CN106397259B - A kind of diimide ligand, diimine nickel complex and application - Google Patents
A kind of diimide ligand, diimine nickel complex and application Download PDFInfo
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Abstract
The present invention provides a kind of diimide ligands, have structure shown in Formulas I：In Formulas I, R1‑R10It is identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen.The present invention relates to the diimine nickel complexes that the diimide ligand is formed.The diimine nickel complex of the present invention, as catalyst, is capable of the catalyzed ethylene polymerization of high activity under preferred promoter (such as methylaluminoxane or alkyl aluminum) is active.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of new structural diimide ligand and its diimine of formation
Nickel complex.The invention further relates to the preparation methods of the ligands and complexes and the complex to be urged as olefinic polymerization
Application of the agent in terms of olefinic polymerization.
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 Pat889229 (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, 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 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
It, can be in view of the deficienciess of the prior art, this application provides a kind of new structural diimide ligand
Nickel forms the alpha-nickel diimine compound with good thermal stability.The complex can be realized preferably under co-catalyst activation
Catalyzed ethylene polymerization under higher temperature prepares the branched polyethylene of high molecular weight；And higher second can be still kept under higher temperature
Alkene polymerization activity, and resulting polymers molecular weight is higher, molecular weight distribution is relatively narrow.
According to an aspect of the invention, there is provided a kind of diimide ligand, has structure shown in Formulas I：
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, R1-R10It is identical or different, it is each independently selected from hydrogen, C1-C10Saturation or unsaturated alkyl, C1-C10Alkoxy
And halogen.
In one specific embodiment of ligand according to the present invention, in the Formulas I, R1-R10It is identical or different, respectively
Independently selected from hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxy 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, a kind of method preparing above-mentioned ligand is provided, including：By compound A with
Aniline or substituted aniline flow back in solvent under the effect of the catalyst, obtain ligand shown in Formulas I,
According to the method for the invention specific embodiment, the compound A and aniline or substituted aniline rub
You are than being 1:2-1:10, preferably 1:2-1:3.The solvent is selected from least one of toluene, methanol, ethyl alcohol and acetonitrile.It is described
Catalyst is selected from least one of p-methyl benzenesulfonic acid, acetic acid and formic acid, and the amount of the preferably described catalyst is compound A amounts
0.01-20mol%.The temperature of the reflux is 40-120 DEG C, preferably 65-110 DEG C.The time of the reflux is 0.5-7 days, excellent
It selects 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 a specific embodiment, process can be for example prepared by the following procedure to prepare in ligand of the invention：
A) compound A and substituted aniline are flowed back 1 day in ethanol using acetic acid as catalyst, and mistake after solvent is removed after filtering
Alkali alumina pillar, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, and it is solid that removing solvent obtains yellow
Body；Or
B) compound A and substituted aniline flow back one day in toluene by catalyst of p-methyl benzenesulfonic acid, and reaction solution steams
Parlkaline aluminium oxide pillar after dry, with petrol ether/ethyl acetate (20:1) it elutes, second is divided into product, removes solvent and obtains
Yellow solid, i.e. alpha-diimine ligand；
The alpha-diimine ligand of above-mentioned all synthesis can be confirmed by nuclear-magnetism, infrared and elemental analysis.
According to another aspect of the present invention, a kind of diimine nickel complex is additionally provided, shown in Formula II
Structure,
In Formula II, R1-R10The same ligand compound of restriction.
According to diimine nickel complex of the present invention specific embodiment, work as R7-R10When being hydrogen, the cooperation
Object has structure shown in formula III,
One specific embodiment of nickel complex according to the present invention, the complex can be selected from following complex
At least one：
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 III, X is Cl or Br, R1、R3、R4
And R6It is each independently selected from methyl, ethyl or isopropyl, fluorine, chlorine or bromine, the R2And R5Be each independently selected from hydrogen, methyl,
Vinyl or bromine.
According to another aspect of the present invention, a kind of method preparing above-mentioned nickel complex is additionally provided, including such as
Lower step：Above-mentioned diimide ligand and nickel halogenide or nickel halogenide derivative are subjected to complexation reaction, is made shown in Formula II and matches
Close object.
A specific embodiment according to the method for the present invention, the nickel halogenide or nickel halogenide derivative and the diimine ligand
The molar ratio of body is 1:1-1.2:1.The nickel halogenide or nickel halogenide derivative are selected from NiBr2、NiCl2、(DME)NiBr2With
(DME)NiCl2.The temperature of the reaction is 0-60 DEG C.The time of reaction is 0.5-12h.
