CN104151455B - A kind of neutral α-amido imine nickel catalyst and its preparation method and application - Google Patents
A kind of neutral α-amido imine nickel catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of neutral α amido imine nickel catalyst and its preparation method and application.This catalyst has following structural formula: wherein, R1For hydrogen, methyl, isopropyl or the tert-butyl group；R2For phenyl, naphthyl or benzyl；L is trimethyl-phosphine, triphenylphosphine or pyridine.The catalyst of the present invention can be under the promoter effects such as MAO, modified methylaluminoxane and two (ring 1,5 diene) nickel, and catalyzed ethylene polymerization reaction obtains the polyethylene of high molecular, narrow ditribution；Catalyzed ethylene and polar monomer copolymerization reaction can also obtain the ethylene copolymer of narrow ditribution.The synthesis material of the neutral α amido imine nickel catalyst of the present invention is simple, operating procedure is simple, and stability is preferable, and this catalyst is good to the tolerance of polar group simultaneously, the microstructure of ethylene copolymer product can be efficiently controlled, obtain the accurate ethylene copolymer of structure.
Description
Technical field
The present invention relates to a kind of neutral α-amido imine nickel catalyst and its preparation method and application, belong to olefin catalytic and gather
Conjunction field.
Background technology
Polyolefin is one of a kind of most widely used resin, and its yield accounts for more than half of macromolecular material total output.
Owing to it has excellent processing and serviceability, and low price, the most become yield and consuming the most in the world
Big synthetic resin kind, is widely used in industry, agricultural, national defence, transportation and daily life.
Wherein, catalyst is the core of polyolefin industry development, is the key controlling polyolefin structure with performance.But due to
Polyolefin structure lacks functional groups, limits polyolefine material wider application.Therefore, nonpolar
Introducing the functional group performance with raising vistanex of polarity in polyolefin, the most always industrial quarters is for it
The research direction made great efforts.
Polyolefin functional modification generally has three kinds of methods: i.e. directly copolymerization method, reactive group functional method and
Post functionalization modification method.Wherein, direct copolymerization method is method the most direct, optimal, by alkene and polar monomer
Effective copolymerization, it becomes possible to prepare functional polyolefin with settling at one go.It addition, different structure and the functionalization of composition
Polyolefin has important impact to its performance, such that it is able to produce different purposes.Thereby through alkene and polar monomer
Directly copolymerization, can accurately control the structure and composition of polymer, prepare the polyolefin of functionalization, always alkene
Polymerization field focus of attention.
Industrial ethylene and some polar monomer can under high pressure carry out radical copolymerization, but the reaction condition of polymerization
Harshness, obtain is the copolymerization product of highly polar content of monomer, and product structure complexity is wayward.Front transition gold
The Ziegler-Natta catalyst at genus center and metallocene catalyst are strong, generally due to the electrophilic oxytropism of its metal center
Easily being passivated by lewis base property group, the addition of polar monomer easily makes catalyst serious inactivation, thus polar monomer one
As must could carry out copolymerization with alkene after chemoproection or space protection, and it is low to insert rate.Developed in recent years
The feature that next late transition metal catalyst is the most prominent is that its oxyphie electrophilicity is weak, good to polar group tolerance, thus
Can be by the MOLECULE DESIGN of catalyst structure being realized the copolymerization of alkene and polar monomer, preparing structure and composition can
The Functional Polyolefins of control.
The alpha-diimine palladium catalyst catalyzed ethylene of the big steric hindrance of Brookhart reporting and acrylate (MA) are altogether
Poly-.Owing to acrylate is with 2, the mode of 1-inserts palladium-alkyl (Pd-alkyl) key, rearranged after can be stablized
Hexa-atomic chelate ring intermediate, continue into vinyl monomer, and then chain walking (Chain-walking) reaction occur,
To highly-branched degree, polar group at the copolymer of branch terminals.But, the degree of branching that polymerizate is high can not be material
Material provides a good mechanical property, and the stability of palladium catalyst is the highest.Neutral phosphono and sulfonic palladium catalyst shows
Show the strongest polar monomer copolymerization ability, this type of catalyst energy catalyzed alkene and polar monomer (alkyl dialkylaminobenzoic acid
Ester, vinyl ethers, acrylonitrile, the norbornene derivative of polar functionalities, fluoroolefin) it is copolymerized conjunction,
Copolymer (typically smaller than 10,000) to low-molecular-weight.The salicylic alidehyde imine nickel that Grubbs reported first [N, O] is neutral
Catalyst can be catalyzed norborene and the ethylene copolymer of polar functionalities in polar solvent, obtains ethylene copolymer.
Neutral salicylic alidehyde imine Raney nickel is owing to cannot introduce the aromatic ring of big steric hindrance, big steric group in its oxygen coordination atom
Being necessary on its ortho position introducing, therefore synthesis step is loaded down with trivial details, substantially increases the synthesis difficulty of ligands and complexes.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of neutral α-amido imine nickel catalyst.Should
Catalyst synthesis is simple, and can obtain the polyethylene of high molecular, narrow ditribution with catalyzed ethylene polymerization reaction, moreover it is possible to
Enough catalyzed ethylenes and polar monomer copolymerization reaction obtain the ethylene copolymer of narrow ditribution.
The present invention also aims to provide the preparation method of a kind of above-mentioned catalyst.
The present invention also aims to provide the synthesis at polyethylene of a kind of above-mentioned catalyst and the synthesis of ethylene copolymer
In application.
