CN104107723B - A kind of ethylene oligomerization carbon monoxide-olefin polymeric and application - Google Patents
A kind of ethylene oligomerization carbon monoxide-olefin polymeric and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
The invention discloses a kind of ethylene oligomerisation catalyst composition, including positive phenanthroline condensed amine iron (II) the complex major catalyst of propiono 1,10 of chlorination 2 shown in formula (I), containing aluminum cocatalyst, water and organic solvent：In formula, R1‑R5It is each independently selected from hydrogen, C1‑C6Alkyl, halogen, C1‑C6Alkoxy or nitro.According to the present invention, ethylene oligomerization is used for using complex major catalyst shown in formula (I), the carbon monoxide-olefin polymeric containing aluminum cocatalyst, water and organic solvent, there is very high oligomerisation reaction activity on the contrary, the selectivity of alhpa olefin is high, and oligomerisation reaction initiation is rapid, operates steadily, be reproducible；Even in low aluminium/iron ratio, still with extraordinary oligomerisation reaction activity；This just overcomes the technology prejudice of those skilled in the art, achieves unexpected technique effect.
Description
Technical field
The present invention relates to field of olefin polymerisation, and in particular to a kind of catalyst combination for ethylene oligomerization reaction process
Thing.The invention further relates to the application of above-mentioned carbon monoxide-olefin polymeric.
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 CN102050841A of Institute of Chemistry, Academia Sinica reports a kind of phenanthroline anil class complex,
It is major catalyst and using MAO or modified methylaluminoxane or modified methylaluminoxane as co-catalyst using the complex
During applied to ethylene oligomerization, only in high co-catalyst dosage（Al/Fe=1000~2000）When, oligomerization activity is just reachable
107g·mol-1·h-1.Regardless of whether be MAO, or cost mistake all be present as co-catalyst in modified methylaluminoxane
Height, the problem of dosage is excessive, as co-catalyst large-scale application when the ethylene oligomerization, it certainly will cause production cost high.
Reaction environment is required today, it is generally accepted that water is very unfavorable therefore current oligomerisation reaction to ethylene oligomerization
It is very harsh, generally it is strict controlled in the environment of anhydrous and oxygen-free and carries out, but the reaction of oligomerization process simultaneously triggers and stably
Property and repeatability it is all excessively poor.
The content of the invention
For deficiency of the prior art, inventor has carried out grinding extensively and profoundly in ethylene oligomerization with catalyst field
Study carefully, it has surprisingly been found that being sponsored using positive propiono -1,10- phenanthroline condensed amine iron (II) complexs of chlorination 2- shown in formula (I)
Agent, the carbon monoxide-olefin polymeric containing aluminum cocatalyst, water and organic solvent are used for ethylene oligomerization, have higher oligomerisation anti-on the contrary
Should be active, also there is extraordinary oligomerisation reaction activity even if under conditions of low-down aluminium/iron ratio, and oligomerisation reaction initiation is fast
Speed, operate steadily, be reproducible, so as to overcome technology prejudice of the those skilled in the art on water, achieving unexpected
Technique effect.
According to an aspect of the invention, there is provided a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including shown in formula (I)
Positive propiono -1,10- phenanthroline condensed amine irons (II) the complex major catalysts of chlorination 2-, containing aluminum cocatalyst, water and organic molten
Agent：
In formula, R1-R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
According to carbon monoxide-olefin polymeric provided by the invention, there is higher ethylene oligomerization reactivity, the selection of alpha-olefin
Property it is high.
In carbon monoxide-olefin polymeric of the present invention, using the weight of organic solvent as calculating benchmark, the weight content of water
For 5~350ppm（That is the organic solvent based on 1g, 5~350 × 10 are contained in composition-6G water）, preferably 20~260ppm, most
Preferably 50~200ppm.In the range of described water content, the carbon monoxide-olefin polymeric has higher ethylene oligomerization activity.
