CN114316101A - Metallocene catalyst, preparation method and application thereof in catalyzing olefin polymerization - Google Patents
Metallocene catalyst, preparation method and application thereof in catalyzing olefin polymerization Download PDFInfo
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Abstract
The invention provides a metallocene catalyst, a preparation method and application thereof in catalyzing olefin polymerization, wherein the structure of the metallocene catalyst is shown as formula 1:
Description
Technical Field
The invention belongs to the technical field of olefin polymerization, and relates to a metallocene catalyst, a preparation method and application thereof in catalyzing olefin polymerization.
Background
The polyolefin material has excellent performances such as good compatibility, good processability, weather resistance and the like, and is widely applied to the fields of national defense science and technology, agriculture, automobiles and the like. Conventional polyolefin materials have failed to satisfy people's daily needs, and therefore, development of polyolefin materials of novel structures is urgently needed. Polyolefin catalysts are the core of their development for the preparation of polyolefin materials.
For example, EP416815A2 discloses a catalyst having the following formula, which is used for producing ethylene propylene diene monomer, but the catalyst cannot regulate the polymer structure, only can produce random copolymer polymer, and the polymer molecular weight is low.
For example, Organometallics (2002,21,934-945) discloses a catalyst having the following formula for catalyzing olefin polymerization, which has the disadvantages of low polymer molecular weight and low isotacticity.
For example, CN1408731A reports that schiff base catalyst with the following formula has low activity, low molecular weight of prepared polymer, wide molecular weight distribution, and also fails to meet the requirement of industrialization.
In addition, the catalyst of the above type needs to add a large amount of aluminoxane or modified aluminoxane in order to improve the activity of the catalyst during catalytic polymerization, resulting in an increase in production cost; and a large amount of aluminoxane or modified aluminoxane used can have a large amount of metal residues in the polymer, so that the mechanical properties of the material are reduced, and the application range of the material is limited.
Therefore, in the research of catalysts, how to obtain polyolefins with high molecular weight, narrow molecular weight distribution, high isotacticity and low metal residue is the core of the research of catalysts and is also a key factor for realizing industrialization.
Disclosure of Invention
In order to solve the above technical problems, it is an object of the present invention to provide a metallocene catalyst useful for catalyzing olefin polymerization and a preparation method thereof. In the catalyst, cyclopentadiene and saturated nitrogen are connected through carbon atoms, so that the complex structure is more stable, the microscopic regulation and control of the polymer structure can be realized by changing the position of a substituent group of a ligand skeleton structure, the size of steric hindrance and the strength of power supply capacity, and the olefin polymer with ultrahigh molecular weight, narrow molecular weight distribution, high temperature resistance (high glass transition temperature of the polymer), ageing resistance (low content of double bonds at the tail end of the polymer) and high isotacticity is prepared, so that the catalyst has a wide industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a metallocene catalyst, which has a structure shown in a formula 1:
wherein M is selected from IVB metal elements, preferably titanium (Ti), zirconium (Zr) and hafnium (Hf);
r1 is independently selected from hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy, C6-C20 arylamino, preferably selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, C3-C6 cycloalkyl, hydrogen, C6-C12 aryl, C6-C12 alkane substituted aryl, 387C 6-C12 aryloxy, C6-C12 arylamino, more preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, anthryl;
R2、R3are respectively and independently selected from hydrogen, halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy, C6-C20 arylamino, preferably selected from hydrogen, C,Halogen, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino, C3-C8 cycloalkyl, C6-C14 aryl, C6-C14 alkane substituted aryl, C6-C14 aryloxy and C6-C14 arylamino; more preferably hydrogen, halogen, C6-C14 aryl such as phenyl, tolyl, dimethylphenyl, tert-butylphenyl, isopropylphenyl, C1-C8 alkyl such as methyl, isobutyl, ethyl, isopropyl, tert-butyl, hexyl; r2、R3May be the same or different, preferably both are the same;
R4selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy and C6-C20 arylamino, preferably selected from C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino, C3-C10 cycloalkyl, C6-C10 aryl, C6-C14 alkane substituted aryl, C6-C14 aryloxy, C6-C14 arylamino, more preferably C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino and C3-C10 cycloalkyl; more preferably a C1-C8 alkyl group such as methyl, ethyl, propyl, isopropyl, tert-butyl;
x is selected from halogen, C1-C20 alkyl, C6-C20 aryl and C1-C20 alkylamino, preferably halogen, C1-C10 alkyl, C6-C10 aryl and C1-C10 alkylamino, more preferably chlorine, methyl, benzyl and dimethylamino.
Further, the metallocene catalyst of the present invention is preferably a compound having a structure represented by the following formulae M1 to M8:
the invention also provides a preparation method of the metallocene catalyst shown in the formula 1, which comprises the following steps:
1) mixing 2-hydroxybenzylamine or a derivative thereof, imidazole and dimethyl tert-butyl chlorosilane, and reacting in tetrahydrofuran to obtain 2- (tert-butyl dimethyl silicon) hydroxybenzylamine or a derivative thereof, namely an intermediate A (the structure is shown as A);
2) mixing the intermediate A, alkali metal and an organic solvent for pre-reaction, and then adding fulvene for reaction to prepare an intermediate B (the structure is shown as a formula B);
3) mixing the intermediate B, an alkylating reagent, alkali metal and an organic solvent for pre-reaction, and then adding fluorine ammonium salt for reaction to prepare an intermediate L (the structure is shown as a formula L);
4) and mixing the intermediate L, a hydrogen extraction reagent and an organic solvent for pre-reaction to generate a salt, and then adding the pre-reaction solution into a mixed solution of a metal salt and the organic solvent for reaction to prepare the metallocene catalyst shown in the formula 1.
In step 1) of the present invention, the 2-hydroxybenzylamine or a derivative thereof has a structure shown in formula 2, and is preferably one or more of 2-hydroxybenzylamine, 2-aminomethyl-3, 5-dimethylphenol, 2-aminomethyl-3, 5-diisopropylphenol, 2-aminomethyl-3, 5-di-tert-butylphenol, 2-aminomethyl-3, 5-diethylphenol, 2-aminomethyl-3, 5-diphenylphenol, and the like.
In step 1) of the present invention, the molar ratio of the 2-hydroxybenzylamine or the derivative thereof, the imidazole, and the dimethyl tert-butyl chlorosilane is 1: 1-10: 1-10, preferably 1: 1-2: 1 to 1.2.
In the step 1), the amount of tetrahydrofuran is 0.5-10 times, preferably 1-5 times of the total mass of 2-hydroxybenzylamine or a derivative thereof, imidazole and dimethyl tert-butyl chlorosilane.
In the step 1), the reaction is carried out at-30-50 ℃, preferably 0-50 ℃ for 0.2-16 h, preferably 0.5-3 h.
The structure of the intermediate A prepared in the step 1) of the invention is shown as a formula A, and the intermediate A is preferably substituted 2- (tert-butyldimethylsilyl) hydroxybenzylamine such as 2- (tert-butyldimethylsilyl) hydroxy-4, 5-dimethylbenzylamine, 2- (tert-butyldimethylsilyl) hydroxy-4, 5-di-tert-butylbenzylamine and 2- (tert-butyldimethylsilyl) hydroxy-4, 5-diisopropylbenzylamine.
