CN113583058A - Iron complex and preparation method thereof, iron catalyst and application thereof, polybutadiene and preparation method thereof - Google Patents
Iron complex and preparation method thereof, iron catalyst and application thereof, 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 is1、R2、R3、R4、R5The same or different, each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x1、X2The same or different, each independently is halogen. The preparation method of the iron complex is simple and stable, the iron catalyst containing the iron complex has stable catalytic performance, and the iron catalyst can catalyze the polymerization of butadiene monomersThe polymerization reaction is fast, 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 the polybutadiene prepared by the method.
Background
Syndiotactic 1, 2-polybutadiene is a thermoplastic resin with unsaturated double bonds in side chains, and the double bonds are arranged in a same way, so that the polymer has higher stereoregularity.
Syndiotactic 1, 2-polybutadiene can be prepared from Co, Ti, V, Mo, Cr, Fe and other transition metal coordination catalysts. Co-based catalysts are currently used in commercial production, the cobalt diacetylacetonate/triisobutylaluminium/carbon disulphide system of the Japan department of Japan, as in US 3778424A. At the same time, modified butadiene rubber containing syndiotactic 1, 2-polybutadiene, under the designations of Ubepol-VCR309 and Ubepol-VCR412, is produced. 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 major problem in using carbon disulfide as one of its components, and the volatile, unpleasant odor, low ignition point and toxicity of carbon disulfide make the production process require expensive protective measures. In addition, the melting point of the catalyst system is very high, 200 ℃ and 210 ℃, making the polymer difficult to process.
Iron-based catalysts have been studied in recent years because of their good stability and simple synthesis. CN1343730A discloses an iron compound/phosphite/alkylaluminum catalyst system, CN1554682A discloses an iron compound/arylphosphite or arylphosphate/alkylaluminum catalyst system, which can obtain syndiotactic 1, 2-polybutadiene with a1, 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 lower, which greatly limits the application of polybutadiene in some specific fields.
Disclosure of Invention
The invention aims to overcome 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 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 is1、R2、R3、R4、R5The same or different, each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x1、X2The same or different, each independently is halogen.
The second aspect of the present invention provides a method for preparing an iron complex, which is characterized by comprising contacting a compound having a structure represented by formula (2) with a halogenated ferrous salt in a first organic solvent under coordination reaction conditions.
Wherein R is1、R2、R3、R4And R5Is defined as in formula (1) and R1、R2、R3、R4And R5The same definition is applied.
In a third aspect, the present invention provides an iron complex prepared by the process of the present invention.
In a fourth aspect, the present invention provides an iron catalyst comprising an iron complex, a phosphate and/or phosphite, and an aluminum alkyl, wherein the iron complex is the iron complex of the present invention.
The fifth aspect of the invention provides the use of the iron catalyst of the invention in the polymerization of conjugated dienes.
In a sixth aspect, the present invention provides a method for preparing polybutadiene, which is characterized by comprising contacting butadiene with a metal catalyst under solution polymerization conditions, wherein the iron catalyst is the iron catalyst according to the present invention.
The seventh aspect of the present invention provides the polybutadiene obtained 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.
By the technical scheme, the iron complex and the preparation method thereof, the iron catalyst and the application thereof, and the preparation method of polybutadiene 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 the polymerization of butadiene monomers. Syndiotactic 1, 2-polybutadiene having a1, 2-structure as the main component and a high crystallinity 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the present invention, there is provided an iron complex characterized in that the iron complex has a structure represented by formula (1):
wherein R is1、R2、R3、R4、R5The same or different, each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x1、X2The same or different, each independently is halogen.
According to the present invention, the alkyl group of C1 to C20 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 are inIn the research, it is found that the complex with a specific structure shown in the formula (1) can achieve excellent catalytic effect when catalyzing the polymerization of butadiene monomer, therefore, preferably, R1、R2、R3、R4、R5Each independently hydrogen, substituted or unsubstituted C1-C10 alkyl.
More preferably, R1、R2、R3、R4And R5Each independently hydrogen, methyl, ethyl, propyl, isopropyl, X1And X2Each independently is chlorine or bromine.
Further preferably, R1And R2Each independently is hydrogen, R3And R4Each independently being methyl, R5Is hydrogen, X1And X2Each independently is chlorine; or, R1And R2Each independently being methyl, R3And R4Each independently is hydrogen, R5Is hydrogen, X1And X2Each independently is chlorine; or, R1And R2Each independently being methyl, R3And R4Each independently being methyl, R5Is hydrogen, X1And X2Each independently is chlorine; or, R1And R2Each independently is isopropyl, R3And R4Each independently being methyl, R5Is methyl, X1And X2Each independently is chlorine; or, R1And R2Each independently being methyl, R3And R4Each independently is isopropyl, R5Is methyl, X1And X2Each independently is chlorine; or, R1And R2Each independently is isopropyl, R3And R4Each independently is isopropyl, R5Is methyl, X1And X2Each independently is chlorine.
