CN109957050B - Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof - Google Patents

Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof Download PDF

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CN109957050B
CN109957050B CN201811560455.3A CN201811560455A CN109957050B CN 109957050 B CN109957050 B CN 109957050B CN 201811560455 A CN201811560455 A CN 201811560455A CN 109957050 B CN109957050 B CN 109957050B
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Shaoxing Pinghe New Materials Technology Co ltd
Hangzhou Xinglu Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Abstract

The invention discloses a large steric hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 1, 2-benzo acenaphthenequinone as a framework, and a preparation method and application thereof. The structural formula of the high steric hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 1, 2-benzo acenaphthenequinone as a framework is shown as a formula (I), wherein R is1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl, and X is chlorine or bromine. The catalyst has simple preparation process, can catalyze ethylene polymerization under the action of the cocatalyst, shows good thermal stability and polymerization activity, and has good industrial application prospect.

Description

Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof
Technical Field
The invention relates to an asymmetric (alpha-diimine) nickel olefin catalyst, a preparation method and application thereof, in particular to a high-steric-hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 1, 2-benzo acenaphthenequinone as a framework, a preparation method thereof and application of the catalyst in catalyzing ethylene or propylene to obtain polyethylene or polypropylene.
Background
Polyolefin is a basic material related to the national civilization, and due to the excellent performance, variety, easily available raw materials and low price, the polyolefin is widely applied to various fields such as industry, agriculture, national defense and the like. The development and application of new catalysts are one of the core driving forces for the advancement and development of the polyolefin industry, and are the key points for controlling the structure and performance of polyolefin materials.
In recent decades, the research of obtaining functionalized and differentiated polyolefin materials by coordination polymerization has received much attention. A new generation of late transition metal catalysts was developed by Brookhart research group sponsored by DuPont in 1995 by which Ni (II) and Pd (II) metal complexes containing an alpha-diimine ligand catalyze the polymerization of ethylene to high molecular weight polymers at atmospheric pressure (J.Am.chem.Soc.,1995,117(23): 6414-. The specific structure of the alpha-diimine nickel olefin catalyst is shown as the formula (IV):
Figure BDA0001913093990000011
to date, considerable research has been conducted to modify the ortho groups of the aryl groups (R' in the formula) and the groups on the diimine backbone (R groups in the formula) while maintaining the bis (aryl) α -diimine ligand arrangement. When R' is changed from isopropyl to methyl, the branching degree and molecular weight of the resulting polymer are reduced and the topology is more linear. However, such catalysts have poor thermal stability, and even when R' is a highly hindered isopropyl group, the molecular weight and catalyst activity of polyethylene produced using such catalysts decrease dramatically with increasing temperature. When the polymerization temperature rises above 60 ℃, the catalyst is rapidly decomposed by heating and deactivated. Rieger (J.AM. CHEM.SOC., 2007,129,9182-9191), Long (J.AM. CHEM.SOC., 2013,135, 16316-16319; ACS Catalysis, 2014, 4, 2501-2504) and the like change R' from alkyl to aryl or substituted aryl, the thermal stability of the prepared catalyst is greatly improved, and when the polymerization temperature is higher than 60 ℃, the catalyst still maintains good catalytic activity. However, the catalyst with the symmetric structure of the large-volume substituent groups on the two sides of the aniline substituent groups has high synthesis cost due to the fact that the steric hindrance is large and the yield of the ligand is very low when the ligand of the catalyst is prepared; meanwhile, the rapid insertion of ethylene is hindered by the R' of the bulky substituent group, so that the polymerization activity of the catalyst is not high when the catalyst is used for catalyzing the polymerization of ethylene, and the industrial application of the catalyst is limited.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provides a large-steric-hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 1, 2-benzo acenaphthenequinone as a framework, and a preparation method and application thereof.
The chemical structural general formula of the asymmetric (alpha-diimine) nickel olefin catalyst provided by the invention is shown as the formula (I):
Figure BDA0001913093990000021
in the formula (I), R1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl, and X is chlorine or bromine. The choice of all aniline substituents in formula (I) is independent of one another.
Preferably, R is represented by formula (I)1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl or bis (4-fluorophenyl) methyl, R3Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl, halogen or methoxy, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Hydrogen or methyl, X is bromine.