In the carbon monoxide-olefin polymeric of the present invention, the dosage of the major catalyst and co-catalyst can according to production scale and
The process conditions during concrete applications such as production equipment are selected.In a specific embodiment of the carbon monoxide-olefin polymeric,
Using the volume of organic solvent as calculating benchmark, the content of the major catalyst is 2~500 μm of ol/L（It is organic molten i.e. based on 1L
Agent, 2~500 × 10 are contained in composition-6Mol major catalyst）, preferably 20~100 μm of ol/L.
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 above-mentioned carbon monoxide-olefin polymeric, in the co-catalyst in aluminium and major catalyst iron mol ratio for 30 to less than
900:1, preferably 100-700:1.In an instantiation of above-mentioned carbon monoxide-olefin polymeric, aluminium is with sponsoring in the co-catalyst
The mol ratio of iron is preferably 148-196 in agent:1.
In above-mentioned carbon monoxide-olefin polymeric, the R in preferably described major catalyst1-R5It is each independently selected from hydrogen, methyl, second
Base, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.R in more preferably described major catalyst1And R5For second
Base, R2-R4It is hydrogen.
Major catalyst shown in the logical formula (I) of the present invention can use the preparation side of Chinese patent application CN102558241A reports
Method is made.Therefore, the specific system of positive propiono -1,10- phenanthroline condensed amine iron (II) complexs of chlorination 2- shown in formula (I) is led to
Standby process is as follows：
A.2- the synthesis of positive propiono -1,10- phenanthroline：Make 1,10- phenanthroline and tri-n-n-propyl aluminum (n-C3H7)3Al is anti-
Should, then obtain formula (b) compound by hydrolysis and the oxidation reaction with nitrobenzene successively.
For positive propiono -1, the 10- phenanthroline of the 2- of formula (b), make 1,10- phenanthroline and tri-n-n-propyl aluminum first
(n-C3H7)3Al reacts in the presence of an organic.Toluene, hexamethylene, ether, four are selected from for this organic solvent that can be used
Hydrogen furans, ethanol, benzene, dimethylbenzene, dichloromethane or its mixture etc., preferably toluene.Using these organic solvents, 1 is prepared,
10- phenanthroline solution, wherein solution concentration are 10~200g/L.The reaction of the 1,10- phenanthroline and tri-n-n-propyl aluminum generally-
At 60~-80 DEG C, preferably carried out at -60~-70 DEG C.In addition, the reaction is advantageously carried out under inert gas shielding, should
The preferred argon gas of inert gas or nitrogen.1,10- phenanthroline can use anhydrous 1,10- phenanthroline, can also use hydration 1,10-
Phenanthroline, preferably anhydrous 1,10- phenanthroline.Tri-n-n-propyl aluminum is generally used with itself.1,10- phenanthroline and tri-n-n-propyl aluminum
Mol ratio be 1:0.5~1:4.5, preferably 1:2.0~1:2.6.Advantageously, the reaction is generally at the reaction temperatures to 1,
Tri-n-n-propyl aluminum is added in 10- phenanthroline solution, such as tri-n-n-propyl aluminum is added dropwise and carries out.After charging, in reaction temperature
Lower stirring 18~28 hours, preferably 18~20 hours.Afterwards, reactant mixture is warming up to 20~40 DEG C to be stirred for 5~10 small
When, preferably 10 hours, more completely to react.Then plus water (preferably deionized water) hydrolyzes at -60~0 DEG C.For example, will be anti-
Answer mixture to remain -30 DEG C of addition water to be hydrolyzed, be preferably added to deionized water and be hydrolyzed.In hydrolytic process, there is bubble
Emerge, hydrolyze untill bubble is no longer emerged.For more complete hydrolysis, reactant mixture is warming up to 20~40 DEG C of stirrings again
5~10 hours.Then liquid separation, organic phase is taken out.In order to isolate required product as much as possible, preferably also to inorganic phase with having
Solvent extracts, and obtained organic phase is merged with the organic phase that liquid separation before obtains, the organic solvent that can be used this can
Think ethyl acetate, acetone, preferably dichloromethane or its mixture etc., dichloromethane.Organic phase or the organic of merging are subtracted each other
After pressure removes solvent, nitrobenzene backflow (such as at 210 DEG C) 10~48 hours, preferably 15~24 hours is added.Filter afterwards,
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 leacheate, is entered
Row silica gel column chromatography, obtain solid product, i.e. formula (b) compound.In the synthesis step, 1,10- phenanthroline and nitrobenzene rub
You are than being 1:0.5~1:30, preferably 1:15~1:20.
