CN108864327B - 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst and preparation and application thereof - Google Patents
5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 54
- -1 nickel olefin Chemical class 0.000 title claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- HMUDLFJQDJVKKZ-UHFFFAOYSA-N 5,6-dimethyl-1,2-dihydroacenaphthylene Chemical compound C1CC2=CC=C(C)C3=C2C1=CC=C3C HMUDLFJQDJVKKZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 91
- 239000003446 ligand Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 10
- XAABPYINPXYOLM-UHFFFAOYSA-N 1,8-dimethylnaphthalene Chemical compound C1=CC(C)=C2C(C)=CC=CC2=C1 XAABPYINPXYOLM-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BTOJSYRZQZOMOK-UHFFFAOYSA-N 4-chloro-7-(4-methylphenyl)sulfonylpyrrolo[2,3-d]pyrimidine Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1C2=NC=NC(Cl)=C2C=C1 BTOJSYRZQZOMOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000005917 acylation reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- FKNSMYUAQAQAQA-UHFFFAOYSA-N 5,6-dimethylacenaphthylene Chemical group C1=CC2=CC=C(C)C3=C2C1=CC=C3C FKNSMYUAQAQAQA-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 72
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 230000000694 effects Effects 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- MCEKFXJTDRWTTJ-UHFFFAOYSA-N 2,4,6-tributylaniline Chemical compound CCCCC1=CC(CCCC)=C(N)C(CCCC)=C1 MCEKFXJTDRWTTJ-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- XAECMISKSZECJD-UHFFFAOYSA-N 2-ethylidene-1H-acenaphthylene Chemical compound C(C)=C1CC2=CC=CC3=CC=CC1=C23 XAECMISKSZECJD-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- YJFYRYLMCZZMIN-UHFFFAOYSA-N C1CC2=CC=CC3=CC=CC1=C23.C=C Chemical compound C1CC2=CC=CC3=CC=CC1=C23.C=C YJFYRYLMCZZMIN-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical group N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7004—Neutral ligand
- C08F4/7006—NN
-
- 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
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- 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
- C08F10/02—Ethene
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- 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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of olefin catalytic polymerization, and aims to provide a 5, 6-dimethyl acenaphthene (α -diimine) nickel olefin catalyst, and preparation and application thereof.
Description
Technical Field
The invention relates to the field of olefin catalytic polymerization, in particular to a preparation method and application of a 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst.
Background
Polyolefin is a basic material related to the national civilization, and due to the excellent performance, variety, easily available raw materials and low price, the polyolefin is widely applied to various fields of industry, agriculture, national defense and the like. The development and application of new catalyst systems are one of the core drivers to advance and develop the polyolefin industry, and are the key to controlling the structure and performance of polyolefin materials.
In recent years, research into obtaining functionalized polyolefin materials by coordination polymerization has received wide attention. A new generation of late transition metal catalysts was developed by Brookhart research group sponsored by DuPont in 1995 to discover that Ni (II) metal complexes containing alpha-diimine ligands can catalyze the polymerization of ethylene at atmospheric pressure to produce polyethylene having high molecular weight and a higher degree of branching (J.Am.chem.Soc.,1995,117(23): 6414-). 6415). The specific structure of the alpha-diimine nickel olefin catalyst is shown as the formula (I):
however, such nickel alpha-diimine olefin catalysts have poor thermal stability, and even when R' is a highly hindered isopropyl group, the molecular weight and catalyst activity of polyethylene prepared using such catalysts decrease with increasing temperature. Especially when the polymerization temperature is more than 60 ℃, when the catalyst is used for catalyzing ethylene polymerization, the activity of the catalyst and the molecular weight of the prepared polyethylene are sharply reduced, and even the catalyst is decomposed and deactivated.
To date, much research has been directed to modifying the ortho groups of the aryl groups (R' in the formula) and the groups on the diimine backbone (R groups in the formula) while maintaining the bis (aryl) α -diimine ligand arrangement. The Chinese invention patent (CN101812145A) designs a diphenyl skeleton or camphyl skeleton alpha-diimine nickel complex. The complex can be used for preparing high molecular weight branched polyethylene at higher temperature by increasing the steric hindrance of a ligand skeleton structure, stabilizing an active center and improving the thermal stability of the catalyst. However, the synthesis of the catalyst ligand is complicated, and the aluminum-nickel ratio in the polymerization process is high (600) due to the activation of methylaluminoxane, which is not favorable for industrialization and commercialization. The Long research group adds steric hindrance of aniline substituent and stabilizes the metal active center by introducing a large steric hindrance substituent of diphenyl methylene into an ortho-position group (R' in the formula) of aryl. The complex has excellent heat resistance, and can still catalyze ethylene polymerization at 100 ℃ to generate high molecular weight polyethylene. However, the yield of the catalyst is low, the process is complex, the branching degree of the polymerized polyethylene is low, and the advantage that the alpha-diimine nickel olefin catalyst can catalyze to obtain the polyethylene with high branching degree is lost.
