CN117843524A - Alpha-diimine ligand compound, nickel complex thereof, supported alpha-diimine nickel catalyst and application - Google Patents
Alpha-diimine ligand compound, nickel complex thereof, supported alpha-diimine nickel catalyst and application Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 79
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 66
- 239000003446 ligand Substances 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- -1 2, 6-di (benzhydryl) -4-methylphenyl Chemical group 0.000 claims abstract description 59
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 239000001257 hydrogen Chemical group 0.000 claims abstract description 20
- 229910052739 hydrogen Chemical group 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 43
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 40
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 150000001336 alkenes Chemical class 0.000 claims description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000012718 coordination polymerization Methods 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- BLMIXWDJHNJWDT-UHFFFAOYSA-N 6-chlorohex-1-ene Chemical compound ClCCCCC=C BLMIXWDJHNJWDT-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 238000010516 chain-walking reaction Methods 0.000 abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 230000009044 synergistic interaction Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 35
- 238000001228 spectrum Methods 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229940126214 compound 3 Drugs 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 244000061458 Solanum melongena Species 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
- C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
-
- 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
-
- 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
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)
Abstract
The invention relates to an alpha-diimine ligand compound, a nickel complex thereof, a supported alpha-diimine nickel catalyst and application thereof, and belongs to the technical field of organic synthesis. The ligand compound has a structural formula shown in a formula I or a formula II,
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to an alpha-diimine ligand compound, a nickel complex thereof, a supported alpha-diimine nickel catalyst and application thereof.
Background
The discovery of the alpha-diimine palladium-nickel complex promotes the development of the olefin polymerization field, and becomes a precursor for producing polyethylene by using a post-transition metal catalyst. Various homogeneous high performance catalysts based on late transition metals have been reported for use in the field of olefin polymerization for decades.
In the related art, ligand space factors play a critical role in different types of late transition metal catalysts, such as salicylaldimine, phosphine sulfonate, pyridyloxyimine, and iminopyridyl. However, the above imine catalysts still have lower thermal stability and are more prone to produce highly branched oily and low molecular weight polymers.
In summary, the imine metal catalyst in the related art has lower thermal stability, and is difficult to control the molecular weight and structure of the prepared polymer in the catalytic polymerization process, and difficult to popularize in production.
Disclosure of Invention
In view of this, the present invention proposes to construct a hydroxyl group-containing α -diimine ligand compound, which can increase steric hindrance of ligand coordination in metal when loading with a carrier in the subsequent step, not only inhibit chain transfer, but also limit rotation of N-aryl moiety at higher temperature, thereby facilitating realization of low branching degree and higher molecular weight of polymer when preparing polymer by catalysis thereof, so that the complex prepared in the subsequent step has higher thermal stability and better activity.
It is an object of the present invention to provide an α -diimine ligand compound.
It is another object of the present invention to provide an α -diimine nickel complex.
The invention also aims to provide a supported alpha-diimine nickel catalyst which is prepared by using the nickel complex.
It is still another object of the present invention to provide the use of the supported alpha-diimine nickel catalyst described above.
The above object of the present invention is achieved by the following means.
According to an embodiment of one aspect of the present invention, there is provided an α -diimine ligand compound of formula I or formula ii, wherein Ar is selected from 2, 6-bis (benzhydryl) -4-methylphenyl or 2, 6-bis (isopropyl) phenyl; each R is independently selected from hydroxyl or hydrogen.
According to some embodiments of the invention, the above-mentioned α -diimine ligand compound includes formula I 1 ～I 4 Or II 1 ～Ⅱ 2 A compound of the structure shown in (a):
according to an embodiment of another aspect of the present invention, there is provided an α -diimine nickel complex of formula iii or formula iv, wherein Ar is selected from 2, 6-bis (benzhydryl) -4-methylphenyl or 2, 6-bis (isopropyl) phenyl; x comprises at least one of methyl, chlorine or bromine; each R is independently selected from hydroxyl or hydrogen.
According to some embodiments of the invention, the above-mentioned alpha-diimine nickel complexes include formula III 1 ～Ⅲ 4 Or IV 1 ～Ⅳ 2 Any one of the structures shown in:
according to an embodiment of a further aspect of the present invention, there is provided a supported α -diimine nickel catalyst prepared using the above-described nickel complex and a support, wherein the nickel complex is supported on the support.
According to some embodiments of the invention, the support comprises at least one of silica, magnesium chloride or aluminum oxide.
According to an embodiment of a further aspect of the present invention, there is provided a supported alpha-diimine nickel catalyst as described above for catalyzing C 2 ～C 11 Is used for the polymerization of olefin monomers.
According to some embodiments of the invention, catalyze C 2 ～C 11 The polymerization of the olefin monomers of (a) comprises: cocatalyst and C 2 ～C 11 Adding olefin monomer into organic solvent, adding supported alpha-diimine nickel catalyst to make C 2 ～C 11 Is subjected to coordination polymerization.
According to some embodiments of the invention, the organic solvent comprises at least one of toluene, benzene, n-heptane; the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tri-n-butylaluminum, alkali metal and alkali metal salt; c (C) 2 ～C 11 The olefin monomer of (2) comprises at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate 10-undecenol, 10-undecylenic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
According to some embodiments of the invention, the coordination polymerization reaction includes the C 2 ～C 11 Olefin monomers homo-and/or co-polymerization.
