CN107282110B - Ethylene oligomerization catalyst composition and application thereof - Google Patents
Ethylene oligomerization catalyst composition and application thereof Download PDFInfo
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- CN107282110B CN107282110B CN201610195750.8A CN201610195750A CN107282110B CN 107282110 B CN107282110 B CN 107282110B CN 201610195750 A CN201610195750 A CN 201610195750A CN 107282110 B CN107282110 B CN 107282110B
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 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 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 alkylaluminum compound Chemical class 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-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
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229960000359 chromic chloride Drugs 0.000 claims description 2
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 claims description 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 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
- 239000008096 xylene Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 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 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 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
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- 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
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- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The application discloses a catalyst composition for ethylene oligomerization, which comprises a ligand compound shown in formula I, a transition metal compound, an aluminum-containing cocatalyst, tert-butyl hydroperoxide and an organic solvent; wherein X is O or S; r1、R2、R3And R4The same or different, each independently selected from hydrogen, alkyl, alkoxy or halogen. The invention also provides an ethylene oligomerization method, which comprises the step of carrying out ethylene oligomerization reaction in the presence of the catalyst composition for ethylene oligomerization. The catalyst composition provided by the invention has the advantages of high activity and high selectivity.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for an ethylene oligomerization reaction process, and correspondingly relates to an ethylene oligomerization method.
Background
Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry by which inexpensive small-molecule olefins can be converted into high value-added products linear α -olefin (LAO) is an important organic chemical raw material4-C8The compound is mainly applied to the field of producing high-quality Polyethylene (PE) as an important organic raw material and a chemical intermediate. The Linear Low Density Polyethylene (LLDPE) produced by copolymerizing 1-hexene or 1-octene with ethylene can obviously improve various properties of PE, in particular can obviously improve the mechanical property, optical property, tear strength and impact strength of polyethylene, and the product is very suitable for the fields of packaging films, agricultural covering films for greenhouses, sheds and the like. LAO C10-C30Can be used as additives for preparing daily detergents, flotation agents, emulsifying agents, lubricating components of refrigerating machines and drilling fluid, plasticizers, various additives, low-viscosity synthetic oils, polymers and copolymers, petroleum and petroleum product additives, higher alkylamines, higher organoaluminum compounds, higher alkylaryl hydrocarbons, higher fatty alcohols and fatty acids, epoxides, heat carriers, and the like. In LAO C20-C30In recent years, with the increasing development of the polyolefin industry, the worldwide demand for α -olefins has increased rapidly, most of the α -olefins being produced by oligomerization of ethylene.
Since the 70's last century, the research of transition metal complexes for the polymerization and oligomerization of olefins has been receiving increasing attention from scientists, and efforts have been made to develop new catalysts and to improve the existing catalysts to increase the activity of the catalysts and the selectivity of the catalytic products among numerous explorations, the earliest, most developed and concentrated nickel-based cationic catalyst systems have been developed, such as U.S. Pat. Nos. 3686351 and 3676523, and the Shell company SHOP process based on the patent technology, in the Shell company SHOP process, O-P bridged ligands have been involved, but the catalysts have toxic organophosphorus groups and have complicated synthesis steps and poor stability, and subsequently, many patents such as O-O, P-N, P-P and N-N coordinated nickel catalysts, such as JP 17611060627, WO 9996, WO991550, CN1401666, CN 9270, etc., the catalysts obtained from the above patents have generally had disadvantages of relatively complicated preparation methods, other catalysts and aluminum catalysts, such as chromium cocatalyst, aluminum cocatalyst, Brookn-aluminum cocatalyst, Brookn aluminoxane, high cost catalyst systems have been found to be used as catalysts for the ethylene oligomerization catalyst (CO 2, CO-9-O-N cocatalyst, CO-9-N cocatalyst has been used in the large-9-N cocatalyst for the production of ethylene oligomerization catalyst systems (CO-9-NH-N cocatalyst, CO-9-N cocatalyst, CO-9-N cocatalyst has been widely used in the production of ethylene oligomerization catalyst for the high-9-N coordination catalyst for the ethylene oligomerization catalyst for the.
At present, water and oxygen are generally considered to be very unfavorable for the ethylene oligomerization reaction process, and the ethylene oligomerization method is strictly controlled to be carried out in an anhydrous and oxygen-free environment, so that the current ethylene oligomerization reaction has very strict process requirements, and the reaction initiation and repeatability of the oligomerization reaction process are very poor.
