CN101812145B - Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene - Google Patents
Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene Download PDFInfo
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- CN101812145B CN101812145B CN2010101777118A CN201010177711A CN101812145B CN 101812145 B CN101812145 B CN 101812145B CN 2010101777118 A CN2010101777118 A CN 2010101777118A CN 201010177711 A CN201010177711 A CN 201010177711A CN 101812145 B CN101812145 B CN 101812145B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- -1 polyethylene Polymers 0.000 title claims abstract description 18
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 18
- 239000004698 Polyethylene Substances 0.000 title abstract description 12
- 229920000573 polyethylene Polymers 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims description 101
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 41
- 239000005977 Ethylene Substances 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 230000003197 catalytic effect Effects 0.000 description 30
- 239000003446 ligand Substances 0.000 description 30
- 229910052799 carbon Inorganic materials 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000155 melt Substances 0.000 description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 11
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- PMOJWDPBNANJEP-UHFFFAOYSA-N C1(C(C2=CC=CC3=CC=CC1=C23)=N)=N.[Ni] Chemical compound C1(C(C2=CC=CC3=CC=CC1=C23)=N)=N.[Ni] PMOJWDPBNANJEP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 0 C*(C)c1ccccc1*(C)=C(C(c1ccc(*)cc1)=*(*(*)*)c1c(*)cccc1)c1ccc(*)cc1 Chemical compound C*(C)c1ccccc1*(C)=C(C(c1ccc(*)cc1)=*(*(*)*)c1c(*)cccc1)c1ccc(*)cc1 0.000 description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- CUOXJPZZVZINEI-UHFFFAOYSA-N acenaphthylene-1,2-diimine Chemical compound C1=CC(C(C2=N)=N)=C3C2=CC=CC3=C1 CUOXJPZZVZINEI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BRKULQOUSCHDGS-UHFFFAOYSA-N 1,2-bis(4-fluorophenyl)ethane-1,2-dione Chemical compound C1=CC(F)=CC=C1C(=O)C(=O)C1=CC=C(F)C=C1 BRKULQOUSCHDGS-UHFFFAOYSA-N 0.000 description 1
- BCWCEHMHCDCJAD-UHFFFAOYSA-N 1,2-bis(4-methylphenyl)ethane-1,2-dione Chemical compound C1=CC(C)=CC=C1C(=O)C(=O)C1=CC=C(C)C=C1 BCWCEHMHCDCJAD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alpha-nickel diimine compound olefin polymerization catalyst, a preparation method and a method for preparing branched polyethylene. The structural formula of the alpha-nickel diimine compound olefin polymerization catalyst is shown as the formula (I) and the formula (II). The alpha-nickel diimine compound olefin polymerization catalyst has simple preparation method and low cost, and ethylene can be catalyzed to polymerize with high activity at a temperature not lower than 80 DEG C to obtain high molecular weight polyethylene. The polyethylene prepared from the alpha-nickel diimine compound olefin polymerization catalyst by catalyzing has high molecular weight, and the molecular weight can reach higher than 102x kg/mol within the range of 0-80 DEG C.
Description
(the application is that name is called: alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof and the method for preparing branched polyethylene, application number are 200910038504.1, and applying date 2009.4.8 divides an application))
Technical field
The present invention relates to the olefin catalytic polymerization field, be specifically related to a class alpha-diimine nickel olefine polymerization catalyzer and technology of preparing thereof and the poly method of catalyzed ethylene polymerization for preparing branched.
Background technology
Polyolefine is one of most widely used resin, owing to have good processing and use properties and low price, has become output and the maximum synthetic resins kind of consumption in the world at present, is widely used in people's the production and consumption field.Wherein, Study of Catalyst is the core technology of polyolefin industry development, is the key factor of control polyolefin structure and performance.
