CN106397259A - Diimine ligand, and diimine-nickel complex and application thereof - Google Patents
Diimine ligand, and diimine-nickel complex and application thereof Download PDFInfo
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Abstract
The invention provides a diimine compound with a structural as shown in a formula I which is defined in the specification. In the formula I, R1 to R10 are same or different and are independently selected from a group consisting of hydrogen, saturated or unsaturated alkyl groups, oxyl groups and halogen. The invention also relates to a diimine-nickel complex formed by the diimine ligand. The diimine-nickel complex can realize high-activity catalysis of vinyl polymerization as a catalyst preferably under the activation of a cocatalyst (such as methylaluminoxane or alkyl aluminum).
Description
Technical field
The present invention relates to catalyst field is and in particular to the diimine nickel complex of a kind of diimide ligand of new structure and its formation.The invention still further relates to the preparation method of described ligands and complexes, and described coordination compound application in terms of olefinic polymerization as olefin polymerization catalysis.
Background technology
China is that synthetic resin consumes fastest-rising country, it is also maximum synthetic resin importer, polyolefin production proportion nearly 60% at present, olefin resin has excellent environment compatibility compared with other resin materials, it is used for the material of emphasis popularization in developed country's automobile industry, the world production amount in 2003 has just reached 83,300,000 tons；The synthetic resin that wherein polyethylene is with fastest developing speed, yield is maximum, purposes is extremely wide, reaches 51,100,000 tons then.Industrialized polyethylene catalysts have Ziegler-Natta type catalyst (DE Pat889229 (1953)；IT Pat 545332 (1956) and IT Pat 536899 (1955)；Chem.Rev., 2000,100,1169 and this special issue pertinent literature), Phillips type catalyst (Belg.Pat.530617 (1955)；Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin:, and the efficient ethylene oligomerization of the late transition metal metal compounding material type developing in recent years and polymerization catalyst Springer, 1999).Such as nineteen ninety-five, Brookhart etc. reports the coordination compound of class alpha-diimine Ni (II), can be with highly active polymerising ethylene.
Because alpha-diimine Raney nickel has high activity, and polymer molecular weight and the degree of branching can regulate and control in very large range and receive much attention.The companies such as Du Pont have applied for multiple patents (WO 96/23010, WO98/03521, WO 98/40374, WO 99/05189, WO 99/62968, WO 00/06620, US 6,103,658, US 6,660,677).This kind of alpha-diimine Raney nickel, can highly active catalyzed ethylene oligomerisation or polymerization under room temperature or low temperature under MAO or alkyl aluminum act on.But when liter high reaction temperature is higher than 50 DEG C, this kind of alpha-diimine nickel catalyst activity reduces rapidly, the molecular weight with polymerisation temperature of prepared polyethylene improves and declines rapidly.Existing ethene gas-phase polymerization technological requirement polymerization temperature is more than 85 DEG C, and vinyl solution polymerization technique requires polymerization temperature to be 150-250 DEG C, and original late transition metal catalyst cannot meet existing gas phase, the requirement of solwution method ethylene polymerization plants.
Content of the invention
In view of the shortcomings of the prior art, this application provides a kind of diimide ligand of new structure, it can form the alpha-nickel diimine compound with good thermal stability with nickel.This coordination compound, preferably under promoter activation, enables catalyzed ethylene polymerization under higher temperature, the branched polyethylene of preparation high molecular；And still can keep higher ethylene polymerization activity under higher temperature, and resulting polymers molecular weight is higher, molecular weight distribution is narrower.
According to an aspect of the invention, it is provided a kind of diimide ligand, there is the structure shown in Formulas I：
In Formulas I, R1-R10Identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen.It preferably is selected from, R1-R10Identical or different, it is each independently selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxyl and halogen.
According in a specific embodiment of part of the present invention, in described Formulas I, R1-R10Identical or different, it is each independently selected from hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxyl and halogen, be preferably selected from hydrogen, methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine.
