CN1374281A - Iron catalyst composition series for ethylene oligomerization and prepn of a-olefin - Google Patents
Iron catalyst composition series for ethylene oligomerization and prepn of a-olefin Download PDFInfo
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- CN1374281A CN1374281A CN01109134A CN01109134A CN1374281A CN 1374281 A CN1374281 A CN 1374281A CN 01109134 A CN01109134 A CN 01109134A CN 01109134 A CN01109134 A CN 01109134A CN 1374281 A CN1374281 A CN 1374281A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The catalyst composite for ethylene oligomerization consists of main catalyst and cocatalyst, the main catalyst is iron system iminocomplex compound, and the cocatalyst is the mixture of methyl aluminum alkoxide, alkylaluminum and GaCl3 with the imino group being obtained through the reaction between 2,6-diformyl pyridine or 2,5-diformyl oyrrole and 2-methyl-4-oxyalkyl aniline or 2-methyl-4-phenoxy aniline. The alpha-olefin has carbon distribution of C6-C28, with the C6-C20 components accounting for over 80%.
Description
The present invention relates to a kind of iron catalyst composition series of preparing alpha-olefin by ethane oligomerisation, gained alpha-olefin carbon number distribution is at C
6-C
28Between, C wherein
6-C
20Greater than 80%.
As the important intermediate of the important comonomer of petrochemical industry, tensio-active agent and lubricating oil and the alpha-olefin of additive is important chemical material always.These alpha-olefins always are the hard-to-get commodities in petrochemicals market.Wherein most alpha-olefins are obtained by ethylene oligomerization.Catalyst system therefor mainly contains nickel system, chromium system, zirconium system, aluminium system and iron system etc.Fe-series catalyst comes into one's own with its highly selective to alpha-olefin, high catalytic activity in recent years.The Fe-series catalyst of having reported (J.Am.Chem.Soc., 1998,120:7143; Chem.Commun.1998,849; WO 99/02472) structure be:
Wherein, R
1, R
2, R
3, R
4Be alkyl, substituted hydrocarbon radical or the inertia group of hydrogen atom, carbon number 1-30 respectively, X is a negatively charged ion; Promotor is an aluminum alkyls.The carbon number distribution of these catalyst composition catalyzed ethylene oligomerisation gained alpha-olefins is at C
10-C
32Between, C wherein
6-C
20The content of alpha-olefin＞50%.
The carbon number distribution that the object of the invention is to improve the alpha-olefin of industrial water requirement maximum is C
6-C
18The preparation method of gained alpha-olefin carbon number greater than the iron catalyst composition series and the alpha-olefin of the 80% a kind of ethylene oligomerization that is provided is provided the content of part alpha-olefin.
Technical solution of the present invention is: a kind of preparation method who is used for the iron catalyst composition series and the alpha-olefin of ethylene oligomerization, and promptly at Primary Catalysts iron system (II) imido grpup coordination compound, promotor methylaluminoxane, triisobutyl aluminium and GaCl
3Mixture exist down; preparing alpha-olefin by ethane oligomerisation is characterized in that: the coordination compound of Fe-series catalyst is 2,6-diformyl pyridine or 2; the product that the reaction of 5-diformyl pyrroles and 2-methyl-4-alkoxyl aniline or 2-methyl-4-phenoxybenzamine obtains, it and FeCl
24H
2O and tetrahydrofuran (THF) one react Primary Catalysts iron system (II) imido grpup coordination compound of obtaining under the condition of anhydrous and oxygen-free, in the time of ethylene pressure 0.1-10MPa, temperature of reaction 0-100 ℃, order adds organic solvent, promotor and Primary Catalysts solution, react after 5-60 minute, be cooled to-10-0 ℃, add the methyl alcohol termination reaction, obtain linear alpha-alkene through rectifying separation.