On the basis of traditional Z iegler-Natta catalyzer, people have developed metallocene catalyst and the single metallocene catalyst with single-activity center in succession, and it is very narrow that catalysis in olefine polymerization can obtain molecular weight distribution, and the polyolefine material of compound with regular structure.Nineteen ninety-five, Brookhart etc. develop a kind of alpha-diimine nickel, palladium catalyst, can obtain high-molecular weight branched polyethylene [J.Am.Chem.Soc.1995,117,6414-6415] by the homogeneous catalysis vinyl polymerization.Wherein α-imines nickel catalyzator is owing to have high reactivity, and polymericular weight and the degree of branching can in very large range be regulated.Subsequently, company such as Du Pond has applied for a plurality of patents (WO 96/23010, and WO 98/03521, and WO 98/40374, and WO 99/05189, and WO 99/62968, and WO 00/06620, and US 6,103,658, and US 6,660,677).This class alpha-diimine nickel catalyzator has following structural formula:
Wherein, R
1Be hydrogen, methyl, acenaphthenyl, cyclohexyl, heterocyclic substituent etc., R
2Be hydrogen, methyl, sec.-propyl, the tertiary butyl, phenyl etc., R
3Be hydrogen, methyl, sec.-propyl, the tertiary butyl, phenyl etc.Under methylaluminoxane (MAO) or aluminum alkyls effect, can high reactivity ground catalyzed ethylene.Work as R
2During for hydrogen replacement or the replacement of little steric hindrance, catalyzed ethylene polymerization can only obtain the oligopolymer or the very little polyethylene of molecular weight of ethene.Work as R
2When replacing for big steric hindrance, catalyzed ethylene obtains ultra high molecular weight polyethylene.But these diimine catalysts is thermally-stabilised relatively poor, works as R
1During for above-mentioned substituting group, even aniline ortho position or contraposition have the substituting group of large volume to exist, prepared its molecular weight of polyethylene of these alpha-diimine nickel catalyzators improves with polymerization temperature and descends rapidly, and generally catalyzer decomposes inactivation rapidly when being higher than 60 ℃.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of alpha-nickel diimine compound catalyzer with good thermal stability is provided, under the methylaluminoxane activation, can be implemented in catalyzed ethylene polymerization under the comparatively high temps, preparation high-molecular weight branched polyethylene.
Above-mentioned purpose of the present invention is achieved by following scheme:
Alpha-nickel diimine compound olefin polymerization catalyst of the present invention is a kind of novel para-orientation two styrene skeletons or the alpha-nickel diimine compound of camphyl skeleton, its structural formula is suc as formula shown in (I) and the formula (II), title complex is by increasing the steric hindrance of part skeleton structure, can the stabilizing active center, prolong the catalytic life in active centre, particularly can obtain the high-molecular weight branched polyethylene at catalyzed ethylene polymerization under the comparatively high temps.
In the formula (I): R
1Be hydrogen, alkyl, halogen etc.; R
2Be alkyl; X is a halogen.R wherein
1Preferred hydrogen, methyl or fluorine, R
2Preferable methyl or sec.-propyl, the preferred Br of X.In the formula (II): R
2Be alkyl; X is a halogen.R wherein
2Preferable methyl or sec.-propyl, the preferred Br of X.
Another object of the present invention provides the preparation method of described alpha-nickel diimine compound olefin polymerization catalyst.
Alpha-nickel diimine compound olefin polymerization catalyst shown in the above-mentioned formula (I), its preparation method is as follows:
(1) by 2 shown in the formula V, the 6-substituted aniline is a raw material, aluminium amine salt with shown in the trimethyl aluminium reaction production (VI) carries out the ketoamine condensation reaction with aluminium amine salt and para-orientation benzil then, obtains the para-orientation two styrene skeleton alpha-diimine parts shown in the formula (III).
(2) under the condition of anhydrous and oxygen-free, alpha-diimine part shown in the formula (III) and (DME) NiX
2Carry out coordination reaction, obtain the alpha-nickel diimine compound shown in the formula (I).
Alpha-nickel diimine compound olefin polymerization catalyst shown in the above-mentioned formula (II), its preparation method is as follows:
(1) aluminium amine salt shown in the formula (VI) and camphyl diketone (camphorquinone) carry out the ketoamine condensation reaction in toluene, obtain the camphyl skeleton alpha-diimine part shown in the formula VI.
(2) under the condition of anhydrous and oxygen-free, alpha-diimine part shown in the formula (VI) and (DME) NiX
2Carry out coordination reaction, obtain the alpha-nickel diimine compound shown in the formula (II).
R in the formula (III)～(VI)
1And R
2With the R in formula (I) and the formula (II)
1And R
2Identical.
