CN108003094A - Ligand, its preparation method, nickel complex, its preparation method and its application - Google Patents
Ligand, its preparation method, nickel complex, its preparation method and its application Download PDFInfo
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- CN108003094A CN108003094A CN201711171977.XA CN201711171977A CN108003094A CN 108003094 A CN108003094 A CN 108003094A CN 201711171977 A CN201711171977 A CN 201711171977A CN 108003094 A CN108003094 A CN 108003094A
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- phenyl
- formula
- hydrogen
- substituted
- alkyl
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 132
- -1 C1~C6Alkyl Chemical class 0.000 claims description 109
- 239000001257 hydrogen Substances 0.000 claims description 82
- 229910052739 hydrogen Inorganic materials 0.000 claims description 82
- 239000004215 Carbon black (E152) Substances 0.000 claims description 68
- 150000002431 hydrogen Chemical class 0.000 claims description 67
- 229930195733 hydrocarbon Natural products 0.000 claims description 63
- 229910052736 halogen Inorganic materials 0.000 claims description 61
- 150000002367 halogens Chemical class 0.000 claims description 61
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 53
- 238000006467 substitution reaction Methods 0.000 claims description 35
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 30
- 125000001624 naphthyl group Chemical group 0.000 claims description 29
- 150000004702 methyl esters Chemical class 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 69
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 125000001841 imino group Chemical group [H]N=* 0.000 description 38
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 13
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 8
- 238000010668 complexation reaction Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 0 C*c1c(C(C)*)c(*)c(*)c(*)c1C(*)* Chemical compound C*c1c(C(C)*)c(*)c(*)c(*)c1C(*)* 0.000 description 7
- 239000007868 Raney catalyst Substances 0.000 description 7
- 229910000564 Raney nickel Inorganic materials 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical class NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 3
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000012869 ethanol precipitation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QQWLGFMKQCGPGH-UHFFFAOYSA-N (2-aminohydrazinyl)benzene Chemical compound NNNC1=CC=CC=C1 QQWLGFMKQCGPGH-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- WYGIWVCWYKSYOE-UHFFFAOYSA-N 1-[bis(4-methylphenyl)methyl]-4-methylbenzene Chemical class C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WYGIWVCWYKSYOE-UHFFFAOYSA-N 0.000 description 1
- PTXWAWIYGFDGMU-UHFFFAOYSA-N 1-oxidopyridin-1-ium-2-carbaldehyde Chemical class [O-][N+]1=CC=CC=C1C=O PTXWAWIYGFDGMU-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- NCXCFZUKRMOFHW-UHFFFAOYSA-N 2,6-dibenzhydryl-4-methylaniline Chemical class NC=1C(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC(C)=CC=1C(C=1C=CC=CC=1)C1=CC=CC=C1 NCXCFZUKRMOFHW-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N alpha-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- RYVPGOYXAXWNER-UHFFFAOYSA-N n-benzhydrylaniline Chemical compound C=1C=CC=CC=1NC(C=1C=CC=CC=1)C1=CC=CC=C1 RYVPGOYXAXWNER-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- KEFOZNJTQPJEOB-UHFFFAOYSA-N pyridine-2,3-diimine Chemical compound N=C1C=CC=NC1=N KEFOZNJTQPJEOB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003944 tolyl 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of ligand, its preparation method with formula (I) structure；Present invention also provides more than one to state pyridine NO free radical type nickel complex, its preparation method and its application with the big steric hindrance aromatic ring of formula (II) or formula (III) structure regulation and control of the ligand for base.The above-mentioned nickel complex that the application provides can be catalyzed the low-carbon alkene polymerization or copolymerization of C2~C6 as catalyst：Low-carbon alkene polymerization for C2~C6 has very high heat endurance and activity, produces the poly- low-carbon alkene of the super high molecular weight with the distribution of adjustable molecular amount and the degree of branching.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to ligand, its preparation method, nickel complex, its preparation method
And its application.
Background technology
Polyolefin becomes in contemporary society's life production due to the price of excellent physical mechanical property and relative moderate
One of indispensable material.In olefin polymetiation process, catalyst decides olefinic polymerization behavior, the particle of polymer
The structure and performance of form and polymer.The continuous development of olefin polymerization catalysis so that polyolefin products species tends to be rich
Richness, excellent performance, promotes the development of whole polyolefin industry.At present, it is still very huge that the demand of polyolefin, which is,
, therefore the research for polyolefin catalyst occupies mostly important status.
Develop the key that new catalyst is invention High performance polyolefin material, and the design of ligand is in the design of catalyst
In it is most important.Based on the transition-metal catalyst of various ligands synthesis, crucial work has been played in field of olefin polymerisation
With.In numerous ligands, imines is probably one of most common structure.Significant example includes pyrrole imine, pyridine-imines,
Pyridine-diimine, beta-diimine, salicylic alidehyde imine, alpha-diimine.These imine ligands are usually by aldehydes or ketones and various aniline
Condensation reaction prepare.Therefore, a series of new imines ylidene ligands and corresponding one will can be produced by developing new aniline molecule
The new olefin polymerization catalysis of series.For example, Long etc. make use of a kind of new benzhydryl aniline, and it is prepared for several
The sub- Raney nickel of high quality alpha-two.Then, Chen etc. contraposition devise some with different substituents (Me, MeO, Cl,
CF3 hexichol diazanyl aniline), corresponding alpha-diimine palladium catalyst is in vinyl polymerization and ethylene-methyl acrylate combined polymerization
Show good performance.Recently, Chen etc., which develops two kinds, has dinaphthyl and the new aniline of dibenzothiophene, and
Olefinic polymerization and copolymerization can be further improved by demonstrating the property of corresponding alpha-diimine palladium catalyst.Chen etc. is also synthesized
Aryl naphthylamines, and show the fabulous performance of corresponding pyridine-imines Raney nickel.Campora et al. is reported
2- iminopyridine N-O compound nickel complexes.
