CN108239102B - Aluminum complex containing salicylaldehyde group and preparation method and application thereof - Google Patents
Aluminum complex containing salicylaldehyde group and preparation method and application thereof Download PDFInfo
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- 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 System
- 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)
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- 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
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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
Abstract
The invention discloses an aluminum complex containing salicylaldehyde groups, and a preparation method and application thereof, wherein the aluminum complex has a structural formula shown in a formula I, and R is hydrogen, C1-C4 alkane or halogen. The aluminum complex catalyst containing salicylaldehyde groups is obtained by the reaction of a ligand and trimethylaluminum, the preparation method is simple, the cost is low, the product yield is high, the compound has a special structure and various structural changes, the divalent N, N, O and O of the metal center aluminum and the ligand are coordinated, the compound can be used as a catalyst for ring-opening polymerization of cyclic lactone, the catalytic activity is high, the stereoselectivity is good, the reaction rate is high, the polymerization operation is simple, the obtained polymerization product has narrow molecular weight distribution, controllable molecular weight and high yield, and the catalyst can be widely used for ring-opening polymerization of cyclic lactone and is an ideal catalyst.
Description
Technical Field
The invention relates to an aluminum complex containing salicylaldehyde groups and a preparation method thereof, and also relates to application of the aluminum complex containing salicylaldehyde groups as a catalyst for ring-opening polymerization reaction of cyclic lactone.
Background
Traditional plastics based on petroleum, which have a considerable impact in industry since the last 40 s, have incomparable advantages but two fatal disadvantages: non-regenerability and non-degradability. Under the condition that petroleum is exhausted as a non-renewable resource, the rapid development of polymer plastic materials depending on petroleum raw materials is greatly restricted, the polymer plastic materials are difficult to degrade, and the pollution to the living environment of human beings, which is caused by the long-term accumulation of a large amount of polymer plastic material wastes in real life, is gradually increased. The renewable resources replacing petroleum are searched, and the development of environment-friendly and biodegradable new materials becomes the development trend of future high-molecular polymer plastic materials.
Polyester is a biodegradable green environment-friendly polymer material, and is receiving more and more attention as a substitute for petroleum products. In a natural living environment, the waste polylactone material can be thoroughly decomposed into water and carbon dioxide by microorganisms in soil, is environment-friendly and is renewable. 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 polylactone make the polylactone become a polymer material with the greatest development prospect in the 21 st century.
The convenient method for synthesizing the polyester is a ring-opening polymerization method of the cyclic lactone, and the synthesis method has the advantages that: controllability of polymerization, narrower molecular weight distribution. The catalyst commonly used at present is a complex formed by a ligand and a metal, and the metal in the catalyst comprises magnesium, calcium, germanium, tin, aluminum, zinc, iron, titanium, zirconium, lanthanide series and the like. In the metal complex catalyst, the selection of the ligand and the selective catalyst of the metal is very critical to the speed of the ring-opening polymerization reaction and the performance of the obtained product, the replacement and selection of the ligand often show unexpected catalytic effects under the condition of the same metal, and the replacement of the metal can also generate different catalytic effects under the condition of the same ligand, so that the research of a new catalyst with good performance is very necessary.
Disclosure of Invention
The invention provides an aluminum complex containing salicylaldehyde groups, which can be used as a catalyst for ring-opening polymerization of cyclic lactone, and has the advantages of high catalytic activity, good stereoselectivity, good controllability of molecular weight of the obtained polymer and good application prospect.
The invention also provides a preparation method of the salicylaldehyde-containing aluminum complex and application of the salicylaldehyde-containing aluminum complex as a catalyst for ring-opening polymerization reaction of cyclic lactone.
The invention is completed under the subsidization of the national Natural fund Commission youth project (No 21104026), and the technical scheme of the invention is as follows:
the salicylaldehyde-containing aluminum complex has a structural formula shown in a formula I:
the aluminum complex containing salicylaldehyde groups is a complex, has excellent performance through selection of a ligand structure and coordination with metal aluminum, has a special ligand structure, and has great influence on the catalytic performance of the aluminum complex serving as a catalyst for ring-opening polymerization of cyclic lactone. Wherein R is hydrogen, C1-C4 alkane or halogen, and the halogen is fluorine, chlorine, bromine or iodine. Furthermore, when R is tert-butyl, the stereoselectivity is best, and when R is bromine, the catalytic activity is best.
The aluminum complex containing salicylaldehyde groups is obtained by reacting a ligand with trimethylaluminum, and the preparation method comprises the following steps: adding the ligand A into an organic solvent at-10-0%oAdding trimethylaluminum under C, naturally raising the reaction temperature to room temperature after the addition is finished, and then raising the temperature to 30-110 DEG CoC, reacting, and then, vacuum-pumping the solvent, washing and filtering to obtain the salicylaldehyde-containing aluminum complex shown in the formula I.
