CN105396617B - Ethylene oligomerisation catalyst composition and its method for being catalyzed ethylene oligomerization - Google Patents
Ethylene oligomerisation catalyst composition and its method for being catalyzed ethylene oligomerization Download PDFInfo
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- CN105396617B CN105396617B CN201510696474.9A CN201510696474A CN105396617B CN 105396617 B CN105396617 B CN 105396617B CN 201510696474 A CN201510696474 A CN 201510696474A CN 105396617 B CN105396617 B CN 105396617B
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Abstract
The present invention provides a kind of ethylene oligomerisation catalyst composition; 1 of formoxyl substitution including following formula (I); the 1 of the isobutyryl of 10 phenanthroline condensed amine irons (II) complex or following formula (II) substitution; 10 phenanthroline condensed amine irons (II) complex is major catalyst and triethyl aluminum is co-catalyst; the mol ratio of metallic aluminium and major catalyst (I) central metal iron is that the mol ratio of metallic aluminium and major catalyst (II) central metal iron in 296 to 496, or the co-catalyst is 148 to 196 in wherein described co-catalyst.In the present invention, the triethyl aluminum as co-catalyst is cheap, and co-catalyst dosage is greatly reduced, and catalyst ethylene oligomerization of the invention has preferable catalytic activity, ethylene oligomerization reaction cost is declined to a great extent；And in oligomerization product linear alpha olefin selectivity it is higher；Oligomerization product distribution is more reasonable；Ethene polymers will not be produced；Therefore industrial prospect of the present invention is wide.
Description
It is March 19, Application No. CN201210072998.7, Publication No. in 2012 applying date that the application, which is,
The divisional application of CN103008011A patent application.
Technical field
The present invention relates to ethylene oligomerization field, and in particular to 1, the 10- phenanthroline contracting substituted containing formoxyl or isobutyryl
Amine closes the carbon monoxide-olefin polymeric of iron (II) complex and triethyl aluminum.The invention further relates to the ethylene oligomerization using above-mentioned composition
Method.
Background technology
Linear alpha-alkene ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and
The fields such as oil dope have a wide range of applications.In recent years, with the continuous development of polyolefin industry, in world wide to α-
The demand rapid development of alkene.The alpha-olefin of the overwhelming majority is prepared to obtain by ethylene oligomerization at present.Ethylene oligomerization method institute
Catalyst mainly has nickel system, chromium system, zirconium system and aluminium system etc., in recent years, Brookhart groups (Brookhart, M et al.,
J.Am.Chem.Soc.,1998,120,7143-7144；WO99/02472,1999), Gibson groups (Gibson, V.C. etc.
People, Chem.Commun., 1998,849-850；Chem.Eur.J., 2000,2221-2231) find respectively some Fe (II) and
Co (II) trident pyridinimine complex can be catalyzed ethylene oligomerization, and not only the catalytic activity of catalyst is very high, and alpha-olefin
Selectivity it is also very high.
The patent CN1850339A of Institute of Chemistry, Academia Sinica reports a kind of ethylene oligomerization that is used for and urged with what is polymerize
Agent, the catalyst are the Fe of 2- imido grpups -1,10- phenanthroline coordination2+、Co2+And Ni2+Chloride, in co-catalyst methyl
Under aikyiaiurnirsoxan beta effect, the catalyst has preferable ethylene oligomerization and polymerization catalyzed performance as major catalyst, and wherein iron coordinates
Thing shows very high oligomerisation and polymerization activity to ethene；And when reaction temperature is 40 DEG C, oligomerization activity highest；And oligomerisation
It is more obvious with the rise increase of pressure with polymerization activity；Oligomerization product includes C4、C6、C8、C10、C12、C14、C16、C18、C20、C22
Deng；Polymer is low-molecular-weight polyolefin and wax-like polyolefin.This patent also discloses one that triethyl aluminum is co-catalyst
Embodiment, it is major catalyst that iron (II) is closed in chlorination [2- acetyl group -1,10- phenanthroline (contracting 2,6- diethylanilines)], Al/Fe ratios
For 40 DEG C of 500, reaction temperature, reaction time 1h, polymerization pressure 1MPa when, oligomerization activity be 2.71 × 105；In this patent also
When disclosing using triisobutyl aluminium and diethylaluminum chloride as co-catalyst, at high co-catalyst dosage (Al/Fe ratios be 500),
Oligomerization activity is relatively low.
It is sub- even in higher co-catalyst dosage, 2- when triethyl aluminum is co-catalyst from the teaching of the patent
Amido -1,10- phenanthroline is coordinated Fe2+Chloride is catalyzed ethylene oligomerization activity still than relatively low, and practicality is poor, thus special at its
MAO in profit mainly using high cost is co-catalyst.But MAO cost is too high, dosage is excessive, as
For co-catalyst large-scale application when ethylene oligomerization, it certainly will cause production cost high.
The content of the invention
The defects of for prior art, it is desirable to seek a kind of practical ethylene oligomerisation catalyst composition of low cost and oligomerisation
Method, so as to its large-scale industrial application.By substantial amounts of experimental study, have surprisingly found that, using a small amount of triethyl aluminum
1,10- phenanthroline condensed amine irons (II) complex substituted for co-catalyst, containing formoxyl or isobutyryl is major catalyst
When carbon monoxide-olefin polymeric carries out ethylene oligomerization, there is acceptable catalytic activity, this has aobvious with the low activity thought in advance
Write difference.The monovalent catalytic activity low, dosage is few and acceptable and suitable of triethyl aluminum, is used in ethylene oligomerization technique
This carbon monoxide-olefin polymeric can provide strength for heavy industrialization and ensure.
A kind of according to an aspect of the invention, there is provided ethene of 1, the 10- phenanthroline complexs of the substitution containing formoxyl
Catalyst for oligomerization composition, including 1, the 10- phenanthroline condensed amine irons (II) of the substitution of the formoxyl with below general formula (I) coordinate
Thing as major catalyst and triethyl aluminum catalyst, wherein metallic aluminium in the co-catalyst with the major catalyst
The mol ratio of central metal is 30 to less than 500：
According to another aspect of the present invention, there is provided a kind of 1,10- phenanthroline condensed amine irons of the substitution containing isobutyryl
(II) the ethylene oligomerisation catalyst composition of complex, including 1,10- of the substitution of the isobutyryl with below general formula (II) are luxuriant and rich with fragrance
Cough up quinoline contracting amine and close iron (II) complex as major catalyst and triethyl aluminum catalyst, wherein the metal in the co-catalyst
The mol ratio of aluminium and the central metal in the major catalyst is 30 to 900：
In formula I and formula II, R1-R5It is each independently hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy or nitro.