Above-mentioned Raney nickel shows absorbing performance in vinyl polymerization：First, in low-down co-catalyst
Under MMAO, it can reach very high activity and (can reach 3.0 × 106g(mol Nih-1)；Secondly, the polyethylene of this kind of catalyst
Relatively low (the Mn to 1.5 × 10 of molecular weight3)；3rd, such catalyst heat is more unstable, is observed very at 50 DEG C
Low activity.It is therefore desirable to improve the heat endurance of catalyst by introducing new big steric hindrance aryl, catalytic activity is improved
And polymer molecular weight.Therefore, a kind of pyridine-NO free radical type Raney nickels of big steric hindrance aromatic ring regulation and control are designed and synthesize,
Property of the corresponding Raney nickel on ethylene homo and copolymerization is studied.
The content of the invention
Present invention solves the technical problem that being to provide a kind of Raney nickel, the Raney nickel that the application provides is used for C2
The homopolymerization of~C6 low-carbon alkenes or copolymerization have higher heat endurance, catalytic activity and polymer molecular weight.
In view of this, this application provides a kind of ligand with formula (I) structure,
Wherein, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substitution hydrocarbon
Base, phenyl or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Hydrocarbon
Base, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl.
Preferably, the R1、R2、R3And R4In 1~3 substituent be hydrogen, phenyl or substituted phenyl；The R8、R9、
R10And R11Independently selected from hydrogen, the alkyl of C2~C6, the substituted hydrocarbon radical of C2~C6, phenyl, the phenyl of substitution, naphthyl, substitution
Naphthyl, benzothienyl or substituted benzothienyl；The R21、R22、R23And R24Independently selected from hydrogen, the hydrocarbon of C1~C6
Base, the substituted hydrocarbon radical of C1~C6, phenyl or substituted phenyl.
Present invention also provides the preparation method of the ligand, including：
Aminated compounds with formula (A) structure and the aldehyde compound with formula (B) structure is anti-in organic solvent
Should, obtain the ligand with formula (I) structure；
H2N-Ar
(A)；
Wherein, the R1Formula, AR2、R3With formula R4Independently selected from hydrogen, C1~C6Formula hydrocarbon (I) base, halogen, nitro, C1
~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Hydrocarbon
Base, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl.
This application provides a kind of nickel complex with formula (II) structure；
Wherein, the R1、R2And R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl, R4Selected from hydrogen, C1~C6Alkyl, halogen, nitro or C1~C6Substituted hydrocarbon radical；
The Ar1Selected from structure shown in formula 101；
Wherein, the R5、R6And R7Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
X is halogen.
Preferably, the R1、R2And R3In 1~3 substituent be hydrogen, phenyl or substituted phenyl；The R4For hydrogen.
This application provides a kind of nickel complex with formula (III) structure；
Wherein, Ar2For formula 101 when, the R1、R2、R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~
C6Substituted hydrocarbon radical, phenyl or substituted phenyl；R4Selected from phenyl or substituted phenyl；
Ar2For formula 102 when, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6
Substituted hydrocarbon radical, phenyl or substituted phenyl；
The Ar2With 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Hydrocarbon
Base, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl；
X is halogen.
Preferably, the R1、R2、R3And R4In 1~3 substituent be hydrogen, phenyl or substituted phenyl, Ar2For formula 102.
Present invention also provides the preparation method of the nickel complex, including：
Ligand is reacted in organic solvent with nickel compound, obtains nickel complex；
The ligand is the ligand described in claim 1, and the nickel compound is (DME) NiX2；
Wherein, DME is glycol dimethyl ether, and X is halogen.
Present invention also provides the preparation method that the low-carbon alkene of C2~C6 a kind of polymerize, including：
Under the catalytic action of nickel complex described in such scheme, the low-carbon alkene of C2~C6 is polymerize, obtains low-carbon alkene
Hydrocarbon polymer.
Present invention also provides the preparation method that the low-carbon alkene and 10- e pioic acid methyl esters of a kind of C2~C6 are copolymerized, including：
Under the catalytic action of nickel complex described in such scheme, the low-carbon alkene of C2~C6 and 10- e pioic acid methyl esters are total to
Poly- reaction, obtains copolymer.
This application provides a kind of nickel complex with formula (II) or formula (III) structure, the Ar in the complex substitutes
Base provides certain steric hindrance for the side of nickle atom, reduces the speed of nickel, so that C2~C6 low-carbon alkenes are equal
Polymers or copolymer have higher heat endurance, molecular weight and polymerization activity；On the other hand, the pyridine in the nickel complex
N-O structures have electronic effect altogether, are conducive to the coordination effect of vinyl monomer and metallic nickel, so as to improve polymerization activity.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The present invention provides a kind of ligand, which is used to synthesize nickel complex, i.e., described ligand is the nickel complex
Basis, specifically, the ligand has formula (I) structure；
Wherein, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substitution hydrocarbon
Base, phenyl or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
The R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Alkyl,
Halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl.
In a particular embodiment, the R1、R2、R3And R4In 1~3 substituent be hydrogen, phenyl or substituted phenyl；Institute
State R8、R9、R10And R11Independently selected from hydrogen, the alkyl of C2~C6, the substituted hydrocarbon radical of C2~C6, phenyl, the phenyl of substitution, naphthalene
Base, naphthyl, benzothienyl or the substituted benzothienyl of substitution；The R21、R22、R23And R24Independently selected from hydrogen, C1
The alkyl of~C6, the substituted hydrocarbon radical of C1~C6, phenyl or substituted phenyl.
More specifically, the ligand with formula (I) structure is with formula (I1), formula (I2), formula (I3), formula (I4), formula
(I5), formula (I6), formula (I7) or formula (I8) structure；
Present invention also provides the preparation method of above-mentioned ligand, including：
Amine with formula (A) structure and the aldehyde with formula (B) structure are reacted in organic solvent, obtained with formula (I)
The ligand of structure；
H2N-Ar
(A)；
Wherein, the R1Formula, R2、R3With formula R4B is independently selected from hydrogen, C1~C6Formula alkyl, halogen, nitro, C1~C6
Substituted hydrocarbon radical, phenyl or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Hydrocarbon
Base, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl.