The second aspect of the present invention provides a method for preparing an iron complex, which is characterized by comprising contacting a compound having a structure represented by formula (2) with a halogenated ferrous salt in a first organic solvent under coordination reaction conditions,
wherein R is1、R2、R3、R4And R5Is defined as in formula (1) and R1、R2、R3、R4And R5The same definition is applied.
According to the present invention, the amounts of the compound having the structure represented by formula (2) and the halogenated ferrous salt to be used may be varied within a wide range as long as an 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: 0.9-1.1, more preferably 1: 0.95-1.
In the present invention, the halogenated ferrous salt may be any of 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 higher yield of the compound represented by formula (1), the halogenated ferrous salt is preferably an anhydrous halogenated ferrous salt.
According to the present invention, the compound having the structure represented by the formula (2) can be synthesized according to a method known in the art, for example, see (a) Zhang d., Zhang y., Hou w., Guan z., huangg z., Organometallics 2017,36, 3758-one 3764; or (b) synthesized as described in US20130023634a 1. For example, a compound having a structure represented by formula (3) and a compound represented by formula (4) are contacted in a second organic solvent to cause a coupling reaction.
Wherein R is1、R2、R3、R4And R5Is defined as in formula (1) and R1、R2、R3、R4And R5The same definition is applied.
Wherein, the structure shown in the formula (3) can be synthesized by referring to the literatures Organometallics 2017,36, 3758-3764.
In the present invention, the organic solvent used in the method for producing an iron complex having a structure represented by formula (1) is referred to as a "first organic solvent" from the viewpoint of convenience of description; the organic solvent used in the method for producing the compound having 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 amount of the compound having the structure represented by the above formula (3) and the compound having the structure represented by the above formula (4) may be varied within a wide range as long as the compound having the structure represented by the formula (2) can be produced. Preferably, the molar ratio of the compound of formula (3) to the compound of formula (4) is 1: 1-2, preferably 1: 1.2-1.6.
In the present invention, the coupling reaction is preferably carried out under an inert gas atmosphere. The inert gas refers to a gas that does not participate in the reaction, such as: nitrogen and a gas of a group zero element of the periodic table, such as argon.
In the present invention, the coupling reaction conditions are not particularly limited, and may be conventionally selected in the art. Generally, the coupling reaction conditions include reaction temperature and reaction time. Wherein the reaction temperature can be selected and varied within a wide range, and in order to facilitate the reaction, the reaction temperature can be 70 to 130 ℃, preferably 90 to 110 ℃. The extension of the reaction time is advantageous for the improvement of the conversion rate of the reactant or the yield of the reaction product, but the extension of the reaction time is not significant for the improvement of the conversion rate of the reactant or the yield of the reaction product, 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 conventional organic substances that can be used as a reaction medium, and preferably, the second organic solvent is one or more selected from benzene, toluene, and xylene, and more preferably toluene. These solvents may be used alone or in combination. Anhydrous toluene is most preferred to obtain a purer product.
In the present invention, the amount of the second organic solvent may be reasonably selected according to the amount of the compound having the structure represented by formula (3), and generally, the amount of the second organic solvent may be such that the concentration of the compound having the structure represented by formula (3) is 0.1 to 1mol/L, which not only enables the reaction to proceed smoothly, but also enables higher production efficiency to be obtained.
In the present invention, the method for preparing the compound having the structure represented by formula (2) further comprises removing the second organic solvent after the 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 organic solvent removal, spin evaporation organic solvent removal, etc., which can be known by those skilled in the art and will not be described herein again.
In addition, the method for preparing the compound having the structure represented by formula (2) may further include a step of purifying the obtained product in order to obtain a pure product, and the purification may be performed by various purification methods known in the art, such as column chromatography, and the like. The eluent used for column chromatography can be a mixed solution 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 halogenated ferrous salt, and generally, the dosage of the first organic solvent can enable the total concentration of the compound with the structure shown in the formula (2) and the halogenated ferrous salt to be 0.02-0.1mol/L, so that not only can the reaction be smoothly carried out, but also higher production efficiency can be obtained.
In the present invention, the first organic solvent is any of various conventional organic substances that can be used as a reaction medium, and is preferably one or more selected from tetrahydrofuran, dichloromethane, 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 in accordance with the above description and is not described herein again.
