CN113045453B - Rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, nickel catalyst, preparation method and application thereof - Google Patents
Rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, nickel catalyst, preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 37
- 239000003446 ligand Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005977 Ethylene Substances 0.000 claims abstract description 28
- -1 polyethylene Polymers 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 125000005594 diketone group Chemical group 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract description 3
- 230000037048 polymerization activity Effects 0.000 abstract description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 1
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D223/18—Dibenzazepines; Hydrogenated dibenzazepines
- C07D223/22—Dibenz [b, f] azepines; Hydrogenated dibenz [b, f] azepines
- C07D223/24—Dibenz [b, f] azepines; Hydrogenated dibenz [b, f] azepines with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
- C07D223/28—Dibenz [b, f] azepines; Hydrogenated dibenz [b, f] azepines with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom having a single bond between positions 10 and 11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/30—Ortho- or ortho- and peri-condensed systems containing three rings containing seven-membered rings
- C07C2603/32—Dibenzocycloheptenes; Hydrogenated dibenzocycloheptenes
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Abstract
The invention provides a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, a nickel catalyst, and a preparation method and application thereof, and belongs to the field of catalysts. The structure of the rotation-limited superimposed large-steric-hindrance alpha-diimine ligand is shown as a formula (c). The invention also provides a preparation method of the superimposed large-steric-hindrance alpha-diimine ligand with limited rotation. The invention also provides a nickel catalyst. The invention also provides application of the nickel catalyst in catalyzing ethylene polymerization. Under certain conditions, the activity of the nickel catalyst for catalyzing ethylene polymerization can reach 1014.0 multiplied by 10 6 g mol ‑1 h ‑1 And the polyethylene with ultra-high molecular weight and adjustable branching degree can be obtained. In addition, at high temperature of 90 ℃, the catalyst still has quite high catalytic activity, and polyethylene with high molecular weight is obtained. The ultra-high molecular weight low branching degree polyethylene has good industrial application prospect, and can be considered as ultra-high molecular weight polyethylene fiber to a certain extent. And the ultra-high polymerization activity of the catalyst can greatly reduce the production cost of the catalyst and meet the potential requirements of industrial production.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, a nickel catalyst, and a preparation method and application thereof.
Background
The alpha-diimine nickel catalyst (J.Am. Chem. Soc.1995,117, 6414) has evolved to now become an important class of ethylene polymerization catalysts due to a unique chain walking mechanism. And molecular weight and catalytic activity are important parameters for evaluating a catalyst. At present, a class of superimposed large-steric-hindrance alpha-diimine nickel catalysts with ultrahigh ethylene polymerization activity has been reported, which can catalyze ethylene polymerization to obtain ultrahigh molecular weight polyethylene (J.Catal.2020,390, 30-36; patent number: 202010434782.5). However, there is still room for improvement in the performance metrics of such catalysts.
Disclosure of Invention
The invention aims to provide a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, a nickel catalyst, a preparation method and application thereof, wherein the nickel catalyst has the characteristics of high heat stability, high activity and high molecular weight when being used for catalyzing ethylene polymerization.
The invention firstly provides a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, the structure of which is shown as a formula (c):
in the formula (c), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
The invention also provides a preparation method of the rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, which comprises the following steps:
dissolving aniline with a general formula (b) and diketone with a general formula (a) in a solvent, adding a catalyst, reacting at 25-80 ℃, and then carrying out reflux reaction on the reaction mixture to obtain an overlapped large steric hindrance alpha-diimine ligand with a structure shown as a formula (c);
preferably, the molar ratio of the diketone of formula (a) to the aniline of formula (b) is 1:2.
Preferably, the reaction temperature of the reflux reaction is 110 ℃ or higher and the reaction time is 48 hours or longer.
