CN111154088B - Method for catalyzing polymerization of glycolide by using asymmetric binuclear amine imine aluminum complex - Google Patents
Method for catalyzing polymerization of glycolide by using asymmetric binuclear amine imine aluminum complex Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 150000001412 amines Chemical class 0.000 title claims abstract description 27
- 150000002466 imines Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000003446 ligand Substances 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 71
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 22
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- -1 amine imine aluminum compound Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for catalyzing glycolide polymerization by using an asymmetric binuclear amine imine aluminum complex, which comprises the following steps: mixing a catalyst, benzyl alcohol, an organic solvent and glycolide, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after reaction to obtain polyglycolide; the catalyst is a binuclear amine imine aluminum complex. The binuclear amine imine aluminum complex which is researched and developed by self is used as the catalyst for the ring-opening polymerization reaction of glycolide, the catalyst is simple in preparation method, low in cost and special in structure, the metal center aluminum is coordinated with N and N atoms of the ligand, the catalytic activity is high, the reaction rate is high, the obtained polymer is narrow in molecular weight distribution, controllable in molecular weight and high in yield.
Description
Technical Field
The invention relates to a method for catalyzing polymerization of glycolide, in particular to a method for catalyzing polymerization of glycolide 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 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 the polyglycolide make the polyglycolide become a polymer material with the most development prospect in the 21 st century. Glycolide monomer raw materials are derived from renewable resources, and the polymer is biodegradable and environment-friendly, so that the glycolide monomer raw materials are generally concerned as novel bio-based materials.
The glycolide ring-opening polymerization can prepare polymers with high molecular weight, and the molecular weight can be controlled through active 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 polymerization of glycolide by using an asymmetric binuclear amine imine aluminum complex, which is simple to operate, takes a self-developed 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 polyglycolide, 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 glycolide 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 glycolide ring-opening polymerization reaction 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 with 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). FIGS. 1 and 2 are eachAs shown in the crystal structure diagram of the complex with R being methyl and ethyl, it is clear from the figure that the methyl group of trimethylaluminum is 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 time is 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 glycolide, the catalytic activity tends to be improved along with the increase of the steric hindrance of a substituent R.
The invention specifically provides a method for catalyzing polymerization of glycolide by using binuclear amine imine aluminum, which comprises the following steps: mixing a catalyst, benzyl alcohol, an organic solvent and glycolide, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after reaction to obtain polyglycolide. 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 glycolide 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 70 to 100 ℃, for example, 70 ℃, 80 ℃, 90 ℃ and 100 ℃. As the polymerization temperature increases, the catalytic activity tends to increase.
In the ring-opening polymerization reaction, the polymerization reaction time is 90 to 1440 minutes, for example, 90 minutes, 120 minutes, 240 minutes, 300 minutes, 600 minutes, 1440 minutes, and 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. In the ring-opening polymerization reaction, cold methanol is added to purify the polyglycolide after the reaction, and the purified polyglycolide is obtained.
The binuclear amine imine aluminum complex is used as a catalyst to carry out the ring-opening polymerization reaction of glycolide, 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, the metal center aluminum is coordinated with N and N atoms of the 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 polyglycolide
Example 5
The asymmetric binuclear amine imine aluminum complex is used as a catalyst to catalyze the ring-opening polymerization of glycolide to obtain the polyglycolide homopolymer. All the 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 glycolide are sequentially added into an ampoule which is washed and baked by high-purity nitrogen, the concentration of the glycolide is 0.25 mol/L, and then the ampoule is placed in a range of 70-100 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 polyglycolide homopolymer.
Wherein the molar ratio of the glycolide 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 70-100 ℃, and the reaction time is 1.5-24 h. Specific reaction conditions are summarized in table 1.
In Table 1, [ GA ]]/[Al]/[BnOH]Represents the molar ratio of glycolide to aluminum to benzyl alcohol in the catalyst. TOF denotes the amount of material that catalyzes glycolide monomer per unit of catalyst per unit time.M n.calcdThe estimated molecular weight of the product is represented by the formulaM n.calcd= molar ratio of glycolide to benzyl alcohol x yieldX 116.07 (glycolide molecular weight) + 108 (benzyl alcohol molecular weight),M nthe molecular weight is expressed as the value determined by GPC (gel permeation chromatography with polystyrene as standard) multiplied by a factor of 0.58. The PDI represents a molecular weight distribution, and is measured 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.
As can be seen from Table 1, when the asymmetric binuclear amine imine aluminum catalyst is used for catalyzing polymerization of glycolide, 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, and the catalytic activity tends to increase 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.
Polyglycolide was prepared according to the polymerization method of example 5 table 1 No. 4, except that: the catalyst used was the above-mentioned aluminum compound, the reaction time was 10 h. The product obtained was 0.66 g, yield 94%, molecular weight 0.7 ten thousand, molecular weight distribution 1.10. The polymerization activity TOF of the catalyst on glycolide is 18.8 h-1With the catalyst of the invention (TOF of 82.5 h)-1) Compared with the catalyst activity is low.
Comparative example 2
Polyglycolide was prepared according to the polymerization method of example 5 table 1 No. 4, except that: the polymerization temperature was 40 deg.CoCOnly 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 C3The hexane solution (2.0 mol/L, 5 mL) was slowly added to 1/2 times molar amount of the ligand A in toluene solution (30 mL), reacted at room temperature for 12 hours, and after the reaction was completed, the hexane and toluene solvents were vacuum-drained, and dry 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 glycolide 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 glycolide, carrying out ring-opening polymerization reaction under the conditions of no water, no oxygen and gas protection, and treating reactants after reaction to obtain polyglycolide; the molar ratio of glycolide to the catalyst is 200-1000:1, the molar ratio of benzyl alcohol to the catalyst is 2-6: 1, the reaction temperature is 70-100 ℃, and the reaction time is 90-1440 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 the asymmetric binuclear amine imineAn amine 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 5, 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 glycolide in the organic solvent is 0.2-0.3 mol/L.
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| CN102627758A (en) * | 2012-03-31 | 2012-08-08 | 济南大学 | Dual-core amine imine zinc catalyst and preparation method and application thereof |
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