Method for preparing N ortho-acyl substituted nitrogen-containing heterocyclic compound and aminated iron (II) complex thereof

Abstract

The invention provides a method for preparing an N-ortho-acyl substituted nitrogen-containing heterocyclic compound and an aminated iron (II) complex thereof, which comprises the following step: carrying out oxidation reaction on the N-ortho-alkyl substituted nitrogen-containing heterocyclic compound and benzoic acid peroxide as shown in a formula (I) in an organic solvent to generate the N-ortho-acyl substituted nitrogen-containing heterocyclic compound. The preparation method provided by the invention is few in synthesis steps, simple in process and low in toxicity, reduces the preparation cost of the catalyst, and has a wide industrial prospect. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the preparation of an olefin polymerization catalyst intermediate, and in particular to a method for preparing an N-ortho-acyl-substituted nitrogen-containing heterocyclic compound and an amine-condensed iron (II) complex thereof. Background Art

[0002] Ethylene oligomerization is one of the most important reactions in the olefin polymerization industry. Through oligomerization, cheap small molecule olefins can be converted into products with high added value. The product of ethylene oligomerization, linear α-olefins (LAO), is an important organic chemical raw material. For example, C4-C 30 LAO can be used to prepare daily detergents, flotation agents, emulsifiers, lubricating components of refrigerators and drilling fluids, plasticizers, various additives, low-viscosity synthetic oils, polymers and copolymers, petroleum and petroleum product additives, higher alkylamines, higher organoaluminum compounds, higher alkylaryl hydrocarbons, higher fatty alcohols and fatty acids, epoxides and heat carrier additives, etc. 20 -C 30 Adhesives, sealants and coatings can also be synthesized based on LAO. In recent years, with the continuous development of the polyolefin industry, the demand for α-olefins has grown rapidly worldwide. Most of the α-olefins are prepared by ethylene polymerization.

[0003] The catalysts used in the ethylene oligomerization method mainly include nickel, chromium, zirconium and aluminum. In recent years, the Brookhart group (Brookhart, M et al., J. Am. Chem. Soc., 1998, 120, 7143-7144; WO99 / 02472, 1999) and the Gibson group (Gibson, VC et al., Chem. Commun., 1998, 849-850; Chem. Eur. J., 2000, 2221-2231) have found that some tridentate pyridine imine complexes of Fe (II) and Co (II) can catalyze ethylene oligomerization. Not only are the catalytic activity of the catalysts very high, but the selectivity of α-olefins is also very high. Therefore, this type of complex has a strong prospect for industrial application. For this type of Fe (II) and Co (II) complex catalyst, the key is the synthesis of the ligand, and whether this type of complex can be obtained and the cost depends on the synthesis method of the ligand.

[0004] Sun Wenhua's group at the Institute of Chemistry, Chinese Academy of Sciences (Sun Wenhua et al., Organometallics 2006, 25, 666-677) first used 1,10-phenanthroline imine compounds to coordinate with Fe (II) to obtain tridentate nitrogen imine complexes to catalyze ethylene polymerization. The catalytic activity and selectivity of this type of catalyst are very high. However, the disadvantage of the catalyst preparation method is that there are too many steps in the synthesis of the ligand, and highly toxic potassium cyanide is required to participate in the reaction to obtain 2-acyl-1,10-phenanthroline. In addition, CN101823996A discloses a method for preparing 2,8-position acyl-substituted quinoline, which is essentially to use selenium dioxide to perform an oxidation reaction to generate an acyl group at the 2-position of quinoline; this method can also be used to generate 2-acyl-1,10-phenanthroline. However, in this method, selenium dioxide itself is a highly toxic chemical, which is expensive and difficult to purchase.

[0005] Therefore, researchers attach great importance to developing a method for preparing ethylene polymerization catalysts with fewer synthesis steps, simple process, low raw material cost and avoiding the use of highly toxic substances to participate in the reaction. Summary of the invention

[0006] In view of the above problems in the prior art, one of the objects of the present invention is to provide a method for preparing an N-ortho-acyl substituted nitrogen-containing heterocyclic compound, which has a simple preparation process, low toxicity and reduced catalyst preparation cost.

[0007] The second object of the present invention is to provide a method for preparing a chloride 2-acyl-1,10-phenanthroline amine condensation iron (II) complex.

[0008] The third object of the present invention is to provide a 2-acyl-1,10-phenanthroline amine condensation iron (II) complex.

[0009] A fourth object of the present invention is to provide an application of a 2-acyl-1,10-phenanthroline amine condensation iron (II) complex.

[0010] To achieve one of the above purposes, the scheme adopted by the present invention is as follows:

[0011] A method for preparing an N-ortho-acyl substituted nitrogen-containing heterocyclic compound comprises: subjecting an N-ortho-hydrocarbon substituted nitrogen-containing heterocyclic compound to an oxidation reaction with peroxybenzoic acid represented by formula (I) in an organic solvent to generate an N-ortho-acyl substituted nitrogen-containing heterocyclic compound;

[0012]

[0013] In formula (I), R 1 -R 5are the same or different, each independently selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy and nitro, preferably R 1 -R 5 Both are H.

[0014] In some preferred embodiments of the present invention, the molar ratio of the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound to the benzoic acid peroxide is 1:0.5 to 1:30, preferably 1:1 to 1:2.

[0015] According to the present invention, the amount of the organic solvent used is not particularly limited, as long as the reaction can proceed smoothly.

[0016] In some preferred embodiments of the present invention, the hydrocarbon group in the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound is selected from C1-C6 alkyl and C6-C 12 Aryl, preferably C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl and C6-C9 aryl, more preferably C1-C4 straight-chain alkyl, C3-C5 branched-chain alkyl and C6-C8 aryl, further preferably methyl, ethyl, propyl, n-butyl, isobutyl and benzyl; more preferably, the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound is 2,6-diethylpyridine or a compound represented by formula (II);

[0017]

[0018] In formula (II), R has the same meaning as the above hydrocarbon group.

[0019] According to the present invention, R is selected from C1-C6 alkyl, preferably C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl and C6-C9 aryl, more preferably C1-C4 straight-chain alkyl, C3-C5 branched-chain alkyl and C6-C8 aryl, further preferably methyl, ethyl, propyl, n-butyl, isobutyl and benzyl.

[0020] According to the present invention, the N-ortho-hydrocarbon group contains a methyl group or a methylene group directly connected to the nitrogen-containing heterocyclic compound.

[0021] In some preferred embodiments of the present invention, the organic solvent is selected from one or more of toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, chlorobenzene and dichloromethane.

[0022] In some preferred embodiments of the present invention, the oxidation reaction is carried out under reflux at the boiling point of the organic solvent; and / or the oxidation reaction time is 1 hour to 10 hours, preferably 1 hour to 5 hours.

[0023] In some preferred embodiments of the present invention, the preparation method further comprises the step of separating the N-ortho-acyl substituted nitrogen-containing heterocyclic compound from the reaction product.

[0024] According to the present invention, the compound represented by formula (II) is prepared by the following steps: 1,10-phenanthroline represented by formula (a) and trialkylaluminum or halogenated alkylaluminum R 6 n AlX m , or benzyl lithium Ph'CH2Li, and then hydrolyzed to prepare a compound of formula (II); in formula R 6 n AlX m Medium R 6 are the same or different C1-C6 alkyl groups, X is a halogen, n is a number from 1 to 3, m is a number from 0 to 2, and m+n is equal to 3.

[0025]

[0026] In this specific embodiment, preferably, R 6 n AlX m The hydrolysis is carried out in water or alcohol, more preferably in water.

[0027] In this specific embodiment, it is preferred that the 1,10-phenanthroline and R 6 n AlX m or Ph'CH2Li in a molar ratio of 1:0.5 to 1:4.5, more preferably 1:2.0 to 1:2.6. Preferably, the 1,10-phenanthroline and R 6 n AlX m Or the reaction temperature of Ph'CH2Li is -60 to -80°C, more preferably -60 to -70°C; and after reacting at this temperature for a period of time, the temperature is raised to 20 to 40°C and the reaction is continued; in addition, the hydrolysis temperature is preferably -60 to 0°C.

