CN113416210B - Rigid tetranitrogen tetradentate fourth subgroup metal complex and application thereof - Google Patents
Rigid tetranitrogen tetradentate fourth subgroup metal complex and application thereof Download PDFInfo
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- CN113416210B CN113416210B CN202110685640.0A CN202110685640A CN113416210B CN 113416210 B CN113416210 B CN 113416210B CN 202110685640 A CN202110685640 A CN 202110685640A CN 113416210 B CN113416210 B CN 113416210B
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- catalyst
- tetradentate
- rigid
- tetranitrogen
- metal complex
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Images
Classifications
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- 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
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Abstract
The invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex, which has a structure shown in a formula (I): wherein n is 2-4; r is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The rigid tetranitrogen tetradentate fourth sub-group metal complex has good thermal stability. The catalyst has the characteristics of low usage amount of the catalyst promoter, high catalytic activity, good thermal stability and long catalytic life, and can be used for catalyzing ethylene polymerization to obtain an ultra-high molecular weight polyethylene product and simultaneously catalyzing ethylene and 1-octene to be copolymerized.
Description
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, in particular to a rigid tetranitrogen tetradentate fourth sub-group metal complex and application thereof.
Background
Polyolefin products become the most popular resin materials at present due to the advantages of easily available raw materials, low price, convenient production and processing, excellent performance and the like. In the current industrial production, polyolefin products have a large specific gravity. Polyethylene (PE) and Linear Low Density Polyethylene (LLDPE) are important synthetic resins and have a wide range of uses. In the process of producing the linear low-density polyethylene, the unsaturated olefin comonomer with the carbon number more than 3 is added for copolymerization with ethylene, so that the density of the polymer can be reduced, the mechanical strength and toughness of the polymer are improved, and the machining performance and heat resistance are improved. The higher the carbon number of the comonomer, the better the overall properties of the polymer. At present, linear low density polyethylene produced by copolymerizing ethylene with alpha-olefins such as 1-hexene, 1-octene, etc. is the fastest growing polyolefin resin variety.
The non-metallocene catalyst is an important olefin polymerization catalyst developed in the middle 90 th century, has a single active center, is relatively high in activity and can catalyze various polar single-point copolymerization. Terunorisfujita et al report that a class of Fujita catalysts can catalyze ethylene polymerization with high activity, but such catalysts have poor thermal stability and low insertion rate for catalyzing the copolymerization of ethylene with alpha-olefins (organometallics, 2011,20,4793-4799). The Jun Okuda task combines a series of [ ONNO ] fourth main group metal complexes to produce linear low density polyethylene with high activity, but its molecular weight is not high, limiting its industrial application (organometallics, 2009,28,5159-5165). The Ying task group reports that a series of [ ONNO ] tetradentate zirconium complexes can catalyze ethylene polymerization with high activity to obtain high molecular weight polyethylene, but the copolymerization capability is poor. The series of bridged tetraoxide fourth-subgroup non-metallocene catalysts (US 2004010103A1; WO03091262A1; US20120108770A1; WO2013090396 Al) applied by Symyx company and Dow company have high catalytic activity and good thermal stability, but a large amount of noble metal palladium catalysts are used in the synthesis process, so that the synthesis steps are complicated, and the synthesis cost is very high. The invention aims to design and synthesize a polyolefin elastomer which has high catalytic activity, high thermal stability and long catalytic life, and can catalyze ethylene to homopolymerize to produce linear low-density polyethylene with higher molecular weight and catalyze ethylene to copolymerize with alpha-olefin by reasonably optimizing catalyst substituent groups and polymerization conditions.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a rigid tetranitrogen tetradentate fourth subgroup metal complex as a catalyst, which has the characteristics of high catalytic activity, good thermal stability and long catalytic life.
The invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex, which has a structure shown in a formula (I):
wherein n is 2-4; r is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl;
x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl;
m is a fourth subgroup transition metal.
Preferably, R is n-propyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzhydryl, adamantyl, phenyl, benzyl, alpha-methylbenzyl, p-tolyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, p-tert-butylphenyl, p-methoxyphenyl, naphthyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl.