B.2- the synthesis of positive propiono -1,10- phenanthroline contracting amine ligand：Make formula (b) compound with formula (c) compound right
Toluenesulfonic acid obtains formula (d) compound as being reacted in the presence of catalyst
Wherein R1-R5As mutual-through type (I) defines.
Product part (d) passes through the positive propiono -1,10- phenanthroline of the 2- for making to obtain in step a in a reservoir and formula (c)
Substituted aniline, react and prepare in the not aqueous and organic solvent of oxygen, positive propiono -1, the 10- phenanthroline of wherein 2- with
The mol ratio of the substituted aniline of formula (c) is 1:1~1:5.The organic solvent that can be used this be selected from toluene, hexamethylene, ether,
Tetrahydrofuran, ethanol, benzene, dimethylbenzene, dichloromethane or its mixture etc., preferably toluene.The reaction is with p-methyl benzenesulfonic acid (p-
TsOH) carry out for catalyst, such as carried out at 110 DEG C under reflux.The quality of p-methyl benzenesulfonic acid and reaction-ure mixture (i.e. formula
(b) compound and formula (c) compound) mass ratio be 0.001:1~0.02:1, the reaction time is 5~10 hours, is supervised with TLC
Reaction is surveyed, treats positive propiono -1, the 10- phenanthroline of 2- after completion of the reaction, removed under reduced pressure solvent, is then 1 with volume ratio: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) is changed
Compound.Target product nuclear-magnetism and mass spectral characteristi.
In one embodiment, the substituted aniline of formula (c) is preferably 1-4 by 1-5, more preferably 1-3 it is identical or
Different is selected from C1-C6Alkyl, C1-C6The aniline of the substituent substitution of alkoxy, halogen and nitro.As example, 2- can be mentioned that
Methylaniline, 3- methylanilines, 4- methylanilines, 23 dimethyl aniline, 2,4- dimethylanilines, 2,5- dimethylanilines,
The bromo- 2,6- dimethyl of 2,6- dimethylanilines, 3,4- dimethylanilines, 3,5- dimethylanilines, 2,4,6- trimethylanilines, 4-
Aniline, 2- MEAs, 2- ethyl -6- methylanilines, 2- isopropyl anilines, 2,6- diethylanilines, 2,6- diisopropyl benzenes
The fluoro- 4- methylanilines of amine, 2- fluoroanilines, 2-, the fluoro- 5- methylanilines of 2-, 2,4 difluorobenzene amine, 2,5- difluoroanilines, 2,6- bis-
Fluoroaniline, 3,4- difluoroanilines, 2,3,4- trifluoromethyl anilines, 2,4,5- trifluoromethyl anilines, 2,4,6- trifluoromethyl anilines, 2,3,4,5,6- five
Fluoroaniline, 3- chloroanilines, 2,6- dichloroanilines, 2,3,4- trichloroanilines, 245 trichloroaniline, 2,4,6- trichloroanilines, 2-
The bromo- 4- methylanilines of bromaniline, 2-, the bromo- 4- fluoroanilines of 2-, the bromo- 2- fluoroanilines of 4-, 2,6- dibromo anilines, the bromo- 4- first of 2,6- bis-
The bromo- 4- chloroanilines of base aniline, 2,6- bis-, 2,4,6- tribromanilines, the chloro- 4- fluoroanilines of the bromo- 6- of 2-, the chloro- 6- fluorobenzene of the bromo- 4- of 2-
The bromo- 4,6- difluoroanilines of amine, 2-, 3- nitroanilines, 4- aminoanisoles, 2- methyl -4- aminoanisoles and 4- ethoxybenzenes
Amine, most preferably 2,6- diethylanilines.
