CN107282107B - Catalyst composition for ethylene oligomerization and application thereof - Google Patents
Catalyst composition for ethylene oligomerization and application thereof Download PDFInfo
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- CN107282107B CN107282107B CN201610195584.1A CN201610195584A CN107282107B CN 107282107 B CN107282107 B CN 107282107B CN 201610195584 A CN201610195584 A CN 201610195584A CN 107282107 B CN107282107 B CN 107282107B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 48
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005977 Ethylene Substances 0.000 title claims abstract description 41
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 substituted-2-acetyl-1, 10-phenanthroline Chemical class 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000004711 α-olefin Substances 0.000 abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IWYAYHRXSODVBC-UHFFFAOYSA-N 1-(1,10-phenanthrolin-2-yl)ethanone Chemical class C1=CN=C2C3=NC(C(=O)C)=CC=C3C=CC2=C1 IWYAYHRXSODVBC-UHFFFAOYSA-N 0.000 description 1
- OEOUWMSQXZQDIP-UHFFFAOYSA-N CC[Al](CC)CC.CC1=CC=CC=C1 Chemical compound CC[Al](CC)CC.CC1=CC=CC=C1 OEOUWMSQXZQDIP-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a catalyst composition for an ethylene oligomerization reaction process and application thereof, wherein the composition comprises a main catalyst chlorinated substituted-2-acetyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process. The invention also relates to the use of the above catalyst composition.
Background
Linear α -olefins have found widespread use in the fields of ethylene comonomers, intermediates for surfactant synthesis, alcohols for plasticizers, synthetic lubricating oils and oil additives, etc. in recent years, with the continuous development of the polyolefin industry, there is a rapidly increasing worldwide demand for α -olefins, the vast majority of α -olefins are currently prepared by ethylene oligomerization, catalysts for ethylene oligomerization are mainly nickel-, chromium-, zirconium-and aluminum-based, etc., and in recent years, the Brookhart group (Brookhart, M et al, J.Am.Chem.Soc.,1998,120,7143 + 7144; WO99/02472,1999), the Gibson group (Gibson, V.C.Commun., 1998,849 + 850; chem.Eur.J.,2000,2221 + 2231) found some tridentate pyridine complexes of Fe (II) and Co (II), respectively, which catalyze ethylene oligomerization catalysts with high selectivity, α -olefin oligomerization catalysts.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and CN200810111717.8 discloses a method for ethylene oligomerization, which is strictly controlled to be performed in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, resulting in very poor reaction initiation and repeatability of the oligomerization reaction process.
Disclosure of Invention
Aiming at the defects in the prior art, the inventor carries out extensive and intensive research in the field of catalysts for ethylene oligomerization, and surprisingly discovers that ethylene is oligomerized under the action of a catalyst composition comprising a main catalyst chlorinated substituted-2-acetyl-1, 10-phenanthroline condensed-2, 6-diethylaniline iron (II) complex shown in a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide (and an organic solvent), and the catalyst composition has higher oligomerization activity, and has the advantages of quick initiation of oligomerization, stable operation and good repeatability; thereby overcoming the technical bias of the technicians in the field and achieving unexpected technical effects.
According to one aspect of the present invention, there is provided a catalyst composition for ethylene oligomerization, the composition comprising a procatalyst substituted-2-acetyl-1, 10-phenanthroline iron (II) complex represented by formula (I), an aluminum-containing cocatalyst, and t-butyl hydroperoxide:
in the formula (I), R1-R6Each independently selected from hydrogen and C1-C6Alkyl, halogen, C1-C6Alkoxy and nitro.
The catalyst composition provided by the invention has higher ethylene oligomerization reaction activity and high α -olefin selectivity.
In the present invention, the term "C1-C6Alkyl "refers to a saturated straight or branched chain hydrocarbon group containing 1 to 6 carbon atoms. As C1-C6Alkyl, there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl and sec-hexyl; particular preference is given to methyl, ethyl, n-propyl and isopropyl.