[0028] To achieve the second purpose above, the technical solution adopted by the present invention is as follows:

[0029] A method for preparing a chlorinated 2-acyl-1,10-phenanthroline amine condensation iron (II) complex comprises:

[0030] S1. The compound represented by formula (III) is prepared by the above method;

[0031] S2. reacting the compound represented by formula (III) with the arylamine represented by formula (IV) to produce a compound represented by formula (V);

[0032] S3. reacting the compound represented by formula (V) with ferrous chloride to produce a 2-acyl-1,10-phenanthroline amine condensation iron (II) complex represented by formula (VI);

[0033]

[0034] R"NH2 Formula (IV)

[0035]

[0036] In formula (III), formula (V) and formula (VI), R' is selected from H, C1-C5 alkyl and C5-C 11 Aryl; in formula (IV) to formula (VI), R" is substituted or unsubstituted phenyl, 1-naphthyl or diphenylmethyl, and its substituents may independently be hydrogen, C1-C6 alkyl, C2-C6 alkenyl or alkynyl, halogen, C1-C6 alkoxy or nitro.

[0037] According to the present invention, the number of substituents is not limited, for example, it can be 1, 2, 3, 4 or 5. In some specific embodiments of the present invention, when R" contains a substituent, it is preferably a phenyl substituted with the above substituent.

[0038] According to the present invention, R' is selected from H, C1-C5 straight chain alkyl, C2-C5 branched chain alkyl and C5-C8 aryl, more preferably H, C1-C3 straight chain alkyl, C2-C4 branched chain alkyl and C5-C7 aryl, further preferably H, methyl, ethyl, n-propyl, isopropyl and phenyl.

[0039] In some preferred embodiments of the present invention, the aromatic amine is selected from 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diethylaniline, 2,6-diisopropylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro-5-methylaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoroaniline, 2,4,5-trifluoroaniline. Fluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromoaniline, 2-bromo-4-methylaniline, 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromoaniline, 2,6-dibromoaniline One or more of 2,6-dibromo-4-chloroaniline, 2,6-dibromo-4-chloroaniline, 2,4,6-tribromoaniline, 2-bromo-6-chloro-4-fluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-methoxyaniline, 2-methyl-4-methoxyaniline and 4-ethoxyaniline; more preferably 2,6-diethylaniline.

[0040] In some preferred embodiments of the present invention, in step 2, the reaction is catalyzed by a strong organic acid; preferably, the strong organic acid is p-toluenesulfonic acid or formic acid, more preferably p-toluenesulfonic acid; more preferably, the ratio of the mass of the strong organic acid to the total mass of the compound represented by formula (III) and the arylamine is 0.001:1 to 0.02:1.

[0041] In some preferred embodiments of the present invention, the reaction conditions include: carrying out the reaction under reflux for a reaction time of 5 to 10 hours.

[0042] In some preferred embodiments of the present invention, the molar ratio of the compound represented by formula (III) to the arylamine is 1:1 to 1:5.

[0043] In some preferred embodiments of the present invention, in step three, the reaction temperature is 20°C to 30°C, the reaction time is 24 hours to 48 hours, and the pressure is 0.01 MPa to 0.5 MPa.

[0044] In some preferred embodiments of the present invention, in step S3, the molar ratio of the compound represented by formula (V) to the ferrous chloride is 1:1-1.2:1, preferably 1.05:1-1.1:1.

[0045] In some preferred embodiments of the present invention, in step three, the ferrous chloride is dispersed in an organic solvent.

[0046] According to the present invention, the ferrous chloride may also be ferrous chloride hydrate.

[0047] In some preferred embodiments of the present invention, in step 2 and step 3, the reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane. Preferably, the organic solvent in step 2 is toluene, and the organic solvent in step 3 is tetrahydrofuran; more preferably, the amount of the organic solvent in step 2 is 10 to 50 times the mass of the solute, and the amount of the organic solvent in step 3 is 10 to 50 times the mass of the solute.

[0048] According to the present invention, the types of the organic solvent are not limited to the types listed above. As long as it can dissolve the reactants, it can be used in the present invention and obtain equivalent technical effects.

[0049] In a specific embodiment of the present invention, in order to prepare 2-acyl-1,10-phenanthroline of formula (II), 1,10-phenanthroline and trialkylaluminum or substituted or unsubstituted benzyl lithium are first reacted in the presence of an organic solvent. The organic solvent that can be used for this purpose is selected from toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane or a mixture thereof, preferably toluene. Using these organic solvents, a 1,10-phenanthroline solution is prepared, wherein the solution concentration is 10 to 200 g / L. The reaction of 1,10-phenanthroline with trialkylaluminum or benzyl lithium is usually carried out at -60 to -80°C, preferably at -60 to -70°C. In addition, the reaction is advantageously carried out under the protection of an inert gas, preferably argon or nitrogen. 1,10-phenanthroline can use anhydrous 1,10-phenanthroline or hydrated 1,10-phenanthroline, preferably anhydrous 1,10-phenanthroline. Trialkylaluminum or benzyllithium is usually used as it is. The molar ratio of 1,10-phenanthroline to trialkylaluminum or benzyllithium is 1:0.5 to 1:4.5, preferably 1:2.0 to 1:2.6. Advantageously, the reaction is usually carried out by adding trialkylaluminum or benzyllithium to the 1,10-phenanthroline solution at the reaction temperature, for example, by dropping trialkylaluminum or benzyllithium. After the addition is completed, stirring is carried out at the reaction temperature for 18 to 28 hours, preferably 18 to 20 hours. Thereafter, the reaction mixture is heated to 20 to 40°C and stirred for another 5 to 10 hours, preferably 10 hours, to react more completely. Then water is added to hydrolyze at -60 to 0°C, preferably deionized water. For example, the reaction mixture is kept at -30°C and water is added for hydrolysis. During the hydrolysis process, bubbles emerge, and the hydrolysis reaction is carried out until bubbles no longer emerge. For more complete hydrolysis, the reaction mixture is heated to 20 to 40°C and stirred for 5 to 10 hours. Then separate the liquids and take out the organic phase. In order to separate as many desired products as possible, it is preferred to extract the inorganic phase with an organic solvent, and combine the obtained organic phase with the organic phase obtained by the previous separation. The organic solvent that can be used for this purpose can be ethyl acetate, acetone, dichloromethane or a mixture thereof, preferably dichloromethane. After the organic phase or the combined organic phase is decompressed to remove the solvent, substituted or unsubstituted peroxybenzoic acid and toluene are added and refluxed at 110°C for 1 to 10 hours, preferably 1 to 5 hours. Afterwards, filter and remove the solvent toluene under reduced pressure. Use a mixed solution of ethyl acetate: petroleum ether with a volume ratio of 1:1 to 1:5, preferably 1:2 as the eluent, and perform silica gel column chromatography to obtain a solid product, i.e., a compound of formula b. In this synthesis step, the ratio of the amount of 1,10-phenanthroline to the amount of substituted or unsubstituted peroxybenzoic acid is 1:0.5-1:30, preferably 1:1-1:2.

[0050] In this specific embodiment, step B, synthesis of 2-acyl-1,10-phenanthroline condensate ligand: reacting a compound of formula (III) with a compound of formula (IV) in the presence of p-toluenesulfonic acid as a catalyst to obtain a compound of formula (V),

[0051]

[0052] Ligand (V) is prepared by reacting the 2-acyl-1,10-phenanthroline obtained in step A with the substituted aniline, 1-naphthylamine or diphenylmethylamine represented by formula (IV) in an organic solvent free of water and oxygen in a container, wherein the amount ratio of 2-acyl-1,10-phenanthroline to the substituted aniline, 1-naphthylamine or diphenylmethylamine represented by formula (C) is 1:1 to 1:5. The organic solvent that can be used for this is selected from toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane or a mixture thereof, preferably toluene. The reaction is carried out under reflux with p-toluenesulfonic acid (p-TsOH) as a catalyst, for example, at 110°C. The ratio of the mass of p-toluenesulfonic acid to the total mass of the reactants is 0.001:1 to 0.02:1, the reaction time is 5 to 10 hours, and the reaction is monitored by TLC. After the reaction of 2-acyl-1,10-phenanthroline is completed, the solvent is removed under reduced pressure, and then a mixed solution of ethyl acetate: petroleum ether in a volume ratio of 1:1 to 1:9, preferably 1:4, is used as an eluent, and silica gel column chromatography is performed to obtain the target product, that is, the compound of formula d. The target product is characterized by nuclear magnetic resonance and mass spectrometry.

