CN114249849B - Highly branched iron conjugated diene polymer and preparation method thereof - Google Patents

Highly branched iron conjugated diene polymer and preparation method thereof Download PDF

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CN114249849B
CN114249849B CN202210158690.8A CN202210158690A CN114249849B CN 114249849 B CN114249849 B CN 114249849B CN 202210158690 A CN202210158690 A CN 202210158690A CN 114249849 B CN114249849 B CN 114249849B
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conjugated diene
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CN114249849A (en
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王庆刚
王亮
匡佳
陈小羽
周丽
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7004—Neutral ligand
    • C08F4/7006—NN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F136/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/08—Isoprene

Abstract

The invention provides a high branched chain iron conjugated diene polymer and a preparation method thereof, belonging to the field of conjugated diene catalytic polymerization. In the iron conjugated diene polymer provided by the invention, the proportion of 3,4- (1, 2-) structure is 60% -80%, the proportion of 1,4 structure is 20% -40%, the gel content is less than 1%, and the glass transition temperature is-80 ℃ -10 ℃. The modified aluminum reagent obtained by the reaction of the modifier and the aluminum alkyl has excellent reactivity with the iron complex, and compared with the prior art, the modified aluminum reagent avoids the use of a necessary dealkylation reagent in an aluminum alkyl system, reduces the process flow, reduces the reaction cost and provides important technical support for the industrial production of the iron rubber. The conjugated diene polymer has the characteristics of high branching, low gel content, no gel and low glass transition temperature, and the quality and performance of the product are obviously improved.

Description

Highly branched iron conjugated diene polymer and preparation method thereof
Technical Field
The invention belongs to the field of conjugated diene catalytic polymerization, and particularly relates to a high-branched iron conjugated diene polymer and a preparation method thereof.
Background
The artificially synthesized high-branched-chain poly-conjugated diene is an ideal sizing material for high-performance environment-friendly tires, has excellent wet skid resistance, low rolling resistance, low compression heat generation and high ageing resistance, and is more and more favored by the rubber industry. Gao Zhilian butyl-isoprene rubber is used as tyre supporting rubber, can obviously improve the wet skid resistance of the tyre without increasing the rolling resistance of the tyre, can greatly reduce the compression heat generation of the tyre, is called as 'China potential eighth class synthetic rubber' by the synthetic rubber industry association, and has great application prospect in the aspects of high-performance tyres such as aviation tyres, noise elimination and noise reduction materials of ships and the like. In the transition metal catalyzed conjugated diene polymerization system, the iron catalyst has the advantages of low toxicity, low cost, rich content, unique catalytic effect and the like, and is widely researched.
The Wang Fosong subject group prepares polyisoprene with high 3.4-structure content, but the gel content of the polymer is high and can reach 10%, which affects the processing performance of the product. The system reacts in an aromatic hydrocarbon solvent at low temperature, has high reaction toxicity and does not meet the production requirements of green chemistry. Giovanni Ricci et al use a bidentate ligand/FeCl 2 MAO catalytic systems, which produce highly branched isoprene polymers, are rarely reported for iron-catalyzed copolymerization of isoprene and butadiene. In the catalytic system, the catalyst reacts in the form of suspension, the poor solubility can cause difficulty in continuous production and feeding, and MAO aluminum reagent is used, so that the cost is high, and the requirement of industrial production is not met. Thus pushThere are still great limitations in the commercial production of highly branched poly-conjugated dienes.
Disclosure of Invention
The invention provides a high-branched iron conjugated diene polymer and a preparation method thereof, and the iron conjugated diene polymer with high 3, 4-structure, low gel content and low glass transition temperature can be prepared by using a bipyridine iron complex/modified aluminum catalytic system which is low in cost, high in efficiency, excellent in solubility and definite in molecular structure.
In order to solve the technical problems, the invention provides an iron conjugated diene polymer, wherein in the molecular chain, the proportion of 3,4- (1, 2-) structures is 60-80%, the proportion of 1,4 structures is 20-40%, the gel content is less than 1%, and the glass transition temperature is-80-10 ℃.
Preferably, the number average molecular weight of the iron-based conjugated diene polymer is 10 to 80 tens of thousands, and the molecular weight distribution is 1.0 to 5.0.
The invention also provides a preparation method of the iron conjugated diene polymer, which comprises the following steps:
under argon atmosphere, adding bipyridine iron complex, modified aluminum catalyst system, conjugated diene monomer and solvent into a reactor to form a reaction system, stirring at 0-90 ℃ for polymerization reaction for 10-30 min, adding a quenching agent and an anti-aging agent after the reaction is finished, washing and drying to obtain the iron conjugated diene polymer.
