CN109956979B - Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof - Google Patents

Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof Download PDF

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CN109956979B
CN109956979B CN201711418973.7A CN201711418973A CN109956979B CN 109956979 B CN109956979 B CN 109956979B CN 201711418973 A CN201711418973 A CN 201711418973A CN 109956979 B CN109956979 B CN 109956979B
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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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract

The invention discloses a large steric hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 5, 6-dimethyl acenaphthenequinone as a framework, and a preparation method and application thereof. The structural formula of the large steric hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 5, 6-dimethyl acenaphthenequinone as a framework is shown as a formula (I). Wherein R is 1 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 2 Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R 3 Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R 4 Is methyl, ethyl or isopropyl, R 5 Is methyl, ethyl or isopropyl, R 6 Is hydrogen, methyl, ethyl or isopropyl, and X is chlorine or bromine. The catalyst has simple preparation process, can catalyze the ethylene polymerization under the action of a cocatalyst, shows better thermal stability and polymerization activity, and has good industrial application prospect.

Description

Heat-resistant asymmetric alpha-diimine nickel olefin catalyst and preparation method and application thereof
The technical field is as follows: the invention relates to a heat-resistant asymmetric (alpha-diimine) nickel olefin catalyst, a preparation method and application thereof, in particular to a large steric hindrance asymmetric (alpha-diimine) nickel olefin catalyst based on 5, 6-dimethyl acenaphthenequinone as a framework, a preparation method thereof and application of the catalyst in catalyzing ethylene or propylene to obtain polyethylene or polypropylene.
Technical 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 to discover that Ni (II) and Pd (II) metal complexes containing alpha-diimine ligands can catalyze the polymerization of ethylene to high molecular weight polymers at atmospheric pressure (J.Am.chem.Soc., 1995,117 (23): 6414-6415). The specific structure of the alpha-diimine nickel olefin catalyst is shown as the formula (IV):
Figure SMS_1
to date, considerable research has been done 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 topology. 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 sterically hindered isopropyl group, the molecular weight and catalyst activity of polyethylene produced using such catalysts decrease sharply 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 R' of the bulky substituent group prevents the rapid insertion of ethylene, 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 5, 6-dimethyl acenaphthenequinone as a framework, and a preparation method and application thereof.
The invention provides an asymmetric (alpha-diimine) nickel olefin catalyst based on 5, 6-dimethyl acenaphthenequinone as a framework, which has a chemical structure general formula shown in a formula (I):
Figure SMS_2
in the formula (I), R 1 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 2 Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R 3 Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R 4 Is methyl, ethyl or isopropyl, R 5 Is methyl, ethyl or isopropyl, R 6 Is 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) 1 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 2 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 3 Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl, halogen or methoxy, R 4 Is methyl, ethyl or isopropyl, R 5 Is methyl, ethyl or isopropyl, R 6 Hydrogen or methyl, X is bromine.
The general structural formula of the catalyst ligand provided by the invention is shown as formula (II):
Figure SMS_3
in the formula (II), R 1 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 2 Is diphenylmethyl, bis (4-fluorophenyl) methyl or methyl, R 3 Is methyl, ethyl, isopropyl, benzhydryl, bis (4-fluorophenyl) methyl, halogen, trifluoromethyl or methoxy, R 4 Is methyl, ethyl or isopropyl, R 5 Is methyl, ethyl or isopropyl, R 6 Is hydrogen, methyl, ethyl or isopropyl. The choice of all aniline substituents in formula (II) is independent of one another.
Preference is given toR is represented by the formula (II) 1 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 2 Is diphenylmethyl or bis (4-fluorophenyl) methyl, R 3 Is methyl, ethyl, isopropyl, diphenylmethyl, bis (4-fluorophenyl) methyl, halogen or methoxy, R 4 Is methyl, ethyl or isopropyl, R 5 Is methyl, ethyl or isopropyl, R 6 Is 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 SMS_4
Figure SMS_5
The present invention also provides a method for preparing the above ligand compound, which comprises the steps of:
1) 5, 6-dimethyl acenaphthenequinone and aniline with large steric hindrance substituent are subjected to ketone amine condensation reaction to obtain a compound shown as a formula (III):