Preferably, n is 2, 3, 4;
x is halogen, methyl or benzyl; m is any one of titanium, zirconium or hafnium.
Preferably, the complex having the structure represented by formula (I) is specifically a structure represented by the following N1 to N12:
n1: r=n-propyl, n=2, m=ti, x=chloro;
n2: r=isopropyl, n=2, m=zr, x=chlorine;
and N3: r=tert-butyl, n=2, m=zr, x=chloro;
n4: r=phenyl, n=2, m=zr, x=chloro;
n5: r=p-methylphenyl, n=2, m=zr, x=chlorine;
n6: r=n-propyl, n=3, m=zr, x=chlorine;
n7: r=isopropyl, n=3, m=zr, x=chlorine;
n8: r=cyclohexyl, n=3, m=hf, x=chloro;
n9: r=cyclopentyl, n=3, m=hf, x=chloro;
n10: r=isopropyl, n=4, m=zr, x=chlorine;
n11: r=cyclohexyl, n=4, m=zr, x=chlorine;
n12: r=cyclopentyl, n=4, m=zr, x=chlorine.
The invention provides a catalyst for olefin polymerization, which comprises a main catalyst and a cocatalyst; the main catalyst comprises the rigid tetranitrogen tetradentate fourth sub-group metal complex according to any one of the technical schemes.
Preferably, the cocatalyst comprises one or more of alkylaluminoxane, modified alkylaluminoxane, trialkylaluminum and organoboron compound.
Preferably, the molar ratio of aluminum atoms in the cocatalyst to metal atoms in the main catalyst is 1: (5-10000);
the molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (1-1.5): 1.
The invention provides a preparation method of polyolefin, which comprises the following steps:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the main catalyst comprises the rigid tetranitrogen tetradentate fourth sub-group metal complex according to any one of the technical schemes.
The invention provides a preparation method of polyolefin, which is characterized by comprising the following steps:
copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst comprising a rigid tetradentate fourth subgroup metal complex according to any one of claims 1-4.
Preferably, the temperature of the homo-polymerization or copolymerization reaction is 0-200 ℃, and the ethylene pressure during polymerization is 0.1-10 MPa.
Compared with the prior art, the invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex, which has a structure shown in a formula (I): wherein n is 2-4; r is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The rigid tetranitrogen tetradentate fourth sub-group metal complex has good thermal stability. The catalyst has the characteristics of low usage amount of the catalyst promoter, high catalytic activity, good thermal stability and long catalytic life, and can be used for catalyzing ethylene polymerization to obtain an ultra-high molecular weight polyethylene product and simultaneously catalyzing ethylene and 1-octene to be copolymerized.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a complex N2 provided in example 2 of the present invention.
Detailed Description
The invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex and application thereof, and a person skilled in the art can properly improve the process parameters by referring to the content of the present disclosure. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex, which has a structure shown in a formula (I):
wherein n is 2-4; n is 2, 3 or 4;
r is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; preferably, R is a C1-C20 alkyl group, a C6-C20 aryl group or a C6-C20 substituted aryl group; more preferably, R is n-propyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, benzhydryl, adamantyl, phenyl, benzyl, α -methylbenzyl, p-tolyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, 2, 6-diethylphenyl, 2, 6-diisopropylphenyl, p-tert-butylphenyl, p-methoxyphenyl, naphthyl, 3, 5-dimethylphenyl or 3, 5-di-tert-butylphenyl; most preferably, R is n-propyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, benzyl, α -methylbenzyl, p-tolyl, 2-isopropylphenyl, 2, 6-dimethylphenyl, p-tert-butylphenyl, p-methoxyphenyl, naphthyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl.
X is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; preferably, X is halogen, C1-C10 alkyl, silicon-based, amino or C6-C20 aryl; more preferably, X is halogen, methyl or benzyl; most preferably X is halogen; particularly preferably, X is F, cl or Br; chlorine is particularly preferred.
M is a fourth subgroup transition metal; preferably, M is any one of titanium, zirconium or hafnium.