The general structural formula of the catalyst ligand provided by the invention is shown as formula (II):
Figure BDA0001913093990000031
in the formula (II), R1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl. The choice of all aniline substituents in formula (II) is independent of one another.
Preferably, R in the formula (II)1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl or bis (4-fluorophenyl) methyl, R3Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl, halogen or methoxy, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen or methyl.
More preferably, the ligand represented by the above (ii) is selected from any one of the compounds shown in table 1:
TABLE 1 ligands
Figure BDA0001913093990000032
Figure BDA0001913093990000041
The present invention also provides a method for preparing the above ligand compound, which comprises the steps of:
1) and 1, 2-benzo acenaphthenequinone and aniline with a large steric hindrance substituent are subjected to ketone-amine condensation reaction to obtain a compound shown in a formula (III):
Figure BDA0001913093990000042
the aniline substituent used in this step can be referred to in table 1; the solvent adopted in the reaction in the step can be at least one of toluene, acetonitrile, acetic acid and absolute ethyl alcohol, and toluene and acetonitrile are preferred; the catalyst adopted in the reaction is at least one of p-toluenesulfonic acid and acetic acid; the dosage ratio of the catalyst, 1, 2-benzo acenaphthenequinone, aniline with large steric hindrance substituent and solvent is 0.1-0.15mmol: 1.1-1.1 mmol:1.1-1.4mmol:5-10ml, preferably 0.1mmol:1mmol:1.1mmol:8 ml; the reaction time for this step is from 2 to 8 hours, preferably from 3 to 6 hours. And (3) carrying out column chromatography on the product in a silica gel column by using a mixed solvent of dichloromethane and petroleum ether or a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain a product shown in a formula (III).
2) And (3) reacting the compound shown in the formula (III) with aniline with a small steric hindrance substituent to obtain a corresponding compound shown in a formula (II) through a ketone-amine condensation reaction:
Figure BDA0001913093990000043
the aniline substituent used in this step can be referred to in table 1; the solvent adopted in the reaction is at least one of toluene, acetonitrile, acetic acid and absolute ethyl alcohol, and toluene and acetonitrile are preferred; the catalyst adopted in the reaction is at least one of p-toluenesulfonic acid and acetic acid; the dosage ratio of the catalyst, the compound shown in the formula (III), the aniline with the small steric hindrance substituent and the solvent is 0.2-0.5mmol:1-1.1mmol:1.1-1.4mmol:30-70ml, preferably 0.3mmol:1mmol:1.1mmol:50 ml; the reaction time in this step is 6 to 16 hours, preferably 8 to 12 hours. And (3) carrying out column chromatography on the product on a silica gel column by using a mixed solvent of dichloromethane and petroleum ether or a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain a product shown in a formula (II).
The invention also provides a preparation method of the catalyst shown in the formula (I), which comprises the following steps: in the atmosphere of inert gas, the compound shown in the formula (II) is complexed with one of ethylene glycol dimethyl ether nickel dibromide, ethylene glycol dimethyl ether nickel dichloride or hexahydrated nickel dichloride, and the catalyst can be obtained. X in the structural formula of the catalyst is chlorine or bromine, and the polymerization effect is not substantially influenced.
Preferably, the compound of formula (II) is selected from the group consisting of the ligands shown in Table 1, complexed with a ligand under a nitrogen atmosphereThe synthetic nickel-containing compound is selected from ethylene glycol dimethyl ether nickel Dibromide (DME) NiBr2Said ligand being in combination with (DME) NiBr2In a molar ratio of 1:1 to 1.2, preferably 1: 1.1; the solvent is dichloromethane, the reaction temperature is 15-35 ℃, preferably 25 ℃, and the reaction time is 8-30 hours, preferably 16-24 hours. When X is bromine, the catalyst of the present invention may be selected from any one of table 2, with reference to the ligand scheme of table 1:
TABLE 2 catalysts
Figure BDA0001913093990000051
Figure BDA0001913093990000061
The invention also provides a catalyst composition for catalyzing olefin polymerization, which consists of the catalyst shown in the formula (I) and a cocatalyst, wherein the cocatalyst is selected from at least one of alkyl aluminum chloride, alkyl aluminum and aluminoxane, and the olefin is ethylene or propylene.
