WO2020124556A1 - Catalyseur d'oléfine d'(alpha-diimine)nickel asymétrique , et procédé de préparation et application associé - Google Patents

Catalyseur d'oléfine d'(alpha-diimine)nickel asymétrique , et procédé de préparation et application associé Download PDF

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WO2020124556A1
WO2020124556A1 PCT/CN2018/122681 CN2018122681W WO2020124556A1 WO 2020124556 A1 WO2020124556 A1 WO 2020124556A1 CN 2018122681 W CN2018122681 W CN 2018122681W WO 2020124556 A1 WO2020124556 A1 WO 2020124556A1
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methyl
isopropyl
ethyl
bis
fluorophenyl
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PCT/CN2018/122681
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Chinese (zh)
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徐涛
傅智盛
吴安洋
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杭州星庐科技有限公司
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Publication of WO2020124556A1 publication Critical patent/WO2020124556A1/fr

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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
    • 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
    • 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

Definitions

  • the invention relates to an asymmetric ( ⁇ -diimine) nickel olefin catalyst and a preparation method and application thereof, in particular to a large sterically hindered asymmetric ( ⁇ -diimine) based on 1,2-benzoacenaphthoquinone as a skeleton ) Nickel olefin catalyst and preparation method thereof, and application of using the catalyst to catalyze ethylene or propylene to obtain polyethylene or polypropylene.
  • Polyolefin is a basic material related to national economy and people's death, and because of its excellent performance, variety, easy availability and low price, it is widely used in various fields such as industry, agriculture and national defense.
  • the development and application of new catalysts is one of the core driving forces for the progress and development of the polyolefin industry, and is the key to controlling the structure and performance of polyolefin materials.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, to provide a large sterically hindered asymmetric ( ⁇ -diimine) nickel olefin catalyst based on 1,2-benzoacenaphthoquinone as a skeleton, its preparation method and application.
  • the asymmetric ( ⁇ -diimine) nickel olefin catalyst provided by the present invention has the general chemical structure as shown in formula (I):
  • R 1 is benzhydryl or bis(4-fluorophenyl)methyl
  • R 2 is benzhydryl, 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
  • X is chlorine or bromine.
  • R 1 in formula (I) is benzhydryl or bis(4-fluorophenyl)methyl
  • R 2 is benzhydryl or bis(4-fluorophenyl)methyl
  • R 3 is Methyl, ethyl, isopropyl, benzhydryl, bis(4-fluorophenyl)methyl, halogen or methoxy
  • R 4 is methyl, ethyl or isopropyl
  • R 5 is methyl
  • R 6 is hydrogen or methyl
  • X is bromine.
  • R 1 is benzhydryl or bis(4-fluorophenyl)methyl
  • R 2 is benzhydryl, bis(4-fluorophenyl)methyl or methyl
  • R 3 is Methyl, ethyl, isopropyl
  • R 4 is methyl, ethyl or isopropyl
  • R 5 is methyl, ethyl or isopropyl
  • R 6 is hydrogen, methyl, ethyl or isopropyl.
  • R 1 is benzhydryl or bis(4-fluorophenyl)methyl
  • R 2 is benzhydryl or bis(4-fluorophenyl)methyl
  • R 3 Is methyl, ethyl, isopropyl
  • R 4 is methyl, ethyl or isopropyl
  • R 5 is methyl Group, ethyl or isopropyl
  • R 6 is hydrogen or methyl.
  • the ligand shown in (II) above is selected from any of the compounds shown in Table 1:
  • the invention also provides a method for preparing the above ligand compound, which comprises the following steps:
  • the solvent used in this step can be selected from at least one of toluene, acetonitrile, acetic acid and absolute ethanol, preferably toluene and acetonitrile;
  • the catalyst used in this step is selected from At least one of p-toluenesulfonic acid and acetic acid;
  • the dosage ratio of the catalyst, 1,2-benzoacenaphthoquinone, aniline with a large steric substituent and the solvent is 0.1-0.15mmol:1-1.1mmol:1.1 -1.4mmol: 5-10ml, preferably 0.1mmol: 1mmol: 1.1mmol: 8ml;
  • the reaction time in this step is 2-8 hours, preferably 3-6 hours.
  • the product is subjected to column chromatography on a silica gel column with a mixed solvent of methylene chloride and petroleum ether or a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain the product represented by formula (III).