It is above-mentioned prepare ligand during, the organic solvent is solvent well known to those skilled in the art, to this
Application has no particular limits；It is exemplary, the organic solvent be selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane,
One or more in tetrachloromethane, ether, 2,4- dioxane and 1,2- dichloroethanes；In a particular embodiment, it is described to have
Solvent is toluene.The molar ratio of the amine and the aldehyde is 1：(0.1~10)；In a particular embodiment, the amine with it is described
The molar ratio of aldehyde is：(1~5).Above-mentioned reaction carries out under -78 DEG C of reflux temperature.Above-mentioned amine and above-mentioned aldehyde are this area skill
Compound known to art personnel, to its source, the application has no particular limits.
Present invention also provides the nickel complex using above-mentioned ligand as essential groups, its nickel with formula (II) structure is matched somebody with somebody
Compound；
Wherein, the R1、R2And R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl, R4Selected from hydrogen, C1~C6Alkyl, halogen, nitro or C1~C6Substituted hydrocarbon radical；
The Ar1Selected from structure shown in formula 101；
Wherein, the R5、R6And R7Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution.
In a particular embodiment, the R1、R2And R3In 1~3 substituent be hydrogen, phenyl or substituted phenyl；It is described
R4For hydrogen.
More specifically, the nickel complex has formula (II1), formula (II2), formula (II3) or formula (II4) structure；
Due to the difference of R4 or the difference of Ar, present invention also provides a kind of nickel complex with formula (III) structure；
Wherein, Ar2For formula 101 when, the R1、R2、R3Independently selected from hydrogen, C1-C6Alkyl, halogen, nitro, C1~C6
Substituted hydrocarbon radical, phenyl or substituted phenyl；
R4Phenyl selected from phenyl, substitution；
Ar2For formula 102 when, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6
Substituted hydrocarbon radical, phenyl or substituted phenyl；
The Ar2With 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Hydrocarbon
Base, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical,
Phenyl, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical,
Phenyl or substituted phenyl；
X is halogen.
As described above, in Ar2During with formula 102, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen
Element, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
In a particular embodiment, the nickel complex has formula (III1) structure；
In Ar2During with formula 101, the R1、R2、R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6
Substituted hydrocarbon radical, phenyl or substituted phenyl；R4Selected from phenyl or substituted phenyl；
In a particular embodiment, the nickel complex has formula (III2), formula (III3) or formula (III4) structure；
Present invention also provides the preparation method of the nickel complex, comprise the following steps：
Ligand is reacted in organic solvent with nickel compound, obtains nickel complex；The ligand is matched somebody with somebody for such scheme
Body, the nickel compound are (DME) NiX2；
Wherein, DME is glycol dimethyl ether, and X is halogen.
It is above-mentioned prepare nickel complex during, the organic solvent is well known to those skilled in the art organic molten
Agent, exemplary, the organic solvent is selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, ether, 2,
One or more in 4- dioxane and 1,2- dichloroethanes；In a particular embodiment, the organic solvent is selected from dichloromethane
Alkane.The molar ratio of the ligand and nickel compound is 1：(0.1~6), in a particular embodiment, the ligand and the nickel
The molar ratio of compound is 1：(1~3).The reaction carries out under -78 DEG C of reflux temperatures.The time of the reaction is 1~50h；
In a particular embodiment, the time of the reaction is 12~24h.
The nickel complex of the above-mentioned preparation of the application is mainly used for the preparation of polyolefin, and in particular to the low-carbon alkene of C2~C6
The low-carbon alkene and 10- e pioic acid methyl esters of polymerized hydrocarbon and C2~C6 are copolymerized；Specifically, this application provides a kind of the low of C2~C6
The preparation method of carbene polymerized hydrocarbon, including：
Under the catalytic action of above-mentioned nickel complex, the low-carbon alkene of C2~C6 is polymerize, obtains low-carbon alkene polymerization
Thing.
Present invention also provides the preparation method that the low-carbon alkene and 10- e pioic acid methyl esters of a kind of C2~C6 are copolymerized, including：
Under the catalytic action of above-mentioned nickel complex, by the low-carbon alkene of C2~C6 and 10- e pioic acid methyl ester copolyreaction,
Obtain copolymer.
Above-mentioned olefin-copolymerization or the process of homopolymerization are well known to those skilled in the art, herein without repeating；Difference exists
In：The nickel complex that the catalyst that above-mentioned olefin polymer uses provides for the application.Above-mentioned C2~C6 low-carbon alkenes are specific
Ethene is selected from embodiment.Test result indicates that：The nickel complex that the application provides, which is used for olefinic polymerization, has higher catalysis
Activity and stability, can produce the poly- low-carbon alkene of super high molecular weight with the distribution of adjustable molecular amount and the degree of branching.
The present invention provides a kind of pyridine-NO free radical types Raney nickel of big steric hindrance aromatic ring regulation and control, its preparation method and
It is applied, which has structure shown in formula (II) or (III).The catalyst can be catalyzed the low-carbon alkene polymerization of C2~C6
Or copolymerization；Low-carbon alkene polymerization for C2~C6 has very high heat endurance and activity, and generation has adjustable molecular amount
The poly- low-carbon alkene of the super high molecular weight of distribution and the degree of branching；For the low-carbon alkene of C2~C6 and being total to for 10- e pioic acid methyl esters
It is poly-, the copolymer with high molecular weight polar monomer is produced, and have higher insertion ratio.Test result indicates that：The catalyst is urged
Change ethylene homo, activity up to 107g of PE (mol of Ni)-1h-1；Weight average molecular weight is up to during Unimodal Distribution
3016500g/mol, molecular weight distribution 2.49；When producing bimodal distribution, molecular weight distribution maximum can reach 59.67；Ethene
Weight average molecular weight with the copolymerization product of 10- e pioic acid methyl esters is up to 184700g/mol；10- e pioic acid methyl esters are inserted into ratio
1.50%.
