CN109593149A - A kind of alpha-diimine nickel olefine polymerization catalyst and its preparation method and application - Google Patents
A kind of alpha-diimine nickel olefine polymerization catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of alpha-diimine nickel olefine polymerization catalyst and its preparation method and application, and steps are as follows for the preparation method of the catalyst: (1) compound C1 reacts to obtain compound C2 by bisacylation；(2) compound C2 and substituted aniline carry out condensation reaction, obtain α diimide ligand C3；(3) α diimide ligand C3 and (DME) NiX2Complexing, can be obtained α diimine nickel olefine polymerization catalyst.The catalyst can be used for the polymerization or copolyreaction of catalyzed alkene.Catalyst of the invention not only maintains higher polymerization activity at a higher temperature, but also polymerization activity decaying is slow, and thermal stability is further enhanced, and the molecular weight of resulting polymers is also higher, provides more choices for the application of product.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalysis, specifically a kind of alpha-diimine nickel olefine polymerization catalyst and
Preparation method and application in field of olefin polymerisation.
Background technique
Have found that the Ni (II) of the ligand containing alpha-diimine and Pd (II) complex can make alpha-olefines polymerization from Brookhart etc.
Since the polymer for synthesizing high molecular weight, late transition metal catalyst has caused scientists and has widely paid close attention to.Transition earlier above
Metallic catalyst is compared, and also there is late transition metal catalyst catalytic activity height, major catalyst to be readily synthesized, performance is stable, belongs to
In the catalyst of single-activity center the advantages that.The complex structure of Brookhart research group discovery is as shown in Figure 1.It is this kind of to urge
The thermal stability of agent is poor, and when polymerization temperature rises to 60 DEG C, catalyst is by thermal decomposition fast deactivation, this is for industry
It is unfavorable for changing the higher concentration of slurry that application needs.
Then, people start to be dedicated to improving this kind of catalyst thermal stability (Catal.Sci.Technol.2013,3,
1172；Macromolecules 42,2009,7789；Angew.Chem.Int.Ed.2004,43,1821；J.Am.
Chem.Soc.2013,135,16316；Organometallics 23,2004,3276-3283), develop a series of (α-two
Imines) Raney nickel, the thermal stability of these catalyst has certain improvement.Zhejiang University Fu Zhi Sheng etc. devises one kind
The catalyst of ethylidene acenaphthene alpha-nickel diimine compound structure can gather highly active catalytic ethylene in the case where being greater than 60 DEG C
Conjunction obtains high molecular weight hyperbranched polyethylene, and when aluminium nickel ratio is 100 just shows high activity.Yuan Jianchao is in Fig. 1 structure
On the basis of in the contraposition of 2,6 1 dimethylaniline groups introduce the catalyst ethylene of strong supplied for electronic, large volume tertiary butyl groups
Polymerization shows very high catalytic activity, and branch number is also up to 127 branch/1000C.
Summary of the invention
The present invention has been synthetically prepared a kind of alpha-diimine nickel olefine polymerization catalyst and existing skill in prior art basis
Art is compared, which not only maintains higher polymerization activity at a higher temperature, but also polymerization activity decaying is slow, heat
Stability is further enhanced, and the molecular weight of resulting polymers is also higher, provides more choosings for the application of product
It selects.
To achieve the purpose of the present invention, using following technical scheme:
A kind of α diimine nickel olefine polymerization catalyst, shown in structural formula such as formula (I):
Wherein, R1 is C1-C3 alkyl；R2, R3, R5, R6, R7, R8, R10, R11 H, C1-C6 alkyl, can be identical or not
Together；R4 and R9 is C1-C6 alkyl, be may be the same or different；X is halogen.
According to the present invention, as the α diimine nickel olefine polymerization catalyst, preferred structure formula (II) compound represented
One of or its arbitrary proportion mixture.
Wherein, R1 is C1-C2 alkyl；R2, R4, R5, R7 H, C1-C6 alkyl, may be the same or different；R3 and R6 is C1-
C6 alkyl, may be the same or different；X is Cl or Br.