Alpha-nickel diimine compound olefin polymerization catalyst of the present invention is the alpha-diimine nickel compound of the novel skeleton structure of a class, is characterized in having good thermostability, can prepare high molecular weight branched polyolefine at catalysis in olefine polymerization under the higher temperature.Alpha-nickel diimine compound olefin polymerization catalyst shown in formula of the present invention (I) and the formula (II) is under general promotor MAO activation, can be in-40～100 ℃ of scopes catalyzed ethylene polymerization, the preparation ultra high molecular weight polyethylene, preferred polymerization temperature scope is 0～80 ℃.The priming reaction of promotor MAO adopts those skilled in the art's method in common.
Compared with prior art, the present invention has following beneficial effect:
1. the preparation method of alpha-nickel diimine compound olefin polymerization catalyst of the present invention is simple, with low cost, and can obtain High molecular weight polyethylene by the highly active catalytic vinyl polymerization under more than or equal to 80 ℃ of temperature, the alpha-diimine nickel olefine polymerization catalyzer of prior art report just descends rapidly 60 ℃ of catalytic activitys;
2. the polyethylene of alpha-nickel diimine compound olefin polymerization catalyst catalytic preparation of the present invention has high molecular, can prepare molecular weight and reach 10 in 0～80 ℃ of scope
2More than the x kg/mol, the alpha-diimine nickel olefine polymerization catalyzer of prior art report is at the polyethylene of preparation more than 60 ℃, its molecular weight≤10x kg/mol.
Embodiment
The invention will be further described by the following examples.
In order concisely clearly to explain part and title complex in an embodiment, be described as follows:
Ligand L 1a is the alpha-diimine part shown in the formula (III), wherein R
1Be hydrogen, R
2Be methyl;
Ligand L 2a is the alpha-diimine part shown in the formula (III), wherein R
1Be methyl, R
2Be methyl;
Ligand L 2b is the alpha-diimine part shown in the formula (III), wherein R
1Be methyl, R
2Be sec.-propyl;
Ligand L 3a is the alpha-diimine part shown in the formula (III), wherein R
1Be fluorine, R
2Be methyl;
Ligand L 4a is the alpha-diimine part shown in the formula (IV), wherein R
2Be methyl;
Ligand L 4b is the alpha-diimine part shown in the formula (IV), wherein R
2Be sec.-propyl;
Title complex 1a is alpha-nickel diimine compound, wherein R shown in the formula (I)
1Be hydrogen, R
2For methyl, X are Br;
Title complex 2a is alpha-nickel diimine compound, wherein R shown in the formula (I)
1Be methyl, R
2For methyl, X are Br;
Title complex 2b is alpha-nickel diimine compound, wherein R shown in the formula (I)
1Be methyl, R
2For sec.-propyl, X are Br;
Title complex 3a is alpha-nickel diimine compound, wherein R shown in the formula (I)
1Be fluorine, R
2For methyl, X are Br;
Title complex 4a is alpha-nickel diimine compound, wherein R shown in the formula (II)
2For methyl, X are Br;
Title complex 4b is alpha-nickel diimine compound, wherein R shown in the formula (II)
2For sec.-propyl, X are Br;
One, the preparation of part
Embodiment 1
Ligand L 1a's is synthetic
Under nitrogen atmosphere and the room temperature condition, in mouthful bottle of 100ml, add toluene 20ml successively, 2,6-xylidine 1.45g (1.5ml, 12mmol), trimethyl aluminium 12ml (1.0M, 12mmol).Reacted 2 hours down at 110 ℃, temperature of reaction is reduced to room temperature, add benzil 1.05 grams (5mmol) then.This moment, reaction system was by the colourless scarlet that becomes, and emitted a large amount of heats.Continue reaction 6 hours down at 110 ℃, be cooled to 0 ℃ again, reaction system stops with 5% sodium hydroxide frozen water solution.The organic phase ethyl acetate extraction is used anhydrous MgSO then
4Drying is spin-dried for solvent and obtains orange.Product separates by silicagel column, leacheate (petrol ether/ethyl acetate=15: 1).Obtain orange crystal at ethyl alcohol recrystallization, productive rate: 69.2%.There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 2.1:1.
1HNMR (300MHz, CDCl
3), δ (ppm)
1H NMR (300MHz, CDCl
3), δ (ppm): isomer 1:7.96-6.51 (m, 16H, Ar-H), 1.33 (s, 12H, CH
3).Isomer 2:7.96-6.51 (m, 16H, Ar-H), 1.60 (s, 12H, CH
3).
