CN108003094B - Ligand, preparation method thereof, nickel complex, preparation method thereof and application thereof - Google Patents
Ligand, preparation method thereof, nickel complex, preparation method thereof and application thereof Download PDFInfo
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- CN108003094B CN108003094B CN201711171977.XA CN201711171977A CN108003094B CN 108003094 B CN108003094 B CN 108003094B CN 201711171977 A CN201711171977 A CN 201711171977A CN 108003094 B CN108003094 B CN 108003094B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003446 ligand Substances 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 41
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 26
- 238000009826 distribution Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 150000003254 radicals Chemical class 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 90
- -1 pyrrole imine Chemical class 0.000 description 71
- 239000001257 hydrogen Substances 0.000 description 49
- 229910052739 hydrogen Inorganic materials 0.000 description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 45
- 150000002431 hydrogen Chemical class 0.000 description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 43
- 125000001183 hydrocarbyl group Chemical group 0.000 description 41
- 150000002367 halogens Chemical class 0.000 description 40
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 36
- 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 22
- 239000005977 Ethylene Substances 0.000 description 22
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 20
- 125000001624 naphthyl group Chemical group 0.000 description 20
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 20
- 125000001841 imino group Chemical group [H]N=* 0.000 description 19
- 239000007787 solid Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000003780 insertion Methods 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000002815 nickel Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000000463 material Substances 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
- 229920002223 polystyrene Polymers 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 compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 2
- IESAODRGYAJIDR-UHFFFAOYSA-N 2,6-bis[bis(4-methylphenyl)methyl]-4-methylaniline Chemical compound C1(=CC=C(C=C1)C(C1=C(N)C(=CC(=C1)C)C(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C IESAODRGYAJIDR-UHFFFAOYSA-N 0.000 description 2
- NCXCFZUKRMOFHW-UHFFFAOYSA-N 2,6-dibenzhydryl-4-methylaniline Chemical compound 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000035484 reaction time 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
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PTXWAWIYGFDGMU-UHFFFAOYSA-N 1-oxidopyridin-1-ium-2-carbaldehyde Chemical compound [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
- LIHRSHFNTQBGQB-UHFFFAOYSA-N 2,6-bis(dinaphthalen-2-ylmethyl)-4-methylaniline Chemical compound Cc1cc(C(c2ccc3ccccc3c2)c2ccc3ccccc3c2)c(N)c(c1)C(c1ccc2ccccc2c1)c1ccc2ccccc2c1 LIHRSHFNTQBGQB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000010224 classification analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000005292 vacuum distillation Methods 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)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a ligand with a structure of a formula (I) and a preparation method thereof; the application also provides a pyridine-NO free radical type nickel complex which takes the ligand as a base and is regulated and controlled by the large steric hindrance aromatic ring with the structure of the formula (II) or the formula (III), and a preparation method and application thereof. The nickel complex provided by the application can be used as a catalyst to catalyze the polymerization or copolymerization of C2-C6 low-carbon olefins: the catalyst has high thermal stability and activity for the polymerization of the low-carbon olefin of C2-C6, and produces the poly low-carbon olefin with adjustable molecular weight distribution and branching degree and ultrahigh molecular weight.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a ligand, a preparation method thereof, a nickel complex, a preparation method thereof and application thereof.
Background
Polyolefins are one of the indispensable materials in modern social life and production due to excellent physical and mechanical properties and relatively low price. In olefin polymerization processes, the catalyst determines the olefin polymerization behavior, the particle morphology of the polymer, and the structure and properties of the polymer. The continuous development of olefin polymerization catalysts leads to the rich variety and excellent performance of polyolefin products, and promotes the development of the whole polyolefin industry. Currently, the demand for polyolefins is still enormous, and thus the research on polyolefin catalysts is the most important position.
The development of new catalysts is key to the invention of high performance polyolefin materials, and the design of ligands is of fundamental importance in the design of catalysts.transition metal catalysts synthesized based on various ligands have played a key role in the field of olefin polymerization.among numerous ligands, imine may be one of the most common structures.notable examples include pyrrole imine, pyridine-diimine, β -diimine, salicylaldimine, α -diimine, these imine ligands are usually prepared by condensation of aldehydes or ketones with various anilines.thus, the development of new aniline molecules will enable the generation of a series of new imine ligands and a corresponding series of new olefin polymerization catalysts.for example, Long et al utilize a new benzhydrylaniline and prepare several high performance α -diiickel catalysts.subsequently, Chen et al design some diphylhydrazino anilines with different substituents (Me, MeO, Cl, CF3) at the para position, the corresponding α -diirdiline catalysts show very good performance in ethylene polymerization and ethylene-methyl acrylate, the development of corresponding Chempn catalysts show further improved performance of bis-naphthylimine and corresponding pyridine-bis-arylimine catalysts, and similar catalysts have been reported.
