CN112142775B - Phenolphenanthroline IVB group metal complex and preparation and application thereof - Google Patents
Phenolphenanthroline IVB group metal complex and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a phenol phenanthroline IVB group metal complex and preparation and application thereof, wherein the phenol phenanthroline IVB group metal complex is shown as a formula I.
Description
Technical Field
The invention relates to the technical field of olefin polymerization catalysts, and particularly relates to a phenol phenanthroline IVB group metal complex, and preparation and application thereof.
Background
Polyolefin elastomers are a class of thermoplastic elastomers having a narrow relative molecular mass distribution and a uniform distribution of short chain branches, and their use is increasing due to their superior properties.
Research and development and industrialization of olefin polymerization catalysts are key links in the field of polyolefin production, and under the drive of the large demand of the market for novel polyolefin materials, the development of novel olefin polymerization catalysts has become a focus of attention of researchers. Currently, there are Ziegler-Natta Catalysts (DE Pat.889229 (1953), IT Pat.545332 (1956), IT Pat.536899 (1956), chem.Rev.2000,100,1169, etc.), phillips Catalysts (Belg. Pat.530617 (1955), chem.Rev.1996,96,3327) and metallocene Catalysts (W.Kaminsky, metaorganic Catalysts for Synthesis and Polymerization, berlin: springer, 1999) among others, which have been commercialized. Different types of catalysts have the advantages and disadvantages, are combined with different polymerization processes and are respectively used for producing polyolefin products with different brands, but most of the catalysts cannot be used for catalyzing and producing polyolefin elastomers, particularly supported catalysts.
Group IVB metal complex catalysts are of increasing interest to researchers. Because the catalyst is mainly a homogeneous system, the catalyst can realize higher catalytic activity than the traditional catalyst by modifying the ligand, and the microstructure of the polymer is easier to regulate and control. IVB metal complex catalysts include, mainly, metallocene catalysts and derivatives thereof (EP 0420436B1 (1991), U.S. Pat. No. 5,5064802 (1991)), FI catalysts (chem. Lett.1999,10,1065, J.am. Chem. Soc.2001,123,6847), PI catalysts (Organometallics 2001,20,4793, J.am. Chem. Soc.2004,126, 12023), and the like. The catalyst with a limited geometric configuration in the metallocene derivative has excellent catalytic activity and copolymerization performance, but the catalyst has poor temperature resistance, high cost in industrial production, and relatively low molecular weight of the obtained polymer, so the catalyst has low competitiveness. FI catalysts based on phenolic imine ligands also have poor temperature resistance and poor copolymerization performance of most catalysts, and are used for catalyzing the production of hard segments (segments with few comonomer insertions) of OBC by DOW, so that the FI catalysts cannot be directly used for producing POE. Therefore, the development of a catalyst which has good temperature resistance and copolymerization performance and meets the requirements of the solution polymerization process in industry is the premise of POE development.
Disclosure of Invention
Based on the research background, the invention provides a phenol phenanthroline IVB group metal complex and preparation and application thereof, the preparation method has the advantages of cheap and easily-obtained raw materials and simple synthesis, and can catalyze ethylene/alpha-olefin copolymerization under the activation of a cocatalyst of alkyl aluminum, alkoxy aluminum or an organic boride, particularly ethylene and high-grade alpha-olefin copolymerization such as 1-octene.
The specific technical scheme is as follows:
a phenol phenanthroline IVB group metal complex has a structure shown in a formula I:
wherein R is 1 Selected from hydrogen, halogen, C 1-30 Alkyl radical, C 1-30 Alkoxy radical, C 1-30 Dialkylamino radical, C 3-30 Cycloalkyl radical, C 3-30 Cycloalkyl oxy, C 3-30 Bicycloalkylamino, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 An arylamino group;
R 2 –R 4 the same or different, each independently selected from hydrogen, halogen, C 1-30 Alkyl radical, C 1-30 Alkoxy radical, C 1-30 Dialkylamino, C 3-30 Cycloalkyl, C 3-30 Cycloalkyl oxy, C 3-30 Bicycloalkylamino, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 Arylamino, C 3-40 Trihydrocarbylsilyl group of (C) 3-40 (trihydrocarbylsilyl) alkyl of (i);
x is one or two, and when X is two, X is a monovalent substituent having 1 to 20 atoms other than hydrogen; when X is one, X is a divalent substituent having 1 to 40 atoms other than hydrogen.
M is selected from group IVB metals.
Preferably, R 1 Selected from hydrogen, halogen, C 1-20 Alkyl radical, C 1-20 Alkoxy radical, C 1-20 Dialkylamino radical, C 3-20 Cycloalkyl, C 3-20 Cycloalkyl oxy, C 3-20 Bicycloalkylamino, C 6-30 Aryl radical, C 6-30 Aryloxy radical, C 6-30 An arylamino group;
preferably, R 2 –R 4 Are the same or different and are each independently selected from hydrogen, halogen,C 1-20 Alkyl radical, C 1-20 Alkoxy radical, C 1-20 Dialkylamino radical, C 3-20 Cycloalkyl radical, C 3-20 Cycloalkyl oxy, C 3-20 Bicycloalkylamino, C 6-30 Aryl radical, C 6-30 Aryloxy radical, C 6-30 Arylamino, C 3-30 Trihydrocarbylsilyl of (C) 3-30 (trihydrocarbylsilyl) alkyl of (i);
x is halogen or monovalent substituent such as alkyl or substituted alkyl, aryl or substituted aryl, amino or substituted aminosilyl or substituted silyl having 1 to 10 atoms except hydrogen, or X is divalent substituent such as alkylene, arylene or diamido, diene having 1 to 20 atoms except hydrogen;
m is selected from group IVB metals.
Preferably, R 1 Selected from the group consisting of hydrogen, dicyclohexylmethyl, benzhydryl, dibenzocycloheptyl, fluorenyl, carbazolyl, anthracyl, dicyclohexylphenyl, 3,5-di (t-butyl) phenyl, 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, 3,5-di (t-octyl) phenyl, 3,5-di (2,4,6-trimethylphenyl) phenyl, 3,5-di (2,6-dimethylphenyl) phenyl, 3,5-di (2,4,6-triisopropylphenyl) phenyl, 3,5-di (3,5-di-t-butylphenyl) phenyl;
preferably, R 2 –R 4 The same or different, each independently selected from hydrogen, halogen, C 1-10 Alkyl radical, C 1-10 An alkoxy group;
preferably, X is two monovalent substituents selected from the group consisting of halogen, methyl, benzyl, dimethylamino, diethylamino, phenyl, or when X is a divalent substituent, the structure of X is selected from the group consisting of 1,3-butadiene, 1,3 pentadiene directly coordinated to M or two carbon atoms at 1,4 can form a covalent bond with M.
M is selected from titanium, zirconium and hafnium.
The preparation method of the phenol phenanthroline IVB group metal complex comprises the following steps:
in an organic solvent I, reacting a compound shown as a formula II with a hydrogen extraction reagent to generate a salt, and then complexing with an M salt to obtain a complex shown as a formula I;
in the formula II, R 1 、R 2 、R 3 、R 4 Is as defined for formula I;
preferably, the M salt is a group IVB metal salt, which may be one or more of a halide, an alkyl compound or an amino compound;
preferably, the hydrogen-withdrawing agent is sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, lithium diisopropylamide, C 1 -C 6 One or more of alkyl lithium, more preferably sodium hydride, potassium hydride, C 1 -C 6 One or more of alkyl lithium;
preferably, the organic solvent one is one or more of tetrahydrofuran, anhydrous diethyl ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, octane, isooctane, toluene and xylene. More preferably tetrahydrofuran, diethyl ether, n-hexane or toluene.