For a further understanding of the present invention, nickel complex provided by the invention is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The particular content of the present invention has been illustrated in following embodiments, and the data provided include the synthesis of ligand, metallization
The synthesis of synthesis, vinyl polymerization or the copolymerization process, wherein complex of compound, polymerization process be all under anhydrous and oxygen-free into
OK, all sensitive materials are stored in glove box, and all solvents all pass through water removal by stringent dry water removal, ethylene gas
Deoxygenation pillar purifies, and methyl acrylate is purified by removing water deoxygenation distillation under vacuum.It is not particularly illustrated, all raw materials are equal
It is commercially available.
The silica gel of silicagel column 200-300 mesh, nuclear-magnetism Bruker 400MHz nuclear-magnetism instruments；Elemental analysis is by Chinese section
Learn technology university physics and chemistry center measure；Molecular weight and molecualr weight distribution measured by GPC (polystyrene type pillar, HR2 and
HR4, box temperature are 45 DEG C, are pumped using Water 1515 and Water 2414；Mobile phase is tetrahydrofuran, and flow velocity is every for 1.0 milliliters
Minute, the polystyrene of polydispersion is used as standard)；Mass spectrum Thermo LTQ Orbitrap XL (ESI+) or P-
SIMS-Gly of Bruker Daltonics Inc (EI+) are measured；Single crystal X diffraction analysis uses Oxford
Diffraction Gemini S Ultra CCD single crystal diffraction instruments, Cu K αRoom temperature radiates.
Embodiment 1：The preparation of 2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides
By 2- pyridine carboxaldehyde N- oxides (123 milligrams, 1 mM), 2,6- bis- (diphenyl methyl) -4- methylanilines
The mixture stirring of (440 milligrams, 1 mM) and p-methyl benzenesulfonic acid (20 milligrams) in toluene (50 milliliters), in 130 DEG C of guarantors
Hold 24 it is small when；Solvent is partly evaporated under reduced pressure until forming gray solid, and by remaining solution at methanol (30 milliliters)
Middle dilution；Gray solid is isolated by filtration, is washed three times with 10 ml methanols, obtains with formula (I1) structure ligand 2-
(((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides (480 milligrams, yield 62.9%).1H NMR(400MHz, CDCl3) δ 8.21 (Py, s, 1H), 8.06 (Py, d, J=6.4Hz, 1H), 7.71 (Py, d, J=8.4Hz,
1H), 7.33-7.12 (m, 14H), 7.09 (Py, d, J=6.8Hz, 1H), 7.03 (m, 7H), 6.65 (s, 2H), 5.47 (s,
2H),2.15(CH3,s,3H).13C NMR(101MHz,CDCl3)δ156.35,147.47,145.24, 143.49,139.63,
133.26,132.85,129.61,128.98,128.25,127.13,126.25,124.66, 124.51,51.80,
21.44.HRMS(m/z):calcd for C39H33ON2:[M]545.2587 found:545.2605.
Embodiment 2：2- (((double (naphthalene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxidations
The preparation of thing
Synthesis step with embodiment 1, difference lies in：Double (two (naphthalene -2- bases) methyl) -4- methylanilines of 2,6- are put into
(640 milligrams, 1 mM), have obtained yellow solid (522 milligrams, yield 72%), i.e., with formula (I2) structure 2- (((2,
Double (naphthalene -2- bases) methyl of 6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides.
1H NMR(400MHz,CDCl3) δ 8.49 (Py, s, 1H), 7.93 (Py, d, J=6.8Hz, 1H), 7.79 (d, J=
6.8Hz, 4H), 7.73 (d, J=8.4Hz, 4H), 7.64 (d, J=6.4Hz, 4H), 7.50 (d, J=10.4Hz, 2H), 7.47-
7.36 (m, 12H), 7.14 (t, J=9.2Hz, 1H), 6.98 (t, J=8.8Hz, 1H), 6.79 (s, 2H), 5.83 (s, 2H),
2.13(CH3,s,3H).13C NMR(101MHz,CDCl3)δ 155.00,146.72,144.12,139.78,139.11,
138.39,132.59,132.46,132.37,131.55, 131.36,131.17,128.51,128.42,127.97,
127.26,127.12,126.84,126.81,126.51, 125.95,124.96,124.81,124.70,124.50,
123.43,123.39,51.64,51.14,20.35,19.95. HRMS(m/z):calcd for C55H41ON2:[M]
745.3213,found:745.3225.
Embodiment 3：2- ((double (benzothiophene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -
The preparation of 1- oxides
Synthesis step with embodiment 1, difference lies in：Double (two (benzothiophene -2- bases) methyl) -4- first of 2,6- are put into
Base aniline (666 milligrams, 1 mM), has obtained yellow solid (431 milligrams, yield 56%), i.e., with formula (I3) structure
2- ((double (benzothiophene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides.1H NMR
(400MHz,CDCl3) δ 7.85 (Py, s, 1H), 7.82 (Py, d, J=8.0Hz, 1H), 7.72 (d, J=8.0Hz, 4H), 7.70
(Py, d, J=6.8Hz, 1H), 7.66 (Py, d, J=7.2Hz, 1H), 7.53 (d, J=8.0Hz, 1H), 7.45 (d, J=
7.2Hz, 1H), 7.38-7.28 (m, 6H), 7.27 (s, 1H), 7.22 (s, 1H), 7.16 (m, 3H) 7.02 (d, J=4.0Hz,
2H), 6.95 (s, 1H), 6.75 (m, 2H), 6.55 (s, 1H), 6.36 (t, J=7.8Hz, 1H), 6.01 (s, 1H), 2.26
(CH3,s,3H).13C NMR(101MHz,CDCl3)13C NMR(101MHz,CDCl3)δ150.88,150.06,145.42,
144.41,144.32,143.81,138.96,138.88,138.76,138.72,138.68,138.50,138.44,
137.96,137.61,133.55,128.75,128.30,125.73,123.79,123.68,123.57,123.53,
123.46,123.42,123.35,123.15,123.11,122.84,122.81,122.75,122.63,122.60,
122.56,122.55,121.68,121.36,121.26,121.11,120.66,68.40,59.88,43.91,20.18.
HRMS(m/z):calcd for C47H33ON2S4:[M]769.1470,found:769.1462.