According to the present invention, the complex having the structure represented by formula (1) is specifically a structure represented by the following N1 to N12:
n1: r=n-propyl, n=2, m=ti, x=chloro;
n2: r=isopropyl, n=2, m=zr, x=chlorine;
and N3: r=tert-butyl, n=2, m=zr, x=chloro;
n4: r=phenyl, n=2, m=zr, x=chloro;
n5: r=p-methylphenyl, n=2, m=zr, x=chlorine;
n6: r=n-propyl, n=3, m=zr, x=chlorine;
n7: r=isopropyl, n=3, m=zr, x=chlorine;
n8: r=cyclohexyl, n=3, m=hf, x=chloro;
n9: r=cyclopentyl, n=3, m=hf, x=chloro;
n10: r=isopropyl, n=4, m=zr, x=chlorine;
n11: r=cyclohexyl, n=4, m=zr, x=chlorine;
n12: r=cyclopentyl, n=4, m=zr, x=chlorine.
The invention provides a synthesis method of the rigid tetranitrogen tetradentate fourth sub-group metal complex, and the synthesis route is shown as the following formula:
(1) When R-NH 2 In the case of fatty amines
(2) When R-NH 2 In the case of aromatic amines
The specific preparation process of the rigid tetranitrogen tetradentate fourth subgroup metal complex comprises the following steps:
general procedure for ligand Synthesis
(1) When R-NH 2 In the case of fatty amines
Weighing the same amount of o-fluorobenzaldehyde, fatty amine and potassium carbonate into a round-bottomed flask, adding a proper amount of water, reacting for 12 hours at 100 ℃, recovering to room temperature, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, and removing the solvent in vacuum to obtain a crude product.
The crude product obtained in the previous step, bridged N, N' -dimethylamine (0.5 equivalent) and sodium triacetyl borohydride (0.5 equivalent) and a proper amount of 1, 2-dichloroethane are weighed under nitrogen atmosphere, reacted for 12 hours at 60 ℃, cooled to room temperature, extracted with dichloromethane and water, the organic phase is collected, dried over anhydrous magnesium sulfate, the solvent is removed in vacuo, and the ligand is obtained by column chromatography separation.
(2) When R-NH 2 In the case of aromatic amines
O-bromobenzaldehyde, 3 equivalent of ethylene glycol and 0.05 equivalent of p-toluenesulfonic acid are weighed into a round bottom flask, a proper amount of toluene is added, a water separator is added, reflux water diversion is carried out for 16 hours, sodium hydroxide solution is used for extraction, water washing is carried out, organic phases are combined, reaction solvent is removed in vacuum, and reduced pressure distillation is carried out to obtain 2- (2-bromophenyl) -1, 3-dioxolane.
2- (2-bromophenyl) -1, 3-dioxolan (1.0 equivalent), the corresponding amine, sodium t-butoxide (1.05 equivalent), bis (2-diphenylphosphine) phenyl ether (1.2%) and palladium acetate (0.7%) were weighed into a round bottom flask under nitrogen atmosphere, a suitable amount of dry toluene was added, refluxed for 10 hours, cooled to room temperature, then added with a suitable amount of water and toluene, separated, the organic phase was collected, 5% of p-toluenesulfonic acid was added, refluxed for 2 hours, cooled and washed with saturated aqueous sodium bicarbonate, the organic phase was collected, the solvent was removed in vacuo, and the pure corresponding intermediate product was obtained by column chromatography separation.
The intermediate obtained in the previous step, bridged N, N' -dimethylamine (0.5 equivalent) and sodium triacetyl borohydride (0.5 equivalent) and a proper amount of 1, 2-dichloroethane are weighed under nitrogen atmosphere, reacted at 60 ℃ for 12h, cooled to room temperature, extracted with dichloromethane and water, the organic phase is collected, dried over anhydrous magnesium sulfate, the solvent is removed in vacuo, and the ligand is obtained by column chromatography separation.
