CN106397260A - Diimine ligand compound, and nickel complex and application thereof - Google Patents
Diimine ligand compound, and nickel complex and application thereof Download PDFInfo
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Abstract
The invention provides a diimine ligand compound with a structural formula as shown in the specification. In the structural 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 preparation method for the ligand, a nickel complex formed by the ligand and a preparation method and application of the nickel complex. When the nickel complex is used as a main catalyst, higher polymerization activity is obtained under a high-temperature polymerization condition, and an obtained polymer has high molecular weight.
Description
Technical field
The present invention relates to catalyst field is and in particular to a kind of new diimide ligand and its prepared nickel complex.The invention still further relates to the application in olefin polymerization as catalyst of above-mentioned nickel complex.
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 Pat 889229 (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, WO 98/03521, 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, the invention provides a kind of diimide ligand compound of new structure, it can form a kind of alpha-nickel diimine compound with good thermal stability with nickel.Under described coordination compound (as MAO or alkyl aluminum activation) under promoter activation, enable catalyzed ethylene polymerization under higher temperature, keep higher ethylene polymerization activity, branched polyethylene can be obtained.Meanwhile, resulting polymers molecular weight is higher, and molecular weight distribution is narrower.
According to a specific embodiment of the present invention, there is provided a kind of diimide ligand compound, its structural formula is as follows：
In Formulas I, R1-R10Identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen, preferably be selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxyl and halogen.
According in ligand compound 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.
Another embodiment according to the present invention, provide a kind of method preparing ligand compound shown in above-mentioned Formulas I, flowed back in solvent in the presence of catalyst with aniline or substituted aniline including by compound A, obtained the ligand compound shown in Formulas I
According to method of the present 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 can be 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 can be 40-120 DEG C, preferably 65-110 DEG C.The time of described backflow can be 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 the synthetic method of ligand compound of the present invention, for example, described ligand compound can be prepared by following method：
A) compound A and aniline or substituted aniline 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 aniline or substituted aniline 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 synthesis can be confirmed by nuclear-magnetism, infrared and elementary analysiss.
A kind of another embodiment according to the present invention, there is provided nickel complex, its structural formula is as shown in Formula II：
In Formula II, R1-R10The same ligand compound of restriction.
According to a preferred embodiment of the present invention, described nickel complex is selected from least one in following coordination compound, wherein, in following coordination compound, R7-R10It is hydrogen：
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, the structure shown in described Formula II, R7-R10It is hydrogen, 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.
A kind of another embodiment according to the present invention, there is provided method preparing above-mentioned nickel complex, including：Above-mentioned diimide ligand compound is carried out complexation reaction with nickel halogenide or nickel halogenide derivant, obtains the coordination compound shown in Formula II.
According to method of the present invention, described nickel halogenide or nickel halogenide derivant are 1 with the mol ratio of described diimide ligand compound: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 described reaction is 0.5-12h.Described complexation reaction is carried out generally under the conditions of anhydrous and oxygen-free, such as can carry out under an inert atmosphere.Wherein, DME is the abbreviation of dimethyl ether.
According to the present invention, a specifically exemplary preparation process of described nickel (II) coordination compound is as follows：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 or infrared spectrum.
A kind of another embodiment according to the present invention, there is provided catalyst system, is major catalyst including the nickel complex shown in above-mentioned Formula II.And preferably described catalyst system further includes promoter.
A preferred embodiment according to catalyst system of the present invention, 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.
According to a preferred embodiment of catalyst system of the present invention, the mol ratio of the aluminum in described promoter and the nickel in described major catalyst is (50-5000):1.The mol ratio of the boron in described promoter and the nickel in described major catalyst is (1-50):1.
A kind of another embodiment according to the present invention, there is provided method of olefinic polymerization, including alkene in the presence of above-mentioned catalyst system, carries out olefinic polyreaction.
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 preferred embodiment of the present invention, the temperature of described polyreaction is -78 to 200 DEG C, preferably -20 to 150 DEG C, more preferably 50-120 DEG C.The pressure of described polyreaction is 0.01-10.0MPa, preferably 0.01-2.0MPa.
In some currently preferred embodiments of the present invention, wherein polyreaction can be carried out in a solvent, and 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.