Based on the technical scheme, the alpha-diimine ligand compound, the nickel complex thereof, the supported alpha-diimine nickel catalyst and the application thereof provided by the invention have one or a part of the following beneficial effects:
the invention utilizes the synergistic effect of the framework of diimine, phenyl and hydroxy benzhydryl to jointly construct larger steric hindrance, and when the diimine is subsequently loaded on a carrier, the coordination polymerization localizes metallic nickel in a very small space coordinated with nitrogen, so that the chain running condition of a metallic complex is further inhibited through the regulation and control of the steric hindrance, and the selectivity and the yield of the metallic complex are improved during the coordination. And can limit the rotation of the N-aryl moiety at high temperatures, prevent unwanted branching from occurring, and reduce the branching of subsequently prepared polymers. And hydroxyl is used for regulating and controlling the loading capacity of the subsequent carrier, so that the complex formed after loading has higher thermal stability, and the polyethylene prepared by using the complex has lower branching degree and higher molecular weight.
Drawings
The present invention is described in further detail below with reference to the accompanying drawings.
FIG. 1a is a nuclear magnetic resonance hydrogen spectrum of intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol in example 1 of the present invention;
FIG. 1b is a nuclear magnetic resonance carbon spectrum of intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol in example 1 of the present invention;
FIG. 2a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 1 in example 1 of the invention;
FIG. 2b is a nuclear magnetic resonance carbon spectrum of the ligand compound 1 in example 1 of the present invention;
FIG. 3a is a nuclear magnetic resonance hydrogen spectrum of intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol in example 2 of the present invention;
FIG. 3b is a nuclear magnetic resonance carbon spectrum of intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol in example 2 of the present invention;
FIG. 4a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 2 in example 2 of the invention;
FIG. 4b is a nuclear magnetic resonance carbon spectrum of ligand compound 2 in example 2 of the present invention;
FIG. 5a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 3 in example 3 of the invention;
FIG. 5b is a nuclear magnetic resonance carbon spectrum of ligand compound 3 in example 3 of the present invention;
FIG. 6a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 4 in example 4 of the invention;
FIG. 6b is a nuclear magnetic resonance carbon spectrum of ligand compound 4 in example 4 of the present invention; and
FIG. 7 is a view showing the structure of an X-ray diffraction single crystal of Ni1 as a nickel complex in example 5 of the present invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The endpoints and any values of the ranges invented in this invention are not limited to the precise range or value, and such range or value should be understood to include values approaching those range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically invented in the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms "comprises," "comprising," and/or the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It should be noted that the terms used herein should be construed to have meanings consistent with the context of the present specification and should not be construed in an idealized or overly formal manner.
Similarly, in the description of exemplary embodiments of the invention above, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. The description of the terms "one embodiment," "some embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
Neutral nickel complexes based on salicylaldimine ligands are used in the related art. Such neutral nickel complexes are capable of synthesizing polyolefins having relatively excellent high molecular weights, but the molecular weight of the polyolefin they synthesize has been limited to thousands of years. In the process of realizing the invention, the diphenyl methyl with hydroxyl substituent is introduced into the alpha-diimine skeleton, so that a larger steric hindrance effect can be cooperatively constructed, and the space range of the subsequent coordination of metal and nitrogen is controlled.
On the basis of the conception of the invention, the alpha-diimine nickel complex with a hydroxyl structure is synthesized and forms a supported catalyst with a carrier. Compared with a homogeneous nickel complex with a hydroxyl structure, the thermal stability of the supported catalyst is greatly improved, and the supported alpha-diimine nickel catalysts with different hydroxyl numbers have different supporting capacities on the carrier, so that the higher the number of hydroxyl groups, the stronger the supporting capacity and the relatively better the thermal stability.
The catalytic mechanism of the nickel complex with the hydroxyl structure and the supported alpha-diimine nickel catalyst obtained by loading in actual catalytic polymerization is as follows:
it is well known to those skilled in the art that ethylene polymerization processes mainly comprise three steps of chain extension, chain transfer and chain walking. The chain extension process refers to the coordination of ethylene to the metal center of the nickel complex, inserting a metal-alkyl bond. The chain transfer process refers to the elimination of beta-H during ethylene insertion, with the metal center vacancies of the nickel complex coordinated with the new ethylene. The chain walking process means that after the ethylene is eliminated by beta-H, the ethylene turns 180 degrees and is coordinated with and inserted into the metal center of the nickel complex again. When the nickel complex with the hydroxyl structure and the supported alpha-diimine nickel catalyst obtained by the support thereof are applied, on one hand, the larger steric hindrance effect constructed in the nickel complex is utilized to control the space range of the subsequent coordination of metal and nitrogen, and on the other hand, the shielding effect of the carrier on the metal center is utilized to lead to the reduction of chain transfer and chain walking capacity, thus being beneficial to improving the molecular weight of polyethylene and reducing the branching degree.
According to an embodiment of one aspect of the present invention, there is provided an α -diimine ligand compound of formula I or formula ii, wherein Ar is selected from 2, 6-bis (benzhydryl) -4-methylphenyl or 2, 6-bis (isopropyl) phenyl; each R is independently selected from hydroxyl or hydrogen.
In some embodiments of the invention, the ligand compound shown in formula I or formula II, the framework of diimine, phenyl and hydroxy benzhydryl synergistically interact to jointly construct larger steric hindrance, and when the ligand compound is subsequently loaded on a carrier, metal nickel is limited in a very small space coordinated with nitrogen during coordination polymerization, so that the chain running condition of a metal complex is further inhibited through regulation and control of the steric hindrance, and the selectivity and yield of the metal coordination are improved. And can limit the rotation of the N-aryl moiety at high temperatures, prevent unwanted branching from occurring, and reduce the branching of subsequently prepared polymers. The nickel complex formed after loading has higher thermal stability, and is beneficial to promoting the prepared olefin polymerization to have lower branching degree and higher molecular weight.
Further, the R group is a hydroxyl group. When the R group is a hydroxyl group, the plurality of hydroxyl groups can form coordinate bonds with groups on the surface of the carrier when the carrier is subsequently loaded. When the supported alpha-diimine nickel catalyst is formed subsequently, the combination effect between a plurality of hydroxyl groups and the carrier is beneficial to regulating and controlling the loading capacity of the nickel catalyst to the carrier, and a more sufficient and stable loading structure is formed, so that the formation of a higher olefin polymer molecular weight is facilitated, and a better polymerization effect is realized.
