CN101607934B - 2-ammonia methyl-pyridine nickel complex, preparation method and application thereof - Google Patents
2-ammonia methyl-pyridine nickel complex, preparation method and application thereof Download PDFInfo
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- CN101607934B CN101607934B CN2009100402437A CN200910040243A CN101607934B CN 101607934 B CN101607934 B CN 101607934B CN 2009100402437 A CN2009100402437 A CN 2009100402437A CN 200910040243 A CN200910040243 A CN 200910040243A CN 101607934 B CN101607934 B CN 101607934B
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- pyridine
- hydrogen
- methyl
- ammonia methyl
- ammonia
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- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 59
- DHHSEURIQNJKLC-UHFFFAOYSA-N [Ni].CC1=NC=CC=C1 Chemical compound [Ni].CC1=NC=CC=C1 DHHSEURIQNJKLC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 2-pyridine imine compound Chemical class 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000003446 ligand Substances 0.000 abstract description 29
- 239000004698 Polyethylene Substances 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000012280 lithium aluminium hydride Substances 0.000 abstract description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- HMWQCKBVWWXMJD-UHFFFAOYSA-L magnesium 1,2,3-trimethylbenzene dibromide Chemical compound [Br-].[Mg+2].CC=1C(=C(C=CC1)C)C.[Br-] HMWQCKBVWWXMJD-UHFFFAOYSA-L 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- 230000003197 catalytic effect Effects 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 239000013078 crystal Substances 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 15
- 238000010550 living polymerization reaction Methods 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 238000003810 ethyl acetate extraction Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 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 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NXMPBBJGEDKGHU-UHFFFAOYSA-L [Mg++].[Br-].[Br-].Cc1ccccc1 Chemical compound [Mg++].[Br-].[Br-].Cc1ccccc1 NXMPBBJGEDKGHU-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- GCSHUYKULREZSJ-UHFFFAOYSA-N phenyl(pyridin-2-yl)methanone Chemical compound C=1C=CC=NC=1C(=O)C1=CC=CC=C1 GCSHUYKULREZSJ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical group OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Pyridine Compounds (AREA)
Abstract
The invention discloses a 2-ammonia methyl-pyridine nickel composition, a preparation method and the application thereof. The composition has a structure of a formula I, wherein R1 stands for hydrogen or alkyl, R2 stands for hydrogen or alkyl, R3 stands for hydrogen or alkyl, and X stands for halogen. The preparation method of the composition comprises the following steps: (1) generating 2-pyridine imine compound through the ketone-ammonia condensation reaction of an aromatic ketone compound and 2,6-diisopropyl aniline; then, reacting with trimethylbenzene magnesium bromide, trimethylaluminium or lithium aluminum hydride to obtain 2-ammonia methyl-pyridine ligand; and (2) under a waterless and anoxic condition, obtaining a 2-ammonia methyl-pyridine nickel composition I by the complexationreaction of the 2-ammonia methyl-pyridine ligand III and (DME) NiX2. The 2-ammonia methyl-pyridine nickel composition has a specific ligand substitute structure, can catalyze ethylene to actively polymerize so as to obtain polyethylene with high molecular weight, narrow distribution and a certain branching degree.
Description
Technical field
The invention belongs to the olefin catalytic polymerization field, the application of particularly a kind of 2-ammonia methyl-pyridine nickel composition and preparation method thereof and catalyzed ethylene living polymerization.
Background technology
Living polymerization is meant the polyreaction of no chain transfer and chain termination in polymerization process, can be used to prepare the polymer materials etc. of superpolymer, segmented copolymer and the end-functionalization of the controlled and relative molecular mass narrowly distributing of relative molecular mass.By the design to catalyst structure, the catalyzed alkene living polymerization obtains narrow distribution polyolefin or block, functional polyolefin, has widened the range of application of olefin polymer greatly.