Embodiment 4：((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) pyridine 1- is aoxidized 2-
The preparation of thing
With embodiment 1, difference is synthesis step：2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- base amine is put into
(566 milligrams, 1 mM), have obtained yellow solid (576 milligrams, yield 86%), i.e., with formula (I4) structure 2-
((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) pyridine 1- oxides.1H NMR(400MHz,
CDCl3) δ 7.99 (t, J=8.0Hz, 2H), 7.95 (s, 1H), 7.53 (Py, d, J=8.1Hz, 1H), 7.38 (Py, t, J=
8.8Hz, 1H), 7.13-7.25 (m, 8H), 7.11-6.98 (m, 13H), 6.89 (d, J=8.0Hz, 2H), 6.87-6.79 (m,
4H),6.67(s,1H),6.22(s,1H), 5.67(s,1H),1.98(CH3,s,3H).13C NMR(101MHz,CDCl3)δ
154.11,145.19, 143.86,142.71,142.44,141.30,138.27,138.19,135.30,134.36,
131.61,129.51, 129.25,129.18,128.47,128.19,127.77,127.41,127.29,126.99,
125.45,125.23, 124.93,124.13,123.55,122.89,122.72,52.35,50.58,19.79.HRMS(m/
z):calcd for C49H39ON2[M]:671.3057,found:671.3055。
Embodiment 5：2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) pyridine 1- oxygen
The preparation of compound
Synthesis step with embodiment 1, difference lies in：Double (di-p-tolyl the methyl) -4- methylanilines of 2,6- are put into
(496 milligrams, 1 mM), have obtained yellow solid (450 milligrams, yield 75%), i.e., with formula (I5) structure 2- (((2,
Double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 6-) imino group) methyl) pyridine 1- oxides.1H NMR(400MHz,CDCl3)
δ 8.27 (Py, s, 1H), 8.36 (Py, d, J=6.4Hz, 1H), 7.71 (Py, d, J=8.4Hz, 1H), 7.33-7.13 (m,
14H), 7.09 (Py, d, J=6.8Hz, 1H), 7.03 (m, 7H), 6.65 (s, 2H), 5.47 (s, 2H), 2.15 (CH3,s,3H),
2.15(CH3,s,12H).13C NMR(101MHz,CDCl3)δ156.35,148.47,145.84,143.49,139.65,
133.26,132.85, 129.61,128.98,128.25,127.63,126.25,124.66,124.51,51.80,21.44,
20.56,20.49, 20.31,19.73.HRMS(m/z):calcd for C43H40N2O:[M]600.3141found:
600.3242.
Embodiment 6：2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) -6- phenylpyridine 1- oxides
Preparation
By 2- formaldehyde -6- phenylpyridine N- oxides (199 milligrams, 1 mM), 2,6- bis- (diphenyl methyl) -4- first
It is small that base aniline (440 milligrams, 1 mM) and p-methyl benzenesulfonic acid (20 milligrams) in toluene (50 milliliters) stir 24 at 130 DEG C
When；Solvent is partly evaporated under reduced pressure until formed gray solid, and by remaining solution in methanol (30 milliliters) it is dilute
Release；Gray solid is isolated by filtration, is washed three times with 10 ml methanols, obtains with formula (I6) structure 2- (((2,6- bis-
Phenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) -6- phenylpyridine 1- oxides (550 milligrams, yield 90%).1H NMR
(400MHz,CDCl3) δ 8.36 (Py, s, 1H), 7.72 (Py, d, J=7.2Hz, 2H), 7.68 (Py, d, J=8.0Hz, 1H),
7.46 (m, 3H), 7.41 (d, J=7.6Hz, 1H), 7.13-7.25 (m, 13H), 7.04 (d, J=7.2Hz, 2H), 6.65 (s,
2H),5.52(s,2H),2.15(CH3,s,1H).13C NMR(101MHz,CDCl3)δ157.42,149.42, 147.87,
145.84,143.41,133.04,132.82,132.56,129.67,129.59,129.29,128.89, 128.52,
128.33,128.22,126.22,124.07,123.40,51.74,21.44.HRMS(m/z):calcd for C45H36ON2
[M]:621.2900,found:621.2885.
Embodiment 7：2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) -6- phenyl pyrazolines
The preparation of pyridine 1- oxides
Synthesis step with embodiment 6, difference lies in：Double (di-p-tolyl the methyl) -4- methylanilines of 2,6- are put into
(496 milligrams, 1 mM), have obtained yellow solid (541 milligrams, yield 80%), i.e., with formula (I7) structure 2- (((2,
Double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 6-) imino group) methyl) -6- phenylpyridine 1- oxides.1H NMR
(400MHz,CDCl3) δ 8.46 (Py, s, 1H), 7.76 (Py, d, J=7.2Hz, 2H), 7.68 (Py, d, J=8.0Hz, 1H),
7.46 (m, 3H), 7.41 (d, J=7.6Hz, 1H), 7.13-7.25 (m, 13H), 7.04 (d, J=7.2Hz, 2H), 6.65 (s,
2H),5.52(s,2H),2.15(CH3, s,1H),2.10(CH3,s,12H).13C NMR(101MHz,CDCl3)δ157.42,
149.42,147.87, 145.84,143.41,133.04,132.82,132.56,129.67,129.59,129.29,
128.89,128.52, 128.33,128.22,126.22,124.07,123.40,51.74,21.44,21.34,20.56,
20.49,20.31. HRMS(m/z):calcd for C49H44ON2[M]:676.3454,found:676.3466.
Embodiment 8：2- (((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) -6- phenylpyridines
The preparation of 1- oxides
Synthesis step with embodiment 6, difference lies in：2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- amine (566 is put into
Milligram, 1 mM), yellow solid (545 milligrams, yield 73%) has been obtained, i.e., with formula (I8) structure 2- (((2,4- bis-
Benzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) -6- phenylpyridine 1- oxides.