General method for catalyst Synthesis
Dissolving the ligand in 30-100 mL anhydrous tetrahydrofuran, dropwise adding 2.0-2.5 equivalents (preferably 2.0 equivalents) of n-butyllithium at-78 ℃, stirring at room temperature under the protection of nitrogen for 0.5-5 h (preferably 2 h), slowly adding the lithium salt compound generated by the reaction into the corresponding metal halide tetrahydrofuran solution at-78 ℃, stirring at room temperature under the protection of nitrogen for 12-24 h (preferably 16 h), filtering after the reaction is finished, washing the reaction system three times with toluene, and pumping out the toluene. Recrystallizing in a mixed solvent of dichloromethane and normal hexane to obtain the metal halide. The resulting metal halides are readily converted to the corresponding metallocene alkyl, alkoxy and amine compounds by reaction with the appropriate alkali or alkaline earth reagents for alkyl, alkoxy and amine groups, as desired.
The synthesis of the rigid tetranitrogen tetradentate fourth subgroup metal complex is not limited to the aforementioned synthesis method, and one skilled in the art can synthesize the metallocene complex by different methods according to the existing chemical knowledge.
The invention provides a catalyst for olefin polymerization, which comprises a main catalyst and a cocatalyst; the main catalyst comprises the rigid tetranitrogen tetradentate fourth sub-group metal complex according to any one of the technical schemes.
The rigid tetranitrogen tetradentate fourth subgroup metal complex and the preparation method of the present invention have been described above for clarity and are not described in detail herein.
In the catalytic system, the catalyst promoter can be various alkylaluminoxane, trialkylaluminum/organoboron compound composite catalyst promoter, alkylaluminum chloride/organoboron compound composite catalyst promoter or other reagents which can play the same role in activation. Wherein alkyl aluminoxanes include (but are not limited to): methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, alkylaluminum chlorides including, but not limited to: diethylaluminum chloride, ethylaluminum dichloride, sesquiethylaluminum chloride or ethylaluminum dichloride, trialkylaluminum including (but not limited to): trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, organoboron compounds include (but are not limited to): b (C) 6 F 5 ) 3 、 Ph 3 CB(C 6 F 5 ) 4 、Me 3 CB(C 6 F 5 ) 4 、PhMe 2 HNB(C 6 F 5 ) 4 PhR 2 HNB(C 6 F 5 ) 4 (R is alkyl of 2 to 18 carbon atoms). The cocatalyst is preferably Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, triisobutylaluminum/tetra (pentafluorophenyl) borate composite cocatalyst.
According to the invention, the molar ratio of aluminium atoms in the cocatalyst to metal atoms in the main catalyst is 1: (5-10000); preferably 1:60 to 1:8000, more preferably 1:100 to 1:1000;
the molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (1-1.5): 1.
The rigid tetranitrogen tetradentate fourth subgroup metal complex is used for catalyzing olefin polymerization reaction, can adopt a bulk polymerization process, a slurry polymerization process or a solution polymerization process, and can be carried out in a batch reactor or a continuous reaction device. When a slurry polymerization process or a solution polymerization process is employed, toluene, xylene, chlorobenzene, dichlorobenzene, hexane, octane, other high boiling alkanes, petroleum ether, liquid paraffin, etc. may be used as a solvent as required.
In the polymerization reaction, the molar ratio of the catalyst to the aluminum-containing cocatalyst ranges from 1:5 to 1:10000, preferably from 1:60 to 1:8000, more preferably from 1:100 to 1:1000; when an alkyl aluminum/organoboron compound composite cocatalyst is used, the molar ratio of the catalyst to the boron cocatalyst ranges from 1:1 to 1:2, preferably from 1:1 to 1:1.5;
the invention provides a preparation method of polyolefin, which comprises the following steps:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the main catalyst comprises the rigid tetranitrogen tetradentate fourth sub-group metal complex according to any one of the technical schemes.
The invention provides a preparation method of polyolefin, which is characterized by comprising the following steps:
copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst comprising a rigid tetradentate fourth subgroup metal complex according to any one of claims 1-4.