In the step 1), the reaction is carried out in a nitrogen atmosphere; after the reaction is completed, the reaction also includes post-treatment processes such as separation, purification and the like, and the invention is not particularly required for the conventional operation in the field, for example, in some embodiments, the method can be adopted and includes: and (3) removing the solvent under reduced pressure, extracting and separating the liquid by using water and ethyl acetate, and performing column chromatography (the eluent preferably contains petroleum ether and ethyl acetate in a volume ratio of 1-20: 1) to obtain an intermediate A.
In step 2) of the invention, the alkali metal is selected from one or more of sodium hydride, sodium metal, potassium metal and C1-C6 alkyl lithium, preferably from one or more of n-butyl lithium, sodium hydride, methyl lithium and sodium metal;
preferably, the molar ratio of the intermediate A to the alkali metal is 1: 1-5, preferably 1: 1-2.
In the step 2), the fulvene structure is shown as a formula 3, and is preferably 6, 6-diphenyl fulvene, 6-dimethyl fulvene and 6-isopropyl fulvene;
preferably, the molar ratio of the intermediate A to the fulvene is 1: 1-2, and more preferably 1: 1-1.5.
In step 2) of the present invention, the organic solvent is selected from one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, chloroform, 1, 2-dichloroethane, tetrachloroethane, acetone, diethyl ether, and methyl tert-butyl ether, preferably one or more of tetrahydrofuran, diethyl ether, toluene, and methyl tert-butyl ether;
preferably, the dosage of the organic solvent is 0.5-10 times, preferably 1-5 times of the total mass of the intermediate A, the alkali metal and the fulvene.
In the step 2), the pre-reaction is carried out at the temperature of-80-30 ℃, preferably-40-30 ℃, and the pre-reaction time is 0.1-5 hours, preferably 0.5-1 hour;
the reaction temperature is-80-30 ℃, preferably-40-30 ℃, and the reaction time is 3-24 hours, preferably 3-6 hours.
In the step 2), the reaction is carried out in a nitrogen atmosphere; after the reaction is completed, the reaction also includes post-treatment processes such as separation, purification and the like, and the invention is not particularly required for the conventional operation in the field, for example, in some embodiments, the method can be adopted and includes: and (3) removing the solvent under reduced pressure, extracting and separating the liquid by using water and ethyl acetate, and performing column chromatography (the eluent preferably contains petroleum ether and ethyl acetate in a volume ratio of 1-30: 1) to obtain an intermediate B.
In step 3) of the invention, the alkylating reagent has a structure of R4-A, wherein R4As in formula 1, a is halogen, preferably iodine, bromine, chlorine;
preferably, the alkylating agent is one or more of methyl iodide, ethyl bromide, tert-butyl bromide and isopropyl bromide, more preferably one or more of methyl iodide, ethyl iodide and isopropyl bromide;
preferably, the molar ratio of the intermediate B to the alkylating agent is 1: 1-5, and more preferably 1: 1-2.
In step 3) of the invention, the alkali metal is selected from one or more of sodium hydride, calcium hydride, potassium hydride, sodium metal, potassium metal, and C1-C6 alkyllithium reagent, preferably from one or more of sodium hydride, calcium hydride, and sodium metal;
preferably, the molar ratio of the intermediate B to the alkali metal is 1: 0.5-5, preferably 1: 0.8-1.
In step 3), the fluorine ammonium salt is selected from one or more of tetrabutylammonium fluoride (TBAF), tetraethylammonium fluoride, tetrapropylammonium fluoride, tetra-tert-butylammonium fluoride and tetrabenzylammonium fluoride, preferably from one or more of tetrabutylammonium fluoride, tetrapropylammonium fluoride and tetra-tert-butylammonium fluoride;
preferably, the molar ratio of the intermediate B to the fluorine ammonium salt is 1: 1-5, and more preferably 1: 1-2.
In step 3), the organic solvent is selected from one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, chloroform, 1, 2-dichloroethane, tetrachloroethane, acetone, diethyl ether and methyl tert-butyl ether, and is preferably selected from one or more of tetrahydrofuran, toluene, diethyl ether and 2-methyltetrahydrofuran;
preferably, the amount of the organic solvent is 0.5 to 10 times, preferably 1 to 5 times of the total mass of the intermediate B, the alkylating agent, the alkali metal and the fluorine ammonium salt.
In the step 3), the pre-reaction is carried out at the temperature of-80-35 ℃, preferably-40-0 ℃, and the pre-reaction time is 2-24 hours, preferably 5-8 hours;
the reaction temperature is-80-30 ℃, preferably 0-30 ℃, and the reaction time is 1-16 h, preferably 1-6 h.
In the step 3), the reaction is carried out in a nitrogen atmosphere; after the reaction is completed, the reaction also includes post-treatment processes such as separation, purification and the like, and the invention is not particularly required for the conventional operation in the field, for example, in some embodiments, the method can be adopted and includes: and (3) removing the solvent under reduced pressure, extracting and separating the liquid by using water and ethyl acetate, and performing column chromatography (the eluent preferably contains petroleum ether and ethyl acetate in a volume ratio of 1-50: 1) to obtain an intermediate L.
In step 4) of the present invention, the hydrogen abstraction reagent is selected from one or more of metallic sodium, metallic potassium, methyl magnesium bromide, sodium hydride, potassium hydride, lithium hydride, C1-C6 alkyl lithium, lithium diisopropylamide and lithium bistrimethylsilyl amide, preferably one or more of metallic sodium, sodium hydride, potassium hydride and C1-C6 alkyl lithium, more preferably one or more of methyl lithium, n-butyl lithium, metallic sodium, n-hexyl lithium and metallic potassium;
preferably, the molar ratio of the intermediate L to the hydrogen abstraction reagent is 1: 2 to 12, preferably 1:4 to 10.
In step 4) of the present invention, the metal salt is selected from one or more of a halide of ivb metal, an alkyl metal compound, an alkylamino metal compound, an aryl metal compound, and a metal halide with ether coordination, preferably from one or more of a halide of ivb metal, an alkyl metal compound, an alkylamino metal compound, and an aryl metal compound; more preferably one or more of IVB metal chloride, alkyl amino metal compound and benzyl metal compound; the substituent X in the metallocene catalyst shown in the formula 1 is a residue introduced by the metal salt;
preferably, the molar ratio of the intermediate L to the metal salt is 1:1 to 2, preferably 1:1 to 1.5.
In step 4), the organic solvents added twice are respectively and independently selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, cyclopentane, n-pentane, n-hexane, n-heptane, methylcyclohexane, benzene, toluene and xylene, preferably one or more of tetrahydrofuran, diethyl ether, methyl tert-butyl ether, toluene and n-hexane; the organic solvents added in two times can be the same or different;
preferably, the dosage of the organic solvent is 0.5-10 times, preferably 1-5 times of the total mass of the intermediate L, the hydrogen-extracting reagent and the metal salt;
preferably, the mass ratio of the organic solvent added twice is 1:0.8 to 1.1 such as 1: 1.
in the step 4), the pre-reaction is carried out at the temperature of-80-35 ℃, preferably-40-35 ℃, and the pre-reaction time is 1-24 hours, preferably 1-6 hours;
the reaction temperature is-80-35 ℃, preferably-40-35 ℃, and the reaction time is 2-24 hours, preferably 3-6 hours.
