CN104109069A - Ethylene oligomerization method - Google Patents
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Abstract
The invention discloses an ethylene oligomerization method. Ethylene is subjected to oligomerization in a reaction system consisting of chlorinated-2-n-propiono-substituted-1,10-phenanthroline amine iron (II) which is shown in a formula (I) as described in the specification and is used as a main catalyst, an aluminum-containing cocatalyst, water and an organic solvent. In the formula (I), R1 to R5 are independently selected from the group consisting of hydrogen, C1-C6 alkyl groups, halogen, C1-C6 alkoxy groups and a nitro group. According to the invention, the catalyst system consisting of the complex main catalyst as shown in the formula (I) and the aluminum-containing cocatalyst is adopted for ethylene oligomerization in the water-containing solvent, and high oligomerization reaction activity and high selectivity of alpha-olefin are obtained; even under the condition of a low aluminum/iron ratio, good oligomerization reaction activity is maintained, so technical biases of the skilled in the art are overcome and unexpected technical effects are obtained.
Description
Technical field
The present invention relates to ethylene oligomerization field, be specifically related to a kind of method of ethylene oligomerization.
Background technology
Linear alpha-alkene is at ethylene comonomer, synthesis of surfactant intermediate, for softening agent, the field such as alcohol, ucon oil and oil dope has a wide range of applications.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 overwhelming majority is obtained by ethylene oligomerization preparation at present.Ethylene oligomerization method catalyzer used mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (Brookhart, the people such as M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (Gibson, the people such as V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find respectively that the trident pyridinimine title complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation, not only the catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin is also very high.
The patent CN102050841A of Institute of Chemistry, Academia Sinica has reported a kind of 2-propionic acid amide-1,10-phenanthroline anil class title complex, take this title complex as Primary Catalysts and take methylaluminoxane or modified methylaluminoxane when promotor is applied to ethylene oligomerization, only, when high promotor consumption (Al/Fe=1000～2000), oligomerisation activity just can reach 10
7gmol
-1h
-1.And no matter be methylaluminoxane, or modified methylaluminoxane is as promotor, all has high cost, the problem that consumption is excessive, and as promotor 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 unfavorable to ethylene oligomerization, therefore current oligomerisation reaction requires very harshly to reaction environment, and be conventionally strict controlled under the environment of anhydrous and oxygen-free and carry out, but the reaction initiation of oligomerization process and stability and repeatability non-constant all.
Summary of the invention
For deficiency of the prior art, contriver has carried out research extensively and profoundly at ethylene oligomerization by catalyst field, be surprised to find, employing is in positive propionyl-1 of chlorination 2-shown in formula (I), 10-phenanthroline contracting amine closes the oligomerisation reaction that carries out ethene under the existence that iron (II) title complex is Primary Catalysts, the reaction system that contains aluminum cocatalyst and solvent, there is on the contrary higher oligomerisation reaction active, and oligomerisation reaction cause rapidly, operate steadily, reproducible; Thereby the technology prejudice that has overcome those skilled in the art, has obtained unforeseeable technique effect.
According to an aspect of the present invention; a kind of method of ethylene oligomerization is provided; ethene is comprising positive propionyl-1 of chlorination 2-shown in formula (I); 10-phenanthroline contracting amine closes in iron (II) title complex Primary Catalysts, the reaction system containing aluminum cocatalyst and organic solvent and carries out oligomerisation reaction
In formula, R
1-R
5be selected from independently of one another hydrogen, C
1-C
6alkyl, halogen, C
1-C
6alkoxyl group and nitro.
In the present invention, term " C
1-C
6alkyl " refer to the saturated straight chain or the branched hydrocarbyl that contain 1-6 carbon atom.As C
1-C
6alkyl, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl and Sec-Hexyl; Particularly preferably methyl, ethyl, n-propyl and sec.-propyl.