The above nickel catalysts show very interesting properties in ethylene polymerization: first, very high activity (up to 3.0X 10) can be achieved at very low cocatalyst MMAO6g(mol Nih-1) (ii) a Secondly, the polyethylene molecular weight of such catalysts is relatively low (Mn to 1.5X 10)3) (ii) a Third, this type of catalyst is thermally less stable and very low activity is observed at 50 ℃. Therefore, it is required to improve the thermal stability of the catalyst, the catalytic activity and the polymer molecular weight by introducing a new bulky aryl group. Therefore, a pyridine-NO free radical type nickel catalyst regulated and controlled by a large steric hindrance aromatic ring is designed and synthesized, and the properties of the corresponding nickel catalyst on ethylene homopolymerization and copolymerization are researched.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nickel catalyst, and the nickel catalyst has higher thermal stability, catalytic activity and polymer molecular weight when used for homopolymerization or copolymerization of C2-C6 low-carbon olefin.
In view of the above, the present application provides a ligand having the structure of formula (I),
wherein, R is1、R2、R3And R4Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the Ar has a structure of formula 101 or formula 102:
wherein, R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl.
Preferably, said R is1、R2、R3And R4Wherein 1-3 substituents are hydrogen, phenyl or substituted phenyl; the R is8、R9、R10And R11Independently selected from hydrogen, C2-C6 hydrocarbyl, C2-C6 substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl or substituted benzothienyl; the R is21、R22、R23And R24Independently selected from hydrogen, alkyl of C1-C6, substituted alkyl of C1-C6, phenyl or substituted phenyl.
The application also provides a preparation method of the ligand, which comprises the following steps:
reacting an amine compound with a structure shown in a formula (A) with an aldehyde compound with a structure shown in a formula (B) in an organic solvent to obtain a ligand with a structure shown in a formula (I);
H2N-Ar
(A)；
wherein, R is1Formula (II) and (II) AR2、R3And formula R4Independently selected from hydrogen, C1～C6A hydrocarbon (I) radical of the formula (I), halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the Ar has a structure of formula 101 or formula 102:
wherein, R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substitutedPhenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl;
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl.
The present application provides a nickel complex having the structure of formula (II);
wherein, R is1、R2And R3Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl of (A), R4Selected from hydrogen, C1～C6Alkyl, halogen, nitro or C1～C6Substituted hydrocarbyl groups of (a);
ar is1Selected from the structures represented by formula 101;
wherein, R is5、R6And R7Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
x is halogen.
Preferably, said R is1、R2And R3Wherein 1-3 substituents are hydrogen, phenyl or substituted phenyl; the R is4Is hydrogen.
The present application provides a nickel complex having the structure of formula (iii);
wherein Ar is2When it is of formula 101, R is1、R2、R3Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); r4Selected from phenyl or substituted phenyl;
Ar2when it is of formula 102, R is1、R2、R3And R4Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
ar is2Has a structure of formula 101 or formula 102:
wherein, R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, haloElement, nitro group, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
x is halogen.
Preferably, said R is1、R2、R3And R4Wherein 1 to 3 substituents are hydrogen, phenyl or substituted phenyl, Ar2Is shown as formula 102.
The application also provides a preparation method of the nickel complex, which comprises the following steps:
reacting a ligand with a nickel compound in an organic solvent to obtain a nickel complex;
the ligand is the ligand of claim 1, and the nickel compound is (DME) NiX2；
Wherein DME is ethylene glycol dimethyl ether, and X is halogen.
The application also provides a preparation method for polymerizing the C2-C6 low-carbon olefin, which comprises the following steps:
under the catalytic action of the nickel complex in the scheme, the low-carbon olefin of C2-C6 is polymerized to obtain the low-carbon olefin polymer.