C. the synthesis of positive propiono -1,10- phenanthroline condensed amine irons (II) complexs of chlorination 2-：Make formula (d) compound with
Frerrous chloride reacts, and obtains formula (I) compound
Wherein R1-R5As mutual-through type (I) defines.
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- propiono -1,10- phenanthroline is contracted
Amine ligand (d) is dissolved in the not aqueous and organic solvent of oxygen, forms 0.01~0.1g/ml solution, this can be used
Organic solvent be also selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene, dichloromethane or its mixture
Deng preferred tetrahydrofuran.Then under inert gas such as nitrogen protection, above-mentioned two solution of merging (such as close at room temperature
And), and stirred at room temperature certain time under inert gas such as nitrogen protection, such as be stirred overnight at room temperature.Monitored with TLC
Reaction, after question response finishes, reaction product is post-processed by the conventional post-processing approach such as filtering, washing and dry,
Obtain formula (I) compound complex.The washing can use organic solvent such as absolute ether to carry out.Complex passes through element point
Analysis and infrared spectrum are characterized.In the synthesis step, positive propiono -1, the 10- phenanthroline ligands (d) of 2- and frerrous chloride
Mol ratio is 1:1-1.2:1, preferably 1.05:1-1.1:1.
It is described to be selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferably alkane containing aluminum cocatalyst in above-mentioned carbon monoxide-olefin polymeric
Base aluminium compound.
In above-mentioned carbon monoxide-olefin polymeric, the formula of the alkyl aluminum compound is AlRnXm, wherein R is each independently
Straight or branched C1-C8Alkyl；X is halogen, preferably chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m+n is equal to
3；Preferably, the alkyl aluminum compound is excellent from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-hexyls
Aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In above-mentioned carbon monoxide-olefin polymeric, the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl be straight chain or
The alkyl of side chain；Preferably, the aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl group
Aikyiaiurnirsoxan beta；More preferably MAO.
In above-mentioned carbon monoxide-olefin polymeric, the aluminum cocatalyst that contains can be aikyiaiurnirsoxan beta or alkyl aluminum compound etc..It is described
It is preferably alkyl aluminum compound containing aluminum cocatalyst, has specifically may be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three just
Base aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, wherein it is preferred that triethyl aluminum.The example of the aikyiaiurnirsoxan beta
Including MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide etc., preferably MAO.
In above-mentioned carbon monoxide-olefin polymeric, the organic solvent be selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol,
Benzene, dimethylbenzene and dichloromethane, are preferably selected from toluene and dimethylbenzene.
According to another aspect of the present invention, there is provided a kind of ethylene oligomerization method, ethene is in above-mentioned carbon monoxide-olefin polymeric
In the presence of carry out oligomerisation reaction.
In the above-mentioned methods, positive propiono -1, the 10- phenanthrene of chlorination 2- that the carbon monoxide-olefin polymeric is included shown in formula (I) is coughed up
Quinoline contracting amine closes iron (II) complex major catalyst, containing aluminum cocatalyst and organic solvent：
In formula, R1-R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
It is described to be selected from aikyiaiurnirsoxan beta and alkyl aluminum compound containing aluminum cocatalyst in the carbon monoxide-olefin polymeric of the above method,
It is preferred that alkyl aluminum compound.
In the carbon monoxide-olefin polymeric of the above method, the formula of the alkyl aluminum compound is AlRnXm, wherein R is each only
It is on the spot straight or branched C1-C8Alkyl；X is halogen, preferably chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m
+ n is equal to 3；Preferably, the alkyl aluminum compound it is excellent from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three just
Hexyl aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In above-mentioned carbon monoxide-olefin polymeric, the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl be straight chain or
The alkyl of side chain；Preferably, the aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl group
Aikyiaiurnirsoxan beta；More preferably MAO.