The invention also provides a nickel catalyst, the structure of which is shown as the formula (d):
in the formula (d), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
The invention also provides a preparation method of the nickel catalyst, which comprises the following steps:
alpha-diimine ligand and NiBr 2 (DME), dme=1, 2-dimethoxyethane, and dissolving in a solvent to react to obtain a nickel catalyst with a structure shown as a formula (d);
preferably, the structure is a class of alpha-diimine ligands and NiBr as shown in formula (c) 2 The molar ratio of (DME) was 1:1.
Preferably, the reaction temperature is 20-50 ℃ and the reaction time is more than 24 hours.
The invention also provides application of the nickel catalyst in catalyzing ethylene polymerization.
The invention also provides a method for catalyzing ethylene polymerization by the nickel catalyst, which comprises the following steps:
connecting the reactor with a high-pressure gas pipeline, regulating the temperature of the reactor to 0-90 ℃, adding a solvent and a cocatalyst into the reactor under inert atmosphere, then injecting a dichloromethane or chloroform solution of a nickel catalyst into the reactor, introducing ethylene under stirring and keeping the pressure at 8-30 atm, and reacting for 1-10 min to obtain the polyethylene.
Principles of the invention
The invention provides a rotation-limited superimposed alpha-diimine ligand, a nickel catalyst and a preparation method thereof, wherein the principle of rotation limitation is shown in figure 1, namely the rotation of an N-benzene ring on the second layer of steric hindrance is limited, the steric hindrance of the axial position of the metal center is increased, the chain transfer reaction and the formation of branching degree are limited, and the purposes of increasing the molecular weight of a polymer and regulating the branching degree are achieved.
The beneficial effects of the invention are that
The invention provides a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, a nickel catalyst, a preparation method and application thereof, under certain conditions, the activity of the nickel catalyst for catalyzing ethylene polymerization can reach 1014.0 multiplied by 10 6 g mol -1 h -1 And can obtain the ultra-high molecular weight (M w 37.3 to 794.8 ten thousand), and the branching degree is adjustable (branching degree is 0.8 to 25.8/1000C). In addition, at high temperatures of 90℃the catalysts still have a comparatively high catalytic activity (8.76X10 6 g mol -1 h -1 ) And a polyethylene (M) of high molecular weight is obtained w 110.3 ten thousand). The ultra-high molecular weight low branching degree polyethylene has good industrial application prospect, and can be considered as ultra-high molecular weight polyethylene fiber to a certain extent. And the ultra-high polymerization activity of the catalyst can greatly reduce the production cost of the catalyst and meet the potential requirements of industrial production.
Drawings
FIG. 1 is a schematic diagram of the principle of rotation-limited superimposed large steric hindrance of the present invention;
FIG. 2 is a single crystal diffraction pattern of an α -diimine ligand prepared in example 2 of the present invention;
FIG. 3 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the alpha-diimine nickel catalyst prepared in example 3 of the present invention;
FIG. 4 is a mass spectrum (MALDI-TOF-MS) of the α -diimine nickel catalyst prepared in example 3 of the present invention;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of a polymer prepared in example 4 (Table 4, item 7) of the present invention.
Detailed Description
The invention firstly provides a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, the structure of which is shown as a formula (c):
in the formula (c), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
The invention also provides a preparation method of the rotation-limited superimposed large-steric-hindrance alpha-diimine ligand, which comprises the following steps:
dissolving aniline of the general formula (b) and diketone of the general formula (a) in a solvent, adding a catalyst, reacting for more than 6 hours, more preferably 12-48 hours at 25-80 ℃, then refluxing the reaction mixture, preferably at more than 110 ℃, more preferably at 120-160 ℃, for more preferably at more than 48 hours, more preferably for 3-4 days, cooling to room temperature after the reaction is finished, evaporating the solvent by rotary evaporation until yellow solid appears, adding excessive methanol or ethanol to separate out a product, filtering and separating the yellow solid, washing three times by using methanol or ethanol, and drying under vacuum to obtain an overlapped large steric hindrance alpha-diimine ligand with the structure shown as the formula (c); the solvent is preferably toluene, xylene or chlorobenzene; the catalyst is preferably p-toluenesulfonic acid or formic acid or acetic acid. The molar ratio of the diketone of the general formula (a), the aniline of the general formula (b) and the catalyst is preferably 1:2:0.001.