In the above catalyst composition, the aluminoxane is Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), ethylaluminoxane or isobutylaluminoxane; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum; the alkylaluminum chloride is diethylaluminum chloride, diethylaluminum sesquichloride or ethylaluminum dichloride; from the viewpoint of the effect of using the cocatalyst and the cost, the alkylaluminum chloride is preferred as the cocatalyst, and the molar ratio of the metallic aluminum in the alkylaluminum chloride to the metallic nickel in the catalyst is abbreviated as the aluminum-nickel ratio, and the aluminum-nickel ratio is in the range of 50-1000:1, preferably 100-800:1, more preferably 200-600:1, and more preferably 400: 1.
The invention also discloses the application of the catalyst shown in the formula (I) in catalyzing the polymerization of ethylene and propylene to prepare polyethylene and polypropylene.
The invention has the beneficial effects that the (alpha-diimine) nickel olefin polymerization catalyst with good thermal stability and polymerization activity is provided by improving the ligand framework structure on the premise of not obviously increasing the steric hindrance of the side group substituent.
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Compounds of the formulae (I), (II), (III) which are specifically mentioned in the examples of the present invention are shown in Table 3:
TABLE 3
Figure BDA0001913093990000062
Figure BDA0001913093990000071
Example 1
Preparation A1: to a solution of 2, 6-bis (benzhydryl) -4-methylaniline (8.8g, 20mmol) and 1, 2-benzoacenaphthenequinone (4.2g, 18mmol) in toluene (150mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 6 h. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 2:1 to obtain a1 having a mass of 4.1g, yield: 35 percent.
Example 2
Preparation A2: to a solution of 2, 4-bis (benzhydryl) -6-methylaniline (8.8g, 20mmol) and 1, 2-benzoacenaphthenequinone (4.2g, 18mmol) in toluene (150mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 6 h. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 2:1 to obtain a2 having a mass of 5.0g, yield: 42 percent.
Example 3
Preparation A3: to a solution of 2, 4-bis (4-fluorophenyl) methyl) -6-methylaniline (10.2g, 20mmol) and 1, 2-benzoacenaphthenequinon (4.2g, 18mmol) in toluene (150mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 10 hours. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 2:1 to obtain a3 having a mass of 6.3g, yield: 48 percent.
Example 4
Preparation of L1: to a solution of 2, 6-dimethylaniline (0.133g, 1.1mmol) and A1(0.653g, 1mmol) in toluene (50ml) was added p-toluenesulfonic acid (0.086g, 0.5mmol), and the reaction was refluxed for 12 hours. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L1 with a mass of 0.31g, yield: 41 percent.
Example 5
Preparation of L2: to a solution of 2, 6-diethylaniline (0.164g, 1.1mmol) and A1(0.653g, 1mmol) in toluene (50ml) was added p-toluenesulfonic acid (0.086g, 0.5mmol), and the reaction was refluxed for 12 hours. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to give L2 with a mass of 0.28g, yield: 36 percent.
Example 6
Preparation of L3: to a solution of 2, 6-diisopropylaniline (0.195g, 1.1mmol) and A1(0.653g, 1mmol) in toluene (50ml) was added p-toluenesulfonic acid (0.086g, 0.5mmol), and the reaction was refluxed for 12 h. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L3 with a mass of 0.33g, yield: 41 percent.
Example 7
Preparation of L12: to a solution of 2, 6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A2(0.653g, 1mmol) in toluene (50ml) was added p-toluenesulfonic acid (0.086g, 0.5mmol), and the reaction was refluxed for 12 h. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L12 with a mass of 0.31g, yield: 39 percent.
Example 8
Preparation of L20: to a solution of 2, 6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A3(0.725g, 1mmol) in toluene (50ml) was added p-toluenesulfonic acid (0.086g, 0.5mmol) and the reaction was refluxed for 12 h. The solvent was removed, and silica gel column chromatography was performed on the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to give L20 with a mass of 0.37g, yield: and 43 percent.
Example 9
Preparation C1: under a nitrogen atmosphere, L1(0.151g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol) was dissolved in 20ml of dichloromethane, stirred at room temperature for 24 hours, the dichloromethane was drained and washed 3 times with 20ml of ether each time, and the ether was drained to give C1 as a solid, 0.171g, 88% yield.