In the carbon monoxide-olefin polymeric of the above method, the aluminum cocatalyst that contains can be aikyiaiurnirsoxan beta or alkyl aluminum compound
Deng.Described containing aluminum cocatalyst is preferably alkyl aluminum compound, specifically may be selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium,
Three just base aluminium, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichlorides, wherein it is preferred that triethyl aluminum.The aikyiaiurnirsoxan beta
Example include MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide etc., preferably methyl alumina
Alkane.
In the carbon monoxide-olefin polymeric of the above method, the mol ratio of aluminium and iron in major catalyst is 30 in the co-catalyst
Extremely it is less than 900, preferably 100-700.In an instantiation of above-mentioned carbon monoxide-olefin polymeric, aluminium and master in the co-catalyst
The mol ratio of iron is preferably 148-196 in catalyst.
In the carbon monoxide-olefin polymeric of the above method, the R in preferably described major catalyst1-R5Be each independently selected from hydrogen,
Methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.R in more preferably described major catalyst1
And R5For ethyl, R2-R4It is hydrogen.
In the above-mentioned methods, using the weight of organic solvent as calculating benchmark, the weight content of water is 5~350ppm（That is base
Contain 5~350 × 10 in 1g organic solvent, composition-6G water）, preferably 20~260ppm, most preferably 50~200ppm.
The dosage of the major catalyst and co-catalyst can be entered according to the process conditions during concrete applications such as production scale and production equipment
Row selection.In a specific embodiment of the carbon monoxide-olefin polymeric, using the volume of organic solvent as calculating benchmark, the master
The content of catalyst is 2~500 μm of ol/L（That is the organic solvent based on 1L, 2~500 × 10 are contained in composition-6Mol's sponsors
Agent）, preferably 20~100 μm of ol/L.
The organic solvent is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane, excellent
It is selected from toluene and dimethylbenzene.
In the above-mentioned methods, the temperature of the reaction is -20~150 DEG C, preferably 0~80 DEG C, more preferably 5~35
℃.Pressure is 0.1~30MPa, with ethylene pressure rise oligomerization activity rise.It is described anti-in a specific embodiment
The reaction temperature answered is -20~50 DEG C.
The oligomerisation reaction condition that above-mentioned carbon monoxide-olefin polymeric application is related to is known to those skilled in the art
's.Concrete technical scheme can be as follows：Water, organic solvent, major catalyst and co-catalyst are added in reaction vessel, then in second
Alkene pressure is 0.1~30MPa and reaction temperature is to be reacted 30~100 minutes at -20~150 DEG C, after stopping reaction, is taken out a small amount of
Reactant mixture carries out gas-chromatography (GC) analysis.
By above-mentioned oligomerisation reaction, the ethylene oligomerization product of acquisition includes C4、C6、C8、C10、C12、C14、C16、C18、C20、C22
Deng；The selectivity of alpha-olefin can reach more than 96%.After ethylene oligomerization terminates, take out a small amount of reaction product and carry out GC points
Analysis.As a result show, oligomerization activity is up to 107g·mol-1·h-1More than.In addition, watery hydrochloric acid of the remaining reactant mixture with 5%
The ethanol solution of acidifying neutralizes, and does not obtain polymer.
According to the present invention, coordinated using positive propiono -1, the 10- phenanthroline condensed amine irons (II) of chlorination 2- shown in formula (I)
Owner's catalyst, the carbon monoxide-olefin polymeric containing aluminum cocatalyst, water and organic solvent are used for ethylene oligomerization, have on the contrary very high
Oligomerisation reaction activity, the selectivity of alpha-olefin is high, and oligomerisation reaction trigger it is rapid, operate steadily, be reproducible；Even
Under conditions of low aluminium/iron ratio, oligomerisation reaction still has extraordinary oligomerisation reaction activity；Even if oligomerisation is carried out at low temperature
Reaction, remain on higher oligomerisation reaction activity.Technical scheme in the present invention overcomes the skill of those skilled in the art
Art prejudice, achieve unexpected technique effect.
