CN107641138A - For ethene and the asymmetric α diimine nickels containing the substitution of ortho position benzhydryl of 1 hexene oligomerization（Ⅱ）Complex - Google Patents
For ethene and the asymmetric α diimine nickels containing the substitution of ortho position benzhydryl of 1 hexene oligomerization（Ⅱ）Complex Download PDFInfo
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Abstract
The invention discloses the asymmetric α diimine nickels of a kind of new ortho position benzhydryl substitution for being used for ethene and 1 hexene oligomerization（Ⅱ）Complex, change the coordination environment of metal center, three-dimensional effect and electron density by changing part, the final activity adjusted in ethene and 1 hexene oligomerization simultaneously controls the microstructure of polymer.Under the activation of co-catalyst diethylaluminum chloride, such complex-catalyzed vinyl polymerization has higher heat endurance and catalytic activity, and has obtained the polyethylene of HMW low polydispersity.Space bit by changing complex helps the molecular weight that catalytic activity and polymer can be effectively runed with polymerizing condition, decentralization, the degree of branching and hot property.The catalyst system is also used for the chain walking polymerization for being catalyzed the hexene of long-chain 1, operation can be good at by the change of complex steric hindrance and polymerization temperature and obtain catalytic activity and the performance of polymer, and the steric hindrance for increasing catalyst is advantageous to the 2 of 1 hexene, 1 insertion.
Description
Technical field
The invention belongs to technical field of macromolecules, is related to a kind of chain walking olefinic polymerization late transition metal catalyst, especially
It is related to a kind of asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position diphenyl；Also relate to such complex
Preparation method and its application in ethene and 1- hexene oligomerizations.
Background technology
Polyolefin is the maximum synthetic resin of consumption figure, and polyethylene is most important polyolefin, is largely improved
Daily life.The research and development of new olefine polymerization catalyst have served critical to synthesis high-performance polymer.
Most recent two decades, transition Ni (II) and Pd (II) olefin polymerization catalysis cause section after chain walking alpha-diimine
Scholars widely pay close attention to.Because this kind of catalyst all has unique chain walking property, central metal atom electrophilicity is weak,
Resistance to hetero atom ability is strong, so such catalyst can be not only used for the homogeneous polymerization of ethene, it may also be used for alkene and polarity list
The copolymerization of body, so as to produce the Functional Polyolefins of excellent performance.But the late transition metal olefin catalytic of early stage
Agent stability is poor, is easily lost activity under high temperature.
The content of the invention
Match somebody with somebody it is an object of the invention to provide one kind containing the asymmetric alpha-diimine nickel (II) that ortho position benzhydryl substitutes
Compound.
Another mesh of the present invention is to be to provide above-mentioned asymmetric alpha-diimine nickel (II) complex containing ortho position substitution
For being catalyzed ethene and the walking polymerization of 1- hexenes chain.Under the activation of diethylaluminum chloride, by the space bit for changing complex
Resistance and polymerizing condition (such as ethylene pressure and polymerization temperature) can effectively run the structure and property of catalytic activity and polymer
Energy.
(1) asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl
Asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl that the present invention designs, its structure
It is as follows：
Wherein, R isiPr、Me、H。
The complex of the present invention is to introduce a large volume benzhydryl base at the ortho position of side imine nitrogen atom aromatic ring
Group.Because benzhydryl has larger volume, can effectively guard catalyst metal center, add in ground state activity
Unstability, the process of ethylene insertion is accelerated, so as to improve the activity of catalyst.Meanwhile the space effect of bulky ligand
Transfer rate of the living chain to monomer should be greatly reduced, so as to obtain heavy polymer.In 1- hexene oligomerizations,
The molecular weight of catalytic activity and polymer can be effectively runed by the three-dimensional effect and polymerization temperature that change catalyst, point
Divergence and microcosmic branched structure.
(2) preparation of asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl
The preparation side of asymmetric alpha-diimine nickel (II) complex of the present invention containing the substitution of ortho position benzhydryl
Method, comprise the following steps that：
(1) preparation of the asymmetric alpha-diimine part containing the substitution of ortho position benzhydryl：
By 4- methyl -2,6- benzhydryls aniline with excessive diacetyl with 1:1.5~1:2.0 mixed in molar ratio, with
Toluene is solvent, and the p-methyl benzenesulfonic acid (TsOH) for adding 0.05 times of 4- methyl -2,6- benzhydryl aniline moles is catalyzed
Agent, flowed back at 80~115 DEG C after reaction overnight, rotate solvent and excessive diacetyl, obtain crude product, then use again
C2H5OH washs to obtain the single ketones of the ortho position benzhydryl substitution of yellow crystal.
