CN109134730B - Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof - Google Patents
Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN109134730B CN109134730B CN201810864108.3A CN201810864108A CN109134730B CN 109134730 B CN109134730 B CN 109134730B CN 201810864108 A CN201810864108 A CN 201810864108A CN 109134730 B CN109134730 B CN 109134730B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- iron
- isoprene
- pyridylamine
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses an aryl substituted pyridylamine iron-based catalyst and a preparation method and application thereof, and relates to the technical field of conjugated diene catalytic polymerization, wherein the iron-based catalyst consists of a main catalyst and an auxiliary catalyst, the main catalyst is an aryl substituted pyridylamine iron complex, the auxiliary catalyst is methylaluminoxane or alkylaluminium, and the molar ratio of the auxiliary catalyst to the main catalyst is 100:1-2000: 1. The iron catalytic system has higher activity in isoprene polymerization, the obtained polymer has high molecular weight and narrow molecular weight distribution, the microstructure of the polymer can be regulated and controlled by adjusting the structure of a main catalyst, and meanwhile, the activity of the reaction depends on the main catalysts with different substituent groups and different types of auxiliary catalysts.
Description
Technical Field
The invention relates to the field of conjugated diene catalytic polymerization, in particular to a pyridylamine iron-based catalyst, and also relates to a preparation method and application of the catalyst in isoprene polymerization.
Background
In recent years, more and more attention has been paid to environmentally friendly late transition metal catalyzed olefin polymerizations by scientists. Iron-based catalysts have also gained wide attention in isoprene polymerization due to their environmental friendliness, economy, biocompatibility, and better tolerance to polar monomers. The prior nitrogen-containing ligand for catalyzing isoprene polymerization by using iron catalyst is mainly sp2–N，sp2The catalyst has an undefined catalyst structure or active center, low activity, poor selectivity and low molecular weight of a synthetic polymer.
Disclosure of Invention
In order to solve the problems, the invention provides an aryl substituted pyridylamine iron-based catalyst, and a preparation method and application thereof.
An aryl substituted pyridylamine iron catalyst is characterized in that: comprises a main catalyst and a cocatalyst, wherein the main catalyst is a pyridylamine iron complex with a general structural formula
Wherein R is1Is phenyl, substituted phenyl or substituted heteroaromatic ring; r2Is H, methyl, ethyl or phenyl; r3Hydrogen, hydrocarbyl (not limited to methyl, ethyl, etc.), aryl (not limited to phenyl, other polycyclic aryl, etc.), or halogen (Br, Cl, etc.); the cocatalyst is Methyl Aluminoxane (MAO) or alkyl aluminum, and the structural general formula of the methyl aluminoxane is shown in the specification
Wherein n is a natural number of 4-40, and the alkyl aluminum is one of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum; the molar ratio of the aluminum element in the cocatalyst to the iron element in the main catalyst is (100-2000):1, and the preferred molar ratio is 500: 1. The system has high catalytic activity in catalyzing isoprene polymerization reaction, and the obtained microscopic microstructure of the polymer is mainly trans-1,4 structure.
The pyridylamine iron complex, preferably R1Is phenyl, 2, 6-diisopropylphenyl, 2, 6-bis (benzhydryl) phenyl, 4-trifluoromethylphenyl, 2,4, 6-trifluorophenyl, 4-methoxyphenyl; r2Is H, R3Is H, and the structural formula is one of the following structural formulas:
the invention also provides a preparation method of the pyridylamine iron complex, which comprises the following steps: in anhydrous DCM, pyridylamine ligand was reacted with anhydrous FeCl2In a molar ratio of 1:1, stirring and reacting for 24-48h at room temperature, carrying out post-treatment, and finally drying to obtain the pyridylamine iron complex.
The post-treatment specifically comprises the following steps: filtering under argon atmosphere, collecting residue or filtrate, vacuum drying, and washing with n-hexane for 2-5 times (until the filtrate is colorless and clear). The drying is vacuum pumping.
The DCM was used in such an amount that the concentration of the pyridylamine ligand was 0.1 mol/L.
The structural formula of the pyridylamine ligand is one of the following structural formulas:
the invention also provides the application of the catalyst in isoprene polymerization: under the anhydrous and anaerobic conditions, adding a pyridylamine iron complex, an isoprene monomer, a cocatalyst and a solvent into a reactor to form a reaction system, then stirring to carry out polymerization reaction, adding a quenching agent after the reaction is finished, washing twice with ethanol, and separating and purifying to obtain a polyisoprene product.
