CN104151455A - Neutral alpha-amino-imino nickel catalyst as well as preparation method and application of neutral alpha-amino-imino nickel catalyst - Google Patents
Neutral alpha-amino-imino nickel catalyst as well as preparation method and application of neutral alpha-amino-imino nickel catalyst Download PDFInfo
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Abstract
The invention provides a neutral alpha-amino-imino nickel catalyst as well as a preparation method and application of the neutral alpha-amino-imino nickel catalyst. The catalyst has the structural formula as shown in the specification, wherein R1 is hydrogen, methyl, isopropyl or tertiary butyl; R2 is phenyl, naphthyl or benzyl; and L is trimethylphosphine, triphenylphosphine or pyridine. The catalyst provided by the invention can be used for catalyzing vinyl polymerization reaction under the actions of catalyst promoters such as methylaluminoxane, modified methylaluminoxane and bis(cyclo-1, 5-diene)nickel to obtain polyethylene with high molecular weight and narrow molecular-weight distribution and can also be used for catalyzing the copolymerization reaction between ethylene and a polar monomer to obtain a vinyl copolymer with narrow molecular-weight distribution. The synthesis raw materials of the neutral alpha-amino-imino nickel catalyst are simple; the operation steps are simple and feasible; and the neutral alpha-amino-imino nickel catalyst is relatively good in stability, good in tolerance to polar groups and capable of effectively controlling a microstructure of a vinyl copolymerization product to obtain the vinyl copolymer with a precise structure.
Description
Technical field
The present invention relates to a kind of neutral α-amido imines nickel catalyzator and its preparation method and application, belong to olefin catalytic polymerization field.
Background technology
Polyolefine is one of a kind of most widely used resin, and its output accounts for the over half of macromolecular material ultimate production.Because it has good processing and use properties, and low price, become the synthetic resins kind of consumption and production maximum in the world at present, be widely used in industry, agricultural, national defence, communications and transportation and daily life.Wherein, catalyzer is the core of polyolefin industry development, is the key of controlling polyolefin structure and performance.But owing to lacking functional groups in polyolefin structure, limited polyolefine material and applied widely.Therefore, introduce the functional group of polarity to improve the performance of polyolefin resin in nonpolar polyolefine, be the industry member research direction of effort for it for a long time always.
Polyolefin functional modification has three kinds of methods conventionally: i.e. directly copolymerization method, reactive group functional method and rear functional modification method.Wherein, directly copolymerization method is the most direct, optimal method, by effective copolymerization of alkene and polar monomer, just can prepare functional polyolefin with settling at one go.In addition, the functional polyolefin of different structure and composition has important impact to its performance, thereby can produce different purposes.Thereby by alkene and the direct copolymerization of polar monomer, can accurately control the structure and composition of polymkeric substance, and prepare the polyolefine of functionalization, be the focus that field of olefin polymerisation is paid close attention to always.
Industrially with ethene and some polar monomer, can under high pressure carry out radical copolymerization, but the severe reaction conditions of polymerization, what obtain is the copolymerization product of high polar monomer content, and product structure complexity is wayward.The Ziegler-Natta catalyst at early transition metal center and metallocene catalyst are because parent's electricity oxytropism of its metal center is strong; conventionally easily by the passivation of lewis base property group; adding of polar monomer easily makes the serious inactivation of catalyzer; thereby polar monomer generally must could carry out copolymerization with alkene after chemoproection or space protection, and insertion rate is low.The most outstanding feature of late transition metal catalyst growing up is in recent years a little less than its oxyphie Electron Affinities, good to polar group tolerance, thereby can, by the molecular designing of catalyst structure being realized to the copolymerization of alkene and polar monomer, prepare the controlled Functional Polyolefins of structure and composition.