According to the present invention, as the α diimine nickel olefine polymerization catalyst, more preferably as shown in structure formula (III)
The mixture of one of compound or its arbitrary proportion.
Wherein, R1 H, C1-C4 alkyl, R2 are C1-C4 alkyl.
According to the present invention, as the catalyst, following example can be enumerated, both can be used alone, it can also be any
Ratio is used in mixed way, and but it is not limited to this.
The preparation method of α diimine nickel olefine polymerization catalyst of the present invention, steps are as follows: (1) compound C1 is passed through
Bisacylation is crossed to react to obtain compound C2:
Wherein, R1 is C1-C3 alkyl, and X is halogen.
(2) compound C2 and substituted aniline carry out condensation reaction, obtain α diimide ligand C3:
Wherein, R1 is C1-C3 alkyl；R2, R3, R5, R6, R7, R8, R10, R11 H, C1-C6 alkyl, can be identical or not
Together；R4 and R9 is C1-C6 alkyl, be may be the same or different.
(3) α diimide ligand C3 and (DME) NiX2 is complexed, and α diimine nickel olefine polymerization shown in formula (I) can be obtained
Catalyst.
The application of α diimine nickel olefine polymerization catalyst of the present invention in olefin polymerization, for being catalyzed ethylene, third
The polymerization or copolymerization of alkene, butylene.
Further, when catalyst of the invention is used for the polymerization or copolymerization of ethylene, propylene, butylene, including to be selected from formula
(I) at least one of compound represented is major catalyst；To be selected from aikyiaiurnirsoxan beta, the aikyiaiurnirsoxan beta of modification, alkyl aluminum, alkyl
One of aluminium hydrolysate, halogenated alkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt are a variety of for co-catalyst.
The co-catalyst can enumerate methylaluminoxane (MAO), the methylaluminoxane (MMAO) of modification, ethyl alumina
Alkane, normal-butyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, t-butyl-aluminoxane, trimethyl aluminium (Al (CH3)3), triethyl aluminum (Al
(CH2CH3)3), tri-n-n-propyl aluminum (Al (C3H7)3), triisobutyl aluminium (Al (i-C4H9)3), three n-butylaluminums (Al (C4H9)3)、
Triisopentyl aluminium (Al (i-C5H11)3), three n-pentyl aluminium (Al (C5H11)3), tri-n-hexyl aluminum (Al (C6H13)3), three isohesyls
Aluminium (Al (i-C6H13)3), diethylmethyl aluminium (Al (CH3)(CH3CH2)2), dimethyl ethyl aluminium (Al (CH3CH2)(CH3)2)、
One Chlorodimethyl aluminium (Al (CH3)2Cl), dichloro monomethyl aluminium (Al (CH3)Cl2), aluminium diethyl monochloride (Al (C2H5)2Cl), two
One aluminium ethide of chlorine (Al (C2H5)Cl 2), a chlorine diη-propyl aluminium (Al (C3H7)2Cl), one n-propyl aluminium (Al (C of dichloro3H7)
Cl2), a chloro-di-isobutyl aluminum (Al (i-C4H9)2Cl), one aluminium isobutyl of dichloro (Al (i-C4H9)Cl2), a chlorine di-n-butyl aluminium
(Al(C4H9)2Cl), one n-butylaluminum of dichloro (Al (C4H9)Cl 2), a chlorine diisoamyl aluminium (Al (i-C5H11)2Cl), dichloro
One isopentyl aluminium (Al (i-C5H11)Cl2), a chlorine di-n-hexyl aluminium (Al (C6H13)2Cl), one n-hexyl aluminium (Al (C of dichloro6H13)
Cl2), two isohesyl aluminium (Al (i-C of a chlorine6H13)2) or one isohesyl aluminium (Al (i-C of dichloro Cl6H13)Cl2) in any one
Or any combination.The co-catalyst is more preferably methylaluminoxane (MAO), the methylaluminoxane (MMAO) of modification, triethyl group
Aluminium, triisobutyl aluminium, aluminium diethyl monochloride, one aluminium ethide of dichloro, a chloro-di-isobutyl aluminum (Al (i-C4H9)2Cl), dichloro one
Aluminium isobutyl (Al (i-C4H9)Cl2), a chlorine di-n-butyl aluminium (Al (C4H9)2) and one n-butylaluminum of dichloro (Al (C Cl4H9) Cl2) in any one or any combination.
