CN114249849A - High-branched-chain iron-based conjugated diene polymer and preparation method thereof - Google Patents

High-branched-chain iron-based conjugated diene polymer and preparation method thereof Download PDF

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CN114249849A
CN114249849A CN202210158690.8A CN202210158690A CN114249849A CN 114249849 A CN114249849 A CN 114249849A CN 202210158690 A CN202210158690 A CN 202210158690A CN 114249849 A CN114249849 A CN 114249849A
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conjugated diene
diene polymer
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CN114249849B (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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    • 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
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Abstract

The invention provides a high-branched-chain iron-based conjugated diene polymer and a preparation method thereof, belonging to the field of conjugated diene catalytic polymerization. In the iron-based conjugated diene polymer provided by the invention, the proportion of a 3,4- (1,2-) structure is 60-80%, the proportion of a 1,4 structure is 20-40%, the gel content is less than 1%, and the glass transition temperature is-80-10 ℃. The invention obviously improves the solubility of the iron complex in a reaction solvent by changing anions in the iron complex, and the modified aluminum reagent obtained by the reaction of the modifier and the alkyl aluminum is matched with the iron complex, so that the invention has excellent reaction activity. The obtained conjugated diene polymer has the characteristics of high branching, low gel content, no gel and low glass transition temperature, and the quality and the performance of the product are obviously improved.

Description

High-branched-chain iron-based 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-chain iron-based conjugated diene polymer and a preparation method thereof.
Background
The artificially synthesized high-branched-chain poly-conjugated diene is an ideal rubber material for a high-performance environment-friendly tire, has excellent wet skid resistance, low rolling resistance, low heat generation due to compression and high aging resistance, and is more and more favored by the rubber industry. When the high-branch chain butyl-pentyl rubber is used as a tire supporting rubber, the wet-skid resistance of the tire can be obviously improved on the premise of not increasing the rolling resistance of the tire, the compression heat generation of the tire can be greatly reduced, the high-branch chain butyl-pentyl rubber is called as 'the eighth category of potential synthetic rubber' by the synthetic rubber industry association, and the high-performance tire has great application prospects in the aspects of noise elimination and reduction materials of high-performance tires such as aircraft tires, ships and warships and the like. In the transition metal catalyzed conjugated diene polymerization system, iron catalysts have been widely studied because of their low toxicity, low cost, rich content, and unique catalytic effect.
The preparation of the Wangfang Poisson topic group obtains the polyisoprene with high 3.4-structure content, but the gel content of the polymer is higher and can reach 10 percent, thereby influencing the processing performance of the product. Moreover, the system reacts in an aromatic hydrocarbon solvent at low temperature, has high reaction toxicity and does not meet the production requirement of green chemistry. Giovanni Ricci et al use bidentate ligands/FeCl2The MAO catalytic system produces highly branched isoprene polymer, but iron-catalyzed copolymerization of isoprene and butadiene is rarely reported. In the catalytic system, the catalyst reacts in a suspension form, the poor solubility can cause the difficulty in continuous production and feeding, and the MAO aluminum reagent is used, so the cost is higher, and the requirement of industrial production cannot be met. Therefore, there is still a great limitation in advancing the industrial production of highly branched poly-conjugated dienes.
Disclosure of Invention
The invention provides a high-branched-chain iron-based conjugated diene polymer and a preparation method thereof, wherein the iron-based conjugated diene polymer with high 3, 4-structure content, gel content and glass transition temperature can be prepared by using a bipyridyl iron complex/modified aluminum catalytic system which is cheap and efficient, has excellent solubility and has a definite molecular structure.
In order to solve the above technical problems, the present invention provides an iron-based conjugated diene polymer having a molecular chain in which a proportion of a 3,4- (1,2-) structure is 60 to 80%, a proportion of a 1,4 structure is 20 to 40%, a gel content is less than 1%, and a glass transition temperature is-80 to 10 ℃.
Preferably, the iron-based conjugated diene-based polymer has a number average molecular weight of 10 to 80 ten thousand and a molecular weight distribution of 1.0 to 5.0.