the invention also provides a nickel catalyst, the structure of which is shown as the formula (d):
in the formula (d), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
The invention also provides a preparation method of the nickel catalyst, which comprises the following steps:
overlapping a class of sterically bulky alpha-diimine ligands of formula (c) with NiBr 2 (DME) is dissolved in a solvent and reacted at a temperature of preferably 20 to 50℃for a period of more than 24 hours, more preferably 24 to 48 hours, and then the solvent is evaporated by rotary evaporation, recrystallised from n-hexane or diethyl ether and dichloromethane or chloroform, the solid is isolated by filtration, washed three times with hexane or diethyl ether and dried in the presence of a solventDrying under vacuum to obtain nickel catalyst with structure shown in formula (d); the structure is shown as a formula (c) and is overlapped with a steric alpha-diimine ligand and NiBr 2 The molar ratio of (DME) is preferably 1:1, the solvent is preferably dichloromethane or chloroform.
The invention also provides application of the nickel catalyst in catalyzing ethylene polymerization.
The invention also provides a method for catalyzing ethylene polymerization by the nickel catalyst, which comprises the following steps:
drying the reactor preferably at 90deg.C for more than 1 hr, connecting with high pressure gas line, adjusting the temperature of the reactor to 0-90deg.C, preferably 30deg.C, adding solvent and promoter under inert atmosphere, wherein the solvent is toluene, hexane or chlorobenzene, and the promoter is MAO (methylaluminoxane), MMAO (modified methylaluminoxane), EASC (triethylaluminum trichloride) or AlEt 2 Cl (diethyl aluminum chloride), then dissolving nickel catalyst in solvent to obtain catalyst solution, injecting the catalyst solution into a reactor through a syringe, stirring at a stirring speed of 750 turns or more, introducing ethylene and keeping the pressure at 8-30 atm, preferably 8atm, for 1-10 min, quenching polymerization reaction by adding a large amount of acidic methanol (or ethanol) (5% or more hydrochloric acid alcohol solution) solution, filtering the polymer, and drying in a vacuum oven to obtain polyethylene. The concentration of the nickel catalyst is preferably 1. Mu. Mol, and the concentration of the promoter is preferably 500. Mu. Mol.
The invention is described in further detail below with reference to the specific examples, wherein the starting materials are commercially available.
EXAMPLE 1 preparation of Aniline
4- (9H-carbazol-9-yl) phenylboronic acid (26.55 g,92.45 mmol), 2, 6-dibromo-tetramethylaniline (5.00 g,36.98 mmol), aqueous sodium carbonate (150 ml, 2M), a small amount of ethanol, tetrakis (triphenylphosphine) palladium (4.27 g,3.70 mmol) in toluene (150 ml) were stirred at 90℃and held for 24 hours, cooled to room temperature, the solvent was evaporated by rotary evaporation until a yellow solid appeared, the product was added in excess methanol, the yellow solid was isolated by filtration, washed three times with methanol and dried under vacuum to give the yellow solid product (19.30 g,88.5% yield). 1 H NMR(400MHz,298K,CDCl 3 ,7.26ppm)δ＝8.18(d,4H,aryl-H),7.80(d,4H,aryl-H),7.70(d,4H,aryl-H),7.53(d,4H,aryl-H),7.45(t,4H,aryl-H),7.32(t,4H,aryl-H),7.14(s,2H,aryl-H),3.96(s,2H,NH 2 ),2.41(s,3H,CH 3 )。
Example 2 preparation of ligands