In the step 4), the reaction is carried out in a nitrogen atmosphere; after the reaction is completed, the reaction also includes post-treatment processes such as separation, purification and the like, and the invention is not particularly required for the conventional operation in the field, for example, in some embodiments, the method can be adopted and includes: the solvent was removed under reduced pressure, extracted with toluene and concentrated to crystals.
In the steps of the preparation method, the structural formulas of the raw materials of formula 2, formula 3 and intermediate A, B, L are as follows:
in the formula, R1、R2、R3、R4Are the same as in formula 1.
The invention also provides application of the metallocene catalyst shown in the formula 1, which can be used for catalyzing olefin solution polymerization;
preferably, the olefin is selected from one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, tetracyclododecene;
more preferably, the metallocene catalyst is particularly suitable for catalyzing olefin homopolymerization, such as ethylene and propylene homopolymerization.
The present invention provides a process for carrying out an olefin polymerization reaction comprising the steps of:
the metallocene catalyst and the cocatalyst shown in the formula 1 are dissolved in a solvent, then olefin is introduced, and the temperature is raised for polymerization reaction to prepare the polyolefin product.
In the present invention, the cocatalyst is selected from a boron salt, preferably one or more of trispentafluorophenylboron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and methyldi- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate.
The molar ratio of the metal M in the metallocene catalyst to the boron in the cocatalyst is 1-20, preferably 1-2.
The solvent in the invention is selected from one or more of alkane, cyclane and aromatic chloroalkane, preferably one or more of toluene, hexane, heptane, Isopar E, methylcyclohexane and dichloromethane;
preferably, the concentration of the metallocene catalyst in the solvent is from 0.1ppm to 100ppm, preferably from 1ppm to 5 ppm.
In the invention, the feeding amount of the olefin is controlled by reaction pressure, and the polymerization reaction pressure (gauge pressure) is 0.1-5 MPa, preferably 1-5 MPa; preferably, the feed mass flow rate is 1000-.
In the invention, the polymerization reaction temperature is-20-180 ℃, and preferably 40-120 ℃.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention provides a metallocene catalyst, wherein cyclopentadiene and saturated nitrogen are connected through a carbon atom in the structure, so that the complex structure is more stable, and the regulation and control of the molecular weight and the stereoregularity of a polymer are realized by changing the position of a bridging structure substituent, the size of steric hindrance and the strength of power supply capacity.
The catalyst is used for catalyzing olefin polymerization, and can prepare the polyolefin material with ultrahigh molecular weight, narrow molecular weight distribution, high temperature resistance (high polymer glass transition temperature), aging resistance (low content of double bonds at the tail end of the polymer) and high isotacticity.
Detailed Description
The technical solution of the present invention is further illustrated by examples, but the present invention is not limited thereto. Embodiments of the present invention will allow those skilled in the art to more fully understand the present invention.
The experimental procedures used in the following examples are, unless otherwise specified, all those routine in the art.
The materials, reagents and the like used in the following examples are commercially available, and the information on the sources of the main raw materials is as follows, and the other raw materials are common commercially available raw materials unless otherwise specified:
2-hydroxybenzylamine, pyrrolidine, di-tert-butyl dicarbonate, imidazole, methyl iodide, 4-methoxyaniline, ultra-dry dichloromethane, ultra-dry tetrahydrofuran: AR, Innochem;
2-hydroxy-3, 5-dimethylbenzylamine, 2-hydroxy-3, 5-di-tert-butylbenzylamine, 2-hydroxy-3, 5-diisobutylphenol, benzophenone, dimethyl tert-butylchlorosilane, tetrabutylsodium fluoride, toluene, extra dry n-hexane, ethyl acetate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, trifluorophenylboron, Isopar E, titanium tetrachloride, zirconium tetrachloride, tetradimethylaminotitanium, tetradimethylaminozirconium, hafnium tetrachloride, hafnium tetrabenzyl: AR, Aladdin;
n-butyllithium n-hexane solution (2.5M), methyllithium (1.6M), methylmagnesium bromide (2.2M): AR, Aladdin;
diethyl ether: AR, komemu;
petroleum ether: 60-90 ℃, Chinese medicine;
deuterated chloroform: AR, Acros;
industrial ethanol: 95%, Beijing chemical company;
silica gel: AR, 200-300 mesh, Shanghai Penta chemical company.
The embodiment of the invention adopts the following main test methods:
the compounds in the following examples were characterized by means of nuclear magnetic resonance apparatus (Brucker ARX-400).
The molecular weight distribution of the polymer was determined by PL-GPC220 at 150 ℃ using three PLgel 10 μm MIXED-B columns in series with 1,2, 4-trichlorobenzene as solvent.
The melting point and the glass transition temperature of the polymer are measured according to a conventional DSC (2000) method, and the polymerization activity of the complex is calculated according to the following formula: polymerization activity ═ polymer mass/(metal content of catalyst × -polymerization time); the polymer terminal double bonds were calculated by iodometry.
High temperature13C NMR was measured using Brucker DMX100MHz with 1,1,2,2, -tetrachloroethane as solvent at 120 ℃.
The technical solution of the present invention is described below by way of specific examples.
Example 1
Preparation of catalyst M1:
1) under nitrogen atmosphere, 2-aminomethyl-3, 5-di-tert-butylphenol (23.5g,100mmol) and imidazole (6.8g,100mmol) were mixed in 45.4g tetrahydrofuran, dimethyl-tert-butylchlorosilane (15.1g,100mmol) was added, reaction was carried out at 0 ℃ for 0.5h, tetrahydrofuran was removed under reduced pressure, 100mL each of aqueous and ethyl acetate was added for extraction and separation, ethyl acetate was removed under reduced pressure, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 1: 1) gave intermediate A1, 34.3g, with a yield of 98%.
1H NMR(400MHz,CDCl3):δ8.61(s,2H,NH2),6.94((dd,1H,J＝6.3,11.2Hz),6.81(m,1H),4.32(s,2H,CH2),1.35(s,9H,tBu),1.32(s,9H,tBu),0.96(s,9H,tBuSi),0.19(s,6H,SiMe2).
2) Under nitrogen atmosphere, intermediate A1(34.9g,100mmol) was dissolved in 88.5g of solvent ether, then n-butyllithium (30.6g,100mmol) was added, reaction was carried out at-40 ℃ for 30min, then 6, 6-diphenylfulvene (23g,100mmol) was added, reaction was carried out at-40 ℃ for 3h, extraction separation was carried out with water and ethyl acetate, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 1: 1) was carried out to give 41.1g of intermediate B1, yield 81.1%.
1H NMR(400MHz,CDCl3):1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.88(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,1H,Cp),5.01(s,1H,NH),3.73(s,2H,CH2),2.89-2.86(m,2H),1.35(s,9H,tBu),1.32(s,9H,tBu),0.97(s,9H,tBuSi),0.26(s,6H,SiMe2).
3) Under nitrogen atmosphere, intermediate B1(24.8g,50mmol) and sodium hydride (0.96g,40mmol) were dissolved in 45.8g of anhydrous tetrahydrofuran under stirring for 30min, and methyl iodide (7.1g,50mmol) were added to react at-40 ℃ for 5h, tetrabutylammonium fluoride (13g,50mmol) was added to react at 0 ℃ for 2h, tetrahydrofuran was removed under reduced pressure, water and ethyl acetate were added to conduct extraction and liquid separation, column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 1: 1) was performed to obtain 24.9g of intermediate L1, yield 89%.
