CN106397260B - A kind of diimide ligand compound, nickel complex and application - Google Patents
A kind of diimide ligand compound, nickel complex and application Download PDFInfo
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Abstract
The present invention provides a kind of diimide ligand compound, structural formula is as follows：In Formulas I, R1‑R10It is identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen.The invention further relates to the preparation method of the ligand, the preparation method and application of the nickel complex that the ligand is formed and the complex.Using complex of the invention as major catalyst in use, polymerization activity wants high under the conditions of high temperature polymerization, the molecular weight of resulting polymers is high.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of novel diimide ligand and its nickel complex obtained.This
Invention further relates to the application of above-mentioned nickel complex in olefin polymerization as catalyst.
Background technology
China is that synthetic resin consumes fastest-rising country, is also the largest synthetic resin importer, at present polyolefin
Yield proportion nearly 60%, olefin resin has excellent environment compatibility compared with other resin materials, in flourishing state
It is used for the material of emphasis popularization in family's automobile industry, world's output in 2003 has just reached 83,300,000 tons；It is wherein poly-
Ethylene is synthetic resin with fastest developing speed, that yield is maximum, purposes is extremely wide, reaches 51,100,000 tons for the year.Industrialized polyethylene is urged
Agent has Ziegler-Natta types catalyst (DE Pat 889229 (1953)；IT Pat 545332 (1956) and IT Pat
536899(1955)；Chem.Rev., 2000,100,1169 and the 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:Springer,
1999) the efficient ethylene oligomerization and polymerization catalyst of the late transition metal metal compounding material type, and in recent years developed.Such as
Nineteen ninety-five, Brookhart etc. report the complex of a kind of alpha-diimine Ni (II), can be with the polymerising ethylene of high activity.
Since alpha-diimine Raney nickel has high activity and polymer molecular weight and the degree of branching can be in very wide range
It is interior regulation and control 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 α-two
Imines Raney nickel is under methylaluminoxane or alkyl aluminum effect, the catalysis ethylene oligomerization of energy high activity under room temperature or low temperature
Or polymerization.But when increasing reaction temperature higher than 50 DEG C, this kind of alpha-diimine nickel catalyst activity reduces rapidly, and prepared is poly-
The molecular weight with polymerisation temperature of ethylene improves and declines rapidly.Existing ethene gas-phase polymerization technological requirement polymerization temperature be 85 DEG C with
On, it is 150-250 DEG C that vinyl solution polymerization technique, which requires polymerization temperature, and original late transition metal catalyst cannot be satisfied existing gas
The requirement of phase, solwution method ethylene polymerization plants.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of new structural diimide ligand compound,
A kind of alpha-nickel diimine compound with good thermal stability can be formed with nickel.The complex is activated in co-catalyst
Under under (such as methylaluminoxane or alkyl aluminum activation), can realize catalyzed ethylene polymerization under higher temperature, keep higher ethylene
Branched polyethylene can be made in polymerization activity.Meanwhile resulting polymers molecular weight is higher, molecular weight distribution is relatively narrow.
A specific implementation mode according to the present invention, provides a kind of diimide ligand compound, structural formula is as follows
It is shown：
In Formulas I, R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen,
It preferably is selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxy and halogen.
In ligand compound according to the present invention, in the Formulas I, R1-R10It is identical or different, it is each independently selected from
Hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxy and halogen, be preferably selected from hydrogen, methyl, ethyl, vinyl, different
Propyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine.
Another embodiment according to the present invention provides and a kind of preparing ligand compound shown in above-mentioned Formulas I
Method includes that compound A and aniline or substituted aniline flow back in solvent under the effect of the catalyst, obtains Formulas I
Shown in ligand compound,
Method according to the present invention, the compound A are 1 with the molar ratio of aniline or substituted aniline:2-
1:10, preferably 1:2-1:3.The solvent can be selected from least one of toluene, methanol, ethyl alcohol and acetonitrile.The catalyst
Selected from least one of p-methyl benzenesulfonic acid, acetic acid and formic acid, the amount of the preferably described catalyst is the 0.01- of compound A amounts
20mol%.The temperature of the reflux can be 40-120 DEG C, preferably 65-110 DEG C.The time of the reflux can be 0.5-7
It, preferably 1-2 days.
Wherein, the restriction of the substituent group on the substituted aniline is such as R1-R10, for example, the substituted aniline can
Think 2,6- methylanilines, 2,6- diethylanilines, 2,6- diisopropyl anilines, the bromo- aniline of 2,6- dimethyl -4- and/or 2,
6- difluoroanilines.