The invention also provides a preparation method of the iron conjugated diene polymer, which comprises the following steps:
under the argon atmosphere, adding a bipyridyl iron complex, a modified aluminum catalytic system, a conjugated diene monomer and a solvent into a reactor to form a reaction system, stirring at 0-90 ℃ to perform polymerization reaction for 10-30 min, adding a quencher 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 the argon atmosphere, adding equimolar amounts of an N, N-bidentate electron-rich compound and an organic iron compound into an anhydrous reaction solvent, and stirring and reacting for 1-36 hours at 0-60 ℃ to obtain a bipyridine iron complex, wherein the bipyridine iron complex has the following structural general formula:
Figure BDA0003513334990000021
preferably, the N, N-bidentate electron rich compound is selected from one of the following structures:
Figure BDA0003513334990000022
preferably, the organic iron compound is Fe (X)nAt 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 selected from at least one of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides, and cycloalkanes.
Preferably, the anhydrous reaction solvent is at least one selected from 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:
adding the modifier into an organic aluminum compound under the atmosphere of argon, and stirring and reacting for 1 min-1 h at-10-30 ℃ to obtain the modified aluminum.
Preferably, the organoaluminum compound is at least one member selected from the group consisting of 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 selected from at least one of 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.
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 proportion of isoprene is 1% to 99%.
Preferably, the solvent is a nonpolar solvent or a polar/nonpolar mixed solvent, wherein the nonpolar solvent is selected from at least one of cyclohexane, n-hexane, n-heptane, petroleum ether, benzene, toluene and xylene, and the polar solvent is selected from at least one of tetrahydrofuran, acetone, acetonitrile, pyridine and chlorobenzene.
Preferably, the polar solvent is present in the polar/nonpolar mixed solvent in a concentration of 0ppm to 400 ppm.
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 (10-100: 1), preferably 40: 1.
Preferably, the volume ratio of the conjugated diene monomer to the solvent is 1: (1 to 20), preferably 1: 5.
preferably, the reaction temperature is 40-70 ℃, and the reaction time is 30 min.
Preferably, the quenching agent 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; 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 the mass concentration of 1%.
Compared with the prior art, the invention has the following remarkable effects:
the conjugated diene polymer obtained by the invention has the characteristics of high content of 3, 4-structure, stable molecular weight, wider molecular weight distribution range, low gel content and low glass transition temperature, and is beneficial to improving the processing performance;
aiming at the problems of poor solubility of the iron-based catalyst and complex process in the heterogeneous polymerization reaction, the invention replaces inorganic anions in the iron-based catalyst with proper organic anions to obviously improve the solubility of the iron-based catalyst, so that the homogeneous polymerization system is used for reaction and the production process of the homogeneous polymerization system is optimized;
aiming at the problem that the whole industrialized production cost is high when a conventional MAO two-component system and a three-component system containing a dealkylation reagent are adopted in the conventional iron-based conjugated diene polymerization process, the invention selects a universal and cheaper alkylaluminum reagent to modify the catalyst, so that the reaction system has the reaction activity equivalent to that of the conventional two-component and conventional three-component catalytic systems while the cost is greatly reduced, namely, the yield of most polymerization reactions is more than 90 percent within 30 min;
the invention adjusts the structure of the N, N-bidentate electron-rich compound in the bipyridyl iron complex, coordinates the bipyridyl iron complex with different organic iron compounds to form bipyridyl iron complexes with different catalytic characteristics, utilizes the synergistic effect of the N, N-bidentate electron-rich compound ligand and organic iron anions to effectively change the electronic effect and the metal center electrical property of the bipyridyl iron complex, influences the polymerization reaction speed and the heat release rate, and further achieves the effect of obviously reducing the gel content in the conjugated diene polymer;
the bipyridyl iron complex/modified aluminum catalytic system designed by the invention is different from the existing conjugated diene catalytic system, has good polar functional group tolerance, and does not influence the reaction yield by introducing partial THF in 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 increased 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 the 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-based rubber; the obtained conjugated diene polymer has the characteristics of high branching, low gel content, no gel and low glass transition temperature, and the quality and the 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 a polymer obtained in example 28 provided by the present invention;
FIG. 3 is a GPC of the polymer obtained in example 28 provided by the present invention;
FIG. 4 shows 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 by the present invention;
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 by the present invention;
fig. 8 is a graph comparing the solubility of catalysts 1,2, 13, and 14 according to the present invention and an iron chloride catalyst.