[0053] In this specific embodiment, step C, synthesis of 2-acyl-1,10-phenanthroline amine condensation iron (II) chloride complex: react the compound of formula (V) with ferrous chloride to obtain the compound represented by formula (VI), which is 2-acyl-1,10-phenanthroline amine condensation iron (II) chloride complex.

[0054]

[0055] Under the protection of an inert gas such as nitrogen, ferrous chloride is dissolved in an organic solvent free of water and oxygen to form a 0.01-0.1 g / ml ferrous chloride solution. For this purpose, the organic solvent that can be used is selected from toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane or a mixture thereof, preferably tetrahydrofuran. In order to obtain the aforementioned ferrous chloride solution, hydrated ferrous chloride (FeCl2·4H2O) can also be used instead of ferrous chloride itself. 2-acyl-1,10-phenanthroline condensate ligand d is dissolved separately in an organic solvent free of water and oxygen to form a 0.01-0.1 g / ml solution. For this purpose, the organic solvent that can be used is also selected from toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, dichloromethane or a mixture thereof, preferably tetrahydrofuran. Then, under the protection of an inert gas such as nitrogen, the two solutions are combined (for example, combined at room temperature), and stirred at room temperature for a certain period of time, for example, overnight at room temperature, under the protection of an inert gas such as nitrogen. The reaction is monitored by TLC. After the reaction is completed, the reaction product is post-treated by conventional post-treatment methods such as filtration, washing and drying to obtain a complex shown in formula II. The washing can be carried out using an organic solvent such as anhydrous ether. The complex is characterized by elemental analysis and infrared spectroscopy. In this synthesis step, the molar ratio of 2-acyl-1,10-phenanthroline condensate ligand (V) to ferrous chloride is 1:1-1.2:1, preferably 1.05:1-1.1:1.

[0056] To achieve the third purpose above, the technical solution adopted by the present invention is as follows:

[0057] A 2-acyl-1,10-phenanthroline amine condensation iron (II) complex is prepared according to any of the methods described above.

[0058] To achieve the fourth objective above, the technical solution adopted by the present invention is as follows:

[0059] An application of the above-mentioned 2-acyl-1,10-phenanthroline amine condensation iron (II) complex, wherein the 2-acyl-1,10-phenanthroline amine condensation iron (II) complex is used in olefin polymerization reaction, especially in ethylene polymerization reaction.

[0060] According to the present invention, the conditions of the oligomerization reaction involved at this time are well known to those skilled in the art, for example, the oligomerization can be carried out using the method of pressurized ethylene oligomerization as described in Chinese Patent Application Publication No. CN1850339A, which is incorporated herein by reference. For example, according to the present invention, ethylene oligomerization can be carried out as follows: an organic solvent, a co-catalyst and the 2-acyl-1,10-phenanthroline condensation amine iron (II) complex prepared by the present invention as a main catalyst are added to a reaction vessel, and then reacted for 30-100 minutes at an ethylene pressure of 0.1-30 MPa and a reaction temperature of 20-150° C. to obtain an ethylene oligomerization product. Then cooled to -10 to 10° C., a small amount of the oligomerization product is taken out and neutralized with 5% dilute hydrochloric acid and analyzed by gas chromatography (GC).

[0061] When the 2-acyl-1,10-phenanthroline condensation amine iron (II) complex prepared according to the present invention is used as a main catalyst for ethylene polymerization, a cocatalyst should be used in addition to the above main catalyst. As a cocatalyst, aluminoxane or alkyl aluminum compounds can be used. As aluminoxane, it can be C1-C4 alkyl aluminoxane, wherein the C1-C4 alkyl is straight chain or branched. Examples of aluminoxanes that can be used include methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane or isobutyl aluminoxane, etc., preferably methyl aluminoxane; as an alkyl aluminum compound, it can be a compound of the formula AlR n X m Represents, wherein each R is independently a linear or branched C1-C8 alkyl group, each X is a halogen, preferably chlorine or bromine, n is a number of 1-3, m is a number of 0-2, and m+n is equal to 3. Examples of alkyl aluminum compounds that can be used include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride or ethylaluminum dichloride, etc., preferably triethylaluminum.

[0062] The organic solvent for ethylene polymerization of the present invention is selected from toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene or dichloromethane, etc., preferably toluene. When the main catalyst and co-catalyst prepared by the present invention are used for ethylene polymerization, it is preferred that the polymerization reaction temperature is usually 20-80°C, the pressure is 1-5MPa, and the reaction time is advantageously 30-60 minutes.

[0063] In the present invention, the term "C1-C6 alkyl" refers to a saturated straight or branched hydrocarbon group containing 1 to 6 carbon atoms. As the C1-C6 alkyl, there can be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl and 2,2-dimethylbutyl; methyl, ethyl, n-propyl and isopropyl are particularly preferred.

[0064] In the present invention, the term "C2-C6 alkenyl or alkynyl" refers to an unsaturated straight or branched hydrocarbon group containing 2 to 6 carbon atoms. As C2-C6 alkenyl or alkynyl groups there may be mentioned vinyl, 1-methylvinyl, 2-methylvinyl, 2-ethylvinyl, 2,2-dimethylvinyl, 1,2-dimethylvinyl, 2-propylvinyl, 3-methylbutenyl, 2-methylbutenyl, 1-methylbutenyl, 1,2-dimethylpropenyl, 2-butylvinyl, 4-methylpentenyl, 3-methylpentenyl, 2-methylpentenyl, 1-methylpentenyl, 2,3-dimethylbutenyl, 1,3-dimethylbutenyl, 1,2-dimethylbutenyl, 3,3-dimethylbutenyl, ethynyl, propynyl, butynyl, 2-propylethynyl, 3-methylbutynyl, 2-butylethynyl, 4-methylpentynyl, 3-methylpentynyl; particular preference is given to vinyl, 1-methylvinyl and 2-ethylvinyl.

[0065] In the present invention, the term "C1-C6 alkoxy" refers to a group obtained by connecting the above-mentioned C1-C6 alkyl group to an oxygen atom. As the C1-C6 alkoxy group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, n-hexoxy and sec-hexoxy can be mentioned; methoxy and ethoxy are particularly preferred.

[0066] In the present invention, the term "halogen" refers to fluorine, chlorine, bromine and iodine, with fluorine, chlorine and bromine being particularly preferred.

[0067] In the present invention, preferably, the five substituents on the benzene ring can be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxy, ethoxy or nitro.

[0068] The ethylene polymerization reaction is carried out by using the 2-acyl-1,10-phenanthroline condensation amine iron (II) complex prepared by the method of the present invention to obtain ethylene polymerization products including C4, C6, C8, C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 etc.; the selectivity of α-olefins can reach more than 96%; after the polymerization of ethylene is completed, a small amount of reaction mixture is taken out and neutralized with 5% dilute hydrochloric acid, and the results of GC analysis show that the polymerization activity is high. In addition, the remaining reaction mixture is neutralized with ethanol solution acidified with 5% dilute hydrochloric acid. When aluminoxane is used as the co-catalyst, only a small amount of polymer is produced; when alkyl aluminum compounds are used as the co-catalyst, no polymer is produced.

[0069] Compared with the prior art, the present invention has the following advantages: benzoic acid peroxide is used to replace selenium dioxide in the prior art for oxidation reaction to prepare 2-acyl-1,10-phenanthroline; the process is simple, low toxicity and reduces the cost of catalyst preparation. In addition, compared with the method of using potassium cyanide to prepare 2-acyl-1,10-phenanthroline in the prior art, the present invention uses low-toxic and non-toxic alkyl aluminum or benzyl lithium for nucleophilic substitution reaction, and then uses benzoic acid peroxide for oxidation reaction, which also has the advantages of fewer synthesis steps, simple process, low toxicity and green, and reduced catalyst preparation cost, and has broad industrial prospects. DETAILED DESCRIPTION

[0070] The present invention is described in detail below by way of examples, but the protection scope of the present invention is not limited to the following description.