Embodiment
Below by way of specific embodiment, the invention will be further described and explanation, but does not form to any of the present invention
Limitation.
Embodiment 1
1. the positive propiono -1,10- phenanthroline contracting 2,6- diethylanilines of chlorination 2- close the synthesis of iron (II) complex
A.2- the synthesis of positive propiono -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 13.5ml tri-n-n-propyl aluminums (d=
0.82g/ml, 70.9mmol), 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 2.0g, yield 30%.The product is defined as chemical combination described in title a. through nuclear-magnetism and mass spectral analysis
Positive propiono -1, the 10- phenanthroline of thing, i.e. 2-.
Mass spectrum MS-EI：236.
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)；3.67 (m, J=7.24,
2H)；1.10 (t, J=7.4,3H).
B. the synthesis of the positive propiono -1,10- phenanthroline contracting 2,6- diethylanilines of part 2-
In two mouthfuls of flasks of 100ml equipped with water knockout drum, obtained 2- positive third is put into 0.50g (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 glassy yellow as leacheate, silica gel column chromatography
Product, weight 0.63g, yield 81%.The product confirms as compound described in title b. through nuclear-magnetism, mass spectrum and elementary analysis, i.e.,
Positive propiono -1,10- phenanthroline contracting 2,6- the diethylanilines of 2-.
Mass spectrum MS-EI：367.
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 (t, J=7.84 ,-CNCH2CH3,2H)；2.40 (m, J=7.52,
phCH2CH3,2H)；1.20 (t, J=7.30, phCH2CH3, 6H)；0.90 (t, J=7.32, CH3CH2CN,3H)。
Elementary analysis：C25H25N3(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. the positive propiono -1,10- phenanthroline contracting 2,6- diethylanilines of chlorination 2- 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.Positive propiono -1,10- phenanthroline contracting the 2,6- of 2- that will individually be obtained in 0.50g (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-
Positive propiono -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. positive propiono -1, the 10- phenanthrene of chlorination 2- is coughed up
Quinoline 2,6- of contracting diethylanilines close iron (II), and its elementary analysis result is as follows.
Elementary analysis：C25H25Cl2FeN3(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 reacts
Toluene, water and 1.37ml co-catalyst triethyl aluminum toluene solutions (concentration 715mol/ml) and 2ml are sponsored
The toluene solution of positive propiono -1,10- phenanthroline condensed amine irons (II) complexs of agent chlorination 2- (concentration is 2.5 μm of ol/ml)
It is added in 300ml stainless steel autoclave, makes cumulative volume be 100ml, Al/Fe=196, using the weight of toluene as calculating benchmark,
The weight content of water is 5ppm.When polymerization temperature reaches 30 DEG C, ethene is filled with into reactor, keeps 1MPa ethene pressure
Power, after stirring reaction 30min, take out a small amount of reaction product and carry out GC analyses：Oligomerization activity is 0.57 × 107g·mol-1
(Fe)·h-1, oligomer content is respectively C412.92%, C6~C1042.13%, C6~C1873.32% (wherein containing linear alpha-alkene
97.6%), C20~C2813.76%, K value 0.63.The ethanol solution that remaining mixture is acidified with 5% hydrochloric acid neutralizes, not
To polymer.Data are shown in Table 1.
Embodiment 2
With embodiment 1, difference is, the weight content amount of water is 20ppm.Data are shown in Table 1.
Embodiment 3
With embodiment 1, difference is, the weight content of water is 50ppm.Data are shown in Table 1.
Embodiment 4
With embodiment 1, difference is, the weight content of water is 120ppm.Data are shown in Table 1.
Embodiment 5
With embodiment 1, difference is, the weight content of water is 200ppm.Data are shown in Table 1.
Embodiment 6
With embodiment 1, difference is, the weight content of water is 260ppm.Data are shown in Table 1.
Embodiment 7
With embodiment 1, difference is, the weight content of water is 350ppm, and data are shown 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 shown 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 shown 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 shown 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 shown in Table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 200ppm, Al/Fe=500.Data are shown in Table 1.