Preferably, the bipyridyl iron complex is prepared by the following method:
under argon atmosphere, adding an equimolar amount of N, N-bidentate electron-rich compound and an organic iron compound into an anhydrous reaction solvent, and stirring at 0-60 ℃ for reaction for 1-36 h to obtain a dipyridyl iron complex with the following structural general formula:
preferably, the N, N-bidentate electron-rich compound is selected from one of the following structures:
preferably, the organic iron compound Fe (X) n At least one selected from the group consisting of iron acetylacetonate, iron naphthenate, iron isooctanoate, iron neodecanoate, iron acetylacetonate, iron acetate, iron hexanoate, iron stearate, and iron octanoate.
Preferably, the anhydrous reaction solvent is at least one selected from the group consisting of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes.
Preferably, the anhydrous reaction solvent is selected from at least one of cyclohexane, n-hexane, ethanol, dichloromethane, dichloropropane or toluene and chlorobenzene.
Preferably, the reaction temperature is 20-40 ℃ and the reaction time is 1-12 h.
Preferably, the modified aluminum is prepared by the following method:
and (3) adding the modifier into the organic aluminum compound under the argon atmosphere, and stirring and reacting for 1 min-1 h at the temperature of minus 10-30 ℃ to obtain the modified aluminum.
Preferably, the organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride and dimethylaluminum hydride.
Preferably, the modifier is at least one selected from the group consisting of water, cardanol, phenol, cresol, naphthol, nitrophenol, 2, 6-di-t-butyl-p-cresol, 2, 6-di-t-butylphenol, p-t-butylcatechol, methanol, ethanol, propanol, n-octanol, isooctanol, n-hexanol, t-butanol, triphenylmethanol, benzyl alcohol, formic acid, acetic acid, isooctanoic acid, benzoic acid, stearic acid, naphthenic acid, and neodecanoic acid.
Preferably, the molar ratio of the organic aluminum compound to the modifier in the modified aluminum is 1: (0.01-2).
Preferably, the conjugated diene compound is at least one selected from isoprene and butadiene.
Preferably, when the conjugated diene compound is a mixture of isoprene and butadiene, the ratio of isoprene is 1% to 99%.
Preferably, the solvent is a nonpolar solvent or a polar/nonpolar mixed solvent, wherein the nonpolar solvent is at least one selected from cyclohexane, n-hexane, n-heptane, petroleum ether, benzene, toluene and xylene, and the polar solvent is at least one selected from tetrahydrofuran, acetone, acetonitrile, pyridine and chlorobenzene.
Preferably, the concentration of the polar solvent in the polar/nonpolar mixed solvent is 0ppm to 400ppm.
Preferably, the molar ratio of the conjugated diene monomer to the iron element in the bipyridyl iron complex is (1000 to 20000): 1, preferably 5000:1.
Preferably, the molar ratio of the aluminum element in the modified aluminum to the iron element in the bipyridyl iron complex is (10 to 100): 1, preferably 40:1.
Preferably, the volume ratio of conjugated diene monomer to solvent is 1: (1 to 20), preferably 1:5.
Preferably, the reaction temperature is 40-70 ℃, and the reaction time is 30min.
Preferably, the quencher is a mixed solution of concentrated hydrochloric acid and methanol, wherein the volume ratio of the methanol to the concentrated hydrochloric acid is 50:1, a step of; the volume ratio of the quenching agent to the solvent is 1:2.5.
preferably, the volume ratio of the anti-aging agent to the solvent is 1:25, and the anti-aging agent is an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a mass concentration of 1%.