[0071] Example 1

[0072] 1. Synthesis of the complex of 2-n-butyryl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II):

[0073] Step A, synthesis of 2-n-butyryl-1,10-phenanthroline;

[0074]

[0075] Put 5.1g (28.3mmol) of 1,10-phenanthroline into a 250ml three-necked flask and dissolve it in 100ml toluene under nitrogen protection and magnetic stirring. Slowly add 13.7ml tri-n-butylaluminum (d=0.82g / ml, 56.6mmol) to the three-necked flask at -60℃ with stirring. The addition is completed in about 15 minutes. Continue stirring at this temperature for 18h, then heat to about 30℃ and continue stirring for 10h. Then cool the reaction mixture to about -30℃, slowly add 50ml of distilled water, heat to 30℃ and stir for 10h. Then separate the liquids, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 20ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. Then, add 4.2g of benzoic acid peroxide (30mmol) and 50ml of toluene and reflux at 110℃ for about 5 hours. Filter, evaporate toluene at a temperature below 10 mmHg to obtain a black viscous liquid substance. Use a mixed solution of ethyl acetate: petroleum ether = 1:2 by volume as eluent, and perform silica gel column chromatography on the obtained black viscous liquid substance to obtain a brown product weighing 3.6 g with a yield of 51.3%. The product was determined to be 2-n-butyryl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0076] Mass spectrum MS-EI:250.

[0077] NMR analysis:1 H NMR (400MHz, CDCl3): δ9.26 (dd, J=1.72, 1H); 8.33 (s, 2H); 8.27 (dd, J=1.68, 1H) 7.86 (d, J=8.8, 1H); 7. 80 (d, J=8.8, 1H); 7.68 (dd, J=5.28, 1H); 3.67 (t, J=7.24, 2H); 1.89 (m, J=7.4, 2H); 1.10 (t, J=7.4, 3H).

[0078] Step B, synthesis of the ligand 2-n-butyryl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0079]

[0080] In a 100ml two-necked flask equipped with a water separator, 0.53g (2.12mmol) of 2-n-butyryl-1,10-phenanthroline obtained in step A and 0.95g (6.36mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen are added. A condenser is installed on the water separator, 0.01g of p-toluenesulfonic acid is added, refluxed at 110°C, and reacted for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether with a volume ratio of 1:4 is used as the eluent. A bright yellow product is obtained by silica gel column chromatography, weighing 0.67g, with a yield of 83%. The product is confirmed to be 2-n-butyryl-1,10-phenanthroline and 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0081] Mass spectrum MS-EI:381.

[0082] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.25 (dd, J=2.96, 1H); 8.66 (d, J=8.36, 1H); 8.33 (d, J=8.36, 1H); 8.2 8 (dd, J=7.84, 1H); 7.85 (dd, J=9.02, 2H); 7.65 (dd, J=4.36, 1H); 7.15 (d, J=7.52, 2H); 7.06 (t , J=7.04, 1H); 3.01 (t, J=7.84, -CNCH2CH2CH3,2H); 2.40 (m, J=7.52, phCH2CH3,2H); 1.58 (m, J=7.44, CH3CH2CH2-, 2H); 1.20 (t, J=7.30, phCH2CH3, 6H); 0.90 (t, J=7.32, CH3CH2CH2-, 3H).

[0083] Elemental analysis: C 26H 27 N3 (381.51), theoretical value: C, 81.85; H, 7.13; N, 11.01. Measured value: C, 81.36; H, 7.23; N, 10.55.

[0084] Step C, synthesis of 2-n-butyryl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0085]

[0086] Under nitrogen protection, 0.16g (1.25mmol) of ferrous chloride was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.52g (1.36mmol) of 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution appeared gray-black. Stir overnight under nitrogen protection at room temperature. Monitor using TLC until the ligand of 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline basically disappeared. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid. The solid was determined to be 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride.

[0087] Elemental analysis: C 26 H 27 Cl2FeN3 (508.26), theoretical value: C, 61.44; H, 5.35; N, 8.27. Measured value: C, 61.79; H, 5.60; N, 8.13.

[0088] 2. Ethylene polymerization

[0089] Toluene, 1.33 ml of methylaluminoxane (2.0 mmol) toluene solution (concentration of 1.5 mol / l) and 8 ml of the main catalyst 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride (2.0 μmol) toluene solution were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 1000 (molar ratio). When the polymerization temperature reached 40°C, ethylene was added to the reactor, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid and then analyzed by GC: the polymerization activity was 2.75×10 7 g·mol -1 (Fe)·h -1 The oligomer contents are C4: 24.52%, C6~C 10:55.48%, C6~C 18 :70.99% (including 96.6% linear α-olefins), C 20 ~C 28 : 4.49%, K value 0.63. The remaining mixture was neutralized with 5% hydrochloric acid ethanol solution to obtain a white waxy polymer with a polymerization activity of 4.13×10 4 g·mol -1 ·h -1 .

[0090] Example 2-47

[0091] The catalyst was prepared by repeating steps A, B and C in Example 1, except that the 2,6-diethylaniline in step B of Example 1 was replaced with the following substituted anilines in sequence: 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-Ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diisopropylaniline, 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro-5-methylaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3 ,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromoaniline, 2-bromo-4-methylaniline, 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromoaniline, 2,6-dibromo-4-methylaniline, 2,6-dibromo-4-chloroaniline, 2,4,6-tribromoaniline, 2-bromo-6-chloro-4-fluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-methoxybenzene Amine, 2-methyl-4-methoxyaniline and 4-ethoxyaniline are prepared in step B to obtain 2-n-butyryl-1,10-phenanthroline condensate ligands formed by 2-n-butyryl-1,10-phenanthroline and the aforementioned substituted anilines, and these ligand products are confirmed by nuclear magnetic resonance, mass spectrometry and elemental analysis, and in step C to obtain complexes of the aforementioned 2-n-butyryl-1,10-phenanthroline condensate ligands and ferrous chloride, and these complexes are confirmed by elemental analysis.

[0092] Embodiment 48

[0093] Repeat step A in Example 1.

[0094] Step B of Example 1 was repeated except that 1-naphthylamine was used instead of 2,6-diethylaniline to obtain 2-n-butyryl-1,10-phenanthroline 1-naphthylamine ligand, which was confirmed by NMR and mass spectrometry.

[0095] Repeat step C of Example 1, except that 2-n-butyryl-1,10-phenanthroline 1-naphthylamine is used instead of 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline to obtain 2-n-butyryl-1,10-phenanthroline 1-naphthylamine chloride iron (II), and the complex is confirmed by elemental analysis.

[0096] Embodiment 49

[0097] Repeat step A in Example 1.

[0098] Step B of Example 1 was repeated except that diphenylmethylamine was used instead of 2,6-diethylaniline to obtain 2-n-butyryl-1,10-phenanthroline diphenylmethylamine ligand, which was confirmed by NMR and mass spectrometry.

[0099] Repeat step C of Example 1, except that 2-n-butyryl-1,10-phenanthroline diphenylamine is used instead of 2-n-butyryl-1,10-phenanthroline 2,6-diethylaniline to obtain 2-n-butyryl-1,10-phenanthroline diphenylamine iron (II) chloride, and the complex is confirmed by elemental analysis.

[0100] Embodiment 50

[0101] 1. Synthesis of the complex of 2-acetyl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II):

[0102] Step A, synthesis of 2-acetyl-1,10-phenanthroline;

[0103]

[0104] Put 5.1g (28.3mmol) of 1,10-phenanthroline into a 250ml three-necked flask and dissolve it in 100ml toluene under nitrogen protection and magnetic stirring. Slowly add 10ml triethylaluminum (70.8mmol) to the three-necked flask under stirring at -60℃. The addition is completed in about 15 minutes. Continue stirring at this temperature for 18h, then heat it to about 30℃ and continue stirring for 10h. Then cool the reaction mixture to about -30℃, slowly add 50ml distilled water, and then heat it to 30℃ and stir for 10h. Then separate the liquids, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 20ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. Add 4.2g peroxybenzoic acid (30mmol), 50ml toluene and reflux at 110℃ for about 5 hours. Filter and evaporate toluene at less than 10mmHg to obtain a black viscous liquid substance. The obtained black viscous liquid substance was subjected to silica gel column chromatography using a mixed solution of ethyl acetate: petroleum ether = 1:2 as eluent to obtain a brown product weighing 3.51 g with a yield of 55.0%. The product was determined to be 2-acetyl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0105] Mass spectrum MS-EI: 222.