In the present invention, term " C1-C6Alkyl " refers to saturated straight chain or branched hydrocarbyl containing 1-6 carbon atom.Make
For C1-C6Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, positive penta
Base, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred methyl, ethyl, n-propyl and isopropyl.
In the present invention, term " C1-C6Alkoxy " refers to above-mentioned C1-C6Alkyl is connected what is obtained with an oxygen atom
Group.As C1-C6Alkoxy, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl oxygen
Base, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, positive hexyloxy and secondary hexyloxy；Particularly preferred methoxyl group and second
Epoxide.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, metallic aluminium in the formula I in co-catalyst with it is described
Central metal (Fe in major catalyst2+) mol ratio be 50 to 400, preferably 100~300, more preferably 150~200.Another
In one scheme, the metallic aluminium in the formula I in co-catalyst and the central metal (Fe in the major catalyst2+) mol ratio
For 296~496, preferably 296-396；Or the mol ratio is 148-196.
In the preferred embodiment of above-mentioned carbon monoxide-olefin polymeric, metallic aluminium in the formula II in co-catalyst with it is described
Central metal (Fe in major catalyst2+) mol ratio be 50 to 800, preferably 100~700, more preferably 150~500 are optimal
200~300 are selected, further preferred 148-196.
In a preferred embodiment of the invention, ethylene oligomerisation catalyst is wherein R1-R5It is logical with what is be defined as below
The compound of formula I or II：
R1-R5It is each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitre
Base.
In particularly preferred embodiment of the invention, the R in the compound of formula I or II1And R5For ethyl and R2-
R4It is hydrogen.
The ethylene oligomerization major catalyst of formula (I) of the present invention or (II) can use Chinese patent application
The preparation method of CN201010576856.5 reports is made.Therefore, formula (I) or the formoxyl or isobutyryl of (II) substitute
The specific preparation process of ethylene oligomerization major catalyst of 1,10- phenanthroline condensed amine irons (II) complex is as follows：
A.2- the synthesis of formoxyl -1,10- phenanthroline or 2- isobutyryl -1,10- phenanthroline：Make 1,10- phenanthroline with
Trimethyl aluminium Me3Al reacts, then obtains formula (b) compound by hydrolysis and the oxidation reaction with nitrobenzene successively；Or make 1,
10- phenanthroline and triisobutyl aluminium (i-C4H9)3Al reacts, then obtains formula by hydrolysis and the oxidation reaction with nitrobenzene successively
(b) compound.
For 2- formoxyls -1, the 10- phenanthroline or 2- isobutyryl -1,10- phenanthroline of formula (b), make 1 first,
10- phenanthroline and trimethyl aluminium Me3Al or triisobutyl aluminium (i-C4H9)3Al reacts in the presence of an organic.It can make for this
Organic solvent is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene, dichloromethane or its mixture
Deng preferred toluene.Using these organic solvents, 1,10- phenanthroline solution is prepared, wherein solution concentration is 10~200g/L.Should
The reaction of 1,10- phenanthroline and trimethyl aluminium or triisobutyl aluminium is generally at -60~-80 DEG C, preferably at -60~-70 DEG C
Carry out.In addition, the reaction is advantageously carried out under inert gas shielding, the preferred argon gas of the inert gas or nitrogen.1,10- is luxuriant and rich with fragrance
Anhydrous 1,10- phenanthroline can be used by coughing up quinoline, can also use hydration 1,10- phenanthroline, preferably anhydrous 1,10- phenanthroline.Three
Aluminium methyl or triisobutyl aluminium are generally used with itself.The mol ratio of 1,10- phenanthroline and trimethyl aluminium or triisobutyl aluminium
For 1:0.5~1:4.5, preferably 1:1.0~1:2.6.Advantageously, the reaction is generally at the reaction temperatures to 1,10- phenanthroline
Trimethyl aluminium or triisobutyl aluminium are added in solution, such as trimethyl aluminium or triisobutyl aluminium is added dropwise and carries out.After charging,
Stir 18~28 hours, preferably 18~20 hours at the reaction temperatures.Afterwards, reactant mixture is warming up into 20~40 DEG C to stir again
5~10 hours, preferably 10 hours are mixed, more completely to react.Then plus water (preferably deionized water) hydrolyzes at -60~0 DEG C.
It is hydrolyzed for example, reactant mixture is remained into -30 DEG C and adds water, is preferably added to deionized water and is hydrolyzed.Hydrolytic process
In, there is bubble to emerge, hydrolyze untill bubble is no longer emerged.For more complete hydrolysis, reactant mixture is warming up to 20 again
~40 DEG C are stirred 5~10 hours.Then liquid separation, organic phase is taken out.It is preferably also right in order to isolate required product as much as possible
Inorganic phase is extracted with organic solvent, and obtained organic phase is merged with the organic phase that liquid separation before obtains, this can be used
Organic solvent can be ethyl acetate, acetone, dichloromethane or its mixture etc., preferably dichloromethane.By organic phase or merging
Organic phase removed under reduced pressure solvent after, add nitrobenzene backflow (such as at 210 DEG C) 10~48 hours, preferably 15~24.It
After filter, removed under reduced pressure solvent.It is 1 with volume ratio:1~1:5, preferably 1:2 ethyl acetate:The mixed solution of petroleum ether is leaching
Washing lotion, silica gel column chromatography is carried out, obtains solid product, i.e. formula (b) compound.In the synthesis step, 1,10- phenanthroline and nitro
The mol ratio of benzene is 1:0.5~1:30, preferably 1:15~1:20.