13CNMR (75MHz, CDCl
3), δ (ppm): isomer 1:164.92 (C=N), 147.03 (C-N), 137.73 (CC=N), 134.72 (C
Ar-Me), 129.55,128.34,127.74,127.25,126.36,123.04,18.57 (Me).Isomer 2:165.19 (C=N), 147.44 (C-N), 137.73 (CC=N), 134.72 (C
Ar-Me), 130.68,128.42,127.91,127.33,126.23,123.15,18.85 (Me).Results of elemental analyses C
30H
28N
2: theoretical value: C, 86.50; H, 6.78; N, 6.72%.Measured value: C, 86.33; H, 6.79; N, 6.51%.
Embodiment 2
Ligand L 2a's is synthetic
Press the synthetic method of ligand L 1a among the embodiment 1, with 4,4 '-dimethyl benzil replaces benzil, and other operational condition is identical.Obtain orange, productive rate: 74.1%.There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 2.5:1.
1H NMR (300MHz, CDCl
3), δ (ppm): isomer 1:8.12-6.82 (m, 14H, Ar-H), 2.46 (s, 12H, CH
3At aniline phenyl), 1.79 (s, 6H, CH
3At benzil backbone).Isomer 2:8.12-6.82 (m, 14H, Ar-H), 2.22 (s, 12H, CH
3At aniline phenyl), 1.59 (s, 6H, CH
3At benzil backbone).
13C NMR (75MHz, CDCl
3), δ (ppm): isomer 1:164.49 (C=N), 147.60 (C-N), 140.91 (CC=N), 131.77 (C
Ar-Me), 128.49,127.30,126.32 125.25,122.80,21.46,18.67.Isomer 2:165.00 (C=N), 147.33 (C-N), 139.88 (CC=N), 132.59 (C
Ar-Me), 129.12,127.50,126.78,124.91,122.93,21.31,18.50.Results of elemental analyses C
32H
32N
2: theoretical value: C, 86.44; H, 7.25; N, 6.30.%.Measured value: C, 86.53; H, 7.14; N, 6.05%.
Embodiment 3
Ligand L 2b's is synthetic
Press the synthetic method of ligand L 1a among the embodiment 1, with 2, the 6-diisopropyl aniline replaces 2,6-xylidine and with 4, and 4 '-dimethyl benzil replacement benzil, other operational condition is identical.Obtain orange crystallization, productive rate: 48.6%.
There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 1.9:1.
1H NMR (300MHz, CDCl
3), δ (ppm): isomer 1:7.87-6.86 (m, 14H, Ar-H), 2.98 (m, 4H, CH (CH
3)
2), 2.29 (s, 6H, CH
3), 1.12 (m, 24H, CH (CH
3)
2). isomer 2:7.87-6.86 (m, 14H, Ar-H), 3.13 (m, 4H, CH (CH
3)
2), 2.39 (s, 6H, CH
3), 0.96 (m, 24H, CH (CH
3)
2).
13C NMR (75MHz, CDCl
3), δ (ppm): isomer 1:166.29 (C=N), 145.74 (C-N), 140.34 (CC=N), 134.97 (C
Ar-Me), and 129.07,128.59,123.43,122.97,28.55,23.65,21.44. isomer 2:166.19 (C=N), 142.56 (C-N), 139.97 (CC=N), 134.76 (C
Ar-Me), and 129.07,128.59,123.43,122.97,27.89,24.48,22.63. results of elemental analyses C
40H
48N
2: theoretical value: C, 86.28; H, 8.69; N, 5.03%.Measured value: C, 86.12; H, 8.78; N, 4.96%.
Embodiment 4
Ligand L 3a's is synthetic
Press the synthetic method of ligand L 1a among the embodiment 1, with 4,4 '-difluoro benzil replaces benzil, and other operational condition is identical.Obtain orange, productive rate: 56.2%.There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 2.2:1.
1H NMR (300MHz, CDCl
3), δ (ppm): isomer 1:8.18-6.63 (m, 14H, Ar-H), 1.83 (s, 12H, CH
3).Isomer 2:8.18-6.63 (m, 14H, Ar-H), 1.70 (s, 12H, CH
3).
