CN113583058B - Iron complex and preparation method thereof, iron catalyst and application thereof, and polybutadiene and preparation method thereof - Google Patents
Iron complex and preparation method thereof, iron catalyst and application thereof, and polybutadiene and preparation method thereof Download PDFInfo
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
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- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
Abstract
The invention relates to the field of polymer preparation, and discloses an iron complex and a preparation method thereof, an iron catalyst and application thereof, polybutadiene and a preparation method thereof. The iron complex has a structure represented by formula (1):wherein R is 1 、R 2 、R 3 、R 4 、R 5 The same or different are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x is X 1 、X 2 The same or different, each independently is halogen. The preparation method of the iron complex is simple and stable, and the catalysis performance of the iron catalyst containing the iron complex is stableWhen catalyzing butadiene monomer polymerization, the polymerization reaction speed is high, and the 1, 2-structure selectivity is better.
Description
Technical Field
The invention relates to the field of polymer preparation, in particular to an iron complex, a preparation method of the iron complex, the iron complex prepared by the method, an iron catalyst containing the iron complex, application of the iron catalyst in conjugated diene polymerization, a preparation method of polybutadiene and polybutadiene prepared by the method.
Background
The syndiotactic 1, 2-polybutadiene is a thermoplastic resin with unsaturated double bonds in the side chains, and the double bonds are arranged together to ensure that the polymer has higher stereoregularity, and the unique structure ensures that the polymer becomes a high molecular material with both plastic and rubber properties, and can be used for preparing films, fibers, rubber products, polymer modifiers and the like.
Syndiotactic 1, 2-polybutadiene can be prepared from a transition metal complex catalyst such as Co, ti, V, mo, cr, fe. Co-based catalysts have been used in commercial production today for the cobalt diacetylacetonate/triisobutylaluminum/carbon disulfide system of the Ministry of Japan, as in US3778424A. Butadiene rubber containing syndiotactic 1, 2-polybutadiene modification was also produced under the designations Ubepol-VCR309 and Ubepol-VCR412. The modified butadiene rubber is mainly applied to the field of automobile tires, and can improve the strength of rubber materials and the rolling performance of tires.
However, the catalyst has a great problem in that carbon disulphide is used as one of the components, and the volatile, unpleasant smell, low ignition point and toxicity of carbon disulphide require expensive protection measures in the production process. In addition, the melting point of the catalyst system is very high, 200-210 ℃, making the polymer difficult to process.
Iron-based catalysts have been studied in recent years because of their excellent stability and simple synthesis. CN1343730a discloses a catalytic system of iron compound/phosphite/alkylaluminum, CN1554682a discloses a catalytic system of iron compound/aryl phosphite or aryl phosphate/alkylaluminum, which can obtain syndiotactic 1, 2-polybutadiene having a 1, 2-structure content of 78.3% -94.5%, however, the above documents do not disclose the crystallinity of syndiotactic 1, 2-polybutadiene or the crystallinity of syndiotactic 1, 2-polybutadiene is low, which greatly limits the application of polybutadiene in some specific fields.
Disclosure of Invention
The invention aims to solve the problems of low 1, 2-structure content and low crystallinity in polybutadiene in the prior art, and provides an iron complex, a preparation method of the iron complex, the iron complex prepared by the method, an iron catalyst containing the iron complex, application of the iron catalyst in conjugated diene polymerization and a preparation method of the polybutadiene.
In order to achieve the above object, a first aspect of the present invention provides an iron complex, characterized in that the iron complex has a structure represented by formula (1):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 The same or different are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x is X 1 、X 2 The same or different, each independently is halogen.
In a second aspect, the present invention provides a method for producing an iron complex, which comprises contacting a compound having a structure represented by formula (2) with a ferrous halide in a first organic solvent under a condition of a complexation reaction.
Wherein R is 1 、R 2 、R 3 、R 4 And R is 5 And R in formula (1) 1 、R 2 、R 3 、R 4 And R is 5 Is the same as defined in the following.
In a third aspect, the invention provides an iron complex prepared by the method of the invention.
According to a fourth aspect of the present invention there is provided an iron catalyst comprising an iron complex, a phosphate and/or a phosphite, and an alkyl aluminium, wherein the iron complex is an iron complex according to the present invention.
In a fifth aspect, the invention provides the use of an iron catalyst according to the invention in the polymerisation of conjugated dienes.
In a sixth aspect, the present invention provides a method for producing polybutadiene, which is characterized in that the method comprises contacting butadiene with a metal catalyst under solution polymerization conditions, wherein the iron catalyst is the iron catalyst of the present invention.
The seventh aspect of the present invention provides a polybutadiene produced by the production process according to the present invention, characterized in that the 1, 2-structure content in the polybutadiene is 80 to 99 wt.%, preferably 85.2 to 96.6 wt.%, based on the total weight of the polybutadiene;
preferably, the polybutadiene has a crystallinity of 50 to 90%, preferably 62 to 75.8%;
preferably, the polybutadiene has a weight average molecular weight of 30 to 80 ten thousand, preferably 40 to 70 ten thousand.
Through the technical scheme, the iron complex and the preparation method thereof, the iron catalyst and the application thereof, and the preparation method of polybutadiene provided by the invention have the following beneficial effects:
the preparation method of the iron complex provided by the invention is simple and easy to operate.
Furthermore, the iron catalyst containing the iron complex has stable catalytic performance, and has high polymerization reaction speed and better 1, 2-structure selectivity when catalyzing polymerization of butadiene monomers. Syndiotactic 1, 2-polybutadiene having a high crystallinity and mainly comprising a 1, 2-structure can be obtained. Specifically, the 1, 2-structure content in polybutadiene is 85.2% -96.6%, and the crystallinity of the polybutadiene is 62% -75.8%.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides an iron complex characterized in that the iron complex has a structure represented by formula (1):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 The same or different are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x is X 1 、X 2 The same or different, each independently is halogen.