The Chinese invention patent CN 201210276331 provides a catalyst (the structure is shown in formula (II)),
the catalyst has the advantages that the ethylene bridge bond is introduced into the framework of the catalyst, so that the heat resistance of the catalyst is effectively improved, and the catalyst can catalyze ethylene to polymerize at a temperature of more than or equal to 60 ℃ with high activity to obtain branched polyethylene. However, the catalyst is not sufficiently stable at polymerization temperatures above 80 ℃ and the molecular weight of the polyethylene produced by the catalytic polymerization of ethylene is low.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst and preparation and application thereof.
In order to solve the technical problem, the solution of the invention is as follows:
provided is a 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst, the chemical structural formula of the catalyst is shown as the following formula:
in the formula, wherein R1Is alkyl, R2Is hydrogen or alkyl.
In the invention, in the chemical structural formula of the catalyst, R1Is methyl, isopropyl or tert-butyl, R2Hydrogen, methyl or tert-butyl.
The invention also provides a method for preparing the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst, which comprises the following steps:
(1) carrying out double acylation reaction on 1, 8-dimethylnaphthalene and oxalyl bromide to obtain a compound C1:
(2) and (3) performing ketoamine condensation reaction on the compound C1 and 2 equivalents of aniline to obtain an alpha-diimine ligand C2-C5:
in the above reaction formula, when R1＝Me，R2When H, α -diimine ligand C2 is obtained, or alternatively, R1＝iPr， R2When H, α -diimine ligand C3 is obtained, or alternatively, R1＝R2When Me is not substituted α -diimine ligand C4, or R1＝R2When tBu, α -diimine ligand C5 is obtained;
(3) under the anhydrous and oxygen-free conditions, respectively complexing alpha-diimine ligand C2-C5 with ethylene glycol dimethyl ether nickel dibromide to obtain 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst C6-C9:
in the above reaction formula, when R1＝Me，R2When H, catalyst C6 is obtained; or, R1＝iPr，R2When H, catalyst C7 is obtained; or, R1＝R2Me, catalyst C8 is obtained; or, R1＝R2When tBu, catalyst C9 was obtained.
The invention further provides application of the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst in catalyzing polymerization of ethylene or propylene to prepare polyethylene or polypropylene.
Description of the inventive principles:
the methyl on naphthalene ring of 5, 6-dimethyl acenaphthene (alpha-diimine) nickel catalyst is electron-donating group, the electron-donating property of the methyl is conducted downwards through naphthalene and acts on the metal active center nickel, so that the electronegativity of the nickel is enhanced, and the metal active center can be more stable when ion pairs are formed with a cocatalyst in the process of catalyzing ethylene polymerization. Therefore, the thermal stability of the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel catalyst is higher than that of the ethylidene acenaphthene (alpha-diimine) nickel catalyst (the structure is shown in the formula (II)) and the classical Brookhart catalyst.
The methyl group on the naphthalene ring of the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel catalyst is an electron donating group, which is the structural difference of the catalyst from other catalysts.
Compared with the prior art, the invention has the beneficial effects that:
1. the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst has high activity and good thermal stability, can still maintain higher catalytic activity when catalyzing ethylene polymerization at the polymerization temperature of more than 80 ℃, and can catalyze to obtain high molecular weight hyperbranched polyethylene. However, classical Brookhart catalysts lose their catalytic activity at polymerization temperatures above 60 ℃.
2. Compared with ethylene acenaphthene (alpha-diimine) nickel catalysts (the structure of which is shown in a formula (II)) and classical Brookhart catalysts (the structure of which is shown in a formula (I)), the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst has better thermal stability under the same polymerization conditions.
3. The 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst can show high activity when the aluminum-nickel ratio is 100, the aluminum-nickel ratio required by the thermal stability alpha-diimine nickel olefin polymerization catalyst reported in the prior art when catalyzing ethylene polymerization is generally higher than 500, and the production cost is greatly reduced.
4. The 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst has low cost of raw materials (1, 8-dimethyl naphthalene can be synthesized by simple organic reaction), short synthetic route and high reaction yield, and can realize industrial production.