According to the present invention, the conditions of the coordination reaction are not particularly limited and may be conventionally selected in the art. Generally, the coordination reaction conditions include reaction temperature and reaction time. Wherein the reaction temperature can be selected and varied within a wide range, and in order to facilitate the reaction, the reaction temperature can be 10 to 30 ℃, preferably 15 to 25 ℃. The extension of the reaction time is advantageous for the improvement of the conversion rate of the reactant or the yield of the reaction product, but the extension of the reaction time is not significant for the improvement of the conversion rate of the reactant or the yield of the reaction product, 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 an iron complex having a 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 can be performed by various methods known in the art, for example, vacuum line removal of the organic solvent, spin evaporation of the organic solvent, etc., which can be known by those skilled in the art and will not be described herein again.
In addition, the method for preparing the iron complex having the structure represented by formula (1) may further include a step of purifying the obtained product in order to obtain a pure product, and the purification may be performed by various purification methods known in the art, such as recrystallization and the like. The solvent used for recrystallization may be a mixture of tetrahydrofuran and hexane.
In a third aspect, the present invention provides an iron complex prepared by the process of the invention.
The fourth aspect of the present invention provides an iron catalyst, characterized in that the iron catalyst contains an iron complex, a phosphate and/or phosphite, AlR6R7R8；
Wherein the iron complex is the iron complex of the present invention.
According to the invention, the molar ratio of the phosphoric acid ester or phosphorous acid ester to the iron complex is 2-6: 1, preferably 3 to 5: 1;
the molar ratio of the alkyl aluminum to the iron complex is 20-50: 1, preferably 25 to 35: 1.
according to the present invention, the phosphate or phosphite may be various phosphates or phosphites commonly used in the art, and 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 alkyl may be various aluminum alkyls commonly used in the art, for example, in the aluminum alkyl, R6, R7, R8 are the same or different and each is 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 is further preferably triisobutyl aluminum.
In a fifth aspect, the invention provides the use of the iron catalyst of the invention in the polymerization of conjugated diolefins.
In the present invention, the conjugated diene may be a conjugated diene commonly used in the art, including but not limited to C4-C6The conjugated diene of (b) may be, for example, one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, preferably butadiene and/or isoprene.
The method for applying the iron catalyst in the conjugated diene polymerization can be carried out by referring to the prior art, and is not described in detail herein.
In a sixth aspect, the present invention provides a method for preparing polybutadiene, comprising contacting butadiene with an iron catalyst under solution polymerization conditions, wherein the iron catalyst is the iron catalyst according to the present invention.
The preparation method of polybutadiene provided by the invention is improved in that the iron catalyst containing the iron complex is adopted, and the solution polymerization reaction conditions for butadiene polymerization and the like can be the same as those of the prior art.
In the present invention, the solution polymerization conditions may be conventionally selected in the art, but in order to obtain polybutadiene having a higher content of 1, 2-structures, the solution polymerization conditions may include: the temperature is 10-100 deg.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 used may vary within a wide range, and generally, the molar ratio of butadiene to the iron complex in the iron catalyst is 1000-5000: 1.
in the present invention, the third organic solvent may be an organic solvent commonly used in the art 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 can be reasonably selected by referring to the prior art, and is not described in detail herein.
In the invention, after the polymerization reaction is finished, the active polymer chain can be inactivated by adding a terminator-anti-aging agent, so that the purpose of terminating the polymerization reaction is achieved, and meanwhile, the aging and deterioration in the preparation and storage processes of the raw rubber are prevented. The terminator-anti-aging agent is a terminator mixed solution containing anti-aging agent with a certain concentration. The amount of the terminator-antioxidant to be used may be appropriately selected depending on the amount of butadiene to be used, and is preferably 100-120mL with respect to 1g of butadiene. The mass concentration of the antioxidant may be 1 to 5% by weight.
The antioxidant may be one commonly used in the art, and for example, is at least one of 2, 6-di-tert-butyl-p-methylphenol, 2-sec-butyl-4, 6-dinitrophenol, 2, 4-di (n-octylthiomethylene) -6-methylphenol, trisnonylphenyl phosphite, pentaerythrityl tetrakis [ beta- (3',5') -di-tert-butyl-4 '-hydroxyphenyl ] propionate, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -methylenebis- (4-methyl-6-tert-butylphenol).
The kind and amount of the terminator may be conventionally selected in the art, and is not particularly limited as long as the terminator is capable of inactivating the polymer chain having a living end group. In general, the terminating agent may be selected from water, C1-C6Aliphatic alcohol of (1), C4-C12And (b) one or more of an aliphatic carboxylic acid and an aryl hydroxy compound. Wherein, the aryl hydroxyl compound is a compound formed by replacing at least one hydrogen atom on a benzene ring by hydroxyl. Preferably, the terminating agent is one or more of water, methanol, ethanol and isopropanol.
In a preferred embodiment of the present invention, the terminator-antioxidant is ethanol-2, 6-di-tert-butyl-p-methylphenol.