Compared with the prior art, the invention has the remarkable effects that:
the conjugated diene polymer obtained by the invention has the characteristics of high content of 3, 4-structure, stable molecular weight, wide molecular weight distribution range, low gel content and low glass transition temperature, and is beneficial to improving the processability;
aiming at the problems of poor solubility of the iron-based catalyst and complex process during heterogeneous polymerization, the invention replaces inorganic anions in the iron-based catalyst with proper organic anions, thereby obviously improving the solubility of the iron-based catalyst, and further carrying out reaction by a homogeneous polymerization system and optimizing the production process of the iron-based catalyst;
aiming at the problem of high cost of the whole industrial production when a conventional MAO two-component system and a three-component system containing dealkylation reagent are adopted in the conventional iron conjugated diene polymerization process, a general and cheaper alkyl aluminum reagent is selected to modify the system, so that the cost of the reaction system is greatly reduced, and the reaction system still has the reactivity equivalent to that of a conventional two-component and conventional three-component catalytic system, namely, the majority of polymerization reaction yield is more than 90% in 30 min;
According to the invention, the structure of the N, N-bidentate electron-rich compound in the bipyridine iron complex is regulated, the bipyridine iron complex is coordinated with different organic iron compounds, the bipyridine iron complex with different catalytic characteristics can be formed, and the synergistic effect of the N, N-bidentate electron-rich compound ligand and the organic iron anions can be utilized, so that the electron effect and the metal center electrical property of the bipyridine iron complex can be effectively changed, the polymerization reaction speed and the heat release rate are influenced, and the effect of obviously reducing the gel content in the conjugated diene polymer is further achieved;
the dipyridyl iron complex/modified aluminum catalytic system designed by the invention has good polar functional group tolerance unlike the existing conjugated diene catalytic system, and the reaction yield is not affected by introducing part of THF into the system. In addition, the existence of the polar compound has a stabilizing effect on the active center of the catalytic system, so that the thermal stability of the reaction system is improved, the optimal reaction temperature of the system can be improved from 50 ℃ to 60 ℃ on the premise of ensuring the reaction yield, the production of the iron-based conjugated diene polymer has universality, and a design thought is provided for preparing multifunctional iron-based rubber;
6. the bipyridine iron complex/modified aluminum catalytic reaction system has the characteristics of excellent solubility, high reaction activity, low reaction cost and high temperature resistance, and provides important technical support for industrial production of iron rubber; the conjugated diene polymer has the characteristics of high branching, low gel content, no gel and low glass transition temperature, and the quality and performance of the product are obviously improved.
Drawings
FIG. 1 is a hydrogen spectrum of a polymer obtained in example 28 provided by the present invention;
FIG. 2 is a carbon spectrum of the polymer obtained in example 28 provided by the present invention;
FIG. 3 is a GPC of a polymer obtained in example 28 provided herein;
FIG. 4 is a gel test of the polymer obtained in example 28 provided by the present invention;
FIG. 5 is a DSC of the polymer obtained in example 45 provided herein;
FIG. 6 is a DSC of the polymer obtained in example 53 provided by the present invention;
FIG. 7 is a DSC of the polymer obtained in example 54 provided herein;
fig. 8 is a graph showing the solubility of the catalysts 1, 2, 13, and 14 provided by the present invention and ferric chloride catalysts.
Detailed Description
Example 1: the structural formula of the bipyridine iron complex (catalyst 1) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L1, and stirring and reacting for 1h at room temperature to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 34 H 53 FeN 2 O 6: [M+H] + : theoretical value: 641.3253; actual measurement value: 641.3257.
elemental analysis: c (C) 34 H 53 FeN 2 O 6 : theoretical value: c,63.64% The method comprises the steps of carrying out a first treatment on the surface of the H,8.33%; n,4.37%; found C,63.59%; h,8.37%; n,4.33%.
Example 2: the structural formula of the bipyridine iron complex (catalyst 2) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L2, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 36 H 53 FeN 2 O 6: [M+H] + : theoretical value: 665.3253; actual measurement value: 665.3256.
elemental analysis: c (C) 36 H 53 FeN 2 O 6 : theoretical value: c,64.96%; h,8.03%; n,4.21%; measured value C,64.93%; h,8.09%; n,4.27%.
Example 3: the structural formula of the bipyridine iron complex (catalyst 3) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L3, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 36 H 57 FeN 2 O 6: [M+H] + : theoretical value: 669.3566; actual measurement value: 669.3571.
elemental analysis: c (C) 36 H 57 FeN 2 O 6 : theoretical value: c,64.57%; h,8.58%; n,4.18%; measured value C,64.63%; h,8.52%; n,4.23%.
Example 4: the structural formula of the bipyridine iron complex (catalyst 4) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L4, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 36 H 57 FeN 2 O 6 :[M+H] + : theoretical value: 669.3566; actual measurement value: 669.3568.
elemental analysis: c (C) 36 H 57 FeN 2 O 6 : theoretical value: c,64.57%; h,8.58%; n,4.18%; measured value C,64.61%; h,8.63%; n,4.21%.