By the single ketones that above-mentioned ortho position benzhydryl substitutes from different aniline with 1:1.2~1:1.5 mixed in molar ratio,
Using toluene as solvent, the p-methyl benzenesulfonic acid (TsOH) for adding 0.05 times of aniline moles makees catalyst, at 80~115 DEG C
After back flow reaction 12~24 hours, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2Mixed solvent recrystallization analysis
Go out solid precipitation, filtration drying obtains yellow part.
(2) preparation of asymmetric alpha-diimine nickel (II) catalyst containing the substitution of ortho position benzhydryl:
Under nitrogen protection, using dichloromethane as solvent, asymmetric α-diimine for will substituting containing ortho position benzhydryl
Part and the nickelous bromide [NiBr activated by glycol dimethyl ether2(DME)] with 1:0~1:1.2 mixed in molar ratio, in room temperature
Lower stirring reaction filters suspension, after mother liquor removes solvent under vacuum, washed with ether, vacuum after 12~24 hours
Dry, obtain brown powder solid complexes.
Above-mentioned synthesis type is as follows：
Wherein, R isiPr、Me、H。
Product prepared by the above method uses U.S.'s Mercury-400plus nuclear magnetic resonance through NMR spectrum (NMR)
Instrument；The type X- single crystal diffractometers of Bruker companies APEX CCD II；Elementary analysis is using instruments such as Vario.EL type elemental analysers
Measure, it was demonstrated that the product of synthesis with design compound structure it is consistent.
(3) asymmetric alpha-diimine nickel (II) complex answering in vinyl polymerization containing the substitution of ortho position benzhydryl
With
The present invention relates to asymmetric alpha-diimine nickel (II) complex-catalyzed vinyl polymerization, because the catalyst is in Asia
The aromatic ring ortho position of amine side nitrogen connection introduces big steric hindrance benzhydryl group, is effectively improved catalyst metals center electron
Density and the space steric effect around metal center is increased, therefore such complex has high stability.In co-catalysis
Agent diethylaluminum chloride (Et2AlCl under activation), the complex-catalyzed vinyl polymerization of such nickel has higher activity.
Under low temperature, the catalyst of big steric hindrance is more beneficial for slow chain walking polymerising ethylene and obtains more lightly branched polyethylene.
Experimental results demonstrate in ethylene polymerization, by complex and co-catalyst diethylaluminum chloride with 1:200
~1:1000 mol ratio composition composite catalyst system, reaction temperature is 0~80 DEG C, and the reaction time is 5~30 minutes, catalysis
When agent dosage is 10~400 μm of ol/L, catalyzed ethylene polymerization, the polymer of HMW is obtained.The catalyst system and catalyzing is catalyzed ethene
There is higher catalytic activity (can reach 10 for polymerization6G PE/ (mol Ni h), obtain the polyethylene of HMW have it is low
The degree of branching (up to 57 side chain/1000C).
(4) asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl is in 1- hexene oligomerizations
Using
When being catalyzed alpha-olefine polymerizing, monomer insertion metal center has 1,2- and 2, two kinds of inserted modes of 1-.Generation 2,1- is inserted
After entering, multistep chain walking is carried out along with β-H successive elimination and metal center, obtains methylene sequences (ω, the 1- of line style
Chaining).After 1,2- insertions occur, walked along with further chain, obtain the sequence (ω, 2- chaining) containing methyl branch.
However, metal center always obtains the sequence of alkyl branches with 1,2- insertions (no chain is walked).In the polymerization, monomer
Inserted mode and chain walking path are largely influenceed by complex structure and polymerizing condition.The present invention relates to new
The research of catalyst 1- hexenes chain walking polymerization processed.
Experimental results demonstrate, in the chain walking polymerization of catalysis 1- hexenes, complex and co-catalyst diethylaluminum chloride
(Et2AlCl) with 1:500 mol ratio composition composite catalyst system, the concentration of 1- hexenes is 1mol/L, and reaction temperature control exists
20~80 DEG C, the reaction time, when the dosage of catalyst is 10 μm of ol, catalyst system and catalyzing catalysis 1- hexene oligomerizations all had at 3 hours
There is higher catalytic activity, obtained the branch polymer of HMW.
Beneficial effect：Because such asymmetric catalyst is in the big steric hindrance two of the aromatic ring ortho position that imines side nitrogen connects introducing
Benzyl group, it is effectively improved catalyst metals center electron density and increases the steric hindrance around metal center
Effect, therefore such complex has high stability.Can be fine by the change of complex steric hindrance and polymerization temperature
Operation obtain catalytic activity and the performance (such as molecular weight, decentralization and microcosmic branched structure) of polymer, and increase catalysis
The steric hindrance of agent is advantageous to the 2,1- insertions of 1- hexenes.
Brief description of the drawings
Fig. 1 is the single crystal diffraction figure of alpha-diimine nickel (II) complex prepared by the embodiment of the present invention 1.
Fig. 2 is the single crystal diffraction figure of alpha-diimine nickel (II) complex prepared by the embodiment of the present invention 2.
Fig. 3 is ethene of the present invention and 1- hexenes alpha-diimine nickel (II) complex polymerisation process sketch.
Embodiment
The asymmetric alpha-diimine nickel (II) substituted below by specific embodiment to the present invention containing ortho position benzhydryl
The preparation of complex is described further.
The raw material and reagent used in embodiment：All Organometallic Reac- tions are all in N2Protection is lower to be carried out, and solvent is through dry
Dry deoxygenation processing, dichloromethane are usedIn N after molecular sieve is predrying2Through CaH under atmosphere2Backflow, is steamed before use.Toluene passes through
Nitrogen protection is lower after molecular sieve dehydration adds metallic sodium backflow, is steamed before use.High-purity N2Done with vinyl monomer using preceding deoxygenation
It is dry.1- hexenes are dry by calcium hydride and distillation obtains.Absolute methanol, ethanol (analysis is pure), are directly used.DME (1,2- bis-
Ethyl Methyl Ether) (analysis is pure), useMolecular sieve drying.Benzhydryl alcohol, diacetyl, aniline, 2,6- dimethylanilines, 2,
6- diisopropyl anilines, diethylaluminum chloride (Et2AlCl, 0.9M toluene solution), it is Aldrich product.
NiBr2(DME) preparation method is：Under nitrogen protection, anhydrous nickelous bromide be dissolved in absolute ethyl alcohol be back to it is molten
Liquid is dark green, drains filtrate after filtering, then 1,2- dimethoxy-ethanes and primitive nail triethylenetetraminehexaacetic acid vinegar as a solvent is (abundant in advance
The solvent to have flowed back is stirred) add, return stirring 24h, there is yellow solid precipitation.Concentration of reaction solution, removal of solvent under reduced pressure.
After residual solvent cooling, upper solution is removed, 1, the 2- dimethoxy-ethanes 10mL that the product of institute is dry soaks, washed, and removes
Solvent is gone to obtain powder orange/yellow solid NiBr2(DME)。
Embodiment 1：
(1) preparation of asymmetric alpha-diimine part：
By 4- methyl -2,6- benzhydryls aniline with excessive diacetyl with 1:1.5 mixed in molar ratio, using toluene as
Solvent, the p-methyl benzenesulfonic acid (TsOH) for adding 0.05 times of 4- methyl -2,6- benzhydryl aniline moles make catalyst, in
Flowed back at 105 DEG C after reaction overnight, rotate solvent and excessive diacetyl, obtain crude product, then use C again2H5OH is washed
To yellow solid, the single ketones of ortho position benzhydryl substitution.Yield is 89%.
By the single ketones that above-mentioned ortho position benzhydryl substitutes with 2,6- diisopropyl anilines with 1:1.2 mixed in molar ratio, with
Toluene is solvent, and the p-methyl benzenesulfonic acid (TsOH) for adding 0.05 times of aniline moles makees catalyst, is flowed back at 105 DEG C anti-
After answering 20 hours, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2Mixed solvent recrystallization separates out solid precipitation,
Filtration drying obtains yellow part 0.54g.Yield is 81%.
Its reaction equation is as follows：
(2) synthesis of complex：Under nitrogen protection, above-mentioned part is added in the reaction tube dried to 100mL
(0.67g, 1.0mmol), adds NiBr2(DME) (0.34g, 1.1mmol) and dichloromethane 30mL, it is stirred at room temperature anti-
Answer 12 hours, filter suspension, mother liquor removes solvent under vacuo, and residue is washed three times with ether (3 × 16mL), vacuum
Brown solid powder 0.75g is obtained after drying.Yield is 93%.
Anal.Calcd for(C49H50Br2N2Ni):C,66.47；H,5.69；N,3.16.Found:C, 66.79；H,
5.60；N,3.45.MALDI-TOF-MS(m/z):calcd for C49H50BrN2Ni: 803.2511,found:803.1885
[M-Br]+.
Its reaction equation is as follows：
(3) vinyl polymerization：By the 250mL polymerization bottles vacuum with magnetic stick-nitrogen circulation displacement three times, in nitrogen
Under atmosphere, 20mL toluene solutions are added, then are passed through ethene, ethene is fully absorbed up to saturation, then with graduated note
Emitter is by co-catalyst diethylaluminum chloride (Et2AlCl) (3.3mL, 0.9M, n (Al)/n (Ni)=600) adds reaction bulb
In, design temperature is after 50 DEG C and maintenance reaction temperature stir 10 minutes, is added through syringe above-mentioned containing nickel complex
CH2Cl2Solution (2.4 μm of ol, 2mL), regulation ethene intake make the pressure of polymerization system maintain 9.0atm.At 50 DEG C,
After ethylene polymerization is carried out 30 minutes, acidified methanol (methanol/HCl=50/1) terminating reaction is added.Add 100mL
Methanol vibrates, and is settled out polymerizate.Precipitation filters after standing 24 hours, is fully washed with absolute methanol, 50 DEG C of vacuum are done
Dry 48 hours, polyethylene 2.89g is obtained, activity is 2.41 × 106g PE/(mol Ni h)。
(4) polyethylene product obtained is analyzed through nuclear-magnetism (NMR), gel permeation chromatography (GPC) and differential thermal analysis (DSC),
At 50 DEG C, the polyethylene of the HMW containing side chain is obtained, the degree of branching is 84 side chain/1000C, weight average molecular weight 8.1
×105g mol-1, molecular weight distribution 1.50.At 0 DEG C, polymer (the fusing point T of semicrystalline has been obtainedm=88 DEG C), it is branched
Spend for 57 side chain/1000C.
(5) long-chain 1- hexene oligomerizations：At room temperature, dried 50mL reaction tube vacuum nitrogen gas is replaced three
It is secondary, toluene (15mL), 1- hexenes (1M), diethylaluminum chloride (Et are sequentially added under nitrogen protection2AlCl, 3.3mL, 0.9M,
N (Al)/n (Ni)=300), design temperature is after 20 DEG C and maintenance reaction are stirred 10 minutes, then adds above-mentioned contain with syringe
The CH of nickel complex2Cl2Solution (10 μm of ol, 2mL), after polymerisation is carried out 3 hours, add 5% acidified methanol solution
(30mL) terminating reaction, vibration are settled out polymerizate.Filtering precipitate, fully washed with absolute methanol, 50 DEG C of vacuum drying
12 hours, waxy polymer 0.84g is obtained, activity is 2.80 × 104g PE/(mol Ni h).The weight for obtaining branch polymer is equal
Molecular weight is 3.16 × 104g mol-1, molecular weight distribution 2.14
Embodiment 2
(1) synthesis of complex：Under nitrogen protection, added in the reaction tube dried to 100mL and above-mentioned contain 2,6- diformazans
The asymmetric ligand (0.61g, 1.0mmol, part synthesize with reference to the step of embodiment 1 (1) method) of base substitution, adds NiBr2
(DME) (0.34g, 1.1mmol) and dichloromethane 20mL, reaction 12 hours is stirred at room temperature, filters suspension, mother liquor exists
Solvent is removed under vacuum, residue is washed three times with ether (3 × 15mL), and brown solid powder is obtained after vacuum drying
0.71g.Yield is 95%.
Anal.Calcd for(C45H42Br2N2Ni):C,65.17；H,5.10；N,3.38.Found:C,65.49；H,
5.42；N,3.41.MALDI-TOF-MS(m/z):calcd for C45H42BrN2Ni:747.1885,found: 747.1255
[M-Br]+.
Its reaction equation is as follows：
(2) vinyl polymerization：By the 250mL polymerization bottles vacuum with magnetic stick-nitrogen circulation displacement three times, in nitrogen
Under atmosphere, 20mL toluene solutions are added, then are passed through ethene, ethene is fully absorbed up to saturation, then with graduated note
Emitter is by co-catalyst diethylaluminum chloride (Et2AlCl) (3.3mL, 0.9M, n (Al)/n (Ni)=600) is added in reaction bulb,
Design temperature is after 50 DEG C and maintenance reaction temperature stir 10 minutes, and the above-mentioned CH containing nickel complex is added through syringe2Cl2It is molten
Liquid (2.4 μm of ol, 2mL), regulation ethene intake make the pressure of polymerization system maintain 9.0atm.At 50 DEG C, ethene is gathered
After closing reaction progress 30 minutes, acidified methanol (methanol/HCl=50/1) terminating reaction is added.The vibration of 100mL methanol is added,
It is settled out polymerizate.Precipitation filters after standing 24 hours, is fully washed with absolute methanol, and 50 DEG C are dried in vacuo 48 hours,
Polyethylene 2.85g is obtained, activity is 2.38 × 106g PE/(mol Ni h).The polyethylene that the catalyst obtains, the degree of branching 91
Individual side chain/1000C, weight average molecular weight are 6.5 × 105g mol-1, molecular weight distribution 2.00.
(3) long-chain 1- hexene oligomerizations：At room temperature, dried 50mL reaction tube vacuum nitrogen gas is replaced three
It is secondary, toluene (15mL), 1- hexenes (1M), diethylaluminum chloride (Et are sequentially added under nitrogen protection2AlCl, 3.3mL,
0.9M, n (Al)/n (Ni)=300), design temperature is after 20 DEG C and maintenance reaction are stirred 10 minutes, then added with syringe
The toluene solution (10 μm of ol, 2mL) containing nickel complex is stated, after polymerisation is carried out 3 hours, adds 5% acidified methanol solution
(30mL) terminating reaction, vibration are settled out polymerizate.Filtering precipitate, fully washed with absolute methanol, 50 DEG C of vacuum drying
12 hours, waxy polymer 0.46g is obtained, activity is 1.53 × 104g PE/(mol Ni h).The weight for obtaining branch polymer is equal
Molecular weight is 1.67 × 104g mol-1, molecular weight distribution 1.16.
Embodiment 3
(1) synthesis of complex：Under nitrogen protection, the not right of above-mentioned aniline is added in the reaction tube dried to 100mL
Claim part (0.58g, 1.0mmol, part synthesize with reference to the step of embodiment 1 (1) method), add NiBr2(DME) (0.34g,
1.1mmol) with dichloromethane 20mL, reaction 12 hours is stirred at room temperature, filters suspension, mother liquor removes molten under vacuo
Agent, residue are washed three times with ether (3 × 17mL), and brown solid powder 0.66g is obtained after vacuum drying.Yield is 92%.
Anal.Calcd for(C43H38Br2N2Ni):C,64.45；H,4.78；N,3.50.Found:C,64.49；H,
4.52；N,3.45.MALDI-TOF-MS(m/z):calcd for C43H38BrN2Ni:719.1572,found: 719.1244
[M-Br]+.
Its reaction equation is as follows：
(2) vinyl polymerization：By the 250mL polymerization bottles vacuum with magnetic stick-nitrogen circulation displacement three times, in nitrogen
Under atmosphere, 20mL toluene solutions are added, then are passed through ethene, ethene is fully absorbed up to saturation, then with graduated note
Emitter is by co-catalyst diethylaluminum chloride (Et2AlCl) (3.3mL, 0.9M, n (Al)/n (Ni)=600) adds reaction bulb
In, design temperature is after 50 DEG C and maintenance reaction temperature stir 10 minutes, is added through syringe above-mentioned containing nickel complex
CH2Cl2Solution (2.4 μm of ol, 2mL), regulation ethene intake make the pressure of polymerization system maintain 9.0atm.At 50 DEG C,
After ethylene polymerization is carried out 30 minutes, acidified methanol (methanol/HCl=50/1) terminating reaction is added.Add 100mL
Methanol vibrates, and is settled out polymerizate.Precipitation filters after standing 24 hours, is fully washed with absolute methanol, 50 DEG C of vacuum drying
48 hours, polyethylene 2.76g is obtained, activity is 2.30 × 106g PE/(mol Ni h).The polyethylene that the catalyst obtains, branch
Change degree is 101 side chain/1000C, and weight average molecular weight is 2.9 × 105g mol-1, molecular weight distribution 2.32., should at 80 DEG C
Catalyst has obtained highly branched polyethylene, and the degree of branching is 108 side chain/1000C.