The application also provides a preparation method for the copolymerization of the low-carbon olefin of C2-C6 and 10-methyl enoate, which comprises the following steps:
under the catalytic action of the nickel complex in the scheme, the low-carbon olefin of C2-C6 and 10-methyl enoate are subjected to copolymerization reaction to obtain the copolymer.
The application provides a nickel complex with a structure of a formula (II) or a formula (III), wherein an Ar substituent group in the complex provides certain steric hindrance for one side of a nickel atom, and the rate of nickel is reduced, so that a C2-C6 low-carbon olefin homopolymer or copolymer has higher thermal stability, molecular weight and polymerization activity; on the other hand, the pyridine N-O structure in the nickel complex has a common electron effect, which is beneficial to the coordination effect of ethylene monomers and metallic nickel, thereby improving the polymerization activity.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention, and not to limit the scope of the appended claims.
The invention provides a ligand, which is used for synthesizing a nickel complex, namely the ligand is the basis of the nickel complex, and particularly the ligand has a structure shown in a formula (I);
wherein, R is1、R2、R3And R4Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the Ar has a structure of formula 101 or formula 102:
the R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl.
In specific embodiments, the R is1、R2、R3And R4Wherein 1-3 substituents are hydrogen, phenyl or substituted phenyl; the R is8、R9、R10And R11Independently selected from hydrogen, C2-C6 hydrocarbyl, C2-C6 substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl or substituted benzothienyl; the R is21、R22、R23And R24Independently selected from hydrogen, alkyl of C1-C6, substituted alkyl of C1-C6, phenyl or substituted phenyl.
More specifically, the ligand with the structure of the formula (I) is shown as the formula (I)1) Formula (I)2) Formula (I)3) Formula (I)4) Formula (I)5) Formula (I)6) Formula (I)7) Or formula (I)8) The structure of (1);
the application also provides a preparation method of the ligand, which comprises the following steps:
reacting amine with a structure shown in a formula (A) with aldehyde with a structure shown in a formula (B) in an organic solvent to obtain a ligand with a structure shown in a formula (I);
H2N-Ar
(A)；
wherein, R is1Formula (II) R2、R3And formula R4B is independently selected from hydrogen, C1～C6With the formula (I) hydrocarbyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted benzene ofA group;
the Ar has a structure of formula 101 or formula 102:
wherein, R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl.
In the above-mentioned process for preparing the ligand, the organic solvent is a solvent well known to those skilled in the art, and the present application is not particularly limited; illustratively, the organic solvent is selected from one or more of tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane, tetrachloromethane, diethyl ether, 2, 4-dioxane, and 1, 2-dichloroethane; in a specific embodiment, the organic solvent is toluene. The molar ratio of the amine to the aldehyde is 1: (0.1 to 10); in particular embodiments, the molar ratio of the amine to the aldehyde is: (1-5). The above reaction was carried out at a reflux temperature of-78 ℃. The above amines and aldehydes are compounds well known to those skilled in the art, and the source thereof is not particularly limited in the present application.
The application also provides a nickel complex with the ligand as the main group, which is a nickel complex with a structure of a formula (II);
wherein, R is1、R2And R3Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl of (A), R4Selected from hydrogen, C1～C6Alkyl, halogen, nitro or C1～C6Substituted hydrocarbyl groups of (a);
ar is1Selected from the structures represented by formula 101;
wherein, R is5、R6And R7Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl.
In specific embodiments, the R is1、R2And R3Wherein 1-3 substituents are hydrogen, phenyl or substituted phenyl; the R is4Is hydrogen.
More particularly, the nickel complex has the formula (II)1) Formula (II)2) Formula (II)3) Or formula (II)4) Structure;
due to the difference in R4 or the difference in Ar, the present application also provides a nickel complex having the structure of formula (III);
wherein Ar is2When it is of formula 101, R is1、R2、R3Independently selected from hydrogen, C1-C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
R4selected from phenyl, substituted phenyl;
Ar2when it is of formula 102, R is1、R2、R3And R4Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
ar is2Has a structure of formula 101 or formula 102:
wherein, R is5、R6、R7、R12、R13、R14、R15、R16、R17、R18、R19And R20Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
the R is8、R9、R10And R11Independently selected from hydrogen, C2～C6Alkyl, halogen, nitro, C2～C6Substituted hydrocarbyl, phenyl, substituted phenyl, naphthyl, substituted naphthyl, benzothienyl, or substituted benzothienyl groups of (a);
the R is21、R22、R23And R24Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
x is halogen.