Brookhart reporting alpha-diimine palladium catalyst catalyzed ethylene and acrylate (MA) copolymerization of large steric hindrance.Because acrylate is with 2, the mode of 1-is inserted palladium-alkyl (Pd-alkyl) key, after resetting, can obtain stable hexa-atomic chelate ring intermediate, continue to insert vinyl monomer, and then there is chain walking (Chain-walking) reaction, obtain the high degree of branching, polar group is at the multipolymer of a chain end.Yet the degree of branching that polymerisate is high can not provide a good mechanical property for material, and the stability of palladium catalyst is not high yet.Neutral phosphono and sulfonic palladium catalyst has shown very strong polar monomer copolymerization ability, there is copolymerization in this type of catalyzer energy catalyzed alkene and polar monomer (norbornene derivative of alkyl alkylacrylate, vinyl ether, vinyl cyanide, polar functionalities, fluoroolefins), obtains low-molecular-weight multipolymer (being conventionally less than 10,000).The neutral salicylic alidehyde imine nickel catalyzator of Grubbs reported first [N, O] can be in polar solvent norbornylene and the ethylene copolymer of catalysis polar functionalities, obtain ethylene copolymer.Neutral salicylic alidehyde imine nickel catalyzator is owing to cannot introducing the aromatic ring of large steric hindrance in its oxygen ligating atom, and large steric group just must be introduced on its ortho position, so synthesis step is loaded down with trivial details, has increased widely the synthetic difficulty of ligands and complexes.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of neutral α-amido imines nickel catalyzator.This catalyzer is synthetic simple, and can catalyzed ethylene polymerization reaction obtains the polyethylene of high molecular, narrow distribution, can also catalyzed ethylene and polar monomer copolymerization reaction obtain the ethylene copolymer of narrow distribution.
The present invention also aims to provide a kind of preparation method of above-mentioned catalyzer.
The present invention also aims to provide the application of a kind of above-mentioned catalyzer in poly synthetic and ethylene copolymer synthetic.
For achieving the above object, the invention provides a kind of neutral α-amido imines nickel catalyzator, its have suc as formula 1 or formula 2 shown in structure: R wherein
1for hydrogen, methyl, sec.-propyl or the tertiary butyl; R
2for phenyl, naphthyl or benzyl; L is trimethyl-phosphine, triphenylphosphine or pyridine;
In above-mentioned neutral α-amido imines nickel catalyzator, preferably, R
1for hydrogen, methyl or sec.-propyl; R
2for phenyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
The preparation method who the invention provides a kind of above-mentioned neutral α-amido imines nickel catalyzator, the method comprises the following steps:
A, adding KH below 0 ℃ in α-amido group with imine moiety corresponding with described catalyzer, be warming up to 20-40 ℃, reaction 8-16 hour, under the effect of KH, α-amido group with imine moiety removes the proton on amido, forms anion ligand;
B, make the precursor compound of described anion ligand and nickel under the condition of anhydrous and oxygen-free, 20-40 ℃ of reaction 8-12 hour, obtains neutral α-amido imines nickel catalyzator, reaction process as shown in Equation 3:
Preferably, R
1for hydrogen, methyl or sec.-propyl; R
2for phenyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
In above-mentioned preparation method, preferably, α-amido group with imine moiety of employing is the compound of the alpha-diimine corresponding with it to be reduced under the reductive action of trimethyl aluminium compound to one of them imine group to obtain, reaction process as shown in Equation 4:
In above-mentioned preparation method, preferably, in step c, the precursor compound of nickel is Ni (CH
2ph) Cl (P (CH
3)
3)
2and Ni (Ph) Cl (P (Ph)
3)
2time, the preparation process of neutral α-amido imines nickel catalyzator as shown in Equation 5:
In above-mentioned preparation method, preferably, the intensification in step a is to rise to 30 ℃.
The present invention also provides a kind of poly synthetic method, preferably, the method adopts the catalyzed ethylene polymerization reaction under 0-60 ℃, the condition of 1-30atm ethylene pressure of above-mentioned neutral α-amido imines nickel catalyzator, obtains polyethylene, and the reaction times is in 3 hours.The resulting polyethylene of the method is a kind of High molecular weight polyethylene.
In above-mentioned poly synthetic method, preferably, the method also adopts a promotor, and described promotor comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO) and two (ring 1,5-diene) nickel (Ni (COD)
2) in one or more combination.This promotor is that same catalyzer, solvent join in the middle of reaction system together.
The present invention also provides a kind of synthetic method of ethylene copolymer, preferably, the method adopts catalyzed ethylene and the polar monomer copolymerization reaction under 0-60 ℃, the condition of 1-30atm ethylene pressure of above-mentioned neutral α-amido imines nickel catalyzator, obtains ethylene copolymer, and the reaction times is in 3 hours.