13C NMR (75MHz, CDCl
3), δ (ppm): isomer 1:165.96 (C-F), 164.34 (C=N), 161.84 (C-N), 147.52 (CC=N), 133.98 (C
Ar-Me), and 131.05,129.79,128.33,127.69,125.48,123.70,115.97,115.41,18.82 (Me).Isomer 2:165.71 (C-F), 164.02 (C=N), 161.84 (C-N), 146.99 (CC=N), 133.98 (C
Ar-Me), and 130.71,129.12,128.09,126.40,124.91,123.50,115.75,115.20,18.64 (Me).Results of elemental analyses C
30H
26F
2N
2: theoretical value: C, 79.62; H, 5.79; N, 6.19%.Measured value: C, 79.41; H, 5.62; N, 6.05%.
Embodiment 5
Ligand L 4a's is synthetic
Press the synthetic method of ligand L 1a among the embodiment 1, with (D, L)-camphorquinone replacement benzil, other operational condition is identical.Reaction product recrystallization in ethanol obtains yellow bulk crystals, productive rate: 84.7%.There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 1.2:1.
1H NMR (300MHz, CDCl
3), δ (ppm) isomer 1:6.86-6.70 (m, 6H), 2.07 (s, 12H), 1.79 (m, 4H), 1.39 (m, 1H), 1.26 (s, 3H), 1.07 (s, 6H).Isomer 2:6.86-6.70 (m, 6H), 2.04 (s, 12H), 1.86 (m, 4H), 1.42 (m, 1Hr), 1.26 (s, 3H), 0.93 (s, 6H).
13CNMR (75MHz, CDCl
3), δ (ppm): isomer 1:170.87 (C=N), 149.37 (C-N), 127.53 (C
Ar-Me), 123.96,122.71,55.30,51.18,45.46,32.59,23.38,21.68,18.42,11.20.Isomer 2:168.56 (C=N), 148.11 (C-N), 127.07,124.88,123.17,55.30,51.18,45.46,32.59,23.38,21.68,18.26 (C
Ar-CH
3), 11.20.Results of elemental analyses C
26H
32N
2: theoretical value: C, 83.82; H, 8.66; N, 7.52%.Measured value: C, 83.70%; H, 8.74; N, 7.46%.
Embodiment 6
Ligand L 4b's is synthetic
Press the synthetic method of ligand L 1a among the embodiment 1, with 2, the 6-diisopropyl aniline replaces 2,6-xylidine and with (D, L)-camphorquinone replacement benzil, other operational condition is identical.Reaction product obtains orange crystal at ethyl alcohol recrystallization, productive rate: 38.0%.There is isomer in nuclear-magnetism test shows part under solution state, its isomer is 1.8:1.
1H NMR (300MHz, CDCl
3), δ (ppm) isomer 1:7.06-6.81 (m, 6H), 2.88 (m, 4H), 2.36 (m, 1H), 1.86 (m, 4H), 1.24 (d, 24H), 0.96 (s, 6H), 0.77 (s, 3H).Isomer 2:7.06-6.81 (m, 6H), 2.69 (m, 4H), 2.36 (m, 1H), 1.86 (m, 4H), 1.12 (d, 24H), 0.94 (s, 6H), 0.77 (s, 3H).
13C NMR (75MHz, CDCl
3), δ (ppm): isomer 1:168.57 (C=N), 144.89 (C-N), 136.10 (C
Ar-
iPr), 122.53,121.78,55.92,50.68,45.43,32.27,28.41,24.64,22.44,17.97,11.30.Isomer 2:168.57 (C=N), 144.89 (C-N), 134.71 (C
Ar-
iPr), 123.42,121.46,55.92,50.68,45.43,32.27,28.70,24.73,22.96,17.97,11.30.Results of elemental analyses C
34H
48N
2: theoretical value: C, 84.24; H, 9.98; N, 5.78%.Measured value: C, 84.13; H, 9.87; N, 5.69%.
Two, the inferior nickel complex preparation of α-two
Embodiment 7
The preparation of title complex 1a
Nitrogen atmosphere adds the ligand L 1a that 0.42g embodiment 1 obtains, (DME) NiBr in the Schlenk bottle
2308mg, methylene dichloride 20ml, stirring at room 12 hours.Be evaporated to the 5ml solvent, add normal hexane and be settled out the reddish-brown powder.Product normal hexane solvent wash, vacuum-drying obtain 0.54g title complex 1a, productive rate: 85.4%.
Embodiment 8
The preparation of title complex 2a
With the ligand L 1a that embodiment 2 resulting ligand L 2a 0.44g replace embodiment 1 to obtain, other operational conditions are identical with embodiment 6, obtain 0.62g reddish-brown title complex 2a, productive rate 93.1%.
Embodiment 9
The preparation of title complex 2b
With the ligand L 1a that embodiment 2 resulting ligand L 2b 0.56g replace embodiment 1 to obtain, other operational conditions are identical with embodiment 6, obtain 0.57g reddish-brown title complex 2a, productive rate 74.6%.
Embodiment 10
The preparation of title complex 3a
With the ligand L 1a that embodiment 3 resulting ligand L 3a 0.45g replace embodiment 1 to obtain, other operational conditions are identical with embodiment 6, obtain 0.58g reddish-brown title complex 3a, productive rate 87.1%.
Embodiment 11
The preparation of title complex 4a
With the ligand L 1a that embodiment 4 resulting ligand L 4a 0.37g replace embodiment 1 to obtain, other operational conditions are identical with embodiment 6, obtain 0.51g reddish-brown title complex 4a, productive rate 86.7%.
Embodiment 12
The preparation of title complex 4b
With the ligand L 1a that embodiment 5 resulting ligand L 4b 0.48g replace embodiment 1 to obtain, other operational conditions are identical with embodiment 6, obtain 0.66g scarlet title complex 4b, productive rate 94.2%.
Three, ethylene polymerization
Embodiment 13
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 1a 3.17mg (5 μ mol) of embodiment 7 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With 200ml ethanol solution hydrochloride termination reaction, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 0.83g.Catalytic efficiency is 1.19 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 150.7kg/mol, and the polymkeric substance polydispersity coefficient is 2.2, and the melt temperature that DSC measures polymkeric substance is 125 ℃,
13It is 15.0/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 14
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 13.Obtain polymkeric substance 1.24g, catalytic efficiency is 1.77 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 92.4kg/mol, and the polymkeric substance polydispersity coefficient is 2.3, and the melt temperature that DSC measures polymkeric substance is 85 ℃,
13It is 35.2/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 15
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 13.Obtain polymkeric substance 0.85g, catalytic efficiency is 1.21 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 41.0kg/mol, and the polymkeric substance polydispersity coefficient is 2.0, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 69.6/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 16
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 2a 3.31mg (5 μ mol) of embodiment 8 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With the ethanol solution hydrochloride termination reaction of 200ml, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 0.80g.Catalytic efficiency is 1.14 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 177.2kg/mol, and the polymkeric substance polydispersity coefficient is 2.0, and the melt temperature that DSC measures polymkeric substance is 99 and 110 ℃,
13It is 22.9/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 17
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 16.Obtain polymkeric substance 1.29g, catalytic efficiency is 1.84 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 103.0kg/mol, and the polymkeric substance polydispersity coefficient is 2.2, and the melt temperature that DSC measures polymkeric substance is 66 ℃,
13It is 41.8/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 18
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 16.Obtain polymkeric substance 0.85g, catalytic efficiency is 1.21 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 35.1kg/mol, and the polymkeric substance polydispersity coefficient is 2.1, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 81.8/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 19
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 2b 3.87mg (5 μ mol) of embodiment 9 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With the ethanol solution hydrochloride termination reaction of 200ml, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 0.18g, and catalytic efficiency is 0.26 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 195.1kg/mol, and the polymkeric substance polydispersity coefficient is 1.8, and the melt temperature that DSC measures polymkeric substance is 80 and 104 ℃,
13It is 55.9/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 20
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 19.Obtain polymkeric substance 0.20g, catalytic efficiency is 0.28 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 147.9kg/mol, and the polymkeric substance polydispersity coefficient is 3.1, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 84.7/1000 carbon atom that NMR measures the polymkeric substance degree of branching.
Embodiment 21
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 19.Obtain polymkeric substance 0.33g, catalytic efficiency is 0.47 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 80.4kg/mol, and the polymkeric substance polydispersity coefficient is 3.1, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 97.6/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 22
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 3a 3.35mg (5 μ mol) of embodiment 10 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With the ethanol solution hydrochloride termination reaction of 200ml, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 0.94g, and catalytic efficiency is 1.34 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 119.9kg/mol, and the polymkeric substance polydispersity coefficient is 2.5, and the melt temperature that DSC measures polymkeric substance is 126 ℃,
13It is 13.1/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 23
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 22.Obtain polymkeric substance 1.81g, catalytic efficiency is 2.59 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 68.8kg/mol, and the polymkeric substance polydispersity coefficient is 2.2, and the melt temperature that DSC measures polymkeric substance is 118 ℃,
13It is 20.7/1000 carbon atom that NMR measures the polymkeric substance degree of branching.
Embodiment 24
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 22.Obtain polymkeric substance 1.22g, catalytic efficiency is 1.74 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 27.6kg/mol, and the polymkeric substance polydispersity coefficient is 2.0, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 62.5/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 25
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 4a 2.96mg (5 μ mol) of embodiment 11 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With the ethanol solution hydrochloride termination reaction of 200ml, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 1.36g, and catalytic efficiency is 1.94 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 152.8kg/mol, and the polymkeric substance polydispersity coefficient is 2.4, and the melt temperature that DSC measures polymkeric substance is 115 ℃,
13It is 20.2/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 26
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 25.Obtain polymkeric substance 1.80g, catalytic efficiency is 2.57 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 94.0kg/mol, and the polymkeric substance polydispersity coefficient is 2.3, and the melt temperature that DSC measures polymkeric substance is 64 ℃,
13It is 63.2/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 27
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 25.Obtain polymkeric substance 1.02g, catalytic efficiency is 1.46 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 61.3kg/mol, and the polymkeric substance polydispersity coefficient is 2.3, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 88.5/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 28
Under the ethene atmosphere, in the Schlenk of 50ml polymerization bottle, add the title complex 4b 3.52mg (5 μ mol) of embodiment 12 preparations, toluene 20ml, methylaluminoxane 3.0mmol, at 0 ℃, polyase 13 0min under the 0.5atm.With the ethanol solution hydrochloride termination reaction of 200ml, filter, washing with alcohol three times, 70 ℃ of following vacuum-dryings get polymkeric substance 1.19g, and catalytic efficiency is 170 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 209.4kg/mol, and the polymkeric substance polydispersity coefficient is 2.5, and the melt temperature that DSC measures polymkeric substance is 58 ℃,
13It is 89.3/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 29
Polyreaction is carried out under 20 ℃, and other operational conditions are identical with embodiment 28.Obtain polymkeric substance 1.23g, catalytic efficiency is 1.76 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 199.2kg/mol, and the polymkeric substance polydispersity coefficient is 2.6, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 125.5/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 30
Polyreaction is carried out under 40 ℃, and other operational conditions are identical with embodiment 28.Obtain polymkeric substance 1.37g, catalytic efficiency is 1.96 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 156.0kg/mol, and the polymkeric substance polydispersity coefficient is 2.7, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 133.3/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 31
Polyreaction is carried out under 60 ℃, and other operational conditions are identical with embodiment 28.Obtain polymkeric substance 1.34g, catalytic efficiency is 1.91 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 154.9kg/mol, and the polymkeric substance polydispersity coefficient is 2.7, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 135.5/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Embodiment 32
Polyreaction is carried out under 80 ℃, and other operational conditions are identical with embodiment 28.Obtain polymkeric substance 0.88g, catalytic efficiency is 1.26 * 10
4Mol ethylene/ (mol Nih), number-average molecular weight is 122.9kg/mol, and the polymkeric substance polydispersity coefficient is 2.0, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 129.4/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Comparative example 1
In the 100ml reaction flask, add acenaphthenequinone 0.91g (5mmol), 2,6-diisopropyl aniline 2.12g (2.3ml, 12mmol), 3 in ethanol 40ml, formic acid, heating reflux reaction 12 hours obtains acenaphthenequinone diimide ligand 1.95g, yield 78.2%.
Comparative example 2
The diimide ligand that the acenaphthenequinone diimine compounds that obtains with comparative example 1 replaces embodiment 1 to obtain, other operational conditions are identical with embodiment 7.Obtain the Powdered acenaphthenequinone diimine nickel complex of reddish-brown 0.64g, productive rate 90.2%.