The solvent is one or more of toluene, pentane or hexane, toluene is preferred, and the concentration of isoprene is 4 mol/L.
In the reaction system, the molar ratio of the monomer isoprene to the iron element in the main catalyst in the iron-based catalyst is (1000-.
The temperature of the polymerization reaction is 0-50 ℃, and the polymerization time is 1-4 h. The reaction temperature is preferably 25 ℃ and the reaction time is preferably 2 h.
The reaction system also comprises a dealkylation reagent which is B (C)6F5)3，[Ph3C][B(C6F5)4],[PhNMe2H][B(C6F5)4]One kind of (1); the molar ratio of boron element in the dealkylation reagent to iron element in the main catalyst is (1-10): 1. Preferably in a 1:1 molar ratio.
The quenching agent is methanol hydrochloric acid solution, wherein the volume ratio of methanol to hydrochloric acid is 50: 1; the dosage is 2 times of the volume of the solvent; and after the reaction is finished, an anti-aging agent can be added, wherein the anti-aging agent is an ethanol solution of 1% of 2, 6-di-tert-butyl-4-methylphenol by mass, and the using amount of the anti-aging agent is 20% of the volume of the solvent.
The influence of the sequence of addition on the reactivity and selectivity in the above-mentioned polymerization reactions. The feeding sequence can be as follows:
(1) sequentially adding a cocatalyst, a solvent and isoprene, and then adding a main catalyst for polymerization reaction to obtain polyisoprene;
or (2) sequentially adding the cocatalyst, the solvent and the main catalyst, and then adding isoprene for polymerization reaction to obtain polyisoprene.
Or (3) sequentially adding the main catalyst, the toluene and the isoprene, and then adding the cocatalyst for polymerization reaction to obtain the polyisoprene.
The invention has the beneficial effects that:
1. the iron catalytic system is a first example of pyridine arylamine iron complex for catalyzing isoprene polymerization, and the main catalytic preparation is simple and easy to obtain and low in cost; isoprene polymerization can be carried out in either two components of methylaluminoxane or three components of alkylaluminum and dealkylating agent.
2. The whole catalytic isoprene polymerization system has high reaction activity, and the microstructure of the polymer is mainly cis-1, 4. The obtained polyisoprene has cis-1, 4-structure 0-80%, trans-1, 4-structure 0-30%, and 3, 4-structure 20-60%
3. The iron-based catalyst has high tolerance to industrial isoprene and pure isoprene as a reagent, and the two-component system does not use an expensive dealkylation reagent, so that the cost is lower, and the iron-based catalyst has good industrial value.
Detailed description of the preferred embodiments
The invention is further illustrated by the following specific examples:
preparation of main catalyst pyridine imine iron complex
Example 1
This example prepares an iron pyridinimine complex of formula (A):
the 25mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And isopropyl-substituted pyridimine ligand (1.5mmol) (formula LA), stirred at room temperature for 24 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant to obtain ashWhite solid, structural formula:
mass spectrometry analysis: c12H12Cl2FeN2:[M-Cl]+: theoretical value: 275.0033, respectively; measured value: 275.0042.
elemental analysis: c12H12Cl2FeN2: theoretical value: c, 46.35; h, 3.89; n, 9.01; found C, 46.41%; h, 3.85%; and N, 8.98%.
Example 2
The preparation process of the pyridine imine iron complex shown in the formula (B) prepared in this example is specifically as follows:
the 25mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And tert-butyl substituted pyridinimine ligand (1.5mmol) (formula LB) stirred at room temperature for 24 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant, so that light blue solid with the structural formula:
mass spectrometry analysis: c18H24Cl2FeN2[M-Cl]+: theoretical value: 359.0972, respectively; measured value: 359.0968.
elemental analysis: c18H24Cl2FeN2: theoretical value: c, 54.71; h, 6.12; n, 7.09; found C, 54.68%; h, 6.09%; and 7.13 percent of N.
Example 3
The preparation process of the pyridine imine iron complex shown in the formula (C) prepared in this example is specifically as follows:
the 10mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And cyclohexyl substituted pyridimine ligand (1.5mmol) (formula LC) stirred at room temperature for 48 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant, so that a light red solid with a structural formula:
mass spectrometry analysis: c38H32Cl2FeN2[M-Cl]+: theoretical value: 607.1598, respectively; measured value: 607.1601.
elemental analysis: c38H32Cl2FeN2: theoretical value: c, 70.93; h, 5.01; n, 4.35; found C, 71.01%; h, 4.98%; n,4.30 percent.