Detailed Description
The preparation method of the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst comprises the following steps:
(1) carrying out double acylation reaction on 1, 8-dimethylnaphthalene to obtain a compound C1: 1, 8-dimethylnaphthalene is used as a raw material, and carbon disulfide is used as a solvent. Anhydrous aluminum bromide is added as a catalyst, and 5, 6-dimethyl acenaphthylene diketone C1 is obtained as a light yellow solid under the condition that oxalyl bromide is used as an oxidant.
(2) The compound C1 and 2 equivalents of aniline are subjected to ketoamine condensation reaction to obtain the alpha-diimine ligand C2-C5. And (2) carrying out ketoamine condensation reaction on the 5, 6-dimethyl acenaphthylene diketone (C1) raw material obtained in the step (1) with acetonitrile as a solvent and acetic acid as a catalyst to obtain the alpha-diimine ligand (C2-C5).
In the above reaction formula, when R1＝Me，R2When H, α -diimine ligand C2 is obtained, or alternatively, R1＝iPr， R2When H, α -diimine ligand C3 is obtained, or alternatively, R1＝R2When Me is not substituted α -diimine ligand C4, or R1＝R2When tBu, α -diimine ligand C5 is obtained;
(3) under the anhydrous and oxygen-free conditions, 4 alpha-diimine ligands C2-C5 are complexed with ethylene glycol dimethyl ether nickel dibromide [ (DME) NiBr2] to obtain the olefin polymerization catalyst (C6-C9) in the formula (III).
Formula (III)
In the above reaction formula, when R1＝Me，R2When H, catalyst C6 is obtained; or, R1＝iPr，R2When H, catalyst C7 is obtained; or, R1＝R2Me, catalyst C8 is obtained; or, R1＝R2When tBu, catalyst C9 was obtained.
The chemical structural formula of the 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst C6-C9 is shown as the following formula:
in the formula, wherein R1Is alkyl (methyl, isopropyl or tert-butyl), R2Hydrogen or alkyl (methyl or tert-butyl).
The double acylation reaction, the ketoamine condensation reaction and the complexation reaction involved in the synthesis process of the catalyst are classical reactions in the literature, and the reaction parameters such as the input amount of each reactant and the reaction conditions are universal in the synthesis process, and are known to researchers in the technical field.
The 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst can be applied to the preparation of polyethylene and polypropylene. The 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst in the formula (III) catalyzes ethylene or propylene to polymerize at the temperature of 25-95 ℃ under the activation of any one of cocatalyst methylaluminoxane, modified methylaluminoxane, diethyl aluminum monochloride, ethyl aluminum sesquichloride or ethyl aluminum dichloride, so as to prepare hyperbranched polyethylene or polypropylene with higher molecular weight.
The present invention will be further described with reference to the following specific examples, but the present invention is not limited to the following examples. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.
Preparation of Compound C1
Example 1
To a 500mL three-necked flask, under nitrogen, was added 150mL of carbon disulfide, 6.8g of aluminum bromide, and 3.4mL (23.88mmol) of oxalyl bromide, and the three-necked flask was placed in an ethanol bath at-78 ℃ and stirred. Under the protection of nitrogen, 100mL of carbon disulfide and 1g (6.41mmol) of 1, 8-dimethylnaphthalene are added into another 250mL three-neck flask to prepare a carbon disulfide solution of 1, 8-dimethylnaphthalene. The prepared carbon disulfide solution of 1, 8-dimethylnaphthalene is dripped into a 500mL three-necked bottle within 2 h. After the dropwise addition, the 500mL three-necked flask was placed in an ice-water bath at 0 ℃ for reaction for 3 hours. After the reaction was completed, 100mL of deionized water was slowly added dropwise to a 500mL three-necked flask, and the solvent carbon disulfide was removed by a cold trap at room temperature. The reaction product was extracted from deionized water with dichloromethane to give a dichloromethane solution of the product, which was washed three times with aqueous solutions of hydrochloric acid, sodium bicarbonate and sodium chloride, respectively, after which the dichloromethane solution was rotary evaporated to remove the solvent dichloromethane to give compound C1 as a pale yellow solid giving C1 with a mass of 0.4215g and a yield of 31.31%.