According to the present invention, the complexation reaction can be in anhydrous and oxygen-free solution as carried out under an inert atmosphere.It is specific at one
Implementation in, under inert gas protection, 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, precipitation is precipitated, filtering is dried in vacuo after being washed with ether just to be obtained
To diimine nickel complex.Complex can be characterized by elemental analysis and infrared spectrum.DME is the contracting of dimethyl methyl ether
It writes.
According to another aspect of the present invention, catalyst system of the kind for olefinic polymerization is additionally provided, including
Above-mentioned complex is major catalyst.It is preferred that still further comprising co-catalyst in the catalyst system.
In a specific embodiment of the catalyst system, the co-catalyst can be selected from alkylaluminoxane, alkyl
At least one of aluminium and aryl boron are being preferably selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, three just
Hexyl aluminium, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride, three pentafluorophenyl group boron and N, N- diformazan
At least one of base aniline four (pentafluorophenyl group) borate.
In another specific embodiment of the catalyst system, the aluminium in the co-catalyst and the major catalyst
In nickel molar ratio be (50-5000):The molar ratio of boron and the nickel in the major catalyst in 1 or described co-catalyst
For (1-50):1.
According to another aspect of the present invention, a kind of olefine polymerizing process, including the alkene are additionally provided above-mentioned
Polymerisation is carried out under the action of catalyst system.
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 polymerization of the present invention specific embodiment, the reaction temperature of the polymerisation be -78 to
200 DEG C, preferably -20 to 150 DEG C, further preferably 50 to 120 DEG C.Polymerization pressure is 0.01-10.0MPa, preferably
0.01-2.0MPa。
In some preferred embodiments of the present invention, wherein polymerisation can carry out in a solvent.It is used molten
Agent is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.It is preferred that in hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes
One kind or their mixture, one kind or their mixture most preferably in hexane, toluene, heptane.
The present invention has synthesized new structural diimide ligand compound, can form diimine nickel complex with nickel.
The diimine nickel complex of the present invention, under preferred promoter (such as methylaluminoxane or alkyl aluminum) activity, as catalyst,
It is capable of the catalyzed ethylene polymerization of high activity.Especially (100 degree) it can still keep higher polymerization activity under higher polymerization temperature.
(the diimine nickel catalyst of previous literature or patent report is significantly decayed in 50 degree or more activity, and molecular weight is significantly
It reduces).Catalyst of the present invention has the ability of the copolymerization of good catalysis ethylene and high alpha-olefin, copolymerization
It is active high, extremely-low density, branched polyethylene can be made.
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) preparation of ligand：
Compound A (2.14g, 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 80% to remove solvent and obtain yellow solid yield.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 complex 1：(formula II I, middle R1、R3、R4And R6For methyl, 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 (588mg, 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 (C48H48Br2N2Ni)：C,66.16；H,5.55；N,3.21；Experiment
It is worth (%)：C,66.02；H,5.82；N,3.42.
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.8.7mg (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 0.76 × 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.Complex 1 prepared by 8.7mg (10 μm of ol) embodiment 1 is added then to vacuumize again and use second
Alkene is replaced 3 times.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, 30min is stirred to react.The ethyl alcohol being acidified with 5% hydrochloric acid is molten
Liquid neutralizes, and obtains polyethylene, and polymerization activity is 1.21 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 3
1) preparation of ligand：
Compound A (3.48g, 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):1.09 (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 complex 2：(in formula II I, R1、R3、R4And R6For ethyl, 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 (354mg, 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 92%.Elemental analysis (C52H56Br2N2Ni)：C,67.34；H,6.09；N,3.02；Experiment
It is worth (%)：C,66.02；H,6.21；N,3.44.
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.The complex 2 of 9.2mg (10 μm of ol) embodiment 3 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, is vigorously stirred reaction 30min.It is acidified with 5% hydrochloric acid
Ethanol solution neutralizes, and obtains polyethylene, and polymerization activity is 1.32 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 4
1) preparation of ligand：
Compound A (4.01g, 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
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 complex 3：(in formula II I, R1、R3、R4And R6For isopropyl, R2And R5For hydrogen, X 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 (1224mg, 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 (C56H64Br2N2Ni)：C,68.38；H,6.56；N,2.85；It is real
Test value (%)：C,68.32；H,6.71；N,2.42.
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.9.8mg (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 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 3.52 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 5
1) preparation of ligand：
The bromo- aniline of compound A (2.28g, 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 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) complex 5 preparation (in formula II I, R1、R3、R4And R6For methyl, R2And R5For bromine, 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 (567mg, 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 85%.Elemental analysis (C48H46Br4N2Ni)：C,56.02；H,4.50；N,2.72；Experiment
It is worth (%)：C,56.36；H,4.92；N,2.81.