In the present invention, the term "C1-C6Alkoxy "means C as defined above1-C6Alkyl groups are attached to an oxygen atom. As C1-C6Alkoxy, there may be mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, n-hexoxy and sec-hexoxy; methoxy and ethoxy are particularly preferred.
In the present invention, the term "halogen" means fluorine, chlorine, bromine and iodine, and fluorine, chlorine and bromine are particularly preferred.
In the present invention, said R1-R6The choice of (a) may be any combination of the substituents referred to by the above terms. In a preferred embodiment of the present invention, R in the procatalyst1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro. In one embodiment, R in the procatalyst3And R4Is methyl, and R1、R2、R5And R6Are all hydrogen.
According to a preferred embodiment of the present invention, the aluminium-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminium compound, such as an alkyl aluminium compound. In the present invention, the aluminum alkylThe general formula of the compound is AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; x is halogen, such as chlorine or bromine; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3. The alkyl aluminum compound can be selected from at least one of the following compounds: trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride, such as triethylaluminum. In the present invention, the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group. Specific examples of the aluminoxane include, but are not limited to, at least one of the following compounds: methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; such as methylaluminoxane.
In a preferred embodiment of the invention, the molar ratio of aluminium in the cocatalyst to iron in the procatalyst is from 30:1 to 900:1, such as from 100:1 to 700:1, further such as from 148:1 to 196: 1. In a specific embodiment of the above composition, the molar ratio of aluminum in the co-catalyst to iron in the main catalyst is from 196:1 to 500: 1. The ethylene oligomerization activity is still high even in the lower molar ratio range provided.
In a preferred embodiment of the catalyst composition of the present invention, the content of t-butyl hydroperoxide in the catalyst composition is 5 to 1750ppm by weight, such as 25 to 1750ppm by weight. In a specific example, the weight content of the tert-butyl hydroperoxide is 35-1300 ppm, such as 100-1300 ppm. Under the preferable condition, the weight content of the tert-butyl hydroperoxide is 250-1000 ppm. Within the content range of the tert-butyl hydroperoxide, the catalyst composition has higher ethylene oligomerization activity.
In a preferred embodiment of the present invention, the composition further comprises an organic solvent, i.e., the composition comprises a main catalyst chlorinated substituted 2-acetyl-1, 10-phenanthroline condensation-2, 6-diethylaniline iron (II) complex shown in formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solventAn organic solvent. In the present invention, the weight content of the t-butyl hydroperoxide is calculated based on the weight of the organic solvent. For example, the content of t-butyl hydroperoxide is 5 to 1750ppm by weight based on the weight of the organic solvent, i.e., 5 to 1750X 10 based on 1g of the organic solvent-6g of tert-butyl hydroperoxide. The organic solvent is an organic solvent commonly used in the art, and specific examples thereof include, but are not limited to: at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride, such as toluene, xylene, or a mixture of toluene and xylene.
When the composition of the present invention is used for production, the amounts of the main catalyst and the cocatalyst can be selected according to the production scale and the process conditions of the specific application of the production equipment. In one embodiment of the catalyst composition, the amount of the procatalyst is 2 to 500. mu. mol/L based on the volume of the composition containing the organic solvent (i.e., 2 to 500X 10 in the composition based on 1L of the composition)-6mol of main catalyst), preferably 20 to 100. mu. mol/L, such as 50. mu. mol/L.
In another aspect of the invention, a method for oligomerization of ethylene is also provided. The method comprises the step of applying the catalyst composition to oligomerization of ethylene, wherein the oligomerization of ethylene is carried out under the action of the catalyst composition. One specific embodiment may include the steps of: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding a catalyst composition comprising a main catalyst, a cocatalyst and tert-butyl hydroperoxide (and an organic solvent) into a reaction system, and fully stirring; (4) the oligomerization reaction is carried out by starting the oligomerization reaction with ethylene, and may be carried out, for example, under the following conditions: maintaining the reaction pressure at 0.1 to 30MPa, the reaction temperature at-20 to 150 ℃, and the reaction time at 30 to 100 min; (5) the reaction was stopped after a certain time. The reaction product was analyzed by Gas Chromatography (GC).