Ethene is one of alkene of consumption maximum in the world, though it is simple in structure, can obtain the polymkeric substance (LDPE, HDPE, LLDPE etc.) of many different structures and performance.Accurate control to polyethylene structure and molecular weight has huge industrial application value.In recent years, the report of many transition-metal catalyst catalysis alpha-olefin living polymerizations is arranged, but the report of catalyzed ethylene living polymerization is less relatively.Wherein, be mainly early transition metal titanium catalyst for olefine polymerization catalyzed ethylene living polymerization, obtain high molecular, the linear polyethylene of narrow distribution.Calendar year 2001, the titanium catalyst for olefine polymerization of the double salicylaldehyde imine structure of study group's report of the Fujita of Mitsui company, can be at room temperature, catalyzed ethylene living polymerization in short period of time, obtain high molecular, the linear polyethylene of narrow distribution (Angew.Chem.Int.Ed.2001,40,2918-2920).Subsequently, Fujita study group reported again two indoles imines titanium catalyst for olefine polymerization catalyzed ethylene living polymerizations (Chem.Lett.2001,566-567).Beta-ketimine titanium catalyst for olefine polymerization also can the catalyzed ethylene living polymerization (Organometallics, 2004,23,1223-1230).With respect to the early transition metal catalyzer, the late transition metal catalyst catalyzed ethylene polymerization obtains branched polyethylene more, and can regulate and control reaction conditions by the design catalyst structure, obtains the polyethylene of different topology structure.At present, the example of late transition metal catalyst catalyzed ethylene living polymerization seldom.Calendar year 2001, Gottfried and Brookhart reported can the catalyzed ethylene living polymerization alpha-diimine Pd catalyzer.At 5 ℃, under the pressure of 400p, reaction is ended with triethyl silicane, and it is 250000 that catalyzer can polymerising ethylene obtains Mn, PDI be about 1.1 branched polyethylene (Macromolecules.2001,34:1140-1142).Afterwards they reported again the example that utilizes the active homopolymerization of this class Pd catalyst alpha-olefin and ethylene/alpha-olefin, copolymerization (Macromolecules.2003,36:3085-3100).α-imines acid amides Ni the catalyzer of Bazan etc. report can the accurate living polymerization of catalyzed ethylene (Macromolecules.2003,36:9731-9735).
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect that prior art exists, a kind of 2-ammonia methyl-pyridine nickel composition is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned 2-ammonia methyl-pyridine nickel composition
Another object of the present invention is to provide a kind of application of above-mentioned 2-ammonia methyl-pyridine nickel composition catalyzed ethylene living polymerization.
Purpose of the present invention is achieved through the following technical solutions: a kind of 2-ammonia methyl-pyridine nickel composition has the structure as shown in the formula (I):
Wherein, R
1For hydrogen or carbonatoms are 1～20 alkyl, R
2For hydrogen or carbonatoms are 1～20 alkyl, R
3For hydrogen or carbonatoms are 1～20 alkyl, X is a halogen.
R
1Preferred hydrogen or phenyl; R
2Preferred hydrogen, methyl or 2,4, the 6-trimethylphenyl; R
3Preferred hydrogen, phenyl or naphthyl; The preferred bromine of X.
R
1Hydrogen most preferably, R
2Most preferably 2,4,6-trimethylphenyl, R
3Hydrogen most preferably.
R
1Phenyl most preferably; R
2Most preferable; R
3Hydrogen most preferably.
The preparation method of above-mentioned 2-ammonia methyl-pyridine nickel composition comprises following operation steps:
(1) with aromatic ketone compound and 2, the condensation reaction of 6-diisopropyl aniline generation ketone ammonia generates 2-pyridine imine Compound I I; With Compound I I and Three methyl Benzene magnesium bromide (Grignard reagent), trimethyl aluminium or lithium aluminium hydride reaction, obtain 2-aminomethyl-pyridine ligand i II then;
(2) under the condition of anhydrous and oxygen-free, with step (1) gained 2-aminomethyl-pyridine ligand i II and 1,2-glycol dimethyl ether nickel halogenide ((DME) NiX
2) carry out coordination reaction, obtain 2-ammonia methyl-pyridine nickel composition I;
The building-up process of step (1) is as follows:
Above-mentioned 2-ammonia methyl-pyridine nickel composition is as the purposes of ethylene rolymerization catalyst.
Described 2-ammonia methyl-pyridine nickel composition is under the methylaluminoxane activation condition as ethylene rolymerization catalyst, at polymerization temperature-50～80 ℃ catalyzed ethylene polymerization, preferred-20～40 ℃ of polymerization temperature can prepare the polyethylene of the adjustable and narrowly distributing of molecular weight.
The present invention compared with prior art, have following advantage and beneficial effect: (1) 2-ammonia methyl-pyridine nickel composition of the present invention has specific ligand and replaces structure, by increasing the steric hindrance on the 2-aminomethyl-pyridine skeleton, suppress chain transfer and chain termination, can make catalyzer reach the effect of catalyzed ethylene living polymerization; (2) as the R of 2-ammonia methyl-pyridine nickel composition of the present invention
1Be hydrogen, R
2Be 2,4,6-trimethylphenyl and R
3Be hydrogen or R
1Be phenyl, R
2Be methyl and R
3During for hydrogen, under MAO activation, can the catalyzed ethylene living polymerization, prepare the product polyethylene of high molecular and narrow distribution, and the poly molecular weight of product prolongs and linear increasing with polymerization time.