According to the present invention, the C1-C20 alkyl group may be a linear or branched alkyl group, and specific examples may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 3, 7-dimethyloctyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.
The inventors of the present invention have found in the study that a complex having a structure represented by the specific formula (1) can achieve excellent catalytic effect in catalyzing the polymerization of butadiene monomer, and therefore, R is preferable 1 、R 2 、R 3 、R 4 、R 5 Each independently is hydrogen, substituted or unsubstituted C1-C10 alkyl.
More preferably, R 1 、R 2 、R 3 、R 4 And R is 5 Each independently is hydrogen, methyl, ethyl, propyl, isopropyl, X 1 And X 2 Each independently is chlorine or bromine.
Further preferably, R 1 And R is 2 Each independently is hydrogen, R 3 And R is 4 Each independently is methyl, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; alternatively, R 1 And R is 2 Each independently is methyl, R 3 And R is 4 Each independently is hydrogen, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; alternatively, R 1 And R is 2 Each independently is methyl, R 3 And R is 4 Each independently is methyl, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; alternatively, R 1 And R is 2 Each independently is isopropyl, R 3 And R is 4 Each independently is methyl, R 5 Is methyl, X 1 And X 2 Each independently is chlorine; alternatively, R 1 And R is 2 Each independently is methyl, R 3 And R is 4 Each independently is isopropyl, R 5 Is methyl, X 1 And X 2 Each independently is chlorine; alternatively, R 1 And R is 2 Each independently is isopropyl, R 3 And R is 4 Each independently is isopropyl, R 5 Is methyl, X 1 And X 2 Each independently is chlorine.
In a second aspect, the present invention provides a process for producing an iron complex, which comprises contacting a compound having a structure represented by formula (2) with a ferrous halide in a first organic solvent under conditions of a complexation reaction,
wherein R is 1 、R 2 、R 3 、R 4 And R is 5 And R in formula (1) 1 、R 2 、R 3 、R 4 And R is 5 Is the same as defined in the following.
According to the present invention, the amounts of the compound having the structure represented by formula (2) and the halogenated ferrous salt may vary within a wide range, as long as the iron complex having the structure represented by formula (1) can be produced. In order to obtain a higher yield of the iron complex, it is preferable that the molar ratio of the compound having the structure represented by formula (2) to the halogenated ferrous salt is 1:0.9 to 1.1, more preferably 1:0.95-1.
In the present invention, the halogenated ferrous salt may be various halogenated ferrous salts commonly used in the art, and may be selected from ferrous chloride and/or ferrous bromide, for example. In order to obtain a compound represented by the formula (1) in a higher yield, the ferrous halide salt is preferably an anhydrous ferrous halide salt.
According to the present invention, the compound of the structure represented by the formula (2) may be synthesized according to a method known in the art, for example, refer to literature (a) Zhang d, zhang y, hou w, guan z, huang z, organometallics 2017,36,3758-3764; or (b) the method described in US20130023634A 1. For example, the compound having the structure represented by formula (3) is brought into contact with the compound represented by formula (4) in a second organic solvent to cause a coupling reaction.
Wherein R is 1 、R 2 、R 3 、R 4 And R is 5 And R in formula (1) 1 、R 2 、R 3 、R 4 And R is 5 Is the same as defined in the following.
Wherein the structure of formula (3) can be synthesized by referring to the literature Organometallics 2017,36,3758-3764.
In the present invention, from the viewpoint of convenience of description, an organic solvent used in the method of preparing the iron complex of the structure represented by formula (1) is referred to as "first organic solvent"; the organic solvent used in the method for producing the compound of the structure represented by formula (2) is referred to as "second organic solvent"; the organic solvent used in the process for producing syndiotactic 1, 2-polybutadiene is referred to as "third organic solvent".
In the present invention, the amounts of the compound having the structure represented by the formula (3) and the compound having the structure represented by the formula (4) may vary within a wide range, as long as the compound having the structure represented by the formula (2) can be produced. In order to obtain a higher yield, the molar ratio of the compound of the structure represented by formula (3) to the compound of the structure represented by formula (4) is preferably 1:1-2, preferably 1:1.2-1.6.
In the present invention, the coupling reaction is preferably carried out under the protection of inert gas. The inert gas refers to a gas that does not participate in the reaction, for example: nitrogen and one or more of a group zero element gas of the periodic table, such as argon.
In the present invention, the coupling reaction conditions are not particularly limited, and may be selected conventionally in the art. Generally, the coupling reaction conditions include a reaction temperature and a reaction time. Wherein the reaction temperature may be selected and varied within a wide range, and in order to more facilitate the reaction, the reaction temperature may be 70 to 130 ℃, preferably 90 to 110 ℃. The extension of the reaction time is advantageous for the improvement of the conversion of the reactants or the yield of the reaction products, but the excessively long reaction time does not significantly improve the conversion of the reactants or the yield of the reaction products, and thus, in general, the reaction time may be 2 to 10 hours, preferably 4 to 7 hours.
In the present invention, the second organic solvent is any of various organic substances capable of being used as a reaction medium, and preferably, the second organic solvent is selected from one or more of benzene, toluene and xylene, and more preferably toluene. These solvents may be used alone or in combination. Anhydrous toluene is most preferred for obtaining a purer product.
In the present invention, the amount of the second organic solvent may be appropriately selected according to the amount of the compound of the structure represented by the formula (3), and generally, the amount of the second organic solvent may be such that the concentration of the compound of the structure represented by the formula (3) is 0.1 to 1mol/L, which not only enables the reaction to proceed smoothly, but also enables higher production efficiency.