  • the solvent used in this step is selected from at least one of toluene, acetonitrile, acetic acid, and absolute ethanol, preferably toluene and acetonitrile;
  • the catalyst used in this step is selected from At least one of toluenesulfonic acid and acetic acid; the ratio of the catalyst, the compound represented by formula (III), the aniline with a small steric substituent and the solvent is 0.2-0.5mmol: 1-1.1mmol: 1.1-1.4 mmol: 30-70ml, preferably 0.3mmol: 1mmol: 1.1mmol: 50ml; the reaction time in this step is 6-16 hours, preferably 8-12 hours.
  • the product is subjected to column chromatography on a silica gel column with a mixed solvent of dichloromethane and petroleum ether or a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain the product represented by formula (II).
  • the invention also provides a method for preparing the catalyst represented by formula (I), which comprises the following steps: under an inert gas atmosphere, the compound represented by formula (II) and ethylene glycol dimethyl ether nickel dibromide, ethylene glycol
  • the catalyst of the present invention can be obtained by complexing one of dimethyl ether nickel dichloride or nickel dichloride hexahydrate.
  • X in the catalyst structural formula of the present invention is chlorine or bromine, which has no substantial effect on the polymerization effect, and X is selected as bromine in the embodiments of the present invention.
  • the compound represented by formula (II) may be selected from the ligands shown in Table 1, and the nickel-containing compound complexed with the ligand is selected from ethylene glycol dimethyl ether nickel dibromide (DME) NiBr 2
  • DME nickel-containing compound complexed with the ligand
  • the molar ratio of the ligand to (DME)NiBr 2 is 1:1-1.2, preferably 1:1.1; the solvent is dichloromethane, the reaction temperature is 15-35°C, preferably 25°C, and the reaction time is 8- 30 hours, preferably 16-24 hours.
  • X is bromine
  • the catalyst of the present invention can be selected from any one of Table 2:
  • the invention also provides a catalyst composition for catalyzing the polymerization of olefins.
  • the composition is composed of a catalyst represented by formula (I) and a co-catalyst selected from the group consisting of alkyl aluminum chloride, aluminum alkyl and aluminum At least one of the oxanes, the olefin is ethylene or propylene.
  • the aluminoxane is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane or isobutylaluminoxane;
  • the aluminum alkyl It is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, or tri-n-octyl aluminum;
  • the alkyl aluminum chloride is diethyl aluminum chloride, sesqui-monochlorodiethyl Aluminum or ethyl aluminum dichloride; from the perspective of the use effect and cost of the cocatalyst, alkyl aluminum chloride is preferred as the cocatalyst.
  • the molar ratio of metal aluminum in the aluminum alkyl chloride to metal nickel in the catalyst is referred to as aluminum nickel
  • the ratio of aluminum to nickel is in the range of 50-1000:1, preferably 100-800:1, more preferably 200-600:1, more preferably 400:1.
  • the invention also discloses the application of the catalyst shown in formula (I) in catalyzing the polymerization of ethylene and propylene to prepare polyethylene and polypropylene.
  • the beneficial effect of the present invention is to provide a kind of ( ⁇ -diimine) with good thermal stability and polymerization activity by improving the ligand skeleton structure without significantly increasing the steric hindrance of the pendant substituents Nickel olefin polymerization catalyst.
  • Preparation A1 To a solution of 2,6-bis(diphenylmethyl)-4-methylaniline (8.8g, 20mmol) and 1,2-benzoacenaphthoquinone (4.2g, 18mmol) in toluene (150mL) was added P-toluenesulfonic acid (0.34g, 2mmol) was reacted at reflux for 6h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 2:1 to obtain A1 with a mass of 4.1 g and a yield of 35%.
  • Preparation A2 To a solution of 2,4-bis(diphenylmethyl)-6-methylaniline (8.8g, 20mmol) and 1,2-benzoacenaphthoquinone (4.2g, 18mmol) in toluene (150mL) was added P-toluenesulfonic acid (0.34g, 2mmol) was reacted at reflux for 6h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 2:1 to obtain A2 with a mass of 5.0 g and a yield of 42%.
  • Preparation A3 in 2,4-bis(bis(4-fluorophenyl)methyl)-6-methylaniline (10.2g, 20mmol) and 1,2-benzoacenaphthoquinone (4.2g, 18mmol) in toluene (150mL) To the solution was added p-toluenesulfonic acid (0.34g, 2mmol), and the reaction was refluxed for 10h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 2:1 to obtain A3 with a mass of 6.3 g and a yield of 48%.