Description of drawings
Fig. 1 is the single crystal structure figure of 2-ammonia methyl-pyridine nickel composition 1.
Fig. 2 is the single crystal structure figure of 2-ammonia methyl-pyridine nickel composition 2.
Fig. 3 is the single crystal structure figure of 2-ammonia methyl-pyridine nickel composition 4.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but the working of an invention mode is not limited thereto.
In order concisely clearly to explain part and title complex in an embodiment, be described as follows:
A1 is the 2-pyridine imine compound shown in the formula (II), wherein R
1Be hydrogen, R
3Be hydrogen;
A2 is the 2-pyridine imine compound shown in the formula (II), wherein R
1Be phenyl, R
3Be hydrogen;
A3 is the 2-pyridine imine compound shown in the formula (II), wherein R
1Be hydrogen, R
3Be phenyl;
A4 is the 2-pyridine imine compound shown in the formula (II), wherein R
1Be hydrogen, R
3Be naphthyl;
L1 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be hydrogen, R
2Be methyl, R
3Be hydrogen;
L2 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be hydrogen, R
2Be 2,4,6-Three methyl Benzene, R
3Be hydrogen;
L3 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be phenyl, R
2Be hydrogen, R
3Be hydrogen;
L4 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be phenyl, R
2Be methyl, R
3Be hydrogen;
L5 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be hydrogen, R
2Be methyl, R
3Be phenyl;
L6 is the 2-aminomethyl-pyridine part shown in the formula (III), wherein R
1Be hydrogen, R
2Be methyl, R
3Be naphthyl;
Title complex 1 is the 2-ammonia methyl-pyridine nickel composition shown in the formula (I), wherein R
1Be hydrogen, R
2Be methyl, R
3Be hydrogen;
Title complex 2 is the 2-ammonia methyl-pyridine nickel composition shown in the formula (I), wherein R
1Be hydrogen, R
2Be 2,4,6-Three methyl Benzene, R
3Be hydrogen;
Embodiment 1
Synthesizing of 2-pyridine imine compd A 1:
With 2,6-diisopropyl aniline 10mL (0.048mol) is dissolved in the 60mL ethanol, N
2Protection.Slowly add 2-aldehyde radical pyridine 4.8mL (0.048mol) and 5 formic acid then, in 80 ℃ of following stirring and refluxing 3 hours.Be cooled to room temperature, ethanol is removed in decompression, carries out recrystallization with normal hexane.Obtain yellow crystals 11g, productive rate: 85.8%.Hydrogen spectrum measurement result is as follows:
1H NMR (300MHz, CDCl
3): δ 1.25-1.27 (12H, d, 4CH3), 3.34-3.43 (2H, m, 2CH), 7.50 (1H, S, CH) 7.05-7.14 (3H, m, benzyl), 7.18-7.22 (1H, t, Py-H), 7.30-7.32 (1H, d, Py-H), and 7.62-7.68 (1H, t, Py-H), 8.61-8.63 (1H, d, Py-H).Determine that product is a 2-pyridine imine compd A 1.
Embodiment 2
Synthesizing of 2-pyridine imine compd A 2
In nitrogen protection, and be equipped with in mouthful bottle of prolong and add 4.2503g (24mmol) 2,6-diisopropyl aniline and 20mL toluene are squeezed into the trimethyl aluminium toluene solution of 8mL 3M with syringe, are heated to 120 ℃, stir 2 hours.After the cooling,, add above-mentioned solution then with 8mL toluene dissolving 3.6688g (24mmol) phenyl (2-pyridyl) ketone.Continuation was heated 6 hours down at 120 ℃, adjusted the temperature to 70 ℃ then, and stirring is spent the night.Stir adding distil water termination reaction down, use ethyl acetate extraction 3 times, merge organic phase.Organic phase distilled water wash 1 time, anhydrous Na
2SO
4Drying is filtered, and vacuum is spin-dried for.Use ethyl alcohol recrystallization, obtain product 6.8413g, productive rate 81%.Hydrogen spectrum measurement result is as follows:
1HNMR (300MHz, CDCl
3): δ 0.91-1.27 (12H, d, 4CH3), 2.87 (2H, m, 2CH), 7.09-7.81 (11H, m, pyridyl and phenyl protons), 8.61 (1H, d, Pyridyl α-H).Determine that product is a 2-pyridine imine compd A 2.