Example 5: the bipyridyl iron complex (catalyst 5) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L1, and stirring and reacting for 1h at room temperature to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 32 H 22 FeN 2 O 4 :[M+H] + : theoretical value: 554.0929; actual measurement value: 554.0933.
elemental analysis: c (C) 32 H 22 FeN 2 O 4 : theoretical value: c,69.33%; h,4.00%; n,5.05%; measured value C,69.37%; h,4.11%; n,5.13%.
Example 6: the structural formula of the bipyridine iron complex (catalyst 6) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L2, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 34 H 22 FeN 2 O 4: [M+H] + : theoretical value: 578.0929; actual measurement value: 578.0934.
elemental analysis: c (C) 34 H 22 FeN 2 O 4 : theoretical value: c,70.60%; h,3.83%; n,4.84%; found C,70.55%; h,3.87%; n,4.79%.
Example 7: the structural formula of the bipyridine iron complex (catalyst 7) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L3, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 34 H 26 FeN 2 O 4: [M+H] + : theoretical value: 582.1242; actual measurement value: 582.1247.
elemental analysis: c (C) 34 H 26 FeN 2 O 4 : theoretical value: c,70.11%; h,4.50%; n,4.81%; measured value C,70.17%; h,4.46%; n,4.88%.
Example 8: the structural formula of the bipyridine iron complex (catalyst 8) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L4, and stirring at room temperature for reaction for 1h to obtain brown yellow liquid, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 34 H 26 FeN 2 O 4: [M+H] + : theoretical value: 582.1242; actual measurement value: 582.1245.
elemental analysis: c (C) 34 H 26 FeN 2 O 4 : theoretical value: c,70.11%; h,4.50%; n,4.81%; measured value C,70.19%; h,4.53%; n,4.73%.
Example 9: the structural formula of the bipyridine iron complex (catalyst 9) is:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L1, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a brown yellow solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 20 H 22 FeN 2 O 4: [M+H] + : theoretical value: 411.1002; actual measurement value: 410.0999.
elemental analysis: c (C) 20 H 22 FeN 2 O 4 : theoretical value: c,58.55%; h,5.41%; n,6.83%; measured value C,58.43%; h,5.51%; n,7.02%.
Example 10: the bipyridyl iron complex (catalyst 10) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L2, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 22 H 22 FeN 2 O 4: [M+H] + : theoretical value: 435.1002; actual measurement value: 435.1007.
elemental analysis: c (C) 22 H 22 FeN 2 O 4 : theoretical value: c,60.85%; h,5.11%; n,6.45%; measured value C,61.03%; h,5.31%; n,6.61%.
Example 11: the bipyridine iron complex (catalyst 11) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 2 And 0.2mmol of N, N-bidentate electron-rich compound L3, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 22 H 26 FeN 2 O 4: [M+H] + : theoretical value: 439.1315; actual measurement value: 439.1319.
elemental analysis: c (C) 22 H 26 FeN 2 O 4 : theoretical value: c,60.29%; h,5.98%; n,6.39%; found C,59.97%; h,5.72%; n,6.54%.
Example 12: the bipyridine iron complex (catalyst 12) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L4, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a tan solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 22 H 26 FeN 2 O 4: [M+H] + : theoretical value: 439.1315; actual measurement value: 439.1317.
elemental analysis: c (C) 22 H 26 FeN 2 O 4 : theoretical value: c,60.29%; h,5.98%; n,6.39%; measured value C,60.18%; h,6.11%; n,6.46%.
Example 13: the bipyridine iron complex (catalyst 13) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L1, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 25 H 29 FeN 2 O 6: [M+H] + : theoretical value: 510.1448; actual measurement value: 510.1451.
elemental analysis: c (C) 25 H 29 FeN 2 O 6 : theoretical value: c,58.95%; h,5.74%; n,5.50%; measured value C,58.71%; h,5.67%; n,5.65%.
Example 14: the bipyridine iron complex (catalyst 14) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L2, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 27 H 29 FeN 2 O 6: [M+H] + : theoretical value: 534.1452; actual measurement value: 534.1457.
elemental analysis: c (C) 27 H 29 FeN 2 O 6 : theoretical value: c,60.80%; h,5.48%; n,5.25%; measured value C,60.65%; h,5.37%; n,5.17%.
Example 15: the bipyridine iron complex (catalyst 15) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L3, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 27 H 33 FeN 2 O 6: [M+H] + : theoretical value: 538.1761; actual measurement value: 538.1758.
elemental analysis: c (C) 27 H 33 FeN 2 O 6 : theoretical value: c,60.34%; h,6.19%; n,5.21%; measured value C,60.25%; h,6.34%; n,5.15%.