As mentioned above, in Ar2When having formula 102, R1、R2、R3And R4Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a);
in a particular embodiment, the nickel complex has the formula (III)1) The structure of (1);
at Ar2When having the formula 101, R is1、R2、R3Independently selected from hydrogen, C1～C6Alkyl, halogen, nitro, C1～C6Substituted hydrocarbyl, phenyl or substituted phenyl groups of (a); r4Selected from phenyl or substituted phenyl;
in a particular embodiment, the nickel complex has the formula (III)2) Formula (III)3) Or formula (III)4) Structure;
the application also provides a preparation method of the nickel complex, which comprises the following steps:
reacting a ligand with a nickel compound in an organic solvent to obtain a nickel complex; the ligand is the ligand of the scheme, and the nickel compound is (DME) NiX2；
Wherein DME is ethylene glycol dimethyl ether, and X is halogen.
In the above-described process for preparing the nickel complex, the organic solvent is an organic solvent well known to those skilled in the art, and exemplified by one or more organic solvents selected from the group consisting of tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, diethyl ether, 2, 4-dioxane and 1, 2-dichloroethane; in a particular embodiment, the organic solvent is selected from dichloromethane. The molar ratio of the ligand to the nickel compound is 1: (0.1-6), in specific embodiments, the molar ratio of the ligand to the nickel compound is 1: (1-3). The reaction was carried out at-78 ℃ reflux temperature. The reaction time is 1-50 h; in a specific embodiment, the reaction time is 12-24 h.
The nickel complex prepared by the method is mainly used for preparing polyolefin, and particularly relates to the copolymerization of C2-C6 low-carbon olefin and C2-C6 low-carbon olefin and 10-methyl enoate; specifically, the application provides a preparation method for polymerizing C2-C6 low-carbon olefin, which comprises the following steps:
under the catalytic action of the nickel complex, the low-carbon olefin of C2-C6 is polymerized to obtain the low-carbon olefin polymer.
The application also provides a preparation method for the copolymerization of the low-carbon olefin of C2-C6 and 10-methyl enoate, which comprises the following steps:
under the catalytic action of the nickel complex, the low-carbon olefin of C2-C6 and 10-methyl enoate are copolymerized to obtain the copolymer.
The above-mentioned processes for the copolymerization or homopolymerization of olefins are well known to those skilled in the art and will not be described herein in detail; the difference lies in that: the catalyst used for the olefin polymer is the nickel complex provided by the application. The C2-C6 light olefin is selected from ethylene in specific embodiments. The experimental results show that: the nickel complex provided by the application has higher catalytic activity and stability when used for olefin polymerization, and can generate ultrahigh molecular weight low-carbon olefin with adjustable molecular weight distribution and branching degree.
The invention provides a pyridine-NO free radical type nickel catalyst regulated and controlled by a large steric hindrance aromatic ring, a preparation method and application thereof. The catalyst can catalyze the polymerization or copolymerization of C2-C6 low-carbon olefin; for the polymerization of C2-C6 low-carbon olefinThe product has high thermal stability and activity, and can produce ultra-high molecular weight poly-low-carbon olefin with adjustable molecular weight distribution and branching degree; for the copolymerization of C2-C6 lower olefins and methyl 10-enoate, copolymers with high molecular weight polar monomers are produced, and the insertion ratio is high. The experimental results show that: the catalyst can catalyze ethylene homopolymerization, and the activity can reach up to 107g of PE (mol of Ni)-1h-1(ii) a The weight average molecular weight of the unimodal distribution is 3016500g/mol at most, and the molecular weight distribution is 2.49; when the bimodal distribution is generated, the molecular weight distribution can reach 59.67 at most; the weight-average molecular weight of the copolymerization product of ethylene and methyl 10-enoate is up to 184700 g/mol; the insertion ratio of methyl 10-enoate is at most 1.50%.
For further understanding of the present invention, the following examples are given to illustrate the nickel complexes of the present invention, and the scope of the present invention is not limited by the following examples.