Synthesizing of 2-pyridine imine compound A-13
With 2,6-diisopropyl aniline 10mL (0.05mol) is dissolved in the 60mL ethanol, N
2Protection.Slowly add 2-aldehyde radical-6-phenylpyridine 8.7g (0.05mol) and 5 formic acid then, in 80 ℃ of following stirring and refluxing 3 hours.Be cooled to room temperature, ethanol is removed in decompression, carries out recrystallization with normal hexane.Obtain yellow crystals 10g, productive rate: 62.5%.Mass spectroscopy determines that product is a 2-pyridine imine compound A-13.
Synthesizing of 2-pyridine imine compd A 4
With 2,6-diisopropyl aniline 10mL (0.05mol) is dissolved in the 60mL ethanol, N
2Protection.Slowly add 2-aldehyde radical-6-naphthyl pyridine 11.6g (0.05mol) and 5 formic acid then, in 80 ℃ of following stirring and refluxing 3 hours.Be cooled to room temperature, ethanol is removed in decompression, carries out recrystallization with normal hexane.Obtain yellow crystals 8g, productive rate: 40%.Mass spectroscopy determines that product is a 2-pyridine imine compd A 4.
The preparation of 2-aminomethyl-pyridine ligand L 1
The 2-pyridine imine compd A 1 of 2.26g (8.04mmol) embodiment 1 preparation is dissolved in the 20mL toluene N
2Protection adds 2.5mL (9.6mmol) Al (CH
3)
3Toluene solution, be heated to 80 ℃, refluxed 12 hours.Obtain white needle-like crystals 1.61g, productive rate: 70.6%.Hydrogen spectrum measurement result is as follows:
1HNMR (300MHz, CDCl
3): δ 1.08-1.24 (12H, d, 4CH
3), 1.52 (3H, s, CH
3), 3.23-3.25 (2H, m, 2CH), 4.06 (1H, s, CH), 4.18 (1H, s, NH), and 7.02-7.05 (3H, m, benzyl), 7.14-7.15 (1H, t, Py-H), 7.25-7.30 (1H, d, Py-H), 7.52-7.55 (1H, t, Py-H), 8.61-8.63 (1H, d, Py-H).Ultimate analysis theoretical value (C
19H
26N
2): C, 80.80; H, 9.28; N, 9.92%. measured value: C, 80.61; H, 9.16; N, 10.09%.Determine that product is a 2-aminomethyl-pyridine ligand L 1.
The preparation of 2-aminomethyl-pyridine ligand L 2
The 2-pyridine imine compd A 1 of 2.68g (10mmol) embodiment 1 preparation is put in prolong is housed, in mouthful bottle of nitrogen protection.Secluding air is transferred to this mouth bottle with Three methyl Benzene magnesium bromide grignard reagent solution.Be heated to 60 ℃, stirring is spent the night, and squeezes into the distilled water termination reaction with syringe.Product ethyl acetate extraction three times merge organic phase, with distilled water wash once, use anhydrous Na then
2SO
4Dry.After the filtration, be spin-dried for solvent under the vacuum.Place white solid, use ethyl alcohol recrystallization, obtain product 3.09g, productive rate 80%.Hydrogen spectrum measurement result is as follows:
1H-NMR (300MHz, CDCl
3): δ 0.833-1.25 (12H, d, 4CH
3), 1.864-2.201 (9H, s, 3CH
3), 2.998-3.041 (2H, m, 2CH), 4.744 (1H, m, NH), 5.438 (1H, m, CH), 6.721-7.009 (5H, benzyl), 7.130-7.226 (1H, t, Py-H), 7.284-7.310 (1H, d, Py-H), 7.547-7.592 (1H, t, Py-H), 8.605 (1H, d, Py-H). carbon spectrum measurement result is as follows:
13C-NMR (75MHz, CDCl
3): 20.863,24.147,24.762,27.910,65.212,121.509,123.438,124.658,136.362,136.688,137.443,143.642,145.192,148.585,162.916. ultimate analysis theoretical value (C
27H
34N
2): C, 83.89; H, 8.87; N, 7.25%; Measured value: C, 83.97; H, 8.88; N, 7.09%.Determine that product is a 2-aminomethyl-pyridine ligand L 2.