Example 4
The preparation process of the pyridine imine iron complex shown in formula (D) prepared in this example is specifically as follows:
the 10mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And cyclohexyl-substituted pyridimine ligand (formula LD) (1.5mmol) and stirred at room temperature for 48 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant, so that light yellow solid with the structural formula:
mass spectrometry analysis: c13H11Cl2F3FeN2[M-Cl]+: theoretical value: 342.9907, respectively; measured value: 342.9905.
elemental analysis: c13H11Cl2F3FeN2: theoretical value: c, 41.20; h, 2.93; n,7.39 found C, 41.18%; h, 2.95%; n,7.41 percent.
Example 5
The preparation process of the pyridine imine iron complex shown in the formula (E) prepared in this example is specifically as follows:
the 10mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And cyclohexyl substituted pyridinimine ligand (1.5mmol) (Structure LE), stirred at room temperature for 48 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant, so that a light brown solid with a structural formula:
mass spectrometry analysis: c12H9Cl2F3FeN2[M-Cl]+: theoretical value: 328.9750, respectively; measured value: 328.9755.
elemental analysis: c12H9Cl2F3FeN2: theoretical value: c, 39.49; h, 2.49; n, 7.68; found C, 39.51%; h, 2.51%; n,7.71 percent.
Example 6
The preparation process of the pyridine imine iron complex shown in the formula (F) prepared in this example is specifically as follows:
the 10mL Schlenk reaction tube is pumped and baked for three times, and 15mL redistilled dichloromethane and anhydrous FeCl with equal molar ratio are sequentially added into a glove box2And cyclohexyl substituted pyridimine ligand (1.5mmol) (formula LF), stirred at room temperature for 48 h. After the reaction is finished, the dichloromethane is dried in vacuum, 10mL redistilled n-hexane is added for washing for 2 times (the filtrate is colorless and clear), and the dichloromethane is dried in vacuum until the weight is constant, so that light yellow solid with the structural formula:
mass spectrometry analysis: c13H14Cl2FeN2O[M-Cl]+: theoretical value: 305.0139, respectively; measured value: 305.0142.
elemental analysis: c13H14Cl2FeN2O: theoretical value: c, 45.79; h, 4.14; n, 8.21; found C, 45.82%; h, 4.09%; n, 8.16%.
Isoprene polymerization
In the catalytic polymerization reaction, the main catalyst can be added separately or in the form of its dichloromethane solution.
Example 7
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, trimethylaluminum (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,10 μmol) in 1mL of dichloromethane were sequentially added, and polymerized at 25 ℃ for 2h, and the reaction was quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and no polymer was obtained.
Example 8
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, triethylaluminum (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, and polymerized at 25 ℃ for 2h, and the reaction was quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and no polymer was obtained.
Example 9
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, diethyl aluminum monochloride (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, and polymerized at 25 ℃ for 2h, and the reaction was quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and no polymer was obtained.
Example 10
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, ethyl aluminum dichloride (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. The yield is more than 99%, and the polymer is mostly cation polymerization crosslinking product.
Example 11
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 74%, number average molecular weight (Mn): 52468, molecular weight distribution (PDI): 3.8. the proportion of different structures: cis-1, 4-structure accounts for 40%, trans-1, 4-structure accounts for 11%, and 3, 4-structure accounts for 49%.
Example 12
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (8mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 75%, number average molecular weight (Mn): 35178, molecular weight distribution (PDI): 3.6. the proportion of different structures: cis-1, 4-structure accounts for 45%, trans-1, 4-structure accounts for 15%, and 3, 4-structure accounts for 40%.
Example 13
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (2mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 68%, number average molecular weight (Mn): 56328, molecular weight distribution (PDI): 3.0. the proportion of different structures: cis-1, 4-structure accounts for 48%, trans-1, 4-structure accounts for 11%, and 3, 4-structure accounts for 41%.
Example 14
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (0.8mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 55%, number average molecular weight (Mn): 34958, molecular weight distribution (PDI): 2.8. the proportion of different structures: cis-1, 4-structure accounts for 45%, trans-1, 4-structure accounts for 10%, and 3, 4-structure accounts for 45%.
Example 15
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, anhydrous hexane 5mL, methylaluminoxane (0.16mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in dichloromethane 1mL were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. No polymer was obtained.