For reaching above-mentioned purpose, the present invention provides a kind of neutral α-amido imine nickel catalyst, and it has such as formula 1 or formula
Structure shown in 2: wherein R1For hydrogen, methyl, isopropyl or the tert-butyl group；R2For phenyl, naphthyl or benzyl；L
For trimethyl-phosphine, triphenylphosphine or pyridine；
In above-mentioned neutral α-amido imine nickel catalyst, it is preferable that R1For hydrogen, methyl or isopropyl；R2For
Phenyl or benzyl；L is trimethyl-phosphine or triphenylphosphine.
The invention provides the preparation method of a kind of above-mentioned neutral α-amido imine nickel catalyst, the method includes following step
Rapid:
A, below 0 DEG C in the α corresponding with described catalyst-amido group with imine moiety add KH, be warming up to
20-40 DEG C, react 8-16 hour, the proton on α-amido group with imine moiety removing amido, shape under the effect of KH
Become anion ligand；
B, make the precursor compound of described anion ligand and nickel under conditions of anhydrous and oxygen-free, 20-40 DEG C of reaction
8-12 hour, obtain neutral α-amido imine nickel catalyst, course of reaction as shown in Equation 3:
Preferably, R1For hydrogen, methyl or isopropyl；R2For phenyl or benzyl；L is trimethyl-phosphine or triphenylphosphine.
In above-mentioned preparation method, it is preferable that the α of employing-amido group with imine moiety is by corresponding α-two
The compound of imines reduces what one of them imine group obtained under the reduction of trimethylaluminum compound, reaction
Process is as shown in Equation 4:
In above-mentioned preparation method, it is preferable that when in step c, the precursor compound of nickel is
Ni(CH2Ph)Cl(P(CH3)3)2With Ni (Ph) Cl (P (Ph)3)2Time, the preparation process of neutral α-amido imine nickel catalyst
As shown in Equation 5:
In above-mentioned preparation method, it is preferable that the intensification in step a is to rise to 30 DEG C.
The present invention also provides for the synthetic method of a kind of polyethylene, it is preferable that the method uses above-mentioned neutral α-amido sub-
Amine Raney nickel, 0-60 DEG C, catalyzed ethylene polymerization reaction under conditions of 1-30atm ethylene pressure, obtains polyethylene,
Within response time is 3 hours.Polyethylene obtained by the method is a kind of High molecular weight polyethylene.
In the synthetic method of above-mentioned polyethylene, it is preferable that the method also uses a promoter, described co-catalysis
Agent includes MAO (MAO), modified methylaluminoxane (MMAO) and two (ring 1,5-diene) nickel (Ni (COD)2)
In the combination of one or more.This promoter is that same catalyst, solvent join in the middle of reaction system together.
The present invention also provides for the synthetic method of a kind of ethylene copolymer, it is preferable that the method use above-mentioned neutral α-
Amido imine nickel catalyst 0-60 DEG C, catalyzed ethylene and polar monomer copolymerization are anti-under conditions of 1-30atm ethylene pressure
Should, obtain ethylene copolymer, within the response time is 3 hours.
In the synthetic method of above-mentioned ethylene copolymer, it is preferable that the polar monomer of employing includes methyl methacrylate
Ester, acrylic acid methyl ester., butyl acrylate, norbornene carboxylate derivant in the combination of one or more.
In the synthetic method of above-mentioned ethylene copolymer, it is preferable that the method also uses a promoter, described in help
Catalyst includes MAO (MAO), modified methylaluminoxane (MMAO) and two (ring 1,5-diene) nickel
(Ni(COD)2The combination of one or more in).This promoter is that same catalyst, solvent join reaction together
In the middle of system.
The synthesis material of the neutral α of the present invention-amido imine nickel catalyst is simple, and operating procedure is simple, and surely
Qualitative preferably, this catalyst is good to the tolerance of polar group simultaneously, it is possible to efficiently control the micro-of ethylene copolymer product
See structure, obtain the accurate ethylene copolymer of structure.
Accompanying drawing explanation
Fig. 1 is the mono-crystalline structures figure of neutral α-amido imine nickel catalyst 1b.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.
In order to state ligands and complexes to simplicity and clarity in an embodiment, it is described as follows:
Ligand L 1a is the amido group with imine moiety shown in formula L1, wherein R1For isopropyl；
Ligand L 1b is the amido group with imine moiety shown in formula L1, wherein R1For methyl；
Ligand L 1c is the amido group with imine moiety shown in formula L1, wherein R1For hydrogen.
Ligand L 2a is the amido group with imine moiety shown in formula L2, wherein R1For isopropyl；
Ligand L 2b is the amido group with imine moiety shown in formula L2, wherein R1For methyl；
Ligand L 2c is the amido group with imine moiety shown in formula L2, wherein R1For hydrogen.
Coordination compound 1a is the amido imine nickel compound shown in formula 1, wherein R1For isopropyl, R2For benzyl, L is
Trimethyl-phosphine；
Coordination compound 1b is the amido imine nickel compound shown in formula 1, wherein R1For methyl, R2For benzyl, L is three
Methylphosphine, the mono-crystalline structures figure of neutral α-amido imine nickel catalyst 1b is as shown in Figure 1；
Coordination compound 1c is the amido imine nickel compound shown in formula 1, wherein R1For hydrogen, R2For benzyl, L is front three
Base phosphine；
Coordination compound 1d is the amido imine nickel compound shown in formula 1, wherein R1For isopropyl, R2For phenyl, L is
Triphenylphosphine；
Coordination compound 1e is the amido imine nickel compound shown in formula 1, wherein R1For methyl, R2For phenyl, L is three
Phenylphosphine；
Coordination compound 1f is the amido imine nickel compound shown in formula 1, wherein R1For hydrogen, R2For phenyl, L is triphen
Base phosphine.