Disclosure of Invention
In order to overcome the defects and shortcomings of the catalyst, the inventor of the invention surprisingly finds that ethylene is oligomerized under the action of a catalyst composition comprising a catalyst ligand shown in formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide, so that the catalyst has obviously higher oligomerization activity, and the oligomerization is rapid in initiation, stable in operation and good in repeatability; the tert-butyl hydroperoxide is used as organic peroxide to promote the reaction, thereby overcoming the technical bias of the technical personnel in the field and achieving unexpected technical effect.
Accordingly, in a first embodiment of the present invention, there is provided a catalyst composition for ethylene oligomerization comprising a ligand compound represented by formula I, a transition metal compound, an aluminum-containing cocatalyst and t-butyl hydroperoxide;
wherein X is O or S; r1、R2、R3And R4The same or different, each independently selected from hydrogen, alkyl, alkoxy, and halogen.
In a preferred embodiment of the present invention, the alkyl group is C1-C20Alkyl, preferably C1-C10Alkyl, more preferably C1-C6An alkyl group. The alkyl group in the present invention includes at least one of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl and isomers thereof, with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl or isohexyl being even more preferred; most preferred is methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
In a preferred embodiment of the present invention, the alkoxy group is C1-C20Alkoxy, preferably C1-C10Alkoxy, more preferably C1-C6An alkoxy group. The alkoxy group in the present invention includes at least one of the following groups: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, isopentoxy, n-hexoxy, sec-hexoxy, isohexoxy, n-heptoxy and isomers thereof; still more preferably a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a sec-pentyloxy group, an isopentyloxy group, a n-hexyloxy group or an isohexyloxy group; most preferred is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy.
In a preferred embodiment of the invention, the halogen is selected from fluorine, chlorine or bromine.
In a preferred embodiment of the present invention, the transition metal compound is at least one selected from the group consisting of compounds of chromium, molybdenum, iron, titanium, zirconium and nickel, preferably at least one selected from the group consisting of chromium trichloride, chromium acetylacetonate, chromium isooctanoate and chromium tris (tetrahydrofuran) trichloride.
In a preferred embodiment of the present invention, the cocatalyst is an organoaluminum compound; preferably an alkylaluminum compound and/or an aluminoxane compound, more preferably at least one of the following compounds: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, methylaluminoxane, ethylaluminoxane or modified methylaluminoxane; most preferably methylaluminoxane or triethylaluminium.
In a preferred embodiment of the present invention, the ligand, the transition metal compound and the cocatalyst are present in a molar ratio of 1: (0.1-10): (1-1000), preferably 1: (0.25-2): (10-700), more preferably 1: (0.5-2): (100-500). And the molar ratio of the transition metal in the transition metal compound to the metal in the co-catalyst is preferably 1 (50-1000). Within the above range, a more active catalyst composition can be advantageously obtained.
In a preferred embodiment of the present invention, an organic solvent is further included in the composition. Wherein the weight content of the tert-butyl hydroperoxide contained in the catalyst composition is 25-1000ppm by weight based on the weight of the organic solvent; more preferably 150-750ppm, most preferably 250-500 ppm. Within the above range, higher catalytic activity can be obtained.
In a preferred embodiment of the present invention, the organic solvent is selected from aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds. The aromatic hydrocarbon compound is preferably at least one selected from benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene or monochlorobenzene and derivatives thereof; the aliphatic hydrocarbon compound is preferably at least one selected from linear alkanes, branched alkanes, and cyclic alkanes, and more preferably at least one selected from pentane, heptane, cyclohexane, and hexane.
The second embodiment of the invention also provides an ethylene oligomerization method, which comprises the step of carrying out ethylene oligomerization reaction in the presence of the catalyst composition for ethylene oligomerization.
In a preferred embodiment of the invention, the reaction temperature of the reaction is 0 to 200 ○ C, preferably 0 to 100 ○ C, wherein the reaction pressure is 0.1 to 6.0MPa, preferably 0.5 to 5.0 MPa.
In a preferred embodiment of the present invention, the concentration of the transition metal compound is 0.001 to 1mmol/L based on the volume of the composition.
Specifically, in the ethylene oligomerization or olefin oligomerization process, ethylene or olefin, an optional organic solvent and the catalyst composition are added into a reactor, then the ethylene pressure (i.e. the reaction pressure) is controlled to be 0.1-6.0MPa, preferably 0.5-5.0MPa, the reaction temperature is 0-200 ○ C, preferably 0-100 ○ C, the reaction is carried out, after the reaction is finished, the reaction is cooled to room temperature, and a gas-liquid product is taken for chromatographic analysis.
