CN109957049A - 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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- CN109957049A CN109957049A CN201711419028.9A CN201711419028A CN109957049A CN 109957049 A CN109957049 A CN 109957049A CN 201711419028 A CN201711419028 A CN 201711419028A CN 109957049 A CN109957049 A CN 109957049A
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- methyl
- isopropyl
- ethyl
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- benzhydryl
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- -1 nickel alkene Chemical class 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title abstract description 12
- 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 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 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
- 238000000034 method Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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 53
- 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 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000003446 ligand Substances 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 229910021585 Nickel(II) bromide Inorganic materials 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OIXUMNZGNCAOKY-UHFFFAOYSA-N 2,6-diethyl-4-methylaniline Chemical compound CCC1=CC(C)=CC(CC)=C1N OIXUMNZGNCAOKY-UHFFFAOYSA-N 0.000 description 2
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- GJXSUXPOOZGSPT-UHFFFAOYSA-N CC(C=C1)=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 CC(C=C1)=CC=C1N(C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F)C(C(C=C1)=CC=C1F)C(C=C1)=CC=C1F GJXSUXPOOZGSPT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229960000935 dehydrated alcohol Drugs 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
- 125000001033 ether group Chemical group 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 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
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 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
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
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 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone is skeleton.Shown in structural formula such as formula (I) based on asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance that 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone is skeleton of the invention.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 catalyst preparation process 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, especially a kind of bases
In asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance that 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone is skeleton,
Also relate to the preparation of the nickel alkene catalyst and the application of catalyzed polyeolfin.
Technical background:
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:
It is a kind of based on 9,10- dihydro -9,10- ethylene anthracene-the purpose of the present invention is overcoming the deficiencies of the prior art and provide
11,12- diketone is asymmetric (alpha-diimine) nickel alkene catalyst of big steric hindrance of skeleton and its preparation method and application.
It is provided by the invention asymmetric based on the big steric hindrance that 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone is skeleton
(alpha-diimine) nickel alkene catalyst, shown in general 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, formula (II) R1For benzhydryl or bis- (4- fluorophenyl) methyl, R2For benzhydryl or bis- (4- fluorine
Phenyl) 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), 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone is contracted with the aniline with big steric hindrance substituent group by ketoamine
It closes reaction and obtains compound shown in formula (III):
The aniline substituent group that step reaction uses can refer to table 1；Toluene can be used in the solvent that step reaction uses, and will have
The aniline of big steric hindrance substituent group is reacted with trimethyl aluminium generates aluminum amine salt, then aluminum amine salt and phenanthrenequione are carried out ketoamine condensation reaction.
The mixed solvent or petroleum ether of product methylene chloride and petroleum ether and the mixed solvent of ethyl acetate are eluent in silica gel
Column chromatography is carried out in column, obtains product 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 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 use of compound shown in the catalyst, formula (III), the aniline with small steric hindrance substituent group and solvent
Amount is than being 0.2-0.5mmol:1-1.1mmol:1.1-1.4mmol:30-70ml, preferably 0.3mmol:1mmol:1.1mmol:
50ml, the step reaction time are 6-16 hours, preferably 8-12 hours.The mixed solvent or stone of product methylene chloride and petroleum ether
The mixed solvent of oily 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 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:
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 beneficial effects of the present invention are provide a kind of (Asia α-two with good thermal stability and polymerization activity
Amine) nickel olefin polymerization catalyst.
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, preparation A1: in the toluene of (the benzhydryl) -4- methylaniline of 2,6- bis- (8.8g, 20mmol)
The toluene solution 20ml (1.0M, 20mmol) of trimethyl aluminium is added in (100mL) solution, is reacted 2 hours at 120 DEG C, it will be anti-
It answers temperature to be down to room temperature, 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone (4.2g, 18mmol) is then added, heats up back
Stream reaction for 24 hours, is cooled to room temperature, and is terminated with 5% sodium hydrate aqueous solution.Organic phase is extracted with ethyl acetate, and then uses nothing
Aqueous sodium persulfate is dry, removal solvent, and the mixed solvent that the volume ratio of residue methylene chloride and petroleum ether is 2:1 carries out silica gel
Column chromatography, the quality for obtaining A1 is 5.0g, yield: 38%.