Iron of the present invention is that (II) catalyst composition is: Primary Catalysts is for being (II) imido grpup coordination compound with iron, and promotor is methylaluminoxane, triisobutyl aluminium mixture and GaCl
3Wherein imido grpup is 2,6-diformyl pyridine or 2, and 5-diformyl pyrroles and 2-methyl-4-alkoxyl aniline or 2-methyl-4-phenoxybenzamine reaction obtains.This catalyst composition catalyzed ethylene oligomerisation makes the carbon number distribution of the alpha-olefin that obtains at C
6-C
28Between, C wherein
6-C
20Greater than 80%.
In catalyst composition of the present invention; described Primary Catalysts is with iron system (II) imido grpup coordination compound; wherein imido grpup is 2,6-diformyl pyridine or 2, and 5-diformyl pyrroles and 2-methyl-4-alkoxyl aniline or 2-methyl-4-phenoxybenzamine reaction obtains.
Iron system (II) imido grpup coordination compound, structural formula is:
Wherein R is C
1-C
4Alkyl, phenyl, C
1-C
4One, two or trisubstd phenyl of alkyl and contain halogen (chlorine, bromine), two or tri-substituted phenyl or contain the C of halogen (chlorine, bromine)
1-C
4Alkyl corresponding one, two or tri-substituted phenyl.
In described 2-methyl-4-alkoxyl aniline, alkoxyl group is C
1-C
4Alkyl and oxygen be combined into.As methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy.
Phenoxy group in described 2-methyl-4-phenoxybenzamine is C
6-C
12Phenyl and substituted aryl.As phenoxy group, the 2-methylphenoxy, the 4-methylphenoxy, 2, the 4-dimethyl phenoxy, 2, the 6-dimethyl phenoxy, 2,4,6-trimethylammonium phenoxy group, 2-methoxyl group phenoxy group, 4-methoxyl group phenoxy group, 2,4-dimethoxy phenoxy group, 2,6-dimethoxy phenoxy group, 2,4,6-trimethylammonium phenoxy group, 2-ethyl phenoxy group, 4-ethyl phenoxy group, 2,4-second methylphenoxy, 2,4,6-triethyl phenoxy group, the 2-chlorophenoxy, the 4-chlorophenoxy, 2,4 dichloro benzene oxygen base, 2,4, the 6-Trichlorophenoxy, 2-bromine phenoxy group, 4-bromine phenoxy group, 2,4-dibromo-phenoxy base, 2,4, the 6-tribromophenoxy, 2-bromo-4-methylphenoxy, 2-bromo-6-methylphenoxy, 2,6-two bromo-4-methylphenoxy, 4-bromo-2, the 6-dimethyl phenoxy, 2-chloro-4-methylphenoxy, 2-chloro-6-methylphenoxy, 2,6-two chloro-4-methylphenoxy, 4-chloro-2, the 6-dimethyl phenoxy.
Described promotor is a kind of mixture, it is characterized by by methylaluminoxane triisobutyl aluminium and GaCl
3Three parts are formed.Wherein methylaluminoxane and the amount of substance of triisobutyl aluminium are than 100: 1-1: 1 mixes, and especially 90: 1-10: 1.GaCl
3With the amount of substance ratio of methylaluminoxane and triisobutyl aluminium be 1: 10: 100-1: 100: 10000.
Described linear alpha-alkene is under the anhydrous and oxygen-free condition, and in the time of ethylene pressure 0.1-10MPa, temperature of reaction 0-100 ℃, order adds organic solvent, promotor and Primary Catalysts solution, react after 5-60 minute, is cooled to-10-0 ℃ adding methyl alcohol termination reaction.Obtain linear alpha-alkene through rectifying separation, linear alpha-alkene selectivity＞96%, carbon number distribution is at C
6-C
28Between, C wherein
6-C
20Greater than 80%.Described solvent is sherwood oil, toluene, dimethylbenzene.The solvent of described Primary Catalysts solution is 1,2-ethylene dichloride, methylene dichloride, trichloromethane and orthodichlorobenzene.