Example 16
In a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol) and the catalyst prepared in example 1 (2.48mg,8 μmol) in the order of 1mL of dichloromethane were added, followed by isoprene (2mL,20.0mmol), and polymerized at 25 ℃ for 2h, the reaction was quenched with 10mL of methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 78%, number average molecular weight (Mn): 46482, molecular weight distribution (PDI): 3.0. the proportion of different structures: cis-1, 4-structure accounts for 46%, trans-1, 4-structure accounts for 10%, and 3, 4-structure accounts for 44%.
Example 17
The catalyst prepared in example 1 (2.48mg,8 μmol), 5mL of anhydrous toluene, isoprene (2mL,20.0mmol) and then methylaluminoxane (4mmol) were sequentially added to a 25mL schiekg (Schlenk) tube under an argon atmosphere, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloric acid solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 74%, number average molecular weight (Mn): 53649, molecular weight distribution (PDI): 3.8. the proportion of different structures: the cis-1, 4-structure accounts for 43%, the trans-1, 4-structure accounts for 7%, and the 3, 4-structure accounts for 50%.
Example 18
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous tetrahydrofuran, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, and polymerized at 25 ℃ for 2h, and the reaction was quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and no polymer was obtained.
Example 19
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, anhydrous hexane 5mL, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in dichloromethane 1mL were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 70%, number average molecular weight (Mn): 32498, molecular weight distribution (PDI): 3.4. the proportion of different structures: the cis-1, 4-structure accounts for 55%, the trans-1, 4-structure accounts for 8%, and the 3-4-structure accounts for 37%.
Example 20
To a 25mL schinke (Schlenk) tube under an argon atmosphere, 5mL of anhydrous pentane, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were added in this order, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 69%, number average molecular weight (Mn): 34667 molecular weight distribution (PDI): 4.8. the proportion of different structures: the cis-1, 4-structure accounts for 42%, the trans-1, 4-structure accounts for 16%, and the 3, 4-structure accounts for 42%.
Example 22
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 50 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 35%, number average molecular weight (Mn): 24835, molecular weight distribution (PDI): 3.2. the proportion of different structures: the cis-1, 4-structure accounts for 49%, the trans-1, 4-structure accounts for 11%, and the 3, 4-structure accounts for 40%.
Example 22
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 0 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 60%, number average molecular weight (Mn): 71269, molecular weight distribution (PDI): 4.0. the proportion of different structures: the cis-1, 4-structure accounts for 49%, the trans-1, 4-structure accounts for 11%, and the 3, 4-structure accounts for 40%.
Example 23
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 1 (2.48mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at-25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 30%, number average molecular weight (Mn): 75589, molecular weight distribution (PDI): 2.5. the proportion of different structures: the cis-1, 4-structure accounts for 48%, the trans-1, 4-structure accounts for 10%, and the 3, 4-structure accounts for 42%.
Example 24
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 2 (3.28mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 52%, number average molecular weight (Mn): 46422, molecular weight distribution (PDI): 3.1. the proportion of different structures: the cis-1, 4-structure accounts for 74%, the trans-1, 4-structure accounts for 0%, and the 3, 4-structure accounts for 26%.
Example 25
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 3 (5.26mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 72%, number average molecular weight (Mn): 38249, molecular weight distribution (PDI): 2.8. the proportion of different structures: cis-1-, 4-structure accounts for 80%, trans-1, 4-structure accounts for 0%, and 3, 4-structure accounts for 20%.
Example 26
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 4 (3.02mg,8 μmol) in 1mL of dichloromethane were added in this order, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 63%, number average molecular weight (Mn): 42105, molecular weight distribution (PDI): 3.4. the proportion of different structures: cis-1-, 4-structure accounts for 50%, trans-1, 4-structure accounts for 11%, and 3, 4-structure accounts for 39%.
Example 27
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 5 (2.91mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 23%, number average molecular weight (Mn): 39892, molecular weight distribution (PDI): 2.4. the proportion of different structures: cis-1-, 4-structure accounts for 45%, trans-1, 4-structure accounts for 10%, and 3, 4-structure accounts for 45%.