In some embodiments of the invention, the α -diimine ligand compounds include formula I 1 ～I 4 Or II 1 ～Ⅱ 2 A compound of the structure shown in (a):
according to some embodiments of the present invention, there is also provided a method of preparing a ligand compound of formula I or formula ii. Reacting the compound shown in the formula A with boron tribromide to obtain the compound shown in the formula B. Wherein R in formula A 1 Selected from a hydrogen atom or a methoxy group, and R in the formula B is selected from a hydrogen atom or a hydroxy group.
Specifically, the compound represented by formula a was mixed with boron tribromide at 1: 3-1: 6, reacting for 2 hours at 0 ℃, then heating to room temperature, reacting for 12 hours, and obtaining the compound shown in the formula B after column chromatography.
By R 1 By way of example, the reaction process is as follows:
by R 1 For methoxy as an example, the reaction procedure is as follows:
reacting a compound shown in a formula B with a compound shown in a formula C to obtain a compound shown in a formula I. Ar in the compound shown in the formula C is 2, 6-di (benzhydryl) -4-methylphenyl or 2, 6-di (isopropyl) phenyl. Wherein the compound of formula C can be purchased directly from commercial sources.
Specifically, the compound represented by formula B and the compound represented by formula C are represented by 1:1, adding p-toluenesulfonic acid monohydrate, carrying out water diversion reflux reaction for 40h at the temperature of 140-145 ℃, and separating by column chromatography to obtain the compound shown in the formula I.
Taking Ar as 2, 6-di (benzhydryl) -4-methylphenyl as an example, the reaction process is specifically shown as follows:
a compound of formula B with butanedione at 2:1, adding p-toluenesulfonic acid monohydrate, carrying out reflux reaction for 36h at 75-80 ℃, heating to 140-145 ℃, carrying out water diversion reflux reaction for 40h, and separating by column chromatography to obtain the compound shown in the formula II.
The reaction process is specifically as follows:
according to some embodiments of the present invention there is also provided an α -diimine nickel complex of formula iii or formula iv, ar being selected from 2, 6-bis (benzhydryl) -4-methylphenyl or 2, 6-bis (isopropyl) phenyl; x comprises at least one of methyl, chlorine or bromine; each R is independently selected from hydroxyl or hydrogen.
According to some embodiments of the present invention, the insertion position of the nickel coordination center in the formed complex has better regulation effect on catalyzing olefin monomer polymerization. By constructing an adaptive steric hindrance space, the position space of nickel insertion can be relatively restricted, so that uncontrolled chain walking reaction of nickel groups is inhibited, the selectivity and yield of the reaction are further improved, unnecessary side-chain reaction is prevented, and the controllability of the reaction is improved.
According to some embodiments of the invention, the alpha-diimine nickel complexes include formula III 1 ～Ⅲ 4 Or IV 1 ～Ⅳ 2 A compound of the structure shown in (a):
according to some embodiments of the invention, the nickel complex is formed by coordination of a ligand compound as described above with a halide of divalent metallic nickel. The halide of divalent metallic nickel includes: niCl 2 、NiBr 2 、NiI 2 、(DME)NiBr 2 、Ni(allyl)Cl、[Ni(PPh 3 ) 2 PhCl]At least one of them.
According to some embodiments of the present invention, there is also provided a method of preparing an α -diimine nickel complex of formula iii or formula iv.
According to some embodiments of the invention, specific preparation steps may include: dissolving a ligand compound shown in a formula I or a formula II in an organic solvent, for example, selecting ethylene glycol dimethyl ether nickel bromide for reaction, adding n-hexane, stirring and filtering to obtain a nickel complex.
In particular by III 1 The reaction process of the compound is shown as an example, and is specifically shown as follows:
according to some embodiments of the present invention, the step of preparing the α -diimine nickel complexes of formula iii or formula iv is preferably carried out in a protective atmosphere, more preferably under anhydrous oxygen-free or nearly anhydrous oxygen-free conditions. The protective atmosphere may be, for example, nitrogen or other inert gas.
According to some embodiments of the present invention, there is also provided a supported α -diimine nickel catalyst comprising a nickel complex as described above and a support, wherein the nickel complex is supported on the support.
According to some embodiments of the invention, the support used for the loading is a nickel complex, wherein the hydroxyl groups on the nickel complex are capable of forming coordination bonds with groups on the surface of the support, thereby enhancing the interaction force between the nickel complex and the support and increasing the number of active sites on the surface of the support.
According to some embodiments of the invention, the support comprises at least one of silica, magnesium chloride or aluminum oxide. Preferably, the carrier is magnesium chloride. In the process of carrying out the related pre-experiments of the invention, the interaction force between the nickel complex and the magnesium chloride is relatively stronger when the magnesium chloride is used as a carrier, the relative number of active sites provided on the surface of the magnesium chloride is more, and the obtained catalytic effect is relatively better.
According to some embodiments of the invention, the hydroxyl groups on the nickel complex are capable of forming hydrogen bonding interactions with the hydroxyl groups on the surface of the silica support, thereby enhancing the interaction forces between the nickel complex and the silica support.
According to some embodiments of the invention, the magnesium chloride used for loading is treated with an alcohol solution and an alkyl aluminum before loading, so that the surface of the magnesium chloride solid contains aluminum atoms, and the aluminum atoms can form Al-O coordination bonds with hydroxyl groups on the nickel complex, thereby enhancing the interaction force between the nickel complex and the magnesium chloride of the carrier.
