
Linear alpha-alkene has a wide range of applications with fields such as alcohol, ucon oil and oil dopes at ethylene comonomer, tensio-active agent synthetic intermediate, softening agent.In recent years, along with the continuous development of polyolefin industry, the demand to alpha-olefin in the world wide increases rapidly.The alpha-olefin of the overwhelming majority is obtained by the ethylene oligomerization preparation at present.The used catalyzer of ethylene oligomerization method mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (Brookhart, people such as M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (Gibson, people such as V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find some Fe (II) and Co (II) respectively but the oligomerisation of trident pyridinimine title complex catalyzed ethylene, not only the catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin is also very high.
The patent CN1850339A of Institute of Chemistry, Academia Sinica has reported a kind of ethylene oligomerization and polymeric catalyzer of being used for, and this catalyzer is a 2-imido grpup-1,10-phenanthroline coordinate Fe
2+, Co
2+And Ni
2+Muriate, under the effect of promotor methylaluminoxane, this catalyzer has ethylene oligomerization and polymerization catalyzed performance preferably as Primary Catalysts, wherein iron (II) title complex shows very high oligomerisation and polymerization activity to ethene, has reached 10
7G mol Fe
-1h
-1And when temperature of reaction was lower than 50 ℃, oligomerisation and polymerization activity raise with the rising of temperature of reaction, reduced in the rising that arrives 50 ℃ of following response temperature; And oligomerisation and polymerization activity are 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
22Deng, the selectivity of alpha-olefin is up to more than 99.5%; Polymkeric substance is low-molecular-weight polyolefin and wax shape polyolefine.
As everyone knows, aikyiaiurnirsoxan beta is relatively expensive, if adopt aikyiaiurnirsoxan beta as the promotor large-scale application when the ethylene oligomerization, it certainly will cause production cost high.
Summary of the invention
At the defective of prior art, the object of the present invention is to provide a kind of rationally more economically, ethylene oligomerization method that the polymerization cost is comparatively cheap.The inventor has carried out research extensively and profoundly at ethylene oligomerization with catalyst field, found that, by with chlorination 2-imido grpup-1,10-phenanthroline iron (II), cobalt (II) or nickel (II) title complex are produced ethylene oligomer as Primary Catalysts, triethyl aluminum as promotor, catalytic activity not only can be accepted, and, make the cost reduce oligomerizing ethylene greatly, thereby be beneficial to the suitability for industrialized production of oligomerizing ethylene greatly because triethyl aluminum is cheap.
Therefore, the invention provides a kind of ethylene oligomerization method, wherein adopt the chlorination 2-imido grpup-1 of following formula (I), 10-phenanthroline iron (II), cobalt (II) or nickel (II) title complex as Primary Catalysts and triethyl aluminum as promotor, and the mol ratio of the central metal in metallic aluminium in the described promotor and the described Primary Catalysts is 30 to less than 200 or for greater than 200 to 500
Each variable-definition in its Chinese style is as follows:
M is a central metal, and it is Fe
2+, Co
2+Or Ni
2+
R
1-R
5Be selected from hydrogen, C independently of one another
1-C
6Alkyl, halogen, C
1-C
6Alkoxyl group and nitro.
In the present invention, term " C
1-C
6Alkyl " refer to the saturated direct-connected or branched hydrocarbyl that contains 1-6 carbon atom.As C
1-C
6Alkyl can be mentioned methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl and Sec-Hexyl; Special preferable methyl, ethyl and sec.-propyl.
In the present invention, term " C
1-C
6Alkoxyl group " refer to above-mentioned C
1-C
6Alkyl is connected the group that obtains with a Sauerstoffatom.As C
1-C
6Alkoxyl group can be mentioned methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, secondary pentyloxy, positive hexyloxy and secondary hexyloxy; Preferred especially methoxyl group and oxyethyl group.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, preferred especially fluorine, chlorine and bromine.
