CN111378099B - Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex - Google Patents
Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex Download PDFInfo
- Publication number
- CN111378099B CN111378099B CN202010128398.2A CN202010128398A CN111378099B CN 111378099 B CN111378099 B CN 111378099B CN 202010128398 A CN202010128398 A CN 202010128398A CN 111378099 B CN111378099 B CN 111378099B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- ligand
- caprolactone
- aluminum complex
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for catalyzing caprolactone polymerization by using an asymmetric binuclear amine imine aluminum complex, which comprises the following steps: mixing a catalyst, benzyl alcohol, an organic solvent and caprolactone, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after the reaction to obtain polycaprolactone. The asymmetric binuclear amine imine aluminum complex catalyst is used for the caprolactone ring-opening polymerization reaction, is simple in preparation method, low in cost, high in product yield, special in catalyst structure, high in catalytic activity and high in reaction rate, and the obtained polymer is narrow in molecular weight distribution, controllable in molecular weight and high in yield, and has N and N atom coordination between metal center aluminum and ligand.
Description
Technical Field
The invention relates to a method for catalyzing caprolactone polymerization, in particular to a method for catalyzing caprolactone polymerization by using an asymmetric binuclear amine imine aluminum complex.
Background
With the enhancement of environmental awareness, the development of degradable biological materials capable of reducing environmental pollution is one of important research fields of polymer materials. Polylactone is a biodegradable, green and environment-friendly high polymer material, and is receiving more and more attention as a substitute of petroleum products. In a natural living environment, the waste polylactone material can be thoroughly decomposed into small molecules by microorganisms in soil. Because polyester is non-toxic, non-irritating, and has good biocompatibility, it is widely used in medical and environmental fields, such as surgical sutures, packaging, drug controlled release, and tissue engineering scaffolds, etc. The excellent biocompatibility, biodegradability and sustainable development and utilization performance of polycaprolactone make polycaprolactone become a polymer material with the greatest development prospect in the 21 st century. The caprolactone monomer raw material is derived from renewable resources, and the polycaprolactone polymer is biodegradable and environment-friendly, so that the caprolactone monomer raw material is generally concerned as a novel bio-based material.
The caprolactone ring-opening polymerization can prepare high molecular weight polymers, and the molecular weight can be controlled through activity controllable polymerization. In recent years, scholars at home and abroad make a great deal of research work from the aspects of reducing the preparation cost and low toxicity of the catalyst and improving the molecular weight and stability of the polymer, and develop a plurality of metal complex catalysts with excellent performance. However, a problem still to be solved is that the products obtained from the metal complex catalysts are inevitably accompanied by metal residues, and it is almost impossible to completely remove these residues from the polymers, so that low-toxicity aluminum complexes become more promising catalysts, and such catalysts are more important particularly when the polymers are applied to the biomedical field. Due to the excellent catalytic performance of the binuclear metal catalyst, the research of a new binuclear aluminum catalyst with good performance and low toxicity is necessary.
Disclosure of Invention
The invention provides a method for catalyzing caprolactone polymerization by using an asymmetric binuclear amine imine aluminum complex, which is simple to operate, takes the automatically developed asymmetric binuclear amine imine aluminum complex as a catalyst, and has the advantages of high catalytic activity, low catalyst toxicity, good reaction controllability, controllable molecular weight of the obtained polycaprolactone, narrow molecular weight distribution and high yield.
The specific technical scheme of the invention is as follows:
the invention provides an asymmetric binuclear amine imine aluminum complex catalyst with a special structure, which has a special structure and good caprolactone catalytic activity, and has a structural formula shown as a formula I or a formula II, wherein R is hydrogen or methyl, and R is ethyl or isopropyl, preferably isopropyl.