Embodiment 7
The preparation of 2-aminomethyl-pyridine ligand L 3
Take by weighing 2g LiAlH
4(52.6mmol) in the 30mL anhydrous diethyl ether, make suspended substance.Slowly add the 20mL anhydrous diethyl ether of the 2-pyridine imine compd A 2 that contains 3.42g (10mmol) embodiment 2 preparations then, at room temperature stirred 2 hours.Filter out excessive LiAlH
4, under 0 ℃, add 10mL water and 20ml 20%H successively
2SO
4, extract organic phase and use 10mL distilled water wash 3 times with separating funnel.Inorganicly use the 10mL ethyl acetate extraction mutually 3 times, unite organic phase then, and use anhydrous Na
2SO
4Dry.Filter, under vacuum, remove and desolvate, cross silicagel column with the mixed solution of ethyl acetate/petroleum ether.Carry out recrystallization with normal hexane at last.Obtain white crystal 2.3g, productive rate: 69%.Hydrogen spectrum measurement result is as follows:
1H-NMR (300MHz, CDCl
3): 80.833-1.25 (12H, d, 4CH
3), 3.34-3.43 (2H, m, 2CH)), 4.76 (1H, m, NH), 5.16 (1H, CH), 6.82-8.41 (12H, m, benzyl, Py-H).Carbon spectrum measurement result is as follows:
13C-NMR (75MHz, CDCl
3): 24.289,24.586,28.013,69.013,76.900,77.322,77.744,121.613,122.680,123.628,127.361,127.447,127.885,128.946,135.596,138.851,139.847,141.839,142.084,142.766,148.092,148.173,148.412,161.829.Determine that product is a 2-aminomethyl-pyridine ligand L 3.
Embodiment 8
The preparation of 2-aminomethyl-pyridine ligand L 4
In nitrogen protection, and 2-pyridine imine compd A 2 and the 20mL toluene that adds 3.41g (10mmol) embodiment 2 preparation in mouthful bottle of prolong is housed, carefully squeezes into the trimethyl aluminium toluene solution of 3mL 3M, be heated to 120 ℃, stirred 2 hours with syringe.After the cooling, use the distilled water termination reaction.Product ethyl acetate extraction 3 times merge organic phase, with distilled water wash once, and use anhydrous Na
2SO
4Dry.Filter, under vacuum, remove and desolvate.Use ethyl alcohol recrystallization, get white crystal 3.04g, productive rate 85%.Hydrogen spectrum measurement result is as follows:
1H-NMR (300MHz, CDCl
3): 80.918-1.25 (12H, d, 4CH3), 1.581 (3H, s, CH3), 2.904 (2H, m, 2CH), 5.837 (H, m, NH), 6.984-7.052 (3H, m, benzyl), 7.056-7.295 (5H, m, benzyl), 7.540-7.614 (3H, m, Py-H), 8.565 (H, d, Py-H).Carbon spectrum measurement result is as follows:
13C-NMR (75MHz, CDCl
3): 23.890,24.286,28.679,63.685,121.249,121.461,123.091,124.228,126.338,126.807,128.066,136.710,141.652,146.485,147.880,150.049,167.304. ultimate analysis theoretical value (C
25H
30N
2): C, 83.75; H, 8.43; N, 7.81%. measured value: C, 83.55; H, 8.75; N, 7.73%.Determine that product is a 2-aminomethyl-pyridine ligand L 4.
Embodiment 9
The preparation of 2-aminomethyl-pyridine ligand L 5
In nitrogen protection, and 2-pyridine imine compound A-13 and the 20mL toluene that adds 3.42g (10mmol) embodiment 3 preparation in mouthful bottle of prolong is housed, carefully squeezes into the trimethyl aluminium toluene solution of 3mL 3M, be heated to 120 ℃, stirred 2 hours with syringe.After the cooling, use the distilled water termination reaction.Product ethyl acetate extraction 3 times merge organic phase, with distilled water wash once, and use anhydrous Na
2SO
4Dry.Filter, under vacuum, remove and desolvate.Use ethyl alcohol recrystallization, get white crystal 3.17g, productive rate 88.5%.Hydrogen spectrum and carbon spectrum are measured and are determined that product is a 2-aminomethyl-pyridine ligand L 5.
Embodiment 10
The preparation of 2-aminomethyl-pyridine ligand L 6
In nitrogen protection, and 2-pyridine imine compd A 4 and the 20mL toluene that adds 3.92g (10mmol) embodiment 4 preparation in mouthful bottle of prolong is housed, carefully squeezes into the trimethyl aluminium toluene solution of 3mL 3M, be heated to 120 ℃, stirred 2 hours with syringe.After the cooling, use the distilled water termination reaction.Product ethyl acetate extraction 3 times merge organic phase, with distilled water wash once, and use anhydrous Na
2SO
4Dry.Filter, under vacuum, remove and desolvate.Use ethyl alcohol recrystallization, get white crystal 3.28g, productive rate 83.6%.The hydrogen spectrum is measured and is determined that product is a 2-aminomethyl-pyridine ligand L 6.