1H NMR(400MHz,CDCl3) δ 7.99 (t, J=8.0Hz, 2H), 7.95 (s, 1H), 7.53 (Py, d, J=
8.1Hz, 1H), 7.40 (Py, t, J=8.8Hz, 1H), 7.13-7.26 (m, 8H), 7.11-6.98 (m, 18H), 6.89 (d, J=
8.0Hz,2H),6.87–6.79(m,4H),6.67(s,1H),6.22(s,1H),5.67(s,1H), 1.98(CH3,s,3H).13C
NMR(101MHz,CDCl3)δ154.11,145.19,143.86,142.71, 142.44,141.30,138.27,138.19,
135.30,134.36,132.82,132.56,131.61,129.67, 129.59,129.51,129.29,129.25,
129.18,128.89,128.47,128.19,127.77,127.41, 127.29,126.99,125.45,125.23,
124.93,124.13,123.55,122.89,122.72,52.35, 50.58,19.79.HRMS(m/z):calcd for
C55H42ON2[M]:746.3297,found:746.3267.
Embodiment 9：2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides nickel coordinates
The preparation of thing
By 2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides, (546 milligrams, 1 in the least
Mole) and (DME) NiBr2(154 milligrams 0.5 mM) is added in 20 milliliters of dichloromethane solutions, is stirred at room temperature 12
Hour, add ether (20 milliliters) washed with precipitation and complexation thing, sediment with ether, and be dried under reduced pressure at room temperature 12 it is small when,
Obtain with formula (II1) structure 2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides
Nickel complex.Elemental analysis, theoretical calculation：C78H64Br2N4NiO2:Theoretical calculation：C,71.63；:H,4.93；N, 4.28. are real
Survey:C,71.45； H,4.97；N,4.35.MALDI-TOF:m/z 680.8602[M-L-Br]+；682.8975[M-L-Br+2H
]+。
Embodiment 10：2- (((double (naphthalene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxygen
The preparation of compound nickel complex
By 2- (((double (naphthalene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxides (745
Milligram, 1 mM) and (DME) NiBr2(154 milligrams 0.5 mM) is added in 20 milliliters of dichloromethane solutions, in room temperature
When lower stirring 12 is small, adds ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and decompression is dry at room temperature
It is dry 12 it is small when, obtain with formula (II2) structure 2- (((2,6- double (naphthalene -2- bases) methyl) -4- aminomethyl phenyls) imino group) first
Base) pyridine -1- oxide nickel complexes.Elemental analysis, theoretical calculation：C110H80Br2N4NiO2:C,77.34；H,4.72；N,
3.28. actual measurement:C,77.55；H,4.57；N,3.35.MALDI-TOF:m/z 880.8529[M-L-Br]+；882.8887 [M-
L-Br+2H]+.
Embodiment 11：Preparation
By 2- ((double (benzothiophene -2- bases) methyl of 2,6-) -4- aminomethyl phenyls) imino group) methyl) pyridine -1- oxidations
Thing (769 milligrams, 1 mM) and (DME) NiBr2(154 milligrams 0.5 mM) is added in 20 milliliters of dichloromethane solutions,
Be stirred at room temperature 12 it is small when, add ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and at room temperature
Be dried under reduced pressure 12 it is small when, obtain with formula (II3) structure 2- ((2,6- double (benzothiophene -2- bases) methyl) -4- methylbenzenes
Base) imino group) methyl) pyridine -1- oxide nickel complexes.Elemental analysis, theoretical calculation：C94H66Br2N4NiO2S8:C,
64.20；H,3.78；N, 3.19. are surveyed:C,64.45；H,3.57；N,3.18.MALDI-TOF:m/z 903.9476[M-L-
Br]+； 906.0133[M-L-Br+2H]+.
Embodiment 12：2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) pyridine 1- oxygen
The preparation of compound nickel complex
By 2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) pyridine 1- oxides
(600 milligrams, 1 mM) and (DME) NiBr2(154 milligrams 0.5 mM) is added in 20 milliliters of dichloromethane solutions,
When stirring 12 is small at room temperature, adds ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and subtract at room temperature
Press dry dry 12 it is small when, obtain with formula (II4) structure 2- (((2,6- double (di-p-tolyl methyl) -4- aminomethyl phenyls) it is sub-
Amino) methyl) pyridine 1- oxide nickel complexes.C85H78Br2N4NiO2:Theoretical calculation：C,72.61；H,5.59；N,
3.98 actual measurement:C, 72.64；H,5.69；N,3.90.MALDI-TOF:m/z 767.2147[M-L-Br]+；765.2156[M-L-
Br +2H]+。
Embodiment 13：((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) pyridine 1- is aoxidized 2-
The preparation of thing nickel complex
By 2- ((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) pyridine 1- oxides (672
Milligram, 1 mM) and (DME) NiBr2(308 milligrams, 1 mM) are added in 20 milliliters of dichloromethane solutions, in room temperature
When lower stirring 12 is small, adds ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and decompression is dry at room temperature
It is dry 12 it is small when, obtain with formula (III1) structure 2- ((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) first
Base) pyridine 1- oxide nickel complexes.Elemental analysis, theoretical calculation：C37H30Br2N2NiO:C,60.29；H,4.10；N,
3.80.2- ((((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) pyridine 1- oxide nickel complexes
Actual measurement:C,60.37；H,4.15；N,3.65.MALDI-TOF:m/z 806.7671[M-Br]+；808.7863 [M-Br+2H]+.
Embodiment 14：2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) -6- phenylpyridines 1- is aoxidized
The preparation of thing nickel complex
By 2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) -6- phenylpyridine 1- oxides (623 millis
Gram, 1 mM) and (DME) NiBr2(308 milligrams, 1 mM) are added in 20 milliliters of dichloromethane solutions, at room temperature
Stir 12 it is small when, add ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and is dried under reduced pressure at room temperature
12 it is small when, obtain with formula (III2) structure 2- (((2,6- diphenyl hydrogen -4- aminomethyl phenyls) imino group) methyl) -6- phenyl
Pyridine 1- oxide nickel complexes.Elemental analysis, theoretical calculation：C45H36Br2N2NiO:C,64.40；H,4.32；N, 3.34. are real
Survey:C,64.28； H,4.38；N,3.45.MALDI-TOF:m/z756.8963[M-Br]+；758.8924[M-Br+2H]+.