Detailed Description
Example 1: the structural formula of the bipyridine iron complex (catalyst 1) is as follows:
Figure BDA0003513334990000051
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L1, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c34H53FeN2O6:[M+H]+: theoretical value: 641.3253, respectively; measured value: 641.3257.
elemental analysis: c34H53FeN2O6: theoretical value: c, 63.64%; 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 as follows:
Figure BDA0003513334990000061
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L2, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c36H53FeN2O6:[M+H]+: theoretical value: 665.3253, respectively; measured value: 665.3256.
elemental analysis: c36H53FeN2O6: theoretical value: c, 64.96%; h, 8.03%; n, 4.21%; found C, 64.93%; h, 8.09%; n, 4.27%.
Example 3: the structural formula of the bipyridine iron complex (catalyst 3) is as follows:
Figure BDA0003513334990000062
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L3, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c36H57FeN2O6:[M+H]+: theoretical value: 669.3566, respectively; measured value: 669.3571.
elemental analysis: c36H57FeN2O6: theoretical value: c, 64.57%; h, 8.58%; n, 4.18%; found C, 64.63%; h, 8.52%; n,4.23 percent.
Example 4: the structural formula of the bipyridine iron complex (catalyst 4) is as follows:
Figure BDA0003513334990000071
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (2-EHA) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L4, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c36H57FeN2O6:[M+H]+: theoretical value: 669.3566, respectively; measured value: 669.3568.
elemental analysis: c36H57FeN2O6: theoretical value: c, 64.57%; h, 8.58%; n, 4.18%; found C, 64.61%; h, 8.63%; n,4.21 percent.
Example 5: the structural formula of the bipyridine iron complex (catalyst 5) is as follows:
Figure BDA0003513334990000072
the preparation method comprises the following steps:under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were added thereto in this order2And 0.2mmol of N, N-bidentate electron-rich compound L1, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c32H22FeN2O4:[M+H]+: theoretical value: 554.0929, respectively; measured value: 554.0933.
elemental analysis: c32H22FeN2O4: theoretical value: c, 69.33%; h, 4.00%; n, 5.05%; found C, 69.37%; h, 4.11%; and N, 5.13%.
Example 6: the structural formula of the bipyridine iron complex (catalyst 6) is as follows:
Figure BDA0003513334990000081
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were added thereto in this order2And 0.2mmol of N, N-bidentate electron-rich compound L2, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c34H22FeN2O4:[M+H]+: theoretical value: 578.0929, respectively; measured value: 578.0934.
elemental analysis: c34H22FeN2O4: theoretical value: c, 70.60%; h, 3.83%; n, 4.84%; found C, 70.55%; h, 3.87%; n,4.79 percent.
Example 7: the structural formula of the bipyridine iron complex (catalyst 7) is as follows:
Figure BDA0003513334990000082
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then sequentially added thereto20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) are added2And 0.2mmol of N, N-bidentate electron-rich compound L3, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c34H26FeN2O4:[M+H]+: theoretical value: 582.1242, respectively; measured value: 582.1247.
elemental analysis: c34H26FeN2O4: theoretical value: c, 70.11%; h, 4.50%; n, 4.81%; found C, 70.17%; h, 4.46%; n,4.88 percent.
Example 8: the structural formula of the bipyridine iron complex (catalyst 8) is as follows:
Figure BDA0003513334990000091
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (Naph) were added thereto in this order2And 0.2mmol of N, N-bidentate electron-rich compound L4, and stirring at room temperature for 1h to obtain brown yellow liquid, namely the bipyridyl iron complex solution.
Mass spectrometry analysis: c34H26FeN2O4:[M+H]+: theoretical value: 582.1242, respectively; measured value: 582.1245.
elemental analysis: c34H26FeN2O4: theoretical value: c, 70.11%; h, 4.50%; n, 4.81%; found C, 70.19%; h, 4.53%; n, 4.73%.
Example 9: the structural formula of the bipyridine iron complex (catalyst 9) is as follows:
Figure BDA0003513334990000092
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order2And 0.2mmol of N, N-Stirring and reacting the bidentate electron-rich compound L1 at room temperature for 1h, filtering, concentrating, and vacuum-drying for 12h to obtain a brown yellow solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c20H22FeN2O4:[M+H]+: theoretical value: 411.1002, respectively; measured value: 410.0999.
elemental analysis: c20H22FeN2O4: theoretical value: c, 58.55%; h, 5.41%; n, 6.83%; found C, 58.43%; h, 5.51%; and N,7.02 percent.