In a preferred embodiment of the invention, metallic aluminium in the promotor triethyl aluminum and the central metal in the Primary Catalysts (are Fe
2+, Co
2+Or Ni
2+) mol ratio be 100 to less than 200 or for greater than 200 to 300, be preferably 148 to less than 200, be preferably 148-196 especially.
In particularly preferred embodiment of the present invention, wherein Primary Catalysts is wherein M and R
1-R
5Have compound as giving a definition:
1：M＝Fe
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
2：M＝Fe
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
3：M＝Fe
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
4：M＝Fe
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
5：M＝Fe
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
6：M＝Fe
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
7：M＝Fe
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
8：M＝Fe
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
9：M＝Fe
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
10：M＝Fe
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
11：M＝Fe
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
12：M＝Fe
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
13：M＝Fe
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
14：M＝Fe
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
15：M＝Fe
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H；
16：M＝Co
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
17：M＝Co
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
18：M＝Co
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
19：M＝Co
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
20：M＝Co
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
21：M＝Co
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
22：M＝Co
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
23：M＝Co
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
24：M＝Co
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
25：M＝Co
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
26：M＝Co
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
27：M＝Co
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
28：M＝Co
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
29：M＝Co
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
30：M＝Co
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H；
31：M＝Ni
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
32：M＝Ni
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
33：M＝Ni
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
34：M＝Ni
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
35：M＝Ni
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
36：M＝Ni
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
37：M＝Ni
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
38：M＝Ni
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
39：M＝Ni
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
40：M＝Ni
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
41：M＝Ni
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
42：M＝Ni
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
43：M＝Ni
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
44：M＝Ni
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
45：M＝Ni
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H。
In particularly preferred embodiment of the present invention, preferred R wherein
1And R
5Be ethyl and R
2-R
4Formula (I) compound that is hydrogen is as Primary Catalysts.
The preparation of Primary Catalysts compound of the present invention itself is known, can be to this referring to CN1850339A, and the document is incorporated this paper by reference into.
The method of formula (I) Primary Catalysts that preparation the present invention limits generally includes following steps:
(1) with 2-ethanoyl-1, (substituting group is selected from down group: C to the aniline of 10-phenanthroline and replacement
1-C
6Alkyl, halogen, C
1-C
6Alkoxyl group and nitro) reaction Synthetic 2-imido grpup-1,10-phenanthroline part; And
(2) with the 2-imido grpup-1 that obtains in the step 1,10-phenanthroline part respectively with FeCl
24H
2O, CoCl
2Or NiCl
26H
2The O reaction can obtain title complex.
The concrete preparation process of the Primary Catalysts that the inventive method is used is as follows:
One, part synthetic general method
1) 2-ethanoyl-1,10-phenanthroline and C
1-C
6The aniline that alkyl replaces is that catalyzer refluxed 1～2 day with the tosic acid in ethanol, reaction solution concentrates back parlkaline aluminum oxide pillar, and with petrol ether/ethyl acetate (4: 1) drip washing, second cut is a product, removing desolvates obtains yellow solid 2-imido grpup-1,10-phenanthroline part.
2) 2-ethanoyl-1,10-phenanthroline and fluorine, C
1-C
6The aniline that alkoxyl group or nitro replace is catalyzer with the tosic acid and adds molecular sieve or anhydrous sodium sulphate is made dewatering agent reflux in toluene 1 day, remove solvent toluene parlkaline aluminum oxide pillar after the filtration, with petrol ether/ethyl acetate (4: 1) drip washing, second cut is a product, removing desolvates obtains yellow solid 2-imido grpup-1,10-phenanthroline part.
3) 2-ethanoyl-1; the aniline that 10-phenanthroline and chlorine, bromine replace is made catalyzer with tosic acid; adopt tetraethoxy to make solvent and dewatering agent; 140-150 ℃ of following reacting by heating 1 day, tetraethoxy, parlkaline aluminum oxide pillar were then removed in decompression; with petrol ether/ethyl acetate (4: 1) drip washing; second cut is a product, and removing desolvates obtains yellow solid 2-imido grpup-1,10-phenanthroline part.