  • Preparation L1 p-toluenesulfonic acid (0.086g, 0.5mmol) was added to a solution of 2,6-dimethylaniline (0.133g, 1.1mmol) and A1 (0.653g, 1mmol) in toluene (50ml), and the reaction was refluxed for 12h . The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L1 with a mass of 0.31 g and a yield of 41%.
  • L2 p-toluenesulfonic acid (0.086g, 0.5mmol) was added to a solution of 2,6-diethylaniline (0.164g, 1.1mmol) and A1 (0.653g, 1mmol) in toluene (50ml), and the reaction was refluxed for 12h . The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L2 with a mass of 0.28 g and a yield of 36%.
  • Preparation L3 p-toluenesulfonic acid (0.086g, 0.5mmol) was added to a solution of 2,6-diisopropylaniline (0.195g, 1.1mmol) and A1 (0.653g, 1mmol) in toluene (50ml), and the reaction was refluxed 12h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L3 with a mass of 0.33 g and a yield of 41%.
  • Preparation L12 p-toluenesulfonic acid (0.086g, 0.5mmol) was added to a solution of 2,6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A2 (0.653g, 1mmol) in toluene (50ml) ), refluxing for 12h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L12 with a mass of 0.31 g and a yield of 39%.
  • Preparation L20 p-toluenesulfonic acid (0.086g, 0.5mmol) was added to a solution of 2,6-diethyl-4-methylaniline (0.179g, 1.1mmol) and A3 (0.725g, 1mmol) in toluene (50ml) ), refluxing for 12h. The solvent was removed, and the residue was subjected to silica gel column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 30:1 to obtain L20 with a mass of 0.37 g and a yield of 43%.
  • Preparation C1 Under a nitrogen atmosphere, dissolve L1 (0.151 g, 0.2 mmol) and (DME) NiBr 2 (0.062 g, 0.2 mmol) in 20 ml of dichloromethane, stir at room temperature for 24 hours, and pump dichloromethane Dry and wash with ether three times, each time the amount of ether is 20ml, and then drain off the ether to obtain solid C1, 0.171g, yield 88%.
  • Preparation C2 Under a nitrogen atmosphere, dissolve L2 (0.156 g, 0.2 mmol) and (DME) NiBr 2 (0.062 g, 0.2 mmol) in 20 ml of dichloromethane, stir at room temperature for 24 hours, and pump dichloromethane Dry and wash with ether three times, each time the amount of ether is 20ml, then the ether is drained to obtain solid C2, 0.172g, yield 86%.
  • Preparation C3 Under a nitrogen atmosphere, dissolve L3 (0.162 g, 0.2 mmol) and (DME) NiBr 2 (0.062 g, 0.2 mmol) in 20 ml of dichloromethane, stir at room temperature for 24 hours, and pump dichloromethane Dry and wash with ether three times, each time the amount of ether is 20ml, then the ether is drained to obtain solid C3, 0.188g, yield 89%.
  • Preparation C12 Under a nitrogen atmosphere, dissolve L12 (0.160 g, 0.2 mmol) and (DME) NiBr 2 (0.062 g, 0.2 mmol) in 20 ml of dichloromethane, stir at room temperature for 24 hours, and pump dichloromethane Dry and wash with ether three times, each time the amount of ether is 20ml, and then dry the ether to obtain solid C12, 0.186g, yield 90%.
  • Preparation C20 Under a nitrogen atmosphere, dissolve L20 (0.174 g, 0.2 mmol) and (DME) NiBr 2 (0.062 g, 0.2 mmol) in 20 ml of dichloromethane, stir at room temperature for 24 hours, and pump dichloromethane Dry and wash with ether three times, each time the amount of ether is 20ml, then the ether is drained to obtain solid C20, 0.191g, yield 88%.
  • the pressurized polymerization of ethylene is carried out under anhydrous and anaerobic conditions.
  • the ethylene pressure was 1 MPa
  • the polymerization temperature was 60° C.
  • 1 L of heptane was introduced into a 2000 mL stainless steel reactor, and then 2.5 ml of a diethylaluminum chloride toluene solution with a promoter concentration of 2.0 mol/L was injected into it.
  • Example 14 The C1 in Example 14 was replaced with C2, and the other conditions were not changed. After the polymerization product was vacuum dried at 60°C to constant weight, 25.8 g of polymer was weighed. The catalytic activity was 5.16 ⁇ 10 6 gPE[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 37.2 ⁇ 10 4 g/mol, and the polydispersity coefficient was 2.31.