[0106] NMR analysis: 1 H NMR (300MHz, CDCl3): δ9.26 (d, J=3.9Hz, 1H); 8.37 (s, 2H); 8.29 (d, J=8.1Hz, 1H); 8.7 (dd, J=8.7Hz, 2H); 7.69 (dd, J=7.8Hz, 1H); 3.09 (s, 3H, CH3).

[0107] Step B, synthesis of the ligand 2-acetyl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0108]

[0109] In a 100ml two-necked flask equipped with a water separator, 0.47g (2.12mmol) of 2-acetyl-1,10-phenanthroline obtained in step A and 0.95g (6.36mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen are added. A condenser is installed on the water separator, 0.01g of p-toluenesulfonic acid is added, refluxed at 110°C, and reacted for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether = 1:4 (volume ratio) is used as an eluent. A bright yellow product is obtained by silica gel column chromatography, weighing 0.66g, with a yield of 83.0%. The product is confirmed to be 2-acetyl-1,10-phenanthroline and 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0110] Mass spectrum MS-EI: 353.

[0111] NMR analysis: 1 H NMR (300MHz, CDCl3): δ9.25 (dd, J=3.0Hz, 1H); 8.80 (d, J=8.3Hz, 1H); 8.35 (d, J=8.3Hz, 1H); 8.27 (dd, J=7.8Hz, 1H); 7.86 (s, 2H); 7.66 (m, 1H); 7.15 (d, J=7.6Hz, 2H); 6.96 (t, J=7.5Hz, 1H); 2.58 (s, 3H, CH3); 2.43 (m, 4H, CH2CH3), 1.16 (t, J=7.5Hz, 6H, CH2CH3).

[0112] 13 C NMR (75MHz, CDCl3): δ167.8, 156.2, 150.7, 148.0, 146.4, 145.2, 136.5, 131. 1, 129.5, 129.0, 127.5, 126.5, 126.0, 123.4, 122.9, 120.8, 24.6, 17.3, 13.7.

[0113] Elemental analysis: C 24 H 23 N3 (353.46), theoretical value: C, 81.55; H, 6.56; N, 11.89. Measured value: C, 80.88; H, 6.59; N, 11.78.

[0114] Step C, synthesis of 2-acetyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0115]

[0116] Under nitrogen protection, 0.16g (1.25mmol) of ferrous chloride was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.48g (1.36mmol) of 2-acetyl-1,10-phenanthroline condensed 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution was gray-black. Stir overnight under nitrogen protection at room temperature. Use TLC to monitor until the 2-acetyl-1,10-phenanthroline condensed 2,6-diethylaniline ligands basically disappeared. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid. The solid was determined to be 2-acetyl-1,10-phenanthroline condensed 2,6-diethylaniline iron (II) chloride, and the elemental analysis results are as follows.

[0117] Elemental analysis: C 24 H 23 Cl2FeN3 (480.22), theoretical value: C, 60.09; H, 4.90; N, 8.76. Measured value: C, 60.03; H, 4.83; N, 8.75.

[0118] 2. Ethylene polymerization

[0119] Toluene and 0.53 ml triethylaluminum toluene solution (concentration 0.74 mol / l) and 8 ml toluene solution of the main catalyst 2-acetyl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride (2.0 μmol) were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 196. When the polymerization temperature reached 40 ° C, ethylene was added to the reactor, and the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then GC analysis was performed: the polymerization activity was 2.01×10 6 g·mol -1 (Fe)·h -1 The oligomer contents are C412.2%, C6~C 10 64.9%, C6~C 18 87.5% (including 98.1% linear α-olefins), C 20 ~C 28 0.30%, K value 0.57. The remaining mixture was neutralized with 5% ethanol solution acidified with hydrochloric acid, but no polymer was obtained.

[0120] Embodiment 51

[0121] 1. Synthesis of the complex of 2-n-propionyl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II)

[0122] Step A, synthesis of 2-n-propionyl-1,10-phenanthroline;

[0123]

[0124] Put 5.1g (28.3mmol) of 1,10-phenanthroline into a 250ml three-necked flask and dissolve it with 100ml toluene under nitrogen protection and magnetic stirring. Slowly add 13.5ml tri-n-propylaluminum (d=0.82g / ml, 70.9mmol) to the three-necked flask at -60℃ with stirring. The addition is completed in about 15 minutes. Continue stirring at this temperature for 18h, then heat to about 30℃ and continue stirring for 10h. Then cool the reaction mixture to about -30℃, slowly add 50ml of distilled water, heat to 30℃ and stir for 10h. Then separate the liquids, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 20ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. Then add 4.2g of benzoic acid peroxide (30mmol) and 50ml of toluene and reflux at 110℃ for about 5 hours. Filter, distill off toluene at a temperature below 10 mmHg to obtain a black viscous liquid substance. Use a mixed solution of ethyl acetate: petroleum ether = 1:2 by volume as eluent, and perform silica gel column chromatography on the obtained black viscous liquid substance to obtain a brown product weighing 3.72 g with a yield of 56.2%. The product was determined to be 2-n-propionyl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0125] Mass spectrum MS-EI: 236.

[0126] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.26 (dd, J=1.72, 1H); 8.33 (s, 2H); 8.27 (dd, J=1.68, 1H) 7.86 (d, J=8 .8, 1H); 7.80 (d, J=8.8, 1H); 7.68 (dd, J=5.28, 1H); 3.67 (m, J=7.24, 2H); 1.10 (t, J=7.4, 3H).

[0127] Step B, synthesis of the ligand 2-n-propionyl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0128]

[0129] In a 100ml two-necked flask equipped with a water separator, 0.50g (2.12mmol) of 2-n-propionyl-1,10-phenanthroline obtained in step A and 0.95g (6.36mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen are added. A condenser is installed on the water separator, 0.01g of p-toluenesulfonic acid is added, refluxed at 110°C, and reacted for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether = 1:4 (volume ratio) is used as the eluent. A bright yellow product is obtained by silica gel column chromatography, weighing 0.70g, with a yield of 83%. The product is confirmed to be 2-n-propionyl-1,10-phenanthroline 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0130] Mass spectrum MS-EI:367.

[0131] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.25 (dd, J=2.96, 1H); 8.66 (d, J=8.36, 1H); 8.33 (d, J=8.36 , 1H); 8.28 (dd, J = 7.84, 1H); 7.85 (dd, J = 9.02, 2H); 7.65 (dd, J = 4.36, 1H); 7.15 (d, J=7.52, 2H); 7.06 (t, J=7.04, 1H); 3.01 (t, J=7.84, -CNCH2CH3, 2H); 2.40 (m, J=7.5 2, phCH2CH3, 2H); 1.20 (t, J=7.30, phCH2CH3, 6H); 0.90 (t, J=7.32, CH3CH2CN, 3H).

[0132] Elemental analysis: C 25 H 25 N3 (367.49), theoretical value: C, 81.71; H, 6.86; N, 11.43. Measured value: C, 81.66; H, 6.87; N, 11.47.

[0133] Step C, synthesis of 2-n-propionyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0134]

[0135] Under nitrogen protection, 0.16g (1.25mmol) of ferrous chloride was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.50g (1.36mmol) of 2-n-propionyl-1,10-phenanthroline 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution was gray-black. Stir overnight under nitrogen protection at room temperature. Use TLC to monitor until the ligand of 2-n-propionyl-1,10-phenanthroline 2,6-diethylaniline basically disappears. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid. The solid was determined to be 2-n-propionyl-1,10-phenanthroline 2,6-diethylaniline chloride iron (II), and the elemental analysis results are as follows.