The aniline that described alkyl replaces is preferred 2, the 6-Diethyl Aniline.
Above-mentioned all synthetic 2-imido grpups-1,10-phenanthroline part have all obtained confirmation by nuclear-magnetism, infrared and ultimate analysis.
Two, iron (II), cobalt (II), nickel (II) title complex synthetic general method
With FeCl
24H
2O, CoCl
2Or NiCl
26H
2The ethanolic soln of O in molar ratio 1: 1-1: 1.2 are added drop-wise to 2-imido grpup-1, and in the solution of 10-phenanthroline part, stirring at room is separated out precipitation, filter, and just obtain 2-imido grpup-1,10-phenanthroline title complex with ether washing after drying.Title complex 1-45 is confirmed by ultimate analysis and infrared spectrum characterization.
The oligomerisation reaction condition that the inventive method relates to is known to those skilled in the art, for example can use as the method for the pressurization ethylene oligomerization described among the Chinese patent application publication number CN1850339A and carry out oligomerisation, described document is incorporated this paper by reference into.For example, ethylene oligomerization method according to the present invention can be performed as follows: adding organic solvent, promotor and Primary Catalysts in reaction vessel, is to react 30～100 minutes under 0.1～30MPa and temperature of reaction are 20～150 ℃ at ethylene pressure then; Be cooled to-10～10 ℃ then, take out spiece with in 5% the dilute hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually.
When the Primary Catalysts that the present invention is limited and promotor were used for ethylene oligomerization, preferably, the temperature of oligomerisation reaction was generally 20～80 ℃, and pressure is 1～5MPa, and the reaction times advantageously is 30～60 minutes.
Come oligomerizing ethylene by the inventive method, 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 selectivity of alpha-olefin can reach more than 95%; No polymkeric substance produces.
After ethylene oligomerization finishes, take out a small amount of reaction mixture with in 5% the dilute hydrochloric acid and after carry out the GC analysis.The result shows that the oligomerisation activity can reach 10
6Gmol
-1H
-1More than, it is more reasonable that oligomerization product distributes.In addition, remaining reaction mixture neutralizes with 5% dilute hydrochloric acid acidifying ethanolic soln, does not obtain polymkeric substance.
With respect to prior art, the present invention is owing to adopt triethyl aluminum (AlEt
3) substitute expensive methylaluminoxane (MAO) etc. as promotor (the methylaluminoxane unit price is that triethyl aluminum is monovalent more than tens times), and in the described promotor triethyl aluminum in metallic aluminium and the Primary Catalysts mol ratio (Al/M) of central metal significantly reduce, make ethylene oligomerization and polyreaction cost decline to a great extent, industrial prospect is wide.
Embodiment
Below only be preferred embodiment of the present invention, can not limit scope of the present invention with this.Be every variation and modification of being done according to the present patent application claim, all should still belong in the scope that patent of the present invention contains.
Embodiment 1
One, the preparation of Primary Catalysts
2-ethanoyl-1, (0.4445g, 2mmol) with 2, (0.4175g 2.8mmol) adds the 40mg tosic acid and is catalyzer and adds 2g the 6-Diethyl Aniline 10-phenanthroline
Molecular sieve is made dewatering agent, refluxes 1 day in 30ml ethanol, removes solvent toluene after the filtration; residuum supports with the methylene dichloride dissolving; parlkaline aluminum oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second cut is a product; removing desolvates obtains yellow solid; be 2-ethanoyl-1,10-phenanthroline (contracting 2, the 6-Diethyl Aniline) part; output is 0.6g, and productive rate is 84%.Nmr analysis:
1H NMR (300MHz, CDCl
3): δ 9.25 (dd, J=3.0Hz, 1H); 8.80 (d, J=8.3Hz, 1H); 8.35 (d, J=8.3Hz, 1H); 8.27 (dd, J=7.8Hz, 1H); 7.86 (s, 2H); 7.66 (m, 1H); 7.15 (d, J=7.6Hz, 2H); 6.96 (t, J=7.5Hz, 1H); 2.58 (s, 3H, CH
3); 2.43 (m, 4H, CH
2CH
3); 1.16 (t, J=7.5Hz, 6H, CH
2CH
3).Ultimate analysis: C
24H
23N
3(353.46), theoretical value: C:81.55; H:6.56; N:11.89.Observed value: C:80.88; H:6.59; N:11.78.