In the present invention, the method for preparing a compound having a structure represented by formula (2) further comprises removing the second organic solvent after completion of the above reaction. The method for removing the second organic solvent may be performed by various methods known in the art, for example, vacuum line removing the organic solvent, spin evaporating the organic solvent, etc., which will be known to those skilled in the art, and will not be described herein.
In addition, in order to obtain a pure product, the method for preparing the compound of the structure represented by formula (2) may further include a step of purifying the obtained product, and the purification method may be carried out using various purification methods known in the art, such as column chromatography and the like. The eluent used in the column chromatography may be a mixture of hexane and toluene.
In the method for preparing the iron complex with the structure shown in the formula (1), the dosage of the first organic solvent can be reasonably adjusted according to the dosage of the compound with the structure shown in the formula (2) and the ferric halide, and generally, the dosage of the first organic solvent can ensure that the total concentration of the compound with the structure shown in the formula (2) and the ferric halide is 0.02-0.1mol/L, so that the reaction can be smoothly carried out, and higher production efficiency can be obtained.
In the present invention, the first organic solvent is any of various organic substances capable of being used as a reaction medium, and preferably, the first organic solvent is selected from one or more of tetrahydrofuran, methylene chloride, toluene, methanol and diethyl ether, and more preferably, tetrahydrofuran. These solvents may be used alone or in combination. Anhydrous tetrahydrofuran is most preferred in order to obtain a purer product.
According to the present invention, in the method for preparing the iron complex having the structure represented by formula (1), the coordination reaction is preferably performed under the protection of an inert gas, which is consistent with the above description and will not be described herein.
According to the present invention, the conditions for the coordination reaction are not particularly limited, and may be selected conventionally in the art. Generally, the coordination reaction conditions include a reaction temperature and a reaction time. Wherein the reaction temperature may be selected and varied within a wide range, and in order to more facilitate the reaction, the reaction temperature may be 10 to 30 ℃, preferably 15 to 25 ℃. The extension of the reaction time is advantageous for the improvement of the conversion of the reactants or the yield of the reaction products, but the excessively long reaction time does not significantly improve the conversion of the reactants or the yield of the reaction products, and thus, in general, the reaction time may be 4 to 12 hours, preferably 6 to 10 hours.
In the present invention, the method for preparing the iron complex of the structure represented by formula (1) further comprises removing the organic solvent after the completion of the above reaction. The method for removing the organic solvent may be performed by various methods known in the art, for example, vacuum line removing the organic solvent, spin evaporating the organic solvent, etc., which will be known to those skilled in the art, and will not be described herein.
In addition, in order to obtain a pure product, the method of preparing the iron complex of the structure represented by formula (1) may further include a step of purifying the obtained product, and the purification method may be performed using various purification methods known in the art, such as recrystallization, etc. The solvent used for recrystallization may be a mixed solution of tetrahydrofuran and hexane, or the like.
In a third aspect the invention provides an iron complex prepared by the process of the invention.
In a fourth aspect, the present invention provides an iron catalyst comprising an iron complex, a phosphate and/or a phosphite, alR 6 R 7 R 8 ；
Wherein the iron complex is the iron complex provided by the invention.
According to the invention, the molar ratio of the phosphate or phosphite to the iron complex, calculated on the molar basis of phosphorus, is between 2 and 6:1, preferably 3-5:1, a step of;
The molar ratio of the aluminum alkyl to the iron complex, calculated on the molar basis of aluminum, is 20-50:1, preferably 25-35:1.
according to the present invention, the phosphate or phosphite may be various phosphates or phosphites commonly used in the art, wherein the alkyl group in the phosphate or phosphite is a substituted or unsubstituted C1-C5 alkyl group or a substituted or unsubstituted C6-C10 aryl group.
According to the invention, the phosphite is diethyl phosphite and/or dibutyl phosphite.
According to the invention, the phosphate is triphenyl phosphate and/or tricresyl phosphate;
according to the present invention, the aluminum alkyls may be various aluminum alkyls commonly used in the art, for example, in the aluminum alkyls, R6, R7, R8 are the same or different and are each independently hydrogen, substituted or unsubstituted C1-C5 alkyl; preferably, the alkyl aluminum is one or more of triethyl aluminum, diisobutyl aluminum hydride and triisobutyl aluminum, and more preferably triisobutyl aluminum.
In a fifth aspect, the present invention provides the use of an iron catalyst according to the present invention in the polymerization of conjugated dienes.
In the present invention, the conjugated diene may be a conjugated diene commonly used in the art, including but not limited to C 4 -C 6 Can be, for example, one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, preferably butadiene and/or isoprenePentadiene.
The method for applying the iron catalyst in the polymerization of conjugated diene can be performed with reference to the prior art, and will not be described herein.
In a sixth aspect, the present invention provides a method for producing polybutadiene, which comprises contacting butadiene with an iron catalyst under solution polymerization conditions, wherein the iron catalyst is the iron catalyst of the present invention.
The improvement of the preparation method of polybutadiene provided by the invention is that an iron catalyst containing the iron complex is adopted, and the solution polymerization reaction conditions and the like for butadiene polymerization can be the same as those in the prior art.
In the present invention, the conditions for the solution polymerization may be a conventional choice in the art, but in order to obtain polybutadiene having a higher 1, 2-structure content, the conditions for the solution polymerization may include: the temperature is 10-100deg.C, and the time is 0.5-12 hr. Preferably, the temperature is 40-80℃and the time is 2-6 hours. The solution polymerization is carried out in the presence of a third organic solvent.
