CN103804428B - The preparation method of a kind of coordination compound and the application of coordination compound - Google Patents
The preparation method of a kind of coordination compound and the application of coordination compound Download PDFInfo
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- CN103804428B CN103804428B CN201210446003.9A CN201210446003A CN103804428B CN 103804428 B CN103804428 B CN 103804428B CN 201210446003 A CN201210446003 A CN 201210446003A CN 103804428 B CN103804428 B CN 103804428B
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- 0 *Cc1cnc2c3ncccc3ccc2c1 Chemical compound *Cc1cnc2c3ncccc3ccc2c1 0.000 description 1
- XSTIBSDGNUTMPP-UHFFFAOYSA-N CC(c1nc(c2ncc(C)cc2cc2)c2cc1)=O Chemical compound CC(c1nc(c2ncc(C)cc2cc2)c2cc1)=O XSTIBSDGNUTMPP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides the preparation method of a kind of coordination compound and the application of coordination compound.It is specifically related to one and prepares the application as ethylene oligomerisation catalyst of the method for 2 acetyl group 1,10 phenanthroline condensed amine Ferrox. (II) coordination compounds and thus obtained coordination compound.The method is by 1, and 10 phenanthroline start to prepare 2 acetyl group 1,10 phenanthroline, 2 acetyl group 1,10 phenanthroline and substituted aniline are condensed to yield 2 acetyl group 1,10 phenanthroline contracting amine ligands subsequently, then this part and Ferrox. react acquisition target product.This synthetic method step is few, and technique is simple, reduces catalyst preparation cost, and the coordination compound generated dissolubility in ethylene oligomerization reacts increases, and the conversion ratio of reaction improves, and reactivity can accept, and industrial prospect is wide.
Description
Technical field
The present invention relates to the preparation method of a kind of coordination compound and the application of coordination compound, replace more particularly to acetyl group
1, the preparation method of 10-phenanthroline condensed amine iron (II) coordination compound, and this coordination compound thus prepared is as ethylene oligomerization
The application of catalyst.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry.By oligomerisation reaction, can be by cheap little
Molecular olefine is transformed into and has high value-added product.Ethylene oligomerization product linear alpha-alkene (LAO) is important organising
Work raw material.Such as LAO C4-C30 can be used as preparing daily cleaning agent, flotation agent, emulsifying agent, the emollient component of refrigeration machine and brill
Hole liquid emollient component, plasticizer, various additives, low viscosity artificial oil, polymer and copolymer, oil and oil product add
Agent, senior alkylamines, senior organo-aluminum compound, senior alkaryl Hydrocarbon, high fatty alcohol and fatty acid, epoxidation
Additive of thing and heat carrier etc..Also can composite adhesives, sealant and coating on the basis of LAO C20-C30.In recent years,
Along with the development of polyolefin industry, the interior demand rapid development to alpha-olefin of world wide.Wherein most α-
Alkene is obtained by ethylene oligomerization preparation.
Catalyst used by ethylene oligomerization method mainly has nickel system, chromium system, zirconium system and aluminum system etc., and in recent years, Brookhart is little
Group (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472,1999), Gibson
Group (Gibson, V.C. et al., Chem.Commun., 1998,849-850；Chem.Eur.J., 2000,2221-2231) divide
Do not find that the trident pyridinimine coordination compound of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation, not only the catalysis work of catalyst
Property is the highest, and the selectivity of alpha-olefin is the highest.The most this kind of coordination compound has the strongest prospects for commercial application.
Institute of Chemistry, Academia Sinica grandson Wenhua research group (Sun Wenhua et al., Organometallics 2006,
25,666-677) using 1 first, 10-phenanthroline is that Material synthesis three tooth nitrogen imine composition carrys out catalyzed ethylene oligomerisation, and such is urged
The catalysis activity and selectivity of agent is the highest.But, this catalyst dissolubility in a solvent is very poor, causes at ethylene oligomerization
In successive reaction, catalyst just settles when not arriving reactor in pipeline, has influence on the conversion ratio of reaction and catalyst
Utilization rate.
Summary of the invention
It is an object of the invention to provide a kind of new method preparing solubility ethylene oligomerisation catalyst and thus prepare
The application of catalyst.