Embodiment 15：2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) -6- phenyl
The preparation of pyridine 1- oxide nickel complexes
By 2- (((double (di-p-tolyl the methyl) -4- aminomethyl phenyls of 2,6-) imino group) methyl) -6- phenylpyridine 1- oxygen
Compound (777 milligrams, 1 mM) and (DME) NiBr2(308 milligrams, 1 mM) are added to 20 milliliters of dichloromethane solutions
In, be stirred at room temperature 12 it is small when, add ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and in room temperature
Under be dried under reduced pressure 12 it is small when, obtain with formula (III3) structure 2- (((double (di-p-tolyl methyl) -4- methylbenzenes of 2,6-
Base) imino group) methyl) -6- phenylpyridine 1- oxide nickel complexes.Elemental analysis, theoretical calculation：C49H44Br2N2NiO:C,
65.73；H, 4.95；N, 3.13. are surveyed:C,65.70；H,4.97；N,3.15.MALDI-TOF:m/z 894.1153[M- Br
]+；896.1156[M-Br+2H]+。
Embodiment 16：2- (((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) -6- phenylpyridines
The preparation of 1- oxide nickel complexes
2- (((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imino group) methyl) -6- phenylpyridines 1- is aoxidized
Thing (777 milligrams, 1 mM) and (DME) NiBr2(308 milligrams, 1 mM) are added in 20 milliliters of dichloromethane solutions,
Be stirred at room temperature 12 it is small when, add ether (20 milliliters) and washed with precipitation and complexation thing, sediment with ether, and at room temperature
Be dried under reduced pressure 12 it is small when, obtain with formula (III4) structure 2- (((2,4- dibenzyl -8- (p-methylphenyl) naphthalene -1- bases) imido
Base) methyl) -6- phenylpyridine 1- oxide nickel complexes.Elemental analysis, theoretical calculation：C55H42Br2N2NiO:C,68.42；
H,4.39；N, 2.90. are surveyed:C,68.40；H,4.40；N,2.91.MALDI-TOF:m/z 964.0997[M-Br]+；
965.9997[M-Br+2H]+.
Embodiment 17：Catalyzed ethylene polymerization
In glove box, under nitrogen atmosphere, to 350mL autoclaves (with magnetic stirring apparatus, oil bath heating device
And thermometer) middle addition 18mL toluene, and add 4.6 milligrams of methylaluminoxane；Connect the container to high pressure line and right
Pipeline is vacuumized, and vessel temp is arranged to 20 DEG C, keeps the temperature 15 minutes；2 milliliters of dichloros will be dissolved in by syringe
In (1.7 milligrams) injection polymerization systems of nickel complex prepared by the embodiment 9~15 of methane；Valve is closed, adjusts ethylene pressure
After 8 atmospheric pressure, react 30 minutes；Stop reaction, open reaction kettle, add ethanol precipitation solid thereto, be filtered under diminished pressure,
Vacuum drying chamber dries to obtain white solid (5.28 grams).The result of catalysts towards ethylene polymerization prepared by embodiment 9~15 is such as
Shown in table 1：
The result of catalysts towards ethylene polymerization prepared by 1 embodiment 9~15 of table
aPolymerizing condition:The micromole of nickel complex=1；Toluene=18 milliliter, dichloromethane=2 milliliter, the air of ethene=8
Pressure, time=30 minute；bActivity=106g·mol-1·h-1；cFusing point is measured with differential scanning calorimeter；dEvery 1000 carbon branch
Change degree is by nuclear magnetic resonance hydrogen spectruming determining；eWeight average molecular weight=104g mol-1Molecular weight determination be by GPC by the use of polystyrene as
Standard trichloro-benzenes is as 150 degree of measure of solvent.
Embodiment 18：Ethene is catalyzed to be copolymerized with 10- e pioic acid methyl esters
In glove box, under nitrogen atmosphere, to 350mL autoclaves (with magnetic stirring apparatus, oil bath heating device
And thermometer) in add 17mL toluene, 10- e pioic acid methyl esters, and add 580 milligrams of methylaluminoxane, connect the container to height
Pressure pipeline simultaneously vacuumizes pipeline, and vessel temp is arranged to 20 DEG C, keeps the temperature 15 minutes；It will be dissolved by syringe
In (10 milligrams) injection polymerization systems of nickel complex prepared by the embodiment 9~15 of 2 milliliters of dichloromethane.Valve is closed, is adjusted
It is reaction 60 minutes after 9 atmospheric pressure to save ethylene pressure.Stop reaction, open reaction kettle, add ethanol precipitation solid thereto,
It is filtered under diminished pressure, vacuum drying chamber dries to obtain white solid (70 milligrams).Embodiment 9~15 prepare catalysts towards ethylene and
The results are shown in Table 2 for methyl acrylate copoly：
The result data table that nickel complex prepared by 2 embodiment 9~15 of table is copolymerized ethene and 10- e pioic acid methyl esters
aPolymerizing condition:Toluene and 10- e pioic acid methyl esters cumulative volume=18 milliliter, dichloromethane=2mL, nickel complex=10
The molar ratio of micromole, methylaluminoxane and nickel complex is 1000, the atmospheric pressure of ethene=8,80 DEG C, when time=1 is small, is gathered
It is 20 DEG C to close temperature.bActivity=104g·mol-1·h-1。cFusing point is measured with differential scanning calorimeter.d10- e pioic acid methyl esters are inserted into
Than being measured by nucleus magnetic hydrogen spectrum.eWeight average molecular weight=103g mol-1, molecular weight determination is to be used as standard by GPC polystyrene
Trichloro-benzenes is as 150 degree of measure of solvent.fMethylaluminoxane and the molar ratio of nickel complex are 500.gMethylaluminoxane is matched somebody with somebody with nickel
The molar ratio of compound is 200.
