CN105562086A - Catalyst composition for ethylene oligomerization and application thereof - Google Patents
Catalyst composition for ethylene oligomerization and application thereof Download PDFInfo
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- CN105562086A CN105562086A CN201410535539.7A CN201410535539A CN105562086A CN 105562086 A CN105562086 A CN 105562086A CN 201410535539 A CN201410535539 A CN 201410535539A CN 105562086 A CN105562086 A CN 105562086A
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- carbon monoxide
- olefin polymeric
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Abstract
The invention discloses a catalyst composition for ethylene oligomerization. The catalyst composition comprises a main catalyst chromium (III) chlorinated 2-(1H-2-benzimidazolyl)-8-acetanilide quinoline complex as shown in a formula (I) which is described in the specification, an aluminum-containing cocatalyst, water and an organic solvent. The catalyst composition has high oligomerization reaction activity and high alpha-alkene selectivity when applied to ethylene oligomerization, and oligomerization reaction is rapidly initiated, runs stably and has good repeatability; even under the condition of a low aluminum/chromium ratio, good oligomerization reaction activity is maintained; thus, technical biases of the skilled in the art are overcome, unexpected technical effects are obtained, catalysis effect and cost are better balanced, cost for ethylene oligomerization is greatly reduced and the catalyst has good practicality and wide industrialization prospects.
Description
Technical field
The present invention relates to ethylene oligomerization field, be specifically related to a kind of carbon monoxide-olefin polymeric for ethylene oligomerization reaction process.
Background technology
Linear alpha-alkene has a wide range of applications in fields such as ethylene comonomer, synthesis of surfactant intermediate, plasticizer alcohol, synthetic lubricant fluid and oil dopes.In recent years, along with the development of polyolefin industry, the demand rapid development to alpha-olefin in world wide.The alpha-olefin of the current overwhelming majority is obtained by ethylene oligomerization preparation.Ethylene oligomerization method catalyst used mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (people such as Brookhart, M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (people such as Gibson, V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find that the trident pyridinimine complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation respectively, not only the catalytic activity of catalyst is very high, and alpha-olefin is selective also very high.
Institute of Chemistry, Academia Sinica reports a kind of catalyst (Organometallics2011 for ethylene oligomerization and polymerization, 30,3001 – 3009), this catalyst is that chlorination 2-(1H-2-benzimidazolyl)-8-acetophenone amido quinoline closes chromium (III), under the effect of co-catalyst MAO, when the mol ratio of the metallic aluminium in co-catalyst and the central metal in major catalyst is 200 ~ 2500, and when reaction temperature is 30 ~ 60 DEG C, oligomerisation and polymerization activity have been up to 10
6gmol (Cr)
-1h
-1; And no matter be MAO, or modified methylaluminoxane is as co-catalyst, all there is high cost, the problem that consumption is excessive, and as co-catalyst large-scale application when the ethylene oligomerization, it certainly will cause production cost high.
At present, it has been generally acknowledged that water is very disadvantageous to ethylene oligomerization reaction process, CN200810111717.8 discloses a kind of method of ethylene oligomerization, carry out under being strict controlled in the environment of anhydrous and oxygen-free, therefore current ethylene oligomerization reaction is very harsh to technological requirement, causes the reaction initiation of oligomerisation reaction technique and all non-constant of repeatability.
Summary of the invention
For deficiency of the prior art, inventor has carried out research extensively and profoundly in ethylene oligomerization catalyst field, be surprised to find, ethene comprise major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) close chromium (III), containing the carbon monoxide-olefin polymeric effect of aluminum cocatalyst, water and organic solvent under carry out oligomerisation reaction, there is higher oligomerisation reaction on the contrary active, and oligomerisation reaction cause rapidly, operate steadily, reproducible; Thus overcome the technology prejudice of those skilled in the art, achieve unforeseeable technique effect.
According to an aspect of the present invention, provide a kind of ethylene oligomerization carbon monoxide-olefin polymeric, described carbon monoxide-olefin polymeric comprises major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) and closes chromium (III), containing aluminum cocatalyst, water and organic solvent:
In formula (I), R
1-R
5be selected from hydrogen, C independently of one another
1-C
6alkyl, halogen, C
1-C
6alkoxyl and nitro.
According to carbon monoxide-olefin polymeric provided by the invention, there is higher ethylene oligomerization reactivity, the selective height of alpha-olefin.