Acenaphthoquinone (0.77 g,4.24 mmol), aniline prepared in example 1 (5.00 g,8.48 mmol), a solution of catalytic amount of p-toluene sulfonic acid (20 mg) in toluene (150 ml) were stirred at 130 ℃ under reflux and maintained for 5 days, cooled to room temperature, the solvent was evaporated by rotary evaporation until yellow solid appeared, column chromatography (dichloromethane/petroleum ether=1:1) gave the product (2.88 g,51.2% yield). 1 H NMR(500MHz,298K,CDCl 3 ,7.26ppm)δ＝7.93(d,8H,aryl-H),7.72-7.55(m,10H,aryl-H),7.40-7.31(m,6H,aryl-H),7.07(t,8H,aryl-H),7.00(d,2H,aryl-H),6.96-6.82(m,16H,aryl-H),6.69-6.53(m,8H,aryl-H),2.57(s,6H,aryl-H)。 13 C{ 1 H}NMR(125MHz,298K,CDCl 3 ,77.16ppm):δ＝162.02(N＝C),145.20,140.42,139.99,138.78,135.99,135.04,131.38,131.22,130.74,130.25,129.91,128.84,127.65,125.91,125.76,123.23,122.54,120.07,119.72,109.50,21.25(CH 3 ). The single crystal diffraction pattern of the α -diimine ligand prepared in example 2 is shown in fig. 2;
EXAMPLE 3 preparation of Nickel catalyst
The ligand prepared in example 2 (200 mg,0.151 mmol) and (DME) NiBr were reacted 2 The mixture of (46.6 mg,0.151 mmol) was stirred in 20mL of dichloromethane at 25℃for 24 h. After completion of the reaction the solvent was evaporated under reduced pressure to give a brown solid which was then filtered and recrystallised from methylene chloride/hexane to give the pure product (198mg, 85.0% yield). MALDI-TOF-MS (m/z): 1332.5[ M-Ni-2Br],1390.4[M-2Br] 2+ ,1469.4[M-Br] + 。
Example 3 nuclear magnetic resonance hydrogen spectrum of the nickel catalyst is shown in fig. 3, and mass spectrum (MALDI-TOF-MS) is shown in fig. 4.
Table I shows the reaction conditions and yields of the aniline of partial formula (b)
List one
The molar ratio of reactant a to reactant B in table one is 1:2.5.
table II partial ligand reaction conditions and yields of formula (c)
Watch II
In Table II, the molar ratio of the diketone of formula (a), the aniline of formula (b) and the catalyst is 1:2.
table III shows the synthesis conditions and yields of the nickel catalysts having the partial structure of formula (d)
Watch III
In Table III, a class of stacked sterically hindered alpha-diimine ligands and NiBr as shown in formula (c) 2 The molar ratio of (DME) is 1:1, wherein the solvent is dichloromethane or chloroform.
EXAMPLE 4 use of Nickel catalyst
A 350mL glass pressure reactor connected to a high pressure gas line was first dried in vacuo at 90 ℃ for at least 1 hour. The reactor was then adjusted to 30℃and 98mL of toluene and 500. Mu. Mol of MAO were added to the reactor under an inert atmosphere, and then 1. Mu. Mol of the Ni catalyst shown in Table III was dissolved in 2mL of methylene chloride (or chloroform) and injected into the polymerization system through a syringe. Ethylene was introduced under rapid stirring (750 revolutions or more) and maintained at 8atm. After 10 minutes, the pressure reactor was vented, the polymerization quenched by addition of a large amount of acidic methanol (or ethanol) (5% or more in hydrochloric acid) solution, the polymer filtered and dried in a vacuum oven to constant weight. The effect of different nickel catalysts on ethylene polymerization is shown in table four.
TABLE IV different Nickel catalysts (varying substituents R 1 、R 2 Effect of X) on ethylene polymerization
Note that: r in entries 1-46 in Table IV 1 ＝CH 3 Wherein entry 46:items 47-50: nickel catalyst->Wherein item 47:Items 51-53: nickel catalyst->Entries 54 and 56: nickel catalyst->
All data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity: at 10 6 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. Degree of branching = number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectroscopy. Wherein the nuclear magnetic resonance spectrum of the polymer obtained in item 7 is shown in FIG. 5.