The formula of the reaction of the ligand A and trimethylaluminum is shown as follows, wherein the structural formula of the ligand A is shown as the following formula, R is hydrogen, C1-C4 alkane or halogen, and the halogen is fluorine, chlorine, bromine and iodine; r is preferably tert-butyl or bromine;
in the above preparation method, the preparation method of the ligand A comprises the following steps: dissolving p-toluenesulfonic acid into xylene, slowly adding ethylenediamine with the same molar amount of the p-toluenesulfonic acid, adding phthalic anhydride with the same molar amount of the p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, and filtering to obtain p-toluenesulfonic acid and phthalic anhydride protected ethylenediamine; dissolving p-toluenesulfonic acid and phthalic anhydride protected ethylenediamine into dichloromethane, slowly dropwise adding saturated sodium bicarbonate aqueous solution for reaction to remove the p-toluenesulfonic acid, separating liquid after the reaction is finished, drying the obtained organic phase with anhydrous magnesium sulfate, and then spin-drying the solvent to obtain unilateral phthalic anhydride protected ethylenediamine;
dissolving ethylenediamine protected by single-side phthalic anhydride and equimolar salicylaldehyde or a derivative thereof in methanol, heating for reflux reaction, cooling and filtering after the reaction is finished, and washing and drying the obtained solid with cold methanol to obtain a ligand A; the structural formula of the salicylaldehyde derivative is shown as the following formula B, wherein R is hydrogen, C1-C4 alkane or halogen, and is preferably tert-butyl or bromine;
in the above preparation method, the ligand a and trimethylaluminum undergo an addition reaction, and an alkyl group of trimethylaluminum is added to a C = O double bond in the ligand a, and the C = O double bond is changed to a C — O single bond. Is found in by nuclear magnetic characterizationA group of CH is arranged near the range of = 1.5-2.03The characteristic peak of (A) is NC (O) (Ar) CH 3Middle CH3Characteristic peak of (2).
In the preparation method, the molar ratio of the ligand A to the trimethylaluminum is 1: 1 to 1.3, preferably 1: 1 to 1.05.
In the above preparation method, the organic solvent is one or two of dried hexane, toluene and cyclohexane, and is preferably dried hexane or toluene.
In the preparation method, the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the ligand A and the trimethylaluminum).
In the preparation method, the reaction is carried out under the protection of gas, and the gas is inert gas or nitrogen.
In the preparation method, the reaction is naturally raised to room temperature and then raised to 30-110 DEG CoC by reaction, e.g. 30oC、40oC、50oC、60oC、70oC、80oC、90oC、100oC、110oC, preferably 40 to 60oC. In the range of 30 to 110oC (preferably 40-60)oC) The reaction time is 1 to 12 hours, preferably 3 to 6 hours. After the reaction, the precipitate was washed with n-hexane.
The aluminum complex containing the salicylaldehyde group is an intermediate product for preparing the compound shown in the formula II, is sensitive to water, can be hydrolyzed by adding water into a reaction solution obtained after a ligand A and trimethylaluminum react and fully stirring, and is subjected to liquid separation, organic phase collection and solvent recovery treatment, and the obtained remainder is recrystallized to obtain the compound shown in the formula II. Therefore, the preparation of the aluminum complex is carried out in the absence of water and a protic solvent. In addition, the compound of the formula II is used as a raw material, the ligand A is replaced by the compound of the formula II, and the salicylaldehyde-containing aluminum complex of the formula I can be obtained according to the preparation method of the salicylaldehyde-containing aluminum complex.
When the compound shown in the formula II is used for preparing the salicylaldehyde-containing aluminum complex, the organic solvent is one or two of dry hexane, toluene and cyclohexane, and the organic solvent is preferably hexane or toluene. The dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials (the compound and the trimethylaluminum in the formula II). After the reaction is finished, dried hexane is used for recrystallization, and the high-purity aluminum complex containing salicylaldehyde group in the formula I is obtained.
The aluminum complex containing salicylaldehyde groups is a complex, N, N, O, O of the ligand is coordinated with aluminum, the structure of the complex is very similar to that of a classical cyclic lactone catalyst (salenAl), the catalytic effect is good, and the stereoselectivity is high. The invention also protects the application of the aluminum complex containing salicylaldehyde groups as a catalyst for ring-opening polymerization reaction of cyclic lactone.
