CN109957050A - Asymmetric (alpha-diimine) nickel alkene catalyst and its preparation method and application - Google Patents
Asymmetric (alpha-diimine) nickel alkene catalyst and its preparation method and application Download PDFInfo
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- CN109957050A CN109957050A CN201811560455.3A CN201811560455A CN109957050A CN 109957050 A CN109957050 A CN 109957050A CN 201811560455 A CN201811560455 A CN 201811560455A CN 109957050 A CN109957050 A CN 109957050A
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- Prior art keywords
- methyl
- isopropyl
- ethyl
- bis
- benzhydryl
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- -1 nickel alkene Chemical class 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 40
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 34
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 33
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- YAIBDWAANBTYIA-UHFFFAOYSA-N aceanthrylene-1,2-dione Chemical compound C1=CC=C2C(C(C3=O)=O)=C4C3=CC=CC4=CC2=C1 YAIBDWAANBTYIA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Chemical group 0.000 claims abstract description 8
- 239000003426 co-catalyst Substances 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims 1
- 229910000564 Raney nickel Inorganic materials 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- 230000037048 polymerization activity Effects 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OIXUMNZGNCAOKY-UHFFFAOYSA-N 2,6-diethyl-4-methylaniline Chemical compound CCC1=CC(C)=CC(CC)=C1N OIXUMNZGNCAOKY-UHFFFAOYSA-N 0.000 description 4
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthalene Natural products C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 3
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- IPQOEKGUARIOHW-UHFFFAOYSA-N CC1=CC=CC=C1N(C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F)C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F Chemical class CC1=CC=CC=C1N(C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F)C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F IPQOEKGUARIOHW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- PCVSHUGXWNGOCS-UHFFFAOYSA-M diethylalumanylium;toluene;chloride Chemical compound [Cl-].CC[Al+]CC.CC1=CC=CC=C1 PCVSHUGXWNGOCS-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IIUQQOMGPXVHHU-UHFFFAOYSA-N n-benzhydryl-4-methylaniline Chemical class C1=CC(C)=CC=C1NC(C=1C=CC=CC=1)C1=CC=CC=C1 IIUQQOMGPXVHHU-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of based on asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance and its preparation method and application that 1,2- benzo acenaphthenequinone is skeleton.Structural formula such as formula (I) based on asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance that 1,2- benzo acenaphthenequinone is skeleton of the invention is shown, wherein R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl or methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups, R4For methyl, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl, X is chlorine or bromine.The preparation process of the catalyst is simple, can under the action of co-catalyst catalyzed ethylene polymerization, show preferable thermal stability and polymerization activity, have good prospects for commercial application.
Description
Technical field
The present invention relates to asymmetric (alpha-diimine) nickel alkene catalyst and its preparation method and application more particularly to one
Kind is based on asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance and preparation method thereof that 1,2- benzo acenaphthenequinone is skeleton, and makes
Polyethylene or polyacrylic application are obtained with the catalyst ethylene or propylene.
Background technique
Polyolefin is the basic material to involve the interests of the state and the people, and due to its excellent performance, the multiplicity of kind, raw material is easy
It obtains and cheap, it is made to be widely used in each fields such as industry, agricultural and national defence.The development and application of raw catelyst is to push away
Dynamic one of polyolefin industrial progress and the core drive of development are the key that the structure and performance for controlling polyolefine material.