With 5ml FeCl
24H
2(48mg, ethanol solution 0.24mmol) are added drop-wise to 5ml 2-ethanoyl-1 to O, and the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) part (70.6mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filter; just obtain blackish green powder solid with ether washing after drying, for chlorination [2-imido grpup-1, the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) close iron (II) title complex, productive rate is 95%.Ultimate analysis: test value C:59.95; H:4.92; N:8.80.Theoretical value C:60.03; H:4.83; N:8.75.
Two, ethylene oligomerization reaction
With toluene and 0.53ml triethyl aluminum toluene solution (concentration is 0.74mol/l) and 8ml Primary Catalysts chlorination [2-imido grpup-1, the 10-phenanthroline (contracts 2, the 6-Diethyl Aniline) toluene solution that closes iron (II) (2.0 μ mol) joins in the stainless steel autoclave of 300ml, making cumulative volume is 100ml, Al/Fe=196.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Afterwards, with syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.02 * 10
6Gmol
-1(Fe) h
-1, oligomer content is respectively C
412.0%, C
6～C
1064.7%, C
6～C
1887.0% (wherein containing linear alpha-alkene 98.0%), C
20～C
281.0%, K value 0.57.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 2
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.54ml (concentration is 0.74mol/l), makes Al/Fe=199.8.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.02 * 10
6Gmol
-1H
-1, oligomer content is respectively C
412.1%, C
6～C
1064.5%, C
6～C
1886.8% (wherein containing linear alpha-alkene 97.5%), C
20～C
281.1%, K value 0.57.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 3
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.4ml (concentration is 0.74mol/l), makes Al/Fe=148.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.21 * 10
6Gmol
-1H
-1, oligomer content is respectively C
424.7%, C
6～C
1057.4%, C
6～C
1872.7% (wherein containing linear alpha-alkene 92.9%), C
20～C
282.6%, K value 0.52.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 4
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.81ml (concentration is 0.25mol/l), makes Al/Fe=101.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.01 * 10
6Gmol
-1H
-1, oligomer content is respectively C
421.6%, C
6～C
1053.6%, C
6～C
1875.3% (wherein containing linear alpha-alkene 89.9%), C
20～C
283.1%, K value 0.53.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 5
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.4ml (concentration is 0.25mol/l), makes Al/Fe=50.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 0.12 * 10
6Gmol
-1H
-1, oligomer content is respectively C
47.4%, C
6～C
1086.8%, C
6～C
1892.6% (wherein containing linear alpha-alkene 92.5%), C
20～C
280%, K value 0.69.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 6
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.24ml (concentration is 0.25mol/l), makes Al/Fe=30.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 0.08 * 10
6Gmol
-1H
-1, oligomer content is respectively C
46.9%, C
6～C
1087.1%, C
6～C
1893.1% (wherein containing linear alpha-alkene 91.5%), C
20～C
280%, K value 0.69.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 7
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 0.81ml (concentration is 0.74mol/l), makes Al/Fe=300.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.06 * 10
6Gmol
-1H
-1, oligomer content is respectively C
421.3%, C
6～C
1053.7%, C
6～C
1873.9% (wherein containing linear alpha-alkene 95.8%), C
20～C
284.8%, K value 0.53.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 8
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 1.1ml (concentration is 0.74mol/l), makes Al/Fe=407.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.91 * 10
6Gmol
-1H
-1, oligomer content is respectively C
421.1%, C
6～C
1053.7%, C
6～C
1874.0% (wherein containing linear alpha-alkene 96.5%), C
20～C
284.9%, K value 0.54.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 9
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and be with the difference of embodiment 1: triethyl aluminum toluene solution consumption is 1.35ml (concentration is 0.74mol/l), makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 0.88 * 10
6Gmol
-1H
-1, oligomer content is respectively C
437.0%, C
6～C
1052.0%, C
6～C
1863.0% (wherein containing linear alpha-alkene 91.5%), C
20～C
280%, K value 0.48.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 10
Adopt the preparation method of embodiment 1 Primary Catalysts, difference is: with 5ml CoCl
2(31.2mg, ethanol solution 0.24mmol) are added drop-wise to 5ml 2-ethanoyl-1, and the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) part (70.6mg, in ethanol solution 0.2mmol), stirring at room 6 hours; separate out precipitation, filter) ethanol solution in, stirring at room 6 hours; separate out precipitation, filter, just obtain brown solid with ether washing after drying; be chlorination [2-imido grpup-1; 10-phenanthroline (contracting 2, the 6-Diethyl Aniline) closes cobalt (II) title complex, and productive rate is 95%.Ultimate analysis: test value C:59.69; H:4.86; N:8.62 theoretical value C:59.64; H:4.80; N:8.69.