The asymmetric binuclear amine imine aluminum compound is a complex, has excellent catalytic performance by coordination of N and N atoms of a ligand and a metal aluminum center, has a special ligand structure, and has great influence on the catalytic performance of the aluminum complex as a caprolactone ring-opening polymerization catalyst due to the selection of a substituent group in the ligand. Wherein, the performance is excellent when R is hydrogen, methyl, ethyl or isopropyl. Further, the introduction of a substituent having a large steric hindrance increases the catalytic activity of the aluminum catalyst. Therefore, the catalyst is preferably of the structure shown in formula II, and R is preferably isopropyl.
The binuclear amine imine aluminum complex is prepared from AlMe3The ligand A reacts with the ligand A at the temperature of 60-100 ℃, and the preparation method comprises the following specific steps: firstly, AlMe3Slowly adding the ligand A into the ligand A at room temperature, and raising the temperature to 60-100 ℃ after the ligand A is addedoC, reacting, and then, vacuum-pumping the solvent, washing and filtering to obtain the asymmetric binuclear amine imine aluminum complex.
Ligands A and AlMe3The reaction equation is as follows, wherein the ligand A is reported in the literature, and the specific synthetic method is referred to in the literature (Polyhedron 85 (2015) 537-542). The structural formula of the ligand A is shown as the following formula, R is hydrogen, methyl, ethyl or isopropyl, and R is preferably isopropyl; wherein, when R is hydrogen or methyl, the ligand A and AlMe3The product obtained by the reaction is a compound shown as a formula I, and when R is ethyl or isopropyl, the ligand A and AlMe3The product obtained by the reaction is a compound shown as a formula II.
In the above preparation method, the ligand a and trimethylaluminum undergo an addition reaction, and the methyl group of trimethylaluminum is added to the C = N double bond in the ligand a, and the C = N double bond becomes a C — N single bond. The nuclear magnetism characterization shows that the crystal has a characteristic peak at 1.25-1.30 ppm, and the characteristic peak is CH3Characteristic peak of (2). Fig. 1 and 2 are crystal structures of a complex in which R is methyl and ethyl, respectively, and it is clear from the crystal structures that methyl groups of trimethylaluminum are added to the C = N double bond in the ligand a.
In the preparation method, the ligand A and the AlMe31: 2.
in the above preparation, ligands A and AlMe3The reaction is carried out in an organic solvent, which may be hexane, toluene, etc. The organic solvent is used for providing a medium for the reaction, and the dosage of the organic solvent can be adjusted according to actual needs. Generally, the organic solvent is used as the reaction raw material (AlMe)3And 5-10 times of the total mass of the ligand A).
In one embodiment of the present invention, AlMe is added3Dissolving in hexane to obtain solution, dissolving ligand A in toluene to obtain solution, and dissolving AlMe3And adding the hexane solution into the toluene solution of the ligand A, and heating to 60-100 ℃ for reaction after the hexane solution is added. In the preparation method, the reaction is carried out under the protection of gas, and the gas is inert gas.
In the preparation method, the reaction temperature is 60-100 DEG CoC by reaction, e.g. 60oC、70oC、80oC, preferably 60 to 80oC. In the range of 60 to 100oC (preferably 60 to 80)oC) The reaction is carried out for 1 to 12 hours, preferably 3 to 6 hours. After the reaction, the precipitate was washed with n-hexane.
In the above preparation method, AlMe3And (3) after the reaction with the ligand A, removing the organic solvent from the reaction solution, washing the residue with n-hexane, and filtering to obtain the asymmetric binuclear amine imine aluminum complex product.
When the asymmetric binuclear amine imine aluminum complex is used as a catalyst for the ring-opening polymerization reaction of caprolactone, the catalytic activity tends to be improved along with the increase of the steric hindrance of a substituent R.
The invention also provides a method for catalyzing caprolactone polymerization by using the binuclear amine imine aluminum, which comprises the following steps: mixing the binuclear amine imine aluminum catalyst, benzyl alcohol, an organic solvent and caprolactone, carrying out ring-opening polymerization reaction under the conditions of no water and no oxygen and gas protection, and treating reactants after reaction to obtain polycaprolactone. The structural formula of the binuclear amine imine aluminum catalyst and the preparation method thereof are as described above.