The following examples illustrate the details of the invention and the data presented include the synthesis of ligands, the synthesis of metal compounds, the ethylene polymerization or copolymerization processes, wherein the synthesis of the complex, the polymerization process is carried out in the absence of water and oxygen, all sensitive materials are stored in a glove box, all solvents are rigorously dried to remove water, the ethylene gas is purified by a water and oxygen removal column, and the methyl acrylate is purified by a water and oxygen removal vacuum distillation process. All the raw materials are commercially available without specific mention.
Silica gel column is treated with 200-mesh 300-mesh silica gel, nuclear magnetism is treated with Bruker 400MHz nuclear magnetism instrument, elemental analysis is measured by the physicochemical center of Chinese science and technology university, molecular weight and molecular weight distribution are measured by GPC (polystyrene type column, HR2 and HR4, box temperature is 45 ℃, Water 1515 and Water 2414 pumps are used; mobile phase is tetrahydrofuran, flow rate is 1.0 ml per minute, polydisperse polystyrene is used as standard), mass spectrum is measured with Thermo LTQ Orbitrap XL (ESI +) or P-SIMS-Gly of Bruker Daltonics Inc (EI +), single crystal X diffraction analysis is carried out with Oxford diffraction Gemini S Ultra CCD single crystal diffraction instrument, Cu K α
And (5) irradiating at room temperature.
Example 1: preparation of 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) pyridine-1-oxide
A mixture of 2-pyridinecarboxaldehyde N-oxide (123 mg, 1 mmol), 2, 6-bis (diphenylmethyl) -4-methylaniline (440 mg, 1 mmol) and p-toluenesulfonic acid (20 mg) in toluene (50 ml) was stirred and maintained at 130 ℃ for 24 hours; the solvent was partially evaporated under reduced pressure until a grey solid formed and the remaining solution was diluted in methanol (30 ml); the grey solid was isolated by filtration and washed three times with 10 ml of methanol to give a solid of formula (I)1) Ligand 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) pyridine-1-oxide of structure (480 mg, 62.9% yield).1H NMR(400MHz, CDCl3)δ8.21(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.
Example 2: preparation of 2- (((2, 6-bis (naphthalen-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide
The synthesis procedure is the same as in example 1, except that: 2, 6-bis (di (naphthalen-2-yl) methyl) -4-methylaniline (640 mg, 1 mmol) was charged to give a yellow solid (522 mg, 72% yield) having formula (I)2) 2- (((2, 6-bis (naphthalen-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide of structure (iv).
1H NMR(400MHz,CDCl3)δ8.49(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.
Example 3: preparation of 2- ((2, 6-bis (benzothien-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide
The synthesis procedure is the same as in example 1, except that: 2, 6-bis (di (benzothien-2-yl) methyl) -4-methylaniline (666 mg, 1 mmol) was charged to give a yellow solid (431 mg, 56% yield) of the formula (I)3) 2- ((2, 6-bis (benzothien-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide of structure.1H NMR(400MHz,CDCl3)δ7.85(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.
Example 4: preparation of 2- ((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide
The synthesis procedure was the same as in example 1, except that: 2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-ylamine (566 mg, 1 mmol) was charged to give a yellow solid (576 mg, 86% yield) of formula (I)4) 2- ((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide of structure.1H NMR(400MHz,CDCl3)δ7.99(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)δ154.11,145.19, 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。
Example 5: preparation of 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) pyridine 1-oxide
The synthesis procedure is the same as in example 1, except that: 2, 6-bis (di-p-tolylmethyl) -4-methylaniline (496 mg, 1 mmol) was charged to give a yellow solid (450 mg, 75% yield) of formula (I)5) 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) pyridine 1-oxide of structure (iv).1H NMR(400MHz,CDCl3)δ8.27(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.
Example 6: preparation of 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide
2-Formaldehyde-6-phenylpyridine N-oxide (199 mg, 1 mmol), 2, 6-bis (diphenylmethyl) -4-methylaniline (440 mg, 1 mmol) and p-toluenesulfonic acid (20 mg) were stirred in toluene (50 mL) at 130 ℃ for 24 h; the solvent was partially evaporated under reduced pressure until a grey solid formed and the remaining solution was diluted in methanol (30 ml); the grey solid was isolated by filtration and washed three times with 10 ml of methanol to give a solid of formula (I)6) 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide of structure (550 mg, 90% yield).1H NMR(400MHz,CDCl3) δ8.36(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.