In carbon monoxide-olefin polymeric of the present invention, with the weight of organic solvent for Calculation Basis, the weight content of water is that 5 ~ 350ppm is (namely based on the organic solvent of 1g, containing 5 ~ 350 × 10 in composition
-6the water of g), preferably 20 ~ 260ppm, most preferably is 50 ~ 200ppm.Within the scope of described water content, it is active that described carbon monoxide-olefin polymeric has higher ethylene oligomerization.
In carbon monoxide-olefin polymeric of the present invention, the consumption of described major catalyst and co-catalyst can be selected according to the process conditions during embody rule such as production scale and production equipment.In a specific embodiment of described carbon monoxide-olefin polymeric, with the volume of organic solvent for Calculation Basis, the content of described major catalyst is that 2 ~ 500 μm of ol/L are (namely based on the organic solvent of 1L, containing 2 ~ 500 × 10 in composition
-6the major catalyst of mol), preferably 20 ~ 100 μm of ol/L.
In the present invention, the mol ratio of the chromium in the aluminium in wherein said co-catalyst and described major catalyst is 30 to being less than 900, preferably 100 ~ 700.In a specific embodiment of said method, the mol ratio of described aluminium and chromium is 148 ~ 196.Even if in the lower molar ratio range provided, the ethylene oligomerization activity in described method is still higher.
In the present invention, the R in described major catalyst
1-R
5be selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro independently of one another.In a specific embodiment of said method, the R in described major catalyst
1and R
5for ethyl, R
2-R
4be hydrogen.
In the present invention, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.
In the present invention, term " C
1-C
6alkyl " refer to saturated straight chain containing 1-6 carbon atom or branched hydrocarbyl.As C
1-C
6alkyl, can mention methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl; Particularly preferably methyl, ethyl, n-pro-pyl and isopropyl.
In the present invention, term " C
1-C
6alkoxyl " refer to above-mentioned C
1-C
6alkyl is connected with an oxygen atom group obtained.As C
1-C
6alkoxyl, can mention methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, just own oxygen base and the second month in a season own oxygen base; Particularly preferably methoxyl group and ethyoxyl.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
In the present invention, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.
In the present invention, the general formula of described alkyl aluminum compound is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; X is halogen separately, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferably, described alkyl aluminum compound is excellent in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride and ethylaluminium dichloride, more preferably triethyl aluminum.
In the present invention, described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; More preferably MAO.
Major catalyst chlorination 2-(1H-2-benzimidazolyl)-8-acetophenone amido quinoline shown in general formula of the present invention (I) closes chromium (III) can adopt document (Organometallics2011,30,3001 – 3009) preparation method that reports obtains.
According to another aspect of the present invention, provide a kind of ethylene oligomerization method, described ethene is carrying out oligomerisation reaction under the effect of described carbon monoxide-olefin polymeric.Described carbon monoxide-olefin polymeric comprises major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) and closes chromium (III), containing aluminum cocatalyst, water and organic solvent.
Wherein, a specific embodiment can comprise the steps: that (1) is replaced reaction system by the operation such as hyperthermia drying, vacuum displacement, guarantees anhydrous and oxygen-free in reaction system; (2) use ethene to replace reaction system, make reaction system be in ethene environment; (3) in reaction system, add carbon monoxide-olefin polymeric, comprise major catalyst, co-catalyst, water and the organic solvent shown in formula (I), fully stir; (4) pass into ethene and start oligomerisation reaction, maintenance reaction pressure is 0.1 ~ 30MPa and reaction temperature is react 30 ~ 100min at-20 ~ 150 DEG C; (5) stop reaction, get product gas-chromatography and carry out (GC) analysis.
In the present invention, described major catalyst and co-catalyst first can add reaction system with after organic solvent dissolution again.Described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.Described oligomerisation reaction process, major catalyst and co-catalyst be blended in ethene atmosphere under carry out.The temperature of described oligomerisation reaction is-20 ~ 150 DEG C, is preferably 0 ~ 80 DEG C, is more preferably 5 ~ 35 DEG C.The pressure of described reaction is 0.1 ~ 30MPa, raises along with ethylene pressure raises oligomerization activity.