In the present invention, the amount of the iron catalyst may vary within a wide range, and generally, the molar ratio of butadiene to the iron complex in the iron catalyst is 1000 to 5000:1.
in the present invention, the third organic solvent may be an organic solvent commonly used in the art that can be used as a reaction medium, as long as it does not affect the polymerization reaction, and may be, for example, one or more of pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, and chlorobenzene. Preferably, the third organic solvent is toluene. The amount of the third organic solvent may be reasonably selected with reference to the prior art, and will not be described herein.
In the present invention, after the polymerization reaction is completed, the active polymer chain may be deactivated by adding a terminator-antioxidant to terminate the polymerization reaction while preventing the aging and deterioration during the preparation and storage of raw rubber. The terminator-anti-aging agent is a terminator mixed solution containing a certain concentration of anti-aging agent. The amount of the terminator-anti-aging agent may be appropriately selected depending on the amount of butadiene, and preferably, the amount of the terminator-anti-aging agent is 100 to 120mL relative to 1g of butadiene. The mass concentration of the anti-aging agent may be 1-5 wt%.
The antioxidant may be an antioxidant commonly used in the art, for example, at least one of 2, 6-di-t-butyl-p-methylphenol, 2-sec-butyl-4, 6-dinitrophenol, 2, 4-di (n-octylthiomethylene) -6-methylphenol, trisnonylated phenylphosphite, pentaerythritol tetrakis [ beta- (3 ', 5') -di-t-butyl-4 '-hydroxyphenyl ] propionate, stearyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and 2,2' -methylenebis- (4-methyl-6-t-butylphenol).
The kind and amount of the terminator may be any one conventionally selected in the art, and are not particularly limited as long as the terminator is capable of inactivating a polymer chain having a reactive end group. Typically, the terminating agent may be selected from water, C 1 -C 6 Aliphatic alcohols, C 4 -C 12 One or more of an aliphatic carboxylic acid and an aryl hydroxy compound. Wherein the aryl hydroxyl compound refers to a compound formed by substituting at least one hydrogen atom on a benzene ring with a hydroxyl group. Preferably, the terminator is one or more of water, methanol, ethanol and isopropanol.
In a preferred mode of the invention, the terminator-anti-aging agent is ethanol-2, 6-di-tert-butyl-p-methylphenol.
To remove residual Fe 2+ Ion to prevent Fe 2+ The effect of ions on the polymer properties, small amounts of hydrochloric acid may be added to the above-mentioned terminator-anti-aging agent. The volume ratio of the hydrochloric acid to the terminator is 1:40-120, preferably 1:50-100.
In the present invention, after the polymerization reaction is terminated, the polymer solution obtained by the polymerization may be precipitated, washed and dried by a method conventional in the art to obtain polybutadiene.
The seventh aspect of the present invention provides a polybutadiene produced by the production process according to the present invention, characterized in that the 1, 2-structure content in the polybutadiene is 80 to 99 wt.%, preferably 85.2 to 96.6 wt.%, based on the total weight of the polybutadiene.
According to the invention, the crystallinity of the polybutadiene is 50-90%, preferably 62.0% -75.8%;
according to the invention, the polybutadiene has a weight average molecular weight of 30 to 80 ten thousand, preferably 40 to 70 ten thousand.
The present invention will be described in detail by examples.
In the following examples and comparative examples, the parameter measurements were measured by the following methods:
(1) The crystallinity of the polymer was determined by differential thermal analysis (DSC) using a Perkin-Elmer-7 type differential thermal analyzer with a sample weight of about 10mg in a nitrogen atmosphere at a temperature ranging from 50 to 200deg.C at a rate of 10deg.C/min.
(2) Ligand L 1 -L 6 The structure of (C) is obtained by using a German Bruker 400MHz nuclear magnetic resonance apparatus 1 HNMR assay, solvent is deuterated chloroform.
(3) The 1,2 structure content and composition of the polymer were determined by Bruker 400MHz NMR in Germany 1 HNMR and 13 c NMR measurement, wherein the solvent is deuterated o-dichlorobenzene, and the test temperature is 110 ℃.
(4) Analyzing the content of C, H, N in the iron complex by using an elemental analyzer of Elemental Vario EL company; the iron content of the iron complex was measured by using an inductively coupled plasma atomic emission spectrometer with the model of plasma 1000 from Nake company, and the solid was tested after dissolution with nitric acid.
(5) The relative molecular weight of the polymer was determined by high temperature Gel Permeation Chromatography (GPC) at 130℃with a mobile phase of 1,2, 4-trichlorobenzene to which 0.05wt% of 2, 6-di-tert-butyl-4-methylphenol (BHT) was added as antioxidant, the amount of sample introduced was 200. Mu.L, and the flow rate was 1.0mL/min.
In examples and comparative examples, the compound of the structure shown in formula (4) was purchased from carbofuran technologies, inc;
the other raw materials are all commercial products.
