CN106397263B - Ligand compound, it is prepared and the complex containing the ligand compound - Google Patents
Ligand compound, it is prepared and the complex containing the ligand compound Download PDFInfo
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- CN106397263B CN106397263B CN201510463257.5A CN201510463257A CN106397263B CN 106397263 B CN106397263 B CN 106397263B CN 201510463257 A CN201510463257 A CN 201510463257A CN 106397263 B CN106397263 B CN 106397263B
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Abstract
The present invention provides a kind of ligand compound, structural formula is shown in formula I：In formula, 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 complex containing the ligand 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 new structural ligand compound and its cooperation of the nickel of formation
Object.The invention further relates to the preparation methods and the complex of the ligand compound and 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, 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
For deficiency in the prior art, this application provides a kind of new structural ligand compound, can reach with
Nickel compound forms the alpha-nickel diimine compound with good thermal stability, in co-catalyst (as containing aluminum cocatalyst, boracic
Co-catalyst) activation under, can realize catalyzed ethylene polymerization under higher temperature, prepare Narrow Molecular Weight Distribution, the branch of high molecular weight
Change polyethylene.
An object of the present invention is to provide a kind of ligand compound, and structural formula is shown in formula I：
In formula, R1-R10It is identical or different, it is each independently selected from hydrogen, saturation or unsaturated alkyl, oxyl and halogen.
Preferably, 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 compound according to the present invention, in the Formulas I, R1-R10It is identical or
Difference is each independently selected from hydrogen, C1-C5Saturation or unsaturated alkyl, C1-C5Alkoxy and halogen, be preferably selected from hydrogen,
Methyl, ethyl, vinyl, isopropyl, acrylic, methoxyl groups, ethyoxyl, propoxyl group, fluorine, chlorine and bromine.
The second object of the present invention is to provide a kind of method preparing above-mentioned ligand compound, including：By compound A and benzene
Amine or substituted aniline flow back in solvent under the effect of the catalyst, obtain ligand shown in Formulas I,
One specific embodiment of method according to the present invention, the compound A and aniline or substituted aniline
Molar ratio is 1:2-1:10, preferably 1:2-1:3.The solvent is selected from toluene, methanol, ethyl alcohol and acetonitrile.The catalyst is selected from
P-methyl benzenesulfonic acid, acetic acid and formic acid.It is preferred that the amount of the catalyst is the 0.01-20mol% of compound A.The temperature of the reflux
Degree is 40-120 DEG C, preferably 65-110 DEG C.The time of the reflux is 0.5-7 days, preferably 1-2 days.
Wherein, the restriction of the substituent group on the substituted aniline is such as R1-R10, but R1-R10It is asynchronously hydrogen, example
Such as, the substituted aniline can be 2,6- methylanilines, 2,6- diethylanilines, 2,6-DIPA, 2,6- diformazans
The bromo- aniline of base -4- and/or 2,6- difluoroanilines.
A specific embodiment according to the present invention, the specific preparation process of ligand compound of the invention are as follows：
1, the conventional method of ligand synthesis
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 synthesis can be confirmed by nuclear-magnetism, infrared and elemental analysis.
The third object of the present invention is to provide a kind of complex, has structure shown in Formula Il,
In Formula II, R1-R10Restriction with above-mentioned ligand compound, X is halogen.
A preferred embodiment according to the present invention, the complex can be selected from least one of following complex,
In the complex 1-22, 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.
The fourth object of the present invention is to provide a kind of method preparing the complex, includes the following steps：
1) ligand compound shown in the method formula I according to above-mentioned restriction；
2) ligand compound shown in the Formulas I that obtains in step 1) will be contained to be coordinated with nickel halogenide or nickel halogenide derivative
The complex is made in reaction.
A preferred embodiment according to the present invention, in the step 2), the nickel halogenide or nickel halogenide derivative with
The molar ratio of ligand compound shown in Formulas I is 1:1-1.2:1.The nickel halogenide or nickel halogenide derivative are selected from NiBr2、NiCl2、
(DME)NiBr2(DME) NiCl2.Reaction temperature in the step 2) is 0-60 DEG C, reaction time 0.5-12h.Wherein,
DME is the abbreviation of dimethyl ether.