Data in table four illustrate: when the catalyst substituents R are controlled 1 X is unchanged, and substituent R is changed 2 At the same time, gatherUnder the same conditions (consistent time, temperature, pressure and cocatalyst concentration), R 2 If it is an electron donating group (CH) 3 、OCH 3 ) In comparison with it is an electron-withdrawing group (CF 3 、NO 2 ) Possess higher activity and molecular weight, but similar degrees of branching. Also, when controlling the catalyst substituent R 1 、R 2 The substituent X is unchanged, and has the highest molecular weight and activity under the same polymerization conditions (the time, the temperature, the pressure and the cocatalyst concentration are consistent) when X is N. When the catalyst substituents R are controlled 2 X is unchanged, and substituent R is changed 1 In the same polymerization conditions (time, temperature, pressure, co-catalyst concentration, etc.), R 1 Is CH 3 In this case, the highest activity was obtained,the highest molecular weight is obtained for the polymer. Notably, are: when the catalyst substituents R are controlled 1 、R 2 Unchanged, when the substituent X is changed, +.>Molecular weight under equivalent polymerization conditions (time, temperature, pressure, co-catalyst concentration are uniform)Branching degree-> R 1 ＝CH 3 Molecular weight at the time ofBranching degree->
EXAMPLE 5 use of Nickel catalyst
A 350mL glass pressure reactor or high pressure reactor connected to a high pressure gas line was first dried in vacuo at 90 ℃ for at least 1 hour. The reactor was then adjusted to the corresponding temperature, 98mL of toluene and 500. Mu. Mol of MAO were added to the reactor under an inert atmosphere, and then the Ni catalyst (R 1 ＝CH 3 ,R 2 ＝CH 3 X=n5) was dissolved in 2mL of dichloromethane (or chloroform) and injected into the polymerization system by syringe. Ethylene was introduced under rapid stirring (750 revolutions or more) and maintained at the corresponding pressure. After 10 minutes, the pressure reactor was vented, the polymerization quenched by addition of a large amount of acidic methanol (or ethanol) (5% or more in hydrochloric acid) solution, the polymer filtered and dried in a vacuum oven to constant weight. The effect of different reaction conditions on the polymerization of ethylene catalyzed by the alpha-nickel diimine catalyst is shown in Table five.
TABLE V influence of different reaction conditions on ethylene polymerization catalyzed by the alpha-diimine Nickel catalyst
All data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity at 10 6 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. Degree of branching = number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectroscopy.
Table five data illustrates: when the holding time is unchanged (10 min), the ethylene pressure is unchanged (8 atm), the activity and the molecular weight of the polymer decrease with increasing temperature, and the branching degree increases; when the holding time is unchanged (10 min) and the temperature is unchanged (30 ℃), the activity and the molecular weight of the polymer are improved and the branching degree is reduced along with the increase of the ethylene pressure; when the ethylene pressure was kept constant (8 atm) and the temperature was kept constant (30 ℃ C., the activity decreased with the increase of the polymerization time), the polymer molecular weight was increased.
EXAMPLE 6 use of Nickel catalyst
A 350mL glass pressure reactor connected to a high pressure gas line was first dried in vacuo at 90 ℃ for at least 1 hour. The reactor was then adjusted to 30℃and 98mL of solvent (toluene, hexane, chlorobenzene) and 250 to 2000 equivalents of cocatalyst (MAO, MMAO, EASC, alEt) were reacted under an inert atmosphere 2 Cl) was added to the reactor, followed by 1.0. Mu. Mol of Ni catalyst (R 1 ＝CH 3, R 2 ＝CH 3 X=n5) was dissolved in 2mL of dichloromethane (or chloroform) and injected into the polymerization system by syringe. Ethylene was introduced under rapid stirring (750 revolutions or more) and maintained at 8atm. After 10 minutes, the pressure reactor was vented, the polymerization quenched by addition of a large amount of acidic methanol (or ethanol) (5% or more in hydrochloric acid) solution, the polymer filtered and dried in a vacuum oven to constant weight. The effect of different cocatalysts and solvents on the polymerization of ethylene catalyzed by the alpha-diimine nickel catalyst is shown in Table six.