PREPARATION EXAMPLES 1-6 PREPARATION OF ligand L 1 -L 6 。
Preparation example 1
Under Ar atmosphere, 1mmol of a compound having a structure represented by formula (3) (wherein R 1 、R 2 And R is 5 Each independently is hydrogen; reference is made to the synthesis of Organometallics 2017,36,3758-3764), 1.2mmol of a compound (R) of the structure represented by formula (4) 3 And R is 4 Each independently methyl), sodium t-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylidene acetonate (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.10 mmol) were reacted at 110℃for 4 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=2:1 (volume ratio), gives ligand L 1 . Ligand L 1 Analysis was performed and the results were as follows:
L 1 the yield was 70.5%. 1 H NMR(400MHz,CDCl 3 )δ2.36(s,6H,-CH 3 ),4.12(br,1H,-NH),6.81-6.98(m,4H,Ar),7.19-7.35(m,7H,Ar),7.88(d,J＝8.0Hz,1H,Ar),8.18(d,J＝8.0Hz,1H,Ar),8.45(s,1H,-N＝CH)。
Preparation example 2
Under Ar atmosphere, 1mmol of a compound having a structure represented by formula (3) (wherein R 1 、R 2 Each independently is methyl, R 5 Is hydrogen; 1.4mmol of the compound (R) having the structure represented by the formula (4) was synthesized by the reference Organometallics 2017,36,3758-3764 3 And R is 4 Each independently hydrogen), sodium tert-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylideneacetone (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1 mmol) were reacted at 105℃for 5 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=2:1 (volume ratio), gives ligand L 2 . Ligand L 2 Analysis was performed and the results were as follows:
L 2 the yield was 72.1%. 1 H NMR(400MHz，CDCl 3 )δ2.38(s,6H,-CH 3 ),4.09(br,1H,-NH),6.46-6.62(m,3H,Ar),6.92-7.21(m,8H,Ar),7.87(d,J＝7.8Hz,1H,Ar),8.19(d,J＝7.8Hz,1H,Ar),8.50(s,1H,-N＝CH)。
Preparation example 3
Under Ar atmosphere, 1mmol of the compound represented by formula (3)Compounds of the structure (wherein R 1 、R 2 Each independently is methyl, R 5 Is hydrogen; 1.6mmol of the compound (R) having the structure represented by the formula (4) was synthesized by the reference Organometallics 2017,36,3758-3764 3 And R is 4 Each independently methyl), sodium t-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylidene acetonate (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1 mmol) were reacted at 100℃for 6 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=2:1 (volume ratio), gives ligand L 3 . Ligand L 3 Analysis was performed and the results were as follows:
L 3 : the yield was 68.6%. 1 H NMR(400MHz，CDCl 3 )δ2.37(s,12H,-CH 3 ),4.10(br,1H,-NH),6.42-6.65(m,3H,Ar),6.92-7.21(m,6H,Ar),7.87(d,J＝7.8Hz,1H,Ar),8.19(d,J＝7.8Hz,1H,Ar),8.47(s,1H,-N＝CH)。
Preparation example 4
Under Ar atmosphere, 1mmol of a compound having a structure represented by formula (3) (wherein R 1 、R 2 Each independently is isopropyl, R 5 Is methyl; 1.6mmol of the compound (R) having the structure represented by the formula (4) was synthesized by the reference Organometallics 2017,36,3758-3764 3 And R is 4 Each independently methyl), sodium t-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylidene acetonate (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1 mmol) were reacted at 90℃for 7 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=3:1 (volume ratio), gives ligand L 4 . Ligand L 4 Analysis was performed and the results were as follows:
L 4 The yield was 64.3%. 1 H NMR(400MHz，CDCl 3 )δ1.05(s,3H,N＝C-CH 3 ),1.29(d,12H,J＝6.8Hz, i pr),2.35(s,6H,-CH 3 ),3.19(sept,2H,J＝6.8Hz, i pr),,4.12(br,1H,-NH),6.44-6.62(m,3H,Ar),6.92-7.21(m,6H,Ar),7.90(d,J＝7.8Hz,1H,Ar),8.20(d,J＝7.8Hz,1H,Ar)。
Preparation example 5
Under Ar atmosphere, 1mmol of the compound of formula (I)(3) Compounds of the structure shown (wherein, R 1 、R 2 Each independently is methyl, R 5 Is methyl; 1.5mmol of the compound (R) having the structure represented by the formula (4) was synthesized by the reference Organometallics 2017,36,3758-3764 3 And R is 4 Each independently isopropyl), sodium tert-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylidene acetonate (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1 mmol) were reacted at 100℃for 7 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=3:1 (volume ratio), gives ligand L 5 . Ligand L 5 Analysis was performed and the results were as follows:
L 5 the yield was 75.3%. 1 H NMR(400MHz,CDCl 3 )δ1.07(s,3H,N＝C-CH 3 ),1.25(d,12H,J＝6.8Hz, i pr),2.37(s,6H,-CH 3 ),3.18(sept,2H,J＝6.8Hz, i pr),4.09(br,1H,-NH),6.46-6.68(m,3H,Ar),6.90-7.21(m,6H,Ar),7.89(d,J＝7.8Hz,1H,Ar),8.18(d,J＝7.8Hz,1H,Ar)。
Preparation example 6
Under Ar atmosphere, 1mmol of a compound having a structure represented by formula (3) (wherein R 1 、R 2 Each independently is isopropyl, R 5 Is methyl; 1.6mmol of the compound (R) having the structure represented by the formula (4) was synthesized by the reference Organometallics 2017,36,3758-3764 3 And R is 4 Each independently isopropyl), sodium tert-butoxide (2.1 mmol), toluene 5ml, palladium bis dibenzylideneacetone (0.052 mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1 mmol) were reacted at 110℃for 7 hours with stirring. Concentrating the obtained reaction solution, and subjecting the mixture to SiO 2 Column chromatography, hexane/toluene=3:1 (volume ratio), gives ligand L 6 . Ligand L 6 Analysis was performed and the results were as follows:
L 6 yield 79.2%. 1 H NMR(400MHz，CDCl 3 )δ1.07(s,3H,N＝C-CH 3 ),1.25(d,24H,J＝6.8Hz, i pr),3.18(sept,4H,J＝6.8Hz, i pr),4.07(br,1H,-NH),6.47-6.70(m,3H,Ar),6.90-7.25(m,6H,Ar),7.88(d,J＝8.0Hz,1H,Ar),8.19(d,J＝8.0Hz,1H,Ar)。
Examples 1-6 illustrate the iron complexes of the present invention and methods of making the same.