In the synthetic method of above-mentioned ethylene copolymer, preferably, the polar monomer of employing comprises one or more the combination in the derivative of methyl methacrylate, methyl acrylate, butyl acrylate, norbornene carboxylate.
In the synthetic method of above-mentioned ethylene copolymer, preferably, the method also adopts a promotor, and described promotor comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO) and two (ring 1,5-diene) nickel (Ni (COD)
2) in one or more combination.This promotor is that same catalyzer, solvent join in the middle of reaction system together.
The synthesis material of neutral α-amido imines nickel catalyzator of the present invention is simple, operation steps is simple, and stability is better, and this catalyzer is good to the tolerance of polar group simultaneously, can effectively control the microtexture of ethylene copolymer product, obtain the accurate ethylene copolymer of structure.
Accompanying drawing explanation
Fig. 1 is the single crystal structure figure of neutral α-amido imines nickel catalyzator 1b.
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
In order concisely clearly to explain in an embodiment ligands and complexes, be described as follows:
Ligand L 1a is the amido group with imine moiety shown in formula L1, wherein R
1for sec.-propyl;
Ligand L 1b is the amido group with imine moiety shown in formula L1, wherein R
1for methyl;
Ligand L 1c is the amido group with imine moiety shown in formula L1, wherein R
1for hydrogen.
Ligand L 2a is the amido group with imine moiety shown in formula L2, wherein R
1for sec.-propyl;
Ligand L 2b is the amido group with imine moiety shown in formula L2, wherein R
1for methyl;
Ligand L 2c is the amido group with imine moiety shown in formula L2, wherein R
1for hydrogen.
Title complex 1a is the amido imines nickel compound shown in formula 1, wherein R
1for sec.-propyl, R
2for benzyl, L is trimethyl-phosphine;
Title complex 1b is the amido imines nickel compound shown in formula 1, wherein R
1for methyl, R
2for benzyl, L is trimethyl-phosphine, and the single crystal structure figure of neutral α-amido imines nickel catalyzator 1b as shown in Figure 1;
Title complex 1c is the amido imines nickel compound shown in formula 1, wherein R
1for hydrogen, R
2for benzyl, L is trimethyl-phosphine;
Title complex 1d is the amido imines nickel compound shown in formula 1, wherein R
1for sec.-propyl, R
2for phenyl, L is triphenylphosphine;
Title complex 1e is the amido imines nickel compound shown in formula 1, wherein R
1for methyl, R
2for phenyl, L is triphenylphosphine;
Title complex 1f is the amido imines nickel compound shown in formula 1, wherein R
1for hydrogen, R
2for phenyl, L is triphenylphosphine.
Title complex 2a is the amido imines nickel compound shown in formula 2, wherein R
1for sec.-propyl, R
2for benzyl, L is trimethyl-phosphine;
Title complex 2b is the amido imines nickel compound shown in formula 2, wherein R
1for methyl, R
2for benzyl, L is trimethyl-phosphine;
Title complex 2c is the amido imines nickel compound shown in formula 2, wherein R
1for hydrogen, R
2for benzyl, L is trimethyl-phosphine;
Title complex 2d is the amido imines nickel compound shown in formula 2, wherein R
1for sec.-propyl, R
2for phenyl, L is triphenylphosphine;
Title complex 2e is the amido imines nickel compound shown in formula 2, wherein R
1for methyl, R
2for phenyl, L is triphenylphosphine;
Title complex 2f is the amido imines nickel compound shown in formula 2, wherein R
1for hydrogen, R
2for phenyl, L is triphenylphosphine.
The preparation of alpha-diimine compound:
The preparation of alpha-diimine compound, according to the report method preparation of document, is carried out not alkali reaction of seat with dimethyl diketone compound, acenaphthenequinone compound and corresponding arylamine, and product ethyl alcohol recrystallization slightly obtains the compound of diimine.
The preparation of α-amido imine ligand:
Embodiment 1
Synthetic α-amido imine ligand L1a, specifically carries out according to following steps:
To reflux condensing tube is housed, the 100mL of nitrogen atmosphere protection props up in mouthful bottle and adds 3.24g (8mmol) alpha-diimine compd A 1 (sec.-propyl replacement), then add successively 10mL toluene, 4.0mL (2.0M, 8mmol) trimethyl aluminium, at 100 ℃, stirring reaction is 6 hours;
After cooling, with sodium hydroxide/frozen water solution termination reaction, separatory, be extracted with ethyl acetate 3 times, merge organic phase, add anhydrous magnesium sulfate drying, filter, filtrate is removed after most of solvent, naturally volatilization crystallization, thick product ethyl alcohol recrystallization, obtains 2.47g clear crystal, be α-amido imine ligand L1a, its productive rate is 73.4%.