In order to remove residual Fe2+Ions, prevention of Fe2+The influence of the ions on the properties of the polymer, a small amount of hydrochloric acid may be added to the above-mentioned terminator-antioxidant. 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 the polybutadiene obtained 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 polybutadiene has a crystallinity of 50% to 90%, preferably 62.0% to 75.8%;
according to the invention, the polybutadiene has a weight-average molecular weight of between 30 and 80 ten thousand, preferably between 40 and 70 ten thousand.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the parameters involved 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, a sample weight of about 10mg, a nitrogen atmosphere, a temperature rise range of 50-200 ℃ and a temperature rise rate of 10 ℃/min.
(2) Ligand L1-L6The structure of the probe adopts a German Bruker 400MHz nuclear magnetic resonance instrument1And (4) performing HNMR determination, wherein the solvent is deuterated chloroform.
(3) 1,2 structural content and composition of the Polymer Using a German Bruker 400MHz NMR spectrometer1HNMR and13c NMR determination is carried out, the solvent is deuterated o-dichlorobenzene, and the testing temperature is 110 ℃.
(4) The content of C, H, N in the iron complex was analyzed by an Elemental analyzer from Elemental variao EL corporation; the iron content of the iron complex is measured by adopting an inductively coupled plasma atomic emission spectrometer with the model number of plasma 1000 of Nack company, and the solid is dissolved by nitric acid and then is tested.
(5) The relative molecular weight of the polymer was determined by high temperature Gel Permeation Chromatography (GPC) at 130 ℃ in the form of 1,2, 4-trichlorobenzene in which 0.05 wt% of 2, 6-di-t-butyl-4-methylphenol (BHT) was added as an antioxidant, and the amount of the sample was 200. mu.L at a flow rate of 1.0 mL/min.
Examples and comparative examples, the compound having the structure represented by formula (4) was obtained from carbofuran technologies ltd;
other raw materials are all commercial products.
Preparation examples 1 to 6 for preparing ligand L1-L6。
Preparation example 1
Under Ar atmosphere, 1mmol of a compound (R) with a structure shown in a formula (3)1、R2And R5Each independently is hydrogen; see the Organometallics 2017,36,3758-3764 synthesis), 1.2mmol of a compound (R) having a structure represented by the formula (4)3And R4Each independently being methyl), sodium tert-butoxide (2.1mmol), toluene 5ml, palladium bis (dibenzylideneacetone) (0.052mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.10mmol) were reacted at 110 ℃ with stirring for 4 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene 2:1 (vol/vol) gave ligand L1. For ligand L1The analysis was performed with the following results:
L1the yield was 70.5%.1H NMR(400MHz,CDCl3)δ2.36(s,6H,-CH3),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 (R) with a structure shown in a formula (3)1、R2Each independently being methyl, R5Is hydrogen; reference is made to Organometallics 2017,36,3758-3764 Synthesis) 1.4mmol of a Compound (R) having a structure represented by the formula (4)3And R4Each independently hydrogen), sodium tert-butoxide (2.1mmol), toluene 5ml, palladium bis (dibenzylideneacetone) (0.052mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1mmol) were reacted at 105 ℃ with stirring for 5 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene 2:1 (vol/vol) gave ligand L2. For ligand L2The analysis was performed with the following results:
L2yield 72.1%.1H NMR(400MHz，CDCl3)δ2.38(s,6H,-CH3),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 a compound (R) with a structure shown in a formula (3)1、R2Each independently being methyl, R5Is hydrogen; reference is made to Organometallics 2017,36,3758-3764 Synthesis) 1.6mmol of a Compound (R) having a structure represented by the formula (4)3And R4Each independently methyl), sodium tert-butoxide (2.1mmol), toluene 5ml, bisdibenzylidenePalladium acetylacetonate (0.052mmol) and 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1mmol) were reacted at 100 ℃ with stirring for 6 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene 2:1 (vol/vol) gave ligand L3. For ligand L3The analysis was performed with the following results:
L3: the yield was 68.6%.1H NMR(400MHz，CDCl3)δ2.37(s,12H,-CH3),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 (R) with a structure shown in a formula (3)1、R2Each independently is isopropyl, R5Is methyl; reference is made to Organometallics 2017,36,3758-3764 Synthesis) 1.6mmol of a Compound (R) having a structure represented by the formula (4)3And R4Each independently being methyl), sodium tert-butoxide (2.1mmol), toluene 5ml, palladium bis (dibenzylideneacetone) (0.052mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1mmol) were reacted at 90 ℃ with stirring for 7 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene at 3:1 (vol/vol) gave ligand L4. For ligand L4The analysis was performed with the following results:
L4yield 64.3%.1H NMR(400MHz，CDCl3)δ1.05(s,3H,N＝C-CH3),1.29(d,12H,J＝6.8Hz,ipr),2.35(s,6H,-CH3),3.19(sept,2H,J＝6.8Hz,ipr),,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 a compound (R) with a structure shown in a formula (3)1、R2Each independently being methyl, R5Is methyl; reference is made to Organometallics 2017,36,3758-3764 Synthesis) 1.5mmol of a Compound (R) having a structure represented by the formula (4)3And R4Each independently isopropyl), sodium tert-butoxide (2.1mmol), toluene 5ml palladium bis dibenzylideneacetone (0.052mmol) and 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1mmol) were reacted at 100 ℃ with stirring for 7 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene at 3:1 (vol/vol) gave ligand L5. For ligand L5The analysis was performed with the following results:
L5the yield was 75.3%.1H NMR(400MHz,CDCl3)δ1.07(s,3H,N＝C-CH3),1.25(d,12H,J＝6.8Hz,ipr),2.37(s,6H,-CH3),3.18(sept,2H,J＝6.8Hz,ipr),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 (R) with a structure shown in a formula (3)1、R2Each independently is isopropyl, R5Is methyl; reference is made to Organometallics 2017,36,3758-3764 Synthesis) 1.6mmol of a Compound (R) having a structure represented by the formula (4)3And R4Each independently isopropyl), sodium tert-butoxide (2.1mmol), toluene 5ml, palladium bis (dibenzylideneacetone) (0.052mmol), 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (0.1mmol) were reacted at 110 ℃ with stirring for 7 hours. Concentrating the obtained reaction solution, and subjecting the mixture to SiO2Column chromatography with hexane/toluene at 3:1 (vol/vol) gave ligand L6. For ligand L6The analysis was performed with the following results:
L6the yield was 79.2%.1H NMR(400MHz，CDCl3)δ1.07(s,3H,N＝C-CH3),1.25(d,24H,J＝6.8Hz,ipr),3.18(sept,4H,J＝6.8Hz,ipr),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 to 6 are intended to illustrate the iron complex of the present invention and the process for preparing it.
Example 1
Under the protection of Ar, 0.121g (0.95mmol) of anhydrous FeCl2With 0.351g (1mmol) of ligand L1Into a Schlenk flask, then 50mL of anhydrousTetrahydrofuran, stirred at 15 ℃ for 6 h. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solid was filtered, washed several times with a small amount of n-hexane, and vacuum dried. To obtain iron complex C1It was a dark green solid with a yield of 85.0%.
Iron complex C by using element analyzer1Performing characterization to obtain a test result C24H21Cl2FeN3.C4H8O, calculated value C: 61.1 percent; h: 5.31 percent; n: 7.64 percent. Found value C: 61.3 percent; h: 5.27 percent; n: 7.59 percent. Para-iron complex C by atomic emission spectroscopy1The iron content of (A) was tested and found to be 10.21% and the theoretical value to be 10.15%. The results thus obtained and with respect to ligand L1As a result of the analysis of (2), Complex C1The structural formula of (A) is as follows:
example 2
Under the protection of Ar, 0.123g (0.97mmol) of anhydrous FeCl2With 0.351g (1mmol) of ligand L2Into a Schlenk flask, 40mL of anhydrous tetrahydrofuran was added, and the reaction was stirred at 15 ℃ for 6 h. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solid was filtered, washed several times with a small amount of n-hexane, and vacuum dried. To obtain iron complex C2It was a dark green solid with a yield of 81.5%.
Iron complex C by using element analyzer2Performing characterization to obtain a test result C24H21Cl2FeN3.C4H8O, calculated value C: 61.1 percent; h: 5.31 percent; n: 7.64 percent. Found value C: 60.9 percent; h: 5.34 percent; n: 7.68 percent. By atomic emission spectroscopy to Complex C2Has been tested with a test value of 10.12% and 10.15% of theory. The results thus obtained and with respect to ligand L2As a result of the analysis of (2), Complex C2The structural formula of (A) is as follows:
example 3
Under the protection of Ar, 0.127g (1mmol) of anhydrous FeCl2With 0.379g (1mmol) of ligand L3Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was added, and the reaction was stirred at 20 ℃ for 8 h. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solid was filtered, washed several times with a small amount of n-hexane, and vacuum dried. To obtain iron complex C3It was a dark green solid with a yield of 77.6%.