B.2- the synthesis of formoxyl -1,10- phenanthroline contracting amine ligand or 2- isobutyryl -1,10- phenanthroline contracting amine ligands：
Formula (b) compound is reacted with formula (c) compound in the presence of p-methyl benzenesulfonic acid is as catalyst, obtain formula (d) compound,
Wherein R1-R5As mutual-through type (I) or formula (II) define.
Product part (d) passes through the 2- formoxyl -1,10- phenanthroline or 2- isobutyls that make to obtain in step a in a reservoir
The substituted aniline of acyl group -1,10- phenanthroline and formula (c), react and prepare, wherein 2- in the not aqueous and organic solvent of oxygen
The mol ratio of formoxyl -1,10- phenanthroline or 2- isobutyryl -1,10- phenanthroline and the substituted aniline of formula (c) is 1:1~1:
5.The organic solvent that can be used this is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene, dichloromethane
Or its mixture etc., preferred toluene.The reaction is that catalyst is carried out under reflux with p-methyl benzenesulfonic acid (p-TsOH), such as in
Carried out at 110 DEG C.The quality of p-methyl benzenesulfonic acid and the mass ratio of reaction-ure mixture (i.e. formula (b) compound and formula (c) compound)
For 0.001:1~0.02:1, the reaction time be 5~10 hours, with TLC monitor react, treat 2- formoxyls -1,10- phenanthroline or
2- isobutyryls -1,10- phenanthroline removed under reduced pressure solvent, is then 1 with volume ratio after completion of the reaction:1~1:9, preferably 1:4
Ethyl acetate:For the mixed solution of petroleum ether as leacheate, silica gel column chromatography obtains target product, i.e. formula (d) compound.Target
Product is through nuclear-magnetism and mass spectral characteristi.
In a preferred embodiment of the inventive method, the substituted aniline of formula (c) is that preferably 1-4 is individual by 1-5,
More preferably 1-3 it is identical or different be selected from C1-C6Alkyl, C1-C6The aniline of the substituent substitution of alkoxy, halogen and nitro.
As example, 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2,3- dimethylanilines, 2,4- dimethyl benzenes can be mentioned that
Amine, 2,5- dimethylanilines, 2,6- dimethylanilines, 3,4- dimethylanilines, 3,5- dimethylanilines, 2,4,6- trimethylbenzenes
The bromo- 2,6- dimethylanilines of amine, 4-, 2- MEAs, 2- ethyl -6- methylanilines, 2- isopropyl anilines, 2,6- diethylbenzenes
The fluoro- 4- methylanilines of amine, 2,6- diisopropyl anilines, 2- fluoroanilines, 2-, the fluoro- 5- methylanilines of 2-, 2,4 difluorobenzene amine, 2,
5- difluoroanilines, 2,6- difluoroanilines, 3,4- difluoroanilines, 2,3,4- trifluoromethyl anilines, 2,4,5- trifluoromethyl anilines, 2,4,6- trifluoros
Aniline, 2,3,4,5,6- pentafluoroanilines, 3- chloroanilines, 2,6- dichloroanilines, 2,3,4- trichloroanilines, 245 trichloroaniline,
The bromo- 4- methylanilines of 2,4,6- trichloroanilines, 2- bromanilines, 2-, the bromo- 4- fluoroanilines of 2-, the bromo- 2- fluoroanilines of 4-, 2,6- dibromos
The bromo- 4- methylanilines of aniline, 2,6- bis-, the bromo- 4- chloroanilines of 2,6- bis-, 2,4,6- tribromanilines, the chloro- 4- fluoroanilines of the bromo- 6- of 2-,
The chloro- 6- fluoroanilines of the bromo- 4- of 2-, the bromo- 4,6- difluoroanilines of 2-, 3- nitroanilines, 4- aminoanisoles, 2- methyl -4- methoxyl groups
Aniline and 4- phenetidines, most preferably 2,6- diethylanilines.
C. chlorination 2- formoxyls -1,10- phenanthroline condensed amine irons (II) complex or chlorination 2- isobutyryls -1,10- are luxuriant and rich with fragrance
Cough up the synthesis that quinoline contracting amine closes iron (II) complex：Formula (d) compound is reacted with frerrous chloride, obtain formula (I) or formula (II) is changed
Compound,
Wherein R1-R5As mutual-through type (I) or formula (II) define.
Under inert gas such as nitrogen protection, frerrous chloride is dissolved in the not aqueous and organic solvent of oxygen, shape
Into 0.001~0.1g/ml solution, toluene, hexamethylene, ether, tetrahydrofuran, second are selected from for this organic solvent that can be used
Alcohol, benzene, dimethylbenzene, dichloromethane or its mixture etc., preferably tetrahydrofuran.In order to obtain foregoing solution of ferrous chloride, instead of
Frerrous chloride in itself, can also use chloride hydrate ferrous iron (FeCl2·4H2O).Individually 2- formoxyl -1,10- phenanthroline is contracted
Amine ligand or 2- isobutyryl -1,10- phenanthroline contracting amine ligands (d) are dissolved in the not aqueous and organic solvent of oxygen, are formed
0.01~0.1g/ml solution, the organic solvent that can be used this be also selected from toluene, hexamethylene, ether, tetrahydrofuran,
Ethanol, benzene, dimethylbenzene, dichloromethane or its mixture etc., preferably tetrahydrofuran.Then protected in inert gas such as nitrogen etc.
Under, merge above-mentioned two solution (such as merging at room temperature), and stirring is certain at room temperature under inert gas such as nitrogen protection
Time, such as be stirred overnight at room temperature.Monitored and reacted with TLC, it is normal by filtering, washing and dries etc. after question response finishes
Rule post-processing approach post-processes to reaction product, obtains formula (I) or formula (II) compound complex.The washing can make
Carried out with organic solvent such as absolute ether.Complex is characterized by elementary analysis and infrared spectrum.In the synthesis step,
The mol ratio of 2- formoxyl -1,10- phenanthroline ligands or 2- isobutyryl -1,10- phenanthroline ligands (d) and frerrous chloride is 1:
1-1.2:1, preferably 1.05:1-1.1:1.
According to another aspect of the present invention, there is provided a kind of ethylene oligomerization carried out in the presence of above-mentioned carbon monoxide-olefin polymeric
Method.