In one embodiment of the method of the present invention, the main catalyst and the cocatalyst in step (3) may be dissolved in an organic solvent before being added to the reaction system. In the oligomerization reaction process, the main catalyst and the cocatalyst are mixed in an ethylene atmosphere. The temperature of the oligomerization reaction is-20 to 150 ℃, for example, 0 to 80 ℃. Under preferred conditions, the temperature ranges from-20 to 40 deg.C, such as 5 to 35 deg.C. The reaction pressure is 0.1-30 MPa, and the oligomerization activity is increased along with the increase of the ethylene pressure.
The catalyst composition is used for ethylene oligomerization, and the obtained ethylene oligomerization product comprises C4、C6、C8、C10、C12、C14、C16、C18、C20、C22α -olefin selectivity can reach 96%, after the ethylene oligomerization reaction is finished, GC analysis shows that the oligomerization activity can reach 107g·mol(Fe)-1·h-1The above. In addition, the remaining reaction mixture was neutralized with a 5% diluted hydrochloric acid acidified ethanol solution, and no polymer was obtained.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of a main catalyst substituted chlorination-2-acetyl-1, 10-phenanthroline iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide (and an organic solvent), and the catalyst composition has high oligomerization reaction activity, α -olefin selectivity is high, and the oligomerization reaction is initiated quickly, operates stably and has good repeatability.
Detailed Description
The invention is further illustrated and described with reference to specific examples, which are not intended to be limiting.
Example 1
The ethylene oligomerization reaction specifically comprises the following steps: (1) replacing the reaction system through operations such as high-temperature drying, vacuum replacement and the like to ensure that the reaction system is anhydrous and anaerobic; (2) replacing the reaction system by using ethylene to ensure that the reaction system is in an ethylene environment; (3) adding tert-butyl hydroperoxide and toluene solvent into a reaction kettle, adding 1.37ml triethyl aluminum toluene solution (with the concentration of 715 mu mol/ml), adding 2ml chloro-2-acetyl-1, 10-phenanthroline condensation-2, 6-diethyl aniline iron (II) complex (namely R)3And R4Is methyl, R1、R2、R5And R6Hydrogen) was added to the reaction solution, and the total amount of the composition was adjusted to 100ml, wherein the t-butyl hydroperoxide content by weight was 25ppm and the Al/Fe ratio was 196 based on the weight of the organic solvent (toluene), and after sufficient stirring, ethylene was introduced to initiate oligomerization; (4) keeping the ethylene pressure at 1MPa and the reaction temperature at 30 ℃ for reacting for 30 minutes; (7) the reaction was stopped and a small amount of the reaction product was taken out for analysis by Gas Chromatography (GC): the oligomerization activity is 0.72X 107g·mol(Fe)-1·h-1The oligomer content is respectively C440.40％，C6～C1046.87％，C6～C1858.78% (containing linear α -olefin 97.4%), C20～C280.72 percent. The remaining mixture was neutralized with 5% hydrochloric acid acidified ethanol solution, no polymer was obtained. The analysis results are shown in table one.
Example 2
The same as in example 1, except that the content of t-butyl hydroperoxide was 100ppm by weight. The data are shown in Table 1.
Example 3
The same as in example 1, except that the content of t-butyl hydroperoxide was 250ppm by weight. The data are shown in Table 1.
Example 4
The same as in example 1, except that the content of t-butyl hydroperoxide was 500ppm by weight. The data are shown in Table 1.
Example 5
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 1000 ppm. The data are shown in Table 1.
Example 6
The difference from example 1 is that the t-butyl hydroperoxide content was 1300ppm by weight. The data are shown in Table 1.
Example 7
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 1750ppm by weight, the data being shown in Table 1.
Example 8
The same as in example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the reaction temperature was 0 ℃. The data are shown in Table 1.