In the ring-opening polymerization reaction, the molar ratio of caprolactone to the binuclear amine imine aluminum catalyst is 200-1000:1, e.g., 200:1, 400:1, 600: 1. 800:1 and 1000: 1.
In the ring-opening polymerization reaction, the molar ratio of the benzyl alcohol to the catalyst is 2-6: 1, e.g. 2: 1. 3: 1. 4: 1. 5: 1. 6: 1.
in the ring-opening polymerization, the polymerization temperature is 20 to 70 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃. As the polymerization temperature increases, the catalytic activity tends to increase.
In the ring-opening polymerization reaction, the polymerization reaction time is 1 to 60 minutes, for example, 1 minute, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, or the like.
In the ring-opening polymerization reaction, the organic solvent is toluene, hexane or the like. The organic solvent is used for providing a medium for the reaction, and the dosage of the organic solvent can be adjusted according to actual needs. In one embodiment of the present invention, the concentration of caprolactone in the organic solvent is 0.2 to 0.3 mol/L.
Further, in the ring-opening polymerization reaction, the protective gas is an inert gas or nitrogen.
And in the ring-opening polymerization reaction, cold methanol is added after the reaction to purify polycaprolactone, so that purified polycaprolactone is obtained.
The binuclear amine imine aluminum complex is used as a catalyst to carry out caprolactone ring-opening polymerization reaction, and the binuclear amine imine aluminum catalyst is prepared at a higher temperature, so that the preparation method is simple, the cost is low, the product yield is high, the catalyst structure is special, metal center aluminum is coordinated with N and N atoms of a ligand, the catalytic activity is high, the reaction rate is high, the molecular weight distribution of the obtained polymer is narrow, the molecular weight is controllable, the yield is high, and the market demand is met.
Drawings
FIG. 1 is a crystal structure diagram of a complex in which R is a methyl group prepared in example 2.
FIG. 2 is a crystal structure diagram of a complex prepared in example 3 in which R is ethyl.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
Preparation of aluminum complex by using ligand A as raw material
The asymmetric binuclear amine aluminum complex consists of ligand A and AlMe3Formed by the elimination of alkyl groups and addition reaction, the reaction formula is as follows.
Example 1
The structural formula of the ligand is shown as the formula (A), wherein R is hydrogen, and the reaction process is as follows: under the nitrogen atmosphere, the AlMe is added at room temperature3The hexane solution (2.0 mol/L, 5 mL) was slowly added to 1/2 times molar amount of ligand A in toluene (30 mL), heated to 60 ℃ for reaction for 12 hours, after the reaction was completed, the hexane and toluene solvent were vacuum-drained, washed with dry n-hexane, filtered, collected and dried and weighed to give 5.07 g of solid, 84.5% yield.
The nuclear magnetic information is as follows:
1H NMR (300 MHz, CDCl3, 293K):δ = 8.30 (s, 1H, ArCH=N), 7.48 (d, J = 6.5Hz, 1H, Ar–H), 7.35–7.28 (m, 4H, Ar–H), 6.72–6.55 (m, 6H, Ar–H), 6.34 (d, J = 6.6 Hz, 1H, Ar–H), 6.21(d, J = 6.5 Hz, 1H, Ar–H), 6.00 (d, J = 6.7 Hz, 1H, Ar–H), 3.59 (m, 1H, C=NCH), 3.10 (m, 1H, ArCH(CH3)N), 2.41 (m, 1H, CHNCHCH2), 1.93 (m, 4H, CH 2), 1.66 (m, 2H, CH 2), 1.55 (m, 2H, CH 2), 1.25 (s, 3H, NCHCH 3) , –0.40 (s, 6H, AlCH 3), –0.75 (s, 6H, AlCH 3) ppm.
from the nuclear magnetic information, the resulting product has a structure similar to that of fig. 1.