1H?NMR(CDCl
3,500MHz)：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,CH
3)、1.36(s,6H,CH
3)、1.21-1.18(m,24H,CH
3)。
13C?NMR(CDCl
3,125MHz):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。
Ultimate analysis (C
29h
44n
2, %) theoretical value: C:82.80, H:10.54, N:6.66.Measured value: C:82.96, H:10.33, N:6.68.
Embodiment 2
Synthetic α-amido imine ligand L1b, specifically carries out according to following steps:
Press the synthetic method of ligand L 1a in embodiment 1, with alpha-diimine compd A 2 (methyl substituted), replace compd A 1, other operational conditions, with embodiment 1, obtain 1.02g clear crystal after reaction finishes, be α-amido imine ligand L1b, its productive rate is 66.3%.
1H?NMR(CDCl
3,500MHz)：7.03(t,4H,Ph)、6.90(t,2H,Ph)、4.48(s,1H,NH)、2.37(s,6H,CH
3)、2.05(s,6H,CH
3)、1.87(s,3H,CH
3)、1.43(s,6H,CH
3)。
13C?NMR(CDCl
3,125MHz)：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。
Ultimate analysis (C
21h
28n
2, %) theoretical value: C:81.77, H:9.15, N:9.08.Measured value: C:82.06, H:9.23, N:9.20.
Embodiment 3
Synthetic α-amido imine ligand L1c, specifically carries out according to following steps:
Press the synthetic method of ligand L 1a in embodiment 1, with alpha-diimine compound A-13 (unsubstituted), replace compd A 1, other operational conditions, with embodiment 1, obtain 2.37g clear crystal after reaction finishes, be α-amido imine ligand L1c, its productive rate is 94%.
1H?NMR(CDCl
3,500MHz)：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,CH
3)、1.58(s,6H,CH
3)。
13C?NMR(CDCl
3,125MHz)：176.95、151.54、146.18、129.09、128.96、123.04、118.73、117.39、114.14、59.37、26.32、14.89。
Ultimate analysis (C
17h
20n
2, %) theoretical value: C:80.91, H:7.99, N:11.10.Measured value: C:80.96, H:7.86, N:11.25.
Embodiment 4
Synthetic α-amido imine ligand L2a, specifically carries out according to following steps:
To reflux condensing tube is housed, the 100mL of nitrogen atmosphere protection props up in mouthful bottle and takes 6.0g (12mmol) alpha-diimine compd A 4 (sec.-propyl replacement), then add successively 30mL toluene, 6.0mL (2.0M, 12mmol) trimethyl aluminium, at 110 ℃, stirring reaction, after 4 hours, is cooled to 60 ℃ of stirring reactions and spends the night;
After cooling, with sodium hydroxide/frozen water solution termination reaction, separatory, be extracted with ethyl acetate 3 times, merge organic phase, add anhydrous magnesium sulfate drying, filter, filtrate is removed after most of solvent, naturally volatilization crystallization, thick product ethyl alcohol recrystallization, obtains 5.24g pale yellow crystals, be α-amido imine ligand L2a, its productive rate is 84.5%.
1H?NMR(CDCl
3,500MHz)：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,CH
3)、1.26(d,3H,CH
3)、1.18(d,3H,CH
3)、1.09(s,6H,CH
3)、0.95(t,6H,CH
3)、0.59(s,6H,CH
3)。
13C?NMR(CDCl
3,125MHz)：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。
Ultimate analysis (C
37h
44n
2, %) theoretical value: C:86.00, H:8.58, N:5.42.Measured value: C:86.06, H:8.56, N:5.35.
Embodiment 5
Synthetic α-amido imine ligand L2b, specifically carries out according to following steps:
Press the synthetic method of ligand L 2a in embodiment 4, with alpha-diimine compound A-45 (methyl substituted), replace compd A 4, other operational conditions, with embodiment 4, obtain amido imine ligand L2b after reaction finishes.