Iron complex C by using element analyzer3Performing characterization to obtain a test result C26H25Cl2FeN3Calculating a value C: 61.68 percent; h: 4.98 percent; n: 8.30 percent. Found value C: 61.60 percent; h: 5.02 percent; n: 8.27 percent. By atomic emission spectroscopy to Complex C3The iron content of (A) was tested and found to be 10.99% with a theoretical value of 11.03%. The results thus obtained and with respect to ligand L3As a result of the analysis of (2), Complex C3The structural formula of (A) is as follows:
example 4
Under the protection of Ar, 0.121g (0.95mmol) of anhydrous FeCl2With 0.449g (1mmol) of ligand L4Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was added, and the reaction was stirred at 25 ℃ for 8 h. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solidAfter filtration, the mixture is washed several times by a small amount of n-hexane and dried in vacuum. To obtain a complex C4It was a dark green solid with a yield of 80.5%.
Using an elemental analyzer to match with Complex C4Performing characterization to obtain a test result C31H35Cl2FeN3.0.5C4H8O, calculated value C: 64.72 percent; h: 6.42 percent; n: 6.86 percent. Found value C: 64.65 percent; h: 6.35 percent; n: 6.90 percent. By atomic emission spectroscopy to Complex C4The iron content of (A) was tested and found to be 9.15% with a theoretical value of 9.12%. The results thus obtained and with respect to ligand L4As a result of the analysis of (2), Complex C4The structural formula of (A) is as follows:
example 5
Under the protection of Ar, 0.124g (0.98mmol) of anhydrous FeCl2With 0.449g (1mmol) of ligand L5Into a Schlenk flask, 30mL of anhydrous tetrahydrofuran was added, and the reaction was stirred at 20 ℃ for 8 h. The volume of the solution was concentrated to about 10mL, then 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solid was filtered, washed several times with a small amount of n-hexane, and vacuum dried. To obtain a complex C5It was a dark green solid with a yield of 81.2%.
Using an elemental analyzer to match with Complex C4Performing characterization to obtain a test result C31H35Cl2FeN3Calculating a value C: 64.60 percent; h: 6.12 percent; n: 7.29 percent. Found value C: 64.70 percent; h: 6.20 percent; n: 7.20 percent. By atomic emission spectroscopy to Complex C4The iron content of (A) was tested and found to be 9.63% with a theoretical value of 9.69%. The results thus obtained and with respect to ligand L5As a result of the analysis of (2), Complex C5The structural formula of (A) is as follows:
example 6
Under the protection of Ar, 0.127g (1mmol) of anhydrous FeCl2With 0.477g (1mmol) of ligand L6Into a Schlenk flask, 10mL of anhydrous tetrahydrofuran was added, and the reaction was stirred at room temperature for 10 h. 2mL of n-hexane was added (keeping the solution clear). The mixture was stored at-30 ℃ overnight to precipitate a large amount of solid. The obtained solid was filtered, washed several times with a small amount of n-hexane, and vacuum dried. To obtain a complex C6It was a dark green solid with a yield of 83.7%.
Using an elemental analyzer to match with Complex C6Performing characterization to obtain a test result C35H43Cl2FeN3Calculating a value C: 66.46 percent; h: 6.85 percent; n: 6.64 percent. Found value C: 66.37 percent; h: 6.72 percent; n: 6.71 percent. By atomic emission spectroscopy to Complex C6The iron content of (A) was tested and found to be 8.91% with a theoretical value of 8.83%. The results thus obtained and with respect to ligand L6As a result, it was found that the complex C6The structural formula of (A) is as follows:
examples 7 to 12 are intended to illustrate the preparation of the polybutadienes according to the present invention.
Example 7
Baking a 100mL ampoule bottle under vacuum, filling argon for treatment, and sequentially adding 22mg of the iron complex C prepared in example 112.16g of butadiene and 40mL of anhydrous toluene, 16.6mg of diethyl phosphite and 1mL of a toluene solution of triisobutylaluminum in a concentration of 1.0mol/L were added, the resulting mixed solution was allowed to stand at 40 ℃ for reaction, after 4 hours of reaction, the polymerization reaction was terminated with 100mL of a hydrochloric acid/ethanol solution of 1 wt% of 2, 6-di-t-butyl-4-methylphenol (the volume ratio of hydrochloric acid to ethanol was 1: 50), the resulting polymer was precipitated with ethanol, washed repeatedly, and the temperature was 40 DEG CVacuum drying to constant weight gave 1.92g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Example 8
Baking a 100mL ampoule bottle under vacuum, filling argon, and sequentially adding 14.7mg of the iron complex C prepared in example 222.16g of butadiene and 40mL of anhydrous toluene, 15.5mg of dibutyl phosphite were added, 0.67mL of a toluene solution of triisobutylaluminum having a concentration of 1.0mol/L was added, the resulting mixture solution was placed in a constant temperature bath at 50 ℃ to react for 2 hours, 100mL of a hydrochloric acid/ethanol solution of 1% by weight of 2, 6-di-tert-butyl-4-methylphenol (the volume ratio of hydrochloric acid to ethanol was 1: 50) was used, and after the resulting polymer was precipitated with ethanol and repeatedly washed, it was vacuum-dried at 40 ℃ to a constant weight, whereby 1.94g of polybutadiene was obtained. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Example 9