Repeat the ethylene oligomerization technology described in the embodiment 1, wherein promotor still is a triethyl aluminum, with toluene and 0.53ml triethyl aluminum toluene solution (concentration is 0.74mol/l) and 8ml Primary Catalysts chlorination [2-imido grpup-1, the 10-phenanthroline (contracts 2, the 6-Diethyl Aniline) toluene solution that closes cobalt (II) (2.0 μ mol) joins in the stainless steel autoclave of 300ml, making cumulative volume is 100ml, Al/Co=196.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Afterwards, with syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.51 * 10
6Gmol
-1(Co) h
-1, oligomer content is C
4100%.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 11
Adopt the preparation method of embodiment 1 Primary Catalysts, difference is: with 5ml NiCl
26H
2(57.0mg, ethanol solution 0.24mmol) are added drop-wise to 5ml 2-ethanoyl-1 to O, and the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) part (70.6mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filter; just obtain the tawny solid with ether washing after drying, for chlorination [2-imido grpup-1, the 10-phenanthroline (contracts 2; the 6-Diethyl Aniline) close nickel (II) title complex, productive rate is 96%.Ultimate analysis: test value C:59.64; H:4.82; N:8.53 theoretical value C:59.67; H:4.80; N:8.70.
Repeat the ethylene oligomerization technology described in the embodiment 1, wherein promotor still is a triethyl aluminum, with toluene and 0.53ml triethyl aluminum toluene solution (concentration is 0.74mol/l) and 8ml Primary Catalysts chlorination [2-imido grpup-1, the 10-phenanthroline (contracts 2, the 6-Diethyl Aniline) toluene solution that closes nickel (II) (2.0 μ mol) joins in the stainless steel autoclave of 300ml, making cumulative volume is 100ml, Al/Ni=196.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Afterwards, with syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.40 * 10
6Gmol
-1(Ni) h
-1, oligomer content is C
4100%.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 12
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and the triethyl aluminum consumption is 0.53ml (concentration is 0.74mol/l), makes Al/Fe=196.Be with the difference of embodiment 1: under 40 ℃, keep the ethylene pressure of 2MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.21 * 10
6Gmol
-1H
-1, oligomer content is respectively C
419.40%, C
6～C
1053.02%, C
6～C
1875.68% (wherein containing linear alpha-alkene 96.9%), C
20～C
284.92%, K value 0.60.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 13
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and the triethyl aluminum consumption is 0.54ml (concentration is 0.74mol/l), makes Al/Fe=199.8.Be with the difference of embodiment 1: under 40 ℃, keep the ethylene pressure of 2MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.83 * 10
6Gmol
-1H
-1, oligomer content is respectively C
421.05%, C
6～C
1052.37%, C
6～C
1873.36% (wherein containing linear alpha-alkene 97.5%), C
20～C
285.59%, K value 0.60.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 14
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and the triethyl aluminum consumption is 0.53ml (concentration is 0.74mol/l), makes Al/Fe=196.Be with the difference of embodiment 1: under 40 ℃, keep the ethylene pressure of 3MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.40 * 10
6Gmol
-1H
-1, oligomer content is respectively C
417.5%, C
6～C
1046.2%, C
6～C
1871.5% (wherein containing linear alpha-alkene 98.7%), C
20～C
2811.0%, K value 0.64.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Embodiment 15
Adopt the Primary Catalysts of embodiment 1 preparation, promotor is that triethyl aluminum carries out the ethylene oligomerization reaction, and the triethyl aluminum consumption is 0.4ml (concentration is 0.74mol/l), makes Al/Fe=148.Be with the difference of embodiment 1: under 40 ℃, keep the ethylene pressure of 3MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.21 * 10
6Gmol
-1H
-1, oligomer content is respectively C
419.5%, C
6～C
1053.4%, C
6～C
1875.8% (wherein containing linear alpha-alkene 98.4%), C
20～C
284.7%, K value 0.59.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.Analytical results sees Table one.