According to the preparation method of the phenol phenanthroline IVB group metal complex, the molar ratio of the compound shown in the formula II to the hydrogen drawing reagent is 1:2-3.6, preferably 1:2-2.6;
the temperature of the salt forming reaction is-78 to 35 ℃, and is preferably-78 to 0 ℃;
the time of salifying reaction is 1-24 h;
further, the molar ratio of the compound shown in the formula II to the metal M in the M salt is 1:1-1.8, preferably 1:1-1.4;
the temperature of the complexation reaction is 30 to 120 ℃;
the time of the complex reaction is 4 to 30 hours.
The compound shown in the formula II is obtained by reacting the compound shown in the formula III with protonic acid for 0.5 to 4 hours at a temperature of between 0 and 60 ℃ in an organic solvent II;
the structural formula of the compound of the formula III is as follows:
in the formula III, R 1 、R 2 、R 3 、R 4 Is as defined for formula I; r is a hydroxyl protecting group, preferably dihydropyran.
Preferably, the protic acid is one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid. The molar addition amount of the protonic acid is 2-8 times, preferably 2-5 times of that of the compound III;
preferably, the organic solvent II is one or more of ethyl acetate, methanol and ethanol;
the invention also provides a preparation method of the compound of the formula III, which comprises the following steps:
(a) In the organic solvent III, reacting 2,9-dibromo-1,10-phenanthroline with a hydrogen extraction reagent at low temperature to form salt, adding triisopropyl borate, and continuing to react to obtain a compound VI; the reaction temperature is-78 to 35 ℃, and the reaction time is 1 to 6 hours;
the molar ratio of the compound 2,9-dibromo-1,10-phenanthroline to the hydrogen drawing reagent to the triisopropyl borate is 1:2-4:2-3; preferably 1:2-3:2-2.6;
preferably, the organic solvent three is one or more of tetrahydrofuran, anhydrous diethyl ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, toluene and xylene;
preferably, the hydrogen-withdrawing agent is one or more of sodium hydride, potassium hydride, lithium hydride, and C1-C6 alkyl lithium, more preferably n-butyl lithium.
(b) Under the condition of inert atmosphere, mixing the compound VI, the compound V and an aqueous solution of alkali in an organic solvent IV, then freeze-drying and deoxidizing, then adding a palladium catalyst, reacting for 36-72 h at 50-120 ℃, and separating to obtain a compound III; the molar ratio of the compound VI to the compound V to the alkali to the palladium catalyst is 1:2-4:2-4;
preferably, the organic solvent in step (b) is one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, diethyl ether and tetrahydrofuran. The amount of the solvent added is 2-10mL based on 1g of the reactant, preferably 1g of the reactant, and 3-8mL based on the solvent.
The alkali is preferably metal carbonate, and more preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate;
the palladium catalyst is preferably a tetradentate palladium catalyst, more preferably tetrakis (triphenylphosphine) palladium.
In the present invention, the compound V is
In the formula R 1 、R 2 、R 3 、R 4 Is as defined for formula I;
the substituents R are as defined for formula III.
Preferably, the compound V can be prepared by the following method:
(1) Under the catalytic action of pyridinium tosylate, reacting 2-bromophenol or substituted derivatives thereof with dihydropyran in a solvent at 20-60 ℃ for 4-12 h, and separating to obtain a compound IV; the molar ratio of the 2-bromophenol or substituted derivatives thereof to the dihydropyran is 1:1-2; the addition amount of the pyridinium p-toluenesulfonate is 0.05 to 0.5 times of the molar amount of the 2-bromophenol or the substituted derivative thereof by molar amount;
preferably, the solvent is an organic solvent five, preferably one or more of dichloromethane, chloroform, tetrachloroethane and chlorobenzene; the amount of the solvent added is 2-10mL based on 1g of the reactant, preferably 1g of the reactant, and 3-8mL based on the solvent.
Preferably, the substituted derivative of the 2-bromophenol is one or more of 4-methyl-2-bromophenol, 4-tert-butyl-2-bromophenol and 4-methoxy-2-bromophenol;
(2) Reacting the compound IV with alcohol or phenol in a solvent at the temperature of between 20 and 60 ℃ for 6 to 24 hours in an inert environment and in the presence of a tin halide catalyst, and separating to obtain a compound V; the molar ratio of the compound IV, the alcohol or the phenol and the catalyst is 1:1-1.5;
preferably, the solvent is an organic solvent six, preferably one or more of dichloromethane, chloroform, tetrachloroethane and chlorobenzene; the amount of the solvent added is 2-10mL based on 1g of the reactant, preferably 1g of the reactant, and 3-8mL based on the solvent.
Preferably, the alcohol is one or more of benzhydrol, substituted benzhydrol, dibenzosubenol, t-butanol, phenol, anthral, dicyclohexylmethanol, fluorenol, dicyclohexyl phenol, 3,5-di (t-butyl) phenol, 3,5-di (isopropyl) phenol, 3,5-di (isobutyl) phenol, 3,5-di (t-octyl) phenol, 3,5-di (2,4,6-trimethylphenyl) phenol, 3,5-di (2,6-dimethylphenyl) phenol, 3,5-di (2,4,6-triisopropylphenyl) phenol, 3,5-di (3,5-di-t-butylphenyl) phenol;
preferably, the tin halide catalyst is one or more of tin dibromide, tin tetrabromide, tin diiodide, tin tetraiodide, tin dichloride and tin tetrachloride;
further, when R is 1 When the compound V is the same as the compound VI in the case of H, the step (2) may be omitted;
further, when the 2-bromophenol derivative of step (1) is a 6- (hydroxy ortho) substituted derivative, step (2) may be omitted.
Further, the steps (a), (b), (1) and (2) also respectively comprise a product separation process;
preferably, the step (a), (b), (1) and (2) are separated and purified by column chromatography or recrystallization.
The reaction scheme for the compound of formula III is schematically as follows:
in the reaction scheme, R 1 、R 2 、R 3 、R 4 Is as defined for formula I;
the substituents R are as defined for formula III.
The application of the phenol phenanthroline IVB group metal complex is that the phenol phenanthroline IVB group metal complex is used as an olefin polymerization or olefin/alpha-olefin copolymerization catalyst.
Further, the phenolphenanthroline group IVB metal complex is used for ethylene/1-octene copolymerization.
The catalyst is also added with a cocatalyst which is a composition of one or more of aluminoxane, alkylaluminum compound and alkylaluminum chloride, or a composition of one or more of aluminoxane, alkylaluminum compound and alkylaluminum chloride and one or more organic boride.
Further, the aluminoxane includes Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO); the alkyl aluminum compound comprises triethyl aluminum, triisobutyl aluminum, trioctyl aluminum and the like; the alkyl aluminum chloride comprises monochloro ethyl aluminum, sesquiethyl aluminum, dichloroethyl aluminum and the like; the organic boron compound is trityl tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, dioctadecyl tertiary methyl amine tetrakis (pentafluorophenyl) borate, di-hydrogenated tallow methyl tertiary amine tetrakis (pentafluorophenyl) borate, or other like co-catalysts commonly used in the art for olefin polymerization or olefin/α -olefin copolymerization.