1H-NMR(400MHz，CDCl3，in ppm)：7.96(dd，2H，Ar-H)，7.58(dd，2H，Ar-H)，3.08(s，6H，CH3)。
Preparation of bis, ligands
Example 2
0.40g (1.90mmol) of compound C1 is added into a 250mL three-neck flask under the protection of nitrogen, 150mL of acetonitrile is added, the mixture is heated to 80 ℃, refluxed for 30min, 8mL of acetic acid is added, the temperature is raised to 85 ℃, and then the reflux is continued for 15min, and the solid in the reaction flask is completely dissolved. Then, 0.91mL (4.25mmol) of 2, 6-dimethylaniline was added to the reaction flask while it was still hot, and the reaction was refluxed at 85 ℃ for 24 hours. After the reaction, acetonitrile was removed by rotary evaporation, and column chromatography purification was performed using an eluent of petroleum ether and dichloromethane at a ratio of 1:1 (triethylamine was added to the eluent at a mass ratio of 0.75%) to obtain a total of 0.669g of ligand C2 at a yield of 84.47%.
1H-NMR(400MHz，CD3OD，in ppm)：6.4-7.4(s，10H，Ar-H)，2.89(s，6H， CH3)，2.38(s，12H，CH3)。
Elem.Anal.Calcd.For C30H28N2：C，86.50％；H，6.78％；N，6.72％。Found：C，86.92％；H，6.84％；N，6.24％。
ESI-MS：m/z 417.20([M+H]+)。
Example 3
Adding 0.40g (1.90mmol) of compound C1 into a 250mL three-necked flask under the protection of nitrogen, adding 150mL of acetonitrile, heating to 80 ℃, refluxing for 30min, adding 9mL of acetic acid, heating to 85 ℃, continuing refluxing for 15min, completely dissolving the solid in the reaction flask, then adding 0.81mL (4.29mmol) of 2, 6-diisopropylaniline into the reaction flask while the solution is hot, and refluxing at 85 ℃ for 24 h. After the reaction was completed, acetonitrile was removed by rotary evaporation, and column chromatography purification was performed using an eluent of petroleum ether and dichloromethane to 1:1 (0.75% triethylamine was added to the eluent), whereby a total of 0.766g of ligand C3 was obtained, with a yield of 76.14%.
1H-NMR(400MHz，CD3OD，in ppm)：6.4-7.4(s，10H，Ar-H)，2.90-2.95(sept， 4H，CH(CH3)2)，2.89(s，6H，CH3)，0.84-1.42(dd，24H，CH(CH3)2)。
Elem.Anal.Calcd.For C38H44N2：C，86.31％；H，8.39％；N，5.30％。Found：C，86.52％；H，8.64％；N，4.84％。
ESI-MS：m/z 529.40([M+H]+)。
Example 4
Adding 0.40g (1.90mmol) of compound C1 into a 250mL three-necked flask under the protection of nitrogen, adding 150mL of acetonitrile, heating to 80 ℃, refluxing for 30min, adding 9mL of acetic acid, heating to 85 ℃, continuing refluxing for 15min, completely dissolving the solid in the reaction flask, then adding 0.62mL (4.32mmol) of 2,4, 6-trimethylaniline into the reaction flask while the solution is hot, and refluxing at 85 ℃ for 24 h. After the reaction was completed, acetonitrile was removed by rotary evaporation, and column chromatography purification was performed using an eluent of petroleum ether and dichloromethane to 1:1 (0.75% triethylamine was added to the eluent), to obtain a total of 0.652g of ligand C4 in 77.32% yield.
1H-NMR(400MHz，CD3OD，in ppm)：6.4-7.4(s，8H，Ar-H)，2.89(s，6H， CH3)，2.42(s，12H，CH3)，2.30(s，6H，CH3)。
Elem.Anal.Calcd.For C32H32N2：C，86.44％；H，7.25％；N，6.30％。Found：C，86.25％；H，7.41％；N，6.34％。
ESI-MS：m/z 445.20([M+H]+)。
Example 5
Adding 0.40g (1.90mmol) of compound C1 into a 250mL three-necked flask under the protection of nitrogen, adding 150mL of acetonitrile, heating to 80 ℃, refluxing for 30min, adding 9mL of acetic acid, heating to 85 ℃, continuing refluxing for 15min, completely dissolving the solid in the reaction flask, then adding 1.26mL (4.52mmol) of 2,4, 6-tributylaniline into the reaction flask while the solution is hot, and refluxing at 85 ℃ for 24 h. After the reaction was completed, acetonitrile was removed by rotary evaporation, and column chromatography purification was performed using an eluent of petroleum ether and dichloromethane to 1:1 (0.75% triethylamine was added to the eluent), to obtain a total of 0.905g of ligand C5 in 68.34% yield.