Example 7: preparation of 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide
The synthesis procedure was the same as in example 6, except that: 2, 6-bis (di-p-tolylmethyl) -4-methylaniline (496 mg, 1 mmol) was charged to give a yellow solid (541 mg, 80% yield) of formula (I)7) 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide of structure (iv).1H NMR(400MHz,CDCl3)δ8.46(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.
Example 8: preparation of 2- (((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) -6-phenylpyridine 1-oxide
The synthesis procedure was the same as in example 6, except that: 2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-amine (566 mg, 1 mmol) was charged to give a yellow solid (545 mg, 73% yield) having the formula (I)8) 2- (((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) -6-phenylpyridine 1-oxide of structure.
1H NMR(400MHz,CDCl3)δ7.99(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).13CNMR(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 forC55H42ON2[M]:746.3297,found:746.3267.
Example 9: preparation of nickel complex of 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) pyridine-1-oxide
2- (((2, 6-Diphenylhydro-4-methylphenyl) imino) methyl) pyridine-1-oxide (546 mmol, 1 mmol) and (DME) NiBr2(154 mg 0.5 mmol) was added to 20 ml dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate the complex, the precipitate was washed with ether and dried under reduced pressure at room temperature for 12 hours to give a solution having formula (II)1) A nickel complex of structure 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) pyridine-1-oxide. Elemental analysis, theoretical calculation: c78H64Br2N4NiO2Theoretical calculation: c, 71.63; h, 4.93; n,4.28, actually measuring C, 71.45; h, 4.97; n,4.35.MALDI-TOF M/z 680.8602[ M-L-Br]+；682.8975[M-L-Br+2H]+。
Example 10: preparation of nickel complex of 2- (((2, 6-bis (naphthalen-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide
2- (((2, 6-bis (naphthalen-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide (745 mg, 1 mmol) and (DME) NiBr2(154 mg 0.5 mmol) was added to 20 ml dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate the complex, the precipitate was washed with ether, and dried at room temperature under reduced pressure for 12 hours to give a solution having formula (II)2) A nickel complex of structure 2- (((2, 6-bis (naphthalen-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide. Element classificationAnalysis and theoretical calculation: c110H80Br2N4NiO2C, 77.34; h, 4.72; n,3.28, actual measurement is C, 77.55; h, 4.57; n,3.35.MALDI-TOF M/z 880.8529[ M-L-Br]+；882.8887 [M-L-Br+2H]+.
Example 11: preparation of
2- ((2, 6-bis (benzothien-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide (769 mg, 1 mmol) and (DME) NiBr2(154 mg 0.5 mmol) was added to 20 ml dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate the complex, the precipitate was washed with ether and dried under reduced pressure at room temperature for 12 hours to give a solution having formula (II)3) A nickel 2- ((2, 6-bis (benzothien-2-yl) methyl) -4-methylphenyl) imino) methyl) pyridine-1-oxide complex of the structure. Elemental analysis, theoretical calculation: c94H66Br2N4NiO2S8C, 64.20; h, 3.78; n,3.19, actually measuring C, 64.45; h, 3.57; MALDI-TOF, M/z 903.9476[ M-L-Br]+； 906.0133[M-L-Br+2H]+.
Example 12: preparation of nickel complex of 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) pyridine 1-oxide
2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) pyridine 1-oxide (600 mg, 1 mmol) and (DME) NiBr2(154 mg 0.5 mmol) was added to 20 ml dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate a complex, the precipitate was washed with ether, and dried under reduced pressure at room temperature for 12 hours to obtain a complex having the formula (II)4) 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) of structurePyridine 1-oxide nickel complexes. Theoretical calculation of C85H78Br2N4NiO2: c, 72.61; h, 5.59; n,3.98 actually measured, C, 72.64; h, 5.69; and N, 3.90. MALDI-TOF M/z 767.2147[ M-L-Br]+；765.2156[M-L-Br +2H]+。
Example 13: preparation of nickel complex of 2- ((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide
2- ((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide (672 mg, 1 mmol) and (DME) NiBr2(308 mg, 1 mmol) was added to 20 ml of dichloromethane solution, stirred at room temperature for 12 hours, diethyl ether (20 ml) was added to precipitate the complex, the precipitate was washed with diethyl ether and dried at room temperature under reduced pressure for 12 hours to give a solution of formula (III)1) A nickel complex of the structure 2- ((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide. Elemental analysis, theoretical calculation: c37H30Br2N2NiO is C, 60.29; h, 4.10; the nickel complex of N,3.80.2- (((((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) pyridine 1-oxide was found to be C, 60.37; H, 4.15; N,3.65.MALDI-TOF: M/z 806.7671[ M-Br)]+；808.7863 [M-Br+2H]+.