The specific process of the invention for catalyzing olefin polymerization reaction is as follows: adding comonomer, main catalyst and cocatalyst into polymerization kettle under the condition of ethylene existence, stirring to make reaction for 0-600 min at 0-200 deg.C, then adding proper quantity of ethyl alcohol to terminate ethylene oligomerization reaction. And cooling the reaction system to room temperature, filtering, and drying in vacuum to constant weight to obtain the polymer.
The rigid tetranitrogen tetradentate fourth subgroup metal complex of the present invention is used as active component, and may be used in catalyzing ethylene or alpha-olefin homopolymerization and ethylene and alpha-olefin copolymerization. The alpha-olefin is propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene, preferably propylene, 1-butene, 1-hexene, 1-octene or 1-decene, more preferably 1-octene. Under proper conditions, catalyzing ethylene homopolymerization to obtain high molecular weight and high impact strength polyethylene, wherein the impact strength of the polyethylene is close to that of the ultra-high molecular weight polyethylene; the ethylene and octene copolymerization is catalyzed to obtain the ethylene-octyl copolymer with medium molecular weight.
According to the invention, the polymerization temperature is from 0 to 200 ℃, preferably from 50 to 150 ℃; for non-bulk polymerization, the olefin concentration is greater than 0M or the pressure is greater than 0MPa, with the highest concentration or pressure reaching the bulk polymerization concentration or pressure. The polymerization time is greatly different according to the different factors such as the catalyst, the cocatalyst, the monomer type, the monomer concentration, the reaction temperature and the like; for ethylene, 1-octene polymerization, 0 to 180 minutes is required; for the polymerization of long chain alpha-olefins, 0 to 600 minutes are required.
The invention provides a rigid tetranitrogen tetradentate fourth sub-group metal complex, which has a structure shown in a formula (I): wherein n is 2-4; r is C1-C30 alkyl, C6-C30 aryl or C6-C30 substituted aryl; x is halogen, C1-C30 alkyl, silicon base, amino or C6-C30 aryl; m is a fourth subgroup transition metal. The rigid tetranitrogen tetradentate fourth sub-group metal complex has good thermal stability. The catalyst has the characteristics of low usage amount of the catalyst promoter, high catalytic activity, good thermal stability and long catalytic life, and can be used for catalyzing ethylene polymerization to obtain an ultra-high molecular weight polyethylene product and simultaneously catalyzing ethylene and 1-octene to be copolymerized.
The ligand of the invention has simple synthesis process and high yield. The catalyst disclosed by the invention has the advantages of high resistance to cocatalysts and impurities, good stability and long catalytic life. The catalyst provided by the invention has good thermal stability and high catalytic activity.
To further illustrate the present invention, a rigid tetradentate fourth subgroup metal complex and its use are provided in the present invention in detail below with reference to examples.
Example 1
(1) O-fluorobenzaldehyde (50.0 mmol), aliphatic amine (50.0 mmol) and potassium carbonate (50.0 mmol) were weighed into a round bottom flask, water (100 mL) was added, the reaction was carried out at 100℃for 12 hours, the temperature was returned to room temperature, extraction was carried out with ethyl acetate, drying was carried out with anhydrous magnesium sulfate, and the solvent was removed in vacuo to obtain a crude product.
The crude product obtained in the previous step, bridged N, N' -dimethylamine (0.5 equivalent) and sodium triacetyl borohydride (0.5 equivalent) and a proper amount of 1, 2-dichloroethane are weighed under nitrogen atmosphere, reacted for 12 hours at 60 ℃, cooled to room temperature, extracted with dichloromethane and water, the organic phase is collected, dried over anhydrous magnesium sulfate, the solvent is removed in vacuo, and the ligand is obtained by column chromatography separation.
Dissolving ligand (1.0 mmol) in 20mL anhydrous tetrahydrofuran, dropwise adding n-butyllithium (2.0 mmol) at-78 ℃, stirring at room temperature under nitrogen protection for 2h, slowly adding lithium salt compound generated by the reaction into the corresponding metal halide tetrahydrofuran solution at-78 ℃, stirring at room temperature under nitrogen protection for 16h, filtering after the reaction is finished, washing the reaction system with toluene for three times, and pumping out toluene. Recrystallizing in a mixed solvent of dichloromethane and normal hexane to obtain the metal halide.