The preferable technical scheme of oligomerization is as follows in the present invention：Organic solvent and catalyst group are added in reaction vessel
Compound, then reacted 30~100 minutes in the case where ethylene pressure is 0.1~30MPa and reaction temperature is 20~150 DEG C, Ran Houleng
But to -10~10 DEG C, take out a small amount of reactant mixture and analyzed with 5% watery hydrochloric acid with laggard row gas-chromatography (GC).
In above-mentioned oligomerization, the reaction temperature is preferably 20~80 DEG C, and pressure is preferably 1~5MPa, the reaction time
It is advantageously 30~60 minutes.
In above-mentioned oligomerization, the organic solvent is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, diformazan
Benzene and dichloromethane etc., preferably toluene.
C is included come oligomerizing ethylene, the ethylene oligomerization product of acquisition by above-mentioned oligomerization4、C6、C8、C10、C12、C14、
C16、C18、C20、C22Deng；The selectivity of alpha-olefin is high.After ethylene oligomerization terminates, a small amount of reactant mixture is taken out with 5%
Watery hydrochloric acid carries out GC analyses after neutralizing.As a result show, oligomerization activity is up to 106g·mol-1·h-1More than, oligomerization product is distributed more
Adduction is managed.In addition, the ethanol solution that remaining reactant mixture is acidified with 5% watery hydrochloric acid neutralizes, polymer is not obtained.
Relative to prior art, using low cost, (triethyl aluminum unit price is only the tens of MAO unit price to the present invention
/ mono-) triethyl aluminum (AlEt3) it is the 1,10- phenanthroline condensed amine irons that co-catalyst, formoxyl or isobutyryl substitute
(II) complex is the carbon monoxide-olefin polymeric of major catalyst, the metallic aluminium in co-catalyst and the center in major catalyst (I)
The mol ratio of metal is 30 metallic aluminium in the range of less than 500 or in co-catalyst and the central metal in major catalyst (II)
Mol ratio in the range of 30 to 900, not only catalytic activity can receive, the selectivity of alpha-olefin is high, and co-catalyst is used
Measure low, catalytic effect and cost are preferably balanced, practical.By the present invention, technology prejudice is overcome, optimizes and urges
Agent composition so that ethylene oligomerization reaction cost declines to a great extent, and considers catalytic effect and production cost, industrial prospect
It is wide.
Embodiment
It is only presently preferred embodiments of the present invention below, it is impossible to which the scope of the present invention is limited with this.I.e. every Yi Benfa
The change and modification that bright claim is made, all should still be remained within the scope of the patent.
Embodiment 1
1. catalyst chlorination 2- formoxyl -1,10- phenanthroline contracting 2,6- diethylanilines close the synthesis of iron (II) complex
A.2- the synthesis of formoxyl -1,10- phenanthroline
1,10- phenanthroline 5.1g (28.3mmol) is put into 250ml three-necked flasks, under nitrogen protection and magnetic agitation
Dissolved with 100ml toluene.Slowly be added dropwise into three-necked flask under agitation at -60 DEG C 3ml trimethyl aluminiums (d=0.75g/ml,
31.3mmol), it is added dropwise within 15 minutes or so, continues to stir 18h at such a temperature, be warming up to 30 DEG C or so afterwards, continue to stir
Mix 10h.Then reactant mixture is cooled to -30 DEG C or so, is slowly added into 50ml distilled water thereto, then be warming up to 30 DEG C and stir
Mix 10h.Then liquid separation, organic phase being taken out, inorganic phase is extracted three times with dichloromethane, and the dosage of each dichloromethane is 20ml,
Merge each organic phase.Removed under reduced pressure solvent.Afterwards, 50ml nitrobenzene (1.205g/ml) is added, and is flowed back 18 hours in 210 DEG C
Left and right.Filtering, less than nitrobenzene is evaporated off under 10mmHg, obtains dark thick shape liquid substance.Use ethyl acetate:Petroleum ether
=1:The mixed solution of 2 (volume ratios) is leacheate, carries out silica gel column chromatography to gained dark thick shape liquid substance, obtains palm fibre
Color product, weight 1.8g, yield 30%.The product is defined as compound described in title a., i.e. 2- first through nuclear-magnetism and mass spectral analysis
Acyl group -1,10- phenanthroline.
Mass spectrum MS-EI：208.
Nmr analysis：1H NMR (400MHz, CDCl3)：δ 9.26 (d, J=3.9Hz, 1H)；9.16 (s, 1H)；8.37 (s,
2H)；8.29 (d, J=8.1Hz, 1H)；8.7 (dd, J=8.7Hz, 2H)；7.69 (dd, J=7.8Hz, 1H).
B. the synthesis of part 2- formoxyls -1,10- phenanthroline contracting 2,6- diethylanilines
In two mouthfuls of flasks of 100ml equipped with water knockout drum, obtained 2- formyls are put into 0.44g (2.12mmol) steps a
Base -1,10- phenanthroline and 0.95g (6.36mmol) 2,6- diethylaniline (mol ratios 1:3) and 35ml is not aqueous and oxygen
The toluene of gas.Condenser pipe is housed on water knockout drum, p-methyl benzenesulfonic acid 0.01g is added and is flowed back at 110 DEG C, reacted 6 hours.Decompression removes
Fall solvent, use ethyl acetate:Petroleum ether=1:The mixed solution of 4 (volume ratios) obtains glassy yellow as leacheate, silica gel column chromatography
Product, weight 0.58g, yield 81%.The product confirms as compound described in title b. through nuclear-magnetism, mass spectrum and elementary analysis,
That is 2- formoxyls -1,10- phenanthroline contracting 2,6- diethylanilines.
Mass spectrum MS-EI：339.
Nmr analysis：1H NMR (400MHz, CDCl3)：δ 9.25 (dd, J=3.0Hz, 1H)；9.16 (s, 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)；2.43 (m, 4H, CH2CH3), 1.16 (t, J=7.5Hz,
6H, CH2CH3)。
Elementary analysis：C24H23N3(353.46), theoretical value：C, 81.38；H, 6.24；N, 12.38.Measured value：C, 81.48；
H, 6.59；N, 12.39.