Further, it is 0-100 DEG C (preferably 20-80 DEG C) that the condition of the polymerization or copolyreaction, which includes: temperature, pressure
For 0.1-6.0MPa (preferably 0.3-4.0MPa), the co-catalyst in terms of aluminium and the major catalyst in terms of metal M
Molar ratio is 20-1000:1 (preferably 50-400:1).
The present invention has the advantage that
(1) when alpha-diimine nickel olefine polymerization catalyst vinyl polymerization of the invention as the temperature rises, it polymerize
Activity first increases and declines afterwards, reaches peak in 50-70 DEG C or so activity, shows preferable thermal stability, this and very much
Other types of alpha-diimine Raney nickel is different in 20-40 DEG C or so active highest.It is special using this of catalyst of the present invention
Point can increase substantially polymerization process in the case where guaranteeing same solution viscosity by the method for improving polymerization temperature
Solution solid content, be conducive to improve production efficiency and production economy.
(2) good thermal stability of catalyst of the present invention is also embodied in polymerization activity under high temperature and decays slowly, and polymerization process is more
For steady (as shown in Figure 1).
(3) catalyst of the invention also helps to obtain the higher polymer of molecular weight, and the application of product is provided
More selections.
(4) catalyst of the invention can also use alkyl aluminum or chloro in catalyzed ethylene polymerization other than (M) MAO
Alkyl aluminum can effectively reduce cost as co-catalyst.When wherein using alkyl aluminum or chloro alkyl aluminum, Al/Ni ratio reaches
Higher polymerization activity is just shown to 100-150.
(5) catalyst preparation process of the invention is simple, and synthetic route is short, at low cost, and yield is high, is easy to industrialize.
Detailed description of the invention
Fig. 1 is a kind of structural formula of Raney nickel in background technique；
Fig. 2 is the dynamic curve diagram of catalyst polymerization process of the present invention.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention
Range is not limited to these specific embodiments, but is determined by claims.
Manufacture embodiment 1
0.01mol acenaphthene diketone, toluene 150mL, 0.028mol 4- isopropyl aniline are successively added in 250mL single port bottle
And p-methyl benzenesulfonic acid 10mg, back flow reaction 36h.After reaction, system is cooled to room temperature, and is rotated out most of toluene, is added
Enter methanol and obtains yellow mercury oxide, it is washed to be dried to obtain the total 2.85g of ligand P1.Elemental analysis: 87.02% (theoretical value of C
86.84%)；H 6.55% (theoretical value 6.83%)；N 6.45% (theoretical value 6.33%).1HNMR(CDCl3): analysis: δ
7.33 (t, 2H, Ar-H), δ 7.12 (s, 4H, Ar-H), 6.58 (d, 2H, Ar-H), δ 3.65 (s, 4H), δ 3.01 (m, 6H,
CHMe2),δ0.95(d,12H,CH-CH3)。
Manufacture embodiment 2
0.01mol acenaphthene diketone, toluene 150mL, tri- isopropyl of 0.03mol 2,4,6- are successively added in 250mL single port bottle
Base aniline and p-methyl benzenesulfonic acid 10mg, back flow reaction 48h.After reaction, system is cooled to room temperature, and is rotated out most of
Toluene is added methanol and obtains yellow mercury oxide, washed to be dried to obtain the total 2.98g of ligand P2.Elemental analysis: C 86.35% is (theoretical
Value 86.51%)；H 9.02% (theoretical value 8.91%)；N 4.65% (theoretical value 4.58%).1HNMR(CDCl3): analysis: δ
7.35 (t, 2H, Ar-H), δ 7.10 (s, 4H, Ar-H), 6.56 (d, 2H, Ar-H), δ 3.65 (s, 4H), δ 3.00 (m, 6H,
CHMe2),δ1.31(d,24H,CH-CH3),δ0.96(d,12H,CH-CH3)。
Manufacture embodiment 3
Successively be added in 250mL single port bottle 0.005mol acenaphthene diketone, toluene 70mL, 0.011mol 4- methylaniline and
P-methyl benzenesulfonic acid 5mg, back flow reaction is for 24 hours.After reaction, system is cooled to room temperature, and is rotated out most of toluene, is added
Methanol obtains yellow mercury oxide, washed to be dried to obtain the total 1.2g of ligand P3.Elemental analysis: C 86.68% (theoretical value 87.01%)；
H 5.92% (theoretical value 5.74%)；N 7.39% (theoretical value 7.25%).