1H-NMR(400MHz，CD3OD，in ppm)：6.4-7.4(s，8H，Ar-H)，2.89(s，6H， CH3)，1.45(s，36H，C(CH3)3)，1.32(s，18H，C(CH3)3)。
Elem.Anal.Calcd.For C50H68N2：C，86.15％；H，9.83％；N，4.02％。Found：C，86.04％；H，9.75％；N，4.24％。
ESI-MS：m/z 698.40([M+H]+)。
Preparation of tri, 5, 6-dimethyl acenaphthene (alpha-diimine) nickel complex
Example 6
0.324g (1.05mmol) of (DME) NiBr2The mixture was added to a 50mL Schlenk flask under nitrogen, and 15mL of dichloromethane was injected and stirred to form a light yellow suspension. 0.428g (1.03mmol) of C2 was added under nitrogen to a 50mL single neck round bottom flask and 15mL of dichloromethane was injected and the solution was dark red. The dark red solution was injected into (DME) NiBr with a syringe2The suspension was reacted at 25 ℃ for 24 hours. After the reaction, the dichloromethane was drained, the solid was washed 4 times with 25mL of ether, and the ether was drained to give 0.583g of brick-red solid powder, catalyst C6, in 89.15% yield.
Elem.Anal.Calcd.For C30H28N2NiBr2：C，56.74％；H，4.44％；N，4.41％。Found： C，56.95％；H，4.21％；N，4.32％。
In the infrared spectrum, the characteristic absorption peak of the stretching vibration of C ═ N double bonds in the ligand is mainly 1625-1680cm-1. The stretching vibration absorption peak of the C ═ N double bond in the catalyst is obviously shifted to a low wave number (1605-1655 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Example 7
0.318g (1.03mmol) of (DME) NiBr2The mixture was added to a 50mL Schlenk flask under nitrogen, and 15mL of dichloromethane was injected and stirred to form a light yellow suspension. 0.533g (1.01mmol) of C3 was placed in a 50mL single neck round bottom flask under nitrogen and 15mL of dichloromethane was injected and the solution was dark red. The dark red solution was injected into (DME) NiBr with a syringe2The suspension was reacted at 25 ℃ for 24 hours, dichloromethane was drained, the solid was washed 4 times with 25mL of ether, and ether was drained to give 0.658g of a brick-red solid as a powder, catalyst C7, in 87.61% yield.
Elem.Anal.Calcd.For C38H44N2NiBr2：C，61.08％；H，5.93％；N，3.75％。Found： C，61.47％；H，6.04％；N，3.78％。
In the infrared spectrum, the characteristic absorption peak of the stretching vibration of the C ═ N double bond in the ligand is mainly 1625-1680 cm-1. The stretching vibration absorption peak of the C ═ N double bond in the catalyst is obviously shifted to a low wave number (1605-1655 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Example 8
0.334g (1.09mmol) of (DME) NiBr2The mixture was added to a 50mL Schlenk flask under nitrogen, and 15mL of dichloromethane was injected and stirred to form a light yellow suspension. 0.471g (1.06mmol) of C4 was added under nitrogen to a 50mL single-necked round-bottomed flask, and 15mL of dichloromethane were injected to obtain a dark red solution. The dark red solution was injected into (DME) NiBr with a syringe2The suspension was reacted at 25 ℃ for 24 hours, dichloromethane was drained, the solid was washed 4 times with 25mL of ether, and ether was drained to give 0.605g of a brick-red solid powder, catalyst C8, yield 86.47%.
Elem.Anal.Calcd.For C32H32N2NiBr2：C，57.96％；H，4.86％；N，4.22％。Found： C，58.25％；H，4.74％；N，4.02％。
In the infrared spectrum, the characteristic absorption peak of the stretching vibration of the C ═ N double bond in the ligand is mainly 1625-1680 cm-1. The stretching vibration absorption peak of the C ═ N double bond in the catalyst is obviously shifted to a low wave number (1605-1655 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Example 9
0.297g (0.97mmol) of (DME) NiBr2The mixture was added to a 50mL Schlenk flask under nitrogen, and 15mL of dichloromethane was injected and stirred to form a light yellow suspension. 0.661g (0.95mmol) of C5 was added under nitrogen to a 50mL single neck round bottom flask and 15mL of dichloromethane was injected and the solution was dark red. The dark red solution was injected into (DME) NiBr with a syringe2The suspension was reacted at 25 ℃ for 24 hours, dichloromethane was drained, the solid was washed 4 times with 25mL of ether, and ether was drained to give 0.695g of a brick-red solid as a powder, catalyst C9, yield 80.24%.