Example 9
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-10 ℃. The data are shown in Table 1.
Example 10
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and the reaction temperature is-20 ℃. The data are shown in Table 1.
Example 11
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 40 ℃. The data are shown in Table 1.
Example 12
The procedure is as in example 1, except that the t-butyl hydroperoxide content is 500ppm by weight and that Al/Fe is 500. The data are shown in Table 1.
Comparative example 1
The same as example 1, except that t-butyl hydroperoxide was not present in the composition. The data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, according to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of the composition comprising the main catalyst chlorinated substituted-2-acetyl-1, 10-phenanthroline iron (II) condensation-2, 6-diethylaniline complex shown in the formula (I), an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent, and the catalyst composition has higher oligomerization reaction activity, α -olefin selectivity is high, and the oligomerization reaction is initiated quickly, stably operated and has good repeatability.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (19)
1. A catalyst composition for ethylene oligomerization comprises a main catalyst chlorinated substituted-2-acetyl-1, 10-phenanthroline iron (II) complex shown as a formula (I), an aluminum-containing cocatalyst and tert-butyl hydroperoxide:
in the formula, R1～R6Each independently selected from hydrogen and C1～C6Alkyl, halogen, C1～C6Alkoxy and nitro;
wherein the catalyst composition further comprises an organic solvent, and the weight content of the tert-butyl hydroperoxide is 5-1750 ppm by taking the weight of the organic solvent as a reference;
the molar ratio of aluminum in the aluminum-containing cocatalyst to iron in the main catalyst is 30:1 to 900: 1.
2. The catalyst composition of claim 1, wherein the weight content of t-butyl hydroperoxide in the catalyst composition is 35 to 1300ppm, based on the weight of the organic solvent.
3. The catalyst composition of claim 2, wherein the t-butyl hydroperoxide is present in the catalyst composition in an amount of 250 to 1000ppm by weight, based on the weight of the organic solvent.
4. The catalyst composition of any of claims 1-3, wherein the molar ratio of aluminum in the aluminum-containing co-catalyst to iron in the main catalyst is from 100:1 to 700: 1.
5. The catalyst composition of claim 4, wherein the molar ratio of aluminum in the aluminum-containing co-catalyst to iron in the main catalyst is from 196:1 to 500: 1.
6. The catalyst composition of any of claims 1-3, wherein R in the procatalyst is1-R6Each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitro.
7. The catalyst composition of claim 6, wherein R is3And R4Is methyl, and R1、R2、R5And R6Are all hydrogen.
8. The catalyst composition of any of claims 1-3, wherein the aluminum-containing cocatalyst is selected from at least one of an aluminoxane and an alkyl aluminum compound.
9. The catalyst composition according to claim 8, characterized in that the alkylaluminum compound has the general formula AlRnXmWherein each R is independently a straight or branched chain C1-C8An alkyl group; x is halogen; n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3.
10. The catalyst composition of claim 9, wherein X is chlorine or bromine.
11. The catalyst composition of claim 9, wherein the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.
12. The catalyst composition of claim 8, wherein the aluminoxane is C1-C4Alkylaluminoxane of which C1-C4The alkyl group is a linear or branched alkyl group.
13. The catalyst composition of claim 12, wherein the aluminoxane is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.
14. The catalyst composition of any one of claims 1-3, wherein the organic solvent is selected from at least one of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and methylene chloride.
15. The catalyst composition of claim 14, wherein the amount of the main catalyst in the catalyst composition is 2 to 500 μmol/L, based on the volume of the composition.
16. The catalyst composition of claim 15, wherein the amount of the main catalyst in the catalyst composition is 20 to 100 μmol/L, based on the volume of the composition.
17. A process for the oligomerization of ethylene by reacting ethylene with the catalyst composition of any one of claims 1 to 16.
18. The process of claim 17, wherein the reaction temperature is from-20 to 150 ℃.
19. The process of claim 18, wherein the reaction temperature is from-20 to 40 ℃.
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