In recent decades, it has been obtained widely by the research that coordination polymerization obtains functionalization and differential polyolefine material
Concern.The Ni (II) and Pd for Brookhart research group discovery ligand containing alpha-diimine that nineteen ninety-five is subsidized by E.I.Du Pont Company
(II) thus metal complex can develop the rear transition of a new generation at heavy polymer by catalyzed ethylene polymerization under normal pressure
Metallic catalyst (J.Am.Chem.Soc., 1995,117 (23): 6414-6415).This kind of alpha-diimine nickel alkene catalyst
Shown in specific structure such as formula (IV):
Up to the present, a large amount of research work keep two (aryl) alpha-diimine ligands layout it is constant in the case where,
Group (R group of formula) on the neighboring group (R' in formula) and diimine skeleton of aryl is modified.When R' is from different
When propyl changes methyl into, the degree of branching and molecular weight of resulting polymers are all reduced, and topological structure is more linear.However, this
The thermal stability of class catalyst is poor, even if using the sub-polyethylene of this kind of catalyst preparation when R' is the isopropyl of big steric hindrance
Son amount and catalyst activity all sharply decline with the rising of temperature.When polymerization temperature rises above 60 DEG C, catalyst is heated
It decomposes rapidly and inactivates.Rieger (J.AM. CHEM.SOC., 2007,129,9182-9191), Long
(J.AM.CHEM.SOC., 2013,135,16316-16319；ACS Catalysis, 2014,4,2501-2504) et al. by R'
Aryl or substituted aryl are become by alkyl, prepared catalyst thermal stability increases substantially, when polymerization temperature is higher than 60
DEG C when, catalyst still maintains good catalytic activity.But, this two sides aniline substituent group is what bulky substituent was rolled into a ball
The catalyst of symmetrical structure, when the ligand for preparing catalyst, since steric hindrance is big, the yield of ligand is very low, leads
Cause the synthesis cost of catalyst high；Meanwhile the R' of bulky substituent group hinders the quick insertion of ethylene, causes
When catalyzed ethylene polymerization, the polymerization activity of catalyst is not high, limits its industrial applications.
Summary of the invention:
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of big position based on 1,2- benzo acenaphthenequinone for skeleton
Hinder asymmetric (alpha-diimine) nickel alkene catalyst and its preparation method and application.
Asymmetry (alpha-diimine) nickel alkene catalyst provided by the invention, shown in general formula of the chemical structure such as formula (I):
In formula (I), R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl or
Methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups, R4For
Methyl, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl, X is chlorine or bromine.Formula
(I) selection of all aniline substituent groups is independent from each other in.
Preferably, formula (I) R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl or bis- (4- fluorobenzene
Base) methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen or methoxyl groups, R4For methyl,
Ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen or methyl, X is bromine.
Shown in catalyst ligand general structure provided by the invention such as formula (II):
In formula (II), R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl
Or methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups, R4
For methyl, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl.Institute in formula (II)
There is the selection of aniline substituent group to be independent from each other.
Preferably, R described in formula (II)1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl or bis- (4-
Fluorophenyl) methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen or methoxyl groups, R4For first
Base, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen or methyl.
It is furthermore preferred that any one of ligand in compound as shown in table 1 shown in above-mentioned (II):
1 ligand of table
The present invention also provides a kind of methods for preparing above-mentioned ligand compound, and it includes following steps:
1), 1,2- benzo acenaphthenequinone is obtained shown in formula (III) with the aniline with big steric hindrance substituent group by ketoamine condensation reaction
Compound:
The aniline substituent group that step reaction uses can refer to table 1；The step reaction use solvent can be selected from toluene, acetonitrile,
At least one of acetic acid and dehydrated alcohol, preferably toluene and acetonitrile；The catalyst that step reaction uses is selected from p-methyl benzenesulfonic acid
At least one of with acetic acid；The catalyst, 1,2- benzo acenaphthenequinone, the aniline with big steric hindrance substituent group and solvent amount ratio
For 0.1-0.15mmol:1-1.1mmol:1.1-1.4mmol:5-10ml, preferably 0.1mmol:1mmol:1.1mmol:8ml；
The step reaction time is 2-8 hours, preferably 3-6 hours.The mixed solvent or petroleum ether of product methylene chloride and petroleum ether
Mixed solvent with ethyl acetate is that eluent carries out column chromatography in silicagel column, obtains the product as shown in formula (III).
2), compound shown in formula (III) obtains formula (II) by ketoamine condensation reaction with the aniline with small steric hindrance substituent group
Corresponding compound:
The aniline substituent group that step reaction uses can refer to table 1；The solvent that step reaction uses is selected from toluene, acetonitrile, second
At least one of acid and dehydrated alcohol, preferably toluene and acetonitrile；The step reaction use catalyst be selected from p-methyl benzenesulfonic acid and
At least one of acetic acid；The dosage of compound shown in the catalyst, formula (III), the aniline with small steric hindrance substituent group and solvent
Than for 0.2-0.5mmol:1-1.1mmol:1.1-1.4mmol:30-70ml, preferably 0.3mmol:1mmol:1.1mmol:
50ml；The step reaction time is 6-16 hours, preferably 8-12 hours.The mixed solvent of product methylene chloride and petroleum ether or
The mixed solvent of petroleum ether and ethyl acetate is eluent in silicagel column progress column chromatography, obtains product shown in formula (II).