The molar ratio Al/M of the metal aluminum in the cocatalyst to the central metal M of the catalyst is 1-10000, preferably 1-4000; the molar ratio B/M of boron in the organic boride to the catalyst central metal M is 0 to 10, preferably 0 to 8; the polymerization temperature is 20-250 ℃, preferably 120-220 ℃; the polymerization pressure is from 0.1 to 10MPa, preferably from 1 to 5MPa.
More preferably, the molar ratio Al/M of the aluminum metal in the cocatalyst to the metal M in the catalyst center is in the range of 3 to 1000; the molar ratio B/M of boron in the organic boride to the catalyst central metal M is 1-4; the polymerization temperature is 150-220 ℃; the polymerization pressure is 3-5MPa.
The addition amount of the phenolic phenanthroline IVB group metal complex is 0.1-3 mu mol/L (total amount of each liter of solvent and octene), and the appropriate adjustment by those skilled in the art according to the reaction type is still within the protection scope of the invention
The invention provides a phenolic phenanthroline IVB group metal complexThe compound has cheap and easily obtained raw materials and simple synthesis. Can catalyze the copolymerization of ethylene/alpha-olefin under the activation of a cocatalyst of aluminum alkyl, aluminum alkoxide or organic boride, particularly the copolymerization of ethylene and higher alpha-olefin, such as 1-octene and the like, and the catalytic activity can reach 10 8 g·mol -1 (M)·h -1 Above, the molecular weight of the polymerization product is 10000-500000g/mol, and the insertion capacity of the comonomer is above 40 wt%. The complex has the characteristics of high temperature resistance, high activity and strong comonomer insertion capability, and has good industrial application prospect.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further described below with specific examples for the convenience of better understanding of the present invention by those skilled in the art, but the present invention will be described in further detail only, and is not limited to the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The concentrations in the following examples are molar concentrations unless otherwise specified.
Materials, reagents, etc. used in the following examples are commercially available, and specific information is as follows:
2-bromo-4-tert-butylphenol: 97% of Aladdin
Dichloromethane: AR, innochem
Dihydropyran: AR, innochem
Pyridinium p-toluenesulfonate: AR, aladdin
Anhydrous sodium sulfate: AR, innochem
Petroleum ether: AR, innochem
Ethyl acetate: AR, aladdin
Benzhydrol: AR, innochem
Tin tetrabromide: AR, aldrich
Sodium bicarbonate: AR, innochem
2,9-dibromo-1,10-phenanthroline: 95% of Aladdin
N-butyl lithium: 1.6M Hexane solution, innochem
Anhydrous sodium carbonate: AR, innochem
Ultra-dry tetrahydrofuran: AR, innochem
Triisopropyl borate: AR, innochem
Ethylene glycol dimethyl ether: AR, innochem
Palladium tetrakistriphenylphosphine: AR, innochem
Anhydrous methanol: AR, innochem
Ethyl acetate: AR, innochem
Concentrated hydrochloric acid: AR, innochem
Ultra-dry toluene: AR, innochem
Ultra-dry n-hexane: AR, innochem
Bis (tetrahydrofuran) titanium tetrachloride: AR, alfa
Zirconium bis (tetrahydrofuran) tetrachloride: AR, alfa
Bis (tetrahydrofuran) hafnium tetrachloride: AR, alfa
2-bromo-4,6-di-tert-butylphenol: 97% of Alfa
Methyl magnesium bromide in ether: 3M, innochem
Sodium hydride, 60%, aladine, petroleum ether are washed for three times and dried for use
Petroleum ether: 60-90 ℃ C, beijing chemical Agents Co
2-bromo-4,5-dimethoxyphenol, 98%, ark
3,5-Di-tert-butylphenol, 98%, aladdin
Tetrakis (dimethylamino) zirconium, 99%, strem
1,1,2,2-tetrachloroethane, 99%, innochem
Potassium carbonate, 99%, innochem
Deuterated chloroform: AR, acros
IsoparE: EXXONMOBIL, which is used after being deaerated by bubbling nitrogen and dewatered by a molecular sieve column.
1-octene: 98 percent of the total weight of the components, namely the alatin, and the nitrogen is used for removing oxygen by a drum, and the components are used after being dehydrated by a molecular sieve column.
1-hexene: 98 percent of the above-mentioned components are made into the invented product, and the above-mentioned material is passed through a molecular sieve column to remove water, and then the above-mentioned material is used.
IsoparE solution of MMAO: 1.98mol/L (Al), langshen
Trityl tetrakis (pentafluorophenyl) borate, 99%, TCI, as B1
N, N-Dimethylanilinium tetrakis (pentafluorophenyl) borate, 99%, TCI, as B2
99% of dioctadecyl methyl tertiary amine tetra (pentafluorophenyl) borate, yangzhou chemical industry
Triisobutylaluminum hexane solution, 1M (Al), innochem
Industrial alcohol: 95% of Beijing chemical reagent Co
The compounds in the following examples were characterized using a nuclear magnetic resonance apparatus (Brucker ARX-400).
The molecular weight, molecular weight distribution and 1-octene insertion rate of the polymers obtained in the following polymerization examples were obtained by GPC-IR measurement of a polymer char at a measurement temperature of 150 ℃ with a product recovery rate of over 95%. The melting peak temperature of the polymer is tested by DSC, and data obtained by the second temperature rise is adopted, and the temperature rise and fall speed is 10 ℃/min.
The synthesis of the complex in the following examples was carried out according to the following reaction equation:
synthetic route of complex
Example 1 preparation of Compound 1-1
45.82g (0.2 mol) 2-bromo-4- (tert-butyl) phenol was dissolved in 500mL of ultra dry methylene chloride under nitrogen, and then 25.236g dihydropyran (0.3mol, 1.5eq.) and 5.03g pyridinium p-toluenesulfonate (0.02mol, 0.1eq.) were added and reacted at 30 ℃ for 6h. Extraction with dichloromethane, washing with saturated brine, and then combining the organic phases and drying over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =300 (v/v)) to give 55.50g of a colorless oil in 88.6% yield.
Compound 1-1 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.58(d,J＝8.0Hz,1H),7.22-7.20(dd,J＝8.0Hz,1H),7.04(dt,J＝8.0Hz,1H),5.42(m,1H),3.88–3.84(m,1H),3.55-3.51(m,1H),2.14-2.10(m,1H),2.05-2.03(m,2H),2.02-2.01(m,1H),1.45–1.40(m,2H),1.22(s,9H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ152.74,144.83,130.36,125.16,114.62,96.23,61.40,34.10,31.30,30.00,25.10,18.20.
example 2 preparation of Compounds 1-2
31.32g (0.1 mol) of compound 1-1 and 18.42g of benzhydrol (0.1mol, 1.0eq.) were dissolved in 200mL of ultra-dry dichloromethane, respectively, under a nitrogen atmosphere, 2.19g of tin tetrabromide (0.005mol, 0.05eq.) was slowly added, and the reaction was stirred at 20 ℃ for 16 hours. The reaction was quenched by the addition of 10mL of saturated aqueous sodium bicarbonate solution, extracted with dichloromethane, washed with saturated brine, the organic phases were combined and dried over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =250 (v/v)) to obtain 44.64g of a white solid in a yield of 93.1%.