Example 2
The structural formula of the ligand is shown as the formula (A), wherein R is methyl, and the reaction process is as follows: under the nitrogen atmosphere, the AlMe is added at room temperature3The hexane solution (2.0 mol/L, 5 mL) was slowly added to 1/2 times molar amount of ligand A in toluene (40 mL), heated to 100 ℃ for reaction for 1 hour, after the reaction was completed, the hexane and toluene solvent were vacuum-drained, washed with dry n-hexane, filtered, collected and dried and weighed to give 5.76 g of solid, 87.8% yield.
The nuclear magnetic information is as follows:
1H NMR (300 MHz, CDCl3, 293K):δ = 8.33 (s, 1H, ArCH=N), 7.52 (d, J = 7.0 Hz, 1H, Ar–H), 7.38–7.28 (m, 4H, Ar–H), 6.70–6.58 (m, 6H, Ar–H), 6.31 (d, J = 6.5 Hz, 1H, Ar–H), 6.23(d, J = 7.4 Hz, 1H, Ar–H), 5.98 (d, J = 8.0 Hz, 1H, Ar–H), 3.58 (m, 1H, C=NCH), 3.08 (m, 1H, ArCH(CH3)N), 2.43 (m, 1H, CHNCHCH2), 2.39 (s, 6H, ArCH 3), 2.30 (s, 6H, ArCH 3), 1.94 (m, 4H, CH 2), 1.64 (m, 2H, CH 2), 1.54 (m, 2H, CH 2), 1.30 (s, 3H, NCHCH 3) , –0.44 (s, 6H, AlCH 3), –0.72 (s, 6H, AlCH 3) ppm.
the crystal structure of the obtained product is shown in fig. 1, and is consistent with nuclear magnetic information.
Example 3
The structural formula of the ligand is shown as the formula (A), wherein R is ethyl, and the reaction process is as follows: under the nitrogen atmosphere, the AlMe is added at room temperature3The hexane solution (2.0 mol/L, 5 mL) was slowly added to 1/2 times molar amount of ligand A in toluene (50 mL), heated to 80 ℃ for reaction for 3 hours, after the reaction was completed, the hexane and toluene solvent were vacuum-drained, washed with dry n-hexane, filtered, collected and dried and weighed to give 6.07 g of solid, 87.2% yield.
The nuclear magnetic information is as follows:
1H NMR (400 MHz, CDCl3, 293K):δ = 8.28 (s, 1H, ArCH=N), 7.42 (d, J = 7.2 Hz, 1H, Ar–H), 7.35–7.28 (m, 7H, Ar–H), 6.74 (d, J = 7.5 Hz, 1H, Ar–H), 6.52–6.43 (m, 2H, Ar–H), 6.20 (d, J = 6.8 Hz, 1H, Ar–H), 6.08(d, J = 7.0 Hz, 1H, Ar–H), 5.90 (d, J = 8.0 Hz, 1H, Ar–H), 3.52 (m, 1H, C=NCH), 3.08 (m, 1H, ArCH(CH3)N), 2.79–2.72 (m, 4H, ArCH 2CH3), 2.64–2.58 (m, 4H, ArCH 2CH3), 2.48 (m, 1H, CHNCHCH2), 2.02–1.90 (m, 4H, CH 2), 1.68–1.62 (m, 2H, CH 2), 1.50–1.42 (m, 2H, CH 2), 1.33 (t, J = 7.6 Hz, 6H, CH2CH 3), 1.28 (s, 3H, NCHCH 3), 1.24 (t, J = 7.2 Hz, 6H, CH2CH 3), –0.40 (s, 3H, AlCH 3), –0.52 (s, 6H, AlCH 3) ppm.
the crystal structure of the obtained product is shown in fig. 2, consistent with nuclear magnetic information.