The invention provides acetyl group substituted 1,10-phenanthroline condensed amine iron (II) coordination compound that a kind of formula is (i) shown
Preparation method:
Wherein,
R1-R5It is each independently selected from hydrogen, C1-C6Alkyl, halogen, C1-C6One in alkoxyl or nitro；Preferably,
Described R1-R5It is each independently hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitro.
Described method comprises the steps:
A) synthesis of 2-acetyl group-1,10-phenanthroline: make 1,10-phenanthroline and triethyl aluminum Et3Al deposits at organic solvent
React under, then sequentially pass through hydrolysis and the oxidation reaction with Nitrobenzol, it is thus achieved that formula (ii) compound: 2-acetyl group-
1,10-phenanthroline;
B) synthesis of 2-acetyl group-1,10-phenanthroline contracting amine ligand: make formula (ii) compound and formula (iii) compound exist
P-methyl benzenesulfonic acid reacts as in the presence of catalyst, it is thus achieved that formula (iv) compound;
Wherein, R1-R5As formula (i) defines；And
C) synthesis of solubility 2-acetyl group-1,10-phenanthroline condensed amine iron (II) coordination compound: make formula (iv) compound with
Ferrox. reacts, it is thus achieved that formula (i) shown compound
Wherein, R1-R5As formula is (i) defined.
In the present invention,
Described C1-C6Alkyl is saturated straight chain or the branched hydrocarbyl of 1-6 carbon atom.It is selected from following compound: first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl
Or Sec-Hexyl；Preferably methyl, ethyl, n-pro-pyl or isopropyl.
Described halogen is fluorine, chlorine, bromine or iodine；Preferably fluorine, chlorine or bromine.
Described C1-C6Alkoxyl is C1-C6 alkyl and oxygen atom connects the group obtained；It is selected from following chemical combination
Thing: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, positive penta oxygen
Base, secondary amoxy, positive hexyloxy or secondary hexyloxy；Preferably methoxy or ethoxy.
What in described 1,10-phenanthroline condensed amine iron (II) coordination compound, ferrum (II) represented is ferrous iron.
R in particularly preferred embodiment of the invention, in formula (i) compound1And R5For ethyl and R2-R4All
For hydrogen.
In the step a) of preparation method of the present invention, 1,10-phenanthroline is 1:0.5～1 with the mol ratio of triethyl aluminum:
4.5, preferably 1:2.0～1:2.6；And/or 1, the mol ratio of 10-phenanthroline and Nitrobenzol is 1:0.5～1:30, preferably 1:15～
1:20。
At least one in following compound of organic solvent described in step a): toluene, hexamethylene, ether, tetrahydrochysene
Furan, ethanol, benzene, dimethylbenzene or dichloromethane；Preferably toluene.Utilize these organic solvents, prepare 1,10-phenanthroline solution,
Wherein solution concentration is 10 ~ 200g/L.
Reaction described in step a) is to carry out under inert gas shielding, the preferred argon of described noble gas or nitrogen.1,
10-phenanthroline can use anhydrous 1,10-phenanthroline, it is possible to use hydration 1,10-phenanthroline, the most anhydrous 1,10-phenanthrene is coughed up
Quinoline.Triethyl aluminum generally uses with itself.
Described in step a) 1, first 10-phenanthroline and triethyl aluminum react is-80～-60 DEG C in reaction temperature, preferably-
70～-60 DEG C at carry out, the most again reactant mixture is warming up to 20～40 DEG C and reacts.
The described hydrolysis of step a) is first carried out at temperature is for-60～0 DEG C, is heated up by reactant mixture more again
React to 20～40 DEG C.
Preferably, in the method for the invention, described reaction generally reaction temperature (-80～-60 DEG C, preferably-70～-
60 DEG C) under to 1, in 10-phenanthroline solution add triethyl aluminum, such as dropping triethyl aluminum and carry out.After charging, upper
State under reaction temperature stir 18～28 hours, preferably 18～20 hours.Afterwards, reactant mixture is warming up to 20～40 DEG C stir again
Mix 5～10 hours, preferably 10 hours, to react more completely.
Then add water (preferably deionized water) hydrolyze at-60～0 DEG C.Such as, reactant mixture is remained-30 DEG C to add
Enter water to be hydrolyzed, be preferably added to deionized water and be hydrolyzed.In hydrolytic process, having bubble to emerge, hydrolysis is until bubble no longer
Till emerging.For more complete hydrolysis, reactant mixture is warming up to 20～40 DEG C again and stirs 5～10 hours.Then separatory, takes
Go out organic facies.In order to isolate required product as much as possible, the most also inorganic phase organic solvent is extracted, by having of obtaining
The organic facies that machine phase obtains with separatory before merges, and the organic solvent that can use this can be ethyl acetate, acetone, dichloro
Methane or its mixture etc., preferably dichloromethane.