Compound 1-2 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.41(d,J＝8.0Hz,1H),7.31-7.27(t,J＝8.0Hz,4H),7.27-7.23(t,J＝8.0Hz,2H),7.23(t,J＝8.0Hz,4H),7.00(d,J＝8.0Hz,1H),5.67(d,J＝8.0Hz,1H),5.31(m,1H),3.71-3.59(m,2H),2.12-2.04(m,2H),1.91-1.83(m,2H),1.41(s,9H),1.38-1.97(m,2H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ155.48,144.78,143.69,132.10,129.69,128.87,128.31,126.51,115.74,97.19,56.06,50.81,32.46,32.02,29.43,24.90,12.61.
example 3 preparation of Compounds 1-3
67.18g (0.2 mol) 2,9-dibromo-1,10-phenanthroline is dissolved in 600mL of ultra-dry tetrahydrofuran under the nitrogen atmosphere, the system temperature is reduced to-78 ℃, 300mL of hexane solution of n-butyllithium (0.48mol, 2.4eq, 1.6M) is slowly and dropwise added to react for 30min under the condition of-78 ℃, 82.76g of triisopropyl borate (0.44mol, 2.2eq) is slowly and dropwise added to react for 2h, 80.0mL of water is added to quench after slowly returning to the room temperature, reaction liquid is concentrated, ethyl acetate is extracted, saturated water-washed salt water is used for organic phase combination, anhydrous sodium sulfate is dried, filtrate is concentrated, n-hexane is added for recrystallization and washing, 40.34g of white solid is obtained, and the yield is 75.3%.
Compound 1-3 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.45-8.43(dd,J＝8.0Hz,2H),8.28-8.26(dd,J＝8.0Hz,2H),7.84(d,J＝8.0Hz,2H),7.35(s,4H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ149.31,148.75,147.62,147.06,146.50,145.37,144.81,130.17,129.06,128.81,126.08.
example 4 preparation of Compounds 1-4
5.35g of the compounds 1 to 3 (0.02 mol) and 21.10g of the compounds 1 to 2 (0.044mol, 2.2eq.) were dissolved in 200mL of ethylene glycol dimethyl ether, 40mL of an aqueous solution of sodium carbonate (0.08mol, 4eq, 2M) was added, liquid nitrogen was frozen, vacuum was applied to remove oxygen, 9.24g of tetrakistriphenylphosphine palladium (0.008mol, 0.4eq.) was added under nitrogen protection, and the mixture was heated to 90 ℃ for reflux reaction for 72 hours. The reaction mixture was concentrated, extracted with ethyl acetate, washed with saturated brine, and the organic phases were combined and dried over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =220 (v/v)) to obtain 15.28g of a white solid in a yield of 78.2%.
Compound 1-4 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.27-8.25(dd,J＝8.0Hz,2H),8.06(t,J＝8.0Hz,2H),7.95-7.93(dd,J＝8.0Hz,2H),7.32(t,J＝8.0Hz,2H),7.32-7.22(m J＝8.0Hz,12H),7.14(t,J＝8.0Hz,8H),6.99(t,J＝8.0Hz,2H),6.95(s,2H),5.79(d,2H,-CHPh 2 ),5.35(bs,2H),1.44-1.37(m,4H),2.14–2.03(m,4H),1.89-1.83(m,4H),1.52(s,18H),1.61–1.56(m,4H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.81,155.77,146.28,144.24,142.37,138.02,130.99,130.02,129.77,128.99,128.31,126.91,126.51,125.58,121.20,120.24,91.36,55.37,55.09,36.28,31.59,29.37,24.87,11.94.
example 5 preparation of Compounds 1-5
14.66g of Compound 1-4 (0.015 mol) was dissolved in a mixed solution of 50mL of ethyl acetate and 50mL of methanol, and 5mL of concentrated hydrochloric acid (12 mol/L) was added thereto, followed by stirring at 60 ℃ for 30min. The solvent was spin dried to give 11.81g of a white solid in 97.3% yield.
Nuclear magnetic results for compounds 1-5: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.18(dd,J＝8.0Hz,2H),8.07(t,J＝8.0Hz,2H),7.88(dd,J＝8.0Hz,2H),7.69(t,J＝8.0Hz,2H),7.36(m J＝8.0Hz,8H),7.29(t,J＝8.0Hz,4H),7.21(t,J＝8.0Hz,8H),6.87(d,J＝8.0Hz,2H),5.74(s,2H),5.64(d,2H,-CHPh 2 ),1.52(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ157.64,152.71,146.00,144.01,141.67,137.95,130.87,129.33,129.05,128.97,128.49,126.70,126.51,125.58,120.70,117.30,54.96,33.66,31.73.
example 6 preparation of Compounds 1-6
In a glove box, 3.24g of compound 1-5 (0.004 mol) was dissolved in 30mL of dry toluene, 5mL of n-butyllithium (0.008mol, 2.0eq, 1.6M) was slowly added dropwise, after reaction at 0 ℃ for 1.5h, the toluene was drained, 15mL of dry n-hexane was added, the mixture was stirred for 15min, allowed to stand, filtered and washed with dry n-hexane, the residue was dissolved in 30mL of dry toluene, and 1.34g of TiCl was added 4 (THF) 2 (0.004mol, 1.0eq.) and heating to 80 ℃ for reflux reaction for 8h, filtering after the reaction is finished, washing by using dry n-hexane, and draining the filtrate to obtain 2.03 brown solid with the yield of 54.8%.
Compound 1-6 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.21(dd,J＝8.0Hz,2H),8.11(t,J＝8.0Hz,2H),7.89(dd,J＝8.0Hz,2H),7.79(t,J＝8.0Hz,2H),7.34-7.30(dt J＝8.0Hz,8H),7.25(dt,J＝8.0Hz,4H),7.17-7.14(q,J＝8.0Hz,8H),6.91(d,J＝8.0Hz,2H),5.88(s,2H,-CHPh 2 ),1.53(s,18H). 13 C NMR(CDCl 3 100MHz, TMS): delta 160.47,155.79,145.44,144.67,142.33,133.94,131.02,130.44,129.05,128.49,127.30,126.51,125.58,125.45,121.10,52.48,33.68,31.73 preparation of example 7, compounds 1-7
The experimental procedure is essentially the same as in example 6, except that: 2.11g ZrCl was added 4 (THF) 2 (0.0056mol, 1.4eq.) to give 2.54g of an off-white solid in a yield of 65.6%.
Nuclear magnetic results for compounds 1-7: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.23(dd,J＝8.0Hz,2H),8.15(t,J＝8.0Hz,2H),7.94(dd,J＝8.0Hz,2H),7.58(t,J＝8.0Hz,2H),7.41(dt J＝8.0Hz,8H),7.28(dt,J＝8.0Hz,4H),7.21(q,J＝8.0Hz,8H),6.85(d,J＝8.0Hz,2H),5.89(s,2H,-CHPh 2 ),1.62(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.90,156.03,148.47,144.75,142.41,133.24,130.93,130.68,129.85,128.78,128.94,127.45,126.51,125.58,125.36,121.18,53.82,38.41,30.73.
example 8 preparation of Compounds 1-8
The experimental procedure is essentially the same as in example 6, except that: 3.34g of HfCl were added 4 (THF) 2 (0.0072mol, 1.8eq.) to give 2.25g of an off-white solid in 53.2% yield.