Example 4
The structural formula of the ligand is shown as the formula (A), wherein R is isopropyl, and the reaction process is as follows: under the nitrogen atmosphere, the AlMe is added at room temperature3The hexane solution (2.0 mol/L, 5 mL) was slowly added to 1/2 times molar amount of ligand A in toluene (60 mL), heated to 70 ℃ for reaction for 6 hours, after the reaction was completed, the hexane and toluene solvent were vacuum-drained, dried n-hexane was added for washing, filtered, collected, dried and weighed to give 6.26 g of solid, 83.2% yield.
The nuclear magnetic information is as follows:
1H NMR (400 MHz, CDCl3, 293K): δ = 8.20 (s, 1H, ArCH=N), 7.70 (d, J = 6.2 Hz, 1H, Ar–H), 7.25–7.14 (m, 5H, Ar–H), 7.10–7.01 (m, 2H, Ar–H), 6.62 (t, J = 7.0 Hz, 1H, Ar–H), 6.52–6.40 (m, 2H, Ar–H), 6.35 (d, J = 6.5 Hz, 1H, Ar–H), 6.23 (d, J = 6.2 Hz, 1H, Ar–H), 6.00 (d, J = 6.0 Hz, 1H, Ar–H), 4.16 (m, 2H, C=NCH), 3.55–3.47 (m, 2H, CH(CH3)2), 3.40–3.34 (m, 2H, CH(CH3)2), 1.84 (m, 6H, CH 2), 1.69–1.50 (m, 2H, CH 2), 0.73 (s, 6H, CH(CH 3)2), 0.67 (s, 6H, CH(CH 3)2), 0.65 (s, 6H, CH(CH 3)2), 0.62 (s, 6H, CH(CH 3)2), –0.42 (s, 3H, AlCH 3), –0.55 (s, 6H, AlCH 3) ppm.
from the nuclear magnetic information, the resulting product has a structure similar to that of fig. 2.
Preparation of polycaprolactone
Example 5
The asymmetric binuclear amine imine aluminum complex is used as a catalyst to catalyze the ring-opening polymerization of caprolactone to obtain a polycaprolactone homopolymer. All operations are carried out under the protection of anhydrous and oxygen-free inert gas, firstly, 30 mu mol of asymmetric binuclear amine imine aluminum complex catalyst, toluene, benzyl alcohol and caprolactone are sequentially added into an ampoule which is washed and baked by high-purity nitrogen, the concentration of the caprolactone is 0.25 mol/L, and then the ampoule is placed in a range of 20-70 mol/LoC, adding a small amount of water to stop the reaction after the reaction is finished, precipitating and washing the mixture for a plurality of times by using methanol, and drying the mixture in vacuum at room temperature to obtain the polycaprolactone homopolymer.
Wherein the molar ratio of the caprolactone monomer to the catalyst is 200-1000:1, the molar ratio of the catalyst to the benzyl alcohol is 1:2-6, the reaction temperature is 20-70 ℃, and the reaction time is 1-60 min. The specific reaction conditions are summarized in table 1.
In Table 1, [ 2 ]ε-CL]/[Al]/[BnOH]Represents the molar ratio of caprolactone to aluminum to benzyl alcohol in the catalyst. TOF represents the amount of material that catalyzes caprolactone monomer per unit of catalyst per unit of time.M n.calcdThe estimated molecular weight of the product is represented by the formulaM n.calcd= molar ratio caprolactone to benzyl alcohol × yield × 114.14 (caprolactone molecular weight) + 108 (benzyl alcohol molecular weight),M nmolecular weight is represented by a value obtained by GPC (gel permeation chromatography using polystyrene as a standard) multiplied by a factor of 0.58, and PDI represents a molecular weight distribution obtained by GPC (gel permeation chromatography using polystyrene as a standard).
In table 1, catalyst 1 is the aluminum complex of example 1; catalyst 2 is the aluminum complex of example 2; catalyst 3 is the aluminum complex of example 3; catalyst 4 was the aluminum complex of example 4.