Example 10: the structural formula of the bipyridine iron complex (catalyst 10) is:
Figure BDA0003513334990000093
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order2And 0.2mmol of N, N-bidentate electron-rich compound L2, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c22H22FeN2O4:[M+H]+: theoretical value: 435.1002, respectively; measured value: 435.1007.
elemental analysis: c22H22FeN2O4: theoretical value: c, 60.85%; h, 5.11%; n, 6.45%; found C, 61.03%; h, 5.31%; n, 6.61%.
Example 11: the structural formula of the bipyridyl iron complex (catalyst 11) is:
Figure BDA0003513334990000101
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order2And 0.2mmol of N, N-bidentate electron-rich compound L3, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c22H26FeN2O4:[M+H]+: theoretical value: 439.1315, respectively; measured value: 439.1319.
elemental analysis: c22H26FeN2O4: theoretical value: c, 60.29%; h, 5.98%; n, 6.39%; found 59.97% C; h, 5.72%; n,6.54 percent.
Example 12: the structural formula of the bipyridyl iron complex (catalyst 12) is:
Figure BDA0003513334990000102
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L4, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a tan solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c22H26FeN2O4:[M+H]+: theoretical value: 439.1315, respectively; measured value: 439.1317.
elemental analysis: c22H26FeN2O4: theoretical value: c, 60.29%; h, 5.98%; n, 6.39%; found C, 60.18%; h, 6.11%; n,6.46 percent.
Example 13: the structural formula of the bipyridyl iron complex (catalyst 13) is as follows:
Figure BDA0003513334990000111
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of a weight was sequentially added theretoCyclohexane distillation, 0.2mmol Fe (acac)3And 0.2mmol of N, N-bidentate electron-rich compound L1, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c25H29FeN2O6:[M+H]+: theoretical value: 510.1448, respectively; measured value: 510.1451.
elemental analysis: c25H29FeN2O6: theoretical value: c, 58.95%; h, 5.74%; n, 5.50%; found C, 58.71%; h, 5.67%; and N, 5.65%.
Example 14: the structural formula of the bipyridyl iron complex (catalyst 14) is:
Figure BDA0003513334990000112
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L2, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c27H29FeN2O6:[M+H]+: theoretical value: 534.1452, respectively; measured value: 534.1457.
elemental analysis: c27H29FeN2O6: theoretical value: c, 60.80%; h, 5.48%; n, 5.25%; found C, 60.65%; h, 5.37%; and N,5.17 percent.
Example 15: the structural formula of the bipyridyl iron complex (catalyst 15) is as follows:
Figure BDA0003513334990000121
the preparation method comprises the following steps: under argon atmosphere, 25mL Schlenk tube was first vacuum baked three times, thenThen 20mL of redistilled cyclohexane, 0.2mmol of Fe (acac)3And 0.2mmol of N, N-bidentate electron-rich compound L3, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c27H33FeN2O6:[M+H]+: theoretical value: 538.1761, respectively; measured value: 538.1758.
elemental analysis: c27H33FeN2O6: theoretical value: c, 60.34%; h, 6.19%; n, 5.21%; found C, 60.25%; h, 6.34%; and N,5.15 percent.
Example 16: the structural formula of the bipyridyl iron complex (catalyst 16) is:
Figure BDA0003513334990000122
the preparation method comprises the following steps: under argon atmosphere, 25mL of Schlenk tube was first vacuum-baked three times, and then 20mL of redistilled cyclohexane and 0.2mmol of Fe (acac) were added thereto in this order3And 0.2mmol of N, N-bidentate electron-rich compound L4, stirring and reacting for 1h at room temperature, filtering, concentrating, and vacuum drying for 12h to obtain a reddish brown solid product, namely a bipyridyl iron complex solution.
Mass spectrometry analysis: c27H33FeN2O6:[M+H]+: theoretical value: 538.1761, respectively; measured value: 538.1759.
elemental analysis: c27H33FeN2O6: theoretical value: c, 60.34%; h, 6.19%; n, 5.21%; found C, 60.25%; h, 6.27%; and N, 5.25%.
Example 17: modified aluminum reagent 1
The aluminum alloy is prepared from triisobutyl aluminum and water, and the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and 0.1mmol triisobutylaluminum in 6.4. mu. mol of water was mixed to obtain modified aluminum reagent 1.
Example 18: modified aluminum reagent 2
The aluminum alloy is prepared from triisobutyl aluminum and water, and the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and 0.1mmol triisobutylaluminum in 12.8umol water was mixed to obtain modified aluminum reagent 2.