Example 16: the bipyridine iron complex (catalyst 16) has the structural formula:
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were sequentially added thereto 3 And 0.2mmol of N, N-bidentate electron-rich compound L4, stirring at room temperature for reaction for 1h, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely the bipyridine iron complex solution.
Mass spectrometry: c (C) 27 H 33 FeN 2 O 6: [M+H] + : theoretical value: 538.1761; actual measurement value: 538.1759.
elemental analysis: c (C) 27 H 33 FeN 2 O 6 : theoretical value: c,60.34%; h,6.19%; n,5.21%; measured value C,60.25%; h,6.27%; n,5.25%.
Example 17: modified aluminum reagent 1
Is prepared from triisobutylaluminum and water, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times and 6.4 mmoles of water corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain a modified aluminum reagent 1.
Example 18: modified aluminum reagent 2
Is prepared from triisobutylaluminum and water, and the preparation method is as follows:
Under argon atmosphere, a 100mL Schlenk tube was baked three times, and 12.8 mmoles of water corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain modified aluminum reagent 2.
Example 19: modified aluminum reagent 3
Is prepared from triisobutylaluminum and water, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times, and 25.6 mmoles of water corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain a modified aluminum reagent 3.
Example 20: modified aluminum reagent 4
Is prepared from triisobutylaluminum and water, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times, and 0.1mmol of water was mixed with 0.1mmol of triisobutylaluminum to obtain modified aluminum reagent 4.
Example 21: modified aluminum reagent 5
Is prepared from trimethylaluminum and water, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times and 6.4 mmoles of water corresponding to 0.1 mmoles of trimethylaluminum was mixed to obtain a modified aluminum reagent 5.
Example 22: modified aluminum reagent 6
Is prepared from triethylaluminum and water, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times, and 6.4 mmoles of water corresponding to 0.1 mmoles of triethylaluminum was mixed to obtain a modified aluminum reagent 6.
Example 23: modified aluminium reagent 7
The preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times, and 6.4 mmoles of cardanol corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain a modified aluminum reagent 7.
Example 24: modified aluminium reagent 8
The preparation method is as follows: under argon atmosphere, a 100mL Schlenk tube was baked three times, and 12.8 mmoles of cardanol corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain a modified aluminum reagent 8.
Example 25: modified aluminium reagent 9
Is prepared from triisobutylaluminum and isooctanoic acid, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times and 6.4 mmole of isooctanoic acid was mixed with 0.1 mmole of triisobutylaluminum to obtain a modified aluminum reagent 9.
Example 26: modified aluminum reagent 10
Is prepared from triisobutylaluminum and isooctyl alcohol, and the preparation method is as follows:
under argon atmosphere, a 100mL Schlenk tube was baked three times, and 6.4 mmoles of isooctanol corresponding to 0.1 mmoles of triisobutylaluminum was mixed to obtain a modified aluminum reagent 10.
Example 27: iron conjugated diene polymer 1
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent (ethanol solution of 2, 6-di-t-butyl-4-methylphenol having a mass concentration of 1%, the same as in the following examples) and after pouring out the clear liquid, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 1.
Example 28: iron conjugated diene polymer 2
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 2. The hydrogen spectrum, carbon spectrum, GPC test and gel test of the obtained iron-based conjugated diene polymer 2 are shown in FIGS. 1 to 4.
GPC measurement results are shown in tables 1 to 3:
TABLE 1 molecular weight information Table
Table 2 peak information table
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Table 3 peak tracking information table
Example 29: iron conjugated diene polymer 3
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 60℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 3.
Example 30: iron conjugated diene polymer 4
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 70℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 4.
Example 31: iron conjugated diene polymer 5
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 90℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 5.
Example 32: iron conjugated diene polymer 6
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), THF (50 ppm), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL,10 μmol) were sequentially added, polymerization was carried out at 60 ℃ for 30min, then the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 6.
Example 33: iron conjugated diene polymer 7
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), THF (200 ppm), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL,10 μmol) were sequentially added, polymerization was carried out at 60 ℃ for 30min, then the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 7.
Example 34: iron conjugated diene polymer 8
The preparation method comprises the following steps: anhydrous cyclohexane (37.5 mL), isoprene (7.5 mL,75.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added to a 250mL Schlenk tube under argon atmosphere, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 15mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.5mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 8.