Baking a 100mL ampoule bottle under vacuum, filling argon, and sequentially adding 10.2mg of the iron complex C prepared in the example 332.16g of butadiene and 40mL of anhydrous toluene, then 5.5mg of diethyl phosphite and 7.8mg of dibutyl phosphite were added, then 0.6mL of a toluene solution of triisobutylaluminum with a concentration of 1mol/L was added, the resulting mixed solution was placed in a constant temperature bath at 60 ℃ for reaction for 4 hours, and after the reaction, 100mL of a hydrochloric acid/ethanol solution of 1.5% by weight of 2, 6-di-tert-butyl-4-methylphenol (the volume ratio of hydrochloric acid to ethanol was 1: 75) was used, and after the resulting polymer was precipitated with ethanol, washed repeatedly, it was vacuum-dried at 40 ℃ to constant weight, thereby obtaining 2.02g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Example 10
Baking a 100mL ampoule bottle under vacuum, filling argon, and sequentially adding 8.2mg of the iron complex C prepared in example 442.16g of butadiene and 40mL of anhydrous toluene, then 17.4mg of triphenyl phosphate, then 0.4mL of a 1mol/L toluene solution of triisobutylaluminum was added, the mixture was placed in a constant temperature bath at 70 ℃ for reaction, and after 3 hours of reaction, 100mL of 1.5 wt% 2, 6-di-tert-butyl was usedHydrochloric acid/ethanol solution of the base-4-methylphenol (the volume ratio of hydrochloric acid to ethanol is 1: 75), and the obtained polymer was precipitated with ethanol, washed repeatedly, and vacuum-dried at 40 ℃ to constant weight to obtain 1.88g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Example 11
Baking a 100mL ampoule bottle under vacuum, filling argon, and sequentially adding 5.8mg of the iron complex C prepared in example 552.16g of butadiene and 40mL of anhydrous toluene, then 16.3mg of triphenyl phosphate is added, then 0.35mL of a 1mol/L toluene solution of triisobutylaluminum is added, the mixture is placed in a constant temperature bath at 80 ℃ for reaction, after 5 hours of reaction, the polymerization reaction is terminated with 100mL of a 2 wt% hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (the volume ratio of hydrochloric acid to ethanol is 1: 100), the obtained polymer is precipitated with ethanol, washed repeatedly, and then dried in vacuum at 40 ℃ to constant weight, and 1.92g of polybutadiene is obtained. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Example 12
Baking a 100mL ampoule bottle under vacuum, filling argon, and sequentially adding 5.0mg of the iron complex C prepared in the example 662.16g of butadiene and 40mL of anhydrous toluene, then 15.1mg of tricresyl phosphate and then 0.28mL of a toluene solution of triisobutylaluminum of 1mol/L concentration were added, the mixture was placed in a constant temperature bath at 80 ℃ to react for 6 hours, then the polymerization reaction was terminated with 100mL of a 2% by weight hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (the volume ratio of hydrochloric acid to ethanol was 1: 100), the obtained polymer was precipitated with ethanol, washed repeatedly, and then dried under vacuum at 40 ℃ to constant weight, whereby 1.95g of polybutadiene was obtained. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Comparative example 1
Baking a 100mL ampoule bottle under vacuum, filling argon for treatment, 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 the mixture in a constant-temperature bath at 80 ℃ for reaction 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 weight percent (the volume ratio of the hydrochloric acid to the ethanol is 1: 100), settling the obtained polymer by using ethanol, repeatedly washing, and drying the polymer under vacuum at 40 ℃ to constant weight to obtain 1.95g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Comparative example 2
Baking a 100mL ampoule bottle under vacuum, filling argon for treatment, sequentially adding 9.4mg of ferric isooctanoate (trivalent) mineral oil solution 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 triisobutylaluminum toluene solution with the concentration of 1mol/L, placing the mixture in a constant-temperature bath at 80 ℃ for reaction for 6 hours, terminating the polymerization reaction by using 100mL of 2 wt% 2, 6-di-tert-butyl-4-methylphenol hydrochloric acid/ethanol solution (the volume ratio of hydrochloric acid to ethanol is 1: 100), settling the obtained polymer by ethanol, repeatedly washing, and then drying in vacuum at 40 ℃ to constant weight to obtain 1.95g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined in Table 1.