A preferred embodiment according to the present invention, the step 2) specifically include：Under inert gas protection, will
(DME)NiCl2Or (DME) NiBr2Dichloromethane solution in molar ratio (1:1-1:1.2) it is added drop-wise to the solution of diimide ligand
In, it is stirred at room temperature, precipitation is precipitated, filtering is dried in vacuo after being washed with ether and just obtains diimine nickel complex.Gained complex
It can be characterized by elemental analysis.
The fifth object of the present invention is to provide a kind of catalyst for olefinic polymerization, including above-mentioned complex is main reminder
Agent.Co-catalyst can be further included in the catalyst.
A preferred embodiment according to the present invention, the co-catalyst are selected from alkylaluminoxane, alkyl aluminum and aromatic hydrocarbons
At least one of base boron；The more preferable co-catalyst is 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.
Another preferred embodiment according to the present invention, when the co-catalyst contains alkylaluminoxane and/or alkyl aluminum
When, the molar ratio of the aluminium in the co-catalyst and the nickel in the major catalyst is (50-5000)：1；When the co-catalyst
When boron containing aryl, the molar ratio of the boron in the co-catalyst and the nickel in the major catalyst is (1-50)：1.
The sixth object of the present invention is to provide a kind of olefine polymerizing process, including the alkene in the effect of above-mentioned catalyst
Lower carry out polymerisation.
The reaction temperature of a preferred embodiment according to the present invention, the polymerisation is -78 to 200 DEG C, preferably
It is -20 to 150 DEG C, further preferred 60 to 120 DEG C；Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
Catalyst prepared by the present invention can be used for homopolymerization or the copolymerization of alkene, equal especially suitable for ethylene
The copolymerization of polymerization or ethylene and other alpha-olefins, wherein alpha-olefin are selected from propylene, butylene, amylene, hexene, octene or 4-
At least one of methylpentene -1 etc..
In some preferred embodiments of the present invention, wherein described be aggregated in solvent carries out, used solvent choosing
From alkane, aromatic hydrocarbon or halogenated hydrocarbons.It is preferred that one in hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes
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 and diimine nickel metal complex, made from
Catalyst is under (such as methylaluminoxane or alkyl aluminum) effect of co-catalyst, the catalyzed ethylene polymerization of energy high activity.Especially
(100 degree) higher polymerization activity can be still kept under higher polymerization temperature.And diimine nickel catalyst is 50 in the prior art
Du or more activity significantly decay, and molecular weight is greatly lowered).Catalyst of the present invention has good catalysis second
The ability of the copolymerization of alkene and high alpha-olefin, 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) preparation (R in structure formula (I) of ligand1、R3、R4And R6For methyl, R2、R5And R7-R10It is hydrogen)：
Compound A (4.07g, 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 81% to remove solvent and obtain yellow solid yield.1H
NMR(CDCl3,δ,ppm):1.16(s,36H),1.86(s,12H),5.20(s,2H),7.08(m,22H),7.68(m,8H)。
2) preparation of complex 1：
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 (962mg, 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 91%.Elemental analysis (C80H80Br2N2Ni)：C,74.60；H,6.26；N,2.17；Experiment
It is worth (%)：C,74.33；H,6.82；N,2.41.
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.12.9mg (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 2.27 × 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 1 of 12.9mg (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 4.86 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 3
1) preparation (R in structure formula (I) of ligand1、R3、R4And R6For ethyl, R2、R5And R7-R10It is hydrogen)：
Compound A (6.62g, 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
88%.1H NMR(CDCl3,δ,ppm):1.08 (t, 12H, J=7.5Hz), 1.16 (s, 36H), 2.24 (dd, 8H, J=
7.5Hz),5.20(s,2H),7.07(22H),7.68(m,8H)。
2) preparation of complex 2：By 10ml (DME) NiBr2The dichloromethane solution of (155mg, 0.5mmol) is added drop-wise to
It in the dichloromethane solution of the above-mentioned ligands of 10ml (563mg, 0.5mmol), is stirred at room temperature 6 hours, precipitation, filtering ether is precipitated
Dark red powder solid, yield 82% are dried to obtain after washing.Elemental analysis (C84H88Br2N2Ni)：C,75.06；H,6.60；
N,2.08；Experiment value (%)：C,75.42；H,6.56；N,2.31.