Manufacture embodiment 4
0.01mol acenaphthene diketone, toluene 150mL, 0.025mol 2,4,6- trimethyl are successively added in 250mL single port bottle
Aniline and p-methyl benzenesulfonic acid 10mg, back flow reaction 16h.After reaction, system is cooled to room temperature, and rotates out most of first
Benzene is added methanol and obtains yellow mercury oxide, washed to be dried to obtain the total 2.56g of ligand P4.Elemental analysis: 86.78% (theoretical value of C
86.84%)；H 6.81% (theoretical value 6.83%)；N 6.44% (theoretical value 6.33%).
Manufacture embodiment 5
0.01mol acenaphthene diketone, toluene 150mL, tert-butyl -2 0.025mol 4- are successively added in 250mL single port bottle,
6- dimethylaniline and p-methyl benzenesulfonic acid 10mg, back flow reaction 10h.After reaction, system is cooled to room temperature, and is rotated out
Most of toluene is added methanol and obtains yellow mercury oxide, washed to be dried to obtain the total 2.56g of ligand P5.Elemental analysis: C 86.45%
(theoretical value 86.70%)；H 6.81% (theoretical value 6.98%)；N 6.44% (theoretical value 6.52%).
Manufacture embodiment 6
Under anhydrous and oxygen-free atmosphere, 0.0021mol (DME) NiBr2,50ml dichloro is successively added in 250ml single port bottle
Methane, 0.002mol ligand P1, room temperature reaction for 24 hours, methylene chloride vacuum are drained, is washed solid five times with ether, after dry
Obtain salmon pink catalyst M1.Elemental analysis: C 57.75% (theoretical value 58.14%)；H 4.47% (theoretical value 4.57%)；
N 4.37% (theoretical value 4.24%).
Manufacture embodiment 7
Under anhydrous and oxygen-free atmosphere, 0.0027mol (DME) NiBr2,50ml dichloro is successively added in 250ml single port bottle
Methane, 0.0025mol ligand P2 react at room temperature 15h, methylene chloride vacuum are drained, is washed solid five times with ether, dry
After obtain salmon pink catalyst M2.Elemental analysis: C 64.03% (theoretical value 63.72%)；6.38% (theoretical value of H
6.56%)；N 3.36% (theoretical value 3.38%).
Manufacture embodiment 8
Under anhydrous and oxygen-free atmosphere, 0.0021mol (DME) NiBr2,45ml dichloro is successively added in 250ml single port bottle
Methane, 0.002mol ligand P3 react at room temperature 36h, methylene chloride vacuum are drained, is washed solid four times with ether, after dry
Obtain salmon pink catalyst M3.Elemental analysis: C 55.18% (theoretical value 55.59%)；H 3.88% (theoretical value 3.67%)；
N 4.81% (theoretical value 4.63%).
Manufacture embodiment 9
Under anhydrous and oxygen-free atmosphere, 0.0023mol (DME) NiBr2,45ml dichloro is successively added in 250ml single port bottle
Methane, 0.0022mol ligand P4 react at room temperature 12h, methylene chloride vacuum are drained, is washed solid six times with ether, dry
After obtain salmon pink catalyst M4.Elemental analysis: C 58.42% (theoretical value 58.14%)；4.32% (theoretical value of H
4.57%)；N 4.10% (theoretical value 4.24%).