Comparative example 1
With embodiment 1, difference is anhydrous in toluene.Data are shown in Table 1.
Table 1
"-" represents anhydrous
It can be seen from the data in Table 1 that using chlorination 2- positive propiono -1 provided by the invention including shown in formula (I),
10- phenanthroline condensed amine irons (II) complex major catalyst, containing aluminum cocatalyst（Such as triethyl aluminum）, water and organic solvent urge
Agent composition, the carbon monoxide-olefin polymeric is reacted for ethylene oligomerization, there is higher oligomerisation reaction activity, and alpha-olefin
Selectivity it is high；Under conditions of low-down aluminium/iron ratio, still with preferable oligomerisation reaction activity；Even in low
Temperature is lower to carry out oligomerisation reaction, remains on higher oligomerisation reaction activity.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (20)
1. a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including positive propiono -1, the 10- phenanthroline contractings of chlorination 2- shown in formula (I)
Amine closes iron (II) complex major catalyst, containing aluminum cocatalyst, water and organic solvent：
In formula, R1-R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro, wherein, the catalyst
In composition, using the weight of organic solvent as calculating benchmark, the weight content of water is 5~350ppm；The organic solvent is selected from
Toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the weight content of the water be 20~
260ppm。
3. carbon monoxide-olefin polymeric according to claim 2, it is characterised in that the weight content of the water be 50~
200ppm。
4. the carbon monoxide-olefin polymeric according to any one in claims 1 to 3, it is characterised in that the catalyst combination
In thing, using the volume of organic solvent as calculating benchmark, the content of the major catalyst is 2~500 μm of ol/L.
5. carbon monoxide-olefin polymeric according to claim 4, it is characterised in that the content of the major catalyst is 20~100 μ
mol/L。
6. according to the carbon monoxide-olefin polymeric of any one in claims 1 to 3, it is characterised in that in the co-catalyst aluminium with
The mol ratio of iron is 30 to less than 900 in major catalyst：1.
7. 6 carbon monoxide-olefin polymeric is wanted according to right, it is characterised in that aluminium rubs with iron in major catalyst in the co-catalyst
Your ratio is 100-700:1.
8. carbon monoxide-olefin polymeric according to claim 6, it is characterised in that in the co-catalyst in aluminium and major catalyst
The mol ratio of iron is 148-196：1.
9. the carbon monoxide-olefin polymeric according to any one in claims 1 to 3, it is characterised in that in the major catalyst
R1-R5It is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.
10. carbon monoxide-olefin polymeric according to claim 9, it is characterised in that R1And R5For ethyl, and R2-R4It is hydrogen.
11. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the organic solvent is selected from toluene and diformazan
Benzene.
12. the carbon monoxide-olefin polymeric according to any one in claims 1 to 3, it is characterised in that the co-catalysis containing aluminium
Agent is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound.
13. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that described containing aluminum cocatalyst is alkyl calorize
Compound.
14. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the formula of the alkyl aluminum compound is
AlRnXm, wherein R is each independently straight or branched C1-C8Alkyl；X is halogen；N be 1~3 integer, m be 0~2 it is whole
Number, and m+n is equal to 3.
15. carbon monoxide-olefin polymeric according to claim 14, it is characterised in that in the formula of the alkyl aluminum compound, X
For chlorine or bromine.
16. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that, the alkyl aluminum compound is selected from front three
Base aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and dichloride
Aluminium ethide.
17. carbon monoxide-olefin polymeric according to claim 16, it is characterised in that the alkyl aluminum compound is triethyl group
Aluminium.
18. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the aikyiaiurnirsoxan beta is C1-C4Alkyl alumina
Alkane, wherein C1-C4Alkyl is the alkyl of straight or branched.
19. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the aikyiaiurnirsoxan beta be selected from MAO,
Modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide.
20. carbon monoxide-olefin polymeric according to claim 12, it is characterised in that the aikyiaiurnirsoxan beta is MAO.
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