TABLE six influence of different cocatalysts and solvents on ethylene polymerization catalyzed by alpha-diimine nickel catalysts
All data are based at least on the results of two parallel experiments (unless otherwise indicated). Al/Ni: molar ratio of promoter to nickel catalyst. Activity at 10 6 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. Degree of branching = number of branches per 1000 carbons, determined by nuclear magnetic resonance hydrogen spectroscopy.
Table six data illustrates: control polymerization conditions consistent (time, temperature, pressure): when the polymerization solvent is toluene and the cocatalyst is MAO, the activity and the molecular weight of the polymer are increased and then decreased along with the increase of the Al/Ni ratio, and the activity and the molecular weight are maximum when the ratio is 500; the Al/Ni ratio is controlled to be unchanged (the ratio is 500), and different cocatalysts are used, wherein the activity is relatively highest when the cocatalysts are MMAO, and the molecular weight is highest when the cocatalysts are MAO; when MAO was kept unchanged as the cocatalyst, the data showed that toluene activity and molecular weight were dominant in different solvents (toluene, hexane, chlorobenzene).
Claims (10)
1. A rotation-limited superimposed large-steric-hindrance alpha-diimine ligand is characterized by having a structure shown in a formula (c):
in the formula (c), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
2. The method for preparing a class of rotation-limited superimposed large-steric-hindrance alpha-diimine ligands according to claim 1, comprising:
dissolving aniline with a general formula (b) and diketone with a general formula (a) in a solvent, adding a catalyst, reacting at 25-80 ℃, and then carrying out reflux reaction on the reaction mixture to obtain an overlapped large steric hindrance alpha-diimine ligand with a structure shown as a formula (c); the catalyst is p-toluenesulfonic acid;
(a)
3. the method for preparing a class of rotation-limited stacked highly sterically hindered α -diimine ligands of claim 2, wherein the molar ratio of said diketone of formula (a) to said aniline of formula (b) is 1:2.
4. The method for preparing a rotation-limited superimposed large-steric-hindrance alpha-diimine ligand according to claim 2, wherein the reaction temperature of the reflux reaction is above 110 ℃ and the reaction time is above 48 h.
5. A nickel catalyst is characterized in that the structure is shown as a formula (d):
in the formula (d), R 1 Represents H, C to C20 alkyl or
R 2 Representation H, CH 3 、OCH 3 、CF 3 、NO 2 ，
X represents
6. The method for preparing a nickel catalyst according to claim 5, comprising:
alpha-diimine ligand and NiBr 2 (DME), dme=1, 2-dimethoxyethane, and dissolving in a solvent to react to obtain a nickel catalyst with a structure shown as a formula (d);
(c)
7. the method for preparing a nickel catalyst according to claim 6, wherein the structure is a type of alpha-diimine ligand and NiBr as shown in formula (c) 2 The molar ratio of (DME) was 1:1.
8. The method for preparing a nickel catalyst according to claim 6, wherein the reaction temperature is 20-50 ℃ and the reaction time is more than 24 hours.
9. Use of the nickel catalyst of claim 5 for catalyzing the polymerization of ethylene.
10. The use of the nickel catalyst according to claim 9 for catalyzing ethylene polymerization, wherein the method for catalyzing ethylene polymerization by the nickel catalyst comprises the following steps:
connecting the reactor with a high-pressure gas pipeline, regulating the temperature of the reactor to 0-90 ℃, adding a solvent and a cocatalyst into the reactor under inert atmosphere, then injecting a dichloromethane or chloroform solution of a nickel catalyst into the reactor, introducing ethylene under stirring and keeping the pressure at 8-30 atm, and reacting for 1-10 min to obtain the polyethylene.
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