After the organic facies removed under reduced pressure solvent of organic facies or merging, add Nitrobenzol backflow (such as at 210 DEG C) 10 ~
48 hours, preferably 15 ~ 24 hours.Filter afterwards, removed under reduced pressure solvent.By the acetic acid second that volume ratio is 1:1 ~ 1:5, preferably 1:2
Ester: the mixed solution of petroleum ether is leacheate, carries out silica gel column chromatography, obtains solid product, i.e. formula (ii) compound.
In the step b) of the preparation method of the present invention,
Step b) Chinese style (ii) shown in the mol ratio of 2-acetyl group-1,10-phenanthroline and formula substituted aniline (iii) be
1∶1~1:5.Preferably, formula (ii) shown in 2-acetyl group-1,10-phenanthroline and formula substituted aniline (iii) the most aqueous and
The organic solvent of oxygen reacts and prepares.
The organic solvent that this can be used selected from toluene, hexamethylene, ether, oxolane, ethanol, benzene, dimethylbenzene, two
Chloromethanes or its mixture etc., preferably toluene.This reaction is that catalyst is carried out under reflux with p-methyl benzenesulfonic acid (p-TsOH), example
As carried out at 110 DEG C.The quality of p-methyl benzenesulfonic acid and reaction-ure mixture (i.e. formula (ii) compound and formula (iii) compound
Mass ratio is 0.001: 1 ~ 0.02:1, and the response time is 5 ~ 10 hours, with TLC monitoring reaction, treats that 2-acetyl group-1,10-phenanthrene are coughed up
After completion of the reaction, removed under reduced pressure solvent, then by the ethyl acetate that volume ratio is 1:1 ~ 1:9, preferably 1:4: mixing of petroleum ether for quinoline
Close solution and obtain target product as leacheate, silica gel column chromatography, i.e. formula (iv) compound.Target product is through nuclear-magnetism and mass spectrum table
Levy.
In a preferred embodiment of the inventive method, formula (iii) shown in substituted aniline be individual by 1-5, preferably
1-4, more preferably 1-3 substituent group identical or different, selected from C1-C6 alkyl, C1-C6 alkoxyl, halogen and nitro takes
The aniline in generation；
Preferably, described substituted aniline one in following compound: 2-aminotoluene, 3-monomethylaniline., 4-
Monomethylaniline., 23 dimethyl aniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-diformazan
Base aniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-MEA, 2-ethyl-
6-monomethylaniline., 2-isopropyl aniline, 2,6-diethylaniline, 2,6-diisopropyl aniline, 2-fluoroaniline, 2-fluoro-4-methyl
Aniline, 2-fluoro-5-monomethylaniline., 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,
4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloro
Aniline, 2,3,4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, 2-bromo-4-monomethylaniline., 2-
Bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromo aniline, 2,6-bis-bromo-4-monomethylaniline., 2,6-bis-bromo-4-chloroaniline,
The bromo-6-of 2,4,6-tribromaniline, 2-chloro-4-fluoroaniline, the bromo-4-of 2-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitro
Aniline, 4-aminoanisole, 2-methyl-4-aminoanisole and 4-phenetidine；Most preferably 2,6-diethylaniline.
In the step c) of the preparation method of the present invention,
Step c) Chinese style (iv) shown in 2-acetyl group-1,10-phenanthroline ligand and Ferrox. or ferrocene mole
Ratio is 1:1-1.2:1, preferably 1.05:1-1.1:1.