In the synthetic method of ligand compound of the present invention, for example, the ligand compound can be by following
Method prepare：
A) compound A and aniline or substituted aniline are flowed back 1 day in ethanol using acetic acid as catalyst, are removed after filtering molten
Parlkaline aluminium oxide pillar after agent, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains
Yellow solid；Or
B) compound A and aniline or substituted aniline flow back one day in toluene by catalyst of p-methyl benzenesulfonic acid, instead
Liquid is answered to be evaporated rear parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes molten
Agent obtains yellow solid, i.e. alpha-diimine ligand；
The alpha-diimine ligand of above-mentioned synthesis can be confirmed by nuclear-magnetism, infrared and elemental analysis.
Another embodiment according to the present invention provides a kind of nickel complex, and 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, the nickel complex can be selected from least one in following complex
Kind, wherein in following complex, R7-R10It is hydrogen：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；、
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；And
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
In a preferred embodiment of the present invention, in structure shown in the 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, the R2And R5It is each independently selected from
Hydrogen, methyl, vinyl or bromine.
Another embodiment according to the present invention provides a kind of method preparing above-mentioned nickel complex, including：
Above-mentioned diimide ligand compound and nickel halogenide or nickel halogenide derivative are subjected to complexation reaction, obtain coordinating shown in Formula II
Object.
Method according to the present invention, the nickel halogenide or nickel halogenide derivative and the diimide ligand compound
Molar ratio is 1:1-1.2:1.The nickel halogenide or nickel halogenide derivative are selected from NiBr2、NiCl2、(DME)NiBr2(DME)
NiCl2.The temperature of the reaction is 0-60 DEG C.The time of the reaction is 0.5-12h.The complexation reaction is usually anhydrous
It carries out, for example can carry out under an inert atmosphere under oxygen free condition.Wherein, DME is the abbreviation of dimethyl ether.
According to the present invention, a specific illustrative preparation process of nickel (II) complex is as follows：In indifferent gas
Under body protection, by (DME) NiCl2Or (DME) NiBr2Dichloromethane solution in molar ratio (1:1-1:1.2) two Asias are added drop-wise to
It in the solution of amine ligand, is stirred at room temperature, precipitation is precipitated, filtering is dried in vacuo after being washed with ether just obtains diimine nickel cooperation
Object.Complex can be characterized by elemental analysis or infrared spectrum.
Another embodiment according to the present invention provides a kind of catalyst system, including above-mentioned Formula II institute
The nickel complex shown is major catalyst.And the preferably described catalyst system further comprises co-catalyst.
One preferred embodiment of catalyst system according to the present invention, the co-catalyst are selected from alkyl alumina
At least one of alkane, alkyl aluminum and aryl boron are preferably selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three normal-butyls
Aluminium, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride, three pentafluorophenyl group boron and
N, at least one of accelerine four (pentafluorophenyl group) borate.
One preferred embodiment of catalyst system according to the present invention, the aluminium in the co-catalyst and the master
The molar ratio of nickel in catalyst is (50-5000):1.Boron in the co-catalyst rubs with the nickel in the major catalyst
You are than being (1-50):1.
Another embodiment according to the present invention provides a kind of method of olefinic polymerization, including alkene is upper
In the presence of stating catalyst system, olefinic polyreaction is carried out.
Catalyst system prepared by the present invention can be used for homopolymerization or the copolymerization of alkene, especially suitable for second
Polyamino alkenyl closes or the copolymerization of ethylene and other alpha-olefins, and wherein alpha-olefin is selected from propylene, butylene, amylene, hexene, octene
Or at least one of 4- methylpentenes -1 etc..
According to a preferred embodiment of the present invention, the temperature of the polymerisation be -78 to 200 DEG C, preferably -20 to
150 DEG C, further preferably 50-120 DEG C.The pressure of the polymerisation is 0.01-10.0MPa, preferably 0.01-2.0MPa.
In some currently preferred embodiments of the present invention, wherein polymerisation can carry out in a solvent, and used solvent is selected from
Alkane, aromatic hydrocarbon or halogenated hydrocarbons.It is preferred that one kind in hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes
Or their mixture, one kind or their mixture most preferably in hexane, toluene, heptane.