The present invention also provides a kind of preparation methods of catalyst shown in formula (I) comprising the steps of: in atmosphere of inert gases
Under, by compound shown in formula (II) and glycol dimethyl ether Nickel Bromide, glycol dimethyl ether Nickel Chloride or six hydration dichloros
Change one of nickel to be complexed, catalyst of the present invention can be obtained.X in catalyst structure formula of the present invention be chlorine or
Bromine selects X for bromine for polymerization effect without substantial effect in the embodiment of the present invention.
Preferably, under nitrogen atmosphere, compound shown in formula (II) can be selected from ligand shown in table 1, with containing for ligand complex
Nickel compound selects glycol dimethyl ether Nickel Bromide (DME) NiBr2, the ligand and (DME) NiBr2Molar ratio be 1:1-
1.2, preferably 1:1.1；The solvent be methylene chloride, reaction temperature be 15-35 DEG C, preferably 25 DEG C, reaction time 8-30 hour,
It is preferred that 16-24 hours.When X is bromine, referring to the ligand scheme of table 1, catalyst of the invention can be selected from any one in table 2
Kind:
2 catalyst of table
The present invention also provides a kind of carbon monoxide-olefin polymerics for catalysis in olefine polymerization, and the composition is by shown in formula (I)
Catalyst and co-catalyst form, and the co-catalyst is selected from least one of chlorination alkyl aluminum, alkyl aluminum and aikyiaiurnirsoxan beta, institute
Stating alkene is ethylene or propylene.
In above-mentioned carbon monoxide-olefin polymeric, the aikyiaiurnirsoxan beta be methylaluminoxane (MAO), modified methylaluminoxane (MMAO),
Ethylaluminoxane or isobutyl aluminium alkoxide；The alkyl aluminum is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum
Or tri-n-octylaluminium；The chlorination alkyl aluminum is diethylaluminum chloride, sesquialter aluminium diethyl monochloride or ethylaluminium dichloride；From helping
The using effect and cost consideration of catalyst, preferably chlorination alkyl aluminum as co-catalyst, metallic aluminium in chlorination alkyl aluminum with
The molar ratio abbreviation aluminium nickel ratio of metallic nickel in catalyst, aluminium nickel than range be 50-1000:1, preferably 100-800:1, more preferably
200-600:1, more preferable 400:1.
The invention also discloses the catalyst as shown in formula (I) in catalysis ethylene, propylene polymerization, prepares polyethylene, polypropylene
In application.
The invention has the advantages that being matched under the premise of unobvious increase side group substituent group steric hindrance by improving
Frame structure provides a kind of with the catalysis of (alpha-diimine) nickel olefin polymerization of good thermal stability and polymerization activity
Agent.
Specific embodiment:
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.
Be specifically related in the embodiment of the present invention such as chemical structural formula (I), (II), (III) compound represented such as 3 institute of table
Show:
Table 3
Embodiment 1
Prepare A1: in (the benzhydryl) -4- methylaniline of 2,6- bis- (8.8g, 20mmol) and 1,2- benzo acenaphthenequinone (4.2g,
P-methyl benzenesulfonic acid (0.34g, 2mmol) is added in toluene (150mL) solution 18mmol), back flow reaction 6h.Solvent is removed, is remained
The mixed solvent that the volume ratio of excess methylene chloride and petroleum ether is 2:1 carries out silica gel column chromatography, and the quality for obtaining A1 is
4.1g, yield: 35%.
Embodiment 2
Prepare A2: in (the benzhydryl) -6- methylaniline of 2,4- bis- (8.8g, 20mmol) and 1,2- benzo acenaphthenequinone (4.2g,
P-methyl benzenesulfonic acid (0.34g, 2mmol) is added in toluene (150mL) solution 18mmol), back flow reaction 6h.Solvent is removed, is remained
The mixed solvent that the volume ratio of excess methylene chloride and petroleum ether is 2:1 carries out silica gel column chromatography, and the quality for obtaining A2 is
5.0g, yield: 42%.
Embodiment 3
Prepare A3: in bis- (bis- (4- fluorophenyl) methyl) -6- methylanilines (10.2g, 20mmol) and 1 of 2,4-, 2- benzo
P-methyl benzenesulfonic acid (0.34g, 2mmol) is added in toluene (150mL) solution of acenaphthenequinone (4.2g, 18mmol), back flow reaction 10h.