Preferably, Ferrox., under the protections such as noble gas such as nitrogen, is dissolved in and does not contains by the reaction described in step c)
In the organic solvent of water and oxygen, formed 0.001 ~ 0.1g/ml solution, for this organic solvent that can use selected from toluene,
Hexamethylene, ether, oxolane, ethanol, benzene, dimethylbenzene, dichloromethane or its mixture etc., preferably oxolane.Individually will
2-acetyl group-1,10-phenanthroline contracting amine ligand is (iv) dissolved in the most aqueous organic solvent with oxygen, forms 0.01 ~ 0.1g/
The solution of ml, the organic solvent that can use this is also selected from toluene, hexamethylene, ether, oxolane, ethanol, benzene, diformazan
Benzene, dichloromethane or its mixture etc., preferably oxolane.Then, under the protections such as noble gas such as nitrogen, above-mentioned two are merged
Solution (the most at room temperature merges), and stirs certain time, such as room temperature under room temperature under the protections such as noble gas such as nitrogen
Under be stirred overnight.With TLC monitoring reaction, after question response is complete, by sucking filtration, the routine post-processing approach pair such as wash and be dried
Product carries out post processing, obtains formula (i) compound coordination compound.Described washing can use organic solvent such as absolute ether to enter
OK.Coordination compound is characterized by elementary analysis and infrared spectrum.
Present invention also offers a kind of formula prepared by this method (i) 2-acetyl group-1,10-phenanthroline condensed amine oxalic acid sub-
Ferrum (II) coordination compound is as catalyst for oligomerization application in olefin(e) oligomerization；The preferably application in ethylene oligomerization.
Now involved oligomerisation reaction condition such as can use known to being to those skilled in the art
The method of the pressurization ethylene oligomerization as described in Chinese patent application publication number CN1850339A carries out oligomerisation, and described document is to draw
Mode be expressly incorporated herein.
According to the present invention, described ethylene oligomerization can be performed as follows: adds organic solvent in reaction vessel, help and urge
Agent and as prepared by the present invention of major catalyst 2-acetyl group-1,10-phenanthroline condensed amine Ferrox. (II) coordinate
Thing, then reacts 30-100 minute at ethylene pressure is 0.1-30MPa and reaction temperature is 20-150 DEG C, obtains ethylene oligomerization
Product.It is subsequently cooled to-10-10 DEG C, takes out a small amount of oligomerization product and divide with laggard row gas chromatogram (GC) with in the dilute hydrochloric acid of 5%
Analysis.
Invention olefin oligomerisation organic solvent is selected from toluene, hexamethylene, ether, oxolane, ethanol, benzene, dimethylbenzene
Or at least one in dichloromethane, preferably toluene.
In the process for oligomerization of olefine of the present invention, in addition to above-mentioned major catalyst, also should use promoter.Described helping is urged
Agent is selected from aikyiaiurnirsoxan beta and/or alkyl aluminum compound, preferably alkyl aluminum compound.
The formula of described alkyl aluminum compound is AlRnXm, wherein R is each independently straight or branched C1-C8 alkyl；X
It is respectively halogen, preferably chlorine or bromine；N is the integer of 1-3, and m is the integer of 0-2, and m+n is equal to 3；
Preferably, at least one in following compound of described alkyl aluminum compound: trimethyl aluminium, triethyl group
Aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride or ethylaluminium dichloride etc., excellent
Select triethyl aluminum.
Described aikyiaiurnirsoxan beta is C1-C4 alkylaluminoxane, and wherein C1-C4 alkyl is the alkyl of straight or branched；Preferably institute
State at least one in the following compound of aikyiaiurnirsoxan beta: MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl
Base aikyiaiurnirsoxan beta etc.；More preferably MAO.
2-acetyl group-1,10-phenanthroline condensed amine iron (II) catalyst being prepared by the method for the present invention is neat as ethylene
Poly-major catalyst, this major catalyst is conventional with the consumption of promoter, see, for example, CN1850339A and middle promulgated by the State Council
Bright patent application 201010138127.1.
When the major catalyst prepared by the present invention and promoter are used for ethylene oligomerization, preferred oligomerisation reaction temperature
Usually 5-80 DEG C, pressure is 1-5MPa, and the response time is 30-60 minute.
2-acetyl group-1 prepared by the application of the invention method, 10-phenanthroline condensed amine Ferrox. (II) coordinates
Thing carries out ethylene oligomerization reaction, it is thus achieved that ethylene oligomerization product include C4, C6, C8, C10, C12, C14, C16, C18, C20, C22
Deng；The selectivity of alpha-olefin can reach more than 98%；After ethylene oligomerization terminates, take out a small amount of reactant mixture with 5%
In dilute hydrochloric acid and after carry out the result of GC analysis and show, oligomerization activity is high.It addition, remaining reactant mixture with through 5% dilute salt
The ethanol solution of acid acidifying neutralizes, and when promoter uses alkyl aluminum compound, does not has polymer to produce.