According to the present invention, there is provided the nickel complex of a kind of diimide ligand compound of new structure and its synthesis.Nickel complex of the present invention, can highly active catalyzed ethylene polymerization under promoter (such as MAO or alkyl aluminum) effect.Especially (100 degree) can still keep higher polymerization activity under higher polymerization temperature, high molecular or even ultra-high molecular weight polyethylene can be obtained.(the diimine nickel catalyst of previous literature or patent report activity more than 50 degree significantly decays, and molecular weight is greatly lowered).Meanwhile, catalyst of the present invention has the ability of good catalyzed ethylene and the copolymerization of high alpha-olefin, and Copolymerization activity is high.
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) part preparation (in structure Formulas I, R1、R3、R4And R6For isopropyl, R7-R10、R2And R5For hydrogen)：
Compound A (5.85g, 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 80%.1H NMR(CDCl3,δ,ppm):(1.01 d, 12H, J=7.0Hz), 1.15 (d, 12H, J=7.0Hz), 2.52 (m, 4H), 5.59 (s, 2H), 7.06 (m, 6H), 7.41 (s, 4H), 7.82 (s, 4H).
2) coordination compound 3 preparation (in formula II, R1、R3、R4And R6For isopropyl, R7-R10、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 (1550mg, 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 (C48H44Br6N2Ni)：C,48.57；H,3.74；N,2.36；Experiment value (%)：C,48.32；H,3.71；N,2.46.
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 11.9mg (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 solutions of 1.53 mol/l), makes Al/Ni=1000.At 50 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 4.32 × 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 3 of addition 11.9mg (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 5.26 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 3
1) part preparation (in structure Formulas I, R1、R3、R4And R6For ethyl, R7-R10、R2And R5For hydrogen)：
Compound A (5.07g, 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):(1.10 t, 12H, J=7.5Hz), 2.23 (dd, 8H, J=7.5Hz), 5.48 (s, 2H), 7.03-7.10 (m, 6H), 7.40 (s, 4H), 7.82 (s, 4H).
2) coordination compound 2 preparation (in formula II, R1、R3、R4And R6For ethyl, R7-R10、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 (456mg, 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 90%.Elementary analysiss (C44H36Br6N2Ni)：C,46.73；H,3.21；N,2.48；Experiment value (%)：C,46.42；H,3.56；N,2.41.
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 11.3mg (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 1.84 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 4
1) part preparation (in structure Formulas I, R1、R3、R4And R6For methyl, R7-R10、R2And R5For hydrogen)：
Compound A (3.12g, 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 75%.1H NMR(CDCl3,δ,ppm):1.87(s,12H),5.48(s,2H),7.02-7.13(m,6H),7.40(s,4H),7.82(s,4H).
2) coordination compound 1 preparation (in formula II, R1、R3、R4And R6For methyl, R7-R10、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 (771mg, 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 (C40H28Br6N2Ni)：C,44.70；H,2.63；N,2.61；Experiment value (%)：C,44.46；H,2.87；N,2.82.
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 10.7mg (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 1.44 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 5
1) part preparation (in structure Formulas I, R1、R3、R4And R6For methyl, R7-R10For hydrogen, R2And R5For bromine)：
Compound A (3.31g, 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 81%.1H NMR(CDCl3,δ,ppm):1.84(s,12H),5.46 (s,2H),7.03(s,4H),7.40(s,4H),7.82(s,4H).
2) coordination compound 5 preparation (in formula II, R1、R3、R4And R6For methyl, R7-R10For hydrogen, 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 (710mg, 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 82%.Elementary analysiss (C40H26Br8N2Ni)：C,38.98；H,2.13；N,2.27；Experiment value (%)：C,39.24；H,2.52；N,2.67.
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 12.3mg (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 1.78 × 106g·mol-1(Ni)·h-1, result is as shown in table 1.
Embodiment 6
1) part preparation (in structure Formulas I, R1、R3、R4And R6For fluorine, R7-R10、R2And R5For hydrogen)：
Compound A (3.31g, 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):5.48(s,2H),7.04(m,6H),7.40(s,4H),7.82(s,4H).
2) coordination compound 9 preparation (in formula II, R1、R3、R4And R6For fluorine, R7-R10、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 (610mg, 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 (C36H16Br6F4N2Ni)：C,39.65；H,1.48；N,2.57；Experiment value (%)：C,39.82；H,1.76；N,2.60.
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 10.9mg (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 solutions of 1.53 mol/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 0.20 × 106g·mol-1(Ni)·h-1.