Manufacture embodiment 10
Under anhydrous and oxygen-free atmosphere, 0.0023mol (DME) NiBr2,45ml dichloro is successively added in 250ml single port bottle
Methane, 0.0022mol ligand P5 react at room temperature 12h, methylene chloride vacuum are drained, is washed solid six times with ether, dry
After obtain salmon pink catalyst M5.Elemental analysis: C 59.72% (theoretical value 60.29%)；4.32% (theoretical value of H
4.57%)；N 4.10% (theoretical value 4.31%).
Application Example 1
M1 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 39.5g.
Application Example 2
M1 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 40 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 29.9g.
Application Example 3
M2 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 80 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 17.6g.
Application Example 4
M2 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 62.2g.
Application Example 5
M2 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 40 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 40.3g.
Application Example 6
M2 (0.012mmol), toluene (15ml) and ethyl aluminum dichloride (3.2mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 20 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 33.5g.
Application Example 7
M2 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 0.77MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.Polymerization
Ethyl alcohol stopped reaction of the solution containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are gathered after being filtered, washed
Close object 32.2g.
Application Example 8
It is stand-by afterwards with toluene (20ml) dissolution M2 (0.018mmol) in glove box.In the 2L high that one is replaced through nitrogen
Hexane (1L) and ethyl aluminum dichloride (4.8mmol) are sequentially added in pressure polymeric kettle, 2.28MPa ethylene is passed through at 60 DEG C, is passed through
Above-mentioned catalyst solution is added in polymeric kettle simultaneously when ethylene, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 61.5g.
Application Example 9
M2 (0.012mmol), toluene (15ml) and ethyl aluminum dichloride (3.2mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 2.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 47.5g.
Application Example 10
M2 (0.013mmol), toluene (15ml) and MAO (12.79mmol) are added sequentially to 50ml tri- in glove box
It is stand-by after mixing in the bottle of angle.Hexane (1L) and Dichloroethyl are sequentially added in a 2L polymerization autoclave through nitrogen displacement
Aluminium (4.8mmol) is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.Polymeric solution is with containing
The ethyl alcohol stopped reaction of 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and obtain polymer after being filtered, washed
45.0g。
Application Example 11
M2 (0.012mmol), toluene (15ml) and triethyl aluminum (3.2mmol) are added sequentially to 50ml in glove box
It is stand-by after mixing in triangular flask.Hexane (1L) is sequentially added in a 2L polymerization autoclave through nitrogen displacement and above-mentioned is matched
The catalyst solution set is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.Polymeric solution is used
Ethyl alcohol stopped reaction containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and obtain polymer after being filtered, washed
12.4g。
Application Example 12
M2 (0.012mmol), toluene (15ml) and ethyl aluminum dichloride (6.4mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 20.5g.
Application Example 13
M2 (0.012mmol), toluene (15ml) and ethyl aluminum dichloride (1.5mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 50g.
Application Example 14
M3 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 36.6g.
Application Example 15
M4 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 50.3g.
Application Example 16
M5 (0.013mmol), toluene (15ml) and ethyl aluminum dichloride (3.36mmol) are added sequentially in glove box
It is stand-by after mixing in 50ml triangular flask.Hexane (1L) and upper is sequentially added in a 2L polymerization autoclave through nitrogen displacement
The catalyst solution for stating configuration is passed through 1.5MPa ethylene at 60 DEG C, the polymerization reaction 0.5hr under 300rpm stirring.It polymerize molten
Ethyl alcohol stopped reaction of the liquid containing 5% hydrochloric acid, polymer are dried under vacuum to constant weight at 50 DEG C and are polymerize after being filtered, washed
Object 54.8g.
Table 1
As it can be seen from table 1 the rising of catalyst of the invention with temperature, polymerization activity presents first to rise to be declined afterwards
Trend.Reach highest in 60 DEG C or so activity.Show preferable thermal stability.Catalyst of the invention is in catalysis ethylene
It can also can be effectively reduced using alkyl aluminum or chloro alkyl aluminum as co-catalyst other than (M) MAO when polymerization
Cost.When wherein using chloro alkyl aluminum, Al/Ni ratio reaches 100-150 and just shows higher polymerization activity.