Example 14: preparation of nickel complex of 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide
2- (((2, 6-Diphenylhydro-4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide (623 mg, 1 mmol) and (DME) NiBr2(308 mg, 1 mmol) was added to 20 ml of dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate the complex, the precipitate was washed with ether, and dried under reduced pressure at room temperature for 12 hours to obtain a complexHas a formula (III)2) A nickel complex of structure 2- (((2, 6-diphenylhydro-4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide. Elemental analysis, theoretical calculation: c45H36Br2N2NiO is C, 64.40; h, 4.32; n,3.34, actually measuring C, 64.28; h, 4.38; n,3.45.MALDI-TOF M/z756.8963[ M-Br]+；758.8924[M-Br+2H]+.
Example 15: preparation of nickel complex of 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide
2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide (777 mg, 1 mmol) and (DME) NiBr2(308 mg, 1 mmol) was added to 20 ml of dichloromethane solution, stirred at room temperature for 12 hours, ether (20 ml) was added to precipitate the complex, the precipitate was washed with ether and dried under reduced pressure at room temperature for 12 hours to give a solution of formula (III)3) A nickel complex of structure 2- (((2, 6-bis (di-p-tolylmethyl) -4-methylphenyl) imino) methyl) -6-phenylpyridine 1-oxide. Elemental analysis, theoretical calculation: c49H44Br2N2NiO is C, 65.73; h, 4.95; n,3.13, actually measuring C, 65.70; h, 4.97; and N, 3.15. MALDI-TOF M/z 894.1153[ M-Br ]]+；896.1156[M-Br+2H]+。
Example 16: preparation of nickel complex of 2- (((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) -6-phenylpyridine 1-oxide
2- (((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) -6-phenylpyridine 1-oxide (777 mg, 1 mmol) and (DME) NiBr2(308 mg, 1 mmol) was added to 20 ml of dichloromethane solution, stirred at room temperature for 12 hours, addedDiethyl ether (20 ml) to precipitate the complex, the precipitate was washed with diethyl ether and dried at room temperature under reduced pressure for 12 hours to give a solid of formula (III)4) A nickel complex of the structure 2- (((2, 4-dibenzyl-8- (p-tolyl) naphthalen-1-yl) imino) methyl) -6-phenylpyridine 1-oxide. Elemental analysis, theoretical calculation: c55H42Br2N2NiO is C, 68.42; h, 4.39; n, 2.90, actually measuring C, 68.40; h, 4.40; and N, 2.91. MALDI-TOF M/z 964.0997[ M-Br ]]+；965.9997[M-Br+2H]+.
Example 17: catalytic ethylene polymerization
In a glove box, under a nitrogen atmosphere, to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device, and a thermometer) was added 18mL of toluene, and 4.6 mg of methylaluminoxane; connecting the container to a high-pressure pipeline, vacuumizing the pipeline, setting the temperature of the container to be 20 ℃, and preserving the temperature for 15 minutes; the nickel complex (1.7 mg) prepared in examples 9 to 15 dissolved in 2ml of dichloromethane was injected into the polymerization system by a syringe; closing the valve, adjusting the ethylene pressure to 8 atmospheric pressure, and reacting for 30 minutes; the reaction was stopped, the kettle was opened, ethanol was added to precipitate the solid, filtered under reduced pressure, and dried in a vacuum oven to give a white solid (5.28 g). The results of the catalysts prepared in examples 9-15 on ethylene polymerization are shown in Table 1:
TABLE 1 results of ethylene polymerization for catalysts prepared in examples 9-15
aPolymerization conditions, namely nickel complex is 1 micromole; 18ml of toluene, 2ml of dichloromethane, 8 atm of ethylene and 30 min of ethylene;bactivity 10 ═ 106g·mol-1·h-1；cThe melting point is measured by a differential scanning calorimeter;dthe degree of branching per 1000 carbons was determined by nuclear magnetic resonance hydrogen spectroscopy;eweight average molecular weight of 104g mol-1The molecular weight was measured by GPC using polystyrene as a standard trichlorobenzene as a solvent at 150 degrees.