Embodiment 7
1) coordination compound 14 preparation (in formula II, R1、R3、R4And R6For isopropyl, R7-R10、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 (1550mg, 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 (C48H44Br4Cl2N2Ni)：C,52.50；H,4.04；N,2.55；Experiment value (%)：C,52.57；H,4.47；N,2.43.
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 11.0mg (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 4.42 × 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.The coordination compound 14 of addition 11.0mg (10 μm of ol) embodiment 7 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 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 3.14 × 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 11.9mg (10 μm of ol) embodiment 1 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 4.88 × 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 11.9mg (10 μm of ol) embodiment 1 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 5.02 × 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 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 0.02 × 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, the molecular weight of resulting polymers, apparently higher than comparative example resulting polymers, can be obtained ultra-high molecular weight polyethylene.Meanwhile, gained polyethylene still has narrower molecular weight distribution.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute any limitation of the invention.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive and explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be modified by regulation, and in without departing substantially from scope and spirit of the present invention, the present invention be revised.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can be extended to other all methods and applications with identical function.
Claims (13)
1. a kind of diimide ligand compound, its structural formula is as shown in following formula 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. ligand compound 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 compound described in claim 1 or 2, including by compound
A is flowed back in the presence of catalyst with aniline or substituted aniline in solvent, obtains joining shown in Formulas I
Body compound,
4. method according to claim 3 it is characterised in that described compound A and aniline or
The mol ratio of the aniline replacing is 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 nickel complex, its structural formula is as shown in Formula II：
In Formula II, R1-R10Restriction with claim 1 or 2.
6. nickel complex according to claim 5 it is characterised in that described coordination compound be selected from following
At least one in coordination compound, wherein, in following coordination compound, R7-R10It is hydrogen：
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.
7. a kind of method preparing nickel complex described in claim 5 or 6, including：By claim 1 or 2
Described diimide ligand compound carries out complexation reaction with nickel halogenide or nickel halogenide derivant, obtains shown in Formula II
Coordination compound.
8. method according to claim 7 it is characterised in that described nickel halogenide or nickel halogenide derivant with
The mol ratio of described diimide ligand compound is 1:1-1.2:1；And/or,
Described nickel halogenide or nickel halogenide derivant are selected from NiBr2、NiCl2、(DME)NiBr2(DME)
NiCl2；And/or,
The temperature of described reaction is 0-60 DEG C；And/or, the time of described reaction is 0.5-12h.
9. a kind of catalyst system, including the nickel complex described in claim 5 or 6 as major catalyst；Excellent
Described catalyst system is selected to further include promoter.
10. catalyst system according to claim 9 is it is characterised in that described promoter is selected from alkane
At least one in base aikyiaiurnirsoxan beta, alkyl aluminum and aryl boron, be preferably selected from trimethyl aluminium, triethyl aluminum, three
Aluminium isobutyl, three n-butylaluminum, tri-n-hexyl aluminum, three n-pentyl aluminum, tri-n-octylaluminium, diethylaluminum chloride,
Ethylaluminium dichloride, three pentafluorophenyl group boron and N, in accelerine four (pentafluorophenyl group) borate at least
A kind of.
11. catalyst systems according to claim 10 are it is characterised in that in described promoter
The mol ratio of the nickel in aluminum and described major catalyst is (50-5000):Boron in 1, and/or described promoter with
The mol ratio of the nickel in described major catalyst is (1-50):1.
A kind of 12. methods of olefinic polymerization, including catalyst described in alkene any one in claim 9-11
In the presence of system, carry out olefinic polyreaction.