Embodiment 11
The preparation of 2-ammonia methyl-pyridine nickel composition 1
Under the nitrogen atmosphere, in exsiccant Schlenk pipe, add the 2-aminomethyl-pyridine ligand L 1,1 that 0.28g (1mmol) embodiment 5 obtains, 2-glycol dimethyl ether nickelous bromide ((DME) NiBr
2) 0.31g, CH
2Cl
235mL at room temperature stirred 24 hours, and vacuum concentration adds normal hexane and is settled out light brown powder to a small amount of solvent, and product washs with ether/normal hexane mixed solvent, and vacuum-drying obtains 0.46g2-ammonia methyl-pyridine nickel composition 1, yield 78%.Ultimate analysis theoretical value (C
19H
26N
2NiBr
2): C, 45.56; H, 5.23; N, 5.59%. measured value: C, 45.72; H, 4.95; N, 5.23%.2-ammonia methyl-pyridine nickel composition 1 is cultivated into monocrystalline, measure with single crystal diffractometer, software analysis obtains single crystal structure figure (clear in order to show, as to have removed solvent molecule and hydrogen atom) as shown in Figure 1.
Embodiment 12:
The preparation of 2-ammonia methyl-pyridine nickel composition 2
The 2-aminomethyl-pyridine ligand L 2 that the 2-aminomethyl-pyridine ligand L 20.39g (1mmol) that obtains with embodiment 6 replaces embodiment 5 to obtain, operation obtains the 2-ammonia methyl-pyridine nickel composition 2 of 0.53g light brown powder shape, productive rate 76% with embodiment 11.Ultimate analysis theoretical value (C
27H
34N
2NiBr
2): C, 53.59; H, 5.66; N, 4.63. measured value: C, 53.89; H, 5.72; N, 4.42%.2-ammonia methyl-pyridine nickel composition 2 is cultivated into monocrystalline, measure with single crystal diffractometer, software analysis obtains single crystal structure figure (clear in order to show, as to have removed solvent molecule and hydrogen atom) as shown in Figure 2.
Embodiment 13
The preparation of 2-ammonia methyl-pyridine nickel composition 3
The ligand L 3 that the 2-aminomethyl-pyridine ligand L 30.34g (1mmol) that obtains with embodiment 7 replaces embodiment 5 to obtain, operation obtains the pulverous 2-ammonia methyl-pyridine nickel composition 3 of 0.51g yellow-green colour, productive rate 78% with embodiment 11.
Embodiment 14
The preparation of 2-ammonia methyl-pyridine nickel composition 4
The 2-aminomethyl-pyridine ligand L 4 that the 2-aminomethyl-pyridine ligand L 40.36g (1mmol) that obtains with embodiment 8 replaces embodiment 5 to obtain, operation obtains the 2-ammonia methyl-pyridine nickel composition 4 of 0.55g dark-brown toner powder, productive rate 82% with embodiment 11.Ultimate analysis theoretical value (C
27H
34N
2NiBr
2): C, 52.04; H, 5.24; N, 4.85. measured value: C, 51.68; H, 5.43; N, 4.72%.2-ammonia methyl-pyridine nickel composition 4 is cultivated into monocrystalline, measure with single crystal diffractometer, software analysis obtains single crystal structure figure (clear in order to show, as to have removed solvent molecule and hydrogen atom) as shown in Figure 3.
Embodiment 15
The preparation of 2-ammonia methyl-pyridine nickel composition 5
The 2-aminomethyl-pyridine ligand L 5 that the 2-aminomethyl-pyridine ligand L 50.36g (1mmol) that obtains with embodiment 9 replaces embodiment 5 to obtain, operation obtains the pulverous 2-ammonia methyl-pyridine nickel composition 5 of 0.47g purple, productive rate 70% with embodiment 11.Ultimate analysis theoretical value (C
25H
30Br
2N
2Ni): C, 52.04; H, 5.24; N, 4.85 measured values: C, 49.56; H, 5.22; N, 4.57%.
Embodiment 16
The preparation of 2-ammonia methyl-pyridine nickel composition 6
The 2-aminomethyl-pyridine ligand L 6 that the 2-aminomethyl-pyridine ligand L 60.41g (1mmol) that obtains with embodiment 10 replaces embodiment 5 to obtain, operation obtains the pulverous 2-ammonia methyl-pyridine nickel composition 6 of 0.54g purple, productive rate 75% with embodiment 11.Ultimate analysis theoretical value (C
29H
32Br
2N
2Ni): C, 55.54; H, 5.14; N, 4.47 measured values: C, 49.49; H, 5.34; N, 3.88%.
Embodiment 17
Ethylene polymerization: under ethene atmosphere, in 100mL high pressure polymerisation bottle, add the 2-ammonia methyl-pyridine nickel composition 1 (10 μ mol) of 5.0mg embodiment 11 preparations, dry toluene 20mL, methylaluminoxane 8mmol, at 25 ℃, polyase 13 0min under the 20atm.Reaction stops with the ethanol solution hydrochloride of 200mL, filters, and washing with alcohol three times, 70 ℃ of following vacuum-dryings get ethene polymers 0.42g, and catalytic efficiency is 0.84 * 10
5G/mol Nih, weight-average molecular weight is 3.1 * 10
3, polydispersity coefficient is 2.45.
Embodiment 18
The 2-ammonia methyl-pyridine nickel composition 1 that 2-ammonia methyl-pyridine nickel composition 3 (5.6mg, the 10 μ mol) alternate embodiment 11 for preparing with embodiment 13 prepares, other obtains ethene polymers 0.05g with embodiment 17.Catalytic efficiency is 0.10 * 10
5G/mol Nih, weight-average molecular weight is 1.7 * 10
4, polydispersity coefficient is 4.3.
Embodiment 19
The 2-ammonia methyl-pyridine nickel composition 1 that 2-ammonia methyl-pyridine nickel composition 5 (5.7mg, the 10 μ mol) alternate embodiment 11 for preparing with embodiment 15 prepares, other obtains ethene polymers 0.08g with embodiment 17.Catalytic efficiency is 0.16 * 10
5G/mol Nih, weight-average molecular weight is 3.2 * 10
4, polydispersity coefficient is 9.1.
Embodiment 20
The 2-ammonia methyl-pyridine nickel composition 1 that 2-ammonia methyl-pyridine nickel composition 6 (6.3mg, the 10 μ mol) alternate embodiment 11 for preparing with embodiment 16 prepares, other obtains ethene polymers 0.12g with embodiment 17.Catalytic efficiency is 0.24 * 10
5G/mol Nih, weight-average molecular weight is 0.8 * 10
4, polydispersity coefficient is 1.7.
Embodiment 21
Under the ethene atmosphere, in 150mL polymerization under atmospheric pressure bottle, add the 2-ammonia methyl-pyridine nickel composition 2 (20 μ mol) of 12.0mg embodiment 12 preparations, dry toluene 40mL, methylaluminoxane 16mmol, at-20 ℃, under the 1.2atm polymerase 10 .5 hour.Reaction stops with the ethanol solution hydrochloride of 200mL, filters, and washing with alcohol three times, 70 ℃ of following vacuum-dryings obtain ethene polymers 97mg.Catalytic efficiency is 0.97 * 10
4G/mol Nih, weight-average molecular weight is 0.91 * 10
4, polydispersity coefficient is 1.19, the melt temperature that DSC measures polymkeric substance is 99.78 ℃.
Embodiment 22
Polyreaction is carried out under-10 ℃, and other obtains ethene polymers 0.170g with embodiment 21.Catalytic efficiency is 1.70 * 10
4G/mol Nih, weight-average molecular weight is 0.94 * 10
5, polydispersity coefficient is 1.13.
Embodiment 23
Polyreaction is carried out under 0 ℃, and other obtains ethene polymers 0.216g with embodiment 21.Catalytic efficiency is 2.16 * 10
4G/mol Nih, weight-average molecular weight is 1.07 * 10
4, polydispersity coefficient is 1.10.
Embodiment 24
Polyreaction is carried out under 20 ℃, and other obtains ethene polymers 0.573g with embodiment 21.Catalytic efficiency is 5.73 * 10
4G/mol Nih, weight-average molecular weight is 2.01 * 10
4, polydispersity coefficient is 1.30.
Embodiment 25
Polyreaction is carried out under 40 ℃, and other obtains ethene polymers 0.575g with embodiment 21.Catalytic efficiency is 5.75 * 10
4G/mol Nih, weight-average molecular weight is 1.67 * 10
4, polydispersity coefficient is 1.51.
Embodiment 26
Polyreaction was carried out 1 hour, and other obtains ethene polymers 0.4244g with embodiment 22.Catalytic efficiency is 2.12 * 10
4G/mol Nih, weight-average molecular weight is 1.72 * 10
4, polydispersity coefficient is 1.19.
Embodiment 27
Polyreaction was carried out 2 hours, and other obtains ethene polymers 0.7472g with embodiment 22, and catalytic efficiency is 1.87 * 10
4G/mol Nih, weight-average molecular weight is 3.21 * 10
4, polydispersity coefficient is 1.17.
Embodiment 28:
Polyreaction was carried out 3 hours, and other obtains ethene polymers 1.0423g with embodiment 22.Catalytic efficiency is 1.74 * 10
4G/mol Nih, weight-average molecular weight is 4.66 * 10
4, polydispersity coefficient is 1.15.
Embodiment 29
Polyreaction was carried out 4 hours, and other obtains ethene polymers 1.5422g with embodiment 22.Catalytic efficiency is 1.93 * 10
4G/mol Nih, weight-average molecular weight is 6.21 * 10
4, polydispersity coefficient is 1.17.
Embodiment 30
Polyreaction was carried out 5 hours, and other obtains ethene polymers 1.65g with embodiment 22.Catalytic efficiency is 1.65 * 10
4G/mol Nih, weight-average molecular weight is 6.98 * 10
4, polydispersity coefficient is 1.19.
Embodiment 31
Polyreaction was carried out 6 hours, and other obtains ethene polymers 1.91g with embodiment 22.Catalytic efficiency is 1.59 * 10
4G/mol Nih, weight-average molecular weight is 8.67 * 10
4, polydispersity coefficient is 1.21.
Embodiment 32
The 2-ammonia methyl-pyridine nickel composition 2 that 2-ammonia methyl-pyridine nickel composition 4 (6.3mg, the 10 μ mol) alternate embodiment 12 for preparing with embodiment 14 prepares, polymerization time 1 hour, other obtains ethene polymers 0.067g with embodiment 21.Catalytic efficiency is 0.33 * 10
4G/mol Nih, weight-average molecular weight is 1.18 * 10
4, polydispersity coefficient is 1.29.
Embodiment 33
Polyreaction was carried out 2 hours, and other obtains ethene polymers 0.1500g with embodiment 32.Catalytic efficiency is 0.37 * 10
4G/mol Nih, weight-average molecular weight is 0.93 * 10
4, polydispersity coefficient is 1.34.
Embodiment 34
Polyreaction was carried out 3 hours, and other obtains ethene polymers 0.2257g with embodiment 32.Catalytic efficiency is 0.38 * 10
4G/mol Nih, weight-average molecular weight is 1.36 * 10
4, polydispersity coefficient is 1.23.
Embodiment 35
Polyreaction was carried out 4 hours, and other obtains ethene polymers 0.4012g with embodiment 32.Catalytic efficiency is 0.50 * 10
4G/mol Nih, weight-average molecular weight is 1.78 * 10
4, polydispersity coefficient is 1.21.
Embodiment 36
Polyreaction was carried out 5 hours, and other obtains ethene polymers 0.4644g with embodiment 32.Catalytic efficiency is 0.46 * 10
4G/mol Nih, weight-average molecular weight is 1.98 * 10
4, polydispersity coefficient is 1.23.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. 2-ammonia methyl-pyridine nickel composition has the structure as shown in the formula (I):
Wherein, R
1Be hydrogen or phenyl; R
2Be hydrogen, methyl or 2,4,6-trimethylphenyl; R
3Be hydrogen; X is a halogen.
2. a kind of 2-ammonia methyl-pyridine nickel composition according to claim 1 is characterized in that: R
1Be hydrogen, R
2Be 2,4,6-trimethylphenyl, R
3Be hydrogen.
3. a kind of 2-ammonia methyl-pyridine nickel composition according to claim 1 is characterized in that: R
1Be phenyl; R
2Be methyl; R
3Be hydrogen.
4. 2-ammonia methyl-pyridine nickel composition as claimed in claim 1 is as the purposes of ethylene rolymerization catalyst, it is characterized in that: described 2-ammonia methyl-pyridine nickel composition is under the methylaluminoxane activation condition as ethylene rolymerization catalyst, at polymerization temperature-50～80 ℃ catalyzed ethylene polymerization.
5. purposes according to claim 4 is characterized in that: described polymerization temperature is-20～40 ℃.
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Non-Patent Citations (4)
| Title |
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| Junghun Suh,et al..Kinetics and Mechanism of Ni(II) Ion Retarded Schiff-Base Hydrolysis of 2,2’-Dipyridylmethylideneaniline.《J. Org. Chem.》.1991,第56卷5710-5712. * |
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