The mixed solvent that the volume ratio of removal solvent, residue methylene chloride and petroleum ether is 2:1 carries out silica gel column chromatography, obtains A3
Quality be 6.3g, yield: 48%.
Embodiment 4
Prepare L1: in the toluene (50ml) of 2,6- dimethylaniline (0.133g, 1.1mmol) and A1 (0.653g, 1mmol)
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in solution, back flow reaction 12h.Remove solvent, residue petroleum ether and second
The mixed solvent that the volume ratio of acetoacetic ester is 30:1 carries out silica gel column chromatography, and the quality for obtaining L1 is 0.31g, yield: 41%.
Embodiment 5
Prepare L2: in the toluene (50ml) of 2,6- diethylaniline (0.164g, 1.1mmol) and A1 (0.653g, 1mmol)
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in solution, back flow reaction 12h.Remove solvent, residue petroleum ether and second
The mixed solvent that the volume ratio of acetoacetic ester is 30:1 carries out silica gel column chromatography, and the quality for obtaining L2 is 0.28g, yield: 36%.
Embodiment 6
Prepare L3: in the toluene of 2,6-DIPA (0.195g, 1.1mmol) and A1 (0.653g, 1mmol)
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in (50ml) solution, back flow reaction 12h.Remove solvent, residue petroleum
The volume ratio of ether and ethyl acetate be 30:1 mixed solvent carry out silica gel column chromatography, obtain L3 quality be 0.33g, yield:
41%.
Embodiment 7
Prepare L12: in 2,6- diethyl -4- methylaniline (0.179g, 1.1mmol) and A2 (0.653g, 1mmol)
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in toluene (50ml) solution, back flow reaction 12h.Solvent is removed, residue is used
The mixed solvent that the volume ratio of petroleum ether and ethyl acetate is 30:1 carries out silica gel column chromatography, and the quality for obtaining L12 is 0.31g,
Yield: 39%.
Embodiment 8
Prepare L20: in 2,6- diethyl -4- methylaniline (0.179g, 1.1mmol) and A3 (0.725g, 1mmol)
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in toluene (50ml) solution, back flow reaction 12h.Solvent is removed, residue is used
The mixed solvent that the volume ratio of petroleum ether and ethyl acetate is 30:1 carries out silica gel column chromatography, and the quality for obtaining L20 is 0.37g,
Yield: 43%.
Embodiment 9
Prepare C1: under nitrogen atmosphere, by L1 (0.151g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol)
It is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, washed 3 times with ether, each ether
Dosage is 20ml, then ether is drained to obtain solid C1,0.171g, yield 88%.
Embodiment 10
Prepare C2: under nitrogen atmosphere, by L2 (0.156g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol)
It is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, washed 3 times with ether, each ether
Dosage is 20ml, then ether is drained to obtain solid C2,0.172g, yield 86%.
Embodiment 11
Prepare C3: under nitrogen atmosphere, by L3 (0.162g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol)
It is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, washed 3 times with ether, each ether
Dosage is 20ml, then ether is drained to obtain solid C3,0.188g, yield 89%.
Embodiment 12
Prepare C12: under nitrogen atmosphere, by L12 (0.160g, 0.2mmol) and (DME) NiBr2(0.062g,
It 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, wash 3 times with ether, often
Secondary ether dosage is 20ml, then ether is drained to obtain solid C12,0.186g, yield 90%.
Embodiment 13
Prepare C20: under nitrogen atmosphere, by L20 (0.174g, 0.2mmol) and (DME) NiBr2(0.062g,
It 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, wash 3 times with ether, often
Secondary ether dosage is 20ml, then ether is drained to obtain solid C20,0.191g, yield 88%.