Figure SMS_6
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, 5, 6-dimethyl acenaphthenequinone, aniline with large steric hindrance substituent and solvent is 0.1-0.15mmol. 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).
The 5, 6-dimethyl acenaphthenequinone can be obtained by using 1, 8-dimethylnaphthalene as a raw material, carbon disulfide as a solvent and anhydrous aluminum bromide as a catalyst under the condition that oxalyl bromide is used as an oxidant.
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 SMS_7
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, the compound shown in the formula (III), the aniline with the small steric hindrance substituent and the solvent is 0.2-0.5mmol. And carrying out column chromatography on the product, namely the mixed solvent of dichloromethane and petroleum ether or the mixed solvent of petroleum ether and ethyl acetate, serving as eluent, on a silica gel column to obtain a product shown in the 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, under nitrogen atmosphere, the compound shown in formula (II) can be selected from ligands shown in Table 1, and the nickel-containing compound complexed with the ligands is selected from ethylene glycol dimethyl ether nickel Dibromide (DME) NiBr 2 Said ligand being in combination with (DME) NiBr 2 1 to 1.2, preferably 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 bromineReferring to the ligand scheme of table 1, the catalyst of the present invention may be selected from any one of table 2:
TABLE 2 catalysts
Figure SMS_8
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Figure SMS_9
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 co-catalyst and the cost, an alkylaluminum chloride is preferred as the co-catalyst, and the molar ratio of metallic aluminum in the alkylaluminum chloride to metallic nickel in the catalyst is abbreviated as an alnico ratio, and the alnico ratio is in the range of 50 to 1000, preferably 100 to 800, more preferably 200 to 600.
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 effect of providing the (alpha-diimine) nickel olefin polymerization catalyst with good thermal stability and polymerization activity.
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 SMS_10
Example 1 in a nitrogen blanketed glass vial No. 1, 20g of aluminum bromide and 10mL (23.88 mmol) of oxalyl bromide were dissolved in 500mL of carbon disulfide and stirred in a bath of ethanol at-78 ℃. In a nitrogen blanketed glass bottle # 2, 3g (19.2 mmol) of 1, 8-dimethylnaphthalene were dissolved in 100mL of carbon disulfide. The solution in vial No. 2 was added dropwise to vial No. 1 over 2h via a micro syringe pump. After the dropwise addition, the bottle No. 1 was placed in an ice-water bath at 0 ℃ for reaction for 3 hours. After the reaction was completed, 500mL of deionized water was slowly added dropwise to flask 1, and the solvent carbon disulfide was removed by a cold trap at room temperature. And (3) extracting the reaction product from the deionized water by using dichloromethane to obtain a dichloromethane solution of the product, washing the dichloromethane solution for three times by using aqueous solutions of hydrochloric acid, sodium bicarbonate and sodium chloride, and then performing rotary evaporation on the dichloromethane solution to remove a solvent dichloromethane to obtain 5, 6-dimethyl acenaphthenequinone serving as a light yellow solid, wherein the mass is 1.33g, and the yield is 33%.
Example 2, preparation A1: to a solution of 2, 6-bis (benzhydryl) -4-methylaniline (8.8g, 20mmol) and 5, 6-dimethyl acenaphthoquinone (3.8g, 18mmol) in toluene (150 mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 6 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: 42 percent.
Example 3, preparation A2: to a solution of 2, 4-bis (benzhydryl) -6-methylaniline (8.8g, 20mmol) and 5, 6-dimethyl acenaphthoquinone (3.8g, 18mmol) in toluene (150 mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 6 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: and 43 percent.
Example 4, preparation A3: to a solution of 2, 6-bis (4-fluorophenyl) methyl) -4-methylaniline (10.2g, 20mmol) and 5, 6-dimethylacenaphthenequinone (3.8g, 18mmol) in toluene (150 mL) was added p-toluenesulfonic acid (0.34g, 2mmol), and the mixture was refluxed for 10 hours. The solvent was removed, and silica gel column chromatography of the residue using a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 2: 41 percent.
Example 5, preparation L1: to a solution of 2,6-dimethylaniline (0.133g, 1.1mmol) and A1 (0.631g, 1mmol) in toluene (50 ml) was added p-toluenesulfonic acid (0.086 g, 0.5mmol), and the mixture 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: 44 percent.
Example 6, preparation L2: to a solution of 2, 6-diethylaniline (0.164g, 1.1mmol) and A1 (0.631g, 1mmol) in toluene (50 ml) was added p-toluenesulfonic acid (0.086 g,0.5 mmol), and the mixture 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: 45 percent.