In the present invention, term " C
1-C
6alkoxyl group " refer to above-mentioned C
1-C
6alkyl is connected with a Sauerstoffatom group obtaining.As C
1-C
6alkoxyl group, can mention methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, secondary pentyloxy, positive hexyloxy and secondary hexyloxy; Particularly preferably methoxyl group and oxyethyl group.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
According to method provided by the invention, it is active that ethylene oligomerization has higher oligomerisation reaction, and the selectivity of alpha-olefin is high.
In a specific embodiment of method of the present invention, in described reaction system, the weight of organic solvent of take be to be calculated benchmark, and the weight content of water is the i.e. organic solvent based on 1g of 5～350ppm(, in reaction system containing 5～350 * 10
-6the water of g), preferably 20～260ppm, most preferably is 50～200ppm.Within the scope of described water-content, in described method, ethylene oligomerization has higher ethylene oligomerization activity.
In described method of the present invention, the processing condition when consumption of described Primary Catalysts and promotor can be applied according to industrial scale and production unit etc. are concrete are selected.In a specific embodiment of the inventive method, the volume of organic solvent of take be to calculate benchmark, and the content of described Primary Catalysts is the i.e. organic solvents based on 1L of 2～500 μ mol/L(, in reaction system containing 2～500 * 10
-6the Primary Catalysts of mol), preferred 20～100 μ mol/L.
In the present invention, the mol ratio of the iron in the aluminium in wherein said promotor and described Primary Catalysts is 30 to being less than 900:1, is preferably 100～700:1.In a specific embodiment of aforesaid method, the mol ratio of described aluminium and iron is 148～196:1.Even in the lower molar ratio range providing, the ethylene oligomerization activity in described method is still higher.
In the present invention, the R in described Primary Catalysts
1-R
5be selected from independently of one another hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group and nitro; R in preferred described Primary Catalysts
1and R
5for ethyl, R
2-R
4be hydrogen.
Primary Catalysts shown in general formula of the present invention (I) can adopt the preparation method of Chinese patent application CN102558241A report to make.Therefore, positive propionyl-1 of chlorination 2-shown in general formula (I), the concrete preparation process that 10-phenanthroline contracting amine closes iron (II) title complex is as follows:
A.2-positive propionyl-1,10-phenanthroline synthetic: make 1,10-phenanthroline and tri-n-n-propyl aluminum (n-C
3h
7)
3al reaction, more successively through hydrolysis and with the oxidizing reaction of oil of mirbane, acquisition formula (b) compound.
For positive propionyl-1 of 2-of preparation formula (b), 10-phenanthroline, first makes 1,10-phenanthroline and tri-n-n-propyl aluminum (n-C
3h
7)
3al reaction under organic solvent exists.Operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferably toluene.Utilize these organic solvents, preparation 1,10-phenanthroline solution, wherein strength of solution is 10～200g/L.This 1, reacting conventionally at-60～-80 ℃ of 10-phenanthroline and tri-n-n-propyl aluminum preferably carried out at-60～-70 ℃.In addition, this reaction is advantageously carried out under protection of inert gas, the preferred argon gas of this rare gas element or nitrogen.It is anhydrous 1 that 1,10-phenanthroline can be used, and 10-phenanthroline, also can be used hydration 1, and 10-phenanthroline is preferably anhydrous 1,10-phenanthroline.Tri-n-n-propyl aluminum is used with itself conventionally.The mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1:0.5～1:4.5, preferably 1:2.0～1:2.6.Advantageously, this reaction is added tri-n-n-propyl aluminum conventionally under temperature of reaction in 1,10-phenanthroline solution, for example, drip tri-n-n-propyl aluminum and carry out.After reinforced, under temperature of reaction, stir preferably 18～20 hours 18～28 hours.Afterwards, reaction mixture is warming up to 20～40 ℃ and stirs again 5～10 hours, preferably 10 hours, to react more completely.Then add water (preferably deionized water) hydrolysis at-60～0 ℃.For example, reaction mixture is remained to-30 ℃ and add water to be hydrolyzed, preferably add deionized water to be hydrolyzed.In hydrolytic process, there is bubble to emerge, be hydrolyzed until bubble is no longer emerged.For complete hydrolysis more, reaction mixture is warming up to 20～40 ℃ again and stirs 5～10 hours.Then separatory, takes out organic phase.In order to isolate as much as possible required product, preferably also to inorganic phase organic solvent extraction, the organic phase obtaining and the organic phase that separatory obtains are before merged, to this operable organic solvent, it can be ethyl acetate, acetone, methylene dichloride or its mixture etc., preferably methylene dichloride.The organic phase decompression of organic phase or merging is removed after solvent, added oil of mirbane backflow (for example, at 210 ℃) 10～48 hours, preferably 15～24 hours.Filter afterwards, solvent is removed in decompression.By volume ratio, be 1:1～1:5, the ethyl acetate of preferred 1:2: the mixing solutions of sherwood oil is leacheate, carries out silica gel column chromatography, obtains solid product, i.e. formula (b) compound.In this synthesis step, the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:0.5～1:30, preferably 1:15～1:20.