Following embodiment is catalyzed ethylene polymerization:
Embodiment 14
Ethylene pressure polymerization is carried out under the conditions of anhydrous and oxygen-free.Ethylene pressure is 1MPa, and polymerization temperature is 60 DEG C, will
1L heptane imports in the stainless steel cauldron of 2000mL, the co-catalyst that then injection 2.5ml concentration is 2.0 mol/L thereto
Diethylaluminum chloride toluene solution.10 μm of ol major catalyst C1 are dissolved with 10mL toluene solution, is injected into, ethylene is forced into
Polymer solution is poured into the ethanol solution of acidification and is settled after reacting half an hour by 1MPa, stirring, filtered polymeric, so
It is washed for several times with acidic ethanol afterwards, weighs to obtain 24.3g polymer after constant weight is dried under vacuum at 60 DEG C.Catalytic activity is
4.86×106gPE[mol(Ni)h] -1, polymerizate weight average molecular weight is 33.6 × 104G/mol, polydispersity coefficient 2.17.
Embodiment 15
C1 in embodiment 14 is replaced with into C2, other conditions are constant, and polymerizate is dried under vacuum to perseverance at 60 DEG C
25.8g polymer is weighed to obtain after weight.Catalytic activity is 5.16 × 106gPE[mol(Ni)h]-1, polymerizate weight average molecular weight is
37.2×104G/mol, polydispersity coefficient 2.31.
Embodiment 16
C1 in embodiment 14 is replaced with into C3, polymerization temperature is set as 20 DEG C, and other conditions are constant, by polymerizate 60
53.1g polymer is weighed to obtain after being dried under vacuum to constant weight at DEG C.Catalytic activity is 10.6 × 106gPE[mol(Ni)h]-1, polymerization
Product weight average molecular weight is 104.3 × 104G/mol, polydispersity coefficient 2.35.
Embodiment 17
C1 in embodiment 14 is replaced with into C12, polymerization temperature is set as 80 DEG C, and co-catalyst is changed to 10ml concentration and is
The MMAO toluene solution of 3.0mol/L, other conditions are constant, weigh after polymerizate is dried under vacuum to constant weight at 60 DEG C
18.9g polymer.Catalytic activity is 3.78 × 106gPE[mol(Ni)h]-1。
Embodiment 18
C1 in embodiment 14 is replaced with into C20, other conditions are constant, and polymerizate is dried under vacuum to perseverance at 60 DEG C
22.9g polymer is weighed to obtain after weight.Catalytic activity is 4.58 × 106gPE[mol(Ni)h]-1, polymerizate weight average molecular weight is
13.3×104G/mol, polydispersity coefficient 2.56.
Embodiment 19
Polymerization temperature in embodiment 18 is adjusted to 70 DEG C, other conditions are constant, by polymerizate at 60 DEG C vacuum
15.8g polymer is weighed to obtain after drying to constant weight.Catalytic activity is 3.16 × 106gPE[mol(Ni)h]-1, polymerizate weighs equal
Molecular weight is 11.6 × 104G/mol, polydispersity coefficient 2.53.
Comparative example 1
1,2- benzo acenaphthenequinone in embodiment 1 is replaced with to the acenaphthenequinone of same molar, prepares (2,6- bis- (hexichol first
Base) -4- methylaniline) acenaphthene ketone, code name D1, yield: 32%.
Comparative example 2
A1 in embodiment 5 is replaced with to the D1 of same molar, prepares 1- (2,6- diethylaniline) -2- (2,6- bis-
(benzhydryl) -4- methylaniline) acenaphthene, code name E1, yield 34%.
Comparative example 3
L2 in embodiment 10 is replaced with to the E1 of same molar, prepares (1- (2,6- diethylaniline) -2- (2,6-
Two (benzhydryl) -4- methylanilines) acenaphthene) close nickelous bromide, code name F1, yield 85%.
Comparative example 4
C2 in embodiment 15 is replaced with to the F1 of same molar, other conditions are constant, polymerization catalytic activity 4.26
×106gPE[mol(Ni)h]-1, polymerizate weight average molecular weight is 31.2 × 104G/mol, polydispersity coefficient 2.27.
Comparative example 5
1,2- benzo acenaphthenequinone in embodiment 3 is replaced with to the acenaphthenequinone of same molar, prepares (2,4- bis- (bis- (4- fluorobenzene
Base) methyl) -6- methylaniline) acenaphthene ketone, code name D2, yield: 51%.
Comparative example 6
A3 in embodiment 8 is replaced with to the D2 of same molar, prepares 1- (2,6- diethyl -4- methylaniline) -2-
(2,4- bis- (bis- (4- fluorophenyl) methyl) -6- methylaniline) acenaphthene, code name E2, yield 46%.