Example 19: modified aluminum reagent 3
The aluminum alloy is prepared from triisobutyl aluminum and water, and the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and 0.1mmol triisobutylaluminum in 25.6. mu.mol water was mixed to obtain a modified aluminum reagent 3.
Example 20: modified aluminum reagent 4
The aluminum alloy is prepared from triisobutyl aluminum and water, and the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and 0.1mmol of water was mixed with 0.1mmol of triisobutylaluminum to obtain a modified aluminum reagent 4.
Example 21: modified aluminum reagent 5
The aluminum alloy is prepared from trimethylaluminum and water by the following steps:
under argon atmosphere, a 100mL Schlenk tube is firstly roasted for three times by pumping, and then 0.1mmol of trimethylaluminum is mixed with 6.4umol of water, so as to obtain a modified aluminum reagent 5.
Example 22: modified aluminum reagent 6
Is prepared from triethyl aluminum and water, and the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and then mixed with 6.4umol of water in an amount corresponding to 0.1mmol of triethylaluminum to obtain a modified aluminum reagent 6.
Example 23: modified aluminium reagent 7
The preparation method is characterized in that the preparation method is as follows:
under argon atmosphere, 100mL of Schlenk tube was first vacuum-baked three times, and 6.4umol cardanol was mixed with 0.1mmol of triisobutylaluminum to obtain modified aluminum reagent 7.
Example 24: modified aluminum reagent 8
The preparation method is characterized in that the preparation method is as follows: under argon atmosphere, 100mL of Schlenk tube was first vacuum-baked three times, and 12.8umol cardanol was mixed with 0.1mmol of triisobutylaluminum to obtain modified aluminum reagent 8.
Example 25: modified aluminum reagent 9
The preparation method is characterized in that the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube was first vacuum-baked three times, and 6.4umol of isooctanoic acid was mixed with 0.1mmol of triisobutylaluminum, to obtain modified aluminum reagent 9.
Example 26: modified aluminum reagent 10
The preparation method is characterized in that the preparation method comprises the following steps:
under argon atmosphere, a 100mL Schlenk tube is firstly roasted for three times, and 6.4umol isooctanol is mixed with 0.1mmol triisobutyl aluminum, so as to obtain a modified aluminum reagent 10.
Example 27: iron-based conjugated diene polymer 1
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 (an ethanol solution of 1% by mass of 2, 6-di-tert-butyl-4-methylphenol, the same as in the following example), and the polymer was washed with ethanol three times after pouring off the clear liquid, thereby obtaining an iron-based conjugated diene polymer 1.
Example 28: iron-based conjugated diene polymer 2
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 2. The hydrogen spectrum, carbon spectrum, GPC test and gel test of the obtained iron-based conjugated diene-based polymer 2 are shown in FIGS. 1 to 4.
The GPC measurement results are shown in tables 1 to 3:
TABLE 1 molecular weight information Table
Figure BDA0003513334990000141
TABLE 2 Peak information Table
Figure BDA0003513334990000151
TABLE 3 Peak tracking information Table
Figure BDA0003513334990000152
Example 29: iron-based conjugated diene polymer 3
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 3.
Example 30: iron-based conjugated diene polymer 4
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 70 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 4.
Example 31: iron-based conjugated diene polymer 5
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 90 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 5.
Example 32: iron-based conjugated diene polymer 6
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), THF (50ppm), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 6.
Example 33: iron-based conjugated diene polymer 7
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), THF (200ppm), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 7.
Example 34: iron-based conjugated diene polymer 8
The preparation method comprises the following steps: to a 250mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (37.5mL), isoprene (7.5mL,75.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added, and polymerization was carried out at 40 ℃ for 30min, followed by terminating 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 8.
Example 35: iron-based conjugated diene polymer 9
The preparation method comprises the following steps: to a 250mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (37.5mL), isoprene (7.5mL,75.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added, and polymerization was carried out at 50 ℃ for 30min, followed by terminating 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 9.
Example 36: iron-based conjugated diene polymer 10
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 2(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerization was carried out at 50 ℃ for 10min, 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 10.
Example 37: iron-based conjugated diene polymer 11
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 3(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 11.
Example 38: iron-based conjugated diene polymer 12
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 4(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerization was carried out at 50 ℃ for 10min, 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 12.