Example 28
To a 25mL schiekg (Schlenk) tube under an argon atmosphere, 5mL of anhydrous toluene, methylaluminoxane (4mmol), isoprene (2mL,20.0mmol), a solution of the catalyst prepared in example 6 (2.72mg,8 μmol) in 1mL of dichloromethane were sequentially added, polymerized at 25 ℃ for 2h, quenched with 10mL of methanol hydrochloride solution (MeOH/HCl ═ 50/1), and washed twice with ethanol to give an elastomeric polymer. Yield: 56%, number average molecular weight (Mn): 34289, molecular weight distribution (PDI): 2.6. the proportion of different structures: cis-1-, 4-structure accounts for 55%, trans-1, 4-structure accounts for 10%, and 3, 4-structure accounts for 35%.
Example 29
To a 25mL Hilenk (Schlenk) tube under argon atmosphere were added 5mL of anhydrous toluene, 0.16mmol of trimethylaluminum, and 2mL of a solution of the catalyst prepared in example 1 (2.48mg, 8. mu. mol) in 2mL of dichloromethane in that order, followed by stirring for 2min, and then added a boron salt [ CPh ]3][B(C6F5)4](8 μmol), stirred for 2min, isoprene (2mL,20mmol) polymerized at 25 ℃ for 2h, quenched with 10mL methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1) and washed twice with ethanol to give elastomeric polymer. Yield: 65%, number average molecular weight (Mn): 12245, molecular weight distribution (PDI): 2.8. the proportion of different structures: the cis-1, 4-structure accounts for 42%, the trans-1, 4-structure accounts for 14%, and the 3, 4-structure accounts for 34%.
Example 30
To a 25mL Hilenk (Schlenk) tube under an argon atmosphere were added 5mL of anhydrous toluene, triethylaluminum (0.16mmol), and a solution of the catalyst prepared in example 1 (2.48mg, 8. mu. mol) in 2mL of dichloromethane in that order, followed by stirring for 2min, and then added a boron salt [ CPh ]3][B(C6F5)4](8 μmol), stirred for 2min, isoprene (2mL,20mmol) polymerized at 25 ℃ for 2h, quenched with 10mL methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1) and washed twice with ethanol to give elastomeric polymer. Yield: 58%, number average molecular weight (Mn): 10389, molecular weight distribution (PDI): 3.2. the proportion of different structures: cis-1, 4-structure accounts for 48%, trans-1, 4-structure accounts for 13%, and 3, 4-structure accounts for 39%.
Example 31
Under an argon atmosphere, at 25mLTo a leek (Schlenk) tube, 5mL of anhydrous toluene, triisobutylaluminum (0.16mmol), 2mL of a dichloromethane solution of the catalyst (2.48mg, 8. mu. mol) prepared in example 1 were added in this order, stirred for 2min, and a boron salt [ CPh ] was added3][B(C6F5)4](8 μmol), stirred for 2min, isoprene (2mL,20mmol) polymerized at 25 ℃ for 2h, quenched with 10mL methanolic hydrochloric acid solution (MeOH/HCl ═ 50/1) and washed twice with ethanol to give elastomeric polymer. Yield: 60%, number average molecular weight (Mn): 15486, molecular weight distribution (PDI): 2.6. the proportion of different structures: cis-1, 4-structure accounts for 46%, trans-1, 4-structure accounts for 6%, and 3, 4-structure accounts for 48%.
The data set for some of the examples is as follows.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the illustrated embodiments, and any other changes, modifications, combinations, substitutions and simplifications which do not depart from the spirit and principle of the present invention are deemed to be equivalent substitutions and shall be included within the protection scope of the present invention.
Claims (3)
1. The application of the aryl substituted pyridylamine iron catalyst in isoprene polymerization is characterized in that: the aryl substituted pyridylamine iron system catalyst consists of a main catalyst and an auxiliary catalyst, wherein the main catalyst is a pyridylamine iron complex, the pyridylamine iron complex, an isoprene monomer, the auxiliary catalyst and a solvent are added into a reactor to form a reaction system under the anhydrous and anaerobic conditions, then the reaction system is stirred to carry out polymerization reaction, a quenching agent is added after the reaction is finished, the reaction system is washed twice by ethanol, and a polyisoprene product is obtained by separation and purification;
the structural formula of the pyridylamine iron complex is one of the following structural formulas:
the cocatalyst is Methylaluminoxane (MAO), and the structural general formula of the methylaluminoxane is
Wherein n is a natural number of 4-40, and the molar ratio of the aluminum element in the cocatalyst to the iron element in the main catalyst is (100-; the solvent is one of toluene, pentane or hexane, so that the concentration of the isoprene monomer is 4 mol/L.