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 13.4mg (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 5.27 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 4
1) preparation (R in structure formula (I) of ligand1、R3、R4And R6For isopropyl, R2、R5And R7-R10It is hydrogen)：
Compound A (7.63g, 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), 1.16 (m, 48H), 2.50 (m, 4H), 5.20 (s,
2H),7.07(22H),7.69(m,8H)。
2) preparation of complex 3：By 10ml (DME) NiBr2The dichloromethane solution of (506mg, 1.6mmol) is added drop-wise to
It in the dichloromethane solution of the above-mentioned ligands of 10ml (1891mg, 1.6mmol), is stirred at room temperature 6 hours, precipitation, filtering second is precipitated
It is dried to obtain dark red powder solid, yield 80% after ether washing.Elemental analysis (C88H96Br2N2Ni)：C,75.48；H,
6.91；N,2.00；Experiment value (%)：C,75.32；H,7.02；N,2.34.
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.14.0mg (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 8.31 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 5
1) preparation (R in structure formula (I) of ligand1、R3、R4And R6For methyl, R2And R5For bromine, R7-R10It is hydrogen)：
The bromo- aniline of compound A (4.32g, 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 78%.1H NMR(CDCl3,δ,ppm):1.16(s,36H),1.84(s,12H),5.18(s,2H),7.08(m,20H),7.69
(m,8H)。
2) preparation of complex 5：By 10ml (DME) NiBr2The dichloromethane solution of (216mg, 0.7mmol) is added drop-wise to
It in the dichloromethane solution of the above-mentioned ligands of 10ml (859mg, 0.7mmol), is stirred at room temperature 6 hours, precipitation, filtering ether is precipitated
Dark red powder solid, yield 86% are dried to obtain after washing.Elemental analysis (C80H78Br4N2Ni)：C,66.46；H,5.44；
N,1.94；Experiment value (%)：C,66.72；H,5.68；N,2.21.
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.14.4mg (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 3.14 × 106g·mol-1(Ni)·h-1, the results are shown in Table 1.
Embodiment 6
1) preparation (R in structure formula (I) of ligand1、R3、R4And R6For fluorine, R2、R5And R7-R10It is hydrogen)：
Compound A (4.32g, 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 40%.1H
NMR(CDCl3,δ,ppm):1.16(s,36H),5.19(s,2H),7.06(m,22H),7.69(m,8H)。
2) preparation of complex 9：By 10ml (DME) NiBr2The dichloromethane solution of (216mg, 0.7mmol) is added drop-wise to
It in the dichloromethane solution of the above-mentioned ligands of 10ml (760mg, 0.7mmol), is stirred at room temperature 6 hours, precipitation, filtering ether is precipitated
Dark red powder solid, yield 88% are dried to obtain after washing.Elemental analysis (C76H68Br2F4N2Ni)：C,70.01；H,
5.26；N,2.15；Experiment value (%)：C,69.82；H,5.47；N,2.51.
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.13.0mg (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 0.68 × 106g·mol-1(Ni)·h-1。
Embodiment 7
1) preparation of complex 14：(in the ligand of structure formula (I) used, R1、R3、R4And R6For isopropyl, R2、R5And
R7-R10It is hydrogen)：
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 (1891mg, 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 88%.Elemental analysis (C88H96Cl2N2Ni)：C,80.60；H,7.38；N,2.14；It is real
Test value (%)：C,80.82；H,7.42；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.13.1mg (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 7.66 × 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 14.0mg (10 μm of ol) embodiment 4 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 8.87 × 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 14.0mg (10 μm of ol) embodiment 4 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=1000,10ml1- hexenes.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction
30min.It is neutralized with the ethanol solution that 5% hydrochloric acid is acidified, obtains polyethylene, polymerization activity is 9.27 × 106g·mol-1(Ni)·
h-1, the results are shown in Table 1.
Embodiment 10
10atm ethylene copolymerizations：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.The complex 3 prepared in 14.0mg (10 μm of ol) embodiment 4 is added and then vacuumizes again
It is used in combination ethylene to replace 3 times.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000,10ml 1- octenes.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction
30min.It is neutralized with the ethanol solution that 5% hydrochloric acid is acidified, obtains polyethylene, polymerization activity is 9.44 × 106g·mol-1(Ni)·
h-1, the results are shown in Table 1.