Compared with prior art, present invention have the advantage that
The catalyst generated dissolubility in ethylene oligomerization solvent increases, it is possible to participates in reaction with less granule, converts
Rate improves, and the utilization rate of catalyst improves, and oligomerization activity can accept, and industrial prospect is wide.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.But the invention is not restricted to following example.
Embodiment 1
1. catalyst 2-acetyl group-1,10-phenanthroline contracting 2,6-diethylaniline closes the conjunction of Ferrox. (II) coordination compound
Become
A) synthesis (see following reaction process) of 2-acetyl group-1,10-phenanthroline
1,10-phenanthroline 5.1g (28.3mmol) is put into, under nitrogen protection and magnetic agitation in 250ml there-necked flask
Dissolve with 100ml toluene.In there-necked flask, 10ml triethyl aluminum (70.8mmol) is under agitation slowly dripped at-60 DEG C,
Within about 15 minutes, drip complete, continue stirring 18h at such a temperature, be warming up to about 30 DEG C afterwards, continue stirring 10h.Then
Reactant mixture is cooled to about-30 DEG C, is slowly added into 50ml distilled water wherein, then is warming up to 30 DEG C of stirring 10h.Then
Separatory, takes out organic facies, and inorganic phase dichloromethane extracts three times, and the consumption of each dichloromethane is 20ml, merges each organic
Phase.Removed under reduced pressure solvent.Afterwards, add 50ml Nitrobenzol (1.205g/ml), and reflux about 18 hours in 210 DEG C.Filter,
Under less than 10mmHg, Nitrobenzol is evaporated off, obtains dark thick shape liquid substance.By ethyl acetate: petroleum ether=1:2 (volume
Than) mixed solution be leacheate, gained dark thick shape liquid substance is carried out silica gel column chromatography, obtains brown product, weight
1.9g, productivity 30%.This product is defined as compound described in title a., i.e. 2-acetyl group-1,10-through nuclear-magnetism and mass spectral analysis
Phenanthroline.
Mass spectrum MS-EI:222.
Nmr analysis:1H NMR (300MHz, CDCl3): δ 9.26 (d, J=3.9Hz, 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)；3.09 (s, 3H, CH3)。
B) synthesis (see following reaction process) of part 2-acetyl group-1,10-phenanthroline contracting 2,6-diethylaniline
Equipped with in two mouthfuls of flasks of 100ml of water knockout drum, put into the 2-acetyl obtained in 0.47g (2.12mmol) step a)
Base-1,10-phenanthroline and 0.95g (6.36mmol) 2,6-diethylaniline (mol ratio is 1:3) and 35ml is the most aqueous and oxygen
The toluene of gas.Equipped with condensing tube on water knockout drum, add p-methyl benzenesulfonic acid 0.01g and reflux at 110 DEG C, react 6 hours.Decompression removes
Fall solvent, by ethyl acetate: the mixed solution of petroleum ether=1:4 (volume ratio) is as leacheate, and silica gel column chromatography obtains glassy yellow and produces
Thing, weight 0.61g, productivity is 81%.This product confirms as compound described in title b., i.e. 2-through nuclear-magnetism, mass spectrum and elementary analysis
Acetyl group-1,10-phenanthroline contracting 2,6-diethylaniline.
Mass spectrum MS-EI:353.
Nmr analysis:1H NMR (300MHz, CDCl3): δ 9.25 (dd, J=3.0Hz, 1H)；8.80 (d, J=8.3Hz, 1H)；
8.35 (d, J=8.3Hz, 1H)；8.27 (dd, J=7.8Hz, 1H)；7.86 (s, 2H)；7.66 (m, 1H)；7.15 (d, J=7.6Hz,
2H)；6.96 (t, J=7.5Hz, 1H)；2.58 (s, 3H, CH3)；2.43 (m, 4H, CH2CH3), 1.16 (t, J=7.5Hz, 6H,
CH2CH3)。
13C NMR (75MHz, CDCl3): δ 167.8,156.2,150.7,148.0,146.4,145.2,136.5,131.1,
129.5,129.0,127.5,126.5,126.0,123.4,122.9,120.8,24.6,17.3,13.7.
Elementary analysis: C24H23N3(353.46), theoretical value: C, 81.55；H, 6.56；N, 11.89.Measured value: C, 80.88；
H, 6.59；N, 11.78.