C. chlorination 2- formoxyls -1,10- phenanthroline contracting 2,6- diethylanilines close the synthesis of iron (II)
Under nitrogen protection, in two mouthfuls of flasks by 0.16g (1.25mmol) frerrous chlorides with 20ml is not aqueous and oxygen
Tetrahydrofuran dissolving.2- formoxyl -1,10- phenanthroline contractings the 2,6- bis- that will individually be obtained in 0.46g (1.36mmol) steps b
MEA be dissolved in that 20ml is not aqueous and the tetrahydrofuran of oxygen in.Then the lower merging above-mentioned two of nitrogen protection is molten at room temperature
Liquid.Reaction is carried out at once, and grey black is presented in solution.At room temperature, nitrogen protection is stirred overnight.Monitored using TLC, until 2- first
Acyl group -1,10- phenanthroline contracting 2,6- diethylbenzene amine ligands substantially disappear.Filter, washed with absolute ether.Vacuum is done
It is dry to obtain silver gray solid, yield 97%.The solid is defined as compound described in title c., i.e. chlorination 2- formoxyls -1,10- are luxuriant and rich with fragrance
Cough up quinoline 2,6- of contracting diethylanilines and close iron (II), its elementary analysis result is as follows.
Elementary analysis：C24H23Cl2FeN3(480.22), theoretical value：C, 59.26；H, 4.54；N, 9.01.Measured value：C,
59.38；H, 4.83；N, 8.92.
2. ethylene oligomerization reacts
By toluene and 1.34ml triethyl aluminum toluene solutions (concentration 0.74mol/l) and 8ml major catalyst chlorinations 2-
The toluene solution that formoxyl -1,10- phenanthroline contracting 2,6- diethylanilines close iron (II) (2.0 μm of ol) is added to 300ml not
Become rusty in steel autoclave, it is 100ml, Al/Fe=496 to make cumulative volume.When temperature reaches 30 DEG C, ethene is filled with into reactor,
Keep 1MPa ethylene pressure, stirring reaction 30min.Afterwards, a small amount of reactant mixture is taken out with 5% watery hydrochloric acid with syringe
GC analyses are carried out after neutralization：Oligomerization activity is 2.24 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
15.9%, C6~C1060.3%, C6~C1880.8% (wherein containing linear alpha-alkene 90.1%), C20~C283.3%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 2
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 1.07ml (concentration 0.74mol/l), makes Al/Fe=396.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 3.78 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
16.1%, C6~C1059.9%, C6~C1880.6% (wherein containing linear alpha-alkene 91.7%), C20~C283.3%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 3
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.8ml (concentration 0.74mol/l), makes Al/Fe=296.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 4.03 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
21.9%, C6~C1060.8%, C6~C1875.7% (wherein containing linear alpha-alkene 91.8%), C20~C282.4%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 4
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=196.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 4.01 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
20.7%, C6~C1061.1%, C6~C1878.3% (wherein containing linear alpha-alkene 95.1%), C20~C281.0%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 5
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.74mol/l), makes Al/Fe=148.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 3.78 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
16.8%, C6~C1063.1%, C6~C1882.1% (wherein containing linear alpha-alkene 95.7%), C20~C281.1%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 6
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.26ml (concentration 0.74mol/l), makes Al/Fe=96.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 0.71 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
20.8%, C6~C1059.3%, C6~C1878% (wherein containing linear alpha-alkene 93.3%), C20~C281.2%.It is remaining
The ethanol solution that reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 1.
Embodiment 7
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.25mol/l), makes Al/Fe=50.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% dilute salt with syringe
Acid carries out GC analyses after neutralizing：Oligomerization activity is 0.42 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
20.3%, C6~C1060.4%, C6~C1876.8% (wherein containing linear alpha-alkene 90.9%), C20~C282.9%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 8
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.24ml (concentration 0.25mol/l), makes Al/Fe=30.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 0.20 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
16.9%, C6~C1063.4%, C6~C1878.5% (wherein containing linear alpha-alkene 90.8%), C20~C284.6%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 9
The major catalyst prepared using embodiment 1, co-catalyst are that triethyl aluminum carries out ethylene oligomerization reaction, triethyl aluminum
The dosage of toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=196.It is with the difference of embodiment 1：
At 30 DEG C, 2MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 4.22 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
24.5%, C6~C1055.42%, C6~C1871.3% (wherein containing linear alpha-alkene 94.7%), C20~C284.2%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 1.
Embodiment 10
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.74mol/l), makes Al/Fe=148；
At 30 DEG C, 2MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 4.03 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
20.9%, C6~C1052.48%, C6~C1873.9% (wherein containing linear alpha-alkene 93.2%), C20~C285.2%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 1.
Embodiment 11
The major catalyst prepared using embodiment 1, co-catalyst are that triethyl aluminum carries out ethylene oligomerization reaction, triethyl aluminum
The dosage of toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=196.It is with the difference of embodiment 1：
At 30 DEG C, 3MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 5.21 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
17.9%, C6~C1048.9%, C6~C1875.7% (wherein containing linear alpha-alkene 90.5%), C20~C286.4%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 12
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.74mol/l), makes Al/Fe=148；
At 30 DEG C, 3MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 5.03 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
20.1%, C6~C1050.8%, C6~C1874.8% (wherein containing linear alpha-alkene 90.3%), C20~C285.1%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Comparative example 1
The major catalyst prepared using embodiment 1, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with embodiment
1 difference is：The dosage of triethyl aluminum toluene solution is 2.7ml (concentration 0.74mol/l), makes Al/Fe=999.
At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.With syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 2.65 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
14.3%, C6~C1060.1%, C6~C1881.5% (wherein containing linear alpha-alkene 90.1%), C20~C284.2%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Comparative example 2
Technique carries out ethylene oligomerization reaction to the major catalyst prepared using embodiment 1 as described in Example 1, and difference exists
In：Co-catalyst is MAO, and the dosage of methylaluminoxane toluene solution is 0.26ml (concentration 1.5mol/l), is made
Al/Fe=195.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reaction mixing is taken out with syringe
Thing carries out GC analyses after being neutralized with 5% watery hydrochloric acid：Oligomerization activity is 5.1 × 106g·mol-1(Fe)·h-1, oligomer content
Respectively C412.3%, C6~C1045.9%, C6~C1878.8% (wherein containing linear alpha-alkene 80.1%), C20~C28
8.9%.The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid is neutralized, and obtains White waxy polymer, and polymerization is lived
Property be 6.53 × 104g·mol-1·h-1.Analysis result is shown in Table 1.
