CN105478165B - A kind of ethylene oligomerization carbon monoxide-olefin polymeric - Google Patents
A kind of ethylene oligomerization carbon monoxide-olefin polymeric Download PDFInfo
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- CN105478165B CN105478165B CN201410535209.8A CN201410535209A CN105478165B CN 105478165 B CN105478165 B CN 105478165B CN 201410535209 A CN201410535209 A CN 201410535209A CN 105478165 B CN105478165 B CN 105478165B
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Abstract
The invention discloses a kind of carbon monoxide-olefin polymeric for ethylene oligomerization reaction process, including shown in formula (I) the diacetyl quinoline of major catalyst chlorination 2,8 contracting amine close iron (II) complex, containing aluminum cocatalyst and organic solvent.
Description
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of catalyst combination for ethylene oligomerization reaction process
Thing.
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.
Institute of Chemistry, Academia Sinica reports a kind of for ethylene oligomerization and the catalyst of polymerization
(Organometallics2010,29,1168-1173), the catalyst are chlorination 2, and 8- diacetyl quinoline contractings amine closes iron (II)
Complex, under the effect of co-catalyst MAO, the central metal in the metallic aluminium and major catalyst in co-catalyst
Mol ratio be 1500~3000, and reaction temperature be 40~100 DEG C when, oligomerisation and polymerization activity have been up to 106g·
mol(Fe)-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.
Today, it is generally accepted that water is very unfavorable to ethylene oligomerization reaction process, CN200810111717.8 is disclosed
A kind of method of ethylene oligomerization, it is strict controlled in the environment of anhydrous and oxygen-free and carries out, therefore the reaction of current ethylene oligomerization is to work
Skill requires very harsh, causes the reaction initiation of oligomerisation reaction technique and repeatability 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 major catalyst chlorination 2 of the ethene shown in including formula (I), 8- diacetyl quinoline contractings amine closes iron (II) and matched somebody with somebody
Compound, the lower progress oligomerisation reaction of carbon monoxide-olefin polymeric effect containing aluminum cocatalyst, water and organic solvent, have higher on the contrary
Oligomerisation reaction activity, and oligomerisation reaction initiation is rapid, operates steadily, be reproducible；So as to overcome those skilled in the art's
Technology prejudice, achieve unexpected technique effect.
According to an aspect of the invention, there is provided a kind of ethylene oligomerization carbon monoxide-olefin polymeric, the composition include
Major catalyst chlorination 2,8- diacetyls quinoline contracting amine shown in formula (I) closes iron (II) complex, containing aluminum cocatalyst and had
Solvent：
In formula (I), 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
(i.e. the organic solvent based on 1g, 5~350 × 10 are contained in composition for 5~350ppm-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 (organic molten i.e. based on 1L for 2~500 μm of ol/L
Agent, 2~500 × 10 are contained in composition-6Mol major catalyst), preferably 20~100 μm of ol/L.
In the present invention, wherein the mol ratio of aluminium in the co-catalyst and the iron in the major catalyst for 30 to small
In 900, preferably 100~700.In a specific embodiment of the above method, the mol ratio of the aluminium and iron is 148~196.
In the relatively low molar ratio range of offer, the ethylene oligomerization activity in methods described is still higher.
In the present invention, the R in the major catalyst1-R5It is each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl
Base, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.In a specific embodiment of the above method, in the major catalyst
R1And R5For methyl, R2-R4It is hydrogen.
In the present invention, the organic solvent be selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and
Dichloromethane, it is preferably selected from toluene and dimethylbenzene.
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 present invention, it is described to be selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferably alkyl aluminum compound containing aluminum cocatalyst.
In the present invention, the formula of the alkyl aluminum compound is AlRnXm, wherein R is each independently straight or branched
C1-C8Alkyl；X is respectively halogen, preferably chlorine or bromine；N is 1~3 integer, and m is 0~2 integer, and m+n is equal to 3；It is preferred that
Ground, described alkyl aluminum compound are selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three
Octyl aluminum, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In the present invention, the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane, wherein C1-C4Alkyl is the alkane of straight or branched
Base；Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide；
More preferably MAO.
Major catalyst chlorination 2,8- diacetyl quinoline contractings amine shown in the logical formula (I) of the present invention, which closes iron (II) complex, to be adopted
The preparation method reported with document (Organometallics 2010,29,1168-1173) is made.
According to another aspect of the present invention, a kind of ethylene oligomerization method is additionally provided, the ethene is in above-mentioned catalysis
Oligomerisation reaction is being carried out in the presence of agent composition.The composition includes the major catalyst chlorination 2,8- diethyls shown in formula (I)
Acyl group quinoline contracting amine closes iron (II) complex, containing aluminum cocatalyst and organic solvent.