Example 10
Preparation C2: under a nitrogen atmosphere, L2(0.156g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol) was dissolved in 20ml of dichloromethane, stirred at room temperature for 24 hours, the dichloromethane was drained and washed 3 times with 20ml of ether each time, and the ether was drained to give C2 as a solid, 0.172g, 86% yield.
Example 11
Preparation C3: under a nitrogen atmosphere, L3(0.162g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol) was dissolved in 20ml of dichloromethane, stirred at room temperature for 24 hours, the dichloromethane was drained and washed 3 times with 20ml of ether each time, and the ether was drained to give C3 as a solid, 0.188g, 89% yield.
Example 12
Preparation C12: under a nitrogen atmosphere, L12(0.160g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol) was dissolved in 20ml of dichloromethane, stirred at room temperature for 24 hours, the dichloromethane was drained and washed 3 times with 20ml of ether each time, and the ether was drained to give C12 as a solid, 0.186g, 90% yield.
Example 13
Preparation C20: under a nitrogen atmosphere, L20(0.174g, 0.2mmol) and (DME) NiBr2(0.062g,0.2mmol) was dissolved in 20ml of dichloromethane, stirred at room temperature for 24 hours, the dichloromethane was drained and washed 3 times with 20ml of ether each time, and the ether was again drained to give C20 as a solid, 0.191g, 88% yield.
The following examples are for the catalytic ethylene polymerization:
example 14
The ethylene pressure polymerization is carried out in the absence of waterCarried out under oxygen conditions. Ethylene pressure was 1MPa, polymerization temperature was 60 ℃ and 1L of heptane was introduced into a 2000mL stainless steel reaction vessel, to which was subsequently injected 2.5mL of a 2.0 mol/L solution of diethylaluminum chloride as a co-catalyst in toluene. 10 mu mol of main catalyst C1 is dissolved in 10mL of toluene solution, injected, ethylene is pressurized to 1MPa, stirred, reacted for half an hour, the polymer solution is poured into acidified ethanol solution for settling, the polymer is filtered, then washed for a plurality of times by acidified ethanol, dried in vacuum at 60 ℃ to constant weight, and then 24.3g of polymer is weighed. The catalytic activity was 4.86X 106gPE[mol(Ni)h] -1The weight average molecular weight of the polymerization product was 33.6X 104g/mol, polydispersity 2.17.
Example 15
The polymer product obtained in example 14, in which C1 was replaced with C2 and other conditions were not changed, was dried under vacuum at 60 ℃ to a constant weight, and 25.8g of the polymer was weighed. The catalytic activity was 5.16X 106gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 37.2X 104g/mol, polydispersity 2.31.
Example 16
The polymerization product was vacuum-dried at 60 ℃ to a constant weight under conditions in which C1 in example 14 was replaced with C3 and the polymerization temperature was set at 20 ℃ and other conditions were not changed, and 53.1g of the polymer was weighed. The catalytic activity was 10.6X 106gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 104.3X 104g/mol, polydispersity 2.35.
Example 17
The polymerization product of example 14, in which C1 was replaced with C12, the polymerization temperature was set at 80 ℃ and the cocatalyst was replaced with 10ml of a 3.0mol/L MMAO toluene solution, was dried under vacuum at 60 ℃ to a constant weight under otherwise unchanged conditions, and weighed 18.9g of a polymer. The catalytic activity was 3.78X 106gPE[mol(Ni)h]-1。
Example 18
The polymer product obtained in example 14, in which C1 was replaced with C20 and other conditions were not changed, was dried under vacuum at 60 ℃ to a constant weight and 22.9g of a polymer was weighed. The catalytic activity was 4.58X 106gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 13.3X 104g/mol, polydispersity 2.56.
Example 19
The polymerization temperature in example 18 was adjusted to 70 ℃ and the other conditions were not changed, and the polymerization product was vacuum-dried at 60 ℃ to a constant weight and then 15.8g of a polymer was weighed. The catalytic activity was 3.16X 106gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 11.6X 104g/mol, polydispersity 2.53.
Comparative example 1
(2, 6-bis (benzhydryl) -4-methylaniline) acenaphthenone was prepared by substituting 1, 2-benzo acenaphthenequinone in example 1 with the same molar amount of acenaphthenequinone, code D1, yield: 32 percent.