According to another aspect of the present invention, there is provided a kind of method preparing above-mentioned part, including：Compound A is flowed back with aniline or substituted aniline in the presence of catalyst in solvent, is obtained the part shown in Formulas I,
According to a specific embodiment of the method for the invention, described compound A is 1 with the mol ratio of aniline or substituted aniline:2-1:10, preferably 1:2-1:3.Described solvent is selected from least one in toluene, methanol, ethanol and acetonitrile.Described catalyst is selected from p-methyl benzenesulfonic acid, at least one in acetic acid and formic acid, the 0.01-20mol% that the amount of preferably described catalyst is measured for compound A.The temperature of described backflow is 40-120 DEG C, preferably 65-110 DEG C.The time of described backflow is 0.5-7 days, preferably 1-2 days.
Wherein, the restriction of the substituent group on described substituted aniline is such as R1-R10, for example, described substituted aniline can be 2,6- monomethylaniline., 2,6- diethylaniline, 2,6-DIPA, the bromo- aniline of 2,6- dimethyl -4- and/or 2,6- difluoroaniline.
In a specific embodiment, the part of the present invention for example can be prepared by process to prepare：
A) compound A and the aniline replacing are flowed back 1 day with acetic acid in ethanol for catalyst, remove parlkaline aluminium oxide pillar after solvent, with petrol ether/ethyl acetate (20 after filtration:1) drip washing, second is divided into product, removes solvent and obtains yellow solid；Or
B) compound A and the aniline replacing are flowed back one day with p-methyl benzenesulfonic acid for catalyst in toluene, and reactant liquor is evaporated rear parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, removes solvent and obtains yellow solid, i.e. alpha-diimine part；
The alpha-diimine part of above-mentioned all synthesis can be confirmed by nuclear-magnetism, infrared and elementary analysiss.
According to another aspect of the present invention, additionally provide a kind of diimine nickel complex, it has the structure shown in Formula II,
In Formula II, R1-R10The same ligand compound of restriction.
According to a specific embodiment of diimine nickel complex of the present invention, work as R7-R10When being hydrogen, described coordination compound has the structure shown in formula III,
According to a specific embodiment of nickel complex of the present invention, described coordination compound is selected from least one in following coordination compound：
Coordination compound 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Coordination compound 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Coordination compound 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Coordination compound 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Coordination compound 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Coordination compound 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br
Coordination compound 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Coordination compound 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Coordination compound 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Coordination compound 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；、
Coordination compound 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Coordination compound 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Coordination compound 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Coordination compound 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Coordination compound 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Coordination compound 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Coordination compound 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Coordination compound 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Coordination compound 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Coordination compound 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Coordination compound 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；And
Coordination compound 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
In a preferred embodiment of the present invention, in the structure shown in described formula III, X is Cl or Br, R1、R3、R4And R6It is each independently selected from methyl, ethyl or isopropyl, fluorine, chlorine or bromine, described R2And R5It is each independently selected from hydrogen, methyl, vinyl or bromine.
According to another aspect of the present invention, additionally provide a kind of method preparing above-mentioned nickel complex, comprise the steps：Above-mentioned diimide ligand is carried out complexation reaction, the coordination compound shown in prepared Formula II with nickel halogenide or nickel halogenide derivant.
According to a specific embodiment of the inventive method, described nickel halogenide or nickel halogenide derivant are 1 with the mol ratio of described diimide ligand:1-1.2:1.Described nickel halogenide or nickel halogenide derivant are selected from NiBr2、NiCl2、(DME)NiBr2(DME) NiCl2.The temperature of described reaction is 0-60 DEG C.The time of reaction is 0.5-12h.
According to the present invention, described complexation reaction can be in anhydrous and oxygen-free solution as carried out under an inert atmosphere.In a specific enforcement, under inert gas shielding, by (DME) NiCl2Or (DME) NiBr2Dichloromethane solution in molar ratio (1:1-1:1.2) it is added drop-wise in the solution of diimide ligand, is stirred at room temperature, separate out precipitation, filtration is vacuum dried after being washed with ether and just obtains diimine nickel complex.Coordination compound can be characterized by elementary analysiss and infrared spectrum.DME is the abbreviation of dimethyl methyl ether.
According to another aspect of the present invention, additionally provide a kind for the catalyst system of olefinic polymerization, be major catalyst including above-mentioned coordination compound.Promoter is still further comprised in preferably described catalyst system.