Example 1
Under Ar protection, 0.121g (0.95 mmol) of anhydrous FeCl 2 With 0.351g (1 mmol) of ligand L 1 Into a Schlenk flask, 50mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at 15℃for 6 hours. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining the iron complex C 1 As a dark green solid with a yield of 85.0%.
Iron complex C using elemental analyzer 1 Characterization is carried out to obtain a test result C 24 H 21 Cl 2 FeN 3 .C 4 H 8 O, calculated value C:61.1%; h:5.31%; n:7.64%. Measured value C:61.3%; h:5.27%; n:7.59%. Iron complex C by atomic emission spectroscopy 1 The iron content of (2) was tested at 10.21% and theoretical at 10.15%. From this result and with respect to ligand L 1 As can be seen from the analysis results of (C) 1 The structural formula is as follows:
Example 2
Under Ar protection, 0.123g (0.97 mmol) of anhydrous FeCl 2 With 0.351g (1 mmol) of ligand L 2 Into a Schlenk flask, 40mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at 15℃for 6 hours. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining the iron complex C 2 As a dark green solid, the yield was 81.5%.
Iron complex C using elemental analyzer 2 Characterization was performedObtaining a test result C 24 H 21 Cl 2 FeN 3 .C 4 H 8 O, calculated value C:61.1%; h:5.31%; n:7.64%. Measured value C:60.9%; h:5.34%; n:7.68%. Pair of complexes C by atomic emission spectroscopy 2 The iron content of (2) was tested to a value of 10.12% and the theoretical value of 10.15%. From this result and with respect to ligand L 2 As can be seen from the analysis results of (C) 2 The structural formula is as follows:
example 3
Under Ar protection, 0.127g (1 mmol) of anhydrous FeCl 2 With 0.379g (1 mmol) of ligand L 3 Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at 20℃for 8 hours. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining the iron complex C 3 As a dark green solid, the yield was 77.6%.
Iron complex C using elemental analyzer 3 Characterization is carried out to obtain a test result C 26 H 25 Cl 2 FeN 3 Calculated value C:61.68%; h:4.98%; n:8.30%. Measured value C:61.60%; h:5.02%; n:8.27%. Pair of complexes C by atomic emission spectroscopy 3 The iron content of (2) was tested and found to be 10.99% and 11.03% theoretical. From this result and with respect to ligand L 3 As can be seen from the analysis results of (C) 3 The structural formula is as follows:
example 4
Under Ar protection, 0.121g (0.95 mmol) of anhydrous FeCl 2 With 0.449g (1 mmol) of ligand L 4 Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at 25℃for 8 hours. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining complex C 4 As a dark green solid, the yield was 80.5%.
Complex C using elemental analyzer 4 Characterization is carried out to obtain a test result C 31 H 35 Cl 2 FeN 3 .0.5C 4 H 8 O, calculated value C:64.72%; h:6.42%; n:6.86%. Measured value C:64.65%; h:6.35%; n:6.90%. Pair of complexes C by atomic emission spectroscopy 4 The iron content of (2) was tested and found to be 9.15% and 9.12% theoretical. From this result and with respect to ligand L 4 As can be seen from the analysis results of (C) 4 The structural formula is as follows:
example 5
Under Ar protection, 0.124g (0.98 mmol) of anhydrous FeCl 2 With 0.449g (1 mmol) of ligand L 5 Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at 20℃for 8 hours. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining complex C 5 As a dark green solid, the yield was 81.2%.
Complex C using elemental analyzer 4 Characterization is carried out to obtain a test result C 31 H 35 Cl 2 FeN 3 Calculated value C:64.60%; h:6.12%; n:7.29%. Measured value C:64.70%; h:6.20%; n:7.20%. Pair of complexes C by atomic emission spectroscopy 4 The iron content of (2) was tested and found to be 9.63% and 9.69% theoretical. From this result and with respect to ligand L 5 As can be seen from the analysis results of (C) 5 The structural formula is as follows:
example 6
Under Ar protection, 0.127g (1 mmol) of anhydrous FeCl 2 With 0.477g (1 mmol) of ligand L 6 Into a Schlenk flask, 10mL of anhydrous tetrahydrofuran was then added, and the reaction was stirred at room temperature for 10 hours. 2mL of n-hexane was added (keeping the solution clear). The mixture was kept at-30℃overnight to precipitate a large amount of solids. The resulting solid was filtered, washed several times with a small amount of n-hexane and dried in vacuo. Obtaining complex C 6 As a dark green solid, yield was 83.7%.
Complex C using elemental analyzer 6 Characterization is carried out to obtain a test result C 35 H 43 Cl 2 FeN 3 Calculated value C:66.46%; h:6.85%; n:6.64%. Measured value C:66.37%; h:6.72%; n:6.71%. Pair of complexes C by atomic emission spectroscopy 6 The iron content of (2) was tested and found to be 8.91% and the theoretical value 8.83%. From this result and with respect to ligand L 6 As a result of (C), complex C 6 The structural formula is as follows:
examples 7 to 12 illustrate the process for preparing the polybutadiene according to the invention.