(3) O-bromobenzaldehyde (50.0 mmol), ethylene glycol (150.0 mmol) and p-methylbenzenesulfonic acid (2.5 mmol) are weighed into a round bottom flask, toluene (100 mL) is added, a water separator is added, water is added under reflux for 16h, sodium hydroxide solution is used for extraction, water washing is carried out, organic phases are combined, the reaction solvent is removed in vacuum, and reduced pressure distillation is carried out to obtain 2- (2-bromophenyl) -1, 3-dioxolane.
2- (2-bromophenyl) -1, 3-dioxolan (25.0 mmol), the corresponding aromatic amine or substituted aromatic amine, sodium t-butoxide (26.3 mmol), bis (2-diphenylphosphine) phenyl ether (0.3 mmol) and palladium acetate (0.2 mmol) were weighed into a round bottom flask under nitrogen atmosphere, dried toluene was added, refluxed for 10h, cooled to room temperature, then an appropriate amount of water and toluene were added, separated, the organic phase was collected, p-toluenesulfonic acid (1.25 mmol) was added, reflux was continued for 2h, after cooling, washing with saturated aqueous sodium bicarbonate solution, the organic phase was collected, the solvent was removed in vacuo, and the pure corresponding intermediate was obtained by column chromatography separation.
The intermediate obtained in the previous step, bridged N, N' -dimethylamine (0.5 equivalent) and sodium triacetyl borohydride (0.5 equivalent) and a proper amount of 1, 2-dichloroethane are weighed under nitrogen atmosphere, reacted at 60 ℃ for 12h, cooled to room temperature, extracted with dichloromethane and water, the organic phase is collected, dried over anhydrous magnesium sulfate, the solvent is removed in vacuo, and the ligand is obtained by column chromatography separation.
Dissolving ligand (1.0 mmol) in 20mL anhydrous tetrahydrofuran, dropwise adding n-butyllithium (2.0 mmol) at-78 ℃, stirring at room temperature under nitrogen protection for 2h, slowly adding lithium salt compound generated by the reaction into the corresponding metal halide tetrahydrofuran solution at-78 ℃, stirring at room temperature under nitrogen protection for 16h, filtering after the reaction is finished, washing the reaction system with toluene for three times, and pumping out toluene. Recrystallizing in a mixed solvent of dichloromethane and normal hexane to obtain the metal halide.
Example 2
On the basis of example 1, complexes N1 to N12 were further prepared:
experimental data are as follows:
n1, yield: 0.3567g, yield: 71.4%, elemental analysis: actual measurement (calculation): c57.70 (57.73); h7.26 (7.27); n is 11.20 (11.22);
n2, yield: 0.3652g, yield: 67.3%, elemental analysis: actual measurement (calculation): 53.11 (53.12); h6.66 (6.69); n is 10.29 (10.32);
n3, yield: 0.33847g, yield: 67.4%, elemental analysis: actual measurement (calculation): 54.69 (54.71); h7.05 (7.06); n9.80 (9.82);
n4, yield: 0.3398g, yield: 55.6%, elemental analysis: actual measurement (calculation): c58.97 (59.00); h5.25 (5.28); n9.14 (9.17);
n5, yield: 0.4151g, yield: 65.0%, elemental analysis: actual measurement (calculation): 60.15 (60.17); h5.66 (5.68); n:8.74 (8.77);