1H?NMR(CDCl
3,500MHz)：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,CH
3)、2.02(s,3H,CH
3)、1.94(s,3H,CH
3)、1.88(s,6H,CH
3)。
13C?NMR(CDCl
3,125MHz)：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。
Ultimate analysis (C
29h
28n
2, %) theoretical value: C:86.10, H:6.98, N:6.92.Measured value: C:86.16, H:6.85, N:6.95.
Embodiment 6
Synthetic α-amido imine ligand L2c, specifically carries out according to following steps:
Press the synthetic method of ligand L 2a in embodiment 4, with alpha-diimine compd A 6 (unsubstituted), replace compd A 4, other operational conditions, with embodiment 4, obtain amido imine ligand L2c after reaction finishes.
1H?NMR(CDCl
3,500MHz)：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(CDCl
3,125MHz)：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。
Ultimate analysis (C
25h
20n
2) theoretical value: C:86.17, H:5.79, N:8.04.Measured value: C:86.42, H:5.84, N:8.00.
Synthesizing of α-amido imine nickel complex:
Embodiment 7
Synthetic α-amido imine nickel complex 1a, specifically carries out according to following steps:
Under nitrogen atmosphere, to weighing and add 0.63g (1.50mmol) α-amido imine ligand L1a in the Schlenk bottle with stirrer, be injected into 20mL anhydrous tetrahydro furan and then at 0 ℃, add 80mg KH (2mmol), slowly be warming up to stirring at normal temperature 12 hours, with core filter ball, remove after insolubles, vacuum-evaporation, except desolventizing, adds 20mL dichloromethane solvent to dissolve, and then adds 0.33g Ni (CH
2ph) Cl (P (CH
3)
3)
2compound, reaction is spent the night, and filters, and filtrate vacuum concentration is to 5mL, squeeze into 20mL normal hexane again title complex is precipitated out, with core filter ball, filter, vacuum is drained, obtain the blackish green pulverulent solids of 0.63g, i.e. α-amido imine nickel complex 1a, its productive rate is 65%.
1H?NMR(500MHz,C
6D
6)：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,CH
2)、3.25(sp,2H,CH(Me
3)
2)、2.93(sp,2H,CH(Me
3)
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(CH
3)
2)、0.80(s,3H,Me)。
31P?NMR(203MHz,C
6D
6)：-36.0。
Ultimate analysis (C
39h
59n
2niP) theoretical value: C:72.56, H:9.21, N:4.34.Measured value: C:72.40, H:9.18, N:4.35.
Embodiment 8
Synthetic α-amido imine nickel complex 1b, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L1b replaces L1a, and other operational conditions, with embodiment 7, obtain amido imine nickel complex 1b after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
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)、0.80(s,3H,Me)。
31P?NMR(203MHz,C
6D
6)：-35.8。
Ultimate analysis (C
31h
43n
2niP) theoretical value: C:69.81, H:8.13, N:5.25.Measured value: C:69.75, H:8.24, N:5.53.
Embodiment 9
Synthetic α-amido imine nickel complex 1c, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L1c replaces L1a, and other operational conditions, with embodiment 7, obtain amido imine nickel complex 1c after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
2)、1.08(s,9H,Me)。
31P?NMR(203MHz,C
6D
6)：-36.5。
Ultimate analysis (C
27h
35n
2niP) theoretical value: C:67.95, H:7.39, N:5.87.Measured value: C:67.35, H:7.02, N:5.93.
Embodiment 10
Synthetic α-amido imine nickel complex, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with Ni (Ph) Cl (P (Ph)
3)
2replace Ni (CH
2ph) Cl (P (CH
3)
3)
2, other operational conditions, with embodiment 7, obtain amido imine nickel complex 1d after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
2)、3.25(sp,2H,CH(Me
3)
2、2.93(sp,2H,CH(Me
3)
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(CH
3)
2)。
31P?NMR(203MHz,C
6D
6)：24.3。
Ultimate analysis (C
53h
63n
2niP) theoretical value: C:77.84, H:7.77, N:3.43.Measured value: C:77.68, H:7.82, N:5.36.
Embodiment 11
Synthetic α-amido imine nickel complex 1e, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L1b replaces L1a, with Ni (Ph) Cl (P (Ph)
3)
2replace Ni (CH
2ph) Cl (P (CH
3)
3)
2, other operational conditions, with embodiment 7, obtain amido imine nickel complex 1e after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,C
6D
6)：23.9。
Ultimate analysis (C
45h
47n
2niP) theoretical value: C:76.61, H:6.71, N:3.97.Measured value: C:76.49, H:6.69, N:4.02.