Example 35: iron conjugated diene polymer 9
The preparation method comprises the following steps: anhydrous cyclohexane (37.5 mL), isoprene (7.5 mL,75.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added to a 250mL Schlenk tube under argon atmosphere, and polymerization was carried out at 50℃for 30min, followed by termination of the reaction with 15mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.5mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 9.
Example 36: iron conjugated diene polymer 10
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 2 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 10 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 10.
Example 37: iron conjugated diene polymer 11
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 3 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 11.
Example 38: iron conjugated diene polymer 12
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 4 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 10 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 12.
Example 39: iron conjugated diene polymer 13
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 5 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 13.
Example 40: iron conjugated diene polymer 14
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 6 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 14.
Example 41: iron conjugated diene polymer 15
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 7 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 15.
Example 42: iron conjugated diene polymer 16
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 8 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 16.
Example 43: iron conjugated diene polymer 17
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 9 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 17.
Example 44: iron conjugated diene polymer 18
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 10 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 18.
Example 45: iron conjugated diene polymer 19
The preparation method comprises the following steps: to a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 1 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 19. The DSC of the obtained iron-based conjugated diene polymer 19 is shown in FIG. 5.
Example 46: iron conjugated diene polymer 20
Anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) catalyst 1 (1.0 mL, 10. Mu. Mol), THF (50 ppm) were sequentially added to a 100mL Schlenk tube under argon atmosphere, and the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 20.
Example 47: iron conjugated diene polymer 21
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 3 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 21.
Example 48: iron conjugated diene polymer 22
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 4 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 22.
Example 49: iron conjugated diene polymer 23
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 5 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 23.
Example 50: iron conjugated diene polymer 24
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 6 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 24.
Example 51: iron conjugated diene polymer 25
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 7 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 25.
Example 52: iron conjugated diene polymer 26
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 8 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 26.
Example 53: iron conjugated diene polymer 27
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (35 mL), butadiene (3.5 mL,40.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.) and catalyst 2 (1.0 mL, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, then the reaction was terminated with 14mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.4mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 27. The DSC of the obtained iron-based conjugated diene polymer 27 is shown in FIG. 6.
Example 54: iron conjugated diene polymer 28
To a 250mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (35 mL), butadiene (1.75 mL,20.0 mmol) and isoprene (2.0 mL,20.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.), catalyst 2 (1.0 mL,10 μmol) were sequentially added, polymerization was carried out at 50℃for 30 minutes, then the reaction was terminated with 14mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.4mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 28. The DSC of the obtained iron-based conjugated diene polymer 28 is shown in FIG. 7.
Example 55: iron conjugated diene polymer 29
To a 250mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (35 mL), butadiene (0.875 mL,10.0 mmol) and isoprene (3.0 mL,30.0 mmol), modified aluminum reagent 1 (0.4 mmol,40 eq.), catalyst 2 (1.0 mL,10 μmol), were sequentially added, polymerization was carried out at 50℃for 30 minutes, then the reaction was terminated with 14mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.4mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 29.
Example 56: iron conjugated diene polymer 30
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 0℃for 10 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 30.
Example 57: iron conjugated diene polymer 31
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 10℃for 10 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 31.
Example 58: iron conjugated diene polymer 32
Anhydrous cyclohexane (25 mL), isoprene (5 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added to a 100mL Schlenk tube under argon atmosphere, and the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent at 30℃for 10 minutes, and after the supernatant was removed, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene-based polymer 32.
Example 59: iron conjugated diene polymer 33
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, then the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 33.
Example 60: iron conjugated diene polymer 34
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 50℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear liquid, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 34.
Example 61: iron conjugated diene polymer 35
Anhydrous cyclohexane (25 mL), isoprene (5 mL,50.0 mmol), modified aluminum reagent 1 (0.1 mmol,20 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added to a 100mL Schlenk tube under argon atmosphere, and the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent at 40℃for 30 minutes, and after the supernatant was removed, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene-based polymer 35.
Example 62: iron conjugated diene polymer 36
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5 mL,50.0 mmol), modified aluminum reagent 1 (0.3 mmol,60 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30 minutes, then the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 36.
Example 63: iron conjugated diene polymer 37
Anhydrous cyclohexane (37.5 mL), isoprene (7.5 mL,75.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added to a 100mL Schlenk tube under argon atmosphere, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 15mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.5mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 37.
Example 64: iron conjugated diene polymer 38
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 2 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 38.