Coordination compound 2a is the amido imine nickel compound shown in formula 2, wherein R1For isopropyl, R2For benzyl, L is
Trimethyl-phosphine；
Coordination compound 2b is the amido imine nickel compound shown in formula 2, wherein R1For methyl, R2For benzyl, L is three
Methylphosphine；
Coordination compound 2c is the amido imine nickel compound shown in formula 2, wherein R1For hydrogen, R2For benzyl, L is front three
Base phosphine；
Coordination compound 2d is the amido imine nickel compound shown in formula 2, wherein R1For isopropyl, R2For phenyl, L is
Triphenylphosphine；
Coordination compound 2e is the amido imine nickel compound shown in formula 2, wherein R1For methyl, R2For phenyl, L is three
Phenylphosphine；
Coordination compound 2f is the amido imine nickel compound shown in formula 2, wherein R1For hydrogen, R2For phenyl, L is triphen
Base phosphine.
The preparation of alpha-diimine compound:
The preparation of alpha-diimine compound is prepared according to the report method of document, with diacetyl compound, acenaphthenequinone compound
Carry out seat not alkali reaction, thick product ethyl alcohol recrystallization with corresponding arylamine, obtain the compound of diimine.
The preparation of α-amido imine ligand:
Embodiment 1
Synthesis α-amido imine ligand L1a, specifically follows the steps below:
To equipped with reflux condensing tube, the 100mL of nitrogen atmosphere protection props up and adds 3.24g (8mmol) α-two Asia in mouth bottle
Amines A1 (isopropyl replacement), is then sequentially added into 10mL toluene, 4.0mL (2.0M, 8mmol) trimethyl
Aluminum, stirring reaction 6 hours at 100 DEG C；
After cooling, terminate reaction, separatory with sodium hydroxide/ice water solution, be extracted with ethyl acetate 3 times, be associated with
Machine phase, adds anhydrous magnesium sulfate and is dried, filter, after filtrate removes major part solvent, and volatilization crystallization, thick product naturally
With ethyl alcohol recrystallization, obtaining 2.47g clear crystal, i.e. α-amido imine ligand L1a, its productivity is 73.4%.
1H NMR(CDCl3, 500MHz): 7.16-7.06 (m, 6H, Ph), 4.34 (s, 1H, NH), 3.54 (septet, 2H,
CH)、2.82(septet,2H,CH)、1.88(s,3H,CH3)、1.36(s,6H,CH3)、1.21-1.18(m,24H,CH3)。
13C NMR(CDCl3,125MHz):176.46、146.56、145.96、140.15、136.25、124.50、
123.08、122.99、61.73、28.37、27.85、27.08、24.18、23.50、23.19、16.39。
Elementary analysis (C29H44N2, %) and theoretical value: C:82.80, H:10.54, N:6.66.Measured value: C:82.96,
H:10.33, N:6.68.
Embodiment 2
Synthesis α-amido imine ligand L1b, specifically follows the steps below:
By the synthetic method of ligand L 1a in embodiment 1, by alpha-diimine compound A2 (methyl replacement) replacementization
Compound A1, other operating conditions obtain 1.02g clear crystal, i.e. α-amido imines with embodiment 1, reaction after terminating
Ligand L 1b, its productivity is 66.3%.
1H NMR(CDCl3, 500MHz): 7.03 (t, 4H, Ph), 6.90 (t, 2H, Ph), 4.48 (s, 1H, NH), 2.37 (s,
6H,CH3)、2.05(s,6H,CH3)、1.87(s,3H,CH3)、1.43(s,6H,CH3)。
13C NMR(CDCl3, 125MHz): 176.53,148.28,133.99,128.46,128.06,125.69,
122.97、122.67、62.08、27.22、20.62、18.18、15.73。
Elementary analysis (C21H28N2, %) and theoretical value: C:81.77, H:9.15, N:9.08.Measured value: C:82.06,
H:9.23, N:9.20.
Embodiment 3
Synthesis α-amido imine ligand L1c, specifically follows the steps below:
By the synthetic method of ligand L 1a in embodiment 1, by alpha-diimine compound A-13 (unsubstituted) replacementization
Compound A1, other operating conditions obtain 2.37g clear crystal, i.e. α-amido imines with embodiment 1, reaction after terminating
Ligand L 1c, its productivity is 94%.
1H NMR(CDCl3, 500MHz): 7.32 (t, 2H, Ph), 7.18 (t, 2H, Ph), 7.05 (t, 1H, Ph),
6.73-6.67(m,5H,Ph)、4.12(s,1H,NH)、1.82(s,3H,CH3)、1.58(s,6H,CH3)。
13C NMR(CDCl3, 125MHz): 176.95,151.54,146.18,129.09,128.96,123.04,
118.73、117.39、114.14、59.37、26.32、14.89。
Elementary analysis (C17H20N2, %) and theoretical value: C:80.91, H:7.99, N:11.10.Measured value: C:80.96,
H:7.86, N:11.25.