According to some embodiments of the present invention, when the nickel complex is supported with the magnesium chloride support, the thermal stability of the heterogeneous supported alpha-diimine nickel catalyst is greatly improved compared to a homogeneous alpha-diimine nickel complex. Meanwhile, the supported alpha-diimine nickel catalysts with different hydroxyl numbers have different loading capacities on magnesium chloride carriers, and the higher the hydroxyl number is, the stronger the loading capacity and the relatively better the thermal stability are. The coordination capacity of ethylene and the nickel center is reduced due to the shielding effect of the magnesium chloride carrier on the nickel center in the supported alpha-diimine nickel catalyst, so that the activity of the catalyst is reduced. Meanwhile, due to the shielding effect of the magnesium chloride carrier, the chain transfer and chain travelling capacity are reduced, so that the polyethylene obtained by heterogeneous polymerization by using the supported alpha-diimine nickel catalyst has higher molecular weight and lower branching degree.
There is also provided, in accordance with some embodiments of the present invention, a method of preparing a supported alpha-diimine nickel catalyst, comprising: and (3) adding the alpha-diimine nickel complex and the carrier in the formula III or the formula IV into an organic solvent at the temperature of 5-25 ℃, stirring for 8-16 hours, and sequentially filtering and drying to obtain the supported alpha-diimine nickel catalyst.
According to some embodiments of the present invention, there is also provided a supported alpha-diimine nickel catalyst for catalyzing C 2 -C 11 Is used for the polymerization of olefin monomers.
According to some embodiments of the invention, when the supported alpha-diimine nickel catalyst is used for catalyzing olefin monomer polymerization, the process of coordination, insertion, re-coordination and insertion of olefin and nickel metal center can occur, but the steric hindrance of the nickel metal center of the supported catalyst is larger, so that the chain transfer and chain traveling process is inhibited, the molecular weight of an olefin polymerization product is increased, and the branching degree of polyolefin is reduced.
According to some embodiments of the invention, catalyze C 2 ～C 11 The polymerization of the olefin monomers of (a) comprises: cocatalyst and C 2 ～C 11 Adding olefin monomer into organic solvent, adding supported alpha-diimine nickel catalyst to make C 2 ～C 11 Is subjected to coordination polymerization.
According to some embodiments of the invention, the coordination polymerization reaction includes C 2 ～C 11 Olefin monomers homo-and/or co-polymerization.
According to some embodiments of the invention, the organic solvent comprises at least one of toluene, benzene, n-heptane; the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tri-n-butylaluminum, alkali metal and alkali metal salt; c (C) 2 ～C 11 The olefin monomer of (2) comprises at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate 10-undecenol, 10-undecylenic acid, 6-chloro-1-hexene, 1-hexene and 1-octene. In the process of screening the organic solvent, the cocatalyst and the olefin monomer, the obtained polymerization product has higher molecular weight, stronger activity and lower branching degree when the organic solvent, the cocatalyst and the olefin monomer are respectively selected from the specific compounds.
The invention is further illustrated by the following examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict.
It should be noted that the following examples illustrate the details of the present invention and the data presented include ligand synthesis, metal compound synthesis, ethylene polymerization or copolymerization processes, wherein the complex synthesis is carried out in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are strictly dried to remove water, and ethylene gas is purified by a water removal oxygen removal column. All materials are used as they are after being purchased, unless otherwise specified. Methods used in the examples described below, such as column chromatography, are well known in the art and may be described in textbooks or related literature and are not repeated.
The nuclear magnetic detection of the embodiment of the invention uses a Bruker 400MHz nuclear magnetic instrument, the element analysis is measured by China science and technology center of theory, the molecular weight and the molecular weight distribution are measured by high-temperature and/or normal-temperature GPC, and the mass spectrum is measured by using Thermo LTQ Orbitrap XL.
Example 1:
the synthetic route for 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol is specifically shown below:
2- ((4-methoxyphenyl) (phenyl) methyl) -4, 6-dimethylaniline (2.0 g,6.3 mmol) and methylene chloride (20 mL) were charged into a 100mL Shi Laike bottle under nitrogen atmosphere, and placed in an ice-water bath at 0℃to which boron tribromide (35 mL,1 mmol/mL) was slowly added dropwise, and after 1h of reaction, the temperature was raised to 20℃and the reaction was continued for 12h. After the reaction, saturated common salt water was added dropwise to the reaction system to quench boron tribromide at 0 ℃, extracted with water and methylene chloride, the organic phase was collected, the solvent was spin-dried, and the intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol was isolated as a white solid by using a column chromatography method, which had a mass of 1.8g and a reaction yield of 95%.
FIG. 1a is a nuclear magnetic resonance hydrogen spectrum of intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol in example 1 of the present invention. FIG. 1b is an embodiment of the present inventionNuclear magnetic resonance profile of intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol in example 1. The structure of the intermediate product (B-1) is adopted 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and specific characterization results are shown in FIG. 1a and FIG. 1 b.
1 H NMR(400MHz,CDCl 3 )δ7.31–7.26(m,1H,Ar-H),7.25–7.19(m,2H,Ar-H),7.12–7.08(m,2H,Ar-H),6.98–6.93(m,2H,Ar-H),6.83(s,1H,Ar-H),6.75–6.69(m,2H,Ar-H),6.37–6.33(m,1H,Ar-H),5.46(s,1H,CHPhAr),3.74(s,2H,NH 2 ),2.14(d,J＝16.2Hz,6H,CH 3 )。
13 C NMR(101MHz,CDCl 3 )δ154.44(s,COH),143.05(s,CNH 2 ),139.11(s),139.09(s),134.48(s),134.47(s),130.68(s),129.57(s),129.53(s),128.54(s),128.44(s),127.69(s),127.67(s),126.57(s),123.19(s),115.54(s),51.55(s,CHAr 2 ),20.78(s,CH 3 ),17.77(s,CH 3 )。
Synthesis of ligand compound 1:
to a 250mLq eggplant bottle was added the resulting intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol (1.9 g,6.6 mmol), (E) - (3- ((2, 6-benzhydryl-4-methylphenyl) imino) butan-2-ylidene) ammonium carbonyl (3.4 g,6.6 mmol), p-toluenesulfonic acid monohydrate (63 mg,0.33 mmol), and 100mL of toluene solution, the above materials were mixed and stirred and heated to 140 ℃, refluxed for 40h, and cooled to room temperature. Spin-drying the solvent, and separating by column chromatography to obtain yellow solid complex 1, wherein the mass of the complex is 4.7g, and the reaction yield is 90%.