Elem.Anal.Calcd.For C50H68N2NiBr2：C，65.59％；H，7.49％；N，3.06％。Found： C，65.35％；H，7.64％；N，3.21％。
In the infrared spectrum, the characteristic absorption peak of the stretching vibration of the C ═ N double bond in the ligand is mainly 1625-1680 cm-1. The stretching vibration absorption peak of the C ═ N double bond in the catalyst is obviously shifted to a low wave number (1605-1655 cm)-1) Thus, it can be seen that effective coordination occurs between the nitrogen atom and the metallic nickel atom.
Tetra, 5, 6-dimethyl acenaphthene (alpha-diimine) nickel catalyst for catalyzing ethylene polymerization reaction
Example 10
The atmospheric polymerization of ethylene is carried out under anhydrous and oxygen-free conditions. The ethylene pressure was 1atm, the polymerization temperature was 60 ℃, and 40mL of the toluene solution was injected into a 100mL Schlenk flask, followed by injecting 1.0mmol of diethylaluminum chloride as a cocatalyst thereinto. Mu. mol of procatalyst C6 were dissolved in 10mL of toluene solution and injected. Polymerization is carried out for half an hourThe polymer solution was poured into an acidified ethanol solution for settling, the polymer was filtered, then washed several times with ethanol, dried under vacuum at 50 ℃ to constant weight and weighed to give 0.87g of polymer. The catalyst activity was 346kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 24kg/mol, and the polydispersity was 1.85.1The degree of branching of the polymer was determined by H-NMR to be 108/1000 carbon atoms.
Example 11
The other polymerization conditions and the polymer treatment method were the same as in example 10, and the procatalyst used for the polymerization was C7, whereby 2.11 g of a polymer was obtained. The catalyst activity was 842kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 185kg/mol, and the polydispersity was 2.12.1The degree of branching of the polymer was determined by H-NMR to be 109/1000 carbon atoms.
Example 12
Other polymerization conditions and polymer treatment were the same as in example 10, and the procatalyst used in the polymerization was C8, whereby 0.92 g of a polymer was obtained. The catalyst activity was 367kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 29kg/mol, and the polydispersity was 1.97.1The degree of branching of the polymer was determined by H-NMR to be 104/1000 carbon atoms.
Example 13
Other polymerization conditions and polymer treatment were the same as in example 10, and the procatalyst used in the polymerization was C9, whereby 1.72 g of a polymer was obtained. The catalyst activity was 689kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 192kg/mol, and the polydispersity was 1.92.1The degree of branching of the polymer was determined by H-NMR to be 102/1000 carbon atoms.
Example 14
Other polymerization conditions and polymer treatment were the same as in example 10, and the cocatalyst used in the polymerization was ethyl aluminum dichloride, whereby 2.63g of a polymer was obtained. The catalyst activity was 1051kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 83kg/mol, and the polydispersity was 1.72.1The degree of branching of the polymer was determined by H-NMR to be 120/1000 carbon atoms.
Example 15
Other polymerization conditions and methods and apparatus for polymer processingIn the same manner as in example 10, methylaluminoxane was used as a cocatalyst in the polymerization reaction, whereby 1.67g of a polymer was obtained. The catalyst activity was 668kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 238kg/mol, and the polydispersity was 1.96.1The degree of branching of the polymer was determined by H-NMR to be 125/1000 carbon atoms.
Example 16
Other polymerization conditions and polymer treatment were the same as in example 10, and the co-catalyst used in the polymerization reaction was modified methylaluminoxane, whereby 1.06g of a polymer was obtained. The catalyst activity was 423kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 204kg/mol, and the polydispersity was 1.92.1The degree of branching of the polymer was determined by H-NMR to be 118/1000 carbon atoms.
Example 17
Other polymerization conditions and a polymer treatment method were the same as in example 10, and 2.24g of a polymer was obtained by using aluminum sesquiethylate as a cocatalyst in the polymerization reaction. The catalyst activity was 896kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 153kg/mol, and the polydispersity was 1.87.1The degree of branching of the polymer was determined by H-NMR to be 114/1000 carbon atoms.
Example 18
The polymerization conditions and the polymer treatment were the same as in example 14, and the polymerization temperature was 25 ℃ to obtain 2.97g of a polymer. The catalyst activity was 1189kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 192kg/mol, and the polydispersity was 1.99.1The degree of branching of the polymer was determined by H-NMR to be 105/1000 carbon atoms.
Example 19
Other polymerization conditions and the polymer treatment method were the same as in example 14, and the polymerization reaction temperature was 80 ℃ to obtain 2.02g of a polymer. The catalyst activity was 808kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 42kg/mol, and the polydispersity was 1.80.1The degree of branching of the polymer was determined by H-NMR to be 124/1000 carbon atoms.