Example 65: iron conjugated diene polymer 39
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 3 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 39.
Example 66: iron conjugated diene polymer 40
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 4 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 40.
Example 67: iron conjugated diene polymer 41
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 5 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30 minutes, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 41.
Example 68: iron conjugated diene polymer 42
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol), modified aluminum reagent 6 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 42.
Example 69: iron conjugated diene polymer 43
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 7 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 43.
Example 70: iron conjugated diene polymer 44
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 8 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 44.
Example 71: iron conjugated diene polymer 45
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 9 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 45.
Example 72: iron conjugated diene polymer 46
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 10 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 46.
Example 73: iron conjugated diene polymer 47
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 9 (4.1 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 47.
Example 74: iron conjugated diene polymer 48
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 10 (4.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 48.
Example 75: iron conjugated diene polymer 49
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 11 (4.4 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 49.
Example 76: iron conjugated diene polymer 50
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 12 (4.4 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 50.
Example 77: iron conjugated diene polymer 51
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 13 (5.1 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 51.
Example 78: iron conjugated diene polymer 52
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 15 (5.4 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, followed by termination of the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after pouring out the clear solution, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 52.
Example 79: iron conjugated diene polymer 53
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (25 mL), isoprene (5.00 mL,50.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 16 (5.4 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, then the reaction was terminated with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 53.
Example 80: iron conjugated diene polymer 54
To a 100mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (35 mL), butadiene (3.5 mL,40.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.) and catalyst 14 (5.3 mg, 10. Mu. Mol) were sequentially added, and polymerization was carried out at 40℃for 30min, then the reaction was terminated with 14mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.4mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 54.
Example 81: iron conjugated diene polymer 55
To a 250mL Schlenk tube under argon atmosphere, anhydrous cyclohexane (35 mL), butadiene (1.75 mL,20.0 mmol) and isoprene (2.0 mL,20.0 mmol), modified aluminum reagent 1 (0.2 mmol,40 eq.), catalyst 14 (5.3 mg,10 μmol), were sequentially added, polymerization was carried out at 40℃for 30min, then the reaction was terminated with a mixed solution of 14mL of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1.4mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene-based polymer 55.
Comparative example 1 (vs. example 46): iron conjugated diene polymer 56
Anhydrous cyclohexane (25 mL), isoprene (5.0 mL,50.0 mmol) and [ Ph ] were added sequentially to a 100mL Schlenk tube under an argon atmosphere 3 C] + [B(C 6 F 5 ) 4 ] - (9.2mg,10μmol)，Al i Bu 3 (0.4 mmol,40 eq.) catalyst 1 (1.0 mL, 10. Mu. Mol), THF (50 ppm), were polymerized at 50℃for 30min, then the reaction was stopped with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio=50/1) and 1mL of an anti-aging agent, and after the supernatant was removed, the polymer was washed three times with ethanol to give an iron-based conjugated diene-based polymer 56.
Physical parameters of the iron-based conjugated diene polymers obtained in examples 27 to 81 and comparative example 1 are shown in Table 4.
TABLE 4 Table 4
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Comparative example analysis
In order to better prove that the dipyridyl iron complex/modified aluminum catalytic system designed by the invention has good polar functional group tolerance, unlike the existing conjugated diene catalytic system, the reaction yield is not affected by introducing part of THF into the system. Therefore, by experimental comparison of the modified aluminum system (example 46) and the existing conjugated diene three-component system (comparative example 1) in the same THF concentration solvent, it can be found that the reaction yield of the modified aluminum system of the present invention is not affected, complete conversion can be achieved, good polar functional group tolerance is exhibited, and the yield is also significantly better than the yield of the existing conjugated diene three-component system.
Performance testing
The catalysts of examples 1, 2, 13 and 14 were taken as representative for the comparative experiments of solubility with two ferric chloride catalysts. Test method for solubility comparison: 10mg of each of the 5 different catalysts was dissolved in 3mL of n-hexane solvent, and the two ferrous chloride catalysts had poor solubility and remained a large portion of the solids in the bottle. The bipyridine iron complex solution in the invention is transparent and uniform, can ensure that the reaction is carried out in a homogeneous polymerization system, and is favorable for the catalyst to participate in the reaction for catalytic polymerization, thereby obtaining higher reaction yield and representing higher activity.