Wherein, a specific embodiment of methods described may include following steps：(1) dried by high temperature, vacuum is put
The operation such as change and line replacement is entered to reaction system, it is ensured that anhydrous and oxygen-free in reaction system；(2) reaction system is put using ethene
Change, reaction system is in ethene environment；(3) carbon monoxide-olefin polymeric, including sponsoring shown in formula (I) are added in reaction system
Agent, co-catalyst, water and organic solvent, are sufficiently stirred；(4) it is passed through ethene and starts oligomerisation reaction, it is 0.1 to keep reaction pressure
~30MPa and reaction temperature are that 30~100min is reacted at -20~150 DEG C；(5) stop reaction, take reaction product gas phase color
Spectrum carries out (GC) analysis.
In the present invention, described major catalyst and co-catalyst add reactant after first being dissolved with organic solvent
System.The organic solvent is selected from toluene, hexamethylene, ether, tetrahydrofuran, ethanol, benzene, dimethylbenzene and dichloromethane, preferably selects
From toluene and dimethylbenzene.Being blended under ethene atmosphere for the oligomerisation reaction process, major catalyst and co-catalyst is carried out.It is described
The temperature of oligomerisation reaction is -20~150 DEG C, preferably 0~80 DEG C, more preferably 5~40 DEG C.The pressure of the reaction is 0.1
~30MPa, with ethylene pressure rise oligomerization activity rise.
Ethylene oligomerization is carried out using carbon monoxide-olefin polymeric of the present invention, the ethylene oligomerization product of acquisition includes C4、C6、
C8、C10、C12、C14、C16、C18、C20、C22Deng；The selectivity of alpha-olefin can reach more than 96%.Terminate in ethylene oligomerization reaction
Afterwards, GC analyses are carried out.As a result show, oligomerization activity is up to 107g·mol(Fe)-1·h-1More than.In addition, remaining reaction is mixed
The ethanol solution that compound is acidified with 5% watery hydrochloric acid neutralizes, and does not obtain polymer.
According to carbon monoxide-olefin polymeric provided by the invention, major catalyst chlorination 2 of the ethene shown in including formula (I), 8- bis-
Acetylquinoline contracting amine closes iron (II) complex, acts on lower progress oligomerisation containing the composition of aluminum cocatalyst and organic solvent
Reaction, there is higher oligomerisation reaction activity on the contrary, the selectivity of alpha-olefin is high, and oligomerisation reaction trigger it is rapid, operate steadily,
It is reproducible.According to the present invention, under the conditions of low-down Al/Fe ratios, still with preferable oligomerisation reaction activity.Root
According to the present invention, when the reaction is performed at a lower temperature, still with high oligomerisation reaction activity.According to the present invention, overcome
The technology prejudice of those skilled in the art, achieves unexpected technique effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated and explanation, but does not form to any of the present invention
Limitation.
Embodiment 1
1. catalyst chlorination 2,8- diacetyl quinoline contractings amine closes the synthesis of iron (II) complex
Chlorination 2,8- is made in preparation method according to document (Organometallics 2010,29,1168-1173) report
Diacetyl quinoline contracting amine closes iron (II) complex.
2. ethylene oligomerization reacts, specifically comprise the following steps：(1) dried by high temperature, the operation such as vacuum displacement is to reaction
System enters line replacement, it is ensured that anhydrous and oxygen-free in reaction system；(2) line replacement is entered to reaction system using ethene, makes reaction system
In ethene environment；(3) water and toluene solvant are added in a kettle, and adding 1.37ml triethyl aluminums toluene solution, (concentration is
715 μm of ol/ml), 2ml chlorinations 2 are added, 8- diacetyls quinoline 2,6- of contracting dimethyl amines close the toluene solution of iron (II) complex
After (concentration is 2.5 μm of ol/ml), it is 100ml to make total composition, wherein, using the weight of organic solvent (i.e. toluene) as calculating
Benchmark, the weight content of water is 5ppm, Al/Fe=196, after being sufficiently stirred, is passed through ethene and starts oligomerisation reaction；(4) second is kept
Alkene pressure is 1MPa and reaction temperature is to be reacted 30 minutes at 30 DEG C；(7) stop reaction, take out a small amount of reaction product gas phase color
Spectrum carries out (GC) analysis：Oligomerization activity is 0.33 × 107g·mol(Fe)-1·h-1, oligomer content is respectively C439.38%,
C6~C1048.26%, C6~C1859.12% (wherein containing linear alpha-alkene 96.2%), C20~C280.59%.Remaining mixing
The ethanol solution that thing is acidified with 5% hydrochloric acid neutralizes, and does not obtain polymer.Analysis result is shown in Table one.
Embodiment 2
With embodiment 1, difference is, the weight content 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 100ppm.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 100ppm, 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 100ppm, 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 100ppm, 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 100ppm, and reaction temperature is 40 DEG C.Data are shown in Table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 100ppm, Al/Fe=500.Data are shown in Table 1.