n6, yield: 0.3625g, yield: 65.1%, elemental analysis: actual measurement (calculation): c53.93 (53.94); h6.86 (6.88); n is 10.03 (10.06);
n7, yield: 0.3257g, yield: 58.5%, elemental analysis: actual measurement (calculation): 53.92 (53.94); h:6.87 (6.88); n is 10.04 (10.06);
n8, yield: 0.4429g, yield: 61.2%, elemental analysis: actual measurement (calculation): c51.40 (51.42); h6.38 (6.40); n7.73 (7.74);
n9, yield: 0.4057g, yield: 58.3%, elemental analysis: actual measurement (calculation): c50.02 (50.04); h:6.05 (6.08); n is 8.03 (8.05);
n10, yield: 0.3598g, yield: 70.9%, elemental analysis: actual measurement (calculation): 54.68 (54.71); h7.04 (7.06); n9.79 (9.82);
n11, yield: 0.3624g, yield: 55.7%, elemental analysis: actual measurement (calculation): 59.03 (59.05); h7.41 (7.43); n is 8.58 (8.61);
n12, yield: 0.3681g, yield: 59.1%, elemental analysis: actual measurement (calculation): 57.83 (57.85); h7.11 (7.12); n8.98 (9.00);
example 3
Ethylene polymerization
The polymerization was carried out in 500mL stainless steel autoclave, the autoclave equipped with mechanical stirrer was heated to 150 ℃, evacuated for 1h, adjusted to polymerization temperature, charged with ethylene gas of 0.1MPa, added with 400mL of mixed isoparaffin (Isopar E) solution purified with Methylaluminoxane (MAO) or Modified Methylaluminoxane (MMAO), kept at constant temperature for a period of time, charged with ethylene gas of 3.5MPa, then added with main catalyst, and stirred for a period of time. And (3) discharging residual ethylene gas after the polymerization reaction is finished, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirring for 5min, filtering, and drying. Its mass was weighed and its melting point and molecular weight were measured. The data obtained are shown in Table 1.
TABLE 1 ethylene homo-polymerization data a
| Entry | Cat. | Al/M | Temperature/. Degree.C | Yield/g | b Mw×10 -4 | c Tm/℃ |
| 1 | N2 | 80 | 140 | 7.38 | 125.5 | 135.6 |
| 2 | N2 | 100 | 140 | 9.18 | 105.8 | 137.1 |
| 3 | N2 | 140 | 140 | 10.22 | 88.7 | 136.4 |
| 4 | N2 | 120 | 100 | 8.89 | 157.8 | 135.9 |
| 5 | N2 | 120 | 120 | 10.35 | 125.6 | 136.4 |
| 6 | N2 | 120 | 140 | 14.64 | 95.4 | 135.9 |
| 7 | N2 | 120 | 160 | 11.52 | 75.4 | 136.8 |
| 8 | N1 | 120 | 140 | 9.87 | 105.3 | 136.6 |
| 9 | N3 | 120 | 140 | 8.86 | 45.8 | 135.8 |
| 10 | N4 | 120 | 140 | 10.53 | 88.6 | 136.7 |
| 11 | N5 | 120 | 140 | 8.94 | 75.4 | 135.9 |
| 12 | N6 | 120 | 140 | 6.99 | 65.8 | 136.2 |
| 13 | N7 | 120 | 140 | 5.58 | 83.4 | 135.8 |
| 14 | N9 | 120 | 140 | 8.92 | 98.4 | 136.1 |
| 15 | N9 | 120 | 140 | 7.62 | 66.8 | 136.5 |
| 16 | N10 | 120 | 140 | 6.57 | 55.9 | 135.9 |
| 17 | N11 | 120 | 140 | 5.34 | 88.6 | 135.4 |
| 18 | N12 | 120 | 140 | 4.58 | 35.8 | 135.7 |
| 19 e | N2 | 120 | 140 | 10.44 | 115.9 | 136.8 |
| 20 f | N2 | 120 | 140 | 24.37 | 120.3 | 136.5 |
a Polymerization conditions: the dosage of the main catalyst is 2 mu mol, the cocatalyst is MMAO, the polymerization pressure is 3.5MPa, and the polymerization time is 10min; b molecular weight is measured by high temperature GPC, units: g/mol; c melting point as measured by DSC; e the cocatalyst is MAO; f the polymerization time was 1h.