According to the catalyst composition provided by the invention, ethylene is subjected to oligomerization reaction under the action of the catalyst ligand shown in the formula I, the transition metal compound, the aluminum-containing cocatalyst and the tert-butyl hydroperoxide catalyst composition, so that the catalyst composition has high oligomerization reaction activity, and the oligomerization reaction is quick in initiation, stable in operation and good in repeatability. The catalytic system is simple and easy to prepare and control. When the catalyst system is used for ethylene oligomerization, the catalyst has high activity, and C in the product6-C18And the content of the components is high, and the current world pair α -C can be met6、α-C8、α-C10And the above long chain olefin products.
In the invention, especially in the pilot-scale test and industrial production process of ethylene oligomerization, not only does the strict control of an anhydrous oxygen-free system not need to be carried out, but also has higher polymerization reaction activity in the presence of organic peroxide, namely tert-butyl hydroperoxide, and has the advantages of rapid reaction initiation, stable operation and good repeatability, thereby obtaining beneficial effects.
Detailed Description
The present invention will be described in detail with reference to examples, but it should be understood that the scope of the present invention is not limited to the examples.
In the examples of the present invention, NMR was detected by an AV400MHz NMR spectrometer of Bruker, Switzerland.
The gas chromatography was performed using a Hewlett packard 5890 chromatograph. The mass spectrum was detected by a gas chromatograph-mass spectrometer of TraceDSQ model, Phenix, USA.
Example 1
A stainless steel polymerizer is used. Heating a stainless steel polymerization kettle to 100 ℃, vacuumizing, replacing with nitrogen for a plurality of times, and then filling ethylene until the ethylene pressure is 2MPa, and cooling to room temperature. Then toluene was added at 70 deg.C while adding 5. mu. mol of ligand compound 1 (as shown in formula I, wherein X ═ S, R1=R2=R3=R4=CH3) The total volume of the mixed solution is 100mL, wherein the molar ratio of the ligand to the chromium chloride to the methylaluminoxane is 1: 1: 200, namely the adding amount of chromium chloride is 5 mu mol, and the adding amount of triethyl aluminum is 1 mmol; the molar ratio Al/Cr is 200. The content of t-butyl hydroperoxide was 25ppm by weight based on the weight of the organic solvent. Controlling the reaction pressure to be 2.0MPa, and introducing ethylene to carry out ethylene oligomerization.
And after the reaction is finished, cooling the system to room temperature, collecting the gas-phase product in a gas metering tank, collecting the liquid-phase product in a conical flask, and adding 1mL of ethanol as a terminator to terminate the ethylene oligomerization reaction. And (4) carrying out gas chromatographic analysis after the gas-liquid phase product is measured. The results are shown in Table 1.
Example 2
The same as in example 1 except that the content of t-butyl hydroperoxide was 150 ppm; the results are shown in Table 1.
Example 3
The same as in example 1 except that the content of t-butyl hydroperoxide was 300 ppm; the results are shown in Table 1.
Example 4
The same as in example 1 except that the tert-butyl hydroperoxide content was 500 ppm; the results are shown in Table 1.
Example 5
The same as in example 1 except that the content of t-butyl hydroperoxide was 750 ppm; the results are shown in Table 1.
Example 6
The same as in example 1 except that the tert-butyl hydroperoxide content was 1000 ppm; the results are shown in Table 1.
Example 7
The same as in example 1 except that the tert-butyl hydroperoxide content was 1500 ppm; the results are shown in Table 1.
Example 8
The triethyl aluminum was replaced by methyl aluminoxane under the same conditions as in example 6; the results are shown in Table 1.
Example 9
The Al/Cr molar ratio was changed to 50 under the same conditions as in example 6; the results are shown in Table 1.
Example 10
The Al/Cr molar ratio was changed to 1000 under the same conditions as in example 6; the results are shown in Table 1.
Example 11
The same as in example 6, except that a ligand compound 2, wherein X ═ O, R in formula I, was used1=R2=R3=R4=CH3(ii) a The results are shown in Table 1.
Example 12
The same as in example 6, except that a ligand compound 3 is used, wherein X ═ S, R in formula I1=R2=R3=R4H; the results are shown in Table 1.
Comparative example 1
The same as in example 1, except that the content of t-butyl hydroperoxide was 0ppm by weight. The results are shown in Table 1.