Comparative Examples 1
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is that 1.36ml (concentration is the toluene solution of 1.5mol/l) makes Al/Fe=1000.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.41 * 10
7Gmol
-1H
-1, oligomer content is respectively C
435.0%, C
6～C
1040.4%, C
6～C
1864.7% (wherein containing linear alpha-alkene 99.3%), C
20～C
280.3%, K value 0.45.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 4.23 * 10
5Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 2
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 1.1ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=800.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.23 * 10
7Gmol
-1H
-1, oligomer content is respectively C
423.8%, C
6～C
1044.1%, C
6～C
1866.4% (wherein containing linear alpha-alkene 96.9%), C
20～C
289.8%, K value 0.61.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 3.21 * 10
5Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 3
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 0.8ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=600.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.13 * 10
7Gmol
-1H
-1, oligomer content is respectively C
428.7%, C
6～C
1031.7%, C
6～C
1865.2% (wherein containing linear alpha-alkene 95.5%), C
20～C
286.1%, K value 0.58.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 5.14 * 10
5Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 4
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 0.54ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=400.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.08 * 10
7Gmol
-1H
-1, oligomer content is respectively C
416.4%, C
6～C
1045.2%, C
6～C
1873.0% (wherein containing linear alpha-alkene 95.0%), C
20～C
2810.6%, K value 0.66.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 4.65 * 10
5Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 5
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 0.27ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=200.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.60 * 10
6Gmol
-1H
-1, oligomer content is respectively C
414.4%, C
6～C
1045.0%, C
6～C
1874.0% (wherein containing linear alpha-alkene 91.0%), C
20～C
2811.6%, K value 0.68.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 8.78 * 10
4Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 6
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 0.26ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=195.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.50 * 10
6Gmol
-1H
-1, oligomer content is respectively C
414.2%, C
6～C
1044.9%, C
6～C
1874.1% (wherein containing linear alpha-alkene 89.0%), C
20～C
2811.7%, K value 0.68.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 6.21 * 10
4Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 7
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 2.0ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=1500.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.12 * 10
7Gmol
-1H
-1, oligomer content is respectively C
425.0%, C
6～C
1053.8%, C
6～C
1873.7% (wherein containing linear alpha-alkene 95.7%), C
20～C
281.3%, K value 0.60.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 5.12 * 10
5Gmol
-1H
-1Analytical results sees Table one.
Comparative Examples 8
Adopt the Primary Catalysts of embodiment 1 preparation to carry out the ethylene oligomerization reaction as described in embodiment 1, difference is: promotor is a methylaluminoxane, and the methylaluminoxane consumption is 2.67ml (concentration is the toluene solution of 1.5mol/l), makes Al/Fe=2000.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 30min.With syringe take out spiece with in 5% the dilute hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.10 * 10
6Gmol
-1H
-1, oligomer content is respectively C
417.9%, C
6～C
1051.2%, C
6～C
1876.4% (wherein containing linear alpha-alkene 97.4%), C
20～C
285.7%, K value 0.62.Remaining mixture obtains the white wax shaped polymer with the ethanolic soln neutralization of 5% hcl acidifying, and polymerization activity is 7.13 * 10
4Gmol
-1H
-1Analytical results sees Table one.