Embodiment 11
10atm ethylene copolymerizations：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.The complex 3 prepared in 14.0mg (10 μm of ol) embodiment 4 is added and then vacuumizes again
It is used in combination ethylene to replace 3 times.The hexane of 500ml is injected, adding 6.5ml methylaluminoxane (MAO), (toluene of 1.53mol/l is molten
Liquid), make Al/Ni=1000,10ml1- decene.At 100 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction
30min.It is neutralized with the ethanol solution that 5% hydrochloric acid is acidified, obtains polyethylene, polymerization activity is 8.82 × 106g·mol-1(Ni)·
h-1, the results are 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's (its structure is shown in formula B) is added and then vacuumizes again and uses second
Alkene is replaced 3 times.The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), makes
Al/Ni=1000,10ml hexene.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polyethylene, and polymerization activity is 0.08 × 106g·mol-1(Ni)·h-1, as a result such as 1 institute of table
Show.
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's (its structure is shown in formula C) is added and then vacuumizes again and uses second
Alkene is replaced 3 times.The hexane for injecting 500ml, adds 6.5ml methylaluminoxane (MMAO) (toluene solution of 1.53mol/l), makes
Al/Ni=1000,10ml hexene.At 90 DEG C, the ethylene pressure of 10atm is kept, is vigorously stirred reaction 30min.With 5% hydrochloric acid
The ethanol solution of acidification neutralizes, and obtains polyethylene, and polymerization activity is 0.02 × 106g·mol-1(Ni)·h-1, as a result such as 1 institute of table
Show.
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, Copolymerization activity high with alpha-olefin.
Claims (20)
1. a kind of ligand compound, structural formula are shown in formula I：
In formula, 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 Formulas I, R1-R10It is identical or different, it is respectively independent
Ground is 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 ligand compounds, including：By compound A and aniline or
Substituted aniline flows back in solvent under the effect of the catalyst, obtains 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 complex has structure shown in Formula Il,
In Formula II, R1-R10Restriction with any one of claim 1-4, X be halogen.
9. according to complex shown in claim 8, which is characterized in that the complex can be selected from following complex at least
One kind, in the complex 1-22, 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 complex described in claim 8 or 9, includes the following steps：
1) ligand compound shown in the method formula I according to any one of claim 5-7；
2) will contain ligand compound shown in the Formulas I that is obtained in step 1) with nickel halogenide or nickel halogenide derivative be coordinated it is anti-
It answers, the complex is made.
11. according to the method described in claim 10, it is characterized in that, shown in the nickel halogenide or nickel halogenide derivative and Formulas I
The molar ratio of 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 step
It is rapid 2) in reaction temperature be 0-60 DEG C；And/or the time of reaction is 0.5-12h.
12. a kind of complex catalyst for olefinic polymerization, including described in claim 8 or 9 is major catalyst.
13. catalyst according to claim 12, which is characterized in that the catalyst further comprises co-catalyst.
14. catalyst according to claim 13, which is characterized in that the co-catalyst is selected from alkylaluminoxane, alkyl
At least one of aluminium and aryl boron.
15. catalyst according to claim 14, which is characterized in that the co-catalyst is selected from trimethyl aluminium, triethyl group
Aluminium, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, three n-pentyl aluminium, tri-n-octylaluminium, diethylaluminum chloride, dichloride
Aluminium ethide, three pentafluorophenyl group boron and N, at least one of accelerine four (pentafluorophenyl group) borate.
16. according to the catalyst described in any one of claim 13-15, which is characterized in that aluminium in the co-catalyst with
The molar ratio of nickel in the major catalyst is (50-5000):In boron and the major catalyst in 1 or described co-catalyst
Nickel molar ratio be (1-50):1.
17. a kind of olefine polymerizing process, including the alkene is in the effect of any one of the claim 12-16 catalyst
Lower carry out polymerisation.
18. according to the method for claim 17, which is characterized in that the reaction temperature of the polymerisation is -78 to 200
℃；Polymerization pressure is 0.01-10.0MPa.
19. according to the method for claim 18, which is characterized in that the reaction temperature of the polymerisation is -20 to 150
DEG C, polymerization pressure 0.01-2.0MPa.
20. according to the method for claim 18, which is characterized in that the reaction temperature of the polymerisation is 50 to 120 DEG C.
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| CN108864338B (en) * | 2017-05-12 | 2020-11-10 | 中国石油化工股份有限公司 | Catalyst composition for olefin polymerization and olefin polymerization method |
| CN111116408B (en) * | 2018-10-31 | 2022-12-13 | 中国石油化工股份有限公司 | Amino imine ligand, amino imine complex and application thereof |
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