Example 7
Baking 100mL ampoule bottle under vacuum, charging argon gas, sequentially adding 22mg of iron complex C prepared in example 1 1 2.16g of butadiene with 40mL of anhydrous toluene, followed by 16.6mg of diethyl phosphite, and then 1mL of triisobutylaluminum at a concentration of 1.0mol/L Toluene solution, placing the obtained mixed solution in a constant temperature bath at 40 ℃ for reaction, after 4 hours of reaction, stopping the polymerization reaction by using 100mL of hydrochloric acid/ethanol solution (the volume ratio of hydrochloric acid to ethanol is 1:50) of 2, 6-di-tert-butyl-4-methylphenol with the concentration of 1 weight percent, and obtaining 1.92g of polybutadiene after settling the obtained polymer by ethanol and repeatedly washing, and then drying the polymer at 40 ℃ under vacuum to constant weight. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Example 8
Baking 100mL ampoule bottle under vacuum, charging argon gas, sequentially adding 14.7mg of iron complex C prepared in example 2 2 2.16g of butadiene and 40mL of anhydrous toluene, then 15.5mg of dibutyl phosphite, then 0.67mL of toluene solution of triisobutylaluminum with a concentration of 1.0mol/L are added, the resulting mixture solution is placed in a constant temperature bath at 50 ℃ for reaction, after 2 hours of reaction, 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a concentration of 1% by weight (volume ratio of hydrochloric acid to ethanol: 1:50) is used, and the obtained polymer is subjected to sedimentation with ethanol, repeated washing, and then vacuum-dried to constant weight at 40 ℃ to obtain 1.94g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Example 9
Baking 100mL ampoule bottle under vacuum, charging argon gas, sequentially adding 10.2mg of iron complex C prepared in example 3 3 2.16g of butadiene and 40mL of anhydrous toluene, then 5.5mg of diethyl phosphite and 7.8mg of dibutyl phosphite are added, then 0.6mL of toluene solution of triisobutylaluminum with a concentration of 1mol/L is added, the obtained mixed solution is placed in a constant temperature bath at 60 ℃ for reaction, after 4 hours of reaction, 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a concentration of 1.5 wt% (volume ratio of hydrochloric acid to ethanol is 1:75) is used, and after the obtained polymer is subjected to ethanol sedimentation and repeated washing, vacuum drying is carried out at 40 ℃ until the weight is constant, 2.02g of polybutadiene is obtained. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Example 10
Baking 100mL ampoule bottle under vacuum, argon filling treatment, sequentially adding 8.2mg for implementationIron complex C prepared in example 4 4 2.16g of butadiene and 40mL of anhydrous toluene, 17.4mg of triphenyl phosphate is added, then 0.4mL of toluene solution of triisobutylaluminum with a concentration of 1mol/L is added, and the mixture is placed in a constant temperature bath at 70 ℃ for reaction for 3 hours, 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a concentration of 1.5 wt% (the volume ratio of hydrochloric acid to ethanol is 1:75) is used for reaction, and the obtained polymer is subjected to ethanol sedimentation and repeated washing, and then vacuum drying is carried out at 40 ℃ until the weight is constant, thus obtaining 1.88g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Example 11
Baking 100mL ampoule bottle under vacuum, charging argon gas, sequentially adding 5.8mg of iron complex C prepared in example 5 5 2.16g of butadiene and 40mL of anhydrous toluene, then 16.3mg of triphenyl phosphate is added, then 0.35mL of 1mol/L toluene solution of triisobutylaluminum is added and placed in a constant temperature bath at 80 ℃ to react for 5 hours, 100mL of hydrochloric acid/ethanol solution (the volume ratio of hydrochloric acid to ethanol is 1:100) of 2, 6-di-tert-butyl-4-methylphenol with the concentration of 2 wt% is used for terminating the polymerization reaction, and the obtained polymer is subjected to ethanol sedimentation and repeated washing and then dried in vacuum at 40 ℃ to constant weight, thus obtaining 1.92g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Example 12
Baking 100mL ampoule bottle under vacuum, charging argon gas, sequentially adding 5.0mg of iron complex C prepared in example 6 6 2.16g of butadiene and 40mL of anhydrous toluene, then 15.1mg of tricresyl phosphate is added, then 0.28mL of toluene solution of triisobutylaluminum with a concentration of 1mol/L is added, and the mixture is placed in a constant temperature bath at 80 ℃ for reaction, after 6 hours of reaction, 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a concentration of 2 wt% (the volume ratio of hydrochloric acid to ethanol is 1:100) is used for terminating the polymerization reaction, and the obtained polymer is subjected to ethanol sedimentation and repeated washing, and then vacuum drying is carried out at 40 ℃ until the weight is constant, thus obtaining 1.95g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Comparative example 1
Baking a 100mL ampoule bottle under vacuum, filling argon, sequentially adding 9.4mg of mineral oil solution of iron isooctanoate with the iron content of 6%, 2.16g of butadiene and 40mL of anhydrous toluene, then adding 5.5mg of diethyl phosphite, then adding 0.3mL of toluene solution of triisobutylaluminum with the concentration of 1mol/L, placing in a constant temperature bath at 80 ℃ for reaction, reacting for 6 hours, terminating the polymerization reaction by using 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with the concentration of 2 wt% (the volume ratio of hydrochloric acid to ethanol is 1:100), settling the obtained polymer by ethanol, repeatedly washing, and vacuum drying at 40 ℃ to constant weight to obtain 1.95g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Comparative example 2
Baking a 100mL ampoule bottle under vacuum, filling argon, sequentially adding 9.4mg of mineral oil solution of iron (trivalent) isooctanoate with the iron content of 6%, 2.16g of butadiene and 40mL of anhydrous toluene, then adding 15.1mg of tricresyl phosphate, then adding 0.3mL of toluene solution of triisobutylaluminum with the concentration of 1mol/L, placing in a constant temperature bath at 80 ℃ for reaction, after reacting for 6 hours, stopping the polymerization reaction by using 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with the concentration of 2 wt% (the volume ratio of hydrochloric acid to ethanol is 1:100), settling the obtained polymer by ethanol, repeatedly washing, and drying the polymer at 40 ℃ under vacuum until the weight is constant, thereby obtaining 1.95g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
Comparative example 3
Baking a 100mL ampoule bottle under vacuum, filling argon, sequentially adding 3.5mg of ferric triacetylacetonate, 2.16g of butadiene and 40mL of anhydrous toluene, then adding 5.5mg of diethyl phosphite, then adding 0.3mL of toluene solution of triisobutylaluminum with the concentration of 1mol/L, placing in a constant temperature bath at 80 ℃ for reaction, reacting for 6 hours, and stopping polymerization reaction by using 100mL of hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with the concentration of 2 wt% (the volume ratio of hydrochloric acid to ethanol is 1:100), settling the obtained polymer by ethanol, repeatedly washing, and then drying the polymer at 40 ℃ under vacuum to constant weight to obtain 1.88g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, syndiotactic 1, 2-polybutadiene having a predominantly 1, 2-structure can be obtained by catalyzing the polymerization of butadiene monomers with an iron catalyst comprising the iron complex according to the present invention. The polybutadiene has better 1, 2-structure selectivity and higher crystallinity. Specifically, the 1, 2-structure content in polybutadiene is 85.2% -96.6%, and the crystallinity of the polybutadiene is 62% -75.8%. Examples 7 to 9 have a comparable 1, 2-structure content and a higher crystallinity than comparative example 1. Also, examples 10 to 12 have a 1, 2-structure content comparable to that of comparative example 2, and have a higher crystallinity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (16)
1. An iron complex characterized by having a structure represented by formula (1):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently hydrogen, unsubstituted C1-C10 alkyl; x is X 1 、X 2 The same or different, each independently is halogen.