In a specific embodiment of described catalyst system, described promoter is selected from least one in alkylaluminoxane, alkyl aluminum and aryl boron, it is preferably selected from least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminum, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride, three pentafluorophenyl group boron and DMA four (pentafluorophenyl group) borate.
In another specific embodiment of described catalyst system, the mol ratio of the aluminum in described promoter and the nickel in described major catalyst is (50-5000):The mol ratio of the boron in 1, or described promoter and the nickel in described major catalyst is (1-50):1.
According to another aspect of the present invention, additionally provide a kind of olefine polymerizing process, carry out polyreaction in the presence of above-mentioned catalyst system including described alkene.
Catalyst system prepared by the present invention can be used for all polymerizations or the copolymerization of alkene, it is particularly well-suited to the copolymerization of ethylene homo conjunction or ethylene and other alpha-olefins, wherein alpha-olefin is selected from least one in propylene, butylene, amylene, hexene, octene or 4- methylpentene -1 etc..
According to a specific embodiment of polymerization of the present invention, the reaction temperature of described polyreaction is -78 to 200 DEG C, preferably -20 to 150 DEG C, more preferably 50 to 120 DEG C.Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
In some preferred implementations of the present invention, wherein polyreaction can be carried out in a solvent.The solvent being used is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.Preferably one of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, most preferably one of hexane, toluene, heptane or their mixture.
The present invention has synthesized the diimide ligand compound of new structure, and it can form diimine nickel complex with nickel.The diimine nickel complex of the present invention, under preferred promoter (as MAO or alkyl aluminum) activity, as catalyst, being capable of highly active catalyzed ethylene polymerization.Especially (100 degree) can still keep higher polymerization activity under higher polymerization temperature.(the diimine nickel catalyst of previous literature or patent report activity more than 50 degree significantly decays, and molecular weight is greatly lowered).Catalyst of the present invention has the ability of good catalyzed ethylene and the copolymerization of high alpha-olefin, and Copolymerization activity is high, and extremely-low density, branched polyethylene can be obtained.
Specific embodiment
Describe the present invention with reference to embodiments, but it is to be appreciated that described embodiment is only used for carrying out exemplary description to the present invention, and any restriction can not be constituted to protection scope of the present invention.Rational conversion in all invention teachings being included in the present invention and combination each fall within protection scope of the present invention.
Analysis and characterization instrument used in the present invention is as follows:
1st, nuclear magnetic resonance analyser：Bruker DMX 300 (300MHz), tetramethylsilane (TMS) is internal standard
2. elemental analyser：The full-automatic elemental analyser of Italian ThermoQuest company EA1112.
In embodiment, the 5mol% that the amount of catalyst used is measured for compound A.Other compounds in addition to part are commercially available.The synthesis of coordination compound used is all carried out in a nitrogen atmosphere.
Embodiment 1
1) preparation of part：
Compound A (2.14g, 4.8mmol) He 2,6- monomethylaniline. (1.3ml, 10.4mmol), p-methyl benzenesulfonic acid was catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtration, residue dichloromethane dissolves, and parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, and remove solvent to obtain yellow solid yield is 80%.1H NMR(CDCl3,δ,ppm):1.30 (t, J=7.0Hz, 12H), 1.88 (s, 12H), 2.78 (q, J=7.0Hz, 8H), 5.10 (s, 2H), 7.02-7.13 (m, 6H), 7.38 (s, 4H),
7.60(s,4H).
2) preparation of coordination compound 1：(formula II I, middle R1、R3、R4And R6For methyl, R2And R5For hydrogen, X is Br)
By 10ml (DME) NiBr2The dichloromethane solution of (277mg, 0.9mmol) is added drop-wise in the dichloromethane solution of the above-mentioned part of 10ml (588mg, 0.9mmol), it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain dark red powder solid with ether after being washed, yield is 90%.Elementary analysiss (C48H48Br2N2Ni)：C,66.16；H,5.55；N,3.21；Experiment value (%)：C,66.02；H,5.82；N,3.42.