According to the present invention, a kind of new structural diimide ligand compound and its nickel complex of synthesis are provided.This
The invention nickel complex is under co-catalyst (such as methylaluminoxane or alkyl aluminum) effect, the catalysis second of energy high activity
Alkene polymerize.Especially (100 degree) higher polymerization activity can be still kept under higher polymerization temperature, it is even super that high molecular weight can be made
High molecular weight polyethylene.(the diimine nickel catalyst of previous literature or patent report is significantly decayed in 50 degree or more activity,
And molecular weight is greatly lowered).Meanwhile there is good catalysis ethylene and high alpha-olefin to be total to for catalyst of the present invention
The ability of polymerisation, Copolymerization activity are high.
Specific implementation mode
The present invention will be described in detail with reference to embodiments, but it is to be appreciated that the embodiment is only used for pair
The present invention is illustratively described, and can not constitute any restrictions to protection scope of the present invention.It is all to be included in this hair
Reasonable changes and combinations in bright invention teachings each fall within protection scope of the present invention.
Analysis and characterization instrument used in the present invention is as follows:
1, Nuclear Magnetic Resonance：Bruker DMX 300 (300MHz), tetramethylsilane (TMS) are internal standard
2. elemental analyser：The Italian full-automatic elemental analysers of ThermoQuest companies EA1112.
In embodiment, the amount of catalyst used is the 5mol% of compound A amounts.Except with other external compounds be quotient
Purchase.The synthesis of complex used carries out in a nitrogen atmosphere.
Embodiment 1
1) ligand preparation (in structural formula I, R1、R3、R4And R6For isopropyl, R7-R10、R2And R5For hydrogen)：
Compound A (5.85g, 9.0mmol) and 2,6-DIPA (4.0ml, 19.7mmol), p-methyl benzenesulfonic acid are
Catalyst removed solvent, residue is dissolved with dichloromethane, parlkaline aluminium oxide in 100mL reflux in toluene 1 day after filtering
Pillar, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains yellow solid, 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) complex 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 to the above-mentioned ligands of 10ml
It in the dichloromethane solution of (1550mg, 1.6mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
Obtain dark red powder solid, yield 88%.Elemental analysis (C48H44Br6N2Ni)：C,48.57；H,3.74；N,2.36；It is real
Test value (%)：C,48.32；H,3.71；N,2.46.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.11.9mg (10 μm of ol) complexs 3 are added then to vacuumize and replaced 3 times with ethylene again.
The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solutions of 1.53 mol/l), makes Al/Ni=
1000.At 50 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.In ethanol solution with the acidification of 5% hydrochloric acid
With obtain polyethylene, polymerization activity is 4.32 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 2
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.The complex 3 of 11.9mg (10 μm of ol) embodiment 1 preparation is added and then vacuumizes again and is used in combination
Ethylene is replaced 3 times.The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solution of 1.53mol/l),
Make Al/Ni=1000.At 100 DEG C, the ethylene pressure of 10atm is kept, 30min is stirred to react.The ethyl alcohol being acidified with 5% hydrochloric acid
Solution neutralizes, and obtains polyethylene, and polymerization activity is 5.26 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 3
1) ligand preparation (in structural formula I, R1、R3、R4And R6For ethyl, R7-R10、R2And R5For hydrogen)：
Compound A (5.07g, 7.8mmol) and 2,6- diethylanilines (3.0ml, 17.4mmol), p-methyl benzenesulfonic acid are to urge
Agent removed solvent, residue is dissolved with dichloromethane, parlkaline alumina column in 100mL reflux in toluene 1 day after filtering
Son, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains yellow solid, 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) complex 2 preparation (in formula II, R1、R3、R4And R6For ethyl, R7-R10、R2And R5For hydrogen, X Br)：
By 10ml (DME) NiBr2The dichloromethane solution of (155mg, 0.5mmol) is added drop-wise to the above-mentioned ligands of 10ml
It in the dichloromethane solution of (456mg, 0.5mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
To dark red powder solid, yield 90%.Elemental analysis (C44H36Br6N2Ni)：C,46.73；H,3.21；N,2.48；Experiment
It is worth (%)：C,46.42；H,3.56；N,2.41.
3) 10atm vinyl polymerizations：It is 6 hours continuous drying at 130 DEG C that churned mechanically 1L stainless steels polymeric kettle will be housed, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.Complex 2 prepared by 11.3mg (10 μm of ol) embodiment 3 is added then to vacuumize again simultaneously
It is replaced 3 times with ethylene.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% hydrochloric acid acid
The ethanol solution of change neutralizes, and obtains polyethylene, and polymerization activity is 1.84 × 106g·mol-1(Ni)·h-1, as a result such as 1 institute of table
Show.