Use carbon monoxide-olefin polymeric of the present invention to carry out ethylene oligomerization, the ethylene oligomerization product of acquisition comprises C
4, C
6, C
8, C
10, C
12, C
14, C
16, C
18, C
20, C
22deng; The selective of alpha-olefin can reach more than 96%.After ethylene oligomerization reaction terminates, carry out GC analysis.Result shows, oligomerization activity can reach 10
7gmol (Fe)
-1h
-1above.In addition, the remaining reactant mixture ethanolic solution of the watery hydrochloric acid acidifying of 5% neutralizes, and does not obtain polymer.
According to carbon monoxide-olefin polymeric provided by the invention, ethene comprise major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) close chromium (III), containing the composition effect of aluminum cocatalyst, water and organic solvent under carry out oligomerisation reaction, there is higher oligomerisation reaction on the contrary active, the selective height of alpha-olefin, and oligomerisation reaction cause rapidly, operate steadily, reproducible.According to the present invention, even if at low-down Al/Cr than under condition, still there is good oligomerisation reaction active.According to the present invention, when the reaction is performed at a lower temperature, still there is high oligomerisation reaction active.According to the present invention, overcome the technology prejudice of those skilled in the art, achieve unforeseeable technique effect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated and illustrate, but do not form any limitation of the invention.
Embodiment 1
1. catalyst chlorination 2-(1H-2-benzimidazolyl)-8-acetophenone amido quinoline closes the synthesis of chromium (III)
The preparation method reported according to document (Organometallics2011,30,3001 – 3009) obtains chlorination 2-(1H-2-benzimidazolyl)-8-acetophenone amido quinoline and closes chromium (III) complex.
2. ethylene oligomerization reaction, specifically comprises the steps: that (1) is replaced reaction system by the operation such as hyperthermia drying, vacuum displacement, guarantees anhydrous and oxygen-free in reaction system; (2) use ethene to replace reaction system, make reaction system be in ethene environment; (3) water and toluene solvant is added in a kettle., add 1.37ml triethyl aluminum toluene solution (concentration is 715 μm of ol/ml), after adding the toluene solution (concentration is 2.5 μm of ol/ml) of 2ml chlorination 2-(1H-2-benzimidazolyl)-8-acetophenone amido quinoline conjunction chromium (III), total composition is made to be 100ml, wherein, with the weight of organic solvent (i.e. toluene) for Calculation Basis, the weight content of water is 5ppm, Al/Cr=196, after abundant stirring, pass into ethene and start oligomerisation reaction; (4) keep ethylene pressure be 1MPa and reaction temperature be at 30 DEG C react 30 minutes; (7) stop reaction, take out a small amount of product gas-chromatography and carry out (GC) analysis: oligomerization activity is 0.41 × 10
7gmol (Cr)
-1h
-1, oligomer content is respectively C
443.20%, C
6~ C
1045.94%, C
6~ C
1855.29% (wherein containing linear alpha-alkene 96.6%), C
20~ C
280.38%.The remaining mixture ethanolic solution of the hcl acidifying of 5% neutralizes, and does not obtain polymer.Analysis result is in table one.
Embodiment 2
With embodiment 1, difference is, the weight content of water is 20ppm.Data are in table 1.
Embodiment 3
With embodiment 1, difference is, the weight content of water is 50ppm.Data are in table 1.
Embodiment 4
With embodiment 1, difference is, the weight content of water is 100ppm.Data are in table 1.
Embodiment 5
With embodiment 1, difference is, the weight content of water is 200ppm.Data are in table 1.
Embodiment 6
With embodiment 1, difference is, the weight content of water is 260ppm.Data are in table 1.
Embodiment 7
With embodiment 1, difference is, the weight content of water is 350ppm, and data are in table 1.
Embodiment 8
With embodiment 1, difference is, the weight content of water is 100ppm, and reaction temperature is 0 DEG C.Data are in table 1.
Embodiment 9
With embodiment 1, difference is, the weight content of water is 100ppm, and reaction temperature is-10 DEG C.Data are in table 1.
Embodiment 10
With embodiment 1, difference is, the weight content of water is 100ppm, and reaction temperature is-20 DEG C.Data are in table 1.
Embodiment 11
With embodiment 1, difference is, the weight content of water is 100ppm, and reaction temperature is 40 DEG C.Data are in table 1.
Embodiment 12
With embodiment 1, difference is, the weight content of water is 100ppm, Al/Fe=500.Data are in table 1.
Comparative example 1
With embodiment 1, difference is, anhydrous in composition.Data are in table 1.