Nuclear magnetic results for compounds 1-7: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.29(dd,J＝8.0Hz,2H),8.06(t,J＝8.0Hz,2H),7.85(dd,J＝8.0Hz,2H),7.66(t,J＝8.0Hz,2H),7.32(dt J＝8.0Hz,8H),7.21(dt,J＝8.0Hz,4H),7.16(q,J＝8.0Hz,8H),6.71(d,J＝8.0Hz,2H),5.68(s,2H,-CHPh 2 ),1.46(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.71,155.81,145.50,144.83,142.49,133.96,130.86,130.46,129.15,128.56,128.27,127.58,127.11,125.78,125.29,121.26,55.82,35.66,31.89.
complex 2
Synthetic route of complex
Example 9 preparation of Compound 2-1
114.09g (0.4 mol) 2-bromo-4,6-di-tert-butylphenol was dissolved in 600mL of ultra dry dichloromethane under nitrogen, and 33.65g dihydropyran (0.4 mol, 1.0eq.) and 5.03g pyridinium p-toluenesulfonate (0.02mol, 0.05eq.) were added and reacted at 20 ℃ for 12h. Extraction with dichloromethane, washing with saturated brine, combining organic phases, and drying over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =350 (v/v)) to give 63.82g of a colorless oil, in 86.4% yield.
Nuclear magnetic results for compound 2-1: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.54(d,J＝8.0Hz,1H),7.17(d,J＝8.0Hz,1H),5.48(m,1H),3.85–3.71(m,2H),2.20-2.01(m,2H),1.48(s,9H),1.42(s,9H),1.40-1.37(m,2H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ157.61,145.71,136.81,128.69,123.76,115.92,95.38,62.56,32.49,31.55,31.50,30.13,30.04,24.90,24.90,19.11.
example 10 preparation of Compound 2-2
21.43g of the compound 1-3 (0.08 mol) and 88.64g of the compound 2-1 (0.24mol, 3eq.) are respectively dissolved in 600mL of ethylene glycol diethyl ether, 80mL of potassium carbonate aqueous solution (0.11umol, 2eq, 2M) is added, liquid nitrogen is frozen, vacuum is conducted to remove oxygen, 9.24g of tetratriphenylphosphine palladium (0.008mol, 0.1eq.) is added under the protection of nitrogen, heating is conducted to 120 ℃, and reflux reaction is conducted for 48 hours. The reaction mixture was concentrated, extracted with ethyl acetate, washed with saturated brine, and the organic phases were combined and dried over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =250 (v/v)) to give 48.63g of a white solid in 80.3% yield.
Compound 2-2 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.27(d,J＝8.0Hz,2H),8.25(t,J＝8.0Hz,2H),8.00(d,J＝8.0Hz,2H),7.79(t,J＝8.0Hz,2H),7.28(dd J＝8.0Hz,2H),5.51(m,2H),3.81-3.73(m,2H),2.14(bd,4H),2.01(m,4H),2.14–2.03(m,4H),1.89-1.83(m,4H),1.59(s,18H),1.40(s,18H),1.43–1.36(m,4H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.75,157.37,146.14,143.94,137.88,135.45,133.54,126.91,126.21,125.58,123.99,120.47,94.50,61.87,36.31,35.13,31.12,29.98,29.73,24.87,18.44.
example 11 preparation of Compounds 2-3
45.42g of Compound 2-2 (0.06 mol) was dissolved in a mixed solution of 100mL of ethyl acetate and 100mL of methanol, 48mL of an aqueous acetic acid solution (0.48mol, 8eq.10mol/L) was added thereto, and the reaction was stirred at 30 ℃ for 2 hours. The solvent was dried by spinning to give 32.33g of a white solid in 91.5% yield.
Compound 2-3 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.21-8.19(d,J＝8.0Hz,2H),8.19-8.17(d,J＝8.0Hz,2H),7.91(dd,J＝8.0Hz,2H),7.79(t,J＝8.0Hz,2H),7.22(dd J＝8.0Hz,2H),5.74(m,2H),1.60(s,18H),1.44(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ155.10,153.19,145.86,142.95,137.81,136.00,133.32,126.70,125.58,123.72,122.90,120.93,35.11,33.69,31.26,29.86.
example 12 preparation of Compounds 2-4
In a glove box, 5.89g of the compound was chargedDissolving 2-3 (0.01 mol) in 40mL of dry toluene, slowly adding 0.624g of sodium hydride (0.026mol, 2.6 eq.) for reacting at-78 deg.C for 20h, draining the toluene, adding 10mL of dry n-hexane, stirring for 15min, standing, filtering, washing with dry n-hexane, adding 40mL of dry toluene to the filter residue for dissolving, and adding 4.01g of TiCl 4 (THF) 2 (0.012mol, 1.2eq.), heating to 120 deg.C for reflux reaction for 4h, filtering, draining the filtrate, adding 15mL of dry hexane for washing twice, draining the solvent to obtain 3.72g of light brown solid with the yield of 52.8%.
Compound 2-4 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.19(t,J＝8.0Hz,4H),7.95(t,J＝8.0Hz,2H),7.79(t,J＝8.0Hz,2H),7.26(dd,J＝8.0Hz,2H),1.60(s,18H),1.48(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.69,153.25,145.30,137.41,143.61,133.80,132.89,131.05,127.30,125.58,123.26,121.33,34.13,33.71,31.26,30.26.
example 13 preparation of Compounds 2-5
The experimental procedure is essentially the same as in example 12, except that: 4.53g ZrCl was added 4 (THF) 2 (0.012mol, 1.2eq.) to give 4.86g of a white solid in 64.9% yield.
Nuclear magnetic results for compounds 2-5: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.16(t,J＝8.0Hz,4H),7.93(t,J＝8.0Hz,2H),7.59(t,J＝8.0Hz,2H),7.46(dd,J＝8.0Hz,8H),1.81(s,18H),1.51(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.12,153.49,145.38,143.69,137.32,133.43,133.13,130.96,127.10,125.18,123.50,121.41,34.08,33.41,31.16,29.59。
example 14 preparation of Compounds 2-6
The experimental procedure is essentially the same as in example 12, except that: 5.57g of HfCl were added 4 (THF) 2 (0.0.012mol, 1.2eq.) to give 4.83g of an off-white solid, 57.8% yield.
Compound 2-6 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.22(t,J＝8.0Hz,4H),7.97(t,J＝8.0Hz,2H),7.68(t,J＝8.0Hz,2H),7.18(dd,J＝8.0Hz,8H),1.58(s,18H),1.45(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ159.93,153.27,145.45,143.77,137.29,133.80,132.91,130.89,127.24,125.58,123.31,121.49,34.15,33.62,31.37,29.60.
example 15 preparation of Compounds 2-7
In a glove box, 2.12g of compound 2-4 (0.003 mol) is dissolved in 20mL of diethyl ether, 2mL of methyl magnesium bromide diethyl ether solution (0.006mol, 2eq, 3M) is slowly added dropwise, the mixture is stirred and reacted for 6h at room temperature, the diethyl ether is drained, 20mL of super-dry toluene is added, the mixture is stirred for 10min, and the filtrate is collected after filtration. The filtrate was drained, washed twice with 5mL hexane, filtered again and the residue was drained to yield 1.66g of a light brown solid in 83.2% yield.
Compound 2-7 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.20-8.18(dt,J＝8.0Hz,2H),8.14(t,J＝8.0Hz,2H),7.89(dd,J＝8.0Hz,2H),7.49(t,J＝8.0Hz,2H),7.20(dd,J＝8.0Hz,2H),2.46(s,6H,Ti-CH 3 ),1.65(s,18H),1.42(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ163.96,153.75,145.30,143.17,139.28,133.94,133.39,130.64,127.47,126.58,123.76,120.89,71.49,35.39,33.95,31.06,30.04.
example 16 preparation of Compounds 2-8
The experimental procedure is essentially the same as in example 15, except that: 2.25g of Compound 2-5 (0.003 mol) was dissolved in 20mL of diethyl ether to obtain 1.69g of a white solid with a yield of 79.6%.