Embodiment 2, preparation A2: in the toluene of (the benzhydryl) -6- methylaniline of 2,4- bis- (8.8g, 20mmol)
The toluene solution 20ml (1.0M, 20mmol) of trimethyl aluminium is added in (100mL) solution, is reacted 2 hours at 120 DEG C, it will be anti-
It answers temperature to be down to room temperature, 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone (4.2g, 18mmol) is then added, heats up back
Stream reaction for 24 hours, is cooled to room temperature, and is terminated with 5% sodium hydrate aqueous solution.Organic phase is extracted with ethyl acetate, and then uses nothing
Aqueous sodium persulfate is dry, removal solvent, and the mixed solvent that the volume ratio of residue methylene chloride and petroleum ether is 2:1 carries out silica gel
Column chromatography, the quality for obtaining A2 is 5.4g, yield: 41%.
Embodiment 3, preparation A3: in bis- (bis- (4- fluorophenyl) methyl) -4- methylanilines (10.2g, 20mmol) of 2,6-
The toluene solution 20ml (1.0M, 20mmol) of trimethyl aluminium is added in toluene (100mL) solution, is reacted 2 hours at 120 DEG C,
Reaction temperature is down to room temperature, 9,10- dihydro -9,10- ethylene anthracene -11,12- diketone (4.2g, 18mmol) is then added, is heated up
Back flow reaction for 24 hours, is cooled to room temperature, and is terminated with 5% sodium hydrate aqueous solution.Organic phase is extracted with ethyl acetate, and then uses
Anhydrous sodium sulfate is dry, removal solvent, and the mixed solvent that the volume ratio of residue methylene chloride and petroleum ether is 2:1 carries out silicon
Plastic column chromatography, the quality for obtaining A3 is 5.8g, yield: 40%.
Embodiment 4, preparation L1: at 2,6- dimethylaniline (0.133g, 1.1mmol) and A1 (0.656g, 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 L1 is 0.4g, produces
Rate: 53%.
Embodiment 5, preparation L2: at 2,6- diethylaniline (0.164g, 1.1mmol) and A1 (0.656g, 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 L2 is 0.43g, produces
Rate: 55%.
Embodiment 6, preparation L3: in 2,6-DIPA (0.195g, 1.1mmol) and A1 (0.656g, 1mmol)
Toluene (50ml) solution in be added p-methyl benzenesulfonic acid (0.086g, 0.5mmol), back flow reaction 12h.Remove solvent, residue
The mixed solvent that volume ratio with petroleum ether and ethyl acetate is 30:1 carries out silica gel column chromatography, and the quality for obtaining L3 is 0.42g,
Yield: 52%.
Embodiment 7, preparation L12: 2,6- diethyl -4- methylaniline (0.179g, 1.1mmol) and A2 (0.656g,
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in toluene (50ml) solution 1mmol), back flow reaction 12h.Solvent is removed,
The mixed solvent that the volume ratio of residue petroleum ether and ethyl acetate is 30:1 carries out silica gel column chromatography, obtains the quality of L12
For 0.45g, yield: 56%.
Embodiment 8, preparation L20: 2,6- diethyl -4- methylaniline (0.179g, 1.1mmol) and A3 (0.728g,
P-methyl benzenesulfonic acid (0.086g, 0.5mmol) is added in toluene (50ml) solution 1mmol), back flow reaction 12h.Solvent is removed,
The mixed solvent that the volume ratio of residue petroleum ether and ethyl acetate is 30:1 carries out silica gel column chromatography, obtains the quality of L20
For 0.48g, yield: 55%.
Embodiment 9, preparation C1: under nitrogen atmosphere, by L1 (0.152g, 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 C1,0.176g, yield 90%.
Embodiment 10, preparation C2: under nitrogen atmosphere, by L2 (0.157g, 0.2mmol) and (DME) NiBr2
(0.062g, 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, is washed with ether
It washs 3 times, each ether dosage is 20ml, then ether is drained to obtain solid C2,0.177g, yield 88%.