From table one as can be known: adopt chlorination 2-imido grpup-1 ethylene oligomerization, 10-phenanthroline iron (II) title complex as Primary Catalysts and triethyl aluminum as promotor, and the Al/Fe mol ratio is 30 to less than 200 o'clock, and along with the Al/Fe mol ratio increases, reactive behavior increases; And when the Al/Fe mol ratio greater than 200 to 500 the time, along with the Al/Fe mol ratio increases, reactive behavior reduces on the contrary.Also promptly when adopting triethyl aluminum as promotor, in the Al/Fe mol ratio is 30 to 500 scopes, reactive behavior is to reach peak value near 196 in the Al/Fe mol ratio, show near ACTIVITY CHANGE OF FT trend different when adopting methylaluminoxane to be promotor (Comparative Examples in the Al/Fe mol ratio is 195 to 2000 scopes, reactive behavior is to reach peak value 1000 in the Al/Fe mol ratio) with Comparative Examples.
Claims (7)
1. ethylene oligomerization method, wherein adopt the chlorination 2-imido grpup-1 of following formula (I), 10-phenanthroline iron (II), cobalt (II) or nickel (II) title complex as Primary Catalysts and triethyl aluminum as promotor, and the mol ratio of the central metal in metallic aluminium in the described promotor and the described Primary Catalysts is 30 to less than 200 or for greater than 200 to 500
Each variable-definition in its Chinese style is as follows:
M is a central metal, and it is Fe
2+, Co
2+Or Ni
2+
R
1-R
5Be selected from hydrogen, C independently of one another
1-C
6Alkyl, halogen, C
1-C
6Alkoxyl group and nitro.
2. according to the process of claim 1 wherein that the mol ratio of metallic aluminium in the described promotor and the central metal in the described Primary Catalysts is 100 to less than 200 or for greater than 200 to 300, be preferably 148, be preferably 148-196 especially to less than 200.
3. according to the method for claim 1 or 2, R wherein
1-R
5Be hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group and nitro independently of one another.
4. according to the method for claim 1 or 2, R wherein
1And R
5Be ethyl and R
2-R
4Formula (I) compound that is hydrogen is as Primary Catalysts.
5. according to the method for claim 1 or 2, wherein Primary Catalysts is wherein M and R
1-R
5Have formula (I) compound as giving a definition:
1：M＝Fe
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
2：M＝Fe
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
3：M＝Fe
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
4：M＝Fe
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
5：M＝Fe
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
6：M＝Fe
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
7：M＝Fe
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
8：M＝Fe
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
9：M＝Fe
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
10：M＝Fe
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
11：M＝Fe
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
12：M＝Fe
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
13：M＝Fe
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
14：M＝Fe
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
15：M＝Fe
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H；
16：M＝Co
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
17：M＝Co
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
18：M＝Co
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
19：M＝Co
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
20：M＝Co
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
21：M＝Co
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
22：M＝Co
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
23：M＝Co
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
24：M＝Co
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
25：M＝Co
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
26：M＝Co
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
27：M＝Co
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
28：M＝Co
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
29：M＝Co
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
30：M＝Co
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H；
31：M＝Ni
2+，R
1＝Me，R
2＝R
3＝R
4＝R
5＝H；
32：M＝Ni
2+，R
2＝Me，R
1＝R
3＝R
4＝R
5＝H；
33：M＝Ni
2+，R
3＝Me，R
1＝R
2＝R
4＝R
5＝H；
34：M＝Ni
2+，R
1＝R
2＝Me，R
3＝R
4＝R
5＝H；
35：M＝Ni
2+，R
1＝R
3＝Me，R
2＝R
4＝R
5＝H；
36：M＝Ni
2+，R
1＝R
4＝Me，R
2＝R
3＝R
5＝H；
37：M＝Ni
2+，R
1＝R
5＝Me，R
2＝R
3＝R
4＝H；
38：M＝Ni
2+，R
2＝R
3＝Me，R
1＝R
4＝R
5＝H；
39：M＝Ni
2+，R
2＝R
4＝Me，R
1＝R
3＝R
5＝H；
40：M＝Ni
2+，R
1＝R
3＝R
5＝Me，R
2＝R
4＝H；
41：M＝Ni
2+，R
1＝Et，R
2＝R
3＝R
4＝R
5＝H；
42：M＝Ni
2+，R
1＝Et，R
5＝Me，R
2＝R
3＝R
4＝H；
43：M＝Ni
2+，R
1＝R
5＝Et，R
2＝R
3＝R
4＝H；
44：M＝Ni
2+，R
1＝iPr，R
2＝R
3＝R
4＝R
5＝H；
45：M＝Ni
2+，R
1＝R
5＝iPr，R
2＝R
3＝R
4＝H。
6. according to each method among the claim 1-5, therein ethylene oligomerisation reaction temperature is 20～80 ℃.