As known from Table 1：Using 1,10- phenanthroline condensed amine irons (II) complex conduct of formoxyl substitution in ethylene oligomerization
The carbon monoxide-olefin polymeric of major catalyst and triethyl aluminum as co-catalyst, at 30 DEG C, keep 1MPa ethylene pressure, compared with
During high co-catalyst dosage (Al/Fe 1000), there is not high catalytic activity, and in relatively low co-catalyst dosage
(Al/Fe is 150~400), oligomerization activity is close to or reached 4 × 10 on the contrary6g·mol-1·h-1；In addition, being somebody's turn to do in the present invention
Catalyst approaches with catalyst oligomerization activity when (Al/Fe ratios are 200) MAO makees co-catalyst under similar proportions.Again
Have, when carrying out ethylene oligomerization using carbon monoxide-olefin polymeric of the present invention, the selectivity of its linear alpha-alkene is higher (to be exceeded
90%).Further, the oligomerization product distribution of present invention gained is more reasonable；And 5% watery hydrochloric acid acid of remaining reactant mixture
The ethanol solution of change neutralizes, and does not obtain polymer.The triethyl aluminum that above said content illustrates to use low cost is co-catalysis
Agent, there is suitable catalytic activity and more excellent linear alpha-alkene selectivity on the contrary under low dosage, have unexpected
Effect.In addition, from the data in table 1, it can be seen that under the reaction condition such as identical reaction pressure and temperature, Al/Fe mol ratios are most
The figure of merit is between 150 to 400.
Table 1
Embodiment 13
1. catalyst chlorination 2- isobutyryl -1,10- phenanthroline contracting 2,6- diethylanilines close the conjunction of iron (II) complex
Into
A.2- the synthesis of isobutyryl -1,10- phenanthroline
1,10- phenanthroline 5.1g (28.3mmol) is put into 250ml three-necked flasks, under nitrogen protection and magnetic agitation
Dissolved with 100ml toluene.13.7ml triisobutyl aluminiums (d=is slowly added dropwise into three-necked flask under agitation at -60 DEG C
0.82g/ml, 56.6mmol), it is added dropwise within 15 minutes or so, continues to stir 18h at such a temperature, be warming up to 30 DEG C of left sides afterwards
The right side, continue to stir 10h.Then reactant mixture is cooled to -30 DEG C or so, is slowly added into 50ml distilled water thereto, then rise
Warm to 30 DEG C stirring 10h.Then liquid separation, organic phase is taken out, inorganic phase is extracted three times with dichloromethane, the use of each dichloromethane
Measure as 20ml, merge each organic phase.Removed under reduced pressure solvent.Afterwards, 50ml nitrobenzene (1.205g/ml) is added, and is returned in 210 DEG C
Stream 18 hours or so.Filtering, less than nitrobenzene is evaporated off under 10mmHg, obtains dark thick shape liquid substance.With acetic acid second
Ester:Petroleum ether=1:The mixed solution of 2 (volume ratios) is leacheate, and silica gel column layer is carried out to gained dark thick shape liquid substance
Analysis, obtain brown product, weight 2.1g, yield 30%.The product is defined as chemical combination described in title a. through nuclear-magnetism and mass spectral analysis
Thing, i.e. 2- isobutyryls -1,10- phenanthroline.
Mass spectrum MS-EI：250.
Nmr analysis：1H NMR (400MHz, CDCl3)：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)；3.47 (m, J=
7.24,1H)；1.10 (d, J=7.4,6H).
B. the synthesis of part 2- isobutyryls -1,10- phenanthroline contracting 2,6- diethylanilines
In two mouthfuls of flasks of 100ml equipped with water knockout drum, obtained 2- isobutyls are put into 0.53g (2.12mmol) steps a
Acyl group -1,10- phenanthroline and 0.95g (6.36mmol) 2,6- diethylaniline (mol ratios 1:3) and 35ml it is not aqueous and
The toluene of oxygen.Condenser pipe is housed on water knockout drum, p-methyl benzenesulfonic acid 0.01g is added and is flowed back at 110 DEG C, reacted 6 hours.Decompression
Solvent is removed, uses ethyl acetate:Petroleum ether=1:The mixed solution of 4 (volume ratios) obtains bright orange as leacheate, silica gel column chromatography
Color product, weight 0.65g, yield 81%.The product confirms as chemical combination described in title b. through nuclear-magnetism, mass spectrum and elementary analysis
Thing, i.e. 2- isobutyryls -1,10- phenanthroline contracting 2,6- diethylanilines.
Mass spectrum MS-EI：381.
Nmr analysis：1H NMR (400MHz, CDCl3)：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 (m, J=7.84 ,-CNCH (CH3)2,1H)；2.40
(m, J=7.52, phCH2CH3,4H)；1.58 (d, J=7.44 ,-CNCH (CH3)2, 6H)；1.20 (t, J=7.30, phCH2CH3,
6H)。
Elementary analysis：C26H27N3(381.51), theoretical value：C, 81.85；H, 7.13；N, 11.01.Measured value：C, 81.36；
H, 7.23；N, 10.55.
C. chlorination 2- isobutyryls -1,10- phenanthroline contracting 2,6- diethylanilines close the synthesis of iron (II)
Under nitrogen protection, in two mouthfuls of flasks by 0.16g (1.25mmol) frerrous chlorides with 20ml is not aqueous and oxygen
Tetrahydrofuran dissolving.2- isobutyryl -1,10- phenanthroline contractings the 2,6- that will individually be obtained in 0.52g (1.36mmol) steps b
Diethylaniline be dissolved in that 20ml is not aqueous and the tetrahydrofuran of oxygen in.Then nitrogen protection is lower at room temperature merges above-mentioned two
Solution.Reaction is carried out at once, and grey black is presented in solution.At room temperature, nitrogen protection is stirred overnight.Monitored using TLC, until 2-
Isobutyryl -1,10- phenanthroline contracting 2,6- diethylbenzene amine ligands substantially disappear.Filter, washed with absolute ether.Very
Empty dry silver gray solid.The solid is defined as compound described in title c., i.e. chlorination 2- isobutyryls -1,10- phenanthrene is coughed up
Quinoline 2,6- of contracting diethylanilines close iron (II), and its elementary analysis result is as follows.