Example 7, preparation L3: to a solution of 2,6-diisopropylaniline (0.195g, 1.1mmol) and A1 (0.631g, 1mmol) in toluene (50 ml) was added p-toluenesulfonic acid (0.086 g,0.5 mmol), and the mixture 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: 42 percent.
Example 8, preparation L12: to a solution of 2, 6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A2 (0.631g, 1mmol) in toluene (50 ml) was added p-toluenesulfonic acid (0.086 g, 0.5mmol), and the mixture was refluxed for 12 hours. The solvent was removed, and silica gel column chromatography of the residue using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30: and 47 percent.
Example 9, preparation L20: to a solution of 2, 6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A3 (0.7g, 1mmol) in toluene (50 ml) was added p-toluenesulfonic acid (0.086 g, 0.5mmol), and the mixture 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: 49 percent.
Example 10, preparation C1: under a nitrogen atmosphere, L1 (0.147g, 0.2mmol) and (DME) NiBr were mixed 2 (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, 0.169g, 89% yield.
Example 11, preparation C2: under a nitrogen atmosphere, L2 (0.152g, 0.2mmol) and (DME) NiBr were mixed 2 (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, 0.178g, 91% yield.
Example 12, preparation C3: under a nitrogen atmosphere, L3 (0.158g, 0.2mmol) and (DME) NiBr were mixed 2 (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, 0.185g, 92% yield.
Example 13, preparation C12: l12 (0.155g, 0.2mmol) was reacted with (DME) NiBr under a nitrogen atmosphere 2 (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, 0.175g, 88% yield.
Example 14, preparation C20: l20 (0.170g, 0.2mmol) was reacted with (DME) NiBr under a nitrogen atmosphere 2 (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 C20 as a solid, 0.190g, 89% yield.
The following examples are for the catalytic ethylene polymerization:
example 15, the ethylene pressure polymerization was carried out under anhydrous and oxygen-free 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 2.0mol/L solution of diethylaluminum chloride as a co-catalyst in toluene. Dissolving with 10mL of toluene solution10 mu mol of main catalyst C1, injecting it, pressurizing ethylene to 1MPa, stirring, reacting for half an hour, pouring the polymer solution into acidified ethanol solution for settling, filtering the polymer, washing with acidified ethanol for several times, drying in vacuum at 60 ℃ to constant weight, and weighing 27.6g of polymer. The catalytic activity was 5.52X 10 6 gPE[mol(Ni)h] -1 The weight average molecular weight of the polymerization product was 33.6X 10 4 kg/mol, polydispersity 2.17.
Example 16, in example 15, C1 was replaced with C2 and the other conditions were not changed, and the polymerization product was vacuum-dried at 60 ℃ to a constant weight and then 28.9g of a polymer was weighed. The catalytic activity was 5.78X 10 6 gPE[mol(Ni)h] -1 The weight average molecular weight of the polymerization product was 38.3X 10 4 kg/mol, polydispersity 2.35.
Example 17 in example 15, C1 was replaced with C3, the polymerization temperature was set to 20 ℃, other conditions were not changed, and the polymerization product was vacuum-dried at 60 ℃ to a constant weight and then weighed 56.2g of a polymer. The catalytic activity was 11.24X 10 6 gPE[mol(Ni)h] -1 The weight average molecular weight of the polymerization product was 97.3X 10 4 kg/mol, polydispersity 2.45.
Example 18, C1 in example 15 was replaced with C12, the cocatalyst was changed to 10ml of a 3.0mol/L MAO toluene solution, the polymerization product was dried at 60 ℃ in vacuo to constant weight and 28.6g of polymer was weighed out. The catalytic activity was 5.72X 10 6 gPE[mol(Ni)h] -1 The weight average molecular weight of the polymerization product was 12.6X 10 4 kg/mol, polydispersity 2.41.
Example 19 in example 15, C1 was replaced with C20 and the other conditions were not changed, and the polymerization product was vacuum-dried at 60 ℃ to a constant weight and then 25.8g of a polymer was weighed. The catalytic activity was 5.16X 10 6 gPE[mol(Ni)h] -1 The weight-average molecular weight of the polymerization product was 15.1kg/mol, and the polydispersity was 2.44.
Example 20 the polymerization temperature in example 15 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 weighed 17.8g of a polymer. Has catalytic activity of
3.56×10 6 gPE[mol(Ni)h] -1 The weight-average molecular weight of the polymerization product was 11.9kg/mol, and the polydispersity was 2.47.

Claims (4)

1. An (alpha-diimine) nickel catalyst of formula (I):
Figure QLYQS_1
in the formula (I), R 1 Is benzhydryl, R 2 Is benzhydryl, R 3 Is methyl, R 4 Is ethyl, R 5 Is ethyl, R 6 Is hydrogen and X is bromine.
2. A compound of formula (II):
Figure QLYQS_2
in the formula (II), R 1 Is benzhydryl, R 2 Is benzhydryl, R 3 Is methyl, R 4 Is ethyl, R 5 Is ethyl, R 6 Is hydrogen and X is bromine.
3. A catalyst composition for catalyzing olefin polymerization, comprising the procatalyst of claim 1 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.
4. Use of the (alpha-diimine) nickel catalyst of claim 1 in the catalysis of ethylene polymerization to produce polyethylene.
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