3) vinyl polymerization：
Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 8.7mg (10 μm of ol) coordination compound 1 and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 50 DEG C, keep the ethylene pressure of 10atm, stirring reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 0.76 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 2
10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.The coordination compound 1 of addition 8.7mg (10 μm of ol) embodiment 1 preparation and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, stirring reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 1.21 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 3
1) preparation of part：
Compound A (3.48g, 7.8mmol) He 2,6- diethylaniline (3.0ml, 17.4mmol), p-methyl benzenesulfonic acid was catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtration, residue dichloromethane dissolves, and parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, removes solvent and obtains yellow solid, and yield is 80%.1H NMR(CDCl3,δ,ppm):1.09 (t, 12H, J=7.5Hz), 1.30 (t, J=7.5Hz, 12H), 2.21 (dd, 8H,), J=7.5Hz 2.80 (q, J=7.5Hz, 8H), 5.10 (s, 2H), 7.01-7.11 (m, 6H), 7.38 (s, 4H), 7.60 (s, 4H).
2) preparation of coordination compound 2：(in formula II I, R1、R3、R4And R6For ethyl, R2And R5For hydrogen, X is Br)
By 10ml (DME) NiBr2The dichloromethane solution of (155mg, 0.5mmol) is added drop-wise in the dichloromethane solution of the above-mentioned part of 10ml (354mg, 0.5mmol), it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain dark red powder solid with ether after being washed, yield is 92%.Elementary analysiss (C52H56Br2N2Ni)：C,67.34；H,6.09；N,3.02；Experiment value (%)：C,66.02；H,6.21；N,3.44.
3) 10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle continuous drying 6 hours at 130 DEG C, while hot evacuation use N2Gas is replaced 3 times.The coordination compound 2 of addition 9.2mg (10 μm of ol) embodiment 3 preparation and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 1.32 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 4
1) preparation of part：
Compound A (4.01g, 9.0mmol) He 2,6- diisopropyl aniline (4.0ml, 19.7mmol), p-methyl benzenesulfonic acid was catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtration, residue dichloromethane dissolves, and parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, removes solvent and obtains yellow solid, and yield is 82%.1H NMR(CDCl3,δ,ppm):1.02 (d, 12H, J=7.0Hz), 1.15 (d, 12H, J=7.0Hz), 1.28 (t, J=7.0Hz, 12H), 2.50 (m, 4H), 2.79 (q, J=7.0Hz, 8H), 5.21 (s, 2H), 7.01 (m, 6H), 7.40 (s, 4H), 7.62 (s, 4H).
2) preparation of coordination compound 3：(in formula II I, R1、R3、R4And R6For isopropyl, R2And R5For hydrogen, X is Br)
By 10ml (DME) NiBr2The dichloromethane solution of (506mg, 1.6mmol) is added drop-wise in the dichloromethane solution of the above-mentioned part of 10ml (1224mg, 1.6mmol), it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain dark red powder solid with ether after being washed, yield is 88%.Elementary analysiss (C56H64Br2N2Ni)：C,68.38；H,6.56；N,2.85；Experiment value (%)：C,68.32；H,6.71；N,2.42.
3) 10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 9.8mg (10 μm of ol) coordination compound 3 and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 3.52 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 5
1) preparation of part：
Compound A (2.28g, 5.1mmol) He 2,6- dimethyl -4- bromo- aniline (2.3g, 11.3mmol), p-methyl benzenesulfonic acid was catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtration, residue dichloromethane dissolves, and parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, removes solvent and obtains yellow solid, and yield is 80%.1H NMR(CDCl3,δ,ppm):1.30 (t, J=7.5Hz, 12H), 1.83 (s, 12H), 2.79 (q, J=7.5Hz, 8H), 5.09 (s, 2H), 7.04 (s, 4H), 7.38 (s, 4H), 7.61 (s, 4H).
2) coordination compound 5 preparation (in formula II I, R1、R3、R4And R6For methyl, R2And R5For bromine, X is Br)：
By 10ml (DME) NiBr2The dichloromethane solution of (216mg, 0.7mmol) is added drop-wise in the dichloromethane solution of the above-mentioned part of 10ml (567mg, 0.7mmol), it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain dark red powder solid with ether after being washed, yield is 85%.Elementary analysiss (C48H46Br4N2Ni)：C,56.02；H,4.50；N,2.72；Experiment value (%)：C,56.36；H,4.92；N,2.81.