1H NMR(400MHz,CDCl3):1H NMR(400MHz,CDCl3):δ9.67(s,1H,OH),7.39-7.36(m,8H),6.98(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,1H,Cp),3.63(s,2H,CH2),2.89-2.86(m,2H),2.26(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu).
4) Intermediate L1(9.59g,20mmol) was dissolved in 49g of anhydrous tetrahydrofuran under a nitrogen atmosphere, methyllithium (35g,80mmol) was added, reaction was carried out at-40 ℃ for 2 hours, then the reaction solution was added to a mixed solution of titanium tetrachloride (3.79g,20mmol) and 39.2g of anhydrous n-hexane, reaction was carried out at-40 ℃ for 2 hours, the solvent was removed under reduced pressure, extraction was carried out with toluene, concentration and recrystallization were carried out to obtain 7.99g of catalyst M1, yield 67%.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.98(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),6.21(s,1H,Cp),3.63(s,2H,CH2),2.26(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu)，0.91(s,6H).
Example 2
Preparation of catalyst M2:
1) under nitrogen atmosphere, 2-aminomethyl-3, 5-di-tert-butylphenol (23.5g,100mmol) and imidazole (10.2g,150mmol) were mixed in 150.9g tetrahydrofuran, dimethyl-tert-butylchlorosilane (16.6g,110mmol) was added, reaction was carried out at 20 ℃ for 1.5h, tetrahydrofuran was removed under reduced pressure, 100mL each of aqueous and ethyl acetate was added for extraction and separation, ethyl acetate was removed under reduced pressure, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 10: 1) gave intermediate A1, 34.3g, with a yield of 98%.
2) Under nitrogen atmosphere, intermediate A1(34.9g,100mmol) was dissolved in 332.1g of methyl tert-butyl ether solvent, then n-butyllithium (45.9g,150mmol) was added, reaction was carried out at-0 ℃ for 45min, then 6, 6-diphenylfulvene (29.9g,130mmol) was added, reaction was carried out at-0 ℃ for 4.5h, water and ethyl acetate were added for extractive liquid separation, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 11: 1) was carried out to give 41.1g of intermediate B1, with a yield of 81.1%.
3) Under nitrogen atmosphere, intermediate B1(24.8g,50mmol) and sodium hydride (1.08g,45mmol) were stirred for 30min and dissolved in 168g of anhydrous tetrahydrofuran, methyl iodide (10.65g,65mmol) was added, reaction was carried out at-20 ℃ for 6h, tetrabutylammonium fluoride (19.5g,65mmol) was added, reaction was carried out at 15 ℃ for 3h, tetrahydrofuran was removed under reduced pressure, extraction separation was carried out with water and ethyl acetate, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 11: 1) was carried out to give 24.9g of intermediate L1, yield 89%.
4) Intermediate L1(9.59g,20mmol) was dissolved in 255g of anhydrous tetrahydrofuran under a nitrogen atmosphere, methyllithium (70g,160mmol) was added, reaction was carried out at 0 ℃ for 3 hours, and then the reaction solution was added to a mixed solution of zirconium tetrachloride (5.59g,24mmol) and 255g of anhydrous n-hexane, reaction was carried out at 0 ℃ for 4.5 hours, the solvent was removed under reduced pressure, extraction was carried out with toluene, concentration and recrystallization were carried out, whereby 9.21g of catalyst M2 was obtained in a yield of 72%.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.98(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),6.21(s,1H,Cp),3.63(s,2H,CH2),2.26(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu),0.93(s,6H).
Example 3
Preparation of catalyst M3:
1) under nitrogen atmosphere, 2-aminomethyl-3, 5-di-tert-butylphenol (23.5g,100mmol) and imidazole (13.6g,200mmol) were mixed in 276.1g of tetrahydrofuran, dimethyl-tert-butylchlorosilane (18.12g,120mmol) was added, reaction was carried out at 50 ℃ for 3 hours, tetrahydrofuran was removed under reduced pressure, 100mL each of aqueous and ethyl acetate was added for extraction, ethyl acetate was removed under reduced pressure, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 20: 1) gave intermediate A1, 34.3g, and yield 98%.
2) Under nitrogen atmosphere, intermediate A1(34.9g,100mmol) was dissolved in 653g of solvent diethyl ether, n-butyllithium (61.2g,200mmol) was added and reacted at 30 ℃ for 60min, then fulvene 6, 6-diphenyl fulvene (34.5g,150mmol) was added and reacted at 30 ℃ for 6h, water and ethyl acetate were added for extractive liquid separation, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 20: 1) was performed to give 41.1g of intermediate B1 with a yield of 81.1%.
3) Under nitrogen atmosphere, intermediate B1(24.8g,50mmol) and sodium hydride (1.2g,50mmol) were dissolved in 331g of anhydrous tetrahydrofuran under stirring for 30min, methyl iodide (14.2g,100mmol) was added and reacted at 0 ℃ for 8h, tetrabutylammonium fluoride (26g,100mmol) was added and reacted at 30 ℃ for 6h, tetrahydrofuran was removed under reduced pressure, water and ethyl acetate were added for extractive liquid separation, column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 20: 1) was performed to give 24.9g of intermediate L1, 89% yield.
4) Intermediate L1(9.59g,20mmol) was dissolved in 533g of anhydrous tetrahydrofuran under a nitrogen atmosphere, methyllithium (87.5g,200mmol) was added, reaction was carried out at 35 ℃ for 5 hours, and then the reaction solution was added to a mixed solution of hafnium tetrachloride (9.6g,30mmol) and 586.3g of anhydrous n-hexane, reaction was carried out at 35 ℃ for 6 hours, the solvent was removed under reduced pressure, extraction was carried out with toluene, concentration and recrystallization were carried out, whereby 10.9g of catalyst M3 was obtained at a yield of 75%.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.98(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),6.21(s,1H,Cp),3.63(s,2H,CH2),2.26(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu),0.89(s,6H).
Example 4
Preparation of Compound M4
1) Under nitrogen atmosphere, 2-aminomethyl-3, 5-diisopropylphenol (20.7g,100mmol) and imidazole (6.8g,100mmol) were mixed in 42.6g tetrahydrofuran, dimethyl tert-butylchlorosilane (15.1g,100mmol) was added, reaction was carried out at 0 ℃ for 0.5h, tetrahydrofuran was removed under reduced pressure, 100mL each of aqueous and ethyl acetate was added for extraction and separation, ethyl acetate was removed under reduced pressure, and column chromatography (eluent was 20:1 by volume of petroleum ether and ethyl acetate) gave intermediate A2, 31.2g, 97% yield.
1H NMR(400MHz,CDCl3):δ8.59(s,2H,NH2),6.96(d,1H,J＝6.3Hz),6.81(d,1H,J＝8.3Hz),4.33(s,2H,CH2),2.89-2.86(m,2H,CH(CH3)2),1.19(t,12H,J＝7.4,11.3Hz,CH(CH3)2),0.98(s,9H,tBuSi),0.21(s,6H,SiMe2).