Embodiment 4
Synthesis α-amido imine ligand L2a, specifically follows the steps below:
To equipped with reflux condensing tube, the 100mL of nitrogen atmosphere protection props up and weighs 6.0g (12mmol) alpha-diimine in mouth bottle
Compound A4 (isopropyl replacement), is then sequentially added into 30mL toluene, 6.0mL (2.0M, 12mmol) trimethyl
Aluminum, after stirring is reacted 4 hours at 110 DEG C, is cooled to 60 DEG C of stirring reactions overnight；
After cooling, terminate reaction, separatory with sodium hydroxide/ice water solution, be extracted with ethyl acetate 3 times, be associated with
Machine phase, adds anhydrous magnesium sulfate and is dried, filter, after filtrate removes major part solvent, and volatilization crystallization, thick product naturally
With ethyl alcohol recrystallization, obtaining 5.24g pale yellow crystals, i.e. α-amido imine ligand L2a, its productivity is 84.5%.
1H NMR(CDCl3, 500MHz): 7.81 (d, 1H, Ph), 7.64 (d, 1H, Ph), 7.31-7.21 (m, 5H, Ph),
7.12(t,1H,Ph,)、7.02(d,2H,Ph)、6.53(d,1H,Ph)、6.36(d,1H,Ph)、3.89(s,1H,NH)、
3.19-3.01(m,4H,CH(iPr)2)、1.96(s,3H,CH3)、1.26(d,3H,CH3)、1.18(d,3H,CH3)、1.09(s,
6H,CH3)、0.95(t,6H,CH3)、0.59(s,6H,CH3)。
13C NMR(CDCl3, 125MHz): 175.48,146.65,142.48,139.17,138.78,136.16,
136.02、131.02、129.90、128.83、127.61、127.49、125.16、123.93、123.67、123.31、
122.78、121.67、67.91、29.70、28.46、28.21、27.80、24.56、23.80、23.59、23.56、
22.98。
Elementary analysis (C37H44N2, %) and theoretical value: C:86.00, H:8.58, N:5.42.Measured value: C:86.06,
H:8.56, N:5.35.
Embodiment 5
Synthesis α-amido imine ligand L2b, specifically follows the steps below:
By the synthetic method of ligand L 2a in embodiment 4, by alpha-diimine compound A-45 (methyl replacement) replacementization
Compound A4, other operating conditions obtain amido imine ligand L2b with embodiment 4, reaction after terminating.
1H NMR(CDCl3, 500MHz): 7.85 (d, 1H, Ph), 7.71 (d, 1H, Ph), 7.40 (t, 1H, Ph), 7.32 (t,
1H,Ph)、7.12(t,1H,Ph)、7.04(s,1H,Ph)、6.90-6.83(m,4H,Ph)、6.58(d,1H,Ph)、3.89(s,
1H,NH)、2.07(s,3H,CH3)、2.02(s,3H,CH3)、1.94(s,3H,CH3)、1.88(s,6H,CH3)。
13C NMR(CDCl3, 125MHz): 174.09,148.79,143.28,138.47,134.29,130.76,
130.18、128.86、128.40、128.30、128.16、127.77、125.81、125.38、124.06、123.35、
123.26、122.78、121.04、68.17、30.53、19.48、17.78、17.59。
Elementary analysis (C29H28N2, %) and theoretical value: C:86.10, H:6.98, N:6.92.Measured value: C:86.16,
H:6.85, N:6.95.
Embodiment 6
Synthesis α-amido imine ligand L2c, specifically follows the steps below:
By the synthetic method of ligand L 2a in embodiment 4, by alpha-diimine compound A6 (unsubstituted) replacementization
Compound A4, other operating conditions obtain amido imine ligand L2c with embodiment 4, reaction after terminating.
1H NMR(CDCl3, 500MHz): 7.88 (d, 1H, Ph), 7.73 (d, 1H, Ph), 7.42 (t, 1H, Ph), 7.28 (t,
1H,Ph)、7.16(t,1H,Ph)、7.02(s,1H,Ph)、6.95-6.80(m,4H,Ph)、6.54(d,1H,Ph)、3.89(s,
1H,NH)。
13C NMR(CDCl3, 125MHz): 172.19,146.73,141.58,138.47,135.30,131.72,
129.15、128.84、128.40、128.30、128.10、127.76、125.88、125.32、124.09、123.27、
123.06、122.08、121.09、68.15。
Elementary analysis (C25H20N2) theoretical value: C:86.17, H:5.79, N:8.04.Measured value: C:86.42,
H:5.84, N:8.00.
The synthesis of α-amido imine nickel complex:
Embodiment 7
Synthesis α-amido imine nickel complex 1a, specifically follows the steps below:
In a nitrogen atmosphere, in the Schlenk bottle with stirrer, addition 0.63g (1.50mmol) α-amido is weighed
Imine ligand L1a, is injected into 20mL anhydrous tetrahydro furan and then adds 80mg KH (2mmol) at 0 DEG C, slow
Slowly being warming up to stirring at normal temperature 12 hours, after removing insoluble matter with core filter ball, vacuum evaporation removes solvent, adds
20mL dichloromethane solvent dissolves, and is subsequently adding 0.33g Ni (CH2Ph)Cl(P(CH3)3)2Compound, reacts overnight,
Filtering, filter vacuum is concentrated into 5mL, then squeezes into 20mL normal hexane and make coordination compound be precipitated out, and uses core filter ball
Filtering, vacuum is drained, and obtains the blackish green pulverulent solids of 0.63g, i.e. α-amido imine nickel complex 1a, its productivity
It is 65%.