Embodiment 11, preparation C3: under nitrogen atmosphere, by L3 (0.163g, 0.2mmol) and (DME) NiBr2
(0.062g, 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, is washed with ether
It washs 3 times, each ether dosage is 20ml, then ether is drained to obtain solid C3,0.184g, yield 89%.
Embodiment 12, preparation C12: under nitrogen atmosphere, by L12 (0.160g, 0.2mmol) and (DME) NiBr2
(0.062g, 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, is washed with ether
It washs 3 times, each ether dosage is 20ml, then ether is drained to obtain solid C12,0.185g, yield 91%.
Embodiment 13, preparation C20: under nitrogen atmosphere, by L20 (0.175g, 0.2mmol) and (DME) NiBr2
(0.062g, 0.2mmol) is dissolved in 20ml methylene chloride, is stirred at room temperature 24 hours, methylene chloride is drained, is washed with ether
It washs 3 times, each ether dosage is 20ml, then ether is drained to obtain solid C20,0.192g, yield 88%.
Following embodiment is catalyzed ethylene polymerization:
Embodiment 14, ethylene pressure polymerization are carried out under the conditions of anhydrous and oxygen-free.Ethylene pressure is 1MPa, polymerization temperature
It is 60 DEG C, 1L heptane is imported in the stainless steel cauldron of 2000mL, then injection 2.5ml concentration is 2.0mol/L thereto
Co-catalyst diethylaluminum chloride toluene solution.10 μm of ol major catalyst C1 are dissolved with 10mL toluene solution, are injected into, it will
Ethylene is forced into 1MPa, and polymer solution is poured into the ethanol solution of acidification and settled after reacting half an hour by stirring, mistake
Polymer is filtered, is then washed for several times with acidic ethanol, weighs to obtain 24.3g polymer after constant weight is dried under vacuum at 60 DEG C.It urges
Changing activity is 4.86 × 106gPE[mol(Ni)h]-1。
C1 in embodiment 14 is replaced with C2 by embodiment 15, and other conditions are constant, by polymerizate at 60 DEG C vacuum
25.8g polymer is weighed to obtain after drying to constant weight.Catalytic activity is 5.16 × 106gPE[mol(Ni)h]-1。
C1 in embodiment 14 is replaced with C3 by embodiment 16, and polymerization temperature is set as 20 DEG C, and other conditions are constant, will be gathered
It closes after product is dried under vacuum to constant weight at 60 DEG C and weighs to obtain 53.1g polymer.Catalytic activity is 10.6 × 106gPE[mol
(Ni)h]-1。
C1 in embodiment 14 is replaced with C12 by embodiment 17, and it is 3.0mol/L's that co-catalyst, which is changed to 10ml concentration,
MAO toluene solution, other conditions are constant, and polymerizate is dried under vacuum to after constant weight at 60 DEG C and weighs to obtain 18.9g polymer.
Catalytic activity is 3.78 × 106gPE[mol(Ni)h]-1。
C1 in embodiment 14 is replaced with C20 by embodiment 18, and other conditions are constant, and polymerizate is true at 60 DEG C
22.9g polymer is weighed to obtain after sky drying to constant weight.Catalytic activity is 4.58 × 106gPE[mol(Ni)h]-1。
Polymerization temperature in embodiment 18 is adjusted to 70 DEG C by embodiment 19, and other conditions are constant, by polymerizate 60
15.8g polymer is weighed to obtain after being dried under vacuum to constant weight at DEG C.Catalytic activity is 3.16 × 106gPE[mol(Ni)h]-1。
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.
, 9,10- 4. a kind of method for preparing the corresponding compound of formula as claimed in claim 3 (II), it includes following steps: 1)
Dihydro -9,10- ethylene anthracene -11,12- diketone obtains formula (III) by ketoamine condensation reaction with the aniline with big steric hindrance substituent group
Shown compound:
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), it is corresponding with the aniline with small steric hindrance substituent group by ketoamine condensation reaction to obtain formula (II) for compound shown in formula (III)
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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