Embodiment 4
1) ligand preparation (in structural formula I, R1、R3、R4And R6For methyl, R7-R10、R2And R5For hydrogen)：
Compound A (3.12g, 4.8mmol) and 2,6- methylanilines (1.3ml, 10.4mmol), p-methyl benzenesulfonic acid are catalysis
Agent removed solvent in 100mL reflux in toluene 1 day after filtering, residue is dissolved with dichloromethane, parlkaline aluminium oxide pillar,
With petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, and it is 75% to remove solvent and obtain yellow solid yield.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) complex 1 preparation (in formula II, R1、R3、R4And R6For methyl, R7-R10、R2And R5For hydrogen, X Br)：
By 10ml (DME) NiBr2The dichloromethane solution of (277mg, 0.9mmol) is added drop-wise to the above-mentioned ligands of 10ml
It in the dichloromethane solution of (771mg, 0.9mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
To dark red powder solid, yield 90%.Elemental analysis (C40H28Br6N2Ni)：C,44.70；H,2.63；N,2.61；Experiment
It is worth (%)：C,44.46；H,2.87；N,2.82.
3) vinyl polymerization：
Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, vacuumize while hot and use N2Gas
Displacement 3 times.10.7mg (10 μm of ol) complexs 1 are added then to vacuumize and replaced 3 times with ethylene again.The hexane of 500ml is injected,
6.5ml methylaluminoxane (MAO) (toluene solution of 1.53mol/l) is added, Al/Ni=1000 is made.At 50 DEG C, keep
The ethylene pressure of 10atm, is stirred to react 30min.It is neutralized with the ethanol solution that 5% hydrochloric acid is acidified, obtains polyethylene, polymerization activity
It is 1.44 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 5
1) ligand preparation (in structural formula I, R1、R3、R4And R6For methyl, R7-R10For hydrogen, R2And R5For bromine)：
The bromo- aniline of compound A (3.31g, 5.1mmol) and 2,6- dimethyl -4- (2.3g, 11.3mmol), to toluene sulphur
Acid is that catalyst removed solvent, residue is dissolved with dichloromethane, parlkaline oxygen in 100mL reflux in toluene 1 day after filtering
Change aluminium pillar, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains yellow solid, yield
It 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) complex 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 to the above-mentioned ligands of 10ml
It in the dichloromethane solution of (710mg, 0.7mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
To dark red powder solid, yield 82%.Elemental analysis (C40H26Br8N2Ni)：C,38.98；H,2.13；N,2.27；Experiment
It is worth (%)：C,39.24；H,2.52；N,2.67.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.12.3mg (10 μm of ol) complexs 5 are added then to vacuumize and replaced 3 times with ethylene again.
The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=
1000.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethanol solution being acidified with 5% hydrochloric acid
It neutralizes, obtains polyethylene, polymerization activity is 1.78 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 6
1) ligand preparation (in structural formula I, R1、R3、R4And R6For fluorine, R7-R10、R2And R5For hydrogen)：
Compound A (3.31g, 5.1mmol) and 2,6- difluoroanilines (1.3ml, 11.3mmol), p-methyl benzenesulfonic acid are catalysis
Agent removed solvent in 100mL reflux in toluene 1 day after filtering, residue is dissolved with dichloromethane, parlkaline aluminium oxide pillar,
With petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains yellow solid, yield 48%.1H
NMR(CDCl3,δ,ppm):5.48(s,2H),7.04(m,6H),7.40(s,4H),7.82(s,4H).
2) complex 9 preparation (in formula II, R1、R3、R4And R6For fluorine, R7-R10、R2And R5For hydrogen, X Br)：
By 10ml (DME) NiBr2The dichloromethane solution of (216mg, 0.7mmol) is added drop-wise to the above-mentioned ligands of 10ml
It in the dichloromethane solution of (610mg, 0.7mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
To dark red powder solid, yield 88%.Elemental analysis (C36H16Br6F4N2Ni)：C,39.65；H,1.48；N,2.57；It is real
Test value (%)：C,39.82；H,1.76；N,2.60.
3) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.10.9mg (10 μm of ol) complexs 9 are added then to vacuumize and replaced 3 times with ethylene again.