From the polymerization result, the catalyst has high catalytic activity and high reaction rate when being combined with benzyl alcohol, the obtained polymer has narrow molecular weight distribution and controllable molecular weight, and the catalytic activity tends to be improved along with the increase of the steric hindrance of a substituent R.
Comparative example 1
Preparation of aluminum compounds of similar structure, and concrete preparation method thereof (referenceDalton Trans.2008, 3199-3206), the structural formula is shown as follows.
Caprolactone is polymerized by using the aluminum compound with the structure as a catalyst under the condition of the number 8 in the table 1 of the example 5, and the TOF of the obtained product is 972 h-1With the aluminum catalyst of the invention (TOF 11880 h)-1) Compared with the catalyst activity is low.
Comparative example 2
Polycaprolactone was prepared according to the polymerization method of example 5 table 1 No. 8, except that: the polymerization temperature was 0oCOnly a small amount of polymer is produced.
Comparative example 3
The structural formula of the ligand is shown as the formula (A), wherein R is hydrogen, and the reaction process is as follows: under nitrogen atmosphere, AlMe is added at-20 DEG C3Hexane solution (2.0 mol/L, 5 mL) was added slowlyThe reaction mixture was added to 1/2 times molar amount of a toluene solution (30 mL) of ligand A, reacted at room temperature for 12 hours, and after the reaction was completed, the hexane and toluene solvents were vacuum-dried, and dried n-hexane was added. After the addition of hexane, a yellow oil was obtained, which could not be further purified to obtain the desired product.
Claims (10)
1. A method for catalyzing caprolactone polymerization by using an asymmetric binuclear amine imine aluminum complex is characterized by comprising the following steps: mixing a catalyst, benzyl alcohol, an organic solvent and caprolactone, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after the reaction to obtain polycaprolactone; the molar ratio of caprolactone to the catalyst is 200-1000:1, the molar ratio of benzyl alcohol to the catalyst is 2-6: 1, the reaction temperature is 20-70 ℃, and the reaction time is 1-60 minutes;
the catalyst is an asymmetric binuclear amine imine aluminum complex, and the structural formula of the catalyst is shown as a formula I or a formula II, wherein in the formula I, R is hydrogen or methyl, and in the formula II, R is ethyl or isopropyl;
2. the method of claim 1, further comprising: in the formula II, R is isopropyl.
3. The method of claim 1, further comprising: the preparation method of the asymmetric binuclear amine imine aluminum complex catalyst comprises the following steps: mixing AlMe3Reacting with a ligand A at 60-100 ℃ to obtain an asymmetric binuclear amine imine aluminum complex; the structural formula of the ligand A is shown in the specification, wherein R is hydrogen, methyl, ethyl or isopropyl;
4. The method of claim 3, wherein: in the ligand A, R is isopropyl.
5. The method of claim 3, wherein: during the preparation of the catalyst, AlMe is added3And adding the hexane solution into the toluene solution of the ligand A, and heating to 60-100 ℃ for reaction after the hexane solution is added.
6. The method of claim 3, wherein: during catalyst preparation, AlMe3Reacting with the ligand A at 60-80 ℃.
7. The method of claim 3, 5 or 6, wherein: in the preparation process of the catalyst, the reaction time is 1-12 hours.
8. The method of claim 7, wherein: in the preparation process of the catalyst, the reaction time is 3-6 hours.
9. The method of claim 3, wherein: during the preparation of the catalyst, the reaction is carried out under the protection of nitrogen or inert gas.