When the salicylaldehyde-containing aluminum complex is used as a catalyst for ring-opening polymerization reaction of cyclic lactone, ring-opening polymerization of various cyclic lactone can be catalyzed to obtain a series of polylactones. The cyclic lactone may be-one or two of caprolactone, lactide and glycolide, the lactide being, in turn, levolactide, meso-lactide, racemic lactide. When the salicylaldehyde-containing aluminum complex is used as a catalyst to carry out ring-opening polymerization of cyclic lactone, the polymer obtained by the reaction has narrow molecular mass distribution, controllable molecular weight and high yield, and especially when the catalyst is used for catalyzing polymerization of racemic lactide, the isotactic polypropylene with high melting point is obtainedLactide shows higher stereoselectivity which can reach the highestP m= 0.83。
When the salicylaldehyde-containing aluminum complex is used as a catalyst for ring-opening polymerization of cyclic lactone, the stereoselectivity is optimal when R is tert-butyl, and the catalytic activity is optimal when R is bromine.
When the salicylaldehyde-containing aluminum complex is used as a catalyst, the ring-opening polymerization reaction of the cyclic lactone specifically comprises the following steps: mixing an aluminum complex catalyst containing salicylaldehyde, an organic solvent, an alcohol cocatalyst and cyclic lactone, carrying out ring-opening polymerization reaction under the protection of anhydrous oxygen-free and inert gas, and treating reactants after reaction to obtain polylactone.
In the ring-opening polymerization reaction, the molar ratio of the cyclic lactone to the salicylaldehyde-containing aluminum complex catalyst is 50-1500: 1, e.g., 50:1, 100: 1. 150:1, 200:1, 300:1, 400:1, 500:1, 600: 1. 800:1, 1000:1, 1200:1, 1500: 1.
in the ring-opening polymerization reaction, the organic solvent used in the reaction is toluene or tetrahydrofuran, and toluene is preferred.
In the ring-opening polymerization reaction, the alcohol co-catalyst is benzyl alcohol. The molar ratio of the benzyl alcohol cocatalyst to the aluminum complex catalyst containing the salicylaldehyde group is 1-3: 1.
in the ring-opening polymerization, the polymerization temperature is 20 to 110 ℃ such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and 110 ℃. The stereoselectivity of the catalyst tends to be reduced and the catalytic activity tends to be improved along with the increase of the polymerization reaction temperature, and when the reaction temperature is 80 ℃, the stereoselectivity of the racemic lactide can be achievedP m= 0.64, stereoselectivity when catalyzing racemic lactide at 20 deg.CP m= 0.83。
In the ring-opening polymerization reaction, the polymerization reaction time is 1 to 1440 minutes, for example, 1 minute, 10 minutes, 30 minutes, 40 minutes, 60 minutes, 120 minutes, 240 minutes, 600 minutes, 900 minutes, 1200 minutes, 1440 minutes, and the like.
In the ring-opening polymerization reaction, cold methanol or ethanol is added to purify the polylactone after the reaction, so as to obtain the purified polylactone.
The aluminum complex containing salicylaldehyde groups has high catalytic activity when being used as a ring-opening polymerization reaction catalyst, ring opening of cyclic lactone is catalyzed in the presence of benzyl alcohol, and due to the fact that the structure of the aluminum in the metal center of the catalyst is a NNOO coordinated chiral structure, isotactic polylactide with high melting point is obtained when lactide polymerization is catalyzed, and the obtained polymer is a benzyloxy-terminated polymer. In catalyzing caprolactone and glycolide, the resulting polymer is also a benzyloxy-terminated polymer.
The aluminum complex catalyst containing salicylaldehyde groups is obtained by the reaction of a ligand and trimethylaluminum, the preparation method is simple, the cost is low, the product yield is high, the compound has a special structure and various structural changes, the divalent N, N, O and O of the metal center aluminum and the ligand are coordinated, the compound can be used as a catalyst for ring-opening polymerization of cyclic lactone, the catalytic activity is high, the stereoselectivity is good, the reaction rate is high, the polymerization operation is simple, the obtained polymerization product has narrow molecular weight distribution, controllable molecular weight and high yield, and the catalyst can be widely used for ring-opening polymerization of cyclic lactone and is an ideal catalyst.
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.
In the examples described below, the stereoselectivity of isotactic polylactide was tested using NMR homonuclear decoupled hydrogen spectroscopy.