Embodiment 12
Synthetic α-amido imine nickel complex 1f, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L1c replaces L1a, with Ni (Ph) Cl (P (Ph)
3)
2replace Ni (CH
2ph) Cl (P (CH
3)
3)
2, other operational conditions, with embodiment 7, obtain amido imine nickel complex 1f after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,C
6D
6)：25.4。
Ultimate analysis (C
41h
39n
2niP) theoretical value: C:75.38, H:6.05, N:4.31.Measured value: C:75.61, H:6.14, N:4.17.
Embodiment 13
Synthetic α-amido imine nickel complex 2a, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2a replaces L1a, and other operational conditions, with embodiment 7, obtain amido imines nickel 2a after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
2),3.19-3.01(m,4H,CH(
iPr)
2)、1.96(s,3H,CH
3)、1.26(d,3H,CH
3)、1.18(d,3H,CH
3)、1.09(s,6H,CH
3)、0.80(s,9H,Me)，0.95(t,6H,CH
3)、0.59(s,6H,CH
3)。
31P?NMR(203MHz,C
6D
6)：-35.4。
Ultimate analysis (C
47h
59n
2niP) theoretical value: C:76.11, H:8.02, N:3.78.Measured value: C:76.35, H:8.01, N:3.54.
Embodiment 14
Synthetic α-amido imine nickel complex 2b, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2b replaces L1a, and other operational conditions, with embodiment 7, obtain amido imine nickel complex 2b after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
2),1.92(s,3H,CH
3)、1.22(d,3H,CH
3)、1.14(d,3H,CH
3)、1.08(s,6H,CH
3)、0.81(s,9H,Me)。
31P?NMR(203MHz,C
6D
6)：-36.5。
Ultimate analysis (C
39h
43n
2niP) theoretical value: C:74.42, H:6.89, N:4.45.Measured value: C:74.68, H:6.86, N:4.25.
Embodiment 15
Synthetic α-amido imine nickel complex 2c, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2c replaces L1a, and other operational conditions, with embodiment 7, obtain amido imine nickel complex 2c after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
2),1.90(s,3H,CH
3)、1.20(d,3H,CH
3)、1.13(d,3H,CH
3)、1.09(s,6H,CH
3)、0.78(s,9H,Me)。
31P?NMR(203MHz,C
6D
6)：-37.1。
Ultimate analysis (C
35h
35n
2niP) theoretical value: C:73.32, H:6.15, N:4.89.Measured value: C:73.64, H:6.36, N:4.60.
Embodiment 16
Synthetic α-amido imine nickel complex 2d, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2a replaces the L1a in embodiment 7, with Ni (Ph) Cl (P (Ph)
3)
2replace the Ni (CH in embodiment 7
2ph) Cl (P (CH
3)
3)
2, other operational conditions are identical with the operational condition in embodiment 7, and the product obtaining after reaction finishes is amido imine nickel complex 2d.
1H?NMR(500MHz,C
6D
6)：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,CH
3)、1.22(d,3H,CH
3)、1.17(d,3H,CH
3)、1.04(s,6H,CH
3)、0.92(t,6H,CH
3)、0.55(s,6H,CH
3)。
31P?NMR(203MHz,C
6D
6)：24.6。
Ultimate analysis (C
61h
63n
2niP) theoretical value: C:80.17, H:6.95, N:3.07.Measured value: C:80.29, H:7.05, N:2.93.
Embodiment 17
Synthetic α-amido imine nickel complex 2e, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2b replaces L1a, with Ni (Ph) Cl (P (Ph)
3)
2replace Ni (CH
2ph) Cl (P (CH
3)
3)
2, other operational conditions, with embodiment 7, obtain amido imine nickel complex 2e after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
3)、1.22(d,3H,CH
3)、1.14(d,3H,CH
3)、1.08(s,6H,CH
3)。
31P?NMR(203MHz,C
6D
6)：25.2。
Ultimate analysis (C
53h
47n
2niP) theoretical value: C:79.41, H:5.91, N:3.49.Measured value: C:79.65, H:6.08, N:3.41.