Example 39: iron-based conjugated diene polymer 13
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 5(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 13.
Example 40: iron-based conjugated diene polymer 14
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 6(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 14.
Example 41: iron-based conjugated diene polymer 15
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 7(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 15.
Example 42: iron-based conjugated diene polymer 16
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 8(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 16.
Example 43: iron-based conjugated diene polymer 17
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 9(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 17.
Example 44: iron-based conjugated diene polymer 18
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 10(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 18.
Example 45: iron-based conjugated diene polymer 19
The preparation method comprises the following steps: anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 1(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 19. The DSC chart of the obtained iron-based conjugated diene-based polymer 19 is shown in FIG. 5.
Example 46: iron-based conjugated diene polymer 20
To a 100mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), modified aluminum reagent 1(0.4mmol, 40eq.), catalyst 1(1.0mL,10 μmol), and THF (50ppm) were added in this order, and polymerization was carried out at 50 ℃ for 30min, followed by terminating 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, pouring off the clear liquid, and then the polymer was washed with ethanol three times to obtain iron-based conjugated diene polymer 20.
Example 47: iron-based conjugated diene polymer 21
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 3(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 21.
Example 48: iron-based conjugated diene polymer 22
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 4(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 22.
Example 49: iron-based conjugated diene polymer 23
To a 100mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), a catalyst 5(1.0mL,10 μmol) were sequentially added, and polymerization was carried out at 50 ℃ for 30min, followed by terminating the reaction with 10mL of a mixed solution of methanol and hydrochloric acid (MeOH/HCl volume ratio: 50/1) and 1mL of an antiaging agent, and after pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 23.
Example 50: iron-based conjugated diene polymer 24
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 6(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 24.
Example 51: iron-based conjugated diene polymer 25
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 7(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 25.
Example 52: iron-based conjugated diene polymer 26
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 8(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 26.
Example 53: iron-based conjugated diene polymer 27
Anhydrous cyclohexane (35mL), butadiene (3.5mL,40.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 antiaging agent, and after the clear liquid was decanted, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 27. The DSC chart of the obtained iron-based conjugated diene-based polymer 27 is shown in FIG. 6.
Example 54: iron-based conjugated diene polymer 28
To a 250mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (35mL), butadiene (1.75mL,20.0mmol) and isoprene (2.0mL,20.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were added in this order, polymerized at 50 ℃ for 30min, then quenched 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 28. The DSC chart of the obtained iron-based conjugated diene-based polymer 28 is shown in FIG. 7.
Example 55: iron-based conjugated diene polymer 29
To a 250mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (35mL), butadiene (0.875mL,10.0mmol) and isoprene (3.0mL,30.0mmol), a modified aluminum reagent 1(0.4mmol, 40eq.), and a catalyst 2(1.0mL,10 μmol) were added in this order, polymerized at 50 ℃ for 30min, then quenched 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 29.
Example 56: iron-based conjugated diene polymer 30
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerization was carried out at 0 ℃ for 10min, 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 30.
Example 57: iron-based conjugated diene polymer 31
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerization was carried out at 10 ℃ for 10min, 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 31.
Example 58: iron-based conjugated diene polymer 32
Anhydrous cyclohexane (25mL), isoprene (5mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerization was carried out at 30 ℃ for 10min, 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 pouring off the clear liquid, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 32.
Example 59: iron-based conjugated diene polymer 33
To a 100mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), modified aluminum reagent 1(0.2mmol, 40eq.), catalyst 14(5.3mg,10 μmol.) were added in this order, and polymerization was carried out at 40 ℃ for 30min, followed by terminating 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 the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 33.
Example 60: iron-based conjugated diene polymer 34
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol.) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 50 ℃ 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 clear liquid was removed, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 34.
Example 61: iron-based conjugated diene polymer 35
Anhydrous cyclohexane (25mL), isoprene (5mL,50.0mmol), a modified aluminum reagent 1(0.1mmol, 20eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, 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 pouring off the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 35.
Example 62: iron-based conjugated diene polymer 36
Anhydrous cyclohexane (25mL), isoprene (5mL,50.0mmol), a modified aluminum reagent 1(0.3mmol, 60eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, 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 pouring off the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 36.
Example 63: iron-based conjugated diene polymer 37
Anhydrous cyclohexane (37.5mL), isoprene (7.5mL,75.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized at 40 ℃ for 30min, then the reaction was terminated 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 clear liquid was removed, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 37.