(3) long-chain 1- hexene oligomerizations：At room temperature, dried 50mL reaction tube vacuum nitrogen gas is replaced three
It is secondary, toluene (15mL), 1- hexenes (1M), diethylaluminum chloride (Et are sequentially added under nitrogen protection2AlCl, 3.3mL,
0.9M, n (Al)/n (Ni)=300), design temperature is after 20 DEG C and maintenance reaction are stirred 10 minutes, then added with syringe
The toluene solution (10 μm of ol, 2mL) containing nickel complex is stated, after polymerisation is carried out 3 hours, adds 5% acidified methanol solution
(30mL) terminating reaction, vibration are settled out polymerizate.Filtering precipitate, fully washed with absolute methanol, 50 DEG C of vacuum drying
12 hours, waxy polymer 1.10g is obtained, activity is 3.67 × 104g PE/(mol Ni h)
Comparative example 1
(1) vinyl polymerization is carried out with the analog of the alpha-diimine nickel (II) of 2,4,6- trimethylanilines：Polymerizing condition with
The step of embodiment 1 (3) it is consistent, catalytic activity be 3.67 × 105g PE/(mol Ni h).Weight average molecular weight be 6.4 ×
104g mol-1, molecular weight distribution 1.89, the degree of branching is 89 side chain/1000C.
(2) long-chain 2- hexene oligomerizations are carried out with the analog of the alpha-diimine nickel (II) of 2,4,6- trimethylanilines：Polymerization
Condition is consistent with the step of embodiment 1 (5), obtains oily polymer 0.24g, and activity is 0.80 × 103g PE/(mol Ni
h).The weight average molecular weight for obtaining branch polymer is 7.16 × 103g mol-1, molecular weight distribution 2.21.
Claims (6)
- A kind of 1. asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl, it is characterised in that：It is described to match somebody with somebody The structure of compound is：Wherein, R isiPr、Me、H。
- 2. a kind of asymmetric alpha-diimine nickel (II) complex as claimed in claim 1 containing the substitution of ortho position benzhydryl Preparation method, it is characterised in that：The preparation method processing step is：(1) preparation of the asymmetric alpha-diimine part containing the substitution of ortho position benzhydryl：A, by 4- methyl -2,6- benzhydryls aniline and excessive diacetyl with 1:1.5~1:2.0 mixed in molar ratio, with first Benzene is solvent, and the p-methyl benzenesulfonic acid for adding 0.05 times of 4- methyl -2,6- benzhydryl aniline moles makees catalyst, in 80~ Flowed back at 115 DEG C after reaction overnight, rotate solvent and excessive diacetyl, obtain crude product, then use C again2H5OH washs to obtain The single ketones of the ortho position benzhydryl substitution of yellow crystal；B, the single ketones and aniline substituted above-mentioned ortho position benzhydryl is with 1:1.2~1:1.5 mixed in molar ratio, using toluene to be molten Agent, the p-methyl benzenesulfonic acid for adding 0.05 times of aniline moles make catalyst, back flow reaction 12~24 hours at 80~115 DEG C Afterwards, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2Mixed solvent recrystallization separates out solid precipitation, filtration drying Obtain yellow part；(2) preparation of asymmetric alpha-diimine nickel (II) complex containing the substitution of ortho position benzhydryl:Under nitrogen protection, using dichloromethane as solvent, the asymmetric alpha-diimine part that will substitute containing ortho position benzhydryl With the nickelous bromide [NiBr activated by glycol dimethyl ether2(DME)] with 1:0~1:1.2 mixed in molar ratio, is stirred at room temperature After reaction 12~24 hours, suspension is filtered, after mother liquor removes solvent under vacuum, is washed with ether, be dried in vacuo, obtain To brown powder solid complexes.
- 3. the preparation of asymmetric alpha-diimine nickel (II) complex as claimed in claim 2 containing the substitution of ortho position benzhydryl Method, it is characterised in that：Aniline described in step (1) B is 2,6-DIPA, 2,6- dimethylanilines.
- 4. a kind of asymmetric alpha-diimine nickel (II) complex as claimed in claim 1 containing the substitution of ortho position benzhydryl Using, it is characterised in that：The complex is used for the polymerization of ethene and 1- hexenes.