B.2-positive propionyl-1,10-phenanthroline contracting amine ligand synthetic: formula (b) compound and formula (c) compound are reacted under as catalyzer existence, acquisition formula (d) compound at tosic acid
R wherein
1-R
5as mutual-through type (I) defines.
Product part (d) is by positive propionyl-1 of 2-that makes to obtain in step a in container; the substituted aniline of 10-phenanthroline and formula (c); in the organic solvent of not moisture and oxygen, react and prepare; positive propionyl-1 of 2-wherein, the mol ratio of the substituted aniline of 10-phenanthroline and formula (c) is 1:1～1:5.This operable organic solvent is selected to toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc., preferably toluene.This reaction be take tosic acid (p-TsOH) as catalyzer carries out under refluxing, for example, at 110 ℃, carry out.The mass ratio of the quality of tosic acid and reaction-ure mixture (being formula (b) compound and formula (c) compound) is 0.001:1～0.02:1; reaction times is 5～10 hours; with TLC monitoring reaction; treat positive propionyl-1 of 2-, after completion of the reaction, solvent is removed in decompression to 10-phenanthroline; then by volume ratio, be 1:1～1:9; the ethyl acetate of preferred 1:4: the mixing solutions of sherwood oil is as leacheate, and silica gel column chromatography obtains target product, i.e. formula (d) compound.Target product is through nuclear-magnetism and mass spectral characteristi.
In one embodiment, the substituted aniline of formula (c) is by 1-5, preferably 1-4, and more preferably 1-3 the identical or different C that is selected from
1-C
6alkyl, C
1-C
6the aniline that the substituting group of alkoxyl group, halogen and nitro replaces.As an example, can mention 2-aminotoluene, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2，4，6-trimethyl aniline, 4-is bromo-2,6-xylidine, 2-ethylaniline, 2-ethyl-6-monomethylaniline, 2-isopropyl aniline, 2,6-Diethyl Aniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-monomethylaniline of 2-, the fluoro-5-monomethylaniline of 2-, 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-penta fluoro benzene amine, 3-chloroaniline, 2,6-DCA, 2，3，4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-monomethylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-monomethylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-bromamide, the chloro-4-fluoroaniline of the bromo-6-of 2-, the chloro-6-fluoroaniline of the bromo-4-of 2-, 2-is bromo-4,6-difluoroaniline, 3-N-methyl-p-nitroaniline, 4-anisidine, 2-methyl-4-anisidine and 4-phenetidine, most preferably 2,6-Diethyl Aniline.
C. positive propionyl-1 of chlorination 2-, 10-phenanthroline contracting amine closes the synthetic of iron (II) title complex: formula (d) compound is reacted, acquisition formula (I) compound with iron protochloride
R wherein
1-R
5as mutual-through type (I) defines.