FIG. 2a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 1 in example 1 of the invention; FIG. 2b is a nuclear magnetic resonance carbon spectrum of the ligand compound 1 in example 1 of the present invention. Structural use of ligand Compound 1 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and specific characterization results are shown in fig. 2a and 2 b.
1 H NMR(400MHz,C 6 D 6 )δ7.27(d,J＝7.6Hz,2H,Ar-H),7.21–7.17(m,3H,Ar-H),7.15–6.85(m,28H,Ar-H),6.49–6.37(m,2H,Ar-H),5.51(m,2H,CHPh 2 ),5.42(d,J＝3.8Hz,1H,CHPhAr),2.08(d,J＝9.1Hz,3H,CH 3 ),1.95(s,6H,CH 3 ),1.64(d,J＝4.7Hz,3H,N＝C-CH 3 ),1.36(d,J＝9.2Hz,3H,CH 3 ,N＝C-CH 3 )。
13 C NMR(101MHz,C 6 D 6 )δ170.39(s,N＝C-CH 3 ),168.63(s,N＝C-CH 3 ),154.63(s,COH),154.47(s,COH),145.89(s),145.74(s),144.64(s),143.93(s),143.85(s),143.79(s),143.66(s),143.32(s),143.20(s),142.52(s),142.50(s),135.82(s),134.92(s),132.59(s),132.54(s),132.36(s),132.31(s),132.21(s),132.14(s),131.29(s),131.25(s),130.73(s),130.66(s),129.99(s),129.76(s),129.69(s),129.64(s),129.35(s),129.10(s),129.02(s),128.53(s),128.44(s),128.37(s),128.34(s),128.29(s),128.22(s),128.11(s),126.46(s),126.43(s),126.39(s),126.32(s),126.27(s),126.22(s),126.13(s),126.01(s),124.22(s),115.23(s),114.97(s),52.68(s,CHPhAr),51.90(s,CHPh 2 ),51.79(s,CHPh 2 ),51.35(s,CHPh 2 ),51.28(s,CHPh 2 ),20.84(s,CH 3 ),17.95(s,CH 3 ),16.56(s,N＝C-CH 3 ),16.52(s,N＝C-CH 3 ),16.11(s,N＝C-CH 3 ),16.08(s,N＝C-CH 3 )。
Example 2
The synthetic route of 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol is specifically shown below:
2- (bis (4-methoxyphenyl) methyl) -4, 6-dimethylaniline (2.2 g,6.3 mmol) and methylene chloride (20 mL) were charged into a 100mL Shi Laike bottle under nitrogen atmosphere, and placed in a 0℃ice-water bath, and boron tribromide (35 mL,1 mmol/mL) was slowly added dropwise thereto, and after 1 hour of reaction, the temperature was raised to 20℃and the reaction was continued for 12 hours. After the completion of the reaction, saturated brine was added dropwise to the reaction system to quench boron tribromide, extracted with water and methylene chloride, the organic phase was collected, the solvent was spin-dried, and the intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol was obtained as a white solid by column chromatography, which had a mass of 1.7g and a reaction yield of 83%.
FIG. 3a is a nuclear magnetic resonance hydrogen spectrum of intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol in example 2 of the present invention. FIG. 3b is a nuclear magnetic resonance carbon spectrum of intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol in example 2 of the present invention. The structure of the intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol is adopted 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and specific characterization results are shown in FIG. 3a and FIG. 3 b.
1 H NMR(400MHz,DMSO)δ9.20(s,2H,OH),6.83–6.79(m,4H,Ar-H),6.66–6.62(m,5H,Ar-H),6.20(d,J＝2.1Hz,1H,Ar-H),5.26(s,1H,CHAr 2 ),4.04(s,2H,NH 2 ),2.00(d,J＝3.8Hz,6H,CH 3 )。
13 C NMR(101MHz,DMSO)δ155.97(s,COH),141.16(s,CNH 2 ),134.26(s),130.46(s),129.15(s),128.76(s),127.84(s),124.23(s),122.10(s),115.44(s),49.71(s,CHAr 2 ),20.94(s,CH 3 ),18.36(s,CH 3 )。
Synthesis of ligand compound 2:
to a 250mLq eggplant bottle was added the resulting intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol (2.1 g,6.6 mmol), (E) - (3- ((2, 6-benzhydryl-4-methylphenyl) imino) butan-2-ylidene) ammonium carbonyl (3.4 g,6.6 mmol), p-toluenesulfonic acid monohydrate (63 mg,0.33 mmol), and 100mL of toluene solution and 10mL methanol, and the above materials were mixed and stirred and heated to 140 ℃, refluxed for 40h, and cooled to room temperature. Spin-drying the solvent, and separating by column chromatography to obtain yellow solid complex 2, wherein the mass of the complex is 4.3g, and the reaction yield is 80%.
FIG. 4a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 2 in example 2 of the invention; FIG. 4b is a nuclear magnetic resonance carbon spectrum of the ligand compound 2 in example 2 of the present invention. Structural use of ligand Compound 2 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and specific characterization results are shown in fig. 4a and 4 b.