1H NMR(500MHz,C6D6): 7.14-7.02 (m, 5H, Ph), 6.82 (m, 1H, Ph), 6.50 (m, 1H, Ph),
6.28(m,2H,Ph)、6.00(d,1H,Ph)、5.38(s,2H,CH2)、3.25(sp,2H,CH(Me3)2)、2.93(sp,2H,
CH(Me3)2)、2.67(s,6H,Me)、2.07(s,6H,Me)、1.51(s,3H,Me)、1.26(s,3H,Me)、1.18(s,9H,
Me)、1.16-1.02(m,12H,CH(CH3)2)、0.80(s,3H,Me)。
31P NMR(203MHz,C6D6) :-36.0.
Elementary analysis (C39H59N2NiP) theoretical value: C:72.56, H:9.21, N:4.34.Measured value: C:72.40,
H:9.18, N:4.35.
Embodiment 8
Synthesis α-amido imine nickel complex 1b, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L1b
L1a, other operating conditions obtain amido imine nickel complex 1b with embodiment 7, reaction after terminating.
1H NMR(500MHz,C6D6): 7.12-7.00 (m, 5H, Ph), 6.81 (m, 1H, Ph), 6.52 (m, 1H, Ph),
6.30(m,2H,Ph)、6.01(d,1H,Ph)、5.36(s,2H,CH2)、2.67(s,6H,Me)、2.07(s,6H,Me)、
1.51(s,3H,Me)、1.26(s,3H,Me)、1.18(s,9H,Me)、0.80(s,3H,Me)。
31P NMR(203MHz,C6D6) :-35.8.
Elementary analysis (C31H43N2NiP) theoretical value: C:69.81, H:8.13, N:5.25.Measured value: C:69.75,
H:8.24, N:5.53.
Embodiment 9
Synthesis α-amido imine nickel complex 1c, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L1c
L1a, other operating conditions obtain amido imine nickel complex 1c with embodiment 7, reaction after terminating.
1H NMR(500MHz,C6D6): 7.62-7.00 (m, 7H, Ph), 6.75 (m, 1H, Ph), 6.42 (m, 1H, Ph),
6.18(m,2H,Ph)、5.95(d,1H,Ph)、5.12(s,2H,CH2)、1.08(s,9H,Me)。
31P NMR(203MHz,C6D6) :-36.5.
Elementary analysis (C27H35N2NiP) theoretical value: C:67.95, H:7.39, N:5.87.Measured value: C:67.35,
H:7.02, N:5.93.
Embodiment 10
Synthesis α-amido imine nickel complex, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, with Ni (Ph) Cl (P (Ph)3)2Replace
Ni(CH2Ph)Cl(P(CH3)3)2, other operating conditions are with embodiment 7, and reaction obtains amido imine nickel and coordinates after terminating
Thing 1d.
1H NMR(500MHz,C6D6): 7.23 7.03 (m, 20H, Ph), 6.81 (m, 1H, Ph), 6.49 (m, 1H,
Ph)、6.27(m,2H,Ph)、6.00(d,1H,Ph)、5.38(s,2H,CH2)、3.25(sp,2H,CH(Me3)2、2.93(sp,
2H,CH(Me3)2)、2.67(s,6H,Me)、2.07(s,6H,Me)、1.51(s,3H,Me)、1.26(s,3H,Me)、
1.21(s,3H,Me)、1.16-1.02(m,12H,CH(CH3)2)。
31P NMR(203MHz,C6D6): 24.3.
Elementary analysis (C53H63N2NiP) theoretical value: C:77.84, H:7.77, N:3.43.Measured value: C:77.68,
H:7.82, N:5.36.
Embodiment 11
Synthesis α-amido imine nickel complex 1e, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L1b
L1a, with Ni (Ph) Cl (P (Ph)3)2Replace Ni (CH2Ph)Cl(P(CH3)3)2, other operating conditions are with embodiment 7, instead
Amido imine nickel complex 1e should be obtained after terminating.
1H NMR(500MHz,C6D6): 7.32 7.00 (m, 21H, Ph), 6.81 (m, 1H, Ph), 6.52 (m, 1H,
Ph)、6.30(m,2H,Ph)、6.00(d,1H,Ph)、2.67(s,6H,Me)、2.04(s,6H,Me)、1.48(s,3H,Me)、
1.22(s,3H,Me)、1.02(s,3H,Me)。
31P NMR(203MHz,C6D6): 23.9.
Elementary analysis (C45H47N2NiP) theoretical value: C:76.61, H:6.71, N:3.97.Measured value: C:76.49,
H:6.69, N:4.02.
Embodiment 12
Synthesis α-amido imine nickel complex 1f, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L1c
L1a, with Ni (Ph) Cl (P (Ph)3)2Replace Ni (CH2Ph)Cl(P(CH3)3)2, other operating conditions are with embodiment 7, instead
Amido imine nickel complex 1f should be obtained after terminating.
1H NMR(500MHz,C6D6): 7.80 7.00 (m, 18H, Ph), 6.75 (m, 1H, Ph), 6.42 (m, 1H,
Ph)、6.18(m,2H,Ph)、5.95(d,1H,Ph)、2.02(s,6H,Me)、1.41(s,3H,Me)。
31P NMR(203MHz,C6D6): 25.4.
Elementary analysis (C41H39N2NiP) theoretical value: C:75.38, H:6.05, N:4.31.Measured value: C:75.61,
H:6.14, N:4.17.
Embodiment 13
Synthesis α-amido imine nickel complex 2a, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2a
L1a, other operating conditions obtain amido imine nickel 2a with embodiment 7, reaction after terminating.