Embodiment 1:
200 milligram 2,6-diformyl pyridine and 6 milliliters of 2-methyl-4-anisidines join 250 milliliters of bottle with two necks, add 50 milliliters of methylene dichloride, drip 0.2 milliliter of formic acid, reflux 30 hours.-30 ℃ freezing 12 hours.Filter and wash 3 times with refrigerated methanol.Products therefrom is 2,6-two [1-(2-methyl-4-anisole imines) ethyl] pyridine.After the product vacuum-drying, in argon gas, preserve.
Embodiment 2:
200 milligram 2,6-diformyl pyridine and 3 milliliters of 2-methyl-4-tert.-butoxy aniline join 250 milliliters of bottle with two necks, add 50 milliliters of methylene dichloride, drip 0.1 milliliter of formic acid, reflux 30 hours.-30 ℃ freezing 12 hours.Filter and wash 3 times with refrigerated methanol.Products therefrom is 2,6-two [1-(2-methyl-4-tert.-butoxy benzene imines) ethyl] pyridine.After the product vacuum-drying, in argon gas, preserve.
Embodiment 3:
200 milligram 2,6-diformyl pyridine and 8 milliliters of 2-methyl-4-isopropoxy anilines join 250 milliliters of bottle with two necks, add 50 milliliters of methylene dichloride, drip 0.1 milliliter of formic acid, reflux 30 hours.-30 ℃ freezing 12 hours.Filter and wash 3 times with refrigerated methanol.Products therefrom is 2,6-two [1-(2-methyl-4-isopropoxy benzene imines) ethyl] pyridine.After the product vacuum-drying, in argon gas, preserve.
Embodiment 4:
200 milligram 2,6-diformyl pyridine and 10 milliliters of 2-methyl-4-phenoxybenzamines join 250 milliliters of bottle with two necks, add 50 milliliters of methylene dichloride, drip 0.3 milliliter of formic acid, reflux 48 hours.-30 ℃ freezing 12 hours.Filter and wash 3 times with refrigerated methanol.Products therefrom is 2,6-two [1-(2-methyl-4-phenoxy group benzene imines) ethyl] pyridine.After the product vacuum-drying, in argon gas, preserve.
Embodiment 5:
200 milligram 2,6-diformyl pyridine and 3 milliliters of 2-methyl-4-(2, the 6-3,5-dimethylphenyl) aniline join 250 milliliters of bottle with two necks, add 50 milliliter 1, and the 2-ethylene dichloride drips 0.1 milliliter of formic acid, refluxes 30 hours.-30 ℃ freezing 12 hours.Filter and wash 3 times with refrigerated methanol.Products therefrom is 2,6-two [1-(2-methyl-4-(2, the 6-3,5-dimethylphenyl) benzene imines) ethyl] pyridine.After the product vacuum-drying, in argon gas, preserve.
Embodiment 6:
In 100 milliliters of twoport reaction flasks, vacuumize-applying argon gas after three times, adds product and 80 milligrams of FeCl of 120 milligrams of embodiment 1-3 respectively repeatedly under argon shield
24H
2O adds 30 milliliters of anhydrous tetrahydro furans, and stirring at room 10 hours obtains blue look solid.Filter and wash 3 times with freezing anhydrous diethyl ether.Vacuum-drying, argon gas is preserved down.
Embodiment 7:
In 100 milliliters of twoport reaction flasks, vacuumize-applying argon gas after three times, adds product and 80 milligrams of FeCl of 150 milligrams of embodiment 4-5 respectively repeatedly under argon shield
24H
2O adds 30 milliliters of anhydrous tetrahydro furans, and stirring at room 8 hours obtains blue look solid.Filter and wash 3 times with freezing anhydrous diethyl ether.Vacuum-drying, argon gas is preserved down.