[0136] Elemental analysis: C 25 H 25 Cl2FeN3 (494.24), theoretical value: C, 60.75; H, 5.10; N, 8.50. Measured value: C, 60.71; H, 5.00; N, 8.53.

[0137] 2. Ethylene polymerization

[0138] Toluene, 2.66 ml of methylaluminoxane (4.0 mmol) toluene solution (concentration of 1.5 mol / l) and 8 ml of the main catalyst 2-n-propionyl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride (2.0 μmol) toluene solution were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 2000 (molar ratio). When the polymerization temperature reached 40°C, ethylene was added to the reactor, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid and then analyzed by GC: the polymerization activity was 1.51×10 7 g·mol -1 (Fe)·h -1 The oligomer contents are C4: 22.39%, C6~C 10 :61.03%, C6~C 18 :75.78% (including 96.5% linear α-olefins), C 20 ~C 28 : 1.83%, K value 0.64. The remaining mixture was neutralized with 5% hydrochloric acid ethanol solution to obtain a small amount of white waxy polymer with a polymerization activity of 4.75×10 4 g·mol -1 ·h -1 .

[0139] Embodiment 52

[0140] 1. Synthesis of the complex of 2-isobutyryl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II):

[0141] Step A, synthesis of 2-isobutyryl-1,10-phenanthroline;

[0142]

[0143] Put 5.1g (28.3mmol) of 1,10-phenanthroline into a 250ml three-necked flask and dissolve it with 100ml toluene under nitrogen protection and magnetic stirring. Slowly add 13.7ml triisobutylaluminum (d=0.82g / ml, 56.6mmol) to the three-necked flask at -60℃ with stirring. The addition is completed in about 15 minutes. Continue stirring at this temperature for 18h, then heat to about 30℃ and continue stirring for 10h. Then cool the reaction mixture to about -30℃, slowly add 50ml of distilled water, heat to 30℃ and stir for 10h. Then separate the liquids, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 20ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. Then, add 4.2g of benzoic acid peroxide (30mmol) and 50ml of toluene and reflux at 110℃ for about 5 hours. Filter, distill off toluene at a temperature below 10 mmHg to obtain a black viscous liquid substance. Use a mixed solution of ethyl acetate: petroleum ether = 1:2 by volume as eluent, and perform silica gel column chromatography on the obtained black viscous liquid substance to obtain a brown product weighing 4.15 g with a yield of 59.0%. The product was determined to be 2-isobutyryl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0144] Mass spectrum MS-EI:250.

[0145] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.26 (dd, J=1.72, 1H); 8.33 (s, 2H); 8.27 (dd, J=1.68, 1H) 7.86 (d, J=8 .8, 1H); 7.80 (d, J=8.8, 1H); 7.68 (dd, J=5.28, 1H); 3.47 (m, J=7.24, 1H); 1.10 (d, J=7.4, 6H).

[0146] Step B, synthesis of the ligand 2-isobutyryl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0147]

[0148] In a 100ml two-necked flask equipped with a water separator, 0.53g (2.12mmol) of 2-isobutyryl-1,10-phenanthroline obtained in step A and 0.95g (6.36mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen are added. A condenser is installed on the water separator, 0.01g of p-toluenesulfonic acid is added, refluxed at 110°C, and reacted for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether = 1:4 (volume ratio) is used as the eluent. A bright yellow product is obtained by silica gel column chromatography, weighing 0.68g, with a yield of 81%. The product is confirmed to be 2-isobutyryl-1,10-phenanthroline and 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0149] Mass spectrum MS-EI:381.

[0150] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.25 (dd, J=2.96, 1H); 8.66 (d, J=8.36, 1H); 8.33 (d, J=8.36, 1H); 8.28 (dd, J=7.84, 1H); 7.85 (dd, J=9.02, 2H); 7.65 (dd, J=4.36, 1H); 7.15 (d, J=7 .52, 2H); 7.06 (t, J = 7.04, 1H); 3.01 (m, J = 7.84, -CNCH (CH3) 2, 1H); 2.40 (m, J = 7.52, phCH2CH3, 4H); 1.58 (d, J=7.44, -CNCH(CH3-)2, 6H); 1.20 (t, J=7.30, phCH2CH3, 6H).

[0151] Elemental analysis: C 26 H 27 N3 (381.51), theoretical value: C, 81.85; H, 7.13; N, 11.01. Measured value: C, 81.36; H, 7.23; N, 10.55.

[0152] Step C, synthesis of 2-isobutyryl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0153]

[0154] Under nitrogen protection, 0.16g (1.25mmol) of ferrous chloride was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.52g (1.36mmol) of 2-isobutyryl-1,10-phenanthroline 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution was gray-black. Stir overnight under nitrogen protection at room temperature. Use TLC monitoring until the 2-isobutyryl-1,10-phenanthroline 2,6-diethylaniline ligands basically disappeared. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid. The solid was determined to be 2-isobutyryl-1,10-phenanthroline 2,6-diethylaniline chloride iron (II), and the elemental analysis results are as follows.

[0155] Elemental analysis: C 26 H 27 Cl2FeN3 (508.26), theoretical value: C, 61.44; H, 5.35; N, 8.27. Measured value: C, 61.79; H, 5.60; N, 8.13.

[0156] 2. Ethylene polymerization

[0157] Toluene, 1.33 ml of methylaluminoxane (2.0 mmol) toluene solution (concentration of 1.5 mol / l) and 8 ml of the main catalyst 2-isobutyryl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride (2.0 μmol) toluene solution were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 1000 (molar ratio). When the polymerization temperature reached 40°C, ethylene was added to the reactor, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid and then analyzed by GC: the polymerization activity was 2.78×10 7 g·mol -1 (Fe)·h -1 The oligomer contents are C4: 24.52%, C6~C 10 :55.92%, C6~C 18 :72.38% (including 97.1% linear α-olefins), C 20 ~C 28 : 3.10%, K value 0.63. The remaining mixture was neutralized with 5% hydrochloric acid ethanol solution to obtain a white waxy polymer with a polymerization activity of 4.13×10 4 g·mol -1 ·h -1 .

[0158] Embodiment 53

[0159] 1. Synthesis of the complex of 2-formyl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II)

[0160] Step A, synthesis of 2-formyl-1,10-phenanthroline;

[0161]

[0162] Put 5.1g (28.3mmol) of 1,10-phenanthroline into a 250ml three-necked flask and dissolve it with 100ml toluene under nitrogen protection and magnetic stirring. Slowly add 3ml of trimethylaluminum (d=0.75g / ml, 31.3mmol) to the three-necked flask at -60℃ with stirring. The addition is completed in about 15 minutes. Continue stirring at this temperature for 18h, then heat it to about 30℃ and continue stirring for 10h. Then cool the reaction mixture to about -30℃, slowly add 50ml of distilled water, heat it to 30℃ and stir for 10h. Then separate the liquids, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 20ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. Then add 4.2g of benzoic acid peroxide (30mmol) and 50ml of toluene and reflux at 110℃ for about 5 hours. Filter, evaporate toluene at a temperature below 10 mmHg to obtain a black viscous liquid substance. Use a mixed solution of ethyl acetate: petroleum ether = 1:2 by volume as eluent, and perform silica gel column chromatography on the obtained black viscous liquid substance to obtain a brown product weighing 2.60 g with a yield of 49.0%. The product was determined to be 2-formyl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0163] Mass spectrum MS-EI:208.

[0164] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.26 (d, J=3.9Hz, 1H); 9.16 (s, 1H); 8.37 (s, 2H); 8.29 (d, J=8.1Hz, 1H); 8.7 (dd, J=8.7Hz, 2H); 7.69 (dd, J=7.8Hz, 1H).

[0165] Step B, synthesis of the ligand 2-formyl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0166]

[0167] In a 100ml two-necked flask equipped with a water separator, add 0.44g (2.12mmol) of 2-formyl-1,10-phenanthroline obtained in step A and 0.95g (6.36mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen. The water separator is equipped with a condenser, and 0.01g of p-toluenesulfonic acid is added to reflux at 110°C and react for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether = 1:4 (volume ratio) is used as an eluent. Silica gel column chromatography obtains a bright yellow product weighing 0.51g with a yield of 81%. The product is confirmed to be 2-formyl-1,10-phenanthroline condensed with 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0168] Mass spectrum MS-EI:339.