Comparative example 3
The title complex 4b that the acenaphthenequinone diimine nickel complex alternate embodiment 12 for preparing with comparative example 2 prepares, other operational conditions are identical with embodiment 28.Under 0 ℃, obtain polymkeric substance 2.40g, catalytic efficiency is 3.43 * 10
4Mol ethylene/ (molNih), number-average molecular weight is 224.9kg/mol, and the polymkeric substance polydispersity coefficient is 2.9, and the melt temperature that DSC measures polymkeric substance is 81 ℃,
13It is 58.1/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Comparative example 4
The title complex 4b that the acenaphthenequinone diimine nickel complex alternate embodiment 12 for preparing with comparative example 2 prepares, other operational conditions are identical with embodiment 29.Under 20 ℃, obtain polymkeric substance 1.92g, catalytic efficiency is 2.74 * 10
4Mol ethylene/ (molNih), number-average molecular weight is 135.6kg/mol, and the polymkeric substance polydispersity coefficient is 2.7, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 102.4/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Comparative example 5
The title complex 4b that the acenaphthenequinone diimine nickel complex alternate embodiment 12 for preparing with comparative example 2 prepares, other operational conditions are identical with embodiment 30.Under 40 ℃, obtain polymkeric substance 1.54g, catalytic efficiency is 2.20 * 10
4Mol ethylene/ (molNih), number-average molecular weight is 109.5kg/mol, and the polymkeric substance polydispersity coefficient is 2.5, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 209.6/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Comparative example 6
The title complex 4b that the acenaphthenequinone diimine nickel complex alternate embodiment 12 for preparing with comparative example 2 prepares, other operational conditions are identical with embodiment 31.Under 60 ℃, obtain polymkeric substance 1.17g, catalytic efficiency is 1.67 * 10
4Mol ethylene/ (molNih), number-average molecular weight is 56.7kg/mol, and the polymkeric substance polydispersity coefficient is 2.4, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 229.2/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Comparative example 7
The title complex 4b that the acenaphthenequinone diimine nickel complex alternate embodiment 12 for preparing with comparative example 2 prepares, other operational conditions are identical with embodiment 32.Under 80 ℃, obtain polymkeric substance 0.26g, catalytic efficiency is 0.37 * 10
4Mol ethylene/ (molNih), number-average molecular weight is 34.2kg/mol, and the polymkeric substance polydispersity coefficient is 2.7, and DSC test shows polymkeric substance does not have tangible fusing point,
13It is 219.2/1000 carbon atom that C NMR measures the polymkeric substance degree of branching.
Claims (1)
1. the preparation method of alpha-nickel diimine compound olefin polymerization catalyst, the chemical structural formula of described alpha-nickel diimine compound olefin polymerization catalyst is as (I), wherein R
1Be hydrogen, alkyl or halogen, R
2Be alkyl, X is a halogen;
Step is as follows:
(1) reaction of corresponding aniline and trimethyl aluminium is generated the aluminium amine salt, the aluminium amine salt carries out the ketoamine condensation reaction with corresponding diketone and makes skeleton structure suc as formula the alpha-diimine part shown in (III) then;
(2) by the alpha-diimine part of (1) described preparation under the condition of anhydrous and oxygen-free with (DME) NiX
2Carry out coordination reaction, make structure suc as formula the alpha-nickel diimine compound olefin polymerization catalyst shown in (I);
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| CN112920300B (en) * | 2021-02-01 | 2021-12-24 | 中国科学院长春应用化学研究所 | Large steric hindrance alpha-diimine ligand, nickel catalyst, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206016A (en) * | 1997-06-12 | 1999-01-27 | 菲利浦石油公司 | Polymerization catalysts and processes therefor |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206016A (en) * | 1997-06-12 | 1999-01-27 | 菲利浦石油公司 | Polymerization catalysts and processes therefor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467693A (en) * | 2018-05-11 | 2019-11-19 | 中国石油天然气股份有限公司 | Double-core bridging alpha-diimine catalyst and its preparation method and application |
| CN110467693B (en) * | 2018-05-11 | 2021-11-30 | 中国石油天然气股份有限公司 | Binuclear bridged alpha-diimine catalyst and preparation method and application thereof |
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