Rare gas element as the protection such as nitrogen under; iron protochloride is dissolved in the organic solvent of not moisture and oxygen; form the solution of 0.001～0.1g/ml; operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferably tetrahydrofuran (THF).In order to obtain aforementioned solution of ferrous chloride, replace iron protochloride itself, also can use hydration iron protochloride (FeCl
24H
2o).Separately by 2-propionyl-1; 10-phenanthroline contracting amine ligand (d) is dissolved in the organic solvent of not moisture and oxygen; form the solution of 0.01～0.1g/ml; this operable organic solvent is selected to toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. equally, preferably tetrahydrofuran (THF).Then rare gas element as the protection such as nitrogen under, merge above-mentioned two solution (for example at room temperature merging), and stir certain hour under room temperature at rare gas element under as protections such as nitrogen, for example under room temperature, stirring is spent the night.With TLC monitoring reaction, after question response is complete, by suction filtration, washing and the conventional post-treating method such as dry, reaction product is carried out to aftertreatment, obtain formula (I) compound title complex.Described washing can be with an organic solvent as anhydrous diethyl ether carries out.Title complex characterizes by ultimate analysis and infrared spectra.In this synthesis step, positive propionyl-1 of 2-, 10-phenanthroline part (d) is 1:1-1.2:1 with the mol ratio of iron protochloride, is preferably 1.05:1-1.1:1.
In the present invention, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkylaluminium cpd, preferred alkyl aluminum compound.Wherein, the general formula of described alkylaluminium cpd is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; The X halogen of respectively doing for oneself, preferably chlorine or bromine; N is 1～3 integer, the integer that m is 0～2, and m+n equals 3; Preferably, described alkylaluminium cpd 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.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 methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; More preferably methylaluminoxane.
In the present invention, described organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene and methylene dichloride, is preferably selected from toluene and dimethylbenzene.
In the present invention, in described oligomerisation reaction, being blended under ethene atmosphere of Primary Catalysts and promotor carried out.Being Primary Catalysts must be in ethene environment with mixing of promotor, otherwise catalyzer is by inactivation; In other words, Primary Catalysts can not mix in non-ethene environment in advance with promotor.
In aforesaid method, the temperature of described reaction is-20～150 ℃, is preferably 0～80 ℃, more preferably 5～35 ℃.Pressure is 0.1～30MPa, along with ethylene pressure rising oligomerisation is active, raises.In a specific embodiment, the temperature of reaction of described reaction is-20～50 ℃.
In a specific embodiment, described reaction comprises promotor and Primary Catalysts is mixed with organic solvent respectively, then under ethene atmosphere, the organic solvent containing Primary Catalysts is mixed with the organic solvent containing promotor in the present invention.In another specific embodiment, specifically can comprise the steps: that (1) replace reaction system by operations such as hyperthermia drying, vacuum displacements, guarantee anhydrous and oxygen-free in reaction system; (2) use ethene to replace reaction system, make reaction system in ethene environment; (3) in reaction system, add Primary Catalysts, promotor, water, organic solvent, fully stir; (4) pass into ethene and start oligomerisation reaction, keeping reaction pressure is that 0.1～30MPa and temperature of reaction are reacted 30～100min at-20～150 ℃; (5) stopped reaction, gets reaction product and carries out (GC) analysis by gas-chromatography
By above-mentioned oligomerization, carry out oligomerizing ethylene, 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 96%.After ethylene oligomerization finishes, take out a small amount of reaction product and carry out GC analysis.Result shows, oligomerisation activity can reach 10
7gmol
-1h
-1above.In addition, the ethanolic soln neutralization of 5% dilute hydrochloric acid acidifying for remaining reaction mixture, does not obtain polymkeric substance.