[0169] NMR analysis: 1 H NMR (400MHz, CDCl3): δ9.25 (dd, J=3.0Hz, 1H); 9.16 (s, 1H); 8.80 (d, J=8.3Hz, 1H); 8.35 (d, J=8.3Hz, 1H); 8.27 (dd, J=7.8Hz, 1H ); 7.86 (s, 2H); 7.66 (m, 1H); 7.15 (d, J = 7.6Hz, 2H); 6.96 (t, J = 7.5Hz, 1H); 2.43 (m, 4H, CH2CH3), 1.16 (t, J = 7.5Hz, 6H, CH2CH3).

[0170] Elemental analysis: C 24 H 23 N3 (353.46), theoretical value: C, 81.38; H, 6.24; N, 12.38. Measured value: C, 81.48; H, 6.59; N, 12.39.

[0171] Step C, synthesis of 2-formyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0172]

[0173] Under nitrogen protection, 0.16g (1.25mmol) of ferrous chloride was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.46g (1.36mmol) of 2-formyl-1,10-phenanthroline condensed 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution was gray-black. Stir overnight under nitrogen protection at room temperature. Use TLC to monitor until the ligand of 2-formyl-1,10-phenanthroline condensed 2,6-diethylaniline is basically gone. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid with a yield of 97%. The solid was determined to be 2-formyl-1,10-phenanthroline condensed 2,6-diethylaniline iron (II) chloride, and the elemental analysis results are as follows.

[0174] Elemental analysis: C 24 H 23 Cl2FeN3 (480.22), theoretical value: C, 59.26; H, 4.54; N, 9.01. Measured value: C, 59.38; H, 4.83; N, 8.92.

[0175] 2. Ethylene polymerization

[0176] Toluene, 1.33 ml of methylaluminoxane (2.0 mmol) toluene solution (concentration of 1.5 mol / l) and 8 ml of the main catalyst 2-formyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II) (2.0 μmol) toluene solution were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 1000 (amount ratio of substance). When the polymerization temperature reached 40°C, ethylene was charged into the reactor, and the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then GC analysis was performed: the polymerization activity was 1.71×10 6 g·mol -1 (Fe)·h -1 The oligomer contents are C4: 27.69%, C6~C 10 :54.90%, C6~C 18 :70.02% (including 98.4% linear α-olefins), C 20 ~C 28 : 2.29%, K value 0.59. The remaining mixture was neutralized with 5% hydrochloric acid ethanol solution to obtain a white waxy polymer with a polymerization activity of 3.90×10 3 g·mol -1 ·h -1 .

[0177] Embodiment 54

[0178] 1. Synthesis of the complex of 2-benzoyl-1,10-phenanthroline chloride and 2,6-diethylaniline with iron (II):

[0179] Step A, synthesis of 2-benzoyl-1,10-phenanthroline;

[0180]

[0181] 5.1 g (0.03 mol) of 1,10-phenanthroline was added to a 250 ml three-necked flask and dissolved in 100 ml of toluene under nitrogen protection and magnetic stirring. 60 ml of 1.2 M n-hexane solution (0.07 mol) of benzyl lithium was slowly added to the three-necked flask under stirring at -60 ° C. The addition was completed in about 15 minutes. Stirring was continued at this temperature for 18 hours, and then the temperature was raised to about 30 ° C and stirred for 10 hours. Then the reaction mixture was cooled to about -10 ° C, 50 ml of distilled water was slowly added thereto, and the temperature was raised to 30 ° C and stirred for 10 hours. Separate the liquid, take out the organic phase, extract the inorganic phase with dichloromethane three times, each time with 50 ml of dichloromethane, and combine the organic phases. Remove the solvent under reduced pressure. After that, add 4.2 g of benzoic acid peroxide (30 mmol) and 50 ml of toluene and reflux at 110 ° C for about 5 hours. Filter, evaporate toluene at a temperature below 10 mmHg to obtain a black viscous liquid substance. Use a mixed solution of ethyl acetate: petroleum ether = 1:2 as eluent, and perform silica gel column chromatography on the obtained black viscous liquid substance to obtain a brown product weighing 4.8 g with a yield of 61.02%. The product was determined to be 2-benzoyl-1,10-phenanthroline by nuclear magnetic resonance and mass spectrometry analysis.

[0182] Mass spectrum MS-EI: 284.

[0183] NMR analysis: 1 H NMR (300MHz, CDCl3): δ9.18 (dd, J=2.1Hz, 1H); 8.44 (s, 1H); 8.41 (s, 1H); 8.39 (d, J=3. 3Hz, 1H); 8.27~8.23(m, 2H); 7.86~7.83(m, 2H); 7.66~7.58(m, 2H); 7.54~7.49(m, 2H). 13 C NMR (100MHz, CDCl3): δ193.2,154.8,150.7,146.3,144.8,136.9,136.1,135.9,133.1,131.8,129.5,129.0,128.4,128.2,126.0,123.1,122.9.

[0184] Elemental analysis: C 19 H 12 N2O (284.31): Theoretical value: C, 80.27; H, 4.25; N, 9.85; Measured value: C, 80.24; H, 4.24; N, 9.83.

[0185] Step B, synthesis of the ligand 2-benzoyl-1,10-phenanthroline condensed with 2,6-diethylaniline;

[0186]

[0187] In a 100ml two-necked flask equipped with a water separator, add 0.47g (1.65mmol) of 2-benzoyl-1,10-phenanthroline obtained in step A and 0.74g (4.96mmol) of 2,6-diethylaniline (the molar ratio is 1:3) and 35ml of toluene free of water and oxygen. The water separator is equipped with a condenser, and 0.01g of p-toluenesulfonic acid is added to reflux at 110°C and react for 6 hours. The solvent is removed under reduced pressure, and a mixed solution of ethyl acetate: petroleum ether = 1:4 (volume ratio) is used as an eluent. Silica gel column chromatography obtains a bright yellow product weighing 0.72g with a yield of 81%. The product is confirmed to be 2-benzoyl-1,10-phenanthroline condensed with 2,6-diethylaniline by nuclear magnetic resonance, mass spectrometry and elemental analysis.

[0188] Mass spectrum MS-EI:415.

[0189] NMR analysis: 1 H NMR (300MHz, CDCl3): δ9.17~6.80 (m, 15H); 2.85~2.71 (m, 2H); 2.56~2.44 (m, 2H); 1.17 (t, J=7.5Hz, 6H). 13 C NMR (100MHz, CDCl3): δ165.1, 155.5, 150.5, 147.7, 146.3, 145.6, 137.9, 136.5, 135.9, 135.7, 131.9, 130.8, 1 30.1, 129.5, 129.0, 128.3, 127.9, 127.5, 127.3, 126.3, 125.6, 125.1, 123.7, 123.1, 122.0, 24.9, 24.6, 13.5.

[0190] Elemental analysis: C 31 H 29 N3 (415.53.46), theoretical value: C, 83.82; H, 6.06; N, 10.11. Measured value: C, 83.56; H, 6.10; N, 9.98.

[0191] Step C, synthesis of 2-benzoyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II);

[0192]

[0193] Under nitrogen protection, 0.25g (1.25mmol) of ferrous chloride tetrahydrate was dissolved in 20ml of tetrahydrofuran free of water and oxygen in a two-necked flask. Separately, 0.48g (1.36mmol) of 2-benzoyl-1,10-phenanthroline condensed 2,6-diethylaniline obtained in step B was dissolved in 20ml of tetrahydrofuran free of water and oxygen. Then the two solutions were combined under nitrogen protection at room temperature. The reaction proceeded immediately and the solution was gray-black. Stir overnight under nitrogen protection at room temperature. Use TLC monitoring until the 2-benzoyl-1,10-phenanthroline condensed 2,6-diethylaniline ligands basically disappeared. Filter and wash with anhydrous ether. Vacuum dry to obtain a silver-gray solid. The solid was determined to be 2-benzoyl-1,10-phenanthroline condensed 2,6-diethylaniline iron (II) chloride, and the elemental analysis results are as follows.