Claims (13)

1. The preparation method of the iron conjugated diene polymer is characterized by comprising the following steps:
adding a bipyridine iron complex, a modified aluminum catalytic system, conjugated diene monomer and a solvent into a reactor under the argon atmosphere to form a reaction system, stirring at 0-90 ℃ for polymerization for 10-30 min, adding a quenching agent and an anti-aging agent after the reaction is finished, washing and drying to obtain an iron conjugated diene polymer;
wherein the molar ratio of the conjugated diene monomer to the iron element in the bipyridine iron complex is (1000-20000) 1; the molar ratio of the aluminum element in the modified aluminum to the iron element in the bipyridyl iron complex is (10-100) 1; the conjugated diene compound is at least one of isoprene and butadiene, and the solvent is a nonpolar solvent or a polar/nonpolar mixed solvent, wherein the nonpolar solvent is at least one of cyclohexane, n-hexane, n-heptane, petroleum ether, benzene, toluene and xylene, and the polar solvent is at least one of tetrahydrofuran, acetone, acetonitrile, pyridine and chlorobenzene;
In the method, the bipyridyl iron complex is prepared by the following steps:
adding an equimolar amount of an N, N-bidentate electron-rich compound and an organic iron compound into an anhydrous reaction solvent in an argon atmosphere, and stirring and reacting for 1-36 hours at 0-60 ℃ to obtain a bipyridine iron complex;
the obtained bipyridine iron complex has the following structural general formula:
；
the modified aluminum is prepared by the following steps:
adding a modifier into an organic aluminum compound in an argon atmosphere, and stirring and reacting for 1 min-1 h at the temperature of-10-30 ℃ to obtain the modified aluminum compound, wherein the molar ratio of the organic aluminum compound to the modifier is 1: (0.01-2);
the organic aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride and dimethylaluminum hydride;
the modifier is at least one selected from water, cardanol, phenol, cresol, naphthol, nitrophenol, 2, 6-di-tert-butyl-p-cresol, 2, 6-di-tert-butylphenol, p-tert-butyl catechol, methanol, ethanol, propanol, n-octanol, isooctanol, n-hexanol, tert-butanol, triphenylmethanol, benzyl alcohol, formic acid, acetic acid, isooctanoic acid, benzoic acid, stearic acid, naphthenic acid and neodecanoic acid.
2. The preparation method according to claim 1, wherein the proportion of 3,4- (1, 2-) structure is 60% -80%, the proportion of 1,4 structure is 20% -40%, the gel content is < 1%, the glass transition temperature is-80 ℃ -10 ℃, the number average molecular weight is 10 ten thousand-80 ten thousand, and the molecular weight distribution is 1.0-5.0.
3. The method of claim 1, wherein the N, N-bidentate electron-rich compound is selected from one of the following structures:
、/>、/>、/>。
4. the production method according to claim 1, wherein the organic iron compound Fe (X) n is at least one selected from the group consisting of iron acetylacetonate, iron naphthenate, iron isooctanoate, iron neodecanoate, iron acetylacetonate, iron acetate, iron caproate, iron stearate, and iron caprylate.
5. The method according to claim 1, wherein the anhydrous reaction solvent is at least one selected from the group consisting of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes.
6. The method according to claim 5, wherein the anhydrous reaction solvent is at least one selected from cyclohexane, n-hexane, ethanol, methylene chloride, dichloropropane, toluene and chlorobenzene.
7. The preparation method according to claim 1, wherein in the preparation of the bipyridyl iron complex, the reaction temperature is 20-40 ℃ and the reaction time is 1-12 h.
8. The method according to claim 1, wherein when the conjugated diene compound is a mixture of isoprene and butadiene, the ratio of isoprene is 1% to 99%.
9. The method according to claim 1, wherein the concentration of the polar solvent in the polar/nonpolar mixed solvent is 0 ppm to 400 ppm.
10. The process according to claim 1, wherein the volume ratio of conjugated diene monomer to solvent is 1: (1-20).
11. The process according to claim 1, wherein in the preparation of the iron-based conjugated diene polymer, the reaction temperature is 40 to 70 ℃ and the reaction time is 30 minutes.
12. The method of claim 1, wherein the quenching agent is a mixed solution of concentrated hydrochloric acid and methanol, wherein the volume ratio of methanol to concentrated hydrochloric acid is 50:1, a step of; the volume ratio of the quenching agent to the solvent is 1:2.5.
13. the method according to claim 1, wherein the volume ratio of the anti-aging agent to the solvent is 1:25, and the anti-aging agent is an ethanol solution of 2, 6-di-tert-butyl-4-methylphenol with a mass concentration of 1%.
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