Comparative example 1
With embodiment 1, difference is, anhydrous in composition.Data are shown in Table 1.
Table 1
It can be seen from the data in Table 1 that according to carbon monoxide-olefin polymeric provided by the invention, ethene is including formula (I) Suo Shi
Major catalyst chlorination 2,8- diacetyls quinoline contracting amine close iron (II) complex, containing aluminum cocatalyst and organic solvent
Composition effect is lower to carry out oligomerisation reaction, has higher oligomerisation reaction activity on the contrary, the selectivity of alpha-olefin is high, and oligomerisation is anti-
Should trigger it is rapid, operate steadily, be reproducible.According to the present invention, under the conditions of low-down Al/Fe ratios, still have
Preferable oligomerisation reaction activity.According to the present invention, when the reaction is performed at a lower temperature, still lived with high oligomerisation reaction
Property.
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 (23)
1. a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including the major catalyst chlorination 2 shown in formula (I), 8- diacetyl quinoline
The amine that contracts closes iron (II) complex, containing aluminum cocatalyst and organic solvent：
In formula, R1~R5It is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro；With organic solvent
Weight is calculating benchmark, and the weight content of water is 5~350ppm；The organic solvent is selected from toluene, ether, tetrahydrofuran, second
Alcohol, benzene, dimethylbenzene and dichloromethane；It is described to be selected from aikyiaiurnirsoxan beta and alkyl aluminum compound containing aluminum cocatalyst.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The weight of agent is calculating benchmark, and the weight content of water is 20~260ppm.
3. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The weight of agent is calculating benchmark, and the weight content of water is 50~200ppm.
4. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the carbon monoxide-olefin polymeric, with organic molten
The volume of agent is calculating benchmark, and 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 in the carbon monoxide-olefin polymeric, with organic molten
The volume of agent is calculating benchmark, and the content of the major catalyst is 20~100 μm of ol/L.
6. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the organic solvent is selected from toluene and diformazan
Benzene.
7. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in the co-catalyst in aluminium and major catalyst
The mol ratio of iron is 30 to less than 900:1.
8. carbon monoxide-olefin polymeric according to claim 7, it is characterised in that in the co-catalyst in aluminium and major catalyst
The mol ratio of iron is 100-700:1.
9. carbon monoxide-olefin polymeric according to claim 7, it is characterised in that in the co-catalyst in aluminium and major catalyst
The mol ratio of iron is 148-196:1.
10. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the R in the major catalyst1-R5Each solely
On the spot it is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.
11. carbon monoxide-olefin polymeric according to claim 10, it is characterised in that the R in the major catalyst1And R5For first
Base, and R2-R4It is hydrogen.
12. the carbon monoxide-olefin polymeric according to any one in claim 1~11, it is characterised in that described helped containing aluminium is urged
Agent is selected from alkyl aluminum compound.
13. 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.
14. carbon monoxide-olefin polymeric according to claim 13, it is characterised in that in the formula of the alkyl aluminum compound
In, X is selected from chlorine or bromine.
15. carbon monoxide-olefin polymeric according to claim 13, it is characterised in that the alkyl aluminum compound is selected from trimethyl
Aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and dichloride second
Base aluminium.
16. carbon monoxide-olefin polymeric according to claim 13, it is characterised in that the alkyl aluminum compound is triethyl group
Aluminium.
17. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the aikyiaiurnirsoxan beta is C1-C4Alkylaluminoxane,
Wherein C1-C4Alkyl is the alkyl of straight or branched.
18. carbon monoxide-olefin polymeric according to claim 17, it is characterised in that the aikyiaiurnirsoxan beta be selected from MAO,
Modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide.
19. carbon monoxide-olefin polymeric according to claim 17, it is characterised in that the aikyiaiurnirsoxan beta is MAO.
20. a kind of ethylene oligomerization method, ethene carbon monoxide-olefin polymeric described in any one in claim 1-19 is deposited
In lower carry out oligomerisation reaction.
21. according to the method for claim 20, it is characterised in that the temperature of the oligomerisation reaction is -20~150 DEG C.
22. according to the method for claim 21, it is characterised in that the temperature of the oligomerisation reaction is 0~80 DEG C.
23. according to the method for claim 21, it is characterised in that the temperature of the oligomerisation reaction is 5~40 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102060852A (en) * | 2009-11-17 | 2011-05-18 | 中国科学院化学研究所 | Quinoline complexes, preparation method thereof, quinoline complex-containing catalyst and use of catalyst in catalysis of vinyl polymerization |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6825297B1 (en) * | 1999-05-14 | 2004-11-30 | The Dow Chemical Company | Transition metal complexes and olefin polymerization process |
| CN102060852A (en) * | 2009-11-17 | 2011-05-18 | 中国科学院化学研究所 | Quinoline complexes, preparation method thereof, quinoline complex-containing catalyst and use of catalyst in catalysis of vinyl polymerization |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
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