2. Use according to claim 1, characterized in that: in the reaction system, the molar ratio of the monomer isoprene to the iron element in the main catalyst in the iron-based catalyst is (1000- & ltSUB- & gt 5000- & gt) 1.
3. Use according to claim 1, characterized in that: the temperature of the polymerization reaction is 0-50 ℃, and the polymerization time is 1-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864108.3A CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864108.3A CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109134730A CN109134730A (en) | 2019-01-04 |
| CN109134730B true CN109134730B (en) | 2021-03-12 |
Family
ID=64798638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810864108.3A Active CN109134730B (en) | 2018-08-01 | 2018-08-01 | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134730B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912732B (en) * | 2019-03-11 | 2021-04-27 | 中国科学院青岛生物能源与过程研究所 | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof |
| CN109851700B (en) * | 2019-03-11 | 2021-07-27 | 中国科学院青岛生物能源与过程研究所 | Tridentate pyridinimine iron-based catalyst and preparation method and application thereof |
| CN111303214B (en) * | 2020-03-27 | 2023-02-17 | 中国科学院青岛生物能源与过程研究所 | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same |
| CN112175123B (en) * | 2020-09-27 | 2022-09-27 | 中国科学院青岛生物能源与过程研究所 | Poly-conjugated diene liquid rubber and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
| CA3036579A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex |
| WO2018073795A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (iii) complex |
-
2018
- 2018-08-01 CN CN201810864108.3A patent/CN109134730B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
| CA3036579A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex |
| WO2018073795A1 (en) * | 2016-10-20 | 2018-04-26 | Versalis S.P.A. | Process for preparing conjugated diene (co)polymers in the presence of a catalytic system comprising a pyridyl iron (iii) complex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109134730A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
| CN109134730B (en) | Aryl substituted pyridylamine iron catalyst, and preparation method and application thereof | |
| CN109851700B (en) | Tridentate pyridinimine iron-based catalyst and preparation method and application thereof | |
| CN109053937B (en) | Alkyl substituted pyridylamine iron-based catalyst and preparation method and application thereof | |
| CN110452272B (en) | Bipyridine iron complex, preparation method thereof and application thereof in conjugated diene polymerization | |
| CN108586641B (en) | High-efficiency iron-based catalyst for catalyzing isoprene polymerization and preparation method and application thereof | |
| CN109912732B (en) | Bond-forming pyridylamine iron-based catalyst and preparation method and application thereof | |
| Cui | Molecular catalysis of rare-earth elements | |
| CN110305169B (en) | Substituted bipyridyl ferric iron complex and preparation method and application thereof | |
| CN112442092B (en) | 6-methoxypyridine iron imine complex, preparation method thereof and application thereof in preparation of high-cis-poly conjugated diene | |
| CN111303214B (en) | Pyridine tertiary amine iron complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| EP3808753B1 (en) | Bipyridine iron complex, preparation method thereof and application in polymerization of conjugated diene | |
| CN108641026B (en) | Application of benzyl imine pyridine iron complex in preparation of isoprene rubber | |
| CN108659055B (en) | Iron complex based on flexible framework, preparation method thereof and application thereof in isoprene polymerization | |
| CN112062787A (en) | Pyridine imine titanium complex and application thereof in conjugated diene catalytic polymerization | |
| CN108484809B (en) | Olefin polymerization catalyst | |
| CN107312115B (en) | Bis-indole rare earth metal catalyst, preparation method and application | |
| CN110305168B (en) | Substituted bipyridyl ferrous complex and preparation method and application thereof | |
| CN111233938A (en) | Pyrimidineacetylacetone ferrous complex, preparation method thereof and method for catalyzing polymerization of conjugated diene by using same | |
| CN112707937B (en) | Heteroaromatic ring tridentate pyridine imine iron complex, preparation method thereof and application thereof in catalysis of polymerization of conjugated diene | |
| KR100440480B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefins | |
| CN112142893B (en) | Polyisoprene and preparation method thereof | |
| CN114736245B (en) | Pyridine-2-oxime-iron complex, preparation method thereof and application thereof in preparation of conjugated diene rubber | |
| CN115873045B (en) | N, N-bidentate iron carboxylate complex, preparation method and application thereof in conjugated diene polymerization | |
| CN112175122B (en) | Application of tridentate salicylaldiminato titanium complex, poly-conjugated diene, and preparation method and application of poly-conjugated diene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |