CN104107723A - Catalyst composition for ethylene oligomerization and application thereof - Google Patents
Catalyst composition for ethylene oligomerization and application thereof Download PDFInfo
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- CN104107723A CN104107723A CN201310476461.1A CN201310476461A CN104107723A CN 104107723 A CN104107723 A CN 104107723A CN 201310476461 A CN201310476461 A CN 201310476461A CN 104107723 A CN104107723 A CN 104107723A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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Abstract
The invention discloses a catalyst composition for ethylene oligomerization. The catalyst composition comprises chlorinated-2-n-propiono-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, C1-6 alkyl groups, halogen, C1-6 alkoxy groups and a nitro group. According to the invention, the catalyst composition consisting of the complex main catalyst as shown in the formula (I), the aluminum-containing cocatalyst, water and the organic solvent is adopted for ethylene oligomerization, so high oligomerization reaction activity and high selectivity of alpha-olefin are obtained, and rapid initiation, stable operation and good repeatability of oligomerization are realized; 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 field of olefin polymerisation, be specifically related to a kind of carbon monoxide-olefin polymeric for ethylene oligomerization reaction process.The invention still further relates to the application of above-mentioned carbon monoxide-olefin polymeric.
Background technology
Linear alpha-alkene is at ethylene comonomer, synthesis of surfactant intermediate, for plasticizer, the field such as alcohol, synthetic lubricant fluid 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 catalyst 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 that respectively the trident pyridinimine complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation, not only the catalytic activity of catalyst is very high, and alpha-olefin is selective also very high.
The patent CN102050841A of Institute of Chemistry, Academia Sinica has reported a kind of phenanthroline anil class complex, taking this complex as major catalyst with taking MAO or modified methylaluminoxane or modified methylaluminoxane when co-catalyst is applied to ethylene oligomerization, only, in the time of high co-catalyst consumption (Al/Fe=1000～2000), oligomerisation activity just can reach 10
7gmol
-1h
-1.And no matter be MAO, or modified methylaluminoxane is as co-catalyst, all has 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 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 reaction initiation and stability and all non-constants of repeatability of oligomerization process simultaneously.
Summary of the invention
For deficiency of the prior art, inventor has carried out research extensively and profoundly at ethylene oligomerization by catalyst field, be surprised to find, positive propiono-1 of chlorination 2-shown in employing formula (I), 10-phenanthroline contracting amine closes iron (II) complex major catalyst, containing aluminum cocatalyst, the carbon monoxide-olefin polymeric of water and organic solvent is for ethylene oligomerization, there is on the contrary higher oligomerisation reaction activity, even also there is extraordinary oligomerisation reaction activity under the condition of low-down aluminium/iron ratio, and oligomerisation reaction causes rapidly, operate steadily, reproducible, thereby overcome the technology prejudice of those skilled in the art about water, obtain unforeseeable technique effect.
According to an aspect of the present invention; a kind of ethylene oligomerization carbon monoxide-olefin polymeric is provided; comprise positive propiono-1 of chlorination 2-shown in formula (I), 10-phenanthroline contracting amine closes iron (II) complex major catalyst, contains aluminum cocatalyst and organic solvent:
In formula, R
1-R
5be selected from independently of one another hydrogen, C
1-C
6alkyl, halogen, C
1-C
6alkoxyl and nitro.
According to carbon monoxide-olefin polymeric provided by the invention, there is higher ethylene oligomerization reactivity, the selective height of alpha-olefin.
In carbon monoxide-olefin polymeric of the present invention, taking the weight of organic solvent as calculating benchmark, the weight content of water is the i.e. organic solvent based on 1g of 5～350ppm(, in composition containing 5～350 × 10
-6the water of g), preferably 20～260ppm, most preferably is 50～200ppm.Within the scope of described water content, described carbon monoxide-olefin polymeric has higher ethylene oligomerization activity.
In carbon monoxide-olefin polymeric of the present invention, the process conditions when consumption of described major catalyst and co-catalyst can be applied according to production scale and production equipment etc. are concrete are selected.In a specific embodiment of described carbon monoxide-olefin polymeric, taking the volume of organic solvent as calculating benchmark, the content of described major catalyst is the i.e. organic solvents based on 1L of 2～500 μ mol/L(, in composition containing 2～500 × 10
-6the major catalyst of mol), preferably 20～100 μ mol/L.
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-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 obtaining.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 secondary 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 above-mentioned carbon monoxide-olefin polymeric, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is 30 to being less than 900:1, preferably 100-700:1.In an instantiation of above-mentioned carbon monoxide-olefin polymeric, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is preferably 148-196:1.
In above-mentioned carbon monoxide-olefin polymeric, the R in preferred described major catalyst
1-R
5be selected from independently of one another hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.More preferably the R in described major catalyst
1and R
5for ethyl, R
2-R
4be hydrogen.
Major catalyst shown in general formula of the present invention (I) can adopt the preparation method of Chinese patent application CN102558241A report to make.Therefore, positive propiono-1 of chlorination 2-shown in general formula (I), the concrete preparation process that 10-phenanthroline contracting amine closes iron (II) complex is as follows:
A.2-positive propiono-1,10-phenanthroline synthetic: make 1,10-phenanthroline and tri-n-n-propyl aluminum (n-C
3h
7)
3al reaction, then pass through successively hydrolysis and the oxidation reaction with nitrobenzene, acquisition formula (b) compound.
For positive propiono-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, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene, carrene or its mixture etc. for this reason, preferably toluene.Utilize these organic solvents, preparation 1,10-phenanthroline solution, wherein solution concentration is 10～200g/L.This 1, reacting conventionally at-60～-80 DEG C of 10-phenanthroline and tri-n-n-propyl aluminum preferably carried out at-60～-70 DEG C.In addition, this reaction is advantageously carried out under inert gas shielding, the preferred argon gas of this inert gas or nitrogen.It is anhydrous 1 that 1,10-phenanthroline can use, and 10-phenanthroline, also can use hydration 1, and 10-phenanthroline is preferably anhydrous 1,10-phenanthroline.Tri-n-n-propyl aluminum uses 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 reaction temperature in 1,10-phenanthroline solution, for example, drip tri-n-n-propyl aluminum and carry out.After reinforced, under reaction temperature, stir preferably 18～20 hours 18～28 hours.Afterwards, reactant mixture is warming up to 20～40 DEG C and stirs again 5～10 hours, preferably 10 hours, to react more completely.Then (preferably deionized water) hydrolysis at-60～0 DEG C adds water.For example, reactant mixture is remained to-30 DEG C 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, reactant mixture is warming up to 20～40 DEG C 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, can be ethyl acetate to this operable organic solvent, acetone, carrene or its mixture etc., preferably carrene.The organic phase decompression of organic phase or merging is removed after solvent, added nitrobenzene backflow (for example, at 210 DEG C) 10～48 hours, preferably 15～24 hours.Filter afterwards, solvent is removed in decompression.With volume ratio be 1:1～1:5, the preferably ethyl acetate of 1:2: the mixed solution of benzinum 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 nitrobenzene is 1:0.5～1:30, preferably 1:15～1:20.
B.2-positive propiono-1,10-phenanthroline contracting amine ligand synthetic: formula (b) compound and formula (c) compound are reacted under as catalyst existence, acquisition formula (d) compound at p-methyl benzenesulfonic acid
Wherein R
1-R
5as mutual-through type (I) defines.
Product part (d) is by positive propiono-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; wherein positive propiono-1 of 2-, 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, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene, carrene or its mixture etc., preferably toluene.This reaction is carried out under refluxing taking p-methyl benzenesulfonic acid (p-TsOH) as catalyst, for example, at 110 DEG C, carry out.The mass ratio of the quality of p-methyl benzenesulfonic acid and reaction-ure mixture (being formula (b) compound and formula (c) compound) is 0.001:1～0.02:1; reaction time is 5～10 hours; with TLC monitoring reaction; treat positive propiono-1 of 2-; 10-phenanthroline after completion of the reaction; solvent is removed in decompression; then be 1:1～1:9 by volume ratio; the preferably ethyl acetate of 1:4: the mixed solution of benzinum is as leacheate; silica gel column chromatography obtains target product, i.e. formula (d) compound.Nuclear-magnetism and mass spectral characteristi for target product.
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, halogen and nitro replaces.As an example, can mention 2-aminotoluene, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-is bromo-2,6-dimethylaniline, 2-MEA, 2-ethyl-6-methylaniline, 2-isopropyl aniline, 2,6-diethylaniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-methylaniline of 2-, the fluoro-5-methylaniline of 2-, 2,4-difluoroaniline, 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-phenyl-pentafluoride amine, 3-chloroaniline, 2,6-DCA, 2,3,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-methylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-methylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-tribromaniline, 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-nitroaniline, 4-aminoanisole, 2-methyl-4-aminoanisole and 4-phenetidine, most preferably 2,6-diethylaniline.
C. positive propiono-1 of chlorination 2-, 10-phenanthroline contracting amine closes the synthetic of iron (II) complex: formula (d) compound is reacted, acquisition formula (I) compound with frerrous chloride
Wherein R
1-R
5as mutual-through type (I) defines.
Under inert gas is protected as nitrogen etc.; frerrous chloride 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, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene, carrene or its mixture etc. for this reason, preferably oxolane.In order to obtain aforementioned solution of ferrous chloride, replace frerrous chloride itself, also can use hydration frerrous chloride (FeCl
24H
2o).Separately by 2-propiono-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, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene, carrene or its mixture etc. equally, preferably oxolane.Then inert gas 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 inert gas 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-processing approach such as dry, product is carried out to post processing, obtain formula (I) compound complex.Described washing can be with an organic solvent as absolute ether carries out.Complex characterizes by elementary analysis and infrared spectrum.In this synthesis step, positive propiono-1 of 2-, 10-phenanthroline part (d) is 1:1-1.2:1 with the mol ratio of frerrous chloride, is preferably 1.05:1-1.1:1.
In above-mentioned carbon monoxide-olefin polymeric, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.
In above-mentioned carbon monoxide-olefin polymeric, the general formula of 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, preferably chlorine or bromine; N is 1～3 integer, the integer that m is 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 above-mentioned carbon monoxide-olefin polymeric, 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 or isobutyl aluminium alkoxide; More preferably MAO.
In above-mentioned carbon monoxide-olefin polymeric, the described aluminum cocatalyst that contains can be aikyiaiurnirsoxan beta or alkyl aluminum compound etc.The described aluminum cocatalyst that contains is preferably alkyl aluminum compound, specifically can be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three base aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride just, wherein preferred triethyl aluminum.The example of described aikyiaiurnirsoxan beta comprises MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide etc., preferable methyl aikyiaiurnirsoxan beta.
In above-mentioned carbon monoxide-olefin polymeric, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.
According to a further aspect in the invention, provide a kind of ethylene oligomerization method, ethene carries out oligomerisation reaction under the existence of above-mentioned carbon monoxide-olefin polymeric.
In said method, described carbon monoxide-olefin polymeric comprises positive propiono-1 of chlorination 2-shown in formula (I), and 10-phenanthroline contracting amine closes iron (II) complex major catalyst, contains aluminum cocatalyst and organic solvent:
In formula, R
1-R
5be selected from independently of one another hydrogen, C
1-C
6alkyl, halogen, C
1-C
6alkoxyl and nitro.
In the carbon monoxide-olefin polymeric of said method, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.
In the carbon monoxide-olefin polymeric of said method, the general formula of 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, preferably chlorine or bromine; N is 1～3 integer, the integer that m is 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 above-mentioned carbon monoxide-olefin polymeric, 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 or isobutyl aluminium alkoxide; More preferably MAO.
In the carbon monoxide-olefin polymeric of said method, the described aluminum cocatalyst that contains can be aikyiaiurnirsoxan beta or alkyl aluminum compound etc.The described aluminum cocatalyst that contains is preferably alkyl aluminum compound, specifically can be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three base aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride just, wherein preferred triethyl aluminum.The example of described aikyiaiurnirsoxan beta comprises MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide etc., preferable methyl aikyiaiurnirsoxan beta.
In the carbon monoxide-olefin polymeric of said method, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is 30 to being less than 900, preferably 100-700.In an instantiation of above-mentioned carbon monoxide-olefin polymeric, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is preferably 148-196.
In the carbon monoxide-olefin polymeric of said method, the R in preferred described major catalyst
1-R
5be selected from independently of one another hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.More preferably the R in described major catalyst
1and R
5for ethyl, R
2-R
4be hydrogen.
In said method, taking the weight of organic solvent as calculating benchmark, the weight content of water is the i.e. organic solvent based on 1g of 5～350ppm(, in composition containing 5～350 × 10
-6the water of g), preferably 20～260ppm, most preferably is 50～200ppm.The process conditions when consumption of described major catalyst and co-catalyst can be applied according to production scale and production equipment etc. are concrete are selected.In a specific embodiment of described carbon monoxide-olefin polymeric, taking the volume of organic solvent as calculating benchmark, the content of described major catalyst is the i.e. organic solvents based on 1L of 2～500 μ mol/L(, in composition containing 2～500 × 10
-6the major catalyst of mol), preferably 20～100 μ mol/L.