Nuclear magnetic results for compounds 2-8: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.22(dt,J＝8.0Hz,2H),8.04(t,J＝8.0Hz,2H),7.94(dd,J＝8.0Hz,2H),7.84(t,J＝8.0Hz,2H),7.23(dd,J＝8.0Hz,2H),2.43(s,6H,Zr-CH 3 ),1.68(s,18H),1.51(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ163.39,153.99,145.12,143.25,139.19,133.98,133.63,130.55,126.15,125.38,124.00,120.97,40.65,35.18,33.45,32.26,29.37.
example 17 preparation of Compounds 2-9
The experimental procedure is essentially the same as in example 15, except that: 2.51g of Compound 2-6 (0.003 mol) was dissolved in 20mL of diethyl ether to obtain 1.99g of a white solid with a yield of 83.4%.
Chemical combinationObject 2-9 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.16(dt,J＝8.0Hz,2H),8.10(t,J＝8.0Hz,2H),7.82(dd,J＝8.0Hz,2H),7.75(t,J＝8.0Hz,2H),6.91(dd,J＝8.0Hz,2H),2.51(s,6H,Hf-CH 3 ),1.72(s,18H),1.49(s,18H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ163.20,153.77,145.45,143.33,139.16,135.80,133.41,130.48,127.17,125.08,123.81,121.05,40.65,35.41,33.26,31.52,29.38.
synthetic route of complex
Example 18 preparation of Compound 3-1
93.22g (0.4 mol) of 2-bromo-4,5-dimethoxyphenol were dissolved in 800mL of ultra-dry 1,1,2,2-tetrachloroethane under a nitrogen atmosphere, and then 67.30g of dihydropyran (0.8mol, 2.0eq.) and 50.26g of pyridinium p-toluenesulfonate (0.2mol, 0.5eq.) were added and reacted at 60 ℃ for 6 hours. Extraction with dichloromethane, washing with saturated brine, and then combining the organic phases and drying over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =150 (v/v)) to give 109.87g of yellow oil in 86.6% yield.
Nuclear magnetic results for compound 3-1: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.00(t,J＝8.0Hz,1H),6.79(t,J＝8.0Hz,1H),5.39(m,1H),3.90(m,1H),3.85(t,J＝8.0Hz,3H),3.82(t,J＝8.0Hz,3H),3.57(m,1H),2.03(m,4H),1.43(m,2H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ149.98,147.22,145.71,117.86,106.04,104.93,97.19,61.70,56.49,56.36,30.30,25.23,18.33.
example 19 preparation of Compound 3-2
31.72g (0.1 mol) of compound 3-1 and 30.95g of 3, 5-di-tert-butylphenol (0.15mol, 1.5eq.) were dissolved in 400mL of ultra dry tetrachloroethane, respectively, under argon atmosphere, 4.38g of tin tetrabromide (0.01mol, 0.1eq.) was added slowly and stirred at 60 ℃ for 6h. The reaction was quenched by addition of 40mL of saturated aqueous potassium carbonate solution, followed by extraction with methylene chloride, washing with saturated brine, combining the organic phases and drying over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =150 (v/v)) to give 47.67g of a white solid in 94.3% yield.
Compound 3-2 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.66(t,J＝8.0Hz,1H),7.46(t,J＝8.0Hz,2H),7.01(t,J＝8.0Hz,1H),5.48(m,1H),3.88(t,J＝8.0Hz,3H),3.77(m,1H),3.71(m,1H),3.66(t,J＝8.0Hz,3H),2.04(m,2H),2.01(m,2H),1.56(s,18H),1.43(m,2H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ151.84,150.73,150.60,146.35,137.33,126.66,123.12,123.06,117.20,106.93,97.58,62.96,60.72,55.98,34.09,31.33,30.19,24.90,19.51.
example 20 preparation of Compounds 3-4
10.71g of the compounds 1-3 (0.04 mol) and 80.88g of the compounds 3-2 (0.16mol, 4.0eq.) are respectively dissolved in 400mL of ethylene glycol diethyl ether, 60mL of potassium carbonate aqueous solution (0.12mol, 3eq, 2M) is added, liquid nitrogen is frozen, vacuumizing is performed to remove oxygen, 36.98g of tetratriphenylphosphine palladium (0.032mol, 0.8eq.) is added under the protection of nitrogen, and the mixture is heated to 50 ℃ for reaction for 36 hours. The reaction mixture was concentrated, extracted with ethyl acetate, washed with saturated brine, and the organic phases were combined and dried over anhydrous sodium sulfate. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether: ethyl acetate =150 (v/v)) to obtain 31.50g of a white solid with a yield of 76.5%.
Compound 3-4 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.35(dd,J＝8.0Hz,2H),8.20(dt,J＝8.0Hz,2H),7.79(dd,J＝8.0Hz,2H),7.66(m,2H),7.46(d,J＝8.0Hz,4H),7.42(t,J＝8.0Hz,2H),5.52(m,2H),3.83(t,J＝8.0Hz,6H),3.71(m,2H),3.70(m,2H),3.61(t,J＝8.0Hz,6H),206(m,2H),1.97(m,4H),1.56(s,36H),1.43(m,4H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ157.00,151.55,150.45,150.26,146.04,144.01,137.78,135.83,128.84,126.91,125.58,123.12,122.33,121.74,117.28,96.70,62.27,60.50,55.70,34.09,31.33,30.13,24.87,18.84.
example 21 preparation of Compounds 3-5
20.59g of Compound 3-4 (0.015 mol) was dissolved in a mixed solution of 50mL of ethyl acetate and 50mL of ethanol, and 3.34mL of concentrated hydrochloric acid (12 mol/L) was added thereto, followed by stirring at 0 ℃ for reaction for 4 hours. The solvent was dried by spinning to give 16.21g of a white solid in 94.1% yield.
Compound 3-5 nuclear magnetic results: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.29(dd,J＝8.0Hz,2H),8.13(dd,J＝8.0Hz,2H),7.79(t,J＝8.0Hz,2H),7.59(t,J＝8.0Hz,2H),7.49(m,4H),7.36(d,J＝8.0Hz,2H),5.87(s,2H),3.84(s,6H),3.63(s,6H),1.56(s,36H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ155.15,151.48,150.63,148.90,145.76,142.02,137.71,134.58,126.70,125.58,123.12,122.91,122.47,122.20,117.25,115.10,60.29,55.84,38.02,31.33.
example 22 preparation of Compounds 3-6
In a glove box, 4.30g of Compound 3-5 (0.005 mol) was dissolved in 30mL of dry toluene, 11.25mL of n-butyllithium (0.018mol, 3.6eq, 1.6M) was slowly added dropwise, after reaction at 30 ℃ for 10 hours, toluene was drained, 20mL of dry n-hexane was added, the mixture was stirred for 15 minutes, allowed to stand, filtered and washed with dry n-hexane, and the residue was dissolved in 30mL of dry toluene, and 1.87g of Zr (NMe) was added 2 ) 4 (0.007mol, 1.4 eq.) and reacting at 30 deg.C for 30h, filtering after the reaction is finished, draining the filtrate, adding 10mL of dried hexane, washing and draining the solvent to obtain 3.16g of brown solid with the yield of 60.8%.