10. The method according to any of claims 1-6, characterized by: during the ring-opening polymerization reaction, the organic solvent is toluene or hexane; the concentration of the caprolactone in the organic solvent is 0.2-0.3 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010128398.2A CN111378099B (en) | 2020-02-28 | 2020-02-28 | Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010128398.2A CN111378099B (en) | 2020-02-28 | 2020-02-28 | Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111378099A CN111378099A (en) | 2020-07-07 |
| CN111378099B true CN111378099B (en) | 2022-06-07 |
Family
ID=71217148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010128398.2A Active CN111378099B (en) | 2020-02-28 | 2020-02-28 | Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111378099B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516516A (en) * | 2011-11-30 | 2012-06-27 | 济南艾孚特科技有限责任公司 | Quadridentate imine imide aluminum catalyst and preparation method and application thereof |
| CN102627758B (en) * | 2012-03-31 | 2014-06-04 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
| CN102924292B (en) * | 2012-11-06 | 2014-09-03 | 济南大学 | Chiral tetra-amino aniline ligand, aluminum compound thereof, preparation method and application |
| CN108503812B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing o-phenylenediamine group |
| CN109679081B (en) * | 2018-12-14 | 2021-04-13 | 泰山医学院 | Method for catalyzing caprolactone polymerization by using binuclear chiral amine imine magnesium complex |
-
2020
- 2020-02-28 CN CN202010128398.2A patent/CN111378099B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111378099A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109679081B (en) | Method for catalyzing caprolactone polymerization by using binuclear chiral amine imine magnesium complex | |
| CN109485840B (en) | Method for catalyzing lactide polymerization by using amine imine magnesium complex | |
| CN109679082B (en) | Method for catalyzing polymerization of glycolide by using binuclear chiral amine imine magnesium complex | |
| CN109734880B (en) | Method for catalyzing lactide polymerization by using binuclear chiral amine imine magnesium complex | |
| CN109749072B (en) | Method for catalyzing lactide polymerization by dinuclear amine imine magnesium complex | |
| CN108569993B (en) | Tetradentate nitrogen-oxygen symmetric ligand containing chiral cyclohexanediamine and preparation method and application thereof | |
| CN108239102B (en) | Aluminum complex containing salicylaldehyde group and preparation method and application thereof | |
| CN111269402B (en) | Method for catalyzing lactide polymerization by using asymmetric binuclear amine imine aluminum complex | |
| CN111378099B (en) | Method for catalyzing caprolactone polymerization by using asymmetric binuclear amine imine aluminum complex | |
| CN109679080B (en) | Method for catalyzing caprolactone polymerization by using amine imine magnesium complex | |
| CN108570066B (en) | Aluminum compound containing chiral cyclohexanediamine and preparation method and application thereof | |
| CN111154088B (en) | Method for catalyzing polymerization of glycolide by using asymmetric binuclear amine imine aluminum complex | |
| CN108570143B (en) | Method for catalyzing polymerization of glycolide by using aluminum compound containing chiral cyclohexanediamine | |
| CN111285891B (en) | Asymmetric binuclear amine imine aluminum complex and preparation method and application thereof | |
| CN109438486B (en) | Amine imine magnesium complex and preparation method and application thereof | |
| CN104592501A (en) | Preparation method of polycaprolactone | |
| CN109749062B (en) | Method for catalyzing caprolactone polymerization by dinuclear amine imine magnesium complex | |
| CN109694469B (en) | Method for catalyzing polymerization of glycolide by using amine imine magnesium complex | |
| CN109749063B (en) | Method for catalyzing polymerization of glycolide by using binuclear amine imine magnesium complex | |
| CN108503801B (en) | Method for catalyzing lactide polymerization by using o-phenylenediamine-containing asymmetric aluminum complex | |
| CN108503661B (en) | Asymmetric aluminum complex containing o-phenylenediamine group, and preparation method and application thereof | |
| CN108239263B (en) | Method for catalyzing caprolactone polymerization by using salicylaldehyde-containing aluminum complex | |
| CN108003087B (en) | Chiral asymmetric nitrogen-oxygen ligand containing salicylaldehyde group and preparation method and application thereof | |
| CN108503812B (en) | Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing o-phenylenediamine group | |
| CN108084411B (en) | Method for catalyzing glycolide polymerization by using chiral aluminum complex containing acetylacetone derivative |
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 |