Claims (8)
1. a kind of α diimine nickel olefine polymerization catalyst, which is characterized in that have structural formula shown in formula (I):
Wherein, R1 is C1-C3 alkyl；R2, R3, R5, R6, R7, R8, R10, R11 H, C1-C6 alkyl, may be the same or different；R4
It is C1-C6 alkyl with R9, may be the same or different；X is halogen.
2. a kind of α diimine nickel olefine polymerization catalyst as described in claim 1, which is characterized in that have shown in formula (II)
Structural formula:
Wherein, R1 is C1-C2 alkyl；R2, R4, R5, R7 H, C1-C6 alkyl, may be the same or different；R3 and R6 is C1-C6 alkane
Base may be the same or different；X is Cl or Br.
3. a kind of α diimine nickel olefine polymerization catalyst as described in claim 1, which is characterized in that have shown in formula (III)
Structural formula:
Wherein, R1 H, C1-C4 alkyl, R2 are C1-C4 alkyl.
4. a kind of preparation method of α diimine nickel olefine polymerization catalyst described in claim 1, which is characterized in that the system
Preparation Method includes the following steps:
(1) compound C1 reacts to obtain compound C2 by bisacylation:
Wherein, R1 is C1-C3 alkyl, and X is halogen.
(2) above compound C2 and substituted aniline carry out condensation reaction, obtain α diimide ligand C3:
Wherein, R1 is C1-C3 alkyl；R2, R3, R5, R6, R7, R8, R10, R11 H, C1-C6 alkyl, may be the same or different；R4
It is C1-C6 alkyl with R9, may be the same or different.
(3) above-mentioned α diimide ligand C3 and (DME) NiX2Complexing, can be obtained α diimine nickel olefine polymerization shown in formula (I) and urges
Agent.
5. a kind of application of α diimine nickel olefine polymerization catalyst described in claim 1 in olefin polymerization, feature exist
In the α diimine nickel olefine polymerization catalyst is used to be catalyzed the polymerization or copolymerization of ethylene, propylene, butylene.
6. application as claimed in claim 5, which is characterized in that including at least one in formula (I) compound represented
Kind be major catalyst, with selected from aikyiaiurnirsoxan beta, the aikyiaiurnirsoxan beta of modification, alkyl aluminum, alkyl aluminum hydrolysis object, halogenated alkyl aluminium, boron fluothane,
One of boron alkyl and boron alkyl ammonium salt or it is a variety of be co-catalyst, catalytic action, which occurs, makes that polymerization occurs for ethylene or copolymerization is anti-
It answers.
7. such as application described in claim 5 or 6, which is characterized in that the reaction condition of the catalysis includes: that temperature is 0-100
DEG C, the molar ratio of pressure 0.1-6.0MPa, the co-catalyst and the major catalyst in terms of metal M in terms of aluminium are
20-1000:1.
8. the use as claimed in claim 7, which is characterized in that the reaction condition of the catalysis includes: that temperature is 20-80 DEG C,
Pressure is 0.3-4.0MPa, and the molar ratio of the co-catalyst in terms of aluminium and the major catalyst in terms of metal M is 50-
400:1.
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| WO2021083238A1 (en) * | 2019-10-28 | 2021-05-06 | 南京中科康润新材料科技有限公司 | Processing method for directly synthesizing high-performance base oil by means of polymerization of low-carbon olefin |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
| CN115073643A (en) * | 2022-06-10 | 2022-09-20 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene material, catalyst system and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021083238A1 (en) * | 2019-10-28 | 2021-05-06 | 南京中科康润新材料科技有限公司 | Processing method for directly synthesizing high-performance base oil by means of polymerization of low-carbon olefin |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
| CN115073643A (en) * | 2022-06-10 | 2022-09-20 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene material, catalyst system and application thereof |
| CN115073643B (en) * | 2022-06-10 | 2023-11-28 | 宁夏清研高分子新材料有限公司 | Preparation method of poly 4-methyl-1-pentene material, catalyst system and application thereof |
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