2. The iron complex of claim 1, wherein R 1 、R 2 、R 3 And R is 4 Each independently is hydrogen, methyl, ethyl, propyl, isopropyl, R 5 Is hydrogen or methyl, X 1 And X 2 Each independently is chlorine or bromine.
3. The iron complex according to claim 1 or 2, wherein,
R 1 and R is 2 Each independently is hydrogen, R 3 And R is 4 Each independently is methyl, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; or alternatively, the process may be performed,
R 1 and R is 2 Each independently is methyl, R 3 And R is 4 Each independently is hydrogen, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; or alternatively, the process may be performed,
R 1 and R is 2 Each independently is methyl, R 3 And R is 4 Each independently is methyl, R 5 Is hydrogen, X 1 And X 2 Each independently is chlorine; or alternatively, the process may be performed,
R 1 and R is 2 Each independently is isopropyl, R 3 And R is 4 Each independently is methyl, R 5 Is methyl, X 1 And X 2 Each independently is chlorine; or alternatively, the process may be performed,
R 1 and R is 2 Each independently is methyl, R 3 And R is 4 Each independently is isopropyl, R 5 Is methyl, X 1 And X 2 Each independently is chlorine; or alternatively, the process may be performed,
R 1 and R is 2 Each independently is isopropyl, R 3 And R is 4 Each independently is isopropyl, R 5 Is a armorRadical, X 1 And X 2 Each independently is chlorine.
4. A process for producing an iron complex as claimed in any one of claims 1 to 3, characterized in that the process comprises contacting a compound having a structure represented by the formula (2) with a ferrous halide in a first organic solvent under the condition of a complexation reaction,
Wherein R is 1 、R 2 、R 3 、R 4 And R is 5 Is as defined in any one of claims 1 to 3.
5. The method according to claim 4, wherein a molar ratio of the compound having the structure represented by formula (2) to the halogenated ferrous salt is 1:0.9-1.1.
6. The method according to claim 5, wherein a molar ratio of the compound having the structure represented by formula (2) to the halogenated ferrous salt is 1:0.95-1.
7. The method of any of claims 4-6, wherein the contacting is performed under inert gas protection, and the conditions of the coordination reaction include: the reaction temperature is 10-30 ℃ and the reaction time is 4-12 hours.
8. The method of any of claims 4-6, wherein the first organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, toluene, and diethyl ether.
9. An iron complex prepared by the method of any one of claims 4-8.
10. An iron catalyst, characterized in that the ironThe catalyst comprises an iron complex, a phosphate and/or a phosphite, an aluminum alkyl AlR 6 R 7 R 8 ；
In the aluminum alkyl, R6, R7 and R8 are the same or different and are each independently hydrogen or substituted or unsubstituted C1-C5 alkyl;
Wherein the iron complex is according to any one of claims 1-3 or 9.
11. The iron catalyst of claim 10, wherein the molar ratio of phosphate and/or phosphite to iron complex is 2-6, based on moles of phosphorus: 1, a step of;
the molar ratio of the aluminum alkyl to the iron complex, calculated on the molar basis of aluminum, is 20-50:1.
12. the iron catalyst of claim 11, wherein the molar ratio of phosphate and/or phosphite to iron complex is 3-5, based on moles of phosphorus: 1, a step of;
the molar ratio of the aluminum alkyl to the iron complex is 25-35, based on the molar amount of aluminum: 1.
13. the iron catalyst of any one of claims 10-12, wherein the alkyl group in the phosphate and/or phosphite is a substituted or unsubstituted C1-C5 alkyl group or a substituted or unsubstituted C6-C10 aryl group;
and/or the alkyl aluminum is one or more of triethyl aluminum, diisobutyl aluminum hydride and triisobutyl aluminum.
14. The iron catalyst of any of claims 10-12, wherein the phosphite is diethyl phosphite and/or dibutyl phosphite;
And/or the phosphate is triphenyl phosphate and/or tricresyl phosphate;
and/or, the aluminum alkyl is triisobutylaluminum.
15. Use of the iron catalyst of any one of claims 10-14 in the polymerization of conjugated dienes.
16. A process for the preparation of polybutadiene comprising contacting butadiene with an iron catalyst under solution polymerization conditions, wherein the iron catalyst is as defined in any one of claims 10 to 14.
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