According to method provided by the invention; ethene is comprising positive propionyl-1 of chlorination 2-shown in formula (I); 10-phenanthroline contracting amine closes under iron (II) title complex Primary Catalysts and the effect containing the catalyst system of aluminum cocatalyst and in water-containing solvent, carries out oligomerisation reaction; there is on the contrary higher oligomerisation reaction active; the selectivity of alpha-olefin is high, and oligomerisation reaction cause rapidly, operate steadily, reproducible.According to the present invention, though at low-down Al/Fe than under condition, still there is good oligomerisation reaction active.According to the present invention, when reaction is carried out at a lower temperature, still there is high oligomerisation reaction active.According to the present invention, overcome those skilled in the art's technology prejudice, obtained unforeseeable technique effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated and explanation, but do not form any limitation of the invention.
Embodiment 1
1. positive propionyl-1 of catalyzer chlorination 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline closes the synthetic of iron (II) title complex
A.2-positive propionyl-1,10-phenanthroline synthetic
In 250ml there-necked flask, drop into 1,10-phenanthroline 5.1g (28.3mmol), under nitrogen protection and magnetic agitation, with 100ml toluene, dissolve.At-60 ℃, under agitation in there-necked flask, slowly drip 13.5ml tri-n-n-propyl aluminum (d=0.82g/ml, 70.9mmol), about 15 minutes, dropwise, at this temperature, continue to stir 18h, be warming up to afterwards 30 ℃ of left and right, continue to stir 10h.Then reaction mixture is cooled to-30 ℃ of left and right, slowly adds wherein 50ml distilled water, then be warming up to 30 ℃ of stirring 10h.Then separatory, takes out organic phase, inorganic phase dichloromethane extraction three times, and the consumption of each methylene dichloride is 20ml, merges each organic phase.Solvent is removed in decompression.Afterwards, add 50ml oil of mirbane (1.205g/ml), and reflux about 18 hours in 210 ℃.Filter, lower than steaming and remove oil of mirbane under 10mmHg, obtain black viscous liquid material.With the mixing solutions of ethyl acetate: sherwood oil=1:2 (volume ratio), be leacheate, gained black viscous liquid material is carried out to silica gel column chromatography, obtain brown product, heavy 2.0g, productive rate 30%.This product is defined as compound described in title a. through nuclear-magnetism and mass spectroscopy, i.e. positive propionyl-1 of 2-, 10-phenanthroline.
Mass spectrum MS-EI:236.
Nmr analysis:
1h NMR (400MHz, CDCl
3): δ 9.26 (dd, J=1.72,1H); 8.33 (s, 2H); 8.27 (dd, J=1.68,1H) 7.86 (d, J=8.8,1H); 7.80 (d, J=8.8,1H); 7.68 (dd, J=5.28,1H); 3.67 (m, J=7.24,2H); 1.10 (t, J=7.4,3H).
B. positive propionyl-1 of part 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline synthetic
In two mouthfuls of flasks of 100ml of water trap are housed; drop into positive propionyl-1 of 2-obtaining in 0.50g (2.12mmol) step a; 10-phenanthroline and 0.95g (6.36mmol) 2, the toluene of the not moisture and oxygen of 6-Diethyl Aniline (mol ratio is 1:3) and 35ml.Prolong is housed on water trap, adds tosic acid 0.01g to reflux at 110 ℃, react 6 hours.Solvent is removed in decompression, and with the mixing solutions of ethyl acetate: sherwood oil=1:4 (volume ratio), as leacheate, silica gel column chromatography obtains glassy yellow product, heavy 0.63g, and productive rate is 81%.This product is confirmed as compound described in title b. through nuclear-magnetism, mass spectrum and ultimate analysis, i.e. positive propionyl-1 of 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline.
Mass spectrum MS-EI:367.