The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solutions of 1.53 mol/l), makes Al/Ni=
1000.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethanol solution being acidified with 5% hydrochloric acid
It neutralizes, obtains polyethylene, polymerization activity is 0.20 × 106g·mol-1(Ni)·h-1。
Embodiment 7
1) complex 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 to ligand in 10ml embodiments 4
It in the dichloromethane solution of (1550mg, 1.6mmol), is stirred at room temperature 6 hours, precipitation is precipitated, filtering is dry after being washed with ether
Obtain orange red powder solid, yield 90%.Elemental analysis (C48H44Br4Cl2N2Ni)：C,52.50；H,4.04；N,2.55；
Experiment value (%)：C,52.57；H,4.47；N,2.43.
2) 10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken advantage of
Heat vacuumizes and uses N2Gas is replaced 3 times.11.0mg (10 μm of ol) complexs 14 are added then to vacuumize again and replace 3 with ethylene
It is secondary.The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solution of 1.53mol/l), makes Al/Ni=
1000.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethanol solution being acidified with 5% hydrochloric acid
It neutralizes, obtains polyethylene, polymerization activity is 4.42 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 8
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.The complex 14 of 11.0mg (10 μm of ol) embodiment 7 preparation is added and then vacuumizes again and is used in combination
Ethylene is replaced 3 times.The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MAO) (toluene solution of 1.53mol/l),
Make Al/Ni=1000.At 50 DEG C, the ethylene pressure of 10atm is kept, 30min is stirred to react.The ethyl alcohol being acidified with 5% hydrochloric acid
Solution neutralizes, and obtains polyethylene, and polymerization activity is 3.14 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 9
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.The complex 3 prepared in 11.9mg (10 μm of ol) embodiment 1 is added and then vacuumizes again simultaneously
It is replaced 3 times with ethylene.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% hydrochloric acid acid
The ethanol solution of change neutralizes, and obtains polyethylene, and polymerization activity is 4.88 × 106g·mol-1(Ni)·h-1, as a result such as 1 institute of table
Show.
Embodiment 10
10atm vinyl polymerizations：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, while hot
It vacuumizes and uses N2Gas is replaced 3 times.The complex 3 prepared in 11.9mg (10 μm of ol) embodiment 1 is added and then vacuumizes again simultaneously
It is replaced 3 times with ethylene.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000,10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With
The ethanol solution of 5% hydrochloric acid acidification neutralizes, and obtains polyethylene, and polymerization activity is 5.02 × 106g·mol-1(Ni)·h-1, as a result
As shown in table 1.
Comparative example 1
10atm ethylene：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken out while hot true
Sky simultaneously uses N2Gas is replaced 3 times.7.2mg (10 μm of ol) comparative catalyst B are added then to vacuumize and replaced 3 times with ethylene again.Note
The hexane for entering 500ml adds 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000,
10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethyl alcohol being acidified with 5% hydrochloric acid is molten
Liquid neutralizes, and obtains polyethylene, and polymerization activity is 0.08 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Comparative example 2
10atm ethylene：Churned mechanically 1L stainless steels polymeric kettle will be housed in 130 DEG C of continuous drying 6hrs, taken out while hot true
Sky simultaneously uses N2Gas is replaced 3 times.6.2mg (10 μm of ol) comparative catalyst C are added then to vacuumize and replaced 3 times with ethylene again.Note
The hexane for entering 500ml adds 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), makes Al/Ni=1000,
10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.The ethyl alcohol being acidified with 5% hydrochloric acid is molten
Liquid neutralizes, and obtains polyethylene, and polymerization activity is 0.02 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Table 1
As can be seen from Table 1, the complex relative to comparative example 1 and 2, using the metal complex of the present invention as main reminder
For agent in use, polymerization activity is much higher under the conditions of high temperature polymerization, the molecular weight of resulting polymers is apparently higher than comparative example
Ultra-high molecular weight polyethylene can be made in resulting polymers.Meanwhile gained polyethylene still has relatively narrow molecular weight distribution.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (20)
1. a kind of diimide ligand compound, structural formula is as shown in following formula I：
In Formulas I, R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen.
2. ligand compound according to claim 1, which is characterized in that in Formulas I, R1-R10It is identical or different, it is respectively independent
Ground is selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxy and halogen.
3. ligand compound according to claim 1, which is characterized in that in the Formulas I, R1-R10It is identical or different, respectively
Independently selected from hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxy and halogen.
4. ligand compound according to claim 3, which is characterized in that in the Formulas I, R1-R10It is identical or different, respectively
Independently selected from hydrogen, methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl group, ethyoxyl, propoxyl group, fluorine, chlorine and bromine.