Embodiment 8:
In 250 milliliters of twoport reaction flasks, vacuumize-ethene after three times, charges into ethene to 0.1MPa repeatedly, adds 100 milliliters toluene.Inject 5.0 milliliters and press methylaluminoxane: triisobutyl aluminium: GaCl
3The amount of substance ratio is 1000: 10: 1 a promotor toluene mixing solutions, and this mixing solutions counts 10% by aluminium.Inject 1 * 10 of 2.5 milliliters of embodiment 6
-6Mol/L catalyzer 1,2-two aluminium ethane solution.Increase sharply ethylene pressure to 1.5MPa, and 90 ℃ were reacted 20 minutes.Be cooled to 0 ℃, add the acetone termination reaction.The rectifying separation product.Stratographic analysis, linear alpha-alkene is 96%, carbon number distribution is at C
6-C
24Between, C wherein
6-C
20Be 81%.
Embodiment 9:
In 250 milliliters of twoport reaction flasks, vacuumize-ethene after three times, charges into ethene to 0.1MPa repeatedly, adds 100 milliliters sherwood oil.Inject 3.0 milliliters and press methylaluminoxane: triisobutyl aluminium: GaCl
3The amount of substance ratio is 100: 10: 1 a promotor toluene mixing solutions, and this mixing solutions counts 10% by aluminium.Inject 1 * 10 of 2.5 milliliters of embodiment 6
-6Mol/L catalyzer 1, the 2-dichloroethane solution.Increase sharply ethylene pressure to 5.0MPa, and 50 ℃ were reacted 10 minutes.Be cooled to 0 ℃, add the acetone termination reaction.The rectifying separation product.Stratographic analysis, linear alpha-alkene is 96%, carbon number distribution is at C
6-C
24Between, C wherein
6-C
20Be 81%.
Embodiment 10:
In 250 milliliters of twoport reaction flasks, vacuumize-ethene after three times, charges into ethene to 0.1MPa repeatedly, add 100 milliliters 1, the 2-ethylene dichloride.Inject 4.0 milliliters and press methylaluminoxane: triisobutyl aluminium: GaCl
3The amount of substance ratio is 100: 10: 1 a promotor toluene mixing solutions, and this mixing solutions counts 10% by aluminium.Inject 1 * 10 of 2.5 milliliters of embodiment 6
-6Mol/L catalyzer 1,2-two aluminium ethane solution.Increase sharply ethylene pressure to 5.0MPa, and 20 ℃ were reacted 20 minutes.Be cooled to 0 ℃, add the acetone termination reaction.The rectifying separation product.Stratographic analysis, linear alpha-alkene is 96%, carbon number distribution is at C
6-C
24Between, C wherein
6-C
20Be 84%.
Claims (9)
1. a preparation method who is used for the iron catalyst composition series and the alpha-olefin of ethylene oligomerization is (II) imido grpup coordination compound, promotor methylaluminoxane, triisobutyl aluminium and GaCl at Primary Catalysts iron promptly
3Mixture exist down; preparing alpha-olefin by ethane oligomerisation is characterized in that: the coordination compound of Fe-series catalyst is 2,6-diformyl pyridine or 2; the product that the reaction of 5-diformyl pyrroles and 2-methyl-4-alkoxyl aniline or 2-methyl-4-phenoxybenzamine obtains, it and FeCl
24H
2O and tetrahydrofuran (THF) one react Primary Catalysts iron system (II) imido grpup coordination compound of obtaining under the condition of anhydrous and oxygen-free, in the time of ethylene pressure 0.1-10MPa, temperature of reaction 0-100 ℃, order adds organic solvent, promotor and Primary Catalysts solution, react after 5-60 minute, be cooled to-10-0 ℃, add the methyl alcohol termination reaction, obtain linear alpha-alkene through rectifying separation.
2. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 1 is characterized in that: described Primary Catalysts is iron system (II) imido grpup coordination compound, and structural formula is:
Wherein R is C
1-C
4Alkyl, phenyl, C
1-C
4One, two or trisubstd phenyl of alkyl and contain halogen (chlorine, bromine), two or tri-substituted phenyl or contain the C of halogen (chlorine, bromine)
1-C
4Alkyl corresponding one, two or tri-substituted phenyl.
3. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 1 is characterized in that: promotor is methylaluminoxane, triisobutyl aluminium and GaCl
3Mixture, wherein: methylaluminoxane is 100 with the amount of substance ratio of triisobutyl aluminium: 1-1: 1, especially 90: 1-10: 1 is good; GaCl
3With the amount of substance ratio of methylaluminoxane and triisobutyl aluminium be 1: 10: 100-1: 100: 10000.
4. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 2 is characterized in that: Primary Catalysts C
1-C
4Alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.
5. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 2 is characterized in that: Primary Catalysts C
1-C
4One of alkyl, two or trisubstd phenyl be the 2-aminomethyl phenyl, the 4-aminomethyl phenyl, 2, the 4-3,5-dimethylphenyl, 2, the 6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, the 4-ethylphenyl, 2,4-diethyl phenyl, 2,4,6-triethyl phenyl, 2-propyl group phenyl, 4-propyl group phenyl, 2,4-dipropyl phenyl, 2,6-dipropyl phenyl, 2,4,6-tripropyl phenyl, 2-isopropyl phenyl, the 4-isopropyl phenyl, 2, the 4-diisopropyl phenyl, 2, the 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, the 2-butyl phenyl, the 4-butyl phenyl, 2,4-dibutyl phenyl, 2,6-dibutyl phenyl, 2,4,6-tributyl phenyl, the 2-isobutyl phenenyl, the 4-isobutyl phenenyl, 2,4-diisobutyl phenyl, 2,6-diisobutyl phenyl, 2,4,6-triisobutyl phenyl, 2-tert-butyl-phenyl, the 4-tert-butyl-phenyl, 2, the 4-di-tert-butyl-phenyl, 2, the 6-di-tert-butyl-phenyl, 2,4,6-tri-tert phenyl.
6. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 2, it is characterized in that: the phenyl that Primary Catalysts contains halogen (chlorine, bromine) is 2-chloro-phenyl-, 4-chloro-phenyl-, 2,4-dichlorophenyl, 2,4, the 6-trichlorophenyl, 2-bromophenyl, 4-bromophenyl, 2,4-dibromo phenyl, 2,4,6-tribromo phenyl.
7. a kind of iron catalyst composition series that is used for ethylene oligomerization according to claim 2 is characterized in that: the C of Primary Catalysts halogen-containing (chlorine, bromine)
1-C
4Alkyl corresponding one, two or tri-substituted phenyl are 2-bromo-4-aminomethyl phenyl, 2-bromo-6-aminomethyl phenyl, 2,6-two bromo-4-aminomethyl phenyls, 4-bromo-2, the 6-3,5-dimethylphenyl, 2-chloro-4-aminomethyl phenyl, 2-chloro-6-aminomethyl phenyl, 2,6-two chloro-4-aminomethyl phenyls, 4-chloro-2, the 6-3,5-dimethylphenyl.
8. one kind is used for the using method that the ethylene oligomerization iron catalyst composition series prepares linear alpha-alkene, it is characterized in that: described linear alpha-alkene is under the anhydrous and oxygen-free condition, in the time of ethylene pressure 0.1-10MPa, temperature of reaction 0-100 ℃, order adds organic solvent, promotor and Primary Catalysts solution, reacts after 5-60 minute, is cooled to-10-0 ℃, add the methyl alcohol termination reaction, obtain linear alpha-alkene through rectifying separation, linear alpha-alkene selectivity＞96%, carbon number distribution is at C
6-C
28Between, C wherein
6-C
20Greater than 80%.
10. a kind of using method that the ethylene oligomerization iron catalyst composition series prepares linear alpha-alkene that is used for according to claim 8, organic solvent is sherwood oil, toluene, dimethylbenzene, the solvent of described Primary Catalysts solution is 1,2-ethylene dichloride, methylene dichloride, trichloromethane and orthodichlorobenzene, described promotor is 2000 with the amount of substance ratio of Primary Catalysts: 1-200: 1, especially 1500: 1-500: 1.
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