2) Under nitrogen atmosphere, intermediate A2(32.2g,100mmol) was dissolved in 85.8g of solvent diethyl ether, then n-butyllithium (30.6g,100mmol) was added, reaction was carried out at-40 ℃ for 30min, then 6, 6-diphenylfulvene (23g,100mmol) was added, reaction was carried out at-40 ℃ for 3h, extraction separation was carried out with water and ethyl acetate, and column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 20: 1) was carried out to give 48g of intermediate B2, yield 87%.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.96(d,1H,J＝6.3Hz),6.73(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,1H,Cp),5.01(s,1H,NH),3.73(s,2H,CH2),2.89-2.86(m,2H),1.19(m,12H),0.95(s,9H,tBuSi),0.26(s,6H,SiMe2).
3) Under nitrogen atmosphere, intermediate B2(27.6g,50mmol) and sodium hydride (0.96g,40mmol) were dissolved in 48.7g of anhydrous tetrahydrofuran under stirring for 30min, followed by addition of methyl iodide (7.1g,50mmol) followed by reaction at-40 ℃ for 5h, addition of tetrabutylammonium fluoride (13g,50mmol), reaction at 0 ℃ for 2h, removal of tetrahydrofuran under reduced pressure, addition of water and ethyl acetate for extractive separation, and column chromatography (eluent: 20:1 by volume of petroleum ether and ethyl acetate) to give 17.8g of intermediate L2 in 79% yield.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.96(d,1H,J＝6.3Hz),6.73(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,1H,Cp),3.66(s,2H,CH2),2.89-2.86(m,2H),2.34(s,3H,Me),1.19(m,12H),0.95(s,9H,tBuSi),0.26(s,6H,SiMe2).
4) Intermediate L2(9.03g,20mmol) was dissolved in 49g of anhydrous tetrahydrofuran under a nitrogen atmosphere, methyllithium (35g,80mmol) was added, reaction was carried out at-40 ℃ for 2 hours, then the reaction solution was added to a mixed solution of titanium tetrachloride (3.79g,20mmol) and 53.9g of anhydrous n-hexane, reaction was carried out at-40 ℃ for 2 hours, the solvent was removed under reduced pressure, extraction was carried out with toluene, concentration and recrystallization were carried out to obtain 9.30g of catalyst M4, yield 76%.
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.96(d,1H,J＝6.3Hz),6.73(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,2H,Cp),3.66(s,2H,CH2),2.89-2.86(m,2H),2.31(s,3H,Me),1.23-1.18(m,12H),0.91(s,6H).
Example 5
Preparation of catalyst M5
The preparation is as in example 1, except that:
in step 1), the starting material, 2-aminomethyl-3, 5-di-tert-butylphenol, was replaced with an equimolar amount of 2-aminomethyl-3, 5-dimethylphenol (15.1g,100mmol) to give 25.5g of intermediate A3 in 96% yield.
1H NMR(400MHz,CDCl3):δ8.61(s,2H,NH2),6.84((dd,1H,J＝6.3,11.2Hz),6.71(m,1H),4.32(s,2H,CH2),2.29(s,3H,CH3),2.26(s,3H,CH3),0.98(s,9H,tBuSi),0.21(s,6H,SiMe2).
Step 2), starting material a1 was replaced with an equimolar amount of A3(26.5g, 100mmol) to give 41.1g of intermediate B3 in 83% yield;
1H NMR(400MHz,CDCl3):δ7.33-7.29(m,8H),6.66(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.31(s,1H,Cp),5.01(s,1H,NH),3.83(s,2H,CH2),2.89(d,2H,J＝8.3Hz,Cp),2.29(s,3H,CH3),2.26(s,3H,CH3),0.91(s,9H,tBuSi),0.23(s,6H,SiMe2).
in step 3), starting material B1 was replaced with an equimolar amount of B3(24.8g, 50mmol) to give 18.6g of intermediate L3 in 94% yield.
1H NMR(400MHz,CDCl3):δ9.65(s,1H,OH),7.33-7.29(m,8H),6.66(d,1H,J＝6.3Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.31(s,1H,Cp),3.83(s,2H,CH2),2.89(d,2H,J＝8.3Hz,Cp),2.29(s,3H,CH3),2.26(s,6H,CH3).
In step 4), catalyst M5, 8.44g, in 76% yield, was prepared by replacing the starting material L1 with an equimolar amount of L3(7.91g, 20mmol) and replacing the titanium tetrachloride with an equimolar amount of zirconium tetrachloride (4.66g, 20 mmol).
1H NMR(400MHz,CDCl3):δ7.39-7.36(m,8H),6.96(d,1H,J＝6.3Hz),6.73(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.21(s,2H,Cp),3.66(s,2H,CH2),2.31(s,3H,Me),2.26(m,6H),0.89(s,6H).
Example 6
Preparation of Compound M6
The preparation is as in example 1, except that:
in step 1), the starting material, 2-aminomethyl-3, 5-di-tert-butylphenol, was replaced with an equimolar amount of 2-hydroxybenzylamine (12.3g, 100mmol) to give 23.3g of intermediate A4 in 98% yield.
1H NMR(400MHz,CDCl3):δ8.61(s,2H,NH2),7.19(m,1H),7.11(dd,1H,J＝7.3,8.2Hz),6.84((dd,1H,J＝6.3,11.2Hz),6.71(m,1H),4.32(s,2H,CH2),0.98(s,9H,tBuSi),0.21(s,6H,SiMe2).
Step 2), starting material a1 was replaced with an equimolar amount of a4(23.7g, 100mmol) to give 39.8g of intermediate B4 in 85% yield;
1H NMR(400MHz,CDCl3):δ7.34-7.31(m,8H),7.19(m,1H),7.11(d,1H,J＝6.3Hz),6.82(d,1H,J＝7.9Hz),6.63(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,1H,Cp),6.31(s,1H,Cp),5.01(s,1H,NH),3.73(s,2H,CH2),2.78(d,2H,J＝8.3Hz,Cp),0.93(s,9H,tBuSi),0.23(s,6H,SiMe2).
in step 3), starting material B1 was replaced with an equimolar amount of B4(23.4g, 50mmol) to give 17.5g of intermediate L4 in 95% yield.
1H NMR(400MHz,CDCl3):δ9.65(s,1H,OH),7.34-7.31(m,8H),7.19(m,1H),7.11(d,1H,J＝6.3Hz),6.82(d,1H,J＝7.9Hz),6.63(d,1H,J＝8.3Hz),6.48(d,1H,J＝6.7Hz,Cp),6.41(m,1H,Cp),6.33(s,1H,Cp),3.63(s,2H,CH2),2.78(d,2H,J＝8.3Hz,Cp),2.26(s,3H,Me).
In step 4), catalyst M6, 8.14g, in 73% yield was prepared by replacing the starting material L1 with an equimolar amount of L4(7.35g, 20mmol) and replacing the titanium tetrachloride with an equimolar amount of zirconium tetrachloride (4.66g, 20 mmol).
1H NMR(400MHz,CDCl3):δ7.34-7.31(m,8H),7.19(m,1H),7.11(d,1H,J＝6.3Hz),6.82(d,1H,J＝7.9Hz),6.63(d,1H,J＝8.3Hz),6.48(d,1H,J＝6.7Hz,Cp),6.41(m,1H,Cp),6.33(s,2H,Cp),3.63(s,2H,CH2),2.26(s,3H,Me),0.91(s,6H).
Example 7
Preparation of Compound M7
The preparation is as in example 1, except that:
in step 1), the starting material, 2-aminomethyl-3, 5-di-tert-butylphenol, was replaced with an equimolar amount of 2-aminomethyl-3, 5-diisopropylphenol (20.7g,100mmol) to give 31.2g of intermediate A2 in 97% yield.
Step 2) the starting material a1 was replaced with an equimolar amount of a2(32.2g,100mmol) and the starting material 6, 6-diphenylfulvene was replaced with an equimolar amount of 6, 6-dimethylfulvene (10.6g, 100mmol) to give 20.5g of intermediate B5 in 93% yield.
1H NMR(400MHz,CDCl3):δ6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.71(s,2H,CH2),2.89-2.86(m,3H,Cp+CH(CH3)2),2.26(s,3H,Me),1.28(s,6H,Me),1.18-1.15(m,12H,CH(CH3)2),0.97(s,9H,tBuSi),0.26(s,6H,SiMe2).
In step 3), starting material B1 was replaced with an equimolar amount of B5(21.4g, 50mmol) to give 15.2g of intermediate L5 in 93% yield.
1H NMR(400MHz,CDCl3):δ9.65(s,1H,OH),6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.71(s,2H,CH2),2.89-2.86(m,3H,Cp+CH(CH3)2),2.26(s,3H,Me),1.28(s,6H,Me),1.18-1.15(m,12H,CH(CH3)2).
In step 4), catalyst M7, 7.51g, in 77% yield was prepared by replacing the starting material L1 with an equimolar amount of L5(6.55g, 20mmol) and replacing the titanium tetrachloride with an equimolar amount of zirconium tetrachloride (4.66g, 20 mmol).
1H NMR(400MHz,CDCl3):δ6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,2H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.71(s,2H,CH2),2.89-2.86(m,2H,CH(CH3)2),2.26(s,3H,Me),1.28(s,6H,Me),1.18-1.15(m,12H,CH(CH3)2),0.92(s,6H).
Example 8
Preparation of Compound M8
The preparation is as in example 1, except that:
in step 2), the starting material 6, 6-diphenylfulvene was replaced with an equimolar amount of 6, 6-dimethylfulvene (10.6g, 100mmol) to give 22.6g of intermediate B6 in 95% yield.
1H NMR(400MHz,CDCl3):δ6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.73(s,2H,CH2),2.89(d,2H,J＝8.7Hz,Cp),2.29(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu),0.97(s,9H,tBuSi),0.26(s,6H,SiMe2).
In step 3), starting material B1 was replaced with an equimolar amount of B6(22.8g, 50mmol) to afford 16.9g of intermediate L6 in 95% yield.
1H NMR(400MHz,CDCl3):δ9.65(s,1H,OH),6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,1H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.63(s,2H,CH2),2.89(d,2H,J＝8.7Hz,Cp),2.29(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu),1.28(s,6H,Me).
In step 4), catalyst M8, 8.04g, in 78% yield was prepared by replacing the starting material L1 with an equimolar amount of L6(6.83g, 20mmol) and replacing the titanium tetrachloride with an equimolar amount of zirconium tetrachloride (4.66g, 20 mmol).
1H NMR(400MHz,CDCl3):δ6.98(d,1H,J＝6.3Hz),6.65(d,1H,J＝8.3Hz),6.49(d,2H,J＝6.7Hz,Cp),6.42(m,2H,Cp),3.63(s,2H,CH2),2.29(s,3H,Me),1.35(s,9H,tBu),1.32(s,9H,tBu),1.28(s,6H,Me),0.88(s,6H).
Example 9
The catalyst M1 is used for catalyzing propylene homopolymerization:
A1L polymerization kettle was dried, 500mL of toluene was added, and catalyst M1 (0.56mg, 1. mu. mol) was added in a molar ratio of B: adding triphenyl carbenium tetrapentafluorophenyl borate according to the proportion of 1: 1; introducing propylene at the temperature of 30 ℃, wherein the mass flow is 1000g/min, and regulating the gauge pressure to 4MPa and keeping the gauge pressure unchanged; stirring vigorously for 30min, cooling to room temperature, and removing pressure;
the reaction solution was neutralized with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, which was washed with ethanol several times and vacuum-dried to constant weight to obtain 26.4g of polypropylene, and the catalyst and polymer properties were measured as shown in Table 1.
Example 10
The catalyst M2 is used for catalyzing propylene homopolymerization:
A1L polymerization kettle was dried, 500mL of toluene was added, and catalyst M2 (0.6mg, 1. mu. mol) was added in a molar ratio of B: adding triphenyl carbenium tetrapentafluorophenyl borate according to the ratio of Zr to Zr being 1.5: 1; introducing propylene at the temperature of 30 ℃, wherein the mass flow is 2000g/min, and regulating the gauge pressure to 4MPa and keeping the gauge pressure unchanged; stirring vigorously for 30min, cooling to room temperature, and removing pressure;
the reaction solution was neutralized with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, which was washed with ethanol several times and vacuum-dried to constant weight to obtain 60.7g of polypropylene, and the catalyst and polymer properties were measured as shown in Table 1.
Example 11
The catalyst M3 is used for catalyzing propylene homopolymerization:
A1L polymerization kettle was dried, 500mL of toluene was added, and catalyst M3 (0.68mg, 1. mu. mol) was added in a molar ratio of B: adding triphenyl carbenium tetrapentafluorophenyl borate into the Hf-2: 1 ratio; introducing propylene at 30 ℃ with the mass flow of 3000g/min, and adjusting the gauge pressure to 4MPa and keeping the gauge pressure unchanged; stirring vigorously for 30min, cooling to room temperature, and removing pressure;
the reaction solution was neutralized with 5% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, which was washed with ethanol several times and vacuum-dried to constant weight to obtain 33.7g of polypropylene, and the catalyst and polymer properties were measured as shown in Table 1.
Example 12
The catalyst M4 is used for catalyzing propylene homopolymerization:
the preparation is as in example 9, except that:
catalyst M1 was replaced by an equimolar amount of catalyst M4(0.58mg, 1. mu. mol) to give 44.3g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Example 13
The catalyst M5 is used for catalyzing propylene homopolymerization:
the preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M5(0.52mg, 1. mu. mol) to give 55.1g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Examples 14,
The catalyst M6 is used for catalyzing propylene homopolymerization:
the preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M6(0.48mg, 1. mu. mol) to give 23.1g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Example 15
The catalyst M7 is used for catalyzing propylene homopolymerization:
the preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M7(0.44mg, 1. mu. mol) to give 32.3g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Example 16
The catalyst M8 is used for catalyzing propylene homopolymerization:
the preparation is as in example 9, except that:
catalyst M1 was replaced by an equimolar amount of catalyst M8(0.48mg, 1. mu. mol) to give 12.4g of polypropylene, and the catalyst and polymer properties were tested and the results are shown in Table 1.
Comparative example 1
Catalyst M9 was prepared using the method of CN1408731A example 1.
The preparation is as in example 9, except that:
catalyst M1 was replaced by an equimolar amount of catalyst M9(2.4mg, 5. mu. mol) to give 0.2g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Comparative example 2
Catalyst M10 was prepared using the method of CN102464751A example 2.