C) 2-acetyl group-1,10-phenanthroline contracting 2,6-diethylaniline closes the synthesis of Ferrox. (II) (see following reaction
Flow process)
Under nitrogen protection, by the most aqueous for 0.18g (1.25mmol) Ferrox. 20ml and oxygen in two mouthfuls of flasks
Oxolane dissolve.2-acetyl group-1,10-phenanthroline contracting the 2,6-that individually will obtain in 0.48g (1.36mmol) step b)
Diethylaniline is dissolved in the most aqueous oxolane with oxygen of 20ml.The most at room temperature nitrogen protection is lower merges above-mentioned two
Solution.Reaction is carried out at once, and solution presents grey black.At room temperature, nitrogen protection is stirred overnight.Use TLC monitoring, until 2-
Acetyl group-1,10-phenanthroline contracting 2,6-diethylbenzene amine ligand substantially disappears.Sucking filtration, washs with absolute ether.Vacuum
It is dried to obtain silver gray solid.This solid is defined as compound described in title c., i.e. 2-acetyl group-1,10-phenanthroline contracting 2,6-
Diethylaniline closes Ferrox. (II), and its elementary analysis result is as follows.
Elementary analysis: C26H23O4FeN3(497.34), theoretical value: C, 60.09；H, 4.90；N, 8.76.Measured value: C,
60.03；H, 4.83；N, 8.75.
2. ethylene oligomerization reaction
By toluene and 0.53ml triethyl aluminum toluene solution (concentration is 0.74mol/l) and 8ml major catalyst 2-acetyl
Base-1,10-phenanthroline contracting 2,6-diethylaniline closes the toluene solution of Ferrox. (II) (2.0 μm ol) and joins 300ml's
In stainless steel autoclave, making cumulative volume is 100ml, Al/Fe=196.When polymerization temperature reaches 35 DEG C, it is filled with in reactor
Ethylene, keeps the ethylene pressure of 1MPa, stirring reaction 30min.Afterwards, take out, with syringe, the dilute hydrochloric acid that spiece is with 5%
GC analysis is carried out: oligomerization activity is 1.62 × 106g mol-1 (Fe) h after neutralization-1, oligomer content is respectively C415.0%,
C6～C1068.3%, C6～C1888.0% (wherein containing linear alpha-alkene 98.0%), C20～C281.0%, K value 0.62.Remaining
The ethanol solution that mixture is acidified with the hydrochloric acid of 5% neutralizes, and does not obtain polymer.
Embodiment 2
Dissolubility contrasts, with chlorination 2-acetyl group-1, and 10-phenanthroline contracting 2, as a example by 6-diethylaniline closes ferrum (II), its
At ethylene oligomerisation catalyst solvent, as toluene is slightly soluble or indissoluble, after ul-trasonic irradiation, still present graininess；And this
It is solvable in toluene that 2-acetyl group-1,10-phenanthroline contracting 2,6-diethylaniline in bright closes Ferrox. (II).
Embodiment 3
Repeating the step 1 of embodiment 1, difference is that 6-diethylaniline replaces successively by 2 in embodiment 1 step b
It is changed to following substituted aniline: 2-aminotoluene, 3-monomethylaniline., 4-monomethylaniline., 23 dimethyl aniline, 2,4-dimethyl
Aniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethyl
Aniline, 4-bromo-2,6-dimethylaniline, 2-MEA, 2-ethyl-6-monomethylaniline., 2-isopropyl aniline, 2,6-diisopropyl
Base aniline, 2-fluoroaniline, 2-fluoro-4-monomethylaniline., 2-fluoro-5-monomethylaniline., 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,
6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,
6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloro-benzenes
Amine, 2-bromaniline, 2-bromo-4-monomethylaniline., 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromo aniline, 2,6-bis-
Bromo-4-monomethylaniline., 2,6-bis-bromo-4-chloroaniline, 2,4,6-tribromaniline, the bromo-6-of 2-chloro-4-fluoroaniline, the bromo-4-of 2-are chloro-
6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-aminoanisole, 2-methyl-4-aminoanisole or 4-second
Epoxide aniline；It is correspondingly made available each 2-second that 2-acetyl group-1,10-phenanthroline is formed with aforementioned each substituted aniline in stepb
Acyl group-1,10-phenanthroline contracting amine ligand, these part products are confirmed each via nuclear-magnetism, mass spectral analysis and elementary analysis,
And in step c, it is correspondingly made available aforementioned each 2-acetyl group-1,10-phenanthroline contracting amine ligand and Ferrox. or ferrocene
Coordination compound, these coordination compounds are confirmed each via elementary analysis.