1H NMR(500MHz,C6D6): 7.81 (d, 1H, Ph), 7.64 (d, 1H, Ph), 7.31-7.21 (m, 10H, Ph),
7.12(t,1H,Ph,)、7.02(d,2H,Ph)、6.53(d,1H,Ph)、6.36(d,1H,Ph)、5.28(s,2H,CH2),
3.19-3.01(m,4H,CH(iPr)2)、1.96(s,3H,CH3)、1.26(d,3H,CH3)、1.18(d,3H,CH3)、1.09(s,
6H,CH3), 0.80 (s, 9H, Me), 0.95 (t, 6H, CH3)、0.59(s,6H,CH3)。
31P NMR(203MHz,C6D6) :-35.4.
Elementary analysis (C47H59N2NiP) theoretical value: C:76.11, H:8.02, N:3.78.Measured value: C:76.35,
H:8.01, N:3.54.
Embodiment 14
Synthesis α-amido imine nickel complex 2b, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2b
L1a, other operating conditions obtain amido imine nickel complex 2b with embodiment 7, reaction after terminating.
1H NMR(500MHz,C6D6): 7.80 (d, 1H, Ph), 7.60 (d, 1H, Ph), 7.30-7.22 (m, 10H, Ph),
7.10(t,1H,Ph,)、7.00(d,2H,Ph)、6.50(d,1H,Ph)、6.31(d,1H,Ph)、5.24(s,2H,CH2),1.92
(s,3H,CH3)、1.22(d,3H,CH3)、1.14(d,3H,CH3)、1.08(s,6H,CH3)、0.81(s,9H,Me)。
31P NMR(203MHz,C6D6) :-36.5.
Elementary analysis (C39H43N2NiP) theoretical value: C:74.42, H:6.89, N:4.45.Measured value: C:74.68,
H:6.86, N:4.25.
Embodiment 15
Synthesis α-amido imine nickel complex 2c, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2c
L1a, other operating conditions obtain amido imine nickel complex 2c with embodiment 7, reaction after terminating.
1H NMR(500MHz,C6D6): 7.75 (d, 1H, Ph), 7.40 (d, 1H, Ph), 7.30-7.22 (m, 14H, Ph),
7.05(t,1H,Ph,)、6.91(d,2H,Ph)、6.30(d,1H,Ph)、6.21(d,1H,Ph)、5.20(s,2H,CH2),1.90
(s,3H,CH3)、1.20(d,3H,CH3)、1.13(d,3H,CH3)、1.09(s,6H,CH3)、0.78(s,9H,Me)。
31P NMR(203MHz,C6D6) :-37.1.
Elementary analysis (C35H35N2NiP) theoretical value: C:73.32, H:6.15, N:4.89.Measured value: C:73.64,
H:6.36, N:4.60.
Embodiment 16
Synthesis α-amido imine nickel complex 2d, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2a
L1a in embodiment 7, with Ni (Ph) Cl (P (Ph)3)2Replace the Ni (CH in embodiment 72Ph)Cl(P(CH3)3)2,
Other operating conditions are identical with the operating condition in embodiment 7, and the product that reaction obtains after terminating is that amido imine nickel is joined
Compound 2d.
1H NMR(500MHz,C6D6): 7.80-7.15 (m, 27H, Ph), 7.10 (t, 1H, Ph), 7.01 (d, 2H, Ph),
6.51(d,1H,Ph)、6.32(d,1H,Ph)、3.18-3.08(m,4H,CH(iPr)2)、1.94(s,3H,CH3)、1.22(d,
3H,CH3)、1.17(d,3H,CH3)、1.04(s,6H,CH3)、0.92(t,6H,CH3)、0.55(s,6H,CH3)。
31P NMR(203MHz,C6D6): 24.6.
Elementary analysis (C61H63N2NiP) theoretical value: C:80.17, H:6.95, N:3.07.Measured value: C:80.29,
H:7.05, N:2.93.
Embodiment 17
Synthesis α-amido imine nickel complex 2e, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2b
L1a, with Ni (Ph) Cl (P (Ph)3)2Replace Ni (CH2Ph)Cl(P(CH3)3)2, other operating conditions are with embodiment 7, instead
Amido imine nickel complex 2e should be obtained after terminating.
1H NMR(500MHz,C6D6): 7.80-7.15 (m, 27H, Ph), 7.08 (t, 1H, Ph), 6.87 (d, 2H, Ph),
6.46(d,1H,Ph)、6.28(d,1H,Ph)、1.92(s,3H,CH3)、1.22(d,3H,CH3)、1.14(d,3H,CH3)、
1.08(s,6H,CH3)。
31P NMR(203MHz,C6D6): 25.2.
Elementary analysis (C53H47N2NiP) theoretical value: C:79.41, H:5.91, N:3.49.Measured value: C:79.65,
H:6.08, N:3.41.
Embodiment 18
Synthesis α-amido imine nickel complex 2f, specifically follows the steps below:
By the synthetic method of α in embodiment 7-amido imine nickel complex 1a, replace with α-amido imine ligand L2c
L1a, with Ni (Ph) Cl (P (Ph)3)2Replace Ni (CH2Ph)Cl(P(CH3)3)2, other operating conditions are with embodiment 7, instead
Amido imine nickel complex 2f should be obtained after terminating.