Example 20
Other polymerization conditions and the polymer treatment method were the same as in example 14, and the polymerization reaction temperature was 95 ℃ to obtain1.06g of a polymer. The catalyst activity was 425kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 34kg/mol, and the polydispersity was 1.85.1The degree of branching of the polymer was determined by H-NMR to be 126/1000 carbon atoms.
Example 21
Other polymerization conditions and polymer treatment were the same as in example 10, and 0.5mmol of diethylaluminum chloride as a cocatalyst was added to the polymerization reaction, whereby 1.86g of a polymer was obtained. The catalyst activity was 742kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 167kg/mol, and the polydispersity was 2.03.1The degree of branching of the polymer was determined by H-NMR to be 104/1000 carbon atoms.
Example 22
Other polymerization conditions and polymer treatment were the same as in example 10, and 2.0mmol of diethylaluminum chloride as a cocatalyst was added to the polymerization reaction, whereby 2.14g of a polymer was obtained. The catalyst activity was 856kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 195kg/mol, and the polydispersity was 2.15.1The degree of branching of the polymer was determined by H-NMR to be 110/1000 carbon atoms.
Example 23
Other polymerization conditions and polymer treatment were the same as in example 10, and 3.0mmol of diethylaluminum chloride as a cocatalyst was added to the polymerization reaction, whereby 2.23g of a polymer was obtained. The catalyst activity was 892kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 205kg/mol, and the polydispersity was 2.17.1The degree of branching of the polymer was determined by H-NMR to be 112/1000 carbon atoms.
Example 24
Ethylene pressure polymerization Using a stainless steel 2L autoclave manufactured by B ü chi, the ethylene pressure was 0.4MPa, the polymerization temperature was 60 ℃, 1L of n-heptane solution was injected into the autoclave, then 2.0mmol of diethylaluminum chloride as a cocatalyst was injected thereto, 10. mu. mol of the main catalyst C7 was dissolved in 20mL of toluene solution, which was injected, after polymerization for half an hour, the polymer solution was poured into acidified ethanol solution for settling, the polymer was filtered, washed with ethanol, vacuum-dried at 50 ℃ to constant weight, and 26.34g of the polymer was weighed, the catalyst activity was 5268kgPE [ mol (Ni) h]-1Produced by polymerizationThe weight average molecular weight of the product was 192kg/mol, and the polydispersity was 2.01.1The degree of branching of the polymer was determined by H-NMR to be 102/1000 carbon atoms.
Example 25
The other polymerization conditions and the polymer treatment method were the same as in example 24, and the ethylene pressure in the polymerization reaction was 1.4MPa, whereby 41.25g of a polymer was obtained. The catalyst activity was 8250kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 198kg/mol, and the polydispersity was 2.03.1The degree of branching of the polymer was determined by H-NMR to be 92/1000 carbon atoms.
Hexa, 5, 6-dimethyl acenaphthene (alpha-diimine) nickel catalyst for catalyzing propylene polymerization reaction
Example 26
The polymerization conditions and the polymer treatment method were the same as in example 10, and the reaction gas in the polymerization reaction was 1atm of propylene, whereby 0.14g of a polymer was obtained. The catalyst activity was 57kgPP [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 86 kg/mol, the polydispersity was 1.62,1the degree of branching of the polymer was determined by H-NMR to be 22/1000 carbon atoms.
Example 27
Other polymerization conditions and polymer treatment were the same as in example 26, and the reaction temperature in the polymerization reaction was 25 ℃ to obtain 0.37g of a polymer. The catalyst activity was 146kgPP [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 142kg/mol, the polydispersity was 1.25,1the degree of branching of the polymer was determined by H-NMR to be 231/1000 carbon atoms.
Example 28
Other polymerization conditions and polymer treatment were the same as in example 26, and the reaction temperature in the polymerization reaction was 0 ℃ to obtain 0.31g of a polymer. The catalyst activity was 124kgPP [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 134kg/mol, the polydispersity was 1.09,1the degree of branching of the polymer was determined by H-NMR to be 257/1000 carbon atoms.
Example 29
Other polymerization conditions and polymer treatment were the same as in example 28, and methylaluminoxane was used as a co-catalyst in the polymerization reaction, whereby 0.28g of a polymer was obtained. The catalyst activity was 112kgPP [ mol: (Ni)h]-1The weight-average molecular weight of the polymerization product was 152kg/mol, and the polydispersity was 1.16. ,1the degree of branching of the polymer was determined by H-NMR to be 232/1000 carbon atoms.