Elementary analysis：C26H27Cl2FeN3(508.26), theoretical value：C, 61.44；H, 5.35；N, 8.27. measured value：C,
61.79；H, 5.60；N, 8.13.
2. ethylene oligomerization reacts
By toluene and 2.42ml triethyl aluminum toluene solutions (concentration 0.74mol/l) and 8ml major catalyst chlorinations 2-
The toluene solution that isobutyryl -1,10- phenanthroline contracting 2,6- diethylanilines close iron (II) (2.0 μm of ol) is added to 300ml's
In stainless steel autoclave, it is 100ml, Al/Fe=895 to make cumulative volume.When temperature reaches 30 DEG C, second is filled with into reactor
Alkene, keep 1MPa ethylene pressure, stirring reaction 30min.Afterwards, with syringe take out a small amount of reactant mixture with 5% it is dilute
Hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 3.43 × 106g·mol-1(Fe)·h-1, oligomer content is respectively C4
13.1%, C6~C1064.8%, C6~C1885.9% (wherein containing linear alpha-alkene 93.2%), C20~C281.0%.It is remaining
Reactant mixture with 5% hydrochloric acid be acidified ethanol solution neutralize, do not obtain polymer.Analysis result is shown in Table 1.
Embodiment 14
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 2.15ml (concentration 0.74mol/l), makes Al/Fe=
796.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 3.58 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C415.1%, C6~C1063.7%, C6~C1880.3% (wherein containing linear alpha-alkene 92.8%), C20~C284.6%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 15
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 1.88ml (concentration 0.74mol/l), makes Al/Fe=
696.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 4.12 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C420.2%, C6~C1060.8%, C6~C1876.4% (wherein containing linear alpha-alkene 92.7%), C20~C283.4%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 16
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 1.34ml (concentration 0.74mol/l), makes Al/Fe=
496.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 4.43 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C417.3%, C6~C1055.8%, C6~C1878.9% (wherein containing linear alpha-alkene 92.1%), C20~C283.8%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 17
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.8ml (concentration 0.74mol/l), makes Al/Fe=
296.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 4.32 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C422.2%, C6~C1053.1%, C6~C1876.8% (wherein containing linear alpha-alkene 95.4%), C20~C281.0%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 18
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=
196.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 4.11 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C420.8%, C6~C1059.8%, C6~C1876.6% (wherein containing linear alpha-alkene 95.9%), C20~C283.4%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 19
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.74mol/l), makes Al/Fe=
148.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 3.93 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C415.3%, C6~C1060.7%, C6~C1879.8% (wherein containing linear alpha-alkene 90.3%), C20~C284.9%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 20
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.26ml (concentration 0.74mol/l), makes Al/Fe=
96.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 1.63 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C422.8%, C6~C1057.3%, C6~C1872.6% (wherein containing linear alpha-alkene 90.7%), C20~C284.6%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 21
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.4ml (concentration 0.25mol/l), makes Al/Fe=
50.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 0.95 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C419.8%, C6~C1060.4%, C6~C1875.5% (wherein containing linear alpha-alkene 89.1%), C20~C284.7%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 22
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.24ml (concentration 0.25mol/l), makes Al/Fe=
30.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 0.72 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C417.3%, C6~C1063.2%, C6~C1874.3% (wherein containing linear alpha-alkene 88.8%), C20~C288.4%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 23
The major catalyst prepared using embodiment 13, co-catalyst are that triethyl aluminum carries out ethylene oligomerization reaction, triethyl group
The dosage of aluminium toluene solution is 0.8ml (concentration 0.74mol/l), makes Al/Fe=296.Exist with the difference of embodiment 13
In：At 30 DEG C, 2MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 6.13 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C425.5%, C6~C1053.4%, C6~C1870.1% (wherein containing linear alpha-alkene 92.4%), C20~C284.4%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 24
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=
196；At 30 DEG C, 2MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 6.08 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C423.4%, C6~C1052.9%, C6~C1872.3% (wherein containing linear alpha-alkene 91.9%), C20~C284.3%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 25
The major catalyst prepared using embodiment 13, co-catalyst are that triethyl aluminum carries out ethylene oligomerization reaction, triethyl group
The dosage of aluminium toluene solution is 0.8ml (concentration 0.74mol/l), makes Al/Fe=296.Exist with the difference of embodiment 13
In：At 30 DEG C, 3MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 8.14 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C418.8%, C6~C1047.3%, C6~C1872.9% (wherein containing linear alpha-alkene 90.8%), C20~C288.3%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Embodiment 26
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 0.53ml (concentration 0.74mol/l), makes Al/Fe=
196；At 30 DEG C, 3MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with 5% with syringe
Watery hydrochloric acid neutralize after carry out GC analyses：Oligomerization activity is 8.02 × 106g·mol-1(Fe)·h-1, oligomer content is respectively
C419.7%, C6~C1050.7%, C6~C1874.7% (wherein containing linear alpha-alkene 90.5%), C20~C285.6%.It is surplus
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Comparative example 3
The major catalyst prepared using embodiment 13, co-catalyst is that triethyl aluminum carries out ethylene oligomerization reaction, with implementation
The difference of example 13 is：The dosage of triethyl aluminum toluene solution is 4.05ml (concentration 0.74mol/l), makes Al/Fe=
1499.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reactant mixture is taken out with syringe to use
5% watery hydrochloric acid carries out GC analyses after neutralizing：Oligomerization activity is 3.77 × 106g·mol-1(Fe)·h-1, oligomer content difference
For C425.4%, C6~C1052.9%, C6~C1871.3% (wherein containing linear alpha-alkene 91.3%), C20~C283.3%.
The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table 2.