These are only presently preferred embodiments of the present invention, it is impossible to limit the scope of the present invention with this.The most every Yi Benfa
Change that bright claim is made and modification, all should still remain within the scope of the patent.
Claims (29)
1. the preparation method of acetyl group substituted 1,10-phenanthroline condensed amine iron (II) coordination compound shown in a formula (i):
Wherein,
R1-R5It is each independently selected from the one in hydrogen, C1-C6 alkyl, halogen, C1-C6 alkoxyl or nitro；Described method
Comprise the steps:
A) synthesis of 2-acetyl group-1,10-phenanthroline: make 1,10-phenanthroline and triethyl aluminum Et3Al is in the presence of an organic
Reacting, carry out oxidation reaction with Nitrobenzol, it is thus achieved that formula (ii) compound: 2-acetyl group-1 after being then passed through hydrolysis, 10-is luxuriant and rich with fragrance
Cough up quinoline；
B) synthesis of 2-acetyl group-1,10-phenanthroline contracting amine ligand: make formula (ii) compound and formula (iii) compound to first
Benzenesulfonic acid reacts as in the presence of catalyst, it is thus achieved that formula (iv) compound；
Wherein, R1-R5As formula (i) defines；And
C) synthesis of solubility 2-acetyl group-1,10-phenanthroline condensed amine iron (II) coordination compound: make formula (iv) compound and oxalic acid
Ferrous reaction, it is thus achieved that compound shown in formula (i)；
Wherein, R1-R5As formula (i) is defined.
Method the most according to claim 1, it is characterised in that described R1-R5It is each independently hydrogen, methyl, ethyl, just
Propyl group, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl or nitro.
Method the most according to claim 1, it is characterised in that step a) described 1,10-phenanthroline rubs with triethyl aluminum
That ratio is 1:0.5～1:4.5；And/or the mol ratio of 1,10-phenanthroline and Nitrobenzol is 1:0.5～1:30.
Method the most according to claim 3, it is characterised in that step a) described 1,10-phenanthroline rubs with triethyl aluminum
That ratio is 1:2.0～1:2.6；And/or the mol ratio of 1,10-phenanthroline and Nitrobenzol is 1:15～1:20.
Method the most according to claim 1, it is characterised in that the organic solvent described in step a) is in following compound
At least one: toluene, hexamethylene, ether, oxolane, ethanol, benzene, dimethylbenzene or dichloromethane.
Method the most according to claim 1, it is characterised in that the reaction described in step a) is to enter under inert gas shielding
OK.
Method the most according to claim 6, it is characterised in that described noble gas is argon or nitrogen.
Method the most according to claim 1, it is characterised in that 1 described in step a), 10-phenanthroline is anti-with triethyl aluminum
First should carry out at reaction temperature is for-80～-60 DEG C, the most again reactant mixture is warming up to 20～40 DEG C and react.
Method the most according to claim 8, it is characterised in that it is characterized in that, 1 described in step a), 10-phenanthroline with
First triethyl aluminum reaction is carried out at reaction temperature is for-70～-60 DEG C, the most again reactant mixture is warming up to 20～40 DEG C
React.
Method the most according to claim 1, it is characterised in that the described hydrolysis of step a) first temperature be-60～
Carry out at 0 DEG C, the most again reactant mixture is warming up to 20～40 DEG C again and reacts.
11. methods according to claim 1, it is characterised in that 2-acetyl group-1 shown in step b) Chinese style (ii), 10-
Phenanthroline is 1:1～1:5 with the mol ratio of the substituted aniline shown in formula (iii).
12. methods according to claim 1, it is characterised in that the substituted aniline shown in step b) Chinese style (iii) is selected from quilt
1-5 identical or different, selected from the substituted aniline of substituent group of C1-C6 alkyl, C1-C6 alkoxyl, halogen and nitro.
13. methods according to claim 12, it is characterised in that the substituted aniline shown in step b) Chinese style (iii) is selected from
The aniline that substituent group identical or different by 1-4, selected from C1-C6 alkyl, C1-C6 alkoxyl, halogen and nitro replaces.