1 H NMR(400MHz,C 6 D 6 )δ7.29–7.25(m,2H,Ar-H),7.18(m,2H,Ar-H),7.14–6.94(m,22H,Ar-H),6.91(s,1H,Ar-H),6.87(s,1H,Ar-H),6.54–6.46(m,4H,Ar-H),5.51(s,1H,CHAr 2 ),5.44(d,J＝14.4Hz,2H,CHPh 2 ),2.10(s,3H,CH 3 ),1.95(s,6H,CH 3 ),1.64(s,3H,N＝C-CH 3 ),1.39(s,3H,N＝C-CH 3 )。
13 C NMR(101MHz,C 6 D 6 )δ169.58(s,N＝C-CH 3 ),167.77(s,N＝C-CH 3 ),153.92(s,COH),153.79(s,COH),145.05(s),144.80(s),143.09(s),142.85(s),142.43(s),141.66(s),135.40(s),134.42(s),132.11(s),131.48(s),131.30(s),131.23(s),130.43(s),129.80(s),129.76(s),129.15(s),128.91(s),128.79(s),128.37(s),128.16(s),127.67(s),127.61(s),127.48(s),127.40(s),127.25(s),125.60(s),125.53(s),125.39(s),125.26(s),123.29(s),114.42(s),114.16(s),51.80(s,CHPh 2 ),51.05(s,CHPh 2 ),49.63(s,CHAr 2 ),19.98(s,CH 3 ),19.91(s,CH 3 ),17.09(s,CH 3 ),15.73(s,N＝C-CH 3 ),15.26(s,N＝C-CH 3 )。
Example 3
The synthetic route for 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol is specifically shown below:
the preparation of 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol of this example 3 is as described in example 1 and will not be described again here.
Synthesis of ligand compound 3:
to a 250mLq eggplant bottle was added the intermediate 4- ((2-amino-3, 5-dimethylphenyl) (phenyl) methyl) phenol prepared in example 1 (4.0 g,13.2 mmol), 2, 3-butanedione (0.57 g,6.6 mmol), p-toluenesulfonic acid monohydrate (63 mg,0.33 mmol), and 100mL of toluene solution. The resulting mixture was stirred and heated to 75 ℃ and refluxed for 36h. And heating the reaction system to 140 ℃, carrying out water diversion reflux reaction for 40h, and cooling to room temperature. Spin-drying the solvent, and separating by column chromatography to obtain yellow solid ligand compound 3, the mass of which is 3.5g, and the reaction yield is 80%.
FIG. 5a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 3 in example 3 of the invention; FIG. 5b is a nuclear magnetic resonance carbon spectrum of ligand compound 3 in example 3 of the present invention. Structural use of ligand Compound 3 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and specific characterization results are shown in fig. 5a and 5 b.
1 H NMR(400MHz,DMSO)δ9.29(s,2H,OH),7.33–7.11(m,7H,Ar-H),7.06–6.84(m,7H,Ar-H),6.80–6.45(m,10H,Ar-H),5.11(m,2H,CHPhAr),2.21–2.14(m,6H,CH 3 ),1.94–1.83(m,6H,CH 3 ),1.17(m,6H,N＝C-CH 3 )。
13 C NMR(101MHz,DMSO)δ168.80(s,N＝C-CH 3 ),155.99(s,COH),145.64(s),145.50(s),144.22(s),143.38(s),133.80(s),133.02(s),132.86(s),132.79(s),131.69(s),131.62(s),130.61(s),130.50(s),129.63(s),129.52(s),128.79(s),128.54(s),127.44(s),126.38(s),124.27(s),115.63(s),115.41(s),51.55(s,CHAr 2 ),21.16(s,CH 3 ),17.84(s,CH 3 ),15.72(s,N＝C-CH 3 )。
Example 4
The synthetic route of 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol is specifically shown below:
the preparation of 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol of example 4 is shown in example 2 and will not be described in detail herein.
Synthesis of ligand compound 4:
to a 250mLq eggplant bottle was added the intermediate 4,4' - ((2-amino-3, 5-dimethylphenyl) methylene) diphenol (4.2 g,13.2 mmol), 2, 3-butanedione (0.57 g,6.6 mmol), p-toluenesulfonic acid monohydrate (63 mg,0.33 mmol) prepared in example 2, as well as 100mL toluene solution and 10mL methanol. The resulting mixture was stirred and heated to 75 ℃ and refluxed for 36h. And heating the reaction system to 140 ℃, carrying out water diversion reflux reaction for 40h, and cooling to room temperature. Spin-drying the solvent, and separating by column chromatography to obtain yellow solid ligand compound 4, the mass of which is 3.4g, and the reaction yield is 75%.
FIG. 6a is a nuclear magnetic resonance hydrogen spectrum of ligand compound 4 in example 4 of the invention; FIG. 6b is a nuclear magnetic resonance carbon spectrum of ligand compound 4 in example 4 of the present invention. Structural use of ligand Compound 4 1 HNMR spectrum, 13 The CNMR spectrum is characterized, and the specific characterization results are shown in FIG. 6a and FIG. 6 b.
1 H NMR(400MHz,DMSO)δ9.19(d,J＝1.0Hz,4H,OH),6.90(d,J＝1.8Hz,2H,Ar-H),6.75–6.71(m,8H,Ar-H),6.64–6.58(m,8H,Ar-H),6.49–6.46(m,2H,Ar-H),4.96(s,2H,CHAr 2 ),2.15(s,6H,CH 3 ),1.89(s,6H,CH 3 ),1.16(s,6H,N＝C-CH 3 )。
13 C NMR(101MHz,DMSO)δ168.71(s,N＝C-CH 3 ),155.83(s,COH),155.80(s,COH),145.54(s),134.44(s),133.48(s),133.42(s),131.51(s),130.50(s),130.40(s),115.5(s)3,115.28(s),50.61(s,CHAr 2 ),21.19(s,CH 3 ),17.78(s,CH 3 ),15.67(s,N＝C-CH 3 )。
Example 5
Synthesis of nickel complex Ni 1:
in a glove box, ligand Compound 1 (0.79 g,1.0 mmol) prepared in example 1 was added with 20mL of DCM and (DME) NiBr 2 In a mixed solution of (0.31 g,1.0 mmol), the mixture was stirred at room temperature for 12 hours, the solution was dried on a vacuum line, 30mL of n-hexane was added and stirred for 15 minutes, and the filtration was carried out to obtain a dark red solid as nickel complex Ni1, the mass of which was 0.91g, and the reaction yield was 90%.