Comparative example 4
Technique carries out ethylene oligomerization reaction, difference to the major catalyst prepared using embodiment 13 as described in Example 13
It is：Co-catalyst is MAO, and the dosage of methylaluminoxane toluene solution is 0.26ml (concentration 1.5mol/l), is made
Al/Fe=195.At 30 DEG C, 1MPa ethylene pressure, stirring reaction 30min are kept.A small amount of reaction mixing is taken out with syringe
Thing carries out GC analyses after being neutralized with 5% watery hydrochloric acid：Oligomerization activity is 6.3 × 106g·mol-1(Fe)·h-1, oligomer content
Respectively C410.6%, C6~C1043.8%, C6~C1876.6% (wherein containing linear alpha-alkene 82.7%), C20~C28
12.8%.The ethanol solution that remaining reactant mixture is acidified with 5% hydrochloric acid neutralizes, and obtains White waxy polymer, polymerize
Activity is 6.83 × 104g·mol-1·h-1.Analysis result is shown in Table 2.
As known from Table 2：Made in ethylene oligomerization using 1,10- phenanthroline condensed amine irons (II) complex of isobutyryl substitution
For the carbon monoxide-olefin polymeric of major catalyst and triethyl aluminum as co-catalyst, at 30 DEG C, 1MPa ethylene pressure is kept,
During higher co-catalyst dosage (Al/Fe 1500), there is not high catalytic activity, and in relatively low co-catalyst dosage
(Al/Fe is 150~700), oligomerization activity can reach or more than 4 × 10 on the contrary6g·mol-1·h-1；In addition, being somebody's turn to do in the present invention
Catalyst differs not with catalyst oligomerization activity when (Al/Fe ratios are 195) MAO makees co-catalyst under similar proportions
Greatly.Further, when carrying out ethylene oligomerization using carbon monoxide-olefin polymeric of the present invention, the selectivity of its linear alpha-alkene is higher (super
88% is crossed, or even is close to 96%).Further, the oligomerization product distribution of present invention gained is more reasonable；And remaining reaction mixing
The ethanol solution that thing is acidified with 5% watery hydrochloric acid neutralizes, and does not obtain polymer.Above said content illustrates using low cost
Triethyl aluminum is co-catalyst, under low dosage there is suitable catalytic activity and more excellent linear alpha-alkene to select on the contrary
Property, there is unexpected effect.In addition, from the data in table 2, it can be seen that under the reaction condition such as identical reaction pressure and temperature,
The optimal value of Al/Fe mol ratios is between 200 to 300.
Table 2
Claims (19)
1. a kind of ethylene oligomerisation catalyst composition of 1, the 10- phenanthroline complexs of the substitution containing formoxyl, including with following
1,10- phenanthroline condensed amine irons (II) complex of the formoxyl substitution of formula (I) is as major catalyst and triethyl aluminum conduct
Co-catalyst, wherein the mol ratio of the metallic aluminium in the co-catalyst and the central metal iron in the major catalyst is 296
To 496：
Wherein, R1-R5It is each independently hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy or nitro.
2. composition according to claim 1, it is characterised in that metallic aluminium and the main catalytic in the co-catalyst
The mol ratio of central metal iron in agent is 296 to 396.
3. composition according to claim 1, it is characterised in that the R in major catalyst1-R5It is each independently hydrogen, first
Base, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitro.
4. composition according to claim 1, it is characterised in that in major catalyst, R1And R5For ethyl, and R2-R4It is
Hydrogen.
5. a kind of ethylene oligomerization method, second is carried out in the presence of the carbon monoxide-olefin polymeric in Claims 1 to 4 described in any one
Alkene oligomerisation.
6. ethylene oligomerization method according to claim 5, the reaction temperature of the ethylene oligomerization is 20-150 DEG C, reaction pressure
Power is 0.1-30MPa.
7. ethylene oligomerization method according to claim 5, the reaction temperature of the ethylene oligomerization is 20-80 DEG C, reaction pressure
Power is 1-5MPa.
8. a kind of ethylene oligomerisation catalyst composition of 1, the 10- phenanthroline complexs of the substitution containing formoxyl, including with following
1,10- phenanthroline condensed amine irons (II) complex of the formoxyl substitution of formula (I) is as major catalyst and triethyl aluminum conduct
Co-catalyst, wherein the mol ratio of the metallic aluminium in the co-catalyst and the central metal iron in the major catalyst is 148
To 196：
Wherein, R1-R5It is each independently hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy or nitro.
9. composition according to claim 8, it is characterised in that the R in major catalyst1-R5It is each independently hydrogen, first
Base, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitro.
10. composition according to claim 8, it is characterised in that in major catalyst, R1And R5For ethyl, and R2-R4It is
Hydrogen.
11. a kind of ethylene oligomerization method, carried out in the presence of the carbon monoxide-olefin polymeric in claim 8~10 described in any one
Ethylene oligomerization.
12. ethylene oligomerization method according to claim 11, the reaction temperature of the ethylene oligomerization is 20-150 DEG C, reaction
Pressure is 0.1-30MPa.
13. ethylene oligomerization method according to claim 11, the reaction temperature of the ethylene oligomerization is 20-80 DEG C, reaction
Pressure is 1-5MPa.
14. it is a kind of containing isobutyryl substitution 1,10- phenanthroline complexs ethylene oligomerisation catalyst composition, including with
1,10- phenanthroline condensed amine irons (II) complex of the isobutyryl substitution of lower formula (II) is as major catalyst and triethyl aluminum
As co-catalyst, wherein the mol ratio of the metallic aluminium and the central metal iron in the major catalyst in the co-catalyst is
148 to 196：
Wherein, R1-R5It is each independently hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy or nitro.
15. composition according to claim 14, it is characterised in that the R in major catalyst1-R5Be each independently hydrogen,
Methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitro.
16. composition according to claim 14, it is characterised in that in major catalyst, R1And R5For ethyl, and R2-R4
For hydrogen.
17. a kind of ethylene oligomerization method, enter in the presence of the carbon monoxide-olefin polymeric in claim 14~16 described in any one
Row ethylene oligomerization.
18. ethylene oligomerization method according to claim 17, the reaction temperature of the ethylene oligomerization is 20-150 DEG C, reaction
Pressure is 0.1-30MPa.
19. ethylene oligomerization method according to claim 17, the reaction temperature of the ethylene oligomerization is 20-80 DEG C, reaction
Pressure is 1-5MPa.
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