Comparative example 2
1- (2, 6-diethylaniline) -2- (2, 6-bis (benzhydryl) -4-methylaniline) acenaphthylene was prepared in 34% yield with the code E1 by replacing A1 in example 5 with the same molar amount of D1.
Comparative example 3
Nickel (1- (2, 6-diethylaniline) -2- (2, 6-bis (benzhydryl) -4-methylaniline) acenaphthylene) bromide was prepared in 85% yield under the code F1 by substituting L2 in example 10 with the same molar amount of E1.
Comparative example 4
The C2 in example 15 was replaced by the same molar amount of F1, and the polymerization catalyst activity was 4.26X 10 without changing the other conditions6gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 31.2X 104g/mol, polydispersity 2.27.
Comparative example 5
(2, 4-bis (4-fluorophenyl) methyl) -6-methylaniline) acenaphthenone was prepared by replacing 1, 2-benzoacenaphthenequinonediquinone in example 3 with the same molar amount of acenaphthenequinonediquinone, code No. D2, yield: 51 percent.
Comparative example 6
1- (2, 6-diethyl-4-methylanilide) -2- (2, 4-bis (4-fluorophenyl) methyl) -6-methylanilide) acenaphthylene was prepared in 46% yield with the code E2 by replacing A3 in example 8 with the same molar amount of D2.
Comparative example 7
Nickel (1- (2, 6-diethyl-4-methylanilide) -2- (2, 4-bis (4-fluorophenyl) methyl) -6-methylanilide) acenaphthylene) bromide was prepared in 83% yield using the same molar amount of E2 instead of L20 from example 13.
Comparative example 8
The polymerization catalyst activity was 2.41X 10, except that the molar amount of F2 was changed to C20 in example 19, and the polymerization catalyst activity was changed to 2.41X 106gPE[mol(Ni)h]-1The weight average molecular weight of the polymerization product was 9.6X 104g/mol, polydispersity 2.33.

Claims (7)

1. An (alpha-diimine) nickel catalyst of formula (I):
Figure FDA0003445038820000011
in the formula (I), R1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl or trifluoromethyl, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl, and X is chlorine or bromine.
2. The catalyst of claim 1, wherein: the R is1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl or bis (4-fluorophenyl) methyl, R3Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Hydrogen or methyl, X is bromine.
3. A compound of formula (II):
Figure FDA0003445038820000012
in the formula (II), R1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl or trifluoromethyl, R4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl.
4. A process for the preparation of a compound corresponding to formula (ii) as defined in claim 3, comprising the steps of:
1) and 1, 2-benzo acenaphthenequinone and aniline with a large steric hindrance substituent are subjected to ketone-amine condensation reaction to obtain a compound shown in a formula (III):
Figure FDA0003445038820000013
wherein R is1Is diphenylmethyl or bis (4-fluorophenyl) methyl, R2Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R3Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl or trifluoromethyl;
2) and (3) reacting the compound shown in the formula (III) with aniline with a small steric hindrance substituent to obtain a corresponding compound shown in the formula (II) through a ketone-amine condensation reaction:
Figure FDA0003445038820000021
wherein R is4Is methyl, ethyl or isopropyl, R5Is methyl, ethyl or isopropyl, R6Is hydrogen, methyl, ethyl or isopropyl.
5. A process for preparing the catalyst of claim 1 or 2, comprising the steps of: complexing the compound of claim 3 with one of glyme nickel dibromide, glyme nickel dichloride or nickel dichloride hexahydrate under an inert gas atmosphere to obtain the catalyst of claim 1 or 2.
6. A catalyst composition for catalyzing olefin polymerization, comprising the procatalyst of claim 1 or 2 and a cocatalyst, wherein the cocatalyst is at least one selected from the group consisting of alkylaluminum chloride, alkylaluminum, and aluminoxane, and the olefin is ethylene or propylene.
7. Use of the (alpha-diimine) nickel catalyst of claim 1 in catalyzing the polymerization of ethylene and propylene to produce polyethylene and polypropylene.
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CN105646598A (en) * 2014-11-17 2016-06-08 中国科学院化学研究所 Naphthyl-substituted asymmetric acenaphthenediimine nickel complexes, and preparing method and applications thereof
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