Embodiment 18
Synthetic α-amido imine nickel complex 2f, specifically carries out according to following steps:
Press the synthetic method of α-amido imine nickel complex 1a in embodiment 7, with α-amido imine ligand, L2c replaces L1a, with Ni (Ph) Cl (P (Ph)
3)
2replace Ni (CH
2ph) Cl (P (CH
3)
3)
2, other operational conditions, with embodiment 7, obtain amido imine nickel complex 2f after reaction finishes.
1H?NMR(500MHz,C
6D
6)：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,CH
3)、1.18(d,3H,CH
3)、1.11(d,3H,CH
3)、1.05(s,6H,CH
3)。
31P?NMR(203MHz,C
6D
6)：26.8。
Ultimate analysis (C
49h
39n
2niP) theoretical value: C:78.94, H:5.27, N:3.76.Measured value: C:79.07, H:5.43, N:3.52.
Ethylene homo experiment
Embodiment 19
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, add α-amido imine nickel complex 1a, 100mL dry toluene, the 2mmol modified methylaluminoxane of 6.44mg (10 μ mol) embodiment 7 preparation, under 20 ℃, 5atm ethylene pressure, polymerization is 1 hour;
Reaction stops with 200mL ethanol solution hydrochloride, and the product obtaining after ethanol solution hydrochloride stops is filtered, and obtains after filtering polymkeric substance, and by polymkeric substance use washing with alcohol 3 times, vacuum-drying at 60 ℃, obtains 1.35g ethene polymers.
Above-mentioned polyvinyl catalytic activity is that 135.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 126.0kg/mol, polydispersity coefficient are 1.36.
Embodiment 20
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 1b, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.05g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 105.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 76.0kg/mol, polydispersity coefficient are 1.54.
Embodiment 21
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 1c, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 0.76g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 76.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 12.0kg/mol, polydispersity coefficient are 1.87.
Embodiment 22
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 1d, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.24g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 124.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 119.0kg/mol, polydispersity coefficient are 1.35.
Embodiment 23
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 1e, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.01g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 101.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 73.0kg/mol, polydispersity coefficient are 1.56.
Embodiment 24
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 1f, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 0.65g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 65.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 11.0kg/mol, polydispersity coefficient are 1.89.
Embodiment 25
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2a, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.74g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 174kg PE/ (molNih), polymkeric substance number-average molecular weight are that 162.0kg/mol, polydispersity coefficient are 1.41.
Embodiment 26
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2b, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.47g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 147.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 98.0kg/mol, polydispersity coefficient are 1.52.
Embodiment 27
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2c, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 0.62g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 62.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 28.0kg/mol, polydispersity coefficient are 1.92.
Embodiment 28
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2d, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.68g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 168.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 158.0kg/mol, polydispersity coefficient are 1.44.
Embodiment 29
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2e, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 1.32g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 132.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 96.0kg/mol, polydispersity coefficient are 1.54.
Embodiment 30
The present embodiment provides a kind of preparation method of Alathon, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2f, replace α-amido imine nickel complex 1a, other polymerizing condition, with embodiment 19, obtains 0.48g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 48.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 19.0kg/mol, polydispersity coefficient are 2.12.
Ethylene copolymer experiment
Embodiment 31
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
Under ethene atmosphere, in the polymerization bottle of 100mL, α-amido imine nickel complex the 1a, 100mL dry toluene, 4mmol methyl acrylate, the 2mmol modified methylaluminoxane that add 10 μ mol embodiment 7 preparations, under 20 ℃, 5atm ethylene pressure, polymerization is 1 hour.
Reaction stops with 200mL ethanol solution hydrochloride, filters, and washing with alcohol 3 times for polymkeric substance, vacuum-drying at 60 ℃, obtains 0.64g ethene polymers.
Above-mentioned polyvinyl catalytic activity is that 64.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 47.0kg/mol, polydispersity coefficient are 1.36, polar monomer insertion rate is 0.73mol%.
Embodiment 32
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With the methyl methacrylate of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.38g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 38.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 34.0kg/mol, polydispersity coefficient are 1.41, polar monomer insertion rate is 0.52mol%.
Embodiment 33
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With the butyl acrylate of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.58g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 58.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 42.0kg/mol, polydispersity coefficient are 1.50, polar monomer insertion rate is 0.61mol%.