The preparation is as in example 9, except that:
catalyst M1 was replaced by an equimolar amount of catalyst M10(0.64mg, 1. mu. mol) to give 1.2g of polypropylene, and the catalyst and polymer properties were tested and the results are given in Table 1.
Comparative example 3
Catalyst M11 was prepared by the method of EP0941997a2, example 1.
The preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M11(0.42mg, 1. mu. mol) to give 1.4g of polymer, and the catalyst and polymer properties were tested and the results are shown in Table 1.
Comparative example 4
Catalyst M12 was prepared using the method of CN113402641A example 1.
The preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M12(0.4mg, 1. mu. mol) to give 2.7g of polymer, and the catalyst and polymer properties were tested and the results are shown in Table 1.
Comparative example 5
Catalyst M13 was prepared using the method of CN113583158A example 1.
The preparation is as in example 9, except that:
catalyst M1 was replaced with an equimolar amount of catalyst M13(0.48mg, 1. mu. mol) to give 2.1g of polymer, and the catalyst and polymer properties were tested and the results are shown in Table 1.
TABLE 1 catalysts and polymer Performance test results of the examples and comparative examples
In table 1: the activity M respectively represents metal elements Ti, Zr and Hf in the catalyst; polymerization conditions: a: measured by GPC; b: measured by DSC; c: [ mmmm ] of]Representing an isotactic configuration of the polymer, resulting from high temperatures13C NMR is measured; d: measured according to iodometry.
The embodiments of the present invention have been specifically described above, but the present invention is not limited to the above embodiments. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A metallocene catalyst has a structure shown in formula 1:
in the formula, M is selected from IVB metal elements, preferably titanium, zirconium and hafnium;
r1 is independently selected from hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy, C6-C20 arylamino, preferably C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, C3-C6 cycloalkyl, hydrogen, C6-C12 aryl, C6-C12 alkane substituted aryl, C6-C12 aryloxy, C6-C12 arylamino, more preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, anthracenyl;
R2、R3are respectively and independently selected from hydrogen, halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy and C6-C20 arylamino, preferably hydrogen, halogen, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino, C3-C8 cycloalkyl, C6-C14 aryl, C6-C14 alkane substituted aryl, C6-C14 aryloxy and C6-C14 arylamino; more preferably hydrogen, halogen, C6-C14 aryl such as phenyl, tolyl, dimethylphenyl, tert-butylphenyl, isopropylphenyl, C1-C8 alkyl such as methyl, isobutyl, ethyl, isopropyl, tert-butyl, hexyl; r2、R3May be the same or different, preferably both are the same;
R4selected from C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylamino, C3-C20 cycloalkyl, C6-C20 aryl, C6-C20 alkane substituted aryl, C6-C20 aryloxy, C6-C20 arylamino, preferably C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino, C3-C10 cycloalkyl, C6-C10 aryl, C6-C14 alkane substituted aryl, C6-C14 aryloxy, C6-C14 arylamino, more preferably C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylamino and C3-C10 cycloalkyl; more preferably a C1-C8 alkyl group such as methyl, ethyl, propyl, isopropyl, tert-butyl;
x is selected from halogen, C1-C20 alkyl, C6-C20 aryl and C1-C20 alkylamino, preferably halogen, C1-C10 alkyl, C6-C10 aryl and C1-C10 alkylamino, more preferably chlorine, methyl, benzyl and dimethylamino.
2. The metallocene catalyst according to claim 1, characterized by having a structure represented by the following formula M1 to M8:
3. a method for preparing a metallocene catalyst according to claim 1 or 2, comprising the steps of:
1) mixing 2-hydroxybenzylamine or derivatives thereof, imidazole and tert-butyldimethylsilyl chloride, and reacting in tetrahydrofuran to obtain an intermediate A;
2) mixing the intermediate A, alkali metal and an organic solvent for pre-reaction, and then adding fulvene for reaction to prepare an intermediate B;
3) mixing the intermediate B, an alkylating reagent, alkali metal and an organic solvent for pre-reaction, and then adding a fluorine ammonium salt for reaction to prepare an intermediate L;
4) and mixing the intermediate L, a hydrogen extraction reagent and an organic solvent for pre-reaction to generate a salt, and then adding the pre-reaction solution into a mixed solution of a metal salt and the organic solvent for reaction to prepare the metallocene catalyst shown in the formula 1.
4. The method according to claim 3, wherein the 2-hydroxybenzylamine or the derivative thereof in step 1) has a structure represented by formula 2, preferably one or more of 2-hydroxybenzylamine, 2-aminomethyl-3, 5-dimethylphenol, 2-aminomethyl-3, 5-diisopropylphenol, 2-aminomethyl-3, 5-di-tert-butylphenol, 2-aminomethyl-3, 5-diethylphenol, 2-aminomethyl-3, 5-diphenylphenol,
the molar ratio of the 2-hydroxybenzylamine or the derivative thereof to the imidazole to the tert-butyldimethylchlorosilane is 1: 1-10: 1-10, preferably 1: 1-2: 1 to 1.2;
the amount of the tetrahydrofuran is 0.5-10 times, preferably 1-5 times of the total mass of the 2-hydroxybenzylamine or the derivative thereof, the imidazole and the tert-butyldimethylchlorosilane;
in the step 1), the reaction is carried out at-30-50 ℃, preferably 0-50 ℃ for 0.2-16 h, preferably 0.5-3 h.
5. The method according to claim 3 or 4, wherein in step 2), the alkali metal is selected from one or more of sodium hydride, sodium metal, potassium metal, C1-C6 alkyl lithium, preferably from one or more of n-butyl lithium, sodium hydride, methyl lithium, and sodium metal;
preferably, the molar ratio of the intermediate A to the alkali metal is 1: 1-5, preferably 1: 1-2;
the fulvene structure is shown in formula 3, preferably 6, 6-diphenyl fulvene, 6-dimethyl fulvene and 6-isopropyl fulvene;
preferably, the molar ratio of the intermediate A to the fulvene is 1: 1-2, more preferably 1: 1-1.5;
in the step 2), the organic solvent is selected from one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, chloroform, 1, 2-dichloroethane, tetrachloroethane, acetone, diethyl ether and methyl tert-butyl ether, and is preferably one or more of tetrahydrofuran, diethyl ether, toluene and methyl tert-butyl ether;
preferably, the dosage of the organic solvent is 0.5-10 times, preferably 1-5 times of the total mass of the intermediate A, the alkali metal and the fulvene;
in the step 2), pre-reaction is carried out, wherein the pre-reaction temperature is-80-30 ℃, preferably-40-30 ℃, and the pre-reaction time is 0.1-5 h, preferably 0.5-1 h;
the reaction temperature is-80-30 ℃, preferably-40-30 ℃, and the reaction time is 3-24 hours, preferably 3-6 hours.