Nmr analysis:
1h NMR (400MHz, CDCl
3): δ 9.25 (dd, J=2.96,1H); 8.66 (d, J=8.36,1H); 8.33 (d, J=8.36,1H); 8.28 (dd, J=7.84,1H); 7.85 (dd, J=9.02,2H); 7.65 (dd, J=4.36,1H); 7.15 (d, J=7.52,2H); 7.06 (t, J=7.04,1H); 3.01 (t, J=7.84 ,-CNCH
2cH
3, 2H); 2.40 (m, J=7.52, phCH
2cH
3, 2H); 1.20 (t, J=7.30, phCH
2cH
3, 6H); 0.90 (t, J=7.32, CH
3cH
2cN, 3H).
Ultimate analysis: C
25h
25n
3(367.49), theoretical value: C, 81.71; H, 6.86; N, 11.43.Observed value: C, 81.66; H, 6.87; N, 11.47.
C. positive propionyl-1 of chlorination 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline closes the synthetic of iron (II)
Under nitrogen protection, in two mouthfuls of flasks, tetrahydrofuran (THF) 0.16g (1.25mmol) iron protochloride is not moisture with 20ml and oxygen dissolves.Separately by positive propionyl-1 of 2-obtaining in 0.50g (1.36mmol) step b, 10-phenanthroline contracting 2,6-Diethyl Aniline is dissolved in the tetrahydrofuran (THF) of the not moisture and oxygen of 20ml.Then under at room temperature nitrogen protection, merge above-mentioned two solution.Reaction is carried out at once, and solution presents grey black.At room temperature, nitrogen protection is stirred and is spent the night.Use TLC monitoring, until positive propionyl-1 of 2-, 10-phenanthroline contracting 2,6-diethylbenzene amine ligand disappears substantially.Suction filtration, washs with anhydrous diethyl ether.Vacuum-drying obtains silver gray solid.This solid is defined as compound described in title c., i.e. positive propionyl-1 of chlorination 2-, and 10-phenanthroline contracting 2,6-Diethyl Aniline closes iron (II), and its results of elemental analyses is as follows.
Ultimate analysis: C
25h
25cl
2feN
3(494.24), theoretical value: C, 60.75; H, 5.10; N, 8.50.Observed value: C, 60.71; H, 5.00; N, 8.53.
2. ethylene oligomerization reaction, specifically comprises the steps: that (1) replace 300ml stainless steel cauldron by operations such as hyperthermia drying, vacuum displacements, guarantees anhydrous and oxygen-free in system; (2) use ethene to replace reactor, make system in ethene environment; (3) successively by toluene, water and 1.37ml promotor triethyl aluminum toluene solution (concentration is 715mol/ml) and positive propionyl-1 of 2ml Primary Catalysts chlorination 2-; the toluene solution that 10-phenanthroline contracting amine closes iron (II) title complex (concentration is 2.5 μ mol/ml) joins in the stainless steel autoclave of 300ml; making cumulative volume is 100ml; Al/Fe=196; the weight of toluene of take be to be calculated benchmark, and the weight content of water is 5ppm.(4) when polymerization temperature reaches 30 ℃, in reactor, be filled with ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.(5) stop passing into ethene, release, takes out a small amount of reaction product and carries out GC analysis: oligomerisation activity is 0.57 * 10
7gmol
-1(Fe) h
-1, oligomer content is respectively C
412.92%, C
6～C
1042.13%, C
6～C
1873.32% (wherein containing linear alpha-alkene 97.6%), C
20～C
2813.76%, K value 0.63.The ethanolic soln neutralization of 5% hcl acidifying for remaining mixture, does not obtain polymkeric substance.Data are in Table 1.
Embodiment 2
With embodiment 1, difference is, the weight content amount 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 temperature of reaction is 0 ℃.Data are in Table 1.
Embodiment 9
With embodiment 1, difference is, the weight content of water is 200ppm, and temperature of reaction is-10 ℃.Data are in Table 1.
Embodiment 10
With embodiment 1, difference is, the weight content of water is 200ppm, and temperature of reaction is-20 ℃.Data are in Table 1.
Embodiment 11
With embodiment 1, difference is, the weight content of water is 200ppm, and temperature of reaction is 50 ℃.Data are in Table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 200ppm, Al/Fe=500.Data are in Table 1.