Comparative example 1
The same procedures used in example 19 were repeated except that a Brookhart catalyst represented by the formula (I) -3 was used in place of the catalyst used in example 19 and the polymerization temperature was 80 ℃ to obtain 1.54g of a polymer. The catalyst activity was 616kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 27kg/mol, and the polydispersity was 1.75.1The degree of branching of the polymer was determined by H-NMR to be 126/1000 carbon atoms.
Comparative example 2
The same operation as in example 19 was carried out at a polymerization temperature of 80 ℃ using a catalyst having a bridged ethylene skeleton as provided in Chinese patent CN 201210276331 represented by the formula (II) in place of the catalyst in example 19, to obtain 1.64g of a polymer. The catalyst activity was 656kgPE (mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 29kg/mol, and the polydispersity was 1.76.1The degree of branching of the polymer was determined by H-NMR to be 129/1000 carbon atoms.
Comparative example 3
The same procedures used in example 15 were repeated except that a Brookhart catalyst represented by the formula (I) -3 was used in place of the catalyst used in example 15 and the polymerization temperature was 60 ℃ to obtain 0.77g of a polymer. The catalyst activity was 307kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 113kg/mol, and the polydispersity was 1.82.1The degree of branching of the polymer was determined by H-NMR to be 122/1000 carbon atoms.
Comparative example 4
The same operation as in example 15 was carried out except that the catalyst in example 15 was replaced with a catalyst having an ethylene bridged skeleton as provided in Chinese patent CN 201210276331 of the formula (II), and the polymerization temperature was 60 ℃ to obtain 1.17g of a polymer. The catalyst activity was 466kgPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 193kg/mol, and the polydispersity was 1.82.1The degree of branching of the polymer was determined by H-NMR to be 126/1000 carbon atoms.
Comparative example 5
The Brookhart catalyst represented by the formula (I) -3 was used in place of the catalyst in example 20, the polymerization temperature was 95 ℃ and the catalyst was deactivated in the same manner as in example 20.
Comparative example 6
The same operation as in example 20 was carried out except that the catalyst in example 20 was replaced with a catalyst having an ethylene bridged skeleton as provided in Chinese patent CN 201210276331 of the formula (II), and the polymerization temperature was 95 ℃ to obtain 0.51g of a polymer. The catalyst activity was 202gPE [ mol (Ni) h]-1The weight-average molecular weight of the polymerization product was 19kg/mol, and the polydispersity was 1.85.1The degree of branching of the polymer was determined by H-NMR to be 128/1000 carbon atoms.
Claims (2)
1. The application of 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin catalyst in catalyzing ethylene or propylene polymerization to prepare polyethylene or polypropylene is characterized in that the chemical structural formula of the catalyst is shown as the following formula:
in the chemical structural formula of the catalyst, R1Is methyl, isopropyl or tert-butyl, R2Hydrogen, methyl or tert-butyl.
2. Use according to claim 1, the process for the preparation of 5, 6-dimethylacenaphthylene (α -diimine) nickel olefin catalyst used comprises the following steps:
(1) carrying out double acylation reaction on 1, 8-dimethylnaphthalene and oxalyl bromide to obtain a compound C1:
(2) and (3) performing ketoamine condensation reaction on the compound C1 and 2 equivalents of aniline to obtain an alpha-diimine ligand C2-C5:
in the above reaction formula, when R1＝Me，R2When H, α -diimine ligand C2 is obtained, or alternatively, R1＝iPr，R2When H, α -diimine ligand C3 is obtained, or alternatively, R1＝R2When Me is not substituted α -diimine ligand C4, or R1＝R2When tBu, α -diimine ligand C5 is obtained;
(3) under the anhydrous and oxygen-free conditions, respectively complexing alpha-diimine ligand C2-C5 with ethylene glycol dimethyl ether nickel dibromide to obtain 5, 6-dimethyl acenaphthene (alpha-diimine) nickel olefin polymerization catalyst C6-C9:
in the above reaction formula, when R1＝Me，R2When H, catalyst C6 is obtained; or, R1＝iPr，R2When H, catalyst C7 is obtained; or, R1＝R2Me, catalyst C8 is obtained; or, R1＝R2When tBu, catalyst C9 was obtained.
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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 |
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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 |
| CN105693896A (en) * | 2014-11-25 | 2016-06-22 | 中国石油天然气股份有限公司 | Acenaphthenequinone-1,2-asymmetric diketinimatonickel complex catalyst, and preparation method and application thereof |
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