[0194] Elemental analysis: C 29 H 25 Cl2FeN3 (542.28), theoretical value: C, 64.23; H, 4.65; N, 7.75. Measured value: C, 64.04; H, 4.70; N, 7.66.

[0195] The total yield of the target product 2-benzoyl-1,10-phenanthroline chloride condensed with 2,6-diethylaniline iron (II) obtained by the above steps is more than 20.0%.

[0196] 2. Ethylene polymerization

[0197] Toluene and 0.53 ml (1 mmol) triethylaluminum toluene solution (concentration 0.74 mol / l) and 8 ml main catalyst 2-benzoyl-1,10-phenanthroline 2,6-diethylaniline iron (II) chloride (2.0 μmol) toluene solution were added to a 300 ml stainless steel autoclave to make the total volume 100 ml, Al / Fe = 196. When the polymerization temperature reached 40 ° C, ethylene was charged into the reactor, and the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. After that, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid, and then GC analysis was performed: the polymerization activity was 2.12×10 6 g·mol -1 (Fe)·h -1 The oligomer contents are C4 12.6%, C6~C 10 64.9%, C6~C 1887.1% (including 98.1% linear α-olefins), C 20 ~C 28 0.30%, K value 0.58. The remaining mixture was neutralized with 5% ethanol solution acidified with hydrochloric acid, but no polymer was obtained.

[0198] Embodiment 55

[0199] Synthesis of intermediate 2,6-diacetylpyridine:

[0200]

[0201] 5.4 g (40 mmol) of 2,6-diethylpyridine was added to a 250 ml three-necked flask, and 60 ml of toluene and 13.8 g of benzoic acid peroxide were added, and refluxed at 110°C for about 5 hours. Toluene was evaporated at less than 10 mmHg to obtain a black viscous liquid substance. A mixed solution of ethyl acetate and petroleum ether with a volume ratio of 1:2 was used as an eluent, and the obtained black viscous liquid substance was subjected to silica gel column chromatography to obtain a white product weighing 2.7 g with a yield of 40.0%. The product was determined to be 2,6-diacetylpyridine by nuclear magnetic resonance and mass spectrometry analysis.

[0202] Mass spectrum MS-EI:163.

[0203] NMR analysis: 1 H NMR (400MHz, CDCl3): δ8.22 (d, 2H); 8.00 (t, 1H); 2.80 (s, 1H).

[0204] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for preparing an N-ortho-acyl-substituted nitrogen-containing heterocyclic compound, comprising: Allowing an N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound to undergo an oxidation reaction with peroxybenzoic acid represented by formula (I) in an organic solvent to generate an N-ortho-acyl-substituted nitrogen-containing heterocyclic compound; In formula (I), R 1 -R 5 are the same or different, each independently selected from H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, C1-C6 alkoxy and nitro, preferably R 1 -R 5 Both are H.

2. The method according to claim 1, characterized in that The molar ratio of the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound to the benzoic acid peroxide is 1:0.5 to 1:30, preferably 1:1 to 1:

2.

3. The method according to claim 1 or 2, characterized in that: The hydrocarbon group in the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound is selected from C1-C6 alkyl and C6-C 12 Aryl, preferably C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl and C6-C9 aryl, more preferably C1-C4 straight-chain alkyl, C3-C5 branched-chain alkyl and C6-C8 aryl, further preferably methyl, ethyl, propyl, n-butyl, isobutyl and benzyl; more preferably, the N-ortho-hydrocarbon-substituted nitrogen-containing heterocyclic compound is 2,6-diethylpyridine or a compound represented by formula (II); In formula (II), R has the same meaning as the above hydrocarbon group.

4. The method according to any one of claims 1 to 3, characterized in that The organic solvent is selected from one or more of toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene, chlorobenzene and dichloromethane.

5. The method according to any one of claims 1 to 4, characterized in that The oxidation reaction is performed under reflux at the boiling point of the organic solvent; and / or the oxidation reaction time is 1 hour to 10 hours, preferably 1 hour to 5 hours.

6. A method for preparing a chlorinated 2-acyl-1,10-phenanthroline amine condensation iron (II) complex, comprising: Step 1: preparing a compound represented by formula (III) by the method described in any one of claims 1 to 5; Step 2: reacting the compound represented by formula (III) with the arylamine represented by formula (IV) to generate the compound represented by formula (V); Step 3: reacting the compound represented by formula (V) with ferrous chloride to generate a chlorinated 2-acyl-1,10-phenanthroline amine condensation iron (II) complex represented by formula (VI); R"NH2 Formula (IV) In formula (III), formula (V) and formula (VI), R' is selected from H, C1-C5 alkyl and C5-C 11 The aryl group is preferably H, C1-C5 straight-chain alkyl, C2-C5 branched-chain alkyl and C5-C8 aryl group, more preferably H, C1-C3 straight-chain alkyl, C2-C4 branched-chain alkyl and C5-C7 aryl group, and further preferably H, methyl, ethyl, n-propyl, isopropyl and phenyl group; in formula (IV) to formula (VI), R" is substituted or unsubstituted phenyl, 1-naphthyl or diphenylmethyl, and its substituents can independently be hydrogen, C1-C6 alkyl, C2-C6 alkenyl or alkynyl, halogen, C1-C6 alkane Oxy or nitro, preferably, the arylamine is selected from 2-methylaniline, 3-methylaniline, 4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,6-trimethylaniline, 4-bromo-2,6-dimethylaniline, 2-ethylaniline, 2-ethyl-6-methylaniline, 2-isopropylaniline, 2,6-diethylaniline, 2,6-diisopropylaniline. , 2-fluoroaniline, 2-fluoro-4-methylaniline, 2-fluoro-5-methylaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoroaniline, 2,4,5-trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4,5,6-pentafluoroaniline, 3-chloroaniline, 2,6-dichloroaniline, 2,3,4-trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2-bromoaniline, 2-bromo- One or more of 4-methylaniline, 2-bromo-4-fluoroaniline, 4-bromo-2-fluoroaniline, 2,6-dibromoaniline, 2,6-dibromo-4-methylaniline, 2,6-dibromo-4-chloroaniline, 2,4,6-tribromoaniline, 2-bromo-6-chloro-4-fluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2-bromo-4,6-difluoroaniline, 3-nitroaniline, 4-methoxyaniline, 2-methyl-4-methoxyaniline and 4-ethoxyaniline; more preferably 2,6-diethylaniline.

7. The method according to claim 6, characterized in that In step 2, the reaction is catalyzed by a strong organic acid; preferably, the strong organic acid is p-toluenesulfonic acid or formic acid, more preferably p-toluenesulfonic acid; more preferably, the ratio of the mass of the strong organic acid to the total mass of the compound represented by formula (III) and the arylamine is 0.001:1 to 0.02:1; The reaction conditions include: carrying out the reaction under reflux for 5 to 10 hours; and / or The molar ratio of the compound represented by the formula (III) to the arylamine is 1:1 to 1:

5.

8. The preparation method according to claim 6 or 7, characterized in that: In step three, The reaction temperature is 20°C to 30°C, the reaction time is 24 hours to 48 hours, and the pressure is 0.01MPa to 0.5MPa; The molar ratio of the compound represented by formula (V) to the ferrous chloride is 1:1-1.2:1, preferably 1.05:1-1.1:1; and / or The ferrous chloride is dispersed in an organic solvent.

9. The method according to any one of claims 6 to 8, characterized in that: In step 2 and step 3, the reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of toluene, cyclohexane, ether, tetrahydrofuran, ethanol, benzene, xylene and dichloromethane. Preferably, the organic solvent in step 2 is toluene, and the organic solvent in step 3 is tetrahydrofuran; more preferably, the amount of the organic solvent in step 2 is 10 to 50 times the mass of the solute, and the amount of the organic solvent in step S3 is 10 to 50 times the mass of the solute.

10. A 2-acyl-1,10-phenanthroline amine condensation iron (II) complex, which is prepared according to the method according to any one of claims 6 to 9.

11. Use of the 2-acyl-1,10-phenanthroline amine condensation iron (II) complex according to claim 10, characterized in that: The 2-acyl-1,10-phenanthroline amine iron (II) complex is used in olefin polymerization reaction, especially in ethylene polymerization reaction.

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