Table 1
Data as can be seen from table 1, according to carbon monoxide-olefin polymeric provided by the invention, ethene comprise major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) close chromium (III) complex, containing the composition effect of aluminum cocatalyst, water and organic solvent under carry out oligomerisation reaction, there is higher oligomerisation reaction on the contrary active, the selective height of alpha-olefin, and oligomerisation reaction cause rapidly, operate steadily, reproducible.According to the present invention, even if at low-down Al/Fe than under condition, still there is good oligomerisation reaction active.According to the present invention, when the reaction is performed at a lower temperature, still there is high oligomerisation reaction active.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (11)
1. an ethylene oligomerization carbon monoxide-olefin polymeric, comprises major catalyst chlorination 2-(1H-2-the benzimidazolyl)-8-acetophenone amido quinoline shown in formula (I) and closes chromium (III), containing aluminum cocatalyst, water and organic solvent:
In formula, R
1~ R
5be selected from hydrogen, C independently of one another
1~ C
6alkyl, halogen, C
1~ C
6alkoxyl and nitro.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, in described carbon monoxide-olefin polymeric, with the weight of organic solvent for Calculation Basis, the weight content of water is 5 ~ 350ppm, preferably 20 ~ 260ppm, most preferably is 50 ~ 200ppm.
3. carbon monoxide-olefin polymeric according to claim 1 and 2, is characterized in that, in described carbon monoxide-olefin polymeric, with the volume of organic solvent for Calculation Basis, the content of described major catalyst is 2 ~ 500 μm of ol/L, preferably 20 ~ 100 μm of ol/L.
4. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, described organic solvent is selected from toluene, cyclohexane, ether, oxolane, ethanol, benzene, dimethylbenzene and carrene, is preferably selected from toluene and dimethylbenzene.
5. carbon monoxide-olefin polymeric according to claim 1, is characterized in that, in described co-catalyst, in aluminium and major catalyst, the mol ratio of chromium is 30 to being less than 900:1, and preferred 100-700:1, is more preferably 148-196:1.
6. according to the carbon monoxide-olefin polymeric in claim 1 described in any one, it is characterized in that, the R in described major catalyst
1-R
5be selected from hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro independently of one another; Preferred R
1and R
5for methyl, and R
2-R
4be hydrogen.
7. according to the carbon monoxide-olefin polymeric in claim 1 ~ 6 described in any one, it is characterized in that, the described aluminum cocatalyst that contains is selected from aikyiaiurnirsoxan beta and alkyl aluminum compound, preferred alkyl aluminium compound.
8. carbon monoxide-olefin polymeric according to claim 7, is characterized in that, the general formula of described alkyl aluminum compound is AlR
nx
m, wherein R is straight or branched C independently of one another
1-C
8alkyl; X is halogen, preferred chlorine or bromine; N is the integer of 1 ~ 3, and m is the integer of 0 ~ 2, and m+n equals 3; Preferably, described 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 ethylaluminium dichloride; More preferably triethyl aluminum.
9. the carbon monoxide-olefin polymeric according to claim 7 or 8, is characterized in that, described aikyiaiurnirsoxan beta is C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is the alkyl of straight or branched; Preferably, described aikyiaiurnirsoxan beta is selected from MAO, modified methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide; Be more preferably MAO.
10. an ethylene oligomerization method, carries out oligomerisation reaction under the effect of described ethene carbon monoxide-olefin polymeric described in any one in claim 1-9.
11. methods according to claim 10, is characterized in that, the temperature of described oligomerisation reaction is-20 ~ 150 DEG C, are preferably 0 ~ 80 DEG C, are more preferably 5 ~ 35 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 |
| CN102199173A (en) * | 2011-04-07 | 2011-09-28 | 中国科学院化学研究所 | 2-benzimidazolyl-8-methanamide quinoline chromium complexes, its preparation method and application |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
-
2014
- 2014-10-11 CN CN201410535539.7A patent/CN105562086B/en active Active
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 |
| CN102206127A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Ethylene oligomerization method |
| CN102199173A (en) * | 2011-04-07 | 2011-09-28 | 中国科学院化学研究所 | 2-benzimidazolyl-8-methanamide quinoline chromium complexes, its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 汪秋安 等: "《有机化学实验室技术手册》", 29 February 2012, 科学工业出版社 * |
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