1H NMR(500MHz,C6D6): 7.80-7.22 (m, 28H, Ph), 7.01 (t, 1H, Ph), 6.90 (d, 2H, Ph),
6.30-6.21(m,14H,Ph)、1.80(s,3H,CH3)、1.18(d,3H,CH3)、1.11(d,3H,CH3)、1.05(s,6H,
CH3)。
31P NMR(203MHz,C6D6): 26.8.
Elementary analysis (C49H39N2NiP) theoretical value: C:78.94, H:5.27, N:3.76.Measured value: C:79.07,
H:5.43, N:3.52.
Ethylene homo is tested
Embodiment 19
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
Under ethylene atmosphere, in the polymerization bottle of 100mL, the α of addition 6.44mg (10 μm ol) embodiment 7 preparation-
Amido imine nickel complex 1a, 100mL dry toluene, 2mmol modified methylaluminoxane, 20 DEG C, 5atm second
It is polymerized 1 hour under alkene pressure；
Reaction 200mL ethanol solution hydrochloride terminates, and the product obtained is carried out after ethanol solution hydrochloride terminates
Filter, obtains polymer after filtering, by polymer washing with alcohol 3 times, is vacuum dried, obtains 1.35g at 60 DEG C
Ethene polymers.
Above-mentioned polyvinyl catalysis activity for 135.0kg PE/ (molNi h), polymer number-average molecular weight is
126.0kg/mol, polydispersity coefficient are 1.36.
Embodiment 20
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 1b
With embodiment 19, reaction obtains 1.05g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 105.0kg PE/ (molNi h), polymer number-average molecular weight is
76.0kg/mol, polydispersity coefficient are 1.54.
Embodiment 21
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 1c
With embodiment 19, reaction obtains 0.76g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 76.0kg PE/ (molNi h), polymer number-average molecular weight is
12.0kg/mol, polydispersity coefficient are 1.87.
Embodiment 22
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 1d
With embodiment 19, reaction obtains 1.24g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 124.0kg PE/ (molNi h), polymer number-average molecular weight is
119.0kg/mol, polydispersity coefficient are 1.35.
Embodiment 23
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 1e
With embodiment 19, reaction obtains 1.01g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 101.0kg PE/ (molNi h), polymer number-average molecular weight is
73.0kg/mol, polydispersity coefficient are 1.56.
Embodiment 24
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
Replacing α-amido imine nickel complex 1a with 10 μm ol α-amido imine nickel complex 1f, other polymerizing condition is same
Embodiment 19, reaction obtains 0.65g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 65.0kg PE/ (molNi h), polymer number-average molecular weight is
11.0kg/mol, polydispersity coefficient are 1.89.
Embodiment 25
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 2a
With embodiment 19, reaction obtains 1.74g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 174kg PE/ (molNi h), polymer number-average molecular weight is
162.0kg/mol, polydispersity coefficient are 1.41.
Embodiment 26
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 2b
With embodiment 19, reaction obtains 1.47g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 147.0kg PE/ (molNi h), polymer number-average molecular weight is
98.0kg/mol, polydispersity coefficient are 1.52.
Embodiment 27
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 2c
With embodiment 19, reaction obtains 0.62g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 62.0kg PE/ (molNi h), polymer number-average molecular weight is
28.0kg/mol, polydispersity coefficient are 1.92.
Embodiment 28
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 2d
With embodiment 19, reaction obtains 1.68g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 168.0kg PE/ (molNi h), polymer number-average molecular weight is
158.0kg/mol, polydispersity coefficient are 1.44.
Embodiment 29
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
α-amido imine nickel complex 1a, other polymerizing condition is replaced with 10 μm ol α-amido imine nickel complex 2e
With embodiment 19, reaction obtains 1.32g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 132.0kg PE/ (molNi h), polymer number-average molecular weight is
96.0kg/mol, polydispersity coefficient are 1.54.
Embodiment 30
Present embodiments providing the preparation method of a kind of Alathon, it comprises the following steps:
Replacing α-amido imine nickel complex 1a with 10 μm ol α-amido imine nickel complex 2f, other polymerizing condition is same
Embodiment 19, reaction obtains 0.48g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 48.0kg PE/ (molNi h), polymer number-average molecular weight is
19.0kg/mol, polydispersity coefficient are 2.12.
Ethylene copolymer is tested
Embodiment 31
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Under ethylene atmosphere, in the polymerization bottle of 100mL, add the α-amido imines of 10 μm ol embodiment 7 preparations
Nickel complex 1a, 100mL dry toluene, 4mmol acrylic acid methyl ester., 2mmol modified methylaluminoxane, 20 DEG C,
It is polymerized 1 hour under 5atm ethylene pressure.
Reaction 200mL ethanol solution hydrochloride terminates, and filters, polymer washing with alcohol 3 times, vacuum at 60 DEG C
It is dried, obtains 0.64g ethene polymers.
Above-mentioned polyvinyl catalysis activity for 64.0kg PE/ (molNi h), polymer number-average molecular weight is
47.0kg/mol, polydispersity coefficient are 1.36, polar monomer insertion rate is 0.73mol%.
Embodiment 32
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Replacing acrylic acid methyl ester. with the methyl methacrylate of 4mmol, other polymerizing condition is with embodiment 31, reaction
0.38g ethene polymers is obtained after end.
Above-mentioned polyvinyl catalysis activity for 38.0kg PE/ (molNi h), polymer number-average molecular weight is
34.0kg/mol, polydispersity coefficient are 1.41, polar monomer insertion rate is 0.52mol%.
Embodiment 33
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Replacing acrylic acid methyl ester. with the butyl acrylate of 4mmol, other polymerizing condition is with embodiment 31, and reaction terminates
After 0.58g ethene polymers.