3) 10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 10.6mg (10 μm of ol) coordination compound 5 and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 1.31 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 6
1) preparation of part：
Compound A (2.27g, 5.1mmol) He 2,6- difluoroaniline (1.3ml, 11.3mmol), p-methyl benzenesulfonic acid was catalyst, in 100mL reflux in toluene 1 day, solvent is removed after filtration, residue dichloromethane dissolves, and parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) drip washing, second is divided into product, removes solvent and obtains yellow solid, and yield is 48%.1H NMR(CDCl3,δ,ppm):1.30 (t, J=7.5Hz, 12H), 2.80 (q, J=7.5Hz, 8H), 5.10 (s, 2H), 6.96-7.02 (m, 6H), 7.38 (s, 4H), 7.62 (s, 4H).
2) preparation (R in formula II I of coordination compound 91、R3、R4And R6For fluorine, R2And R5For hydrogen, X is Br)：
By 10ml (DME) NiBr2The dichloromethane solution of (216mg, 0.7mmol) is added drop-wise in the dichloromethane solution of the above-mentioned part of 10ml (468mg, 0.7mmol), it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain dark red powder solid with ether after being washed, yield is 88%.Elementary analysiss (C44H36Br2F4N2Ni)：C,59.56；H,4.09；N,3.16；Experiment value (%)：C,59.82；H,3.82；N,3.60.
3) 10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 8.9mg (10 μm of ol) coordination compound 9 and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 0.24 × 106g·mol-1(Ni)·h-1.
Embodiment 7
1) preparation of coordination compound 14：(in formula II I, R1、R3、R4And R6For isopropyl, R2And R5For hydrogen, X is Cl)：
By 10ml (DME) NiCl2The dichloromethane solution of (352mg, 1.6mmol) is added drop-wise in the dichloromethane solution of part (1224mg, 1.6mmol) in 10ml embodiment 4, it is stirred at room temperature 6 hours, separate out precipitation, filtration is dried to obtain orange red powder solid with ether after being washed, yield is 90%.Elementary analysiss (C56H64Cl2N2Ni)：C,75.17；H,7.21；N,3.13；Experiment value (%)：C,75.57；H,7.42；N,3.43.
2) 10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 8.9mg (10 μm of ol) coordination compound 14 and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 100 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 3.89 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 8
10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Add in 9.8mg (10 μm of ol) embodiment 4 coordination compound 3 of preparation and then evacuation being replaced 3 times with ethylene again.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000.At 90 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 3.74 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 9
10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Add in 9.8mg (10 μm of ol) embodiment 4 coordination compound 3 of preparation and then evacuation being replaced 3 times with ethylene again.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000,10ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 3.98 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 10
10atm vinyl polymerization：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Add in 9.8mg (10 μm of ol) embodiment 4 coordination compound 3 of preparation and then evacuation being replaced 3 times with ethylene again.The hexane of injection 500ml, adds 6.5ml MAO (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000,20ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 3.66 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Comparative example 1
10atm ethylene：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 7.2mg (10 μm of ol) comparative catalyst B and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MMAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000,10ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 0.08 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Comparative example 2
10atm ethylene：Will be equipped with churned mechanically 1L rustless steel polymeric kettle in 130 DEG C of continuous drying 6hrs, while hot evacuation use N2Gas is replaced 3 times.Addition 6.2mg (10 μm of ol) comparative catalyst C and then again evacuation are simultaneously replaced 3 times with ethylene.The hexane of injection 500ml, adds 6.5ml MAO (MMAO) (toluene solutions of 1.53 mol/l), makes Al/Ni=1000,10ml hexene.At 90 DEG C, keep the ethylene pressure of 10atm, be stirred vigorously reaction 30min.With the ethanol solution neutralization of 5% hydrochloric acid acidifying, obtain polyethylene, polymerization activity is 0.02 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Table 1
As can be seen from Table 1, with respect to the coordination compound of comparative example 1 and 2, when being used the metal complex of the present invention to use as major catalyst, under the conditions of high temperature polymerization, polymerization activity is much higher, and the molecular weight of resulting polymers is apparently higher than comparative example resulting polymers.The nickel metal complex of the present invention has excellent copolymerization performance, and the ultra-low density polyethylene of high molecular can be obtained.Meanwhile, the molecular weight distribution of polymer is still narrower.
Claims (14)
1. a kind of diimide ligand, has the structure shown in Formulas I：
In Formulas I, R1-R10Identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, hydrocarbon oxygen
Base and halogen, are preferably selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxyl and halogen.
2. diimide ligand according to claim 1 is it is characterised in that in described Formulas I, R1-R10Phase
Same or different, it is each independently selected from hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxyl and halogen
Element, be preferably selected from hydrogen, methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, third
Epoxide, fluorine, chlorine and bromine.
3. a kind of method preparing diimide ligand described in claim 1 or 2, including：By compound A with
Aniline or substituted aniline are flowed back in the presence of catalyst in solvent, obtain the diimine shown in Formulas I
Part,
4. method according to claim 3 is it is characterised in that described compound A and aniline or replacement
Aniline mol ratio be 1:2-1:10, preferably 1:2-1:3；And/or,
Described solvent is selected from least one in toluene, methanol, ethanol and acetonitrile；And/or
Described catalyst is selected from least one in p-methyl benzenesulfonic acid, acetic acid and formic acid, preferably described catalyst
Measure the 0.01-20mol% for compound A amount；And/or,
The temperature of described backflow is 40-120 DEG C, preferably 65-110 DEG C；And/or,
The time of described backflow is 0.5-7 days, preferably 1-2 days.
5. a kind of diimine nickel complex, it has the structure shown in Formula II,
In Formula II, R1-R10Restriction with claim 1 or 2.
6. nickel complex according to claim 5 is it is characterised in that work as R7-R10When being hydrogen, described
Coordination compound has the structure shown in formula III,
7. nickel complex according to claim 6 is it is characterised in that described coordination compound is selected from following joining
At least one in compound：
Coordination compound 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Coordination compound 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Coordination compound 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Coordination compound 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Coordination compound 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Coordination compound 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br
Coordination compound 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Coordination compound 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Coordination compound 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Coordination compound 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；、
Coordination compound 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Coordination compound 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Coordination compound 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Coordination compound 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Coordination compound 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Coordination compound 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Coordination compound 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Coordination compound 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Coordination compound 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Coordination compound 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Coordination compound 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；And
Coordination compound 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
8. a kind of method of the nickel complex prepared described in any one in claim 5-7, comprises the steps：
Diimide ligand described in claim 1 or 2 is carried out complexation reaction with nickel halogenide or nickel halogenide derivant,
Coordination compound shown in prepared Formula II.
9. method according to claim 8 it is characterised in that described nickel halogenide or nickel halogenide derivant with
The mol ratio of described diimide ligand is 1:1-1.2:1；And/or,
Described nickel halogenide or nickel halogenide derivant are selected from NiBr2、NiCl2、（DME）NiBr2With（DME）
NiCl2；And/or,
The temperature of described reaction is 0-60 DEG C, and/or, the time of reaction is 0.5-12h.
10. a kind of catalyst system for olefinic polymerization, including described in any one in claim 5-7
Coordination compound is major catalyst, and preferably described catalyst system further includes promoter.
11. catalyst systems according to claim 10 are it is characterised in that described promoter is selected from alkane
At least one in base aikyiaiurnirsoxan beta, alkyl aluminum and aryl boron, preferably described promoter be selected from trimethyl aluminium,
Triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminum, tri-n-octylaluminium,
Diethylaluminum chloride, ethylaluminium dichloride, three pentafluorophenyl group boron and N, accelerine four（Pentafluorophenyl group）
At least one in borate.
12. catalyst systems according to claim 10 or 11 are it is characterised in that described promoter
In aluminum and described major catalyst in the mol ratio of nickel be（50-5000）:Boron in 1, or described promoter
Mol ratio with the nickel in described major catalyst is（1-50）:1.
A kind of 13. olefine polymerizing process, urge including described in described alkene any one in claim 10-12
Carry out polyreaction in the presence of agent system.
14. methods according to claim 13 are it is characterised in that the reaction temperature of described polyreaction is
- 78 to 200 DEG C, preferably -20 to 150 DEG C, more preferably 50 to 120 DEG C；Polymerization pressure is
0.01-10.0MPa, preferably 0.01-2.0MPa.
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