7. according to each method among the claim 1-6, therein ethylene oligomerisation reaction pressure is 1～5MPa.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101381271A CN102206127A (en) | 2010-03-31 | 2010-03-31 | Ethylene oligomerization method |
| KR1020127028616A KR101760821B1 (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for oligomerization of ethylene and processes of oligomerization |
| SA111320341A SA111320341B1 (en) | 2010-03-31 | 2011-03-30 | Catalyst Composition and Process for Synthesis Ethylene Oligomerization |
| JP2013501602A JP5909224B2 (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for oligomerization of ethylene and process of oligomerization |
| RU2012146245/04A RU2571829C2 (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for ethylene oligomerisation and oligomerisation method |
| US13/637,976 US20130018214A1 (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for oligomerization of ethylene and processes of oligomerization |
| GB1219506.1A GB2494555B (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for oligomerization of ethylene and processes of oligomerization |
| PCT/CN2011/000550 WO2011120336A1 (en) | 2010-03-31 | 2011-03-30 | Catalyst composition for oligomerization of ethylene and processes of oligomerization |
| ZA2012/08192A ZA201208192B (en) | 2010-03-31 | 2012-10-31 | Catalyst compositon for oligomerization of ethylene and processes of oligomerization |
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|---|---|---|---|
| CN2010101381271A CN102206127A (en) | 2010-03-31 | 2010-03-31 | Ethylene oligomerization method |
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| CN102731578A (en) * | 2012-06-08 | 2012-10-17 | 中国科学院化学研究所 | 2,8-diimine-4,5,6 hydro quinoline transition metal complex, preparation method thereof, and application thereof |
| CN103086819A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Method for catalyzing ethylene oligomerization by using 2-n-propionyl-1,10-phenanthroline amine late transition metal chlorides |
| CN104109064A (en) * | 2013-04-17 | 2014-10-22 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850339A (en) * | 2005-04-22 | 2006-10-25 | 中国科学院化学研究所 | Catalyst for oligomerization of ethylene, its preparing method and use |
-
2010
- 2010-03-31 CN CN2010101381271A patent/CN102206127A/en active Pending
-
2011
- 2011-03-30 SA SA111320341A patent/SA111320341B1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850339A (en) * | 2005-04-22 | 2006-10-25 | 中国科学院化学研究所 | Catalyst for oligomerization of ethylene, its preparing method and use |
Non-Patent Citations (1)
| Title |
|---|
| SUYUN JIE ET AL.: "Iron(II)complexes ligated by 2-imino-1,10-phenanthrolines:Preparation and catalytic behavior toward ethylene oligomerization", 《JOURNAL OF MOLECULAR CATALYSIS A：CHEMICAL》, vol. 269, 13 January 2007 (2007-01-13), pages 85 - 96, XP055130603, DOI: doi:10.1016/j.molcata.2007.01.008 * |
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