Embodiment 34
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With 5-norbornylene-2-carboxylate methyl ester of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.40g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 40.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 29.0kg/mol, polydispersity coefficient are 1.43, polar monomer insertion rate is 0.82mol%.
Embodiment 35
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
After finishing with 10 μ mol α-amido imine nickel complex 2a, the identical embodiment 31 of other polymerizing condition, reaction, obtain 0.78g ethene polymers.
Above-mentioned polyvinyl catalytic activity is that 78.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 71.0kg/mol, polydispersity coefficient are 1.32, polar monomer insertion rate is 0.81mol%.
Embodiment 36
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2a, replace α-amido imine nickel complex 1a, with the methyl methacrylate of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.48g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 48.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 35.0kg/mol, polydispersity coefficient are 1.39, polar monomer insertion rate is 0.64mol%.
Embodiment 37
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2a, replace α-amido imine nickel complex 1a, with the butyl acrylate of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.62g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 62.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 55.0kg/mol, polydispersity coefficient are 1.38, polar monomer insertion rate is 0.74mol%.
Embodiment 38
The present embodiment provides a kind of preparation method of ethylene copolymer, and it comprises the following steps:
With 10 μ mol α-amido imine nickel complex 2a, replace α-amido imine nickel complex 1a, with 5-norbornylene-2-carboxylate methyl ester of 4mmol, replace methyl acrylate, other polymerizing condition, with embodiment 31, obtains 0.51g ethene polymers after reaction finishes.
Above-mentioned polyvinyl catalytic activity is that 51.0kg PE/ (molNih), polymkeric substance number-average molecular weight are that 34.0kg/mol, polydispersity coefficient are 1.46, polar monomer insertion rate is 1.14mol%.
Claims (9)
1. neutral α-amido imines nickel catalyzator, its have suc as formula 1 or formula 2 shown in structure: R wherein
1for hydrogen, methyl, sec.-propyl or the tertiary butyl; R
2for phenyl, naphthyl or benzyl; L is trimethyl-phosphine, triphenylphosphine or pyridine;
2. catalyzer according to claim 1, wherein, R
1for hydrogen, methyl or sec.-propyl; R
2for phenyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
3. the preparation method of the neutral α-amido imines nickel catalyzator described in claim 1 or 2, the method comprises the following steps:
A, adding KH below 0 ℃ in α-amido group with imine moiety corresponding with described catalyzer, be warming up to 20-40 ℃, reaction 8-16 hour, under the effect of KH, α-amido group with imine moiety removes the proton on amido, forms anion ligand;
B, make the precursor compound of described anion ligand and nickel under the condition of anhydrous and oxygen-free, at 20-40 ℃ of reaction 8-12 hour, obtain neutral α-amido imines nickel catalyzator, reaction process as shown in Equation 3:
Wherein, R
1for hydrogen, methyl or sec.-propyl; R
2for phenyl or benzyl; L is trimethyl-phosphine or triphenylphosphine.
4. preparation method according to claim 3, wherein, the intensification in step a is to rise to 30 ℃.
5. a poly synthetic method, wherein, the method adopts neutral α-amido imines nickel catalyzator as claimed in claim 1 or 2 catalyzed ethylene polymerization reaction under 0-60 ℃, the condition of 1-30atm ethylene pressure, obtains polyethylene, and the reaction times is in 3 hours.
6. synthetic method according to claim 5, wherein, the method also adopts a promotor, and described promotor comprises one or more the combination in methylaluminoxane, modified methylaluminoxane and two (ring 1,5-diene) nickel.
7. the synthetic method of an ethylene copolymer, wherein, the method adopts neutral α-amido imines nickel catalyzator as claimed in claim 1 or 2 catalyzed ethylene and polar monomer copolymerization reaction under 0-60 ℃, the condition of 1-30atm ethylene pressure, obtain ethylene copolymer, the reaction times is in 3 hours.
8. synthetic method according to claim 7, wherein, the polar monomer that the method adopts comprises one or more the combination in the derivative of methyl methacrylate, methyl acrylate, butyl acrylate, norbornene carboxylate.
9. according to the synthetic method described in claim 7 or 8, wherein, the method also adopts a promotor, and described promotor comprises one or more the combination in methylaluminoxane, modified methylaluminoxane and two (ring 1,5-diene) nickel.
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