As can be seen from the data in Table 1, according to the catalyst composition provided by the present invention, ethylene is oligomerized under the action of the catalyst composition containing tert-butyl hydroperoxide, and rather, the catalyst composition has high oligomerization activity, and as can be seen from the comparison of the activity of the catalyst composition of the comparative example 1, the activity of the catalyst composition of the present invention corresponding to the same oligomerization conditions is increased by several times, and the selectivity of α -olefin obtained in the examples of the present invention is also very high compared with the selectivity of α -olefin in the comparative example.
In addition, the oligomerization reaction of the invention has the advantages of rapid initiation, stable operation and good repeatability. Even when the Al/Cr ratio is as low as 50, the catalyst still has good oligomerization catalytic activity, so that the ethylene oligomerization cost is greatly reduced, and the catalyst has strong practicability and wide industrialization prospect.
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 (21)
1. A catalyst composition for ethylene oligomerization comprises a ligand compound shown in formula (I), a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide;
wherein X is O or S; r1、R2、R3And R4The same or different, each independently selected from hydrogen and alkylAlkyl, alkoxy and halogen;
wherein the composition further comprises an organic solvent, and the weight content of the tert-butyl hydroperoxide is 25-1500ppm by weight based on the weight of the organic solvent;
the ligand compound is: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.1-10) to 1-1000.
2. The composition of claim 1, wherein the alkyl group is C1-C20An alkyl group; and/or the alkoxy is C1-C20An alkoxy group.
3. The composition of claim 2, wherein the alkyl group is C1-C10Alkyl and/or said alkoxy is C1-C10An alkoxy group.
4. The composition of claim 3, wherein the alkyl group is C1-C6An alkyl group; and/or the alkoxy is C1-C6An alkoxy group.
5. The composition as claimed in any one of claims 1 to 4, wherein the tert-butyl hydroperoxide is present in an amount of 150-1000ppm by weight, based on the weight of the organic solvent.
6. The composition as claimed in claim 5, wherein the t-butyl hydroperoxide is present in an amount of 250-750ppm by weight, based on the weight of the organic solvent.
7. The composition of any one of claims 1-4, wherein the ligand compound: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.25-2) to 10-700.
8. The composition of claim 7, wherein the ligand compound: transition metal compound: the molar ratio of the aluminum-containing cocatalyst is 1 (0.5-2) to (100-500).
9. The composition of claim 8, wherein the molar ratio of the transition metal in the transition metal compound to the metal in the aluminum-containing cocatalyst is 1 (50-1000).
10. The composition according to any one of claims 1 to 4, wherein the transition metal compound is selected from at least one of compounds of chromium, molybdenum, iron, titanium, zirconium and nickel.
11. The composition of claim 10, wherein the transition metal compound is selected from at least one of chromium trichloride, chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
12. The composition of any one of claims 1-4, wherein the aluminum-containing co-catalyst is an organoaluminum compound.
13. The composition of claim 12, wherein the aluminum-containing cocatalyst is an alkylaluminum compound and/or an aluminoxane compound.
14. The composition of claim 13, wherein the aluminum-containing co-catalyst is at least one of the following compounds: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, methylaluminoxane, ethylaluminoxane and modified methylaluminoxane.
15. The composition of claim 5, wherein the organic solvent is selected from the group consisting of aromatic hydrocarbons and aliphatic hydrocarbons.
16. The composition of claim 15, wherein the aromatic hydrocarbon compound is selected from at least one of benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene or monochlorobenzene and derivatives thereof; the aliphatic hydrocarbon compound is selected from at least one of linear alkanes, branched alkanes and cyclic alkanes.
17. The composition of claim 16, wherein the aliphatic hydrocarbon compound is selected from at least one of pentane, heptane, cyclohexane, and hexane.
18. A process for oligomerization of ethylene, comprising carrying out the oligomerization of ethylene in the presence of the catalyst composition for oligomerization of ethylene as claimed in any one of claims 1 to 17.
19. The method of claim 18, wherein the reaction temperature of the reaction is 0-200 ℃; and/or the reaction pressure is 0.1-6.0 MPa.
20. The method of claim 19, wherein the reaction temperature of the reaction is 0-100 ℃; and/or the reaction pressure is 0.5-5.0 MPa.
21. The method of claim 18, wherein the transition metal compound is present in a concentration of 0.001 to 1mmol/L, based on the volume of the composition.
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