- 5. asymmetric alpha-diimine nickel (II) complex substituted as claimed in claim 4 containing ortho position benzhydryl is answered With, it is characterised in that：The complex be used for vinyl polymerization method be：By complex and co-catalyst diethylaluminum chloride with 1:200~1:1000 mol ratio composition composite catalyst system, reaction temperature is 0~80 DEG C, and the reaction time is 5~30 minutes, When catalyst amount is 10~400 μm of ol/L, catalyzed ethylene polymerization, the polymer of HMW is obtained.
- 6. asymmetric alpha-diimine nickel (II) complex substituted as claimed in claim 4 containing ortho position benzhydryl is answered With, it is characterised in that：The complex be used for 1- hexene oligomerizations method be：By complex and co-catalyst diethylaluminum chloride With 1:500 mol ratio composition composite catalyst system, reaction temperature is 20~80 DEG C, and the reaction time is 3 hours, catalyst amount For 10 μm of ol when, be catalyzed 1- hexene oligomerizations, obtain the polymer of HMW.
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| CN107759641A (en) * | 2017-11-16 | 2018-03-06 | 海安常州大学高新技术研发中心 | α diimine nickel complexes, preparation method and application |
| CN108822237A (en) * | 2018-07-03 | 2018-11-16 | 常州大学 | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer |
| CN109053818A (en) * | 2018-08-10 | 2018-12-21 | 常州大学 | The preparation of fluorinated alpha-diimine nickel (II) complex replaced containing ortho position benzhydryl for vinyl polymerization |
| CN109762026A (en) * | 2019-01-24 | 2019-05-17 | 常州大学 | A kind of fluorine-containing phenanthrenequione skeleton asymmetry alpha-diimine nickel (II) complex and preparation method and application |
| CN109762027A (en) * | 2019-02-14 | 2019-05-17 | 合肥工业大学 | para-aryl-containing substituted α -diimine nickel complex and preparation method and application thereof |
| CN109942638A (en) * | 2019-04-19 | 2019-06-28 | 常州大学 | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization |
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| CN107759641A (en) * | 2017-11-16 | 2018-03-06 | 海安常州大学高新技术研发中心 | α diimine nickel complexes, preparation method and application |
| CN108822237A (en) * | 2018-07-03 | 2018-11-16 | 常州大学 | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer |
| CN109053818B (en) * | 2018-08-10 | 2021-05-04 | 常州大学 | Preparation of fluorinated nickel (II) complexes containing ortho-diphenylmethyl-substituted alpha-diimines for ethylene polymerization |
| CN109053818A (en) * | 2018-08-10 | 2018-12-21 | 常州大学 | The preparation of fluorinated alpha-diimine nickel (II) complex replaced containing ortho position benzhydryl for vinyl polymerization |
| CN109762026A (en) * | 2019-01-24 | 2019-05-17 | 常州大学 | A kind of fluorine-containing phenanthrenequione skeleton asymmetry alpha-diimine nickel (II) complex and preparation method and application |
| CN109762026B (en) * | 2019-01-24 | 2021-03-02 | 常州大学 | Fluorine-containing phenanthrenequinone skeleton asymmetric alpha-diimine nickel (II) complex and preparation method and application thereof |
| CN109762027A (en) * | 2019-02-14 | 2019-05-17 | 合肥工业大学 | para-aryl-containing substituted α -diimine nickel complex and preparation method and application thereof |
| CN109762027B (en) * | 2019-02-14 | 2021-10-22 | 合肥工业大学 | Para-aryl-containing substituted alpha-diimine nickel complex and preparation method and application thereof |
| CN109942638A (en) * | 2019-04-19 | 2019-06-28 | 常州大学 | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization |
| CN112250782A (en) * | 2020-10-16 | 2021-01-22 | 浙江大学 | Ethylene and 1-hexene copolymer and preparation method thereof |
| CN112210031A (en) * | 2020-10-22 | 2021-01-12 | 华东理工大学 | Ethylene and alpha-olefin copolymerization method catalyzed by late transition metal complex |
| CN112210031B (en) * | 2020-10-22 | 2023-02-24 | 华东理工大学 | Ethylene and alpha-olefin copolymerization method catalyzed by late transition metal complex |
| CN112759689A (en) * | 2021-01-22 | 2021-05-07 | 黄志怀 | Para-methoxy substituted alpha-diimine iron catalyst and preparation method thereof |
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