Nuclear magnetic results for compounds 3-6: 1 H NMR(CDCl 3 ,400MHz,TMS):δ8.18(dd,J＝8.0Hz,2H),8.10(dd,J＝8.0Hz,2H),7.89(t,J＝8.0Hz,2H),7.69(bs,2H),7.47(dt J＝8.0Hz,4H),7.40(t,J＝8.0Hz,2H),3.95(s,6H),3.71(s,6H),2.26(s,12H),1.59(s,36H). 13 C NMR(CDCl 3 ,100MHz,TMS):δ161.11,154.36,151.48,151.26,145.20,141.02,135.22,133.70,127.30,125.58,122.91,122.12,120.94,117.88,112.45,60.29,55.84,38.04,31.33,26.66.
examples 23-37 catalysis of the polymerization of ethylene/1-octene using the compounds 1-6/MMAO,1-7/MMAO,1-8/MMAO,2-4/MMAO,2-5/MMAO,2-6/MMAO,2-7/MMAO,2-8/MMAO,2-9/MMAO, respectively
0.8L of dried IsoparE solvent is added into a 2L reaction kettle, the temperature is raised to 140 ℃, and the reaction kettle is cleaned by stirring for 30min. Cool to room temperature and release the solvent. Then the temperature is increased to 140 ℃ and the vacuum drying is carried out for 30min. During which time nitrogen was continuously used for replacement. The reaction vessel was cooled to 80 ℃ or less, 0.8L of IsoparE and 0.2L of 1-octene were added to the reaction vessel, and the metal compound synthesized in the example of the present invention (wherein, the addition amount of examples 23, 24, 26-30 was 0.8. Mu. Mol, the addition amount of example 25 was 2.7. Mu. Mol, the addition amount of examples 31-32 was 0.8. Mu. Mol, the addition amount of example 33 was 1.5. Mu. Mol, and the addition amount of examples 34-37 was 0.4. Mu. Mol) was added thereto, and an amount of MMAO was added in accordance with Al/M. After the temperature is raised to the set temperature (polymerization temperature), 3MPa of ethylene is introduced to start the polymerization reaction for 6min. Then, ethylene was vented, the reaction solution was placed in ethanol, and the precipitated solid was collected, dried in a vacuum oven at 60 ℃ to constant weight, weighed, and subjected to sample analysis.
TABLE 1 data Table for the catalyzed ethylene/1-octene polymerization of the Compound/MMAO System
a 1-octene insertion rate, wt%, mass percent.
Examples 38 to 44 catalysis of ethylene/1-octene polymerization with Compound 2-8/aluminum alkyl or aluminum alkoxy/organoboron systems
0.8L of dried IsoparE solvent is added into a 2L reaction kettle, the temperature is raised to 140 ℃, and the reaction kettle is cleaned by stirring for 30min. The solvent was discharged by cooling to room temperature. Then the temperature is increased to 140 ℃ and the vacuum drying is carried out for 30min. During which time nitrogen was continuously used for replacement. The reaction vessel was cooled to below 80 ℃ and 0.8L of IsoparE and 0.2L of 1-octene were added to the reaction vessel, 0.3. Mu. Mol of the above synthesized metal compound was added, a certain amount of aluminum alkyl or aluminum alkoxy was added in terms of Al/M, and a certain amount of organic boron compound was added in terms of B/M. Heating to 160 ℃, introducing 3MPa ethylene to start polymerization reaction, and reacting for 6min. Then, ethylene was vented, the reaction solution was placed in ethanol, and the precipitated solid was collected, dried in a vacuum oven at 60 ℃ to constant weight, weighed, and subjected to sample analysis.
TABLE 2 data Table of the compounds 2-8/aluminum alkyl or alkoxy aluminum/organoboron systems catalysing the polymerization of ethylene/1-octene
a B1 denotes trityltetrakis (pentafluorophenyl) borate, B2 denotes N, N-dimethyltetrakis (pentafluorophenyl) borate, B3 denotes dioctadecylmethyl tertiary amine tetrakis (pentafluorophenyl) borate; b 1-octene insertion rate, wt%, mass percent.
Example 45 polymerization Using the Compound 2-8/MMAO/1-hexene
0.8L of dried IsoparE solvent is added into a 2L reaction kettle, the temperature is raised to 140 ℃, and the reaction kettle is cleaned by stirring for 30min. Cool to room temperature and release the solvent. Then the temperature is increased to 140 ℃ and the vacuum drying is carried out for 30min. During which time nitrogen was continuously used for replacement. The reaction kettle is cooled to below 80 ℃, 0.8L IsoparE and 0.2L 1-hexene are added into the reaction kettle, 0.6 mu mol of the metal compound synthesized above is added, MMAO solution is added according to Al/M =400, after the temperature is raised to 160 ℃, 3MPa ethylene is introduced to start polymerization reaction, and the reaction lasts for 6min. Then ethylene was vented, the reaction solution was put into ethanol, the precipitated solid was collected, dried in a vacuum oven at 60 ℃ to constant weight and weighed to obtain 200.8g in total of a polymer having an activity of 3.34X 10 8 g/mol, molecular weight 24.8 ten thousand g/mol, PDI =2.4,1-hexene insertion 44%.
Comparative example 1 catalytic ethylene/1-octene polymerization Using MMAO alone
The polymerization process was essentially the same as in example 23, except that: no compound 1-6 is added in the system, no polymer is obtained, and the reaction system is inactive.
Comparative example 2 catalysis of ethylene/1-octene polymerization Using MMAO/organoboron alone
The polymerization process was essentially the same as in example 38, except that: no compound 2-8 is added in the system, no polymer is obtained, and the reaction system is inactive.
Comparative example 3, use only i Bu 3 Al/organoboron catalyzed ethylene/1-octene polymerization
The polymerization process was essentially the same as in example 40, except that: no compound 2-8 is added in the system, no polymer is obtained, and the reaction system is inactive.
Comparative example 4 catalysis of ethylene/1-hexene polymerization Using MMAO alone
The polymerization process was essentially the same as in example 45, except that: no compound 2-8 is added in the system, no polymer is obtained, and the reaction system is inactive.
As can be seen from the above comparative examples 1-4, the catalyst composition comprising the complex of formula I and the cocatalyst according to the present invention exhibited a high ethylene/alpha-olefin copolymerization activity.
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 (37)
1. A phenol phenanthroline IVB group metal complex is characterized by having a structure shown as a formula I:
wherein R is 1 Selected from the group consisting of hydrogen, C1-20 alkyl, C1-20 alkoxy, benzhydryl, 3,5-di (t-butyl) phenyl, 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, 3,5-di (t-octyl) phenyl;
R 2 –R 4 the same or different, each independently selected from hydrogen and C 1-30 Alkyl radical, C 1-30 An alkoxy group;
x is halogen or alkyl, dimethylamino, diethylamino having 1 to 10 atoms not counting hydrogen;
m is selected from titanium, zirconium and hafnium.
2. The phenantroline group IVB metal complex of claim 1, wherein R is 2 –R 4 The same or different, each independently selected from hydrogen and C 1-20 Alkyl radical、C 1-20 An alkoxy group.
3. The phenantroline group IVB metal complex of claim 2, wherein R is 2 –R 4 The same or different, each independently selected from hydrogen and C 1-10 Alkyl radical, C 1-10 An alkoxy group.