Comparative example 1
With embodiment 1, difference is in toluene anhydrous.Data are in Table 1.
Table 1
"-" represents anhydrous
From table 1, data can be found out, according to method provided by the invention, ethene is comprising positive propionyl-1 of chlorination 2-shown in formula (I), 10-phenanthroline contracting amine closes in iron (II) title complex Primary Catalysts, the reaction system containing aluminum cocatalyst (as triethyl aluminum) and organic solvent and carries out oligomerisation reaction, has higher oligomerisation reaction active; Even under the condition of low-down aluminium/iron ratio, also there is good oligomerisation reaction active, and the selectivity of alpha-olefin is high.In addition,, even if react at a lower temperature, still there is higher oligomerisation active.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, but should be understood to word wherein used, be descriptive and explanatory vocabulary, rather than limited vocabulary.Can in the scope of the claims in the present invention, to the present invention, modify in accordance with regulations, and within not deviating from scope and spirit of the present invention, the present invention be revised.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Claims (10)
1. a method for ethylene oligomerization, ethene is comprising positive propionyl-1 of chlorination 2-shown in formula (I), and 10-phenanthroline contracting amine closes in iron (II) title complex Primary Catalysts, the reaction system containing aluminum cocatalyst and organic solvent and carries out oligomerisation reaction,
In formula, R
1-R
5be selected from independently of one another hydrogen, C
1-C
6alkyl, halogen, C
1-C
6alkoxyl group and nitro.
2. method according to claim 1, is characterized in that, in described reaction system, the weight of organic solvent of take be to be calculated benchmark, and the weight content of water is 5～350ppm, and preferably 20～260ppm, most preferably is 50～200ppm.
3. method according to claim 1 and 2, is characterized in that, in described reaction system, the volume of organic solvent of take be to calculate benchmark, and the content of described Primary Catalysts is 2～500 μ mol/L, preferably 20～100 μ mol/L.
4. according to the method described in any one in claim 1～3, it is characterized in that, the mol ratio of the iron in the aluminium in described promotor and described Primary Catalysts is 30 to being less than 900:1, preferably 100～700:1, more preferably 148～196:1.
5. according to the method described in any one in claim 1～4, it is characterized in that the R in described Primary Catalysts
1-R
5be selected from independently of one another hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group and nitro; R in preferred described Primary Catalysts
1and R
5for ethyl, R
2-R
4be hydrogen.
6. according to the method described in any one in claim 1～5, it is characterized in that, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkylaluminium cpd, preferred alkyl aluminum compound.
7. according to the method described in any one in claim 1～6, it is characterized in that, the general formula of described alkylaluminium cpd is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; The X halogen of respectively doing for oneself, preferably chlorine or bromine; N is 1～3 integer, the integer that m is 0～2, and m+n equals 3; Preferably, described alkylaluminium cpd 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.
8. according to the method described in any one in claim 1～7, it is characterized in that, described organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene and methylene dichloride, is preferably selected from toluene and dimethylbenzene.
9. according to the method described in any one in claim 1～8, it is characterized in that, the temperature of described reaction is-20～150 ℃, is preferably 0～80 ℃, more preferably 5～35 ℃.
10. according to the method described in any one in claim 1～9, it is characterized in that, in described oligomerisation reaction, being blended under ethene atmosphere of Primary Catalysts and promotor carried out.
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| CN102050841A (en) * | 2009-10-30 | 2011-05-11 | 中国科学院化学研究所 | 2-propionamide-1,10-phenanthroline anil coordination compound, preparation method thereof, catalyst comprising same and application thereof |
| CN103008010A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst composition containing 1, 10-phenanthroline amino-iron (II) complex substituted by propionyl |
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| CN103008010A (en) * | 2011-09-23 | 2013-04-03 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst composition containing 1, 10-phenanthroline amino-iron (II) complex substituted by propionyl |
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