Comparative example 3
Baking a 100mL ampoule bottle in vacuum, filling argon for treatment, sequentially adding 3.5mg of ferric triacetylacetonate and 2.16g of butadiene and 40mL of anhydrous toluene, then adding 5.5mg of diethyl phosphite, then adding 0.3mL of 1mol/L toluene solution of triisobutylaluminum, placing the mixture in a constant-temperature bath at 80 ℃ for reaction, after 6 hours of reaction, terminating the polymerization reaction by using 100mL of 2 wt% hydrochloric acid/ethanol solution of 2, 6-di-tert-butyl-4-methylphenol (the volume ratio of the hydrochloric acid to the ethanol is 1: 100), settling the obtained polymer by ethanol, repeatedly washing, and drying in vacuum at 40 ℃ to constant weight to obtain 1.88g of polybutadiene. The structure and molecular weight of the polybutadiene obtained are determined 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 using an iron catalyst containing an 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 7-9 have comparable 1, 2-structure content and higher crystallinity than comparative example 1. Similarly, in examples 10 to 12, the 1, 2-structure content was comparable to that of comparative example 2, and the crystallinity was high.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. An iron complex, characterized in that the iron complex has a structure represented by formula (1):
wherein R is1、R2、R3、R4、R5The same or different, each independently hydrogen, substituted or unsubstituted C1-C20 alkyl; x1、X2The same or different, each independently is halogen.
2. The iron complex according to claim 1, wherein R1、R2、R3、R4、R5Each independently hydrogen, substituted or unsubstituted C1-C10 alkyl;
preferably, R1、R2、R3And R4Each independently hydrogen, methyl, ethyl, propyl, isopropyl, R5Is hydrogen or methyl, X1And X2Each independently is chlorine or bromine.
3. The iron complex according to claim 1 or 2, wherein,
R1and R2Each independently is hydrogen, R3And R4Each independently being methyl, R5Is hydrogen, X1And X2Each independently is chlorine; alternatively, the first and second electrodes may be,
R1and R2Each independently being methyl, R3And R4Each independently is hydrogen, R5Is hydrogen, X1And X2Each independently is chlorine; alternatively, the first and second electrodes may be,
R1and R2Each independently being methyl, R3And R4Each independently being methyl, R5Is hydrogen, X1And X2Each independently is chlorine; alternatively, the first and second electrodes may be,
R1and R2Each independently is isopropyl, R3And R4Each independently being methyl, R5Is methyl, X1And X2Each independently is chlorine; alternatively, the first and second electrodes may be,
R1and R2Each independently being methyl, R3And R4Each independently is isopropyl, R5Is methyl, X1And X2Each independently is chlorine; alternatively, the first and second electrodes may be,
R1and R2Each independently is isopropyl, R3And R4Each independently is isopropyl, R5Is methyl, X1And X2Each independently is chlorine.
4. A preparation method of an iron complex is characterized by comprising the steps of contacting a compound with a structure shown as a formula (2) with a halogenated ferrous salt in a first organic solvent under the condition of coordination reaction,
wherein R is1、R2、R3、R4And R5Is as defined in any one of claims 1 to 3.
5. The method according to claim 4, wherein 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, preferably 1: 0.95-1.
6. The method of claim 4 or 5, wherein the contacting is performed under an inert gas blanket, and the coordination reaction conditions comprise: the reaction temperature is 10-30 ℃ and the reaction time is 4-12 hours.
7. The process according to any one of claims 4-6, wherein the first organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, toluene and diethyl ether.
8. An iron complex prepared by the process of any one of claims 4 to 7.
9. An iron catalyst comprising an iron complex, a phosphate and/or phosphite, an aluminum alkyl AlR6R7R8；
Wherein the iron complex is an iron complex according to any one of claims 1 to 3 or 8.
10. The iron catalyst of claim 9, wherein the molar ratio of the phosphate and/or phosphite to the iron complex, based on the moles of phosphorus, is from 2 to 6: 1, preferably 3 to 5: 1;
the molar ratio of the alkyl aluminum to the iron complex is 20-50: 1, preferably 25 to 35: 1.
11. the iron catalyst of claim 9 or 10, 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;
preferably, the phosphite is diethyl phosphite and/or dibutyl phosphite;
preferably, the phosphate ester is triphenyl phosphate and/or tricresyl phosphate;
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;
preferably, the alkyl aluminum is one or more of triethyl aluminum, diisobutyl aluminum hydride and triisobutyl aluminum, and is further preferably triisobutyl aluminum.
12. Use of an iron catalyst according to any one of claims 9 to 11 in the polymerisation of conjugated dienes.
13. A process for the preparation of polybutadiene, characterized in that it comprises contacting butadiene with an iron catalyst under solution polymerization conditions, characterized in that said iron catalyst is as defined in any one of claims 9 to 11.
14. Polybutadiene obtained by the process according to claim 13, characterized in that the 1, 2-structure content in the polybutadiene ranges from 80 to 99% by weight, preferably from 85.2 to 96.6% by weight, 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.
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