Example 64: iron-based conjugated diene polymer 38
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 2(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 38.
Example 65: iron-based conjugated diene polymer 39
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 3(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 39.
Example 66: iron-based conjugated diene polymer 40
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 4(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 40.
Example 67: iron-based conjugated diene polymer 41
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 5(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 41.
Example 68: iron-based conjugated diene polymer 42
Anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol), a modified aluminum reagent 6(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 42.
Example 69: iron-based conjugated diene polymer 43
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 7(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 43.
Example 70: iron-based conjugated diene polymer 44
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 8(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 44.
Example 71: iron-based conjugated diene polymer 45
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 9(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 45.
Example 72: iron-based conjugated diene polymer 46
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 10(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 46.
Example 73: iron-based conjugated diene polymer 47
To a 100mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), modified aluminum reagent 1(0.2mmol, 40eq.), catalyst 9(4.1mg, 10 μmol) were added in this order, polymerized at 40 ℃ for 30min, then quenched 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 off the clear liquid, the polymer was washed with ethanol three times to obtain iron-based conjugated diene polymer 47.
Example 74: iron-based conjugated diene polymer 48
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 10(4.3mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 48.
Example 75: iron-based conjugated diene polymer 49
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 11(4.4mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 49.
Example 76: iron-based conjugated diene polymer 50
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 12(4.4mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 50.
Example 77: iron-based conjugated diene polymer 51
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 13(5.1mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 51.
Example 78: iron-based conjugated diene polymer 52
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 15(5.4mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 52.
Example 79: iron-based conjugated diene polymer 53
Anhydrous cyclohexane (25mL), isoprene (5.00mL,50.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 16(5.4mg, 10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 antiaging agent, and after the clear liquid was poured off, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 53.
Example 80: iron-based conjugated diene polymer 54
Anhydrous cyclohexane (35mL), butadiene (3.5mL,40.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), and a catalyst 14(5.3mg,10 μmol) were sequentially added to a 100mL Schlenk tube under an argon atmosphere, and polymerized 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 clear liquid was poured off, the polymer was washed three times with ethanol to obtain an iron-based conjugated diene polymer 54.
Example 81: iron-based conjugated diene polymer 55
To a 250mL Schlenk tube under an argon atmosphere, anhydrous cyclohexane (35mL), butadiene (1.75mL,20.0mmol) and isoprene (2.0mL,20.0mmol), a modified aluminum reagent 1(0.2mmol, 40eq.), a catalyst 14(5.3mg,10 μmol) were added in this order, polymerized at 40 ℃ for 30min, then quenched 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 pouring out the clear liquid, the polymer was washed with ethanol three times to obtain an iron-based conjugated diene polymer 55.
Comparative example 1(vs. example 46): iron-based conjugated diene polymer 56
To a 100mL Schlenk tube under an argon atmosphere were added anhydrous cyclohexane (25mL), isoprene (5.0mL,50.0mmol) and [ Ph ] in that order3C]+[B(C6F5)4]-(9.2mg,10μmol)，AliBu3(0.4mmol, 40eq.), catalyst 1(1.0mL, 10. mu. mol), THF (50ppm) was polymerized at 50 ℃ for 30min, 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 clear solution was decanted, the polymer was washed with ethanol three times to obtain iron-based conjugated diene polymer 56.
The physical parameters of the iron-based conjugated diene-based polymers obtained in examples 27 to 81 and comparative example 1 are shown in Table 4.
TABLE 4
Figure BDA0003513334990000271
Figure BDA0003513334990000281
Figure BDA0003513334990000291
Comparative example analysis
In order to better prove that the bipyridyl 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 influenced by introducing partial THF in the system. Therefore, the experimental comparison of the modified aluminum system (example 46) and the conventional conjugated diene three-component system (comparative example 1) in the solvent having the same THF concentration revealed that the reaction yield of the modified aluminum system of the present invention was not affected, complete conversion was achieved, good polar functional group tolerance was exhibited, and the yield was also significantly higher than that of the conventional conjugated diene three-component system.
Performance testing
The catalysts of examples 1,2, 13 and 14 were used as representative examples to perform a solubility comparison experiment with two types of iron chloride catalysts. Test method for solubility comparison: 10mg of 5 different catalysts are respectively dissolved in 3mL of n-hexane solvent, the solubility of the two ferrous chloride catalysts is poor, and most of solid is remained in a bottle. The bipyridyl iron complex solution is transparent and uniform, so that the reaction can be carried out in a homogeneous polymerization system, and the catalytic polymerization of the catalyst participating in the reaction is facilitated, so that the high reaction yield is obtained, and the high activity is represented.