Example 18: catalytic copolymerization of ethylene and 10-methyl enoate
In a glove box, under nitrogen atmosphere, 17mL of toluene and 10-methyl enoate were added to a 350mL autoclave (with a magnetic stirring device, an oil bath heating device, and a thermometer), and 580 mg of methylaluminoxane were added, the vessel was connected to a high-pressure line and the pipe was evacuated, the vessel temperature was set at 20 ℃ and held for 15 minutes; the nickel complex (10 mg) prepared in examples 9 to 15 dissolved in 2ml of dichloromethane was injected into the polymerization system by means of a syringe. After the valve was closed and the ethylene pressure was adjusted to 9 atm, the reaction was carried out for 60 minutes. The reaction was stopped, the kettle was opened, ethanol was added to precipitate a solid, filtered under reduced pressure, and dried in a vacuum oven to give a white solid (70 mg). The results of the copolymerization of ethylene and methyl acrylate with the catalysts prepared in examples 9 to 15 are shown in Table 2:
TABLE 2 data table of results of copolymerization of nickel complexes prepared in examples 9 to 15 with ethylene and methyl 10-enoate
aThe polymerization conditions were 18mL in total of toluene and 10-methyl enoate, 2mL in methylene chloride, 10. mu. mol of nickel complex, 1000 mol of methylaluminoxane to nickel complex, 8 atm of ethylene, 80 ℃ for 1 hour, and 20 ℃.bActivity 10 ═ 104g·mol-1·h-1。cMelting points were determined using differential scanning calorimetry.dThe 10-enoic acid methyl ester insertion ratio was measured by nuclear magnetic hydrogen spectroscopy.eWeight average molecular weight of 103g mol-1The molecular weight is measured by GPC using a polymerStyrene was measured as standard trichlorobenzene as solvent at 150 degrees.fThe molar ratio of methylaluminoxane to nickel complex was 500.gThe molar ratio of methylaluminoxane to nickel complex was 200.
From the above embodiments, the invention provides a pyridine-NO free radical type nickel catalyst regulated and controlled by a large steric hindrance aromatic ring, a preparation method and an application thereof, wherein the catalyst has a structure shown in a formula (II) or (III). The catalyst can catalyze the polymerization or copolymerization of the low-carbon olefin of C2-C6, has high thermal stability and activity for the polymerization of the low-carbon olefin of C2-C6, and generates the poly low-carbon olefin with the adjustable molecular weight distribution and the adjustable branching degree and the ultrahigh molecular weight; for the copolymerization of C2-C6 lower olefins and methyl 10-enoate, copolymers with high molecular weight polar monomers are produced, and the insertion ratio is high. The experimental results show that: the catalyst can catalyze ethylene homopolymerization, and the activity can reach up to 107g of PE(mol of Ni)-1h-1(ii) a The weight average molecular weight of the unimodal distribution is 3016500g/mol at most, and the molecular weight distribution is 2.49; when the bimodal distribution is generated, the molecular weight distribution can reach 59.67 at most; the copolymerization product of ethylene with methyl 10-enoate has a weight-average molecular weight of up to 184700 g/mol; the insertion ratio of methyl 10-enoate is at most 1.50%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. Has a formula (II)1）、（Ⅱ2）、（Ⅱ4) Or (III)1) A nickel complex of structure;
2. a process for preparing a nickel complex according to claim 1, comprising:
reacting a ligand with a nickel compound in an organic solvent to obtain a nickel complex;
the nickel compound is (DME) NiX2；
Wherein DME is ethylene glycol dimethyl ether, and X is halogen.
3. A preparation method for C2-C6 low-carbon olefin polymerization comprises the following steps:
under the catalytic action of the nickel complex of claim 1, polymerizing C2-C6 low-carbon olefin to obtain a low-carbon olefin polymer.
4. A preparation method for copolymerizing C2-C6 low-carbon olefin and 10-methyl enoate comprises the following steps:
under the catalytic action of the nickel complex of claim 1, the low-carbon olefin of C2-C6 and 10-methyl enoate are subjected to copolymerization reaction to obtain a copolymer.
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