Described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.
In said method, the temperature of described reaction is-20～150 DEG C, is preferably 0～80 DEG C, more preferably 5～35 DEG C.Pressure is 0.1～30MPa, raises along with ethylene pressure rising oligomerisation is active.In a specific embodiment, the reaction temperature of described reaction is-20～50 DEG C.
Above-mentioned carbon monoxide-olefin polymeric is applied the oligomerisation reaction condition relating to and is known to those skilled in the art.Concrete technical scheme can be as follows: in reaction vessel, add water, organic solvent, major catalyst and co-catalyst, then be to react 30～100 minutes at 0.1～30MPa and reaction temperature are-20～150 DEG C at ethylene pressure, stop after reaction, take out a small amount of reactant mixture and carry out gas-chromatography (GC) analysis.
By above-mentioned oligomerisation reaction, 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; Selectively can reaching more than 96% of alpha-olefin.After ethylene oligomerization finishes, take out a small amount of product and carry out GC analysis.Result shows, oligomerisation activity can reach 10
7gmol
-1h
-1above.In addition, the ethanolic solution neutralization of 5% watery hydrochloric acid acidifying for remaining reactant mixture, does not obtain polymer.
According to the present invention, positive propiono-1 of chlorination 2-shown in employing formula (I), 10-phenanthroline contracting amine closes iron (II) complex major catalyst, is used for ethylene oligomerization containing the carbon monoxide-olefin polymeric of aluminum cocatalyst and organic solvent, there is on the contrary very high oligomerisation reaction activity, the selective height of alpha-olefin, and oligomerisation reaction cause rapidly, operate steadily, reproducible; Even under the condition of low aluminium/iron ratio, oligomerisation reaction still has extraordinary oligomerisation reaction activity; Even if carry out at low temperatures oligomerisation reaction, also still there is higher oligomerisation reaction activity.Technical scheme in the present invention has overcome those skilled in the art's technology prejudice, has obtained unforeseeable technique effect.
Detailed description of the invention
Below by specific embodiment, the invention will be further described and explanation, but do not form any limitation of the invention.
Embodiment 1
1. positive propiono-1 of chlorination 2-, 10-phenanthroline contracting 2,6-diethylaniline closes the synthetic of iron (II) complex
A.2-positive propiono-1,10-phenanthroline synthetic
In 250ml there-necked flask, drop into 1,10-phenanthroline 5.1g (28.3mmol), under nitrogen protection and magnetic agitation, dissolve with 100ml toluene.At-60 DEG C, 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 DEG C of left and right, continue to stir 10h.Then reactant mixture is cooled to-30 DEG C of left and right, slowly adds wherein 50ml distilled water, then be warming up to 30 DEG C of stirring 10h.Then separatory, takes out organic phase, inorganic phase dichloromethane extraction three times, and the consumption of each carrene is 20ml, merges each organic phase.Solvent is removed in decompression.Afterwards, add 50ml nitrobenzene (1.205g/ml), and reflux about 18 hours in 210 DEG C.Filter, lower than steaming and remove nitrobenzene under 10mmHg, obtain black viscous liquid material.With the mixed solution of ethyl acetate: benzinum=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 spectral analysis, i.e. positive propiono-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 propiono-1 of part 2-, 10-phenanthroline contracts synthesizing of 2,6-diethylaniline
In two mouthfuls of flasks of 100ml that water knockout drum is housed; drop into positive propiono-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-diethylaniline (mol ratio is 1:3) and 35ml.Condenser pipe is housed on water knockout drum, adds p-methyl benzenesulfonic acid 0.01g to reflux at 110 DEG C, react 6 hours.Solvent is removed in decompression, and with the mixed solution of ethyl acetate: benzinum=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 elementary analysis, i.e. positive propiono-1 of 2-, 10-phenanthroline contracting 2,6-diethylaniline.
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).
Elementary analysis: C
25h
25n
3(367.49), theoretical value: C, 81.71; H, 6.86; N, 11.43.Measured value: C, 81.66; H, 6.87; N, 11.47.