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.10.6mg (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 1.31 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 6
1) preparation of ligand：
Compound A (2.27g, 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):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 complex 91、R3、R4And R6For fluorine, 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 (468mg, 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 (C44H36Br2F4N2Ni)：C,59.56；H,4.09；N,3.16；It is real
Test value (%)：C,59.82；H,3.82；N,3.60.
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.8.9mg (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 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 0.24 × 106g·mol-1(Ni)·h-1。
Embodiment 7
1) preparation of complex 14：(in formula II I, R1、R3、R4And R6For isopropyl, R2And R5For hydrogen, X 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 (1224mg, 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 (C56H64Cl2N2Ni)：C,75.17；H,7.21；N,3.13；It is real
Test value (%)：C,75.57；H,7.42；N,3.43.
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.8.9mg (10 μm of ol) complexs 14 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 3.89 × 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 3 prepared in 9.8mg (10 μm of ol) embodiment 4 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 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.It is acidified with 5% hydrochloric acid
Ethanol solution neutralizes, and obtains polyethylene, and polymerization activity is 3.74 × 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 9.8mg (10 μm of ol) embodiment 4 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=1000,10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% salt
The ethanol solution of acid acidification neutralizes, and obtains polyethylene, and polymerization activity is 3.98 × 106g·mol-1(Ni)·h-1, as a result such as table 1
It is shown.
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 9.8mg (10 μm of ol) embodiment 4 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=1000,20ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% salt
The ethanol solution of acid acidification neutralizes, and obtains polyethylene, and polymerization activity is 3.66 × 106g·mol-1(Ni)·h-1, as a result such as table 1
It is shown.
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 solutions of 1.53 mol/l), makes Al/Ni=
1000,10ml hexenes.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.It is acidified with 5% hydrochloric acid
Ethanol solution 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
Resulting polymers.The nickel metal complex of the present invention has excellent copolymerization performance, and the poly- second of extremely-low density of high molecular weight can be made
Alkene.Meanwhile the molecular weight distribution of polymer is still relatively narrow.
Claims (21)
1. a kind of diimide ligand has structure shown in Formulas 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. diimide ligand 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-C10Saturation or unsaturated alkyl, C1-C10Alkoxy and halogen.
3. diimide ligand 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. diimide ligand 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 ligands, including：By compound A and aniline or
Substituted aniline flows back in solvent under the effect of the catalyst, obtains diimide ligand 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 diimine nickel complex, with structure 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 work as R7-R10When being hydrogen, the complex has formula
Structure shown in III,
10. nickel complex according to claim 9, which is characterized in that the complex can be selected from following complex
It is at least one：
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.
11. a kind of method preparing the nickel complex described in any one of claim 8-10, includes the following steps：By right
It is required that the diimide ligand described in any one of 1-4 carries out complexation reaction with nickel halogenide or nickel halogenide derivative, Formula II is made
Shown in complex.
12. according to the method for claim 11, which is characterized in that the nickel halogenide or nickel halogenide derivative and two Asia
The molar ratio of amine ligand 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 reaction is 0.5-12h.
13. the complex described in any one of a kind of catalyst system for olefinic polymerization, including claim 8-10 is
Major catalyst.
14. catalyst system according to claim 13, which is characterized in that the catalyst system, which further comprises helping, urges
Agent.
15. catalyst system according to claim 14, which is characterized in that the co-catalyst be selected from alkylaluminoxane,
At least one of alkyl aluminum and aryl boron.
16. catalyst system according to claim 15, which is characterized in that the co-catalyst is selected from trimethyl aluminium, three
Aluminium ethide, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride, two
Ethylaluminium chloride, three pentafluorophenyl group boron and N, at least one of accelerine four (pentafluorophenyl group) borate.
17. catalyst system according to claim 15 or 16, which is characterized in that aluminium in the co-catalyst with it is described
The molar ratio of nickel in major catalyst is (50-5000):Boron in 1 or described co-catalyst and the nickel in the major catalyst
Molar ratio be (1-50):1.
18. a kind of olefine polymerizing process, including the alkene is in any one of the claim 13-17 catalyst systems
Effect is lower to carry out polymerisation.
19. according to the method for claim 18, which is characterized in that the reaction temperature of the polymerisation is -78 to 200
℃；Polymerization pressure is 0.01-10.0MPa.
20. according to the method for claim 19, which is characterized in that the reaction temperature of the polymerisation is -20 to 150
℃；Polymerization pressure is 0.01-2.0MPa.
21. according to the method for claim 19, which is characterized in that the reaction temperature of the polymerisation is 50 to 120 DEG C.
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