Results of Mass Spectrometry MALDI-TOF (m/z): 931.268[ M-Br)] + . FIG. 7 is an X-ray diffraction single crystal structure diagram of the nickel complex Ni1 prepared in example 5 of the present invention, and the specific spatial structure of the prepared nickel complex Ni1 can be determined with reference to FIG. 7.
Example 6
Synthesis of nickel complex Ni 2:
the synthesis of Ni2 as a nickel complex was carried out in the same manner as in example 5 except that ligand compound 2 was added, and the yield of Ni2 as a nickel complex was 0.90g and 88%.
Results of Mass Spectrometry MALDI-TOF (m/z): 947.399[ M-Br)] + 。
Example 7
Synthesis of nickel complex Ni 3:
the synthesis of Ni3 as a nickel complex was carried out in the same manner as in example 5 except that ligand compound 3 was added, and the yield of Ni3 as a nickel complex was 0.78g and 89%.
Results of Mass Spectrometry MALDI-TOF (m/z): 795.337[ M-Br)] + 。
Example 8
Synthesis of nickel complex Ni 4:
the synthesis of Ni4 as a nickel complex was carried out in the same manner as in example 5 except that ligand compound 4 was added, and the yield of Ni4 as a nickel complex was 0.73g and 80%.
Results of Mass Spectrometry MALDI-TOF (m/z): 827.400[ M-Br)] + 。
Test example 1:
the method for preparing different nickel complexes Ni1, ni2, ni3 and Ni4 with hydroxyl structures in olefin homopolymerization reaction by using the nickel complexes prepared in the embodiments 5 to 8 respectively comprises the following steps:
in a glove box, 18mL of n-heptane, 500eq of Et, were charged into a pressure-resistant bottle of a 350mL autoclave (equipped with a magnetic stirring device, an oil bath heating device, and a thermometer) under nitrogen atmosphere 2 AlCl. The vessel was connected to a high pressure line and the line was evacuated. The vessels were individually controlled to a temperature of 50 to 120℃using an oil bath, and the nickel complexes prepared in examples 5 to 8, which were dissolved in different amounts of 2mL of methylene chloride, were individually injected into the polymerization system by means of a syringe. Closing the valve, adjusting the ethylene pressure to 8atm, then respectively reacting for 10min or 20min, stopping the reaction, opening the reaction kettle, and vacuum-pumping the solvent from the obtained polymer to obtain white rubber-like solid. Wherein the effect of nickel complexes having different numbers of hydroxyl structures on catalyzing ethylene homopolymerization under different reaction conditions is recorded in the following table 1:
TABLE 1 homogeneous Nickel Complex catalyzed ethylene polymerization
The polymerization conditions are as follows: nickel catalyst=0.5 μmol, n-heptane (Hep) =18 mL, ethylene pressure=8 atm. The polymerization is repeated at least a number of timesThe number is more than 2. b Activity=10 6 g·mol -1 ·h -1 。 c The branching degree is determined by 1 Calculated by HNMR, deuterated tetrachloroethane is used as a solvent at 120 ℃. d Melting points were determined using a differential scanning calorimeter. e The molecular weight was determined by GPC using polystyrene as standard trichlorobenzene as solvent at 150 ℃.
Ni1 in Table 1 corresponds to Ni1 as the nickel complex prepared in example 5; ni2 corresponds to the nickel complex Ni2 prepared in example 6; ni3 corresponds to the nickel complex Ni3 prepared in example 7; ni4 corresponds to the nickel complex Ni4 prepared in example 8. In the polymerization of ethylene catalyzed by the homogeneous nickel catalyst, the same catalyst, polymerization time, increases the branching degree of the polymer, decreases the molecular weight, and gradually deteriorates the mechanical properties as the polymerization temperature increases, as shown in the above table 1, lines 1, 2, lines 3, 4, lines 5 to 7, and lines 8 to 11, because the chain traveling ability and chain transfer ability of the polymer molecular chain are improved with the increase in temperature. And the same polymerization time, polymerization temperature, the elongation at break, stress at break, and the degree of branching of the polymer decrease as the number of hydroxyl groups on the catalyst increases, as shown in Table 1 above, lines 1, 3,5, 8, lines 2, 4,6, 9, lines 7, 10.
Example 9
Synthesis of magnesium chloride carrier:
under the protection of nitrogen, sequentially adding anhydrous MgCl into a 250mL three-neck flask with a magnetic stirring and condensing device 2 (10 g,105 mmol) of absolute ethanol (absolute ethanol: anhydrous MgCl) 2 =3), gradually raise the temperature to make MgCl 2 Dissolving to form uniform transparent solution, adding a certain amount of n-heptane to make MgCl 2 Fully dispersing and emulsifying the ethanol complex solution, and vacuum-pumping n-heptane and redundant ethanol to obtain white powdery MgCl 2 Ethanol complex, and sealing and preserving.
Under the protection of nitrogen, mgCl is added 2 Ethanol Complex (5 g) was added to a 250mL glass bottle, 20mL n-heptane was added, stirred into a slurry, and 15mL triethylaluminum (0.3 g +.mL), slowly heating to room temperature, reacting for 24h, filtering, washing with n-heptane for 3 times, and pumping out the n-heptane to obtain the mobile modified MgCl 2 And (3) powder.