  • Example 14 The C1 in Example 14 was replaced with C3, the polymerization temperature was set to 20°C, and other conditions remained unchanged. After the polymerization product was vacuum dried at 60°C to constant weight, 53.1 g of polymer was weighed. The catalytic activity was 10.6 ⁇ 10 6 gPE[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 104.3 ⁇ 10 4 g/mol, and the polydispersity coefficient was 2.35.
  • Example 14 C1 was replaced with C12, the polymerization temperature was set to 80°C, and the cocatalyst was changed to 10 ml of MMAO toluene solution with a concentration of 3.0 mol/L. Other conditions remained unchanged, and the polymerization product was vacuum dried at 60°C to a constant temperature. After weighing, 18.9 g of polymer was weighed. The catalytic activity was 3.78 ⁇ 10 6 gPE[mol(Ni)h] -1 .
  • Example 14 The C1 in Example 14 was replaced with C20, and the other conditions were unchanged. After drying the polymerization product at 60°C under vacuum to constant weight, 22.9 g of polymer was weighed. The catalytic activity was 4.58 ⁇ 10 6 gPE[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 13.3 ⁇ 10 4 g/mol, and the polydispersity coefficient was 2.56.
  • Example 18 The polymerization temperature in Example 18 was adjusted to 70°C, and other conditions were not changed. After the polymerization product was vacuum dried at 60°C to constant weight, 15.8 g of polymer was weighed. The catalytic activity was 3.16 ⁇ 10 6 gPE[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 11.6 ⁇ 10 4 g/mol, and the polydispersity coefficient was 2.53.
  • Example 1 The 1,2-benzoacenaphthoquinone in Example 1 was replaced with the same molar amount of acenaphthoquinone to prepare (2,6-bis(diphenylmethyl)-4-methylaniline) acenaphthene, codenamed D1, Yield: 32%.
  • Example 15 Replace C2 in Example 15 with the same molar amount of F1, other conditions remain unchanged, the polymerization catalytic activity is 4.26 ⁇ 10 6 gPE[mol(Ni)h] -1 , and the weight average molecular weight of the polymerization product is 31.2 ⁇ 10 4 g /mol, the polydispersity coefficient is 2.27.
  • Example 3 The 1,2-benzoacenaphthoquinone in Example 3 was replaced with the same molar amount of acenaphthoquinone to prepare (2,4-bis(bis(4-fluorophenyl)methyl)-6-methylaniline) acenaphthene Ketone, code-named D2, yield: 51%.
  • Example 8 Replace A3 in Example 8 with the same molar amount of D2 to prepare 1-(2,6-diethyl-4-methylaniline)-2-(2,4-bis(bis(4-fluorophenyl ) Methyl)-6-methylaniline) acenaphthene, codenamed E2, yield 46%.
  • Example 19 The C20 in Example 19 was replaced with the same molar amount of F2. Other conditions remained unchanged, the polymerization catalytic activity was 2.41 ⁇ 10 6 gPE[mol(Ni)h] -1 , and the weight average molecular weight of the polymerization product was 9.6 ⁇ 10 4 g /mol, the polydispersity coefficient is 2.33.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un catalyseur d'oléfine d'(α-diimine)nickel asymétrique à encombrement stérique élevé à base de 1,2-benzoacénaphtènequinone en tant que squelette, ainsi qu'un procédé de préparation et une application associés. La formule structurale du catalyseur d'oléfine d'(α-diimine)nickel asymétrique à encombrement stérique élevé à base de 1,2-benzoacénaphtènequinone en tant que squelette est telle que représentée dans la formule (I), dans laquelle R1 représente un benzhydryle ou bis un (4-fluorophényl)méthyle ; R2 représente un benzhydryle, un bis (4-fuorophényl))méthyle ou un méthyle ; R3 représente un méthyle, un éthyle, un isopropyle, un benzhydryle, un bis(4-fluorophényl)méthyle, un halogène, un trifluorométhyle, ou un méthoxy ; R4 représente un méthyle, un éthyle, ou un isopropyle ; R5 représente un méthyle, un éthyle ou un isopropyle ; R6 représente un hydrogène, un méthyle, un éthyle ou un isopropyle ; et X représente un chlore ou un brome. Le procédé de préparation du catalyseur est simple ; le catalyseur est capable de catalyser la polymérisation de l'éthylène sous l'action d'un cocatalyseur, il présente une bonne stabilité thermique et une bonne activité de polymérisation, et présente une bonne perspective d'application industrielle.
PCT/CN2018/122681 2017-12-25 2018-12-21 Catalyseur d'oléfine d'(alpha-diimine)nickel asymétrique , et procédé de préparation et application associé WO2020124556A1 (fr)

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