4. A method for preparing the phenanthroline group IVB metal complex according to any one of claims 1 to 3, comprising the steps of:
in an organic solvent I, reacting a compound shown as a formula II with a hydrogen extraction reagent to generate a salt, and then complexing with a salt M to obtain a complex shown as a formula I;
in the formula II, R 1 、R 2 、R 3 、R 4 Is as defined for formula I;
the M salt is one or more of halides, alkyl compounds or amino compounds of metal titanium, zirconium and hafnium.
5. The method according to claim 4, wherein the hydrogen-withdrawing agent is selected from the group consisting of sodium hydride, potassium hydride, lithium hydride, tetramethylethylenediamine, lithium bistrimethylsilylamide, sodium bistrimethylsilylamide, lithium diisopropylamide, and C 1 -C 6 One or more of alkyl lithium.
6. The method according to claim 5, wherein the hydrogen-extracting agent is selected from the group consisting of sodium hydride, potassium hydride, and C 1 -C 6 One or more of alkyl lithium.
7. The method according to claim 4, wherein the organic solvent is one or more selected from tetrahydrofuran, dehydrated ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, octane, isooctane, toluene, and xylene.
8. The method according to claim 4, wherein the first organic solvent is tetrahydrofuran, diethyl ether, n-hexane or toluene.
9. The method according to claim 4, wherein the molar ratio of the compound represented by the formula II to the hydrogen-withdrawing agent is 1:2-3.6.
10. The method according to claim 9, wherein the molar ratio of the compound represented by formula II to the hydrogen-withdrawing agent is 1:2-2.6.
11. The process according to claim 4, wherein the salt-forming reaction is carried out at a temperature of-78 to 35 ℃.
12. The process according to claim 11, wherein the salt-forming reaction is carried out at a temperature of-78 to 0 ℃.
13. The preparation method of claim 4, wherein the salt-forming reaction time is 1-24 h.
14. The method according to claim 4, wherein the molar ratio of the compound represented by formula II to the metal M in the M salt is 1:1-1.8.
15. The method according to claim 14, wherein the molar ratio of the compound of formula II to the metal M in the M salt is 1:1-1.4.
16. The method according to claim 4, wherein the temperature of the complexation reaction is 30 to 120 ℃.
17. The method according to claim 4, wherein the time for the complexation reaction is 4 to 30 hours.
18. The preparation method of claim 4, wherein the compound shown in formula II is obtained by reacting the compound shown in formula III with protonic acid in an organic solvent at 0-60 ℃ for 0.5-4 h;
the structural formula of the compound of the formula III is as follows:
in the formula III, R 1 、R 2 、R 3 、R 4 Is as defined for formula I; r is a hydroxyl protecting group.
19. The method according to claim 18, wherein R is dihydropyran.
20. The process of claim 18, the process of preparing a compound of formula III, comprising the steps of:
(a) In the organic solvent III, reacting 2,9-dibromo-1,10-phenanthroline with a hydrogen extraction reagent at low temperature to form salt, adding triisopropyl borate, and continuing to react to obtain a compound VI; the reaction temperature is-78 to 35 ℃, and the reaction time is 1 to 6 hours;
(b) Under the condition of inert atmosphere, mixing the compound VI, the compound V and an aqueous solution of alkali in an organic solvent IV, then freeze-drying and deoxidizing, then adding a palladium catalyst, reacting for 36-72 h at 50-120 ℃, and separating to obtain a compound III; the molar ratio of the compound VI to the compound V to the alkali to the palladium catalyst is 1:2-4:2-4;
compound VI is:
the compound V is
R 1 、R 2 、R 3 、R 4 Are as defined for formula I and the substituent R is as defined for formula III.
21. The preparation method according to claim 20, wherein the compound 2,9-dibromo-1,10-phenanthroline, the hydrogen-withdrawing agent and the triisopropyl borate are in a molar ratio of 1:2-4:2-3.
22. The preparation method according to claim 21, wherein the compound 2,9-dibromo-1,10-phenanthroline, the hydrogen-withdrawing agent and the triisopropyl borate are in a molar ratio of 1:2-3:2-2.6.
23. The preparation method of claim 20, wherein the organic solvent is one or more of tetrahydrofuran, anhydrous diethyl ether, pentane, cyclopentane, n-hexane, cyclohexane, heptane, methylcyclohexane, toluene and xylene.
24. The method of claim 20, wherein the hydrogen abstraction agent is one or more of sodium hydride, potassium hydride, lithium hydride, and C1-C6 alkyllithium.
25. The preparation method according to claim 20, wherein the organic solvent of step (b) is one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, diethyl ether and tetrahydrofuran; the amount of the solvent added is 2-10mL based on 1g of the reactant.
26. The method of claim 25, wherein 1g of the reactant solvent is added in a volume of 3-8mL.
27. The method of claim 20, wherein the base is selected from one or more of sodium carbonate, potassium carbonate, cesium carbonate, and lithium carbonate.
28. The production method according to claim 20, wherein the palladium catalyst is a tetradentate palladium catalyst.
29. The production method according to claim 28, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium.
30. Use of a complex according to claims 1 to 3 or a phenolphenanthroline group IVB metal complex prepared by a process according to any one of claims 4 to 29 as a catalyst for the polymerisation of olefins or the copolymerisation of olefins and alpha-olefins.
31. The use according to claim 30, the phenolphenanthroline group IVB metal complex being used as a co-polymer of ethylene and 1-octene.
32. The use of claim 30, wherein a cocatalyst is added in the polymerization of olefins or the copolymerization of olefins and α -olefins, and the cocatalyst is a combination of one or more of aluminoxane, an alkylaluminum compound, and alkylaluminum chloride, or a combination of one or more of aluminoxane, an alkylaluminum compound, and alkylaluminum chloride and one or more organic boron compounds.
33. The use according to claim 32, said aluminoxane comprising methylaluminoxane, modified methylaluminoxane; the alkyl aluminum compound comprises triethyl aluminum, triisobutyl aluminum and trioctyl aluminum; the alkyl aluminum chloride comprises monochloro ethyl aluminum, sesquiethyl aluminum and dichloroethyl aluminum; the organic boron compound is triphenylmethyl tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) boron, N-dimethylanilinium tetra (pentafluorophenyl) borate, dioctadecyl methyl tertiary amine tetra (pentafluorophenyl) borate, or dihydrotallow methyl tertiary amine tetra (pentafluorophenyl) borate.
34. The use according to claim 30, wherein the phenolphenanthroline group IVB metal complex is added in an amount of 0.1-3 μmol/L.
35. The use according to claim 32, wherein the molar ratio Al/M of the aluminum metal in the cocatalyst to the metal M in the catalyst center is in the range of 1 to 10000; the molar ratio B/M of boron in the organic boride to the catalyst central metal M is 0-10; the polymerization temperature is 20-250 ℃; the polymerization pressure is 0.1-10MPa.
36. The use according to claim 35, wherein the molar ratio Al/M of metallic aluminum in the cocatalyst to the catalyst central metal M is in the range of 1 to 4000; the molar ratio B/M of boron in the organic boride to the catalyst central metal M is 0-8; the polymerization temperature is 120-220 ℃; the polymerization pressure is 1-5MPa.
37. Use according to claim 36, wherein the molar ratio Al/M of the aluminum metal of the cocatalyst to the metal M of the catalyst core is between 3 and 1000; the molar ratio B/M of boron in the organic boride to the catalyst central metal M is 1-4; the polymerization temperature is 150-220 ℃; the polymerization pressure is 3-5MPa.
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