6. The process according to any one of claims 3 to 5, wherein in step 3), the alkylating agent has the structure R4-A, wherein R4As in formula 1, a is halogen, preferably iodine, bromine, chlorine;
preferably, the alkylating agent is one or more of methyl iodide, ethyl bromide, tert-butyl bromide and isopropyl bromide, more preferably one or more of methyl iodide, ethyl iodide and isopropyl bromide;
preferably, the molar ratio of the intermediate B to the alkylating agent is 1: 1-5, more preferably 1: 1-2;
the alkali metal is selected from one or more of sodium hydride, calcium hydride, potassium hydride, sodium metal, potassium metal, C1-C6 alkyl lithium reagent, preferably one or more of sodium hydride, calcium hydride and sodium metal;
preferably, the molar ratio of the intermediate B to the alkali metal is 1: 0.5-5, preferably 1: 0.8-1;
the fluorine ammonium salt is selected from one or more of tetrabutylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetra-tert-butylammonium fluoride and tetrabenzylammonium fluoride, preferably from one or more of tetrabutylammonium fluoride, tetrapropylammonium fluoride and tetra-tert-butylammonium fluoride;
preferably, the molar ratio of the intermediate B to the fluorine ammonium salt is 1: 1-5, and more preferably 1: 1-2;
in the step 3), the organic solvent is selected from one or more of benzene, toluene, xylene, chlorobenzene, n-hexane, tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, chloroform, 1, 2-dichloroethane, tetrachloroethane, acetone, diethyl ether and methyl tert-butyl ether, and is preferably one or more of tetrahydrofuran, toluene, diethyl ether and 2-methyltetrahydrofuran;
preferably, the amount of the organic solvent is 0.5-10 times, preferably 1-5 times of the total mass of the intermediate B, the alkylating agent, the alkali metal and the fluorine ammonium salt;
in the step 3), pre-reaction is carried out, wherein the pre-reaction temperature is-80-35 ℃, preferably-40-0 ℃, and the pre-reaction time is 2-24 hours, preferably 5-8 hours;
the reaction temperature is-80-30 ℃, preferably 0-30 ℃, and the reaction time is 1-16 h, preferably 1-6 h.
7. The process according to any one of claims 3 to 6, wherein in step 4), the hydrogen abstraction reagent is selected from one or more of sodium metal, potassium metal, methyl magnesium bromide, sodium hydride, potassium hydride, lithium hydride, alkyl lithium C1-C6, lithium diisopropylamide, lithium bistrimethylsilyl amide, preferably one or more of sodium metal, sodium hydride, potassium hydride, alkyl lithium C1-C6, more preferably one or more of methyl lithium, n-butyl lithium, sodium metal, n-hexyl lithium, potassium metal;
preferably, the molar ratio of the intermediate L to the hydrogen abstraction reagent is 1: 2-12, preferably 1: 4-10;
the metal salt is selected from one or more of IV B metal halide, alkyl metal compound, alkyl amino metal compound, aryl metal compound and metal halide with ether coordination, preferably one or more of IV B metal halide, alkyl metal compound, alkyl amino metal compound and aryl metal compound; more preferably one or more of IVB metal chloride, alkyl amino metal compound and benzyl metal compound;
preferably, the molar ratio of the intermediate L to the metal salt is 1: 1-2, preferably 1: 1-1.5;
in the step 4), the organic solvents added twice are respectively and independently selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, cyclopentane, n-pentane, n-hexane, n-heptane, methylcyclohexane, benzene, toluene and xylene, preferably one or more of tetrahydrofuran, diethyl ether, methyl tert-butyl ether, toluene and n-hexane; the organic solvents added in two times can be the same or different;
preferably, the dosage of the organic solvent is 0.5-10 times, preferably 1-5 times of the total mass of the intermediate L, the hydrogen-extracting reagent and the metal salt; (ii) a
Preferably, the mass ratio of the organic solvent added twice is 1:0.8 to 1.1 such as 1:1
In the step 4), pre-reaction is carried out, wherein the pre-reaction temperature is-80-35 ℃, preferably-40-35 ℃, and the pre-reaction time is 1-24 hours, preferably 1-6 hours;
the reaction temperature is-80-35 ℃, preferably-40-35 ℃, and the reaction time is 2-24 hours, preferably 3-6 hours.
8. Use of a metallocene catalyst according to claim 1 or 2 or prepared by a process according to any one of claims 3 to 7 for catalysing the solution polymerisation of olefins;
preferably, the olefin is selected from one or more of ethylene, propylene, styrene, 1-butene, 1-hexene, 1-octene, norbornene, tetracyclododecene;
more preferably, the metallocene catalyst is particularly suitable for catalyzing olefin homopolymerization, such as ethylene and propylene homopolymerization.
9. A process for the polymerization of olefins, comprising the steps of:
the metallocene catalyst of claim 1 or 2 or the metallocene catalyst of formula 1 prepared by the method of any one of claims 3 to 7, and a cocatalyst are dissolved in a solvent, and then an olefin is introduced into the solvent to carry out polymerization reaction at an elevated temperature, thereby obtaining a polyolefin product.
10. A process according to claim 9, wherein the cocatalyst is selected from one or more of a boron salt, preferably tris-pentafluorophenyl boron, triphenylcarbonium tetrakis (pentafluorophenyl) borate, methyl-bis- (octadecyl) ammonium tetrakis (pentafluorophenyl) borate;
the molar ratio of the metal M in the metallocene catalyst to the boron in the cocatalyst is 1-20, preferably 1-2;
the solvent is selected from one or more of alkane, cyclane and aromatic chloroalkane, preferably one or more of toluene, hexane, heptane, Isopar E, methylcyclohexane and dichloromethane;
preferably, the concentration of the metallocene catalyst in the solvent is from 0.1ppm to 100ppm, preferably from 1ppm to 5 ppm;
the feeding amount of the olefin is controlled by reaction pressure, and the polymerization reaction pressure is 0.1-5 MPa, preferably 1-5 MPa; preferably, the feeding mass flow rate is 1000-;
the polymerization reaction temperature is-20 to 180 ℃, and preferably 40 to 120 ℃.
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| CN116284510A (en) * | 2023-01-03 | 2023-06-23 | 万华化学集团股份有限公司 | Metallocene catalyst, preparation method and application thereof |
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| WO2001077189A1 (en) * | 2000-04-08 | 2001-10-18 | Basf Aktiengesellschaft | Method for producing a supported catalyst for the polymerization of olefins |
| CN111269711A (en) * | 2018-12-04 | 2020-06-12 | 香港大学 | Transition metal luminescent complexes and methods of use |
| CN111909196A (en) * | 2020-08-10 | 2020-11-10 | 万华化学集团股份有限公司 | IVB group-containing bimetallic complex catalyst and preparation method and application thereof |
| CN112358498A (en) * | 2020-10-27 | 2021-02-12 | 万华化学集团股份有限公司 | Tetraaryloxy IVB group binuclear metal complex and preparation and application thereof |
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| WO2001077189A1 (en) * | 2000-04-08 | 2001-10-18 | Basf Aktiengesellschaft | Method for producing a supported catalyst for the polymerization of olefins |
| CN111269711A (en) * | 2018-12-04 | 2020-06-12 | 香港大学 | Transition metal luminescent complexes and methods of use |
| CN111909196A (en) * | 2020-08-10 | 2020-11-10 | 万华化学集团股份有限公司 | IVB group-containing bimetallic complex catalyst and preparation method and application thereof |
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| CN116284510A (en) * | 2023-01-03 | 2023-06-23 | 万华化学集团股份有限公司 | Metallocene catalyst, preparation method and application thereof |
| CN116162185A (en) * | 2023-01-04 | 2023-05-26 | 万华化学集团股份有限公司 | Metallocene catalyst, preparation method and application thereof in olefin polymerization |
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