Claims (23)

1. The iron-based conjugated diene polymer is characterized in that in the molecular chain, the proportion of a 3,4- (1,2-) structure is 60-80%, the proportion of a 1,4 structure is 20-40%, the gel content is less than 1%, and the glass transition temperature is-80-10 ℃.
2. The iron-based conjugated diene polymer according to claim 1, wherein the number average molecular weight of the iron-based conjugated diene polymer is 10 to 80 ten thousand, and the molecular weight distribution is 1.0 to 5.0.
3. The method for producing an iron-based conjugated diene-based polymer according to claim 1 or 2, comprising the steps of:
under the argon atmosphere, adding a bipyridyl iron complex, a modified aluminum catalytic system, a conjugated diene monomer and a solvent into a reactor to form a reaction system, stirring at 0-90 ℃ to perform polymerization reaction for 10-30 min, adding a quencher and an anti-aging agent after the reaction is finished, washing and drying to obtain the iron conjugated diene polymer.
4. The preparation method according to claim 3, wherein the bipyridyl iron complex is prepared by:
under the argon atmosphere, adding equimolar amounts of an N, N-bidentate electron-rich compound and an organic iron compound into an anhydrous reaction solvent, and stirring and reacting at 0-60 ℃ for 1-36 hours to obtain a bipyridine iron complex;
the obtained bipyridyl iron complex has the following structural general formula:
Figure FDA0003513334980000011
5. the process according to claim 4, wherein the N, N-bidentate electron-rich compound is selected from one of the following structures:
Figure FDA0003513334980000012
6. the method according to claim 4, 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 hexanoate, iron stearate, and iron octanoate.
7. The production method according to claim 4, wherein the anhydrous reaction solvent is at least one selected from the group consisting of aliphatic saturated hydrocarbons, aromatic hydrocarbons, aryl halides and cycloalkanes.
8. The method according to claim 7, wherein the anhydrous reaction solvent is at least one selected from cyclohexane, n-hexane, ethanol, dichloromethane, dichloropropane and toluene, and chlorobenzene.
9. The preparation method according to claim 4, wherein the reaction temperature is 20-40 ℃ and the reaction time is 1-12 h.
10. The method according to claim 3, wherein the modified aluminum is prepared by:
adding the modifier into an organic aluminum compound under the atmosphere of argon, and stirring and reacting for 1 min-1 h at-10-30 ℃ to obtain the modified aluminum.
11. The production method according to claim 10, wherein the organoaluminum compound is at least one member selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum chloride, diethylaluminum hydride, diisobutylaluminum hydride and dimethylaluminum hydride.
12. The method according to claim 10, wherein 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-butyl catechol, 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.
13. The method according to claim 10, wherein the molar ratio of the organoaluminum compound to the modifier in the modified aluminum is 1: (0.01-2).
14. The method according to claim 3, wherein the conjugated diene compound is at least one selected from isoprene and butadiene.
15. The method according to claim 14, wherein when the conjugated diene compound is a mixture of isoprene and butadiene, the proportion of isoprene is 1% to 99%.
16. The method according to claim 3, wherein 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.
17. The method according to claim 16, wherein the polar solvent is present in the polar/nonpolar mixed solvent in a concentration of 0ppm to 400 ppm.
18. The method according to claim 3, wherein the molar ratio of the conjugated diene monomer to the iron element in the bipyridyl iron complex is (1000 to 20000) to 1, preferably 5000 to 1.
19. The preparation method according to claim 3, wherein the molar ratio of the aluminum element in the modified aluminum to the iron element in the bipyridyl iron complex is (10-100: 1), preferably 40: 1.
20. The method according to claim 3, wherein the volume ratio of the conjugated diene monomer to the solvent is 1: (1 to 20), preferably 1: 5.
21. the method according to claim 3, wherein the reaction temperature is 40 to 70 ℃ and the reaction time is 30 min.
22. The preparation method according to claim 3, wherein the quenching agent 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; the volume ratio of the quenching agent to the solvent is 1: 2.5.
23. the method according to claim 3, 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 the mass concentration of 1%.
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