As seen from the above embodiment, the present invention provides a kind of pyridine-NO free radical type nickel of big steric hindrance aromatic ring regulation and control to urge
Agent, its preparation method and its application, the catalyst have structure shown in formula (II) or (III).The catalyst can be catalyzed C2
The low-carbon alkene polymerization or copolymerization of~C6, and the low-carbon alkene polymerization for C2~C6 has very high heat endurance and activity,
Produce the poly- low-carbon alkene of the super high molecular weight with the distribution of adjustable molecular amount and the degree of branching；For the low-carbon alkene of C2~C6
The copolymerization of hydrocarbon and 10- e pioic acid methyl esters, produces the copolymer with high molecular weight polar monomer, and has higher insertion ratio.Experiment
The result shows that：The catalyst ethylene homo, activity up to 107g of PE(mol of Ni)-1h-1；Unimodal Distribution
When weight average molecular weight be up to 3016500g/mol, molecular weight distribution 2.49；When producing bimodal distribution, molecular weight distribution is most
It can reach 59.67 greatly；The weight average molecular weight of ethene and the copolymerization product of 10- e pioic acid methyl esters is up to 184700g/mol；10- alkene
Sour methyl esters insertion is than up to 1.50%.
The explanation of above example is only intended to help to understand method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, defined herein
General Principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent most wide scope of point.
Claims (10)
1. one kind has the ligand of formula (I) structure,
Wherein, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, benzene
Base or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Alkyl,
Halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical, phenyl,
Substituted phenyl, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl
Or the phenyl of substitution.
2. ligand according to claim 1, it is characterised in that the R1、R2、R3And R4In 1~3 substituent be hydrogen, benzene
Base or substituted phenyl；The R8、R9、R10And R11Independently selected from hydrogen, the alkyl of C2~C6, the substituted hydrocarbon radical of C2~C6, benzene
Base, the phenyl of substitution, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；The R21、R22、R23And R24
Independently selected from hydrogen, the alkyl of C1~C6, the substituted hydrocarbon radical of C1~C6, phenyl or substituted phenyl.
3. the preparation method of the ligand described in claim 1, including：
Aminated compounds with formula (A) structure and the aldehyde compound with formula (B) structure are reacted in organic solvent, obtained
To the ligand with formula (I) structure；
H2N-Ar (A)；
Wherein, the R1Formula, R2、R3With formula R4Independently selected from hydrogen, C1~C6Formula alkyl, halogen, nitro, C1~C6Substitution
Alkyl, phenyl or substituted phenyl；
The Ar has 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Alkyl,
Halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical, phenyl,
Substituted phenyl, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl
Or the phenyl of substitution.
4. one kind has the nickel complex of formula (II) structure；
Wherein, the R1、R2And R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl
Or the phenyl of substitution, R4Selected from hydrogen, C1~C6Alkyl, halogen, nitro or C1~C6Substituted hydrocarbon radical；
The Ar1Selected from structure shown in formula 101；
Wherein, the R5、R6And R7Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl
Or the phenyl of substitution；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical, phenyl,
Substituted phenyl, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
X is halogen.
5. nickel complex according to claim 4, it is characterised in that the R1、R2And R3In 1~3 substituent be hydrogen,
Phenyl or substituted phenyl；The R4For hydrogen.
6. one kind has the nickel complex of formula (III) structure；
Wherein, Ar2For formula 101 when, the R1、R2、R3Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Take
For alkyl, phenyl or substituted phenyl；R4Selected from phenyl or substituted phenyl；
Ar2For formula 102 when, the R1、R2、R3And R4Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Take
For alkyl, phenyl or substituted phenyl；
The Ar2With 102 structure of formula 101 or formula：
Wherein, the R5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1~C6Alkyl,
Halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl or substituted phenyl；
The R8、R9、R10And R11Independently selected from hydrogen, C2~C6Alkyl, halogen, nitro, C2~C6Substituted hydrocarbon radical, phenyl,
Substituted phenyl, naphthyl, naphthyl, benzothienyl or the substituted benzothienyl of substitution；
The R21、R22、R23And R24Independently selected from hydrogen, C1~C6Alkyl, halogen, nitro, C1~C6Substituted hydrocarbon radical, phenyl
Or the phenyl of substitution；
X is halogen.
7. nickel complex according to claim 6, it is characterised in that the R1、R2、R3And R4In 1~3 substituent be
Hydrogen, phenyl or substituted phenyl, Ar2For formula 102.
8. the preparation method of the nickel complex described in claim 4 or claim 6, including：
Ligand is reacted in organic solvent with nickel compound, obtains nickel complex；
The ligand is the ligand described in claim 1, and the nickel compound is (DME) NiX2；
Wherein, DME is glycol dimethyl ether, and X is halogen.
9. a kind of preparation method of the low-carbon alkene polymerization of C2~C6, including：
Under the catalytic action of the nickel complex of claim 4 or 6, the low-carbon alkene of C2~C6 is polymerize, obtains low-carbon alkene
Hydrocarbon polymer.
10. a kind of preparation method of low-carbon alkene and 10- the e pioic acid methyl esters copolymerization of C2~C6, including：
Under the catalytic action of the nickel complex of claim 4 or 6, the low-carbon alkene of C2~C6 and 10- e pioic acid methyl esters are total to
Poly- reaction, obtains copolymer.
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| CN109879814A (en) * | 2019-02-20 | 2019-06-14 | 中国科学技术大学 | A kind of ligand and its complex and preparation method and application |
| CN109879814B (en) * | 2019-02-20 | 2022-09-30 | 中国科学技术大学 | Ligand and complex thereof, and preparation method and application thereof |
| CN112898166A (en) * | 2021-01-28 | 2021-06-04 | 中国科学院长春应用化学研究所 | Sandwich type large steric hindrance amine, neutral nickel catalyst, preparation method and application thereof in olefin polymerization |
| CN114933542A (en) * | 2022-04-08 | 2022-08-23 | 安徽泽升科技有限公司 | Novel nickel complex and preparation method of olefin polymer |
| CN114933542B (en) * | 2022-04-08 | 2023-02-10 | 安徽泽升科技有限公司 | Novel nickel complex and preparation method of olefin polymer |
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