Example 4
Ethylene/1-octene copolymerization
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with a mechanical stirrer is heated to 150 ℃, vacuum pumping is carried out for 1h, the polymerization temperature is regulated to be the polymerization temperature, ethylene gas with the pressure of 0.1MPa is filled, mixed isoparaffin (Isopar E) solution (total volume of 400 mL) containing a certain amount of Modified Methylaluminoxane (MMAO) and a certain amount of 1-octene is added, the temperature is kept for a period of time until the temperature is constant, ethylene gas with the pressure of 3.5MPa is filled, then a main catalyst is added, and the mixture is stirred for a period of time. And (3) discharging residual ethylene gas after the polymerization reaction is finished, cooling to 40 ℃, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol in a volume ratio of 1:1, stirring for 5min, filtering, and drying in a vacuum oven to constant weight. The mass of the polymer is weighed, the molecular weight and the molecular weight distribution of the polymer are measured, and the comonomer insertion rate is obtained through a high-temperature carbon spectrum.
TABLE 2 ethylene/1-octene copolymerization data a
a Polymerization conditions: the dosage of the main catalyst is 2 mu mol, the cocatalyst is MMAO, the polymerization temperature is 140 ℃, the polymerization pressure is 3.5MPa, and the polymerization time is 10min; b molecular weight and molecular weight distribution were measured by high temperature GPC; c the insertion rate is determined by 13 CNMR measurement.
From the results, the rigid tetranitrogen tetradentate fourth-subgroup metal complex provided by the embodiment of the invention has the characteristics of low cocatalyst usage amount, high catalytic activity, good thermal stability and long catalytic life when in use, can obtain an ultra-high molecular weight polyethylene product when catalyzing ethylene polymerization, can catalyze ethylene and 1-octene to be copolymerized to obtain a polyolefin elastomer, and has wide application fields.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A rigid tetranitrogen tetradentate fourth subgroup metal complex having a structure represented by formula (I):
the complex with the structure shown in the formula (I) specifically has the structure shown in the following N1-N12:
n1: r=n-propyl, n=2, m=ti, x=chloro;
n2: r=isopropyl, n=2, m=zr, x=chlorine;
and N3: r=tert-butyl, n=2, m=zr, x=chloro;
n4: r=phenyl, n=2, m=zr, x=chloro;
n5: r=p-methylphenyl, n=2, m=zr, x=chlorine;
n6: r=n-propyl, n=3, m=zr, x=chlorine;
n7: r=isopropyl, n=3, m=zr, x=chlorine;
n8: r=cyclohexyl, n=3, m=hf, x=chloro;
n9: r=cyclopentyl, n=3, m=hf, x=chloro;
n10: r=isopropyl, n=4, m=zr, x=chlorine;
n11: r=cyclohexyl, n=4, m=zr, x=chlorine;
n12: r=cyclopentyl, n=4, m=zr, x=chlorine.
2. A catalyst for olefin polymerization, which is characterized by comprising a main catalyst and a cocatalyst; the procatalyst is a rigid tetranitrogen tetradentate fourth subgroup metal complex according to claim 1.
3. The catalyst for olefin polymerization according to claim 2, wherein the cocatalyst comprises one or more of alkylaluminoxane, modified alkylaluminoxane, trialkylaluminum, and organoboron compound.
4. The catalyst for olefin polymerization according to claim 3, wherein the molar ratio of aluminum atoms in the cocatalyst to metal atoms in the main catalyst is 1: (5-10000);
the molar ratio of boron atoms in the cocatalyst to metal atoms in the main catalyst is (1-1.5): 1.
5. a process for the preparation of a polyolefin comprising:
homopolymerizing ethylene in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst is a rigid tetranitrogen tetradentate fourth subgroup metal complex according to claim 1.
6. A process for the preparation of a polyolefin, comprising:
copolymerizing ethylene and alpha-olefin in the presence of a catalyst to obtain polyolefin;
the catalyst comprises a main catalyst and a cocatalyst; the procatalyst is a rigid tetranitrogen tetradentate fourth subgroup metal complex according to claim 1.
7. The process according to claim 5 or 6, wherein the temperature of the homo-or copolymerization reaction is 0 to 200℃and the ethylene pressure during polymerization is 0.1 to 10MPa.
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