13. methods according to claim 12 are it is characterised in that the temperature of described polyreaction is -78
To 200 DEG C, preferably -20 to 150 DEG C, more preferably 50-120 DEG C；And/or, described polyreaction
Pressure be 0.01-10.0MPa, preferably 0.01-2.0MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456814A (en) * | 2018-12-29 | 2019-03-12 | 江苏奥克化学有限公司 | A kind of transformer oil composition and preparation method thereof |
| CN109852452A (en) * | 2018-12-29 | 2019-06-07 | 江苏奥克化学有限公司 | A kind of low-temperature resistance hybrid-engine oil and preparation method thereof |
| CN111548285A (en) * | 2020-05-21 | 2020-08-18 | 中国科学院长春应用化学研究所 | Overlapped steric hindrance-enhanced alpha-diimine ligand, nickel catalyst, preparation method and application thereof |
| CN112745358A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN112745359A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| WO2021083330A1 (en) * | 2019-10-31 | 2021-05-06 | 中国石油化工股份有限公司 | Amino-imine metal complex and preparation method therefor and application thereof |
| CN112892596A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Palladium catalyst and application thereof in Heck reaction |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769314A (en) * | 2004-11-03 | 2006-05-10 | 中国石油化工股份有限公司 | Copolymer of olefin and omega-tolyl-alpha-olefin and its preparation method |
| CN101412771A (en) * | 2008-11-25 | 2009-04-22 | 中山大学 | Pyridine diimine iron olefin polymerizing catalyst, as well as preparation method and application thereof |
| CN101531725A (en) * | 2009-04-08 | 2009-09-16 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene |
| CN101812145A (en) * | 2009-04-08 | 2010-08-25 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene |
| CN102093425A (en) * | 2010-12-04 | 2011-06-15 | 西北师范大学 | Tert-butyl-containing alpha-nickel diimine (II) coordination compound and preparation thereof |
| CN102399323A (en) * | 2011-10-09 | 2012-04-04 | 南昌大学 | N,O-single ligand metal catalyst with stereochemical structure and preparation method thereof |
| CN102786435A (en) * | 2011-05-16 | 2012-11-21 | 中国科学院上海有机化学研究所 | Catalysis systems for preparing highly branched alkane by using olefin |
-
2015
- 2015-07-31 CN CN201510462910.6A patent/CN106397260B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769314A (en) * | 2004-11-03 | 2006-05-10 | 中国石油化工股份有限公司 | Copolymer of olefin and omega-tolyl-alpha-olefin and its preparation method |
| CN101412771A (en) * | 2008-11-25 | 2009-04-22 | 中山大学 | Pyridine diimine iron olefin polymerizing catalyst, as well as preparation method and application thereof |
| CN101531725A (en) * | 2009-04-08 | 2009-09-16 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene |
| CN101812145A (en) * | 2009-04-08 | 2010-08-25 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene |
| CN102093425A (en) * | 2010-12-04 | 2011-06-15 | 西北师范大学 | Tert-butyl-containing alpha-nickel diimine (II) coordination compound and preparation thereof |
| CN102786435A (en) * | 2011-05-16 | 2012-11-21 | 中国科学院上海有机化学研究所 | Catalysis systems for preparing highly branched alkane by using olefin |
| CN102399323A (en) * | 2011-10-09 | 2012-04-04 | 南昌大学 | N,O-single ligand metal catalyst with stereochemical structure and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| PING HUO ETAL: "Norbornene/n-Butyl Methacrylate Copolymerization over a-Diimine Nickel and Palladium Catalysts Supported on Multiwalled Carbon Nanotubes", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
| PING HUO ETAL: "Substituent effects and activation mechanism of norbornene polymerization catalyzed by three threedimensional complexes", 《POLYM. CHEM》 * |
| PING HUO: "Nickel(II) Complexes with Three-Dimensional Geometry α Diimine Ligands: Synthesis and Catalytic Activity toward Copolymerization of Norbornene", 《ORGANOMETALLICCS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456814A (en) * | 2018-12-29 | 2019-03-12 | 江苏奥克化学有限公司 | A kind of transformer oil composition and preparation method thereof |
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| CN112745358A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN112745359A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| WO2021083330A1 (en) * | 2019-10-31 | 2021-05-06 | 中国石油化工股份有限公司 | Amino-imine metal complex and preparation method therefor and application thereof |
| CN112745358B (en) * | 2019-10-31 | 2022-10-21 | 中国石油化工股份有限公司 | Diimine metal complex, preparation method and application thereof |
| CN112745359B (en) * | 2019-10-31 | 2022-10-21 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN111548285A (en) * | 2020-05-21 | 2020-08-18 | 中国科学院长春应用化学研究所 | Overlapped steric hindrance-enhanced alpha-diimine ligand, nickel catalyst, preparation method and application thereof |
| CN112892596A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Palladium catalyst and application thereof in Heck reaction |
| CN112892596B (en) * | 2021-01-22 | 2024-03-22 | 邹育英 | Palladium catalyst and application thereof in Heck reaction |
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