5. a kind of method preparing any one of claim 1-4 diimide ligand compounds, including by compound A and benzene
Amine or substituted aniline flow back in solvent under the effect of the catalyst, obtain ligand compound shown in Formulas I,
6. according to the method described in claim 5, it is characterized in that, the compound A and aniline or mole of substituted aniline
Than being 1:2-1:10；And/or
The solvent is selected from least one of toluene, methanol, ethyl alcohol and acetonitrile；And/or
The catalyst is selected from least one of p-methyl benzenesulfonic acid, acetic acid and formic acid；And/or
The temperature of the reflux is 40-120 DEG C；And/or
The time of the reflux is 0.5-7 days.
7. according to the method described in claim 6, it is characterized in that, the compound A and aniline or mole of substituted aniline
Than being 1:2-1:3；And/or
The amount of the catalyst is the 0.01-20mol% of compound A amounts；And/or
The temperature of the reflux is 65-110 DEG C；And/or
The time of the reflux is 1-2 days.
8. a kind of nickel complex, structural formula is as shown in Formula II：
In Formula II, R1-R10Restriction with any one of claim 1-4, X be halogen.
9. nickel complex according to claim 8, which is characterized in that the complex can be selected from following complex extremely
Few one kind, wherein in following complex, R7-R10It is hydrogen：
Complex 1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；
Complex 2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
Complex 3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；
Complex 4：R1=R2=R3=R4=R5=R6=Me, X=Br；
Complex 5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；
Complex 6：R1=R3=R4=R6=Me, R2=R5=Et, X=Br
Complex 7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；
Complex 8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
Complex 9：R1=R3=R4=R6=F, R2=R5=H, X=Br；
Complex 10：R1=R3=R4=R6=Cl, R2=R5=H, X=Br；、
Complex 11：R1=R3=R4=R6=Br, R2=R5=H, X=Br；
Complex 12：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；
Complex 13：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
Complex 14：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；
Complex 15：R1=R2=R3=R4=R5=R6=Me, X=Cl；
Complex 16：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；
Complex 17：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
Complex 18：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；
Complex 19：R1=R3=R4=R6=Et, R2=R5=Br, X=Cl；
Complex 20：R1=R3=R4=R6=F, R2=R5=H, X=Cl；
Complex 21：R1=R3=R4=R6=Cl, R2=R5=H, X=Cl；And
Complex 22：R1=R3=R4=R6=Br, R2=R5=H, X=Cl.
10. a kind of method preparing the nickel complex of claim 8 or 9, including：Described in any one of claim 1-4
Diimide ligand compound and nickel halogenide or nickel halogenide derivative carry out complexation reaction, obtain complex shown in Formula II.
11. according to the method described in claim 10, it is characterized in that, the nickel halogenide or nickel halogenide derivative and two Asia
The molar ratio of amine ligand compound is 1:1-1.2:1；And/or
The nickel halogenide or nickel halogenide derivative are selected from NiBr2、NiCl2、(DME)NiBr2(DME) NiCl2；And/or
The temperature of the reaction is 0-60 DEG C；And/or the time of the reaction is 0.5-12h.
12. a kind of catalyst system includes using the nickel complex described in claim 8 or 9 as major catalyst.
13. catalyst system according to claim 12, which is characterized in that the catalyst system, which further comprises helping, urges
Agent.
14. catalyst system according to claim 13, which is characterized in that the co-catalyst be selected from alkylaluminoxane,
At least one of alkyl aluminum and aryl boron.
15. catalyst system according to claim 14, which is characterized in that the co-catalyst is selected from trimethyl
Aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethyl base
Aluminium, ethylaluminium dichloride, three pentafluorophenyl group boron and N, at least one of accelerine four (pentafluorophenyl group) borate.
16. catalyst system according to claim 14, which is characterized in that the aluminium in the co-catalyst and the main reminder
The molar ratio of nickel in agent is (50-5000):1 and/or the co-catalyst in boron and the major catalyst in nickel
Molar ratio is (1-50):1.
17. a kind of method of olefinic polymerization, including alkene depositing in any one of the claim 12-16 catalyst systems
Under, olefinic polyreaction is carried out.
18. according to the method for claim 17, which is characterized in that the temperature of the polymerisation is -78 to 200 DEG C；With/
Or, the pressure of the polymerisation is 0.01-10.0MPa.
19. according to the method for claim 18, which is characterized in that the temperature of the polymerisation is -20 to 150 DEG C；With/
Or, the pressure of the polymerisation is 0.01-2.0MPa.
20. according to the method for claim 18, which is characterized in that the temperature of the polymerisation is 50-120 DEG C.
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