Comparative example 7
L20 in embodiment 13 is replaced with to the E2 of same molar, prepares (1- (2,6- diethyl -4- methylaniline) -
2- (2,4- bis- (bis- (4- fluorophenyl) methyl) -6- methylaniline) acenaphthene) close nickelous bromide, code name F2, yield 83%.
Comparative example 8
C20 in embodiment 19 is replaced with to the F2 of same molar, other conditions are constant, and polymerization catalytic activity is
2.41×106gPE[mol(Ni)h]-1, polymerizate weight average molecular weight is 9.6 × 104G/mol, polydispersity coefficient 2.33.
Claims (8)
1. (alpha-diimine) Raney nickel shown in formula (I):
In formula (I), R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl or first
Base, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups, R4For first
Base, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl, X is chlorine or bromine.
2. catalyst according to claim 1, it is characterised in that: the R1For benzhydryl or bis- (4- fluorophenyl) methyl,
R2For benzhydryl or bis- (4- fluorophenyl) methyl, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl,
Halogen or methoxyl group, R4For methyl, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen or methyl, X is bromine.
3. compound shown in formula (II):
In formula (II), R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl or first
Base, R3For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups, R4For first
Base, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl.
4. a kind of method for preparing the corresponding compound of formula described in claim 3 (II), it includes following steps:
1), 1,2- benzo acenaphthenequinone obtains chemical combination shown in formula (III) by ketoamine condensation reaction with the aniline with big steric hindrance substituent group
Object:
Wherein, R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl, bis- (4- fluorophenyl) methyl or methyl, R3
For methyl, ethyl, isopropyl, benzhydryl, bis- (4- fluorophenyl) methyl, halogen, trifluoromethyl or methoxyl groups；
2), compound shown in formula (III) obtains the formula (II) by ketoamine condensation reaction with the aniline with small steric hindrance substituent group
Corresponding compound:
Wherein, R4For methyl, ethyl or isopropyl, R5For methyl, ethyl or isopropyl, R6For hydrogen, methyl, ethyl or isopropyl.
5. a kind of method for preparing catalyst as claimed in claim 1 or 2 comprising the steps of: under atmosphere of inert gases, will weigh
Benefit requires 3 compounds and glycol dimethyl ether Nickel Bromide, glycol dimethyl ether Nickel Chloride or six hydration Nickel Chlorides
One of be complexed, catalyst of any of claims 1 or 2 can be obtained.
6. a kind of carbon monoxide-olefin polymeric for catalysis in olefine polymerization, which is characterized in that include master of any of claims 1 or 2
Catalyst and co-catalyst, wherein the co-catalyst is selected from least one of chlorination alkyl aluminum, alkyl aluminum and aikyiaiurnirsoxan beta,
The alkene is ethylene or propylene.
7. a kind of polyethylene, which is characterized in that the polyethylene is catalyzed ethylene by carbon monoxide-olefin polymeric as claimed in claim 6
Polymerization obtains.
8. a kind of polypropylene, which is characterized in that the polypropylene is catalyzed propylene by carbon monoxide-olefin polymeric as claimed in claim 6
Polymerization obtains.
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| CN102827312A (en) * | 2012-08-03 | 2012-12-19 | 浙江大学 | Ethylidene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof |
| CN104926962A (en) * | 2015-05-15 | 2015-09-23 | 浙江大学 | Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst |
| CN105646598A (en) * | 2014-11-17 | 2016-06-08 | 中国科学院化学研究所 | Naphthyl-substituted asymmetric acenaphthenediimine nickel complexes, and preparing method and applications thereof |
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| CN102060944B (en) * | 2010-12-17 | 2012-09-05 | 西北师范大学 | Alpha-diimine nickel (II) olefin polymerization catalyst as well as preparation method and application thereof |
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| CN102827312A (en) * | 2012-08-03 | 2012-12-19 | 浙江大学 | Ethylidene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof |
| CN105646598A (en) * | 2014-11-17 | 2016-06-08 | 中国科学院化学研究所 | Naphthyl-substituted asymmetric acenaphthenediimine nickel complexes, and preparing method and applications thereof |
| CN104926962A (en) * | 2015-05-15 | 2015-09-23 | 浙江大学 | Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst |
| CN105968027A (en) * | 2016-06-13 | 2016-09-28 | 中国科学技术大学 | Asymmetric diimine palladium catalyst and ligand, preparation method and application thereof |
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