Stirring 2 mu mol of nickel complex Ni1 prepared in example 5, 100mg of magnesium chloride prepared in the example and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain solid Ni1@MgCl 2 。
Example 10
Stirring 2 mu mol of nickel complex Ni2 prepared in example 6, 100mg of magnesium chloride prepared in example 9 and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain solid Ni2@MgCl 2 。
Example 11
Stirring 2 mu mol of nickel complex Ni3 prepared in example 7, 100mg of magnesium chloride prepared in example 9 and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain solid Ni3@MgCl 2 。
Example 12
Stirring 2 mu mol of nickel complex Ni4 prepared in example 8, 100mg of magnesium chloride prepared in example 9 and 15ml of dichloromethane in a glove box at 20 ℃ for 12 hours, filtering and drying filter residues to obtain solid Ni4@MgCl 2 。
Test example 2
The method for using the different supported alpha-diimine nickel catalysts prepared in the embodiments 9-12 in the olefin homopolymerization reaction comprises the following steps:
in a glove box, 18mL of n-heptane, 0.5. Mu. Mol of various supported alpha. -diimine nickel catalysts were added to a pressure-resistant flask of a 350mL autoclave (equipped with a magnetic stirring device, an oil bath heating device, and a thermometer) under nitrogen atmosphere. The vessel was connected to a high pressure line and the line was evacuated. The vessel was controlled to different temperatures of 50 to 120℃using an oil bath, and 500eq of Et was injected by a syringe 2 AlCl is injected into the polymerization system. Closing the valve, regulating ethylene pressure to 8atm, and stopping the reaction after 10minThe reaction was carried out, the reaction vessel was opened, and the obtained polymer was vacuum-dried to obtain a white rubbery solid. Wherein the effect of supported alpha-diimine nickel catalysts having different numbers of hydroxyl structures on catalyzing ethylene homopolymerization under different reaction conditions is recorded in table 2 below:
TABLE 2 Supported alpha-diimine Nickel catalyst for ethylene polymerization
The polymerization conditions are as follows: nickel catalyst=0.5 μmol, time=10 min, n-heptane (Hep) =18 mL, ethylene pressure=8 atm. The polymerization is repeated at least 2 times or more. b Activity=10 6 g·mol -1 ·h -1 。 c The branching degree is determined by 1 Calculated by HNMR, deuterated tetrachloroethane is used as a solvent at 120 ℃. d Melting points were determined using a differential scanning calorimeter. e The molecular weight was determined by GPC using polystyrene as standard trichlorobenzene as solvent at 150 ℃. f Time = 20min.
In the polymerization reaction of ethylene catalyzed by the supported alpha-diimine nickel catalyst, the shielding effect of the nickel metal center is increased due to the existence of the carrier magnesium chloride, so that the coordination energy barrier of ethylene and nickel metal is increased. Therefore, under the same catalyst, the same polymerization temperature and the same polymerization time, the supported alpha-diimine nickel catalyst has lower catalytic activity compared with a homogeneous catalyst, and simultaneously the chain transfer and chain traveling capacity of a polymer molecular chain is reduced, so that the branching degree of polyethylene is reduced, the elongation at break is increased and the breaking stress is increased.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. An α -diimine ligand compound having the structural formula (I) or (ii):
wherein Ar is selected from 2, 6-di (benzhydryl) -4-methylphenyl or 2, 6-di (isopropyl) phenyl; each R is independently selected from hydroxyl or hydrogen.
2. The ligand compound of claim 1, wherein the alpha-diimine ligand compound has the formula (I 1 )～(I 4 ) Or (II) 1 )～(Ⅱ 2 ) Any one of the structures shown in:
3. an alpha-diimine nickel complex having a structural formula represented by formula (III) or formula (IV):
wherein Ar is selected from 2, 6-di (benzhydryl) -4-methylphenyl or 2, 6-di (isopropyl) phenyl; x comprises at least one of methyl, chlorine or bromine;
each R is independently selected from hydroxyl or hydrogen.
4. The alpha-nickel diimine complex of claim 3, wherein the alpha-nickel diimine complex has the formula (iii) 1 )～(Ⅲ 4 ) Or (IV) 1 )～(Ⅳ 2 ) Any one of the structures shown in:
5. a supported alpha-diimine nickel catalyst comprising the nickel complex of claim 3 or 4 and a support, wherein said nickel complex is supported on a support.
6. The supported alpha-diimine nickel catalyst of claim 5, wherein the support includes at least one of silica, magnesium chloride, or aluminum oxide.
7. A supported alpha-diimine nickel catalyst as claimed in claim 5 or 6 for catalyzing C 2 ～C 11 Is used for the polymerization of olefin monomers.
8. The use according to claim 7, wherein the catalyst C 2 -C 11 The polymerization of the olefin monomers of (a) comprises:
cocatalyst and C 2 ～C 11 Adding olefin monomer into organic solvent, adding the supported alpha-diimine nickel catalyst to make the C 2 ～C 11 Is subjected to coordination polymerization.
9. The use according to claim 8, wherein,
the organic solvent comprises at least one of toluene, benzene and n-heptane;
the cocatalyst comprises at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum dichloride, tri-n-butylaluminum, alkali metal and alkali metal salt;
the C is 2 -C 11 The olefin monomer of (2) comprises at least one of methacrylic acid, methyl methacrylate, ethyl methacrylate 10-undecenol, 10-undecylenic acid, 6-chloro-1-hexene, 1-hexene and 1-octene.
10. The use according to claim 8 or 9, wherein,
the coordination polymerization reaction comprises the C 2 ～C 11 Olefin monomers homo-and/or co-polymerization.
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