C. positive propiono-1 of chlorination 2-, 10-phenanthroline contracting 2,6-diethylaniline closes the synthetic of iron (II)
Under nitrogen protection, in two mouthfuls of flasks, the oxolane of not moisture with 20ml 0.16g (1.25mmol) frerrous chloride and oxygen is dissolved.Separately by positive propiono-1 of 2-obtaining in 0.50g (1.36mmol) step b, 10-phenanthroline contracting 2,6-diethylaniline is dissolved in the oxolane 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 propiono-1 of 2-, 10-phenanthroline contracting 2,6-diethylbenzene amine ligand disappears substantially.Suction filtration, washs with absolute ether.Vacuum drying obtains silver gray solid.This solid is defined as compound described in title c., i.e. positive propiono-1 of chlorination 2-, and 10-phenanthroline contracting 2,6-diethylaniline closes iron (II), and its results of elemental analyses is as follows.
Elementary analysis: C
25h
25cl
2feN
3(494.24), theoretical value: C, 60.75; H, 5.10; N, 8.50.Measured value: C, 60.71; H, 5.00; N, 8.53.
2. ethylene oligomerization reaction
By toluene, water and 1.37ml co-catalyst triethyl aluminum toluene solution (concentration is 715mol/ml) and positive propiono-1 of 2ml major catalyst chlorination 2-; the toluene solution that 10-phenanthroline contracting amine closes iron (II) complex (concentration is 2.5 μ mol/ml) joins in the stainless steel autoclave of 300ml; making cumulative volume is 100ml; Al/Fe=196; taking the weight of toluene as calculating benchmark, the weight content of water is 5ppm.In the time that polymerization temperature reaches 30 DEG C, in reactor, be filled with ethene, keep the ethylene pressure of 1MPa, after stirring reaction 30min, take out a small amount of product and carry 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 solution neutralization of 5% hcl acidifying for remaining mixture, does not obtain polymer.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 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, 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, adopt positive propiono-1 of chlorination 2-shown in formula (I) that comprises provided by the invention, 10-phenanthroline contracting amine closes iron (II) complex major catalyst, contains the carbon monoxide-olefin polymeric of aluminum cocatalyst (as triethyl aluminum) and organic solvent, described carbon monoxide-olefin polymeric is reacted for ethylene oligomerization, there is higher oligomerisation reaction activity, and the selective height of alpha-olefin; Even under the condition of low-down aluminium/iron ratio, still there is good oligomerisation reaction activity; Even if carry out at low temperatures oligomerisation reaction, also still there is higher oligomerisation reaction activity.
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, be descriptive and explanatory vocabulary but should be understood to word wherein used, instead of limited vocabulary.Can in the scope of the claims in the present invention, modify the present invention in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.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. an ethylene oligomerization carbon monoxide-olefin polymeric, comprises positive propiono-1 of chlorination 2-shown in formula (I), and 10-phenanthroline contracting amine closes iron (II) complex major catalyst, contains aluminum cocatalyst and organic solvent:
In formula, R
1-R
5be selected from independently of one another hydrogen, C
1-C
6alkyl, halogen, C
1-C
6alkoxyl and nitro.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, in described carbon monoxide-olefin polymeric, taking the weight of organic solvent as calculating benchmark, the weight content of water is 5～350ppm, and preferably 20～260ppm, most preferably is 50～200ppm.
3. carbon monoxide-olefin polymeric according to claim 1 and 2, is characterized in that, in described carbon monoxide-olefin polymeric, taking the volume of organic solvent as calculating benchmark, the content of described major catalyst is 2～500 μ mol/L, preferably 20～100 μ mol/L.
4. according to the carbon monoxide-olefin polymeric of any one in claim 1～3, it is characterized in that, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is 30 to being less than 900:1, preferably 100-700:1.
5. according to the carbon monoxide-olefin polymeric described in any one in claim 1～4, it is characterized in that, in described co-catalyst, in aluminium and major catalyst, the mol ratio of iron is 148-196:1.
6. according to the carbon monoxide-olefin polymeric described in any one in claim 1～5, it is characterized in that the R in described major catalyst
1-R
5be selected from independently of one another hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro; Preferably R
1and R
5for ethyl, and R
2-R
4be hydrogen.
7. according to the carbon monoxide-olefin polymeric described in any one in claim 1～6, it is characterized in that, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.
8. according to the carbon monoxide-olefin polymeric described in any one in claim 1～7, it is characterized in that, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.
9. carbon monoxide-olefin polymeric according to claim 8, is characterized in that, the general formula of 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, preferably chlorine or bromine; N is 1～3 integer, the integer that m is 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.
10. carbon monoxide-olefin polymeric according to claim 8 or claim 9, is characterized in that, 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 or isobutyl aluminium alkoxide; More preferably MAO.
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