Above-mentioned polyvinyl catalysis activity for 58.0kg PE/ (molNi h), polymer number-average molecular weight is
42.0kg/mol, polydispersity coefficient are 1.50, polar monomer insertion rate is 0.61mol%.
Embodiment 34
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
Replace acrylic acid methyl ester. with the 5-norborene-2-carboxylate methyl ester of 4mmol, other polymerizing condition with embodiment 31,
Reaction obtains 0.40g ethene polymers after terminating.
Above-mentioned polyvinyl catalysis activity for 40.0kg PE/ (molNi h), polymer number-average molecular weight is
29.0kg/mol, polydispersity coefficient are 1.43, polar monomer insertion rate is 0.82mol%.
Embodiment 35
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
After terminating with 10 μm ol α-amido imine nickel complex 2a, the identical embodiment of other polymerizing condition 31, reaction
0.78g ethene polymers.
Above-mentioned polyvinyl catalysis activity for 78.0kg PE/ (molNi h), polymer number-average molecular weight is
71.0kg/mol, polydispersity coefficient are 1.32, polar monomer insertion rate is 0.81mol%.
Embodiment 36
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
α-amido imine nickel complex 1a is replaced, by the first of 4mmol with 10 μm ol α-amido imine nickel complex 2a
Base acrylic acid methyl ester. replaces acrylic acid methyl ester., and other polymerizing condition is with embodiment 31, and reaction obtains 0.48g ethylene after terminating
Polymer.
Above-mentioned polyvinyl catalysis activity for 48.0kg PE/ (molNi h), polymer number-average molecular weight is
35.0kg/mol, polydispersity coefficient are 1.39, polar monomer insertion rate is 0.64mol%.
Embodiment 37
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
α-amido imine nickel complex 1a is replaced, with the third of 4mmol with 10 μm ol α-amido imine nickel complex 2a
Olefin(e) acid butyl ester replaces acrylic acid methyl ester., and other polymerizing condition is with embodiment 31, and reaction obtains 0.62g vinyl polymerization after terminating
Thing.
Above-mentioned polyvinyl catalysis activity for 62.0kg PE/ (molNi h), polymer number-average molecular weight is
55.0kg/mol, polydispersity coefficient are 1.38, polar monomer insertion rate is 0.74mol%.
Embodiment 38
Present embodiments providing the preparation method of a kind of ethylene copolymer, it comprises the following steps:
α-amido imine nickel complex 1a is replaced, with the 5-of 4mmol with 10 μm ol α-amido imine nickel complex 2a
Norborene-2-carboxylate methyl ester replaces acrylic acid methyl ester., and other polymerizing condition is with embodiment 31, and reaction obtains after terminating
0.51g ethene polymers.
Above-mentioned polyvinyl catalysis activity for 51.0kg PE/ (molNi h), polymer number-average molecular weight is
34.0kg/mol, polydispersity coefficient are 1.46, polar monomer insertion rate is 1.14mol%.
Claims (9)
1. neutral α-amido imine nickel catalyst, it has a structure as shown in formula 1 or formula 2: wherein R1For hydrogen,
Methyl, isopropyl or the tert-butyl group；R2For phenyl or benzyl；L is trimethyl-phosphine or triphenylphosphine；
Catalyst the most according to claim 1, wherein, R1For hydrogen, methyl or isopropyl.
3. the preparation method of the neutral α described in claim 1 or 2-amido imine nickel catalyst, the method includes following
Step:
A, below 0 DEG C in the α corresponding with described catalyst-amido group with imine moiety add KH, be warming up to 20-40 DEG C,
Reacting 8-16 hour, under the effect of KH, the proton on α-amido group with imine moiety removing amido, forms anion and joins
Body；
B, make the precursor compound of described anion ligand and nickel under conditions of anhydrous and oxygen-free, 20-40 DEG C of reaction
8-12 hour, obtain neutral α-amido imine nickel catalyst, course of reaction as shown in Equation 3:
Wherein, R1For hydrogen, methyl or isopropyl；R2For phenyl or benzyl；L is trimethyl-phosphine or triphenylphosphine.
Preparation method the most according to claim 3, wherein, the intensification in step a is to rise to 30 DEG C.
5. a synthetic method for polyethylene, wherein, the method uses neutral α-amine as claimed in claim 1 or 2
Base imine nickel catalyst, 0-60 DEG C, catalyzed ethylene polymerization reaction under conditions of 1-30atm ethylene pressure, obtains polyethylene,
Within response time is 3 hours.
Synthetic method the most according to claim 5, wherein, the method also uses a promoter, described in help and urge
Agent includes the combination of one or more in MAO, modified methylaluminoxane and two (ring 1,5-diene) nickel.
7. a synthetic method for ethylene copolymer, wherein, the method employing neutral α as claimed in claim 1 or 2-
Amido imine nickel catalyst 0-60 DEG C, catalyzed ethylene and polar monomer copolymerization reaction under conditions of 1-30atm ethylene pressure,
Obtain ethylene copolymer, within the response time is 3 hours.
Synthetic method the most according to claim 7, wherein, the polar monomer that the method uses includes metering system
Acid methyl ester, acrylic acid methyl ester., butyl acrylate, norbornene carboxylate derivant in the combination of one or more.
9. according to the synthetic method described in claim 7 or 8, wherein, the method also uses a promoter, described
Promoter includes the combination of one or more in MAO, modified methylaluminoxane and two (ring 1,5-diene) nickel.
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