14. methods according to claim 12, it is characterised in that the substituted aniline shown in step b) Chinese style (iii) is selected from
The aniline that substituent group identical or different by 1-3, selected from C1-C6 alkyl, C1-C6 alkoxyl, halogen and nitro replaces.
15. methods according to claim 12, it is characterised in that described substituted aniline is selected from following compound
Kind: 2-aminotoluene, 3-monomethylaniline., 4-monomethylaniline., 23 dimethyl aniline, 2,4-dimethylaniline, 2,5-dimethyl
Aniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, the bromo-2,6-of 4-
Dimethylaniline, 2-MEA, 2-ethyl-6-monomethylaniline., 2-isopropyl aniline, 2,6-diethylaniline, 2,6-bis-are different
Propyl group aniline, 2-fluoroaniline, 2-fluoro-4-monomethylaniline., 2-fluoro-5-monomethylaniline., 2,4 difluorobenzene amine, 2,5-difluoroaniline,
2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,
5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloro-benzenes
Amine, 2-bromaniline, 2-bromo-4-monomethylaniline., 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromo aniline, 2,6-bis-
Bromo-4-monomethylaniline., 2,6-bis-bromo-4-chloroaniline, 2,4,6-tribromaniline, the bromo-6-of 2-chloro-4-fluoroaniline, the bromo-4-of 2-are chloro-
6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-aminoanisole, 2-methyl-4-aminoanisole or 4-second
Epoxide aniline.
16. methods according to claim 15, it is characterised in that described substituted aniline is 2,6-diethylaniline.
17. methods according to claim 1, it is characterised in that 2-acetyl group-1 shown in step c) Chinese style (iv), 10-
Phenanthroline contracting amine ligand is 1-1.2:1 with the mol ratio of Ferrox..
18. methods according to claim 17, it is characterised in that 2-acetyl group-1 shown in step c) Chinese style (iv), 10-
Phenanthroline contracting amine ligand is 1.05-1.1:1 with the mol ratio of Ferrox..
Acetyl group substituted 1 shown in 19. 1 kinds of formulas (i) prepared according to the method according to any one of claim 1-18,
10-phenanthroline condensed amine iron (II) coordination compound is as catalyst for oligomerization application in olefin(e) oligomerization.
20. application according to claim 19, it is characterised in that described alkene is ethylene.
21. application according to claim 19, it is characterised in that described olefin(e) oligomerization is for there was added in reaction vessel
Machine solvent, promoter and cough up as the substituted 1,10-phenanthrene of the acetyl group shown in the formula (i) prepared by the present invention of major catalyst
Quinoline contracting amine closes ferrum (II) coordination compound, then reacts 30-at olefin pressure is 0.1-30MPa and reaction temperature is 20-150 DEG C
100 minutes, reaction obtained alkene oligomer.
22. application according to claim 19, it is characterised in that described organic solvent selected from toluene, hexamethylene, ether,
At least one in oxolane, ethanol, benzene, dimethylbenzene or dichloromethane.
23. application according to claim 22, it is characterised in that described organic solvent is selected from toluene.
24. application according to claim 19, it is characterised in that promoter is selected from aikyiaiurnirsoxan beta and/or alkyl aluminum chemical combination
Thing.
25. application according to claim 24, it is characterised in that promoter is alkyl aluminum compound.
26. application according to claim 24, it is characterised in that the formula of alkyl aluminum compound is AlRnXm, wherein R is each
From independently be straight or branched C1-C8 alkyl；X is respectively halogen；N is the integer of 1-3, and m is the integer of 0-2, and m+n etc.
In 3.
27. application according to claim 24, it is characterised in that described aikyiaiurnirsoxan beta is C1-C4 alkylaluminoxane, wherein
C1-C4 alkyl is the alkyl of straight or branched.
28. application according to claim 27, it is characterised in that described aikyiaiurnirsoxan beta is selected from following compound at least
A kind of: MAO, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide.
29. application according to claim 19, it is characterised in that the reaction temperature of described oligomerisation is 5-80 DEG C, pressure
For 1-5MPa, the response time is 30-60 minute.
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| 2-Ethyl-ketimino-1,10-phenanthroline iron(II) complexes as highly active catalysts for ethylene oligomerization;Min Zhang等;《Journal of Molecular Catalysis A: Chemical》;ELSEVIER;20100125;第320卷(第1-2期);第92-96页 * |
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