Preparation of one-sided protected ethylenediamine (a)
Dissolving 0.50 g of p-toluenesulfonic acid into xylene, slowly adding ethylenediamine with the same molar amount of the p-toluenesulfonic acid, adding phthalic anhydride with the same molar amount of the p-toluenesulfonic acid, heating and refluxing for 8 hours, cooling to room temperature after the reaction is finished, filtering, washing and drying to obtain the p-toluenesulfonic acid and phthalic anhydride protected ethylenediamine. Dissolving p-toluenesulfonic acid and phthalic anhydride protected ethylenediamine into dichloromethane, slowly dropwise adding an excessive saturated aqueous solution of sodium bicarbonate at room temperature for reaction to remove the p-toluenesulfonic acid, separating liquid after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain 0.48 g of unilateral phthalic anhydride protected ethylenediamine with the yield of 87.3%.
Preparation of salicylaldehyde-containing ligand (A)
The ligand containing salicylaldehyde group is obtained by condensation reaction of unilaterally protected ethylenediamine and salicylaldehyde or a derivative thereof, and different synthetic ligands A are exemplified below.
Example 1
The structural formula of the synthesized ligand is shown as the formula (A), wherein R is hydrogen, and the reaction process is as follows: 0.20 g of the mono-protected ethylenediamine (a) and an equimolar amount of salicylaldehyde were added to 10 mL of methanol, and the mixture was heated under reflux for 12 hours, cooled and filtered after the reaction was completed, and washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.27 g of a solid with a yield of 87.1%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.85 (s, 1H, OH), 8.26 (s, 1H, ArHC=N),7.80 (d,J= 5.4 Hz, 2H, Ar–H), 7.68 (d,J= 5.4Hz, 2H, Ar–H), 7.24–7.16 (m,1H, Ar–H), 7.11 (m, 1H, Ar–H), 6.97 (d,J= 8.3 Hz, 1H, Ar–H), 6.75 (td,J=7.5, 1.0 Hz, 1H, Ar–H), 4.20 (m, 2H, NCH 2), 4.10 (m, 2H, NCH 2). HRESI-MS: m/zcacld. C17H14N2O3[M-H]-; 293.0927, found: 293.0931.
from the above characterization results, the obtained product is the ligand of formula (A) above in which R is hydrogen.
Example 2
The structural formula of the synthesized ligand is shown as the formula (A), wherein R is methyl, and the reaction process is as follows: 0.25 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of 3, 5-dimethyl salicylaldehyde were added to 20 mL of methanol, and the mixture was heated under reflux for 12 hours, cooled and filtered after the reaction was completed, washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.38 g of a solid with a yield of 90.5%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.61 (s, 1H, OH), 8.20 (s, 1H, ArHC=N),7.73 (d,J= 5.5Hz, 2H, Ar–H), 7.66 (d,J= 5.4 Hz, 2H, Ar–H), 6.96 (s, 1H,Ar–H), 6.75 (s, 1H, Ar–H), 4.31– 4.28(m, 2H, NCH 2), 4.20–4.15 (m, 2H, NCH 2),2.17 (s, 3H, CH 3), 2.15 (s, 3H, CH 3)。HRESI-MS: m/z cacld. C19H18N2O3[M-H]-;321.1238, found: 321.1236.
from the above characterization results, the obtained product is the ligand of formula (A) above, wherein R is methyl.
Example 3
The structural formula of the synthesized ligand is shown as the formula (A), wherein R is bromine, and the reaction process is as follows: 0.22 g of mono-edge protected ethylenediamine (a) and an equimolar amount of 3, 5-dibromosalicylaldehyde were added to 15 mL of methanol, and the mixture was heated under reflux for 12 hours, cooled and filtered after the reaction was completed, washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.46 g of a solid with a yield of 88.5%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)13.90 (s, 1H, OH), 8.19 (s, 1H, ArHC=N),7.82–7.74(m, 2H, Ar–H), 7.67–7.60 (m, 2H, Ar–H), 7.54 (s, 1H, Ar–H), 7.15 (s,1H, Ar–H), 4.30–4.27 (m, 2H, NCH 2), 4.25–4.20 (m, 2H, NCH 2)。HRESI-MS: m/zcacld. C17H12Br2N2O3[M-H]-; 448.9136, found: 448.9138.
from the above characterization results, the obtained product is the ligand of formula (A) in which R is bromine.
Example 4
The structural formula of the synthesized ligand is shown as the formula (A), wherein R is tert-butyl, and the reaction process is as follows: 0.30 g of the mono-edge protected ethylenediamine (a) and an equimolar amount of 3, 5-di-tert-butylsalicylaldehyde were added to 20 mL of methanol, and the mixture was refluxed for 12 hours, cooled and filtered after the reaction was completed, washed with cold methanol, filtered, collected, dried, and weighed to obtain 0.53 g of a solid in 82.8% yield.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)13.27 (s, 1H, OH), 8.23 (s, 1H, ArHC=N),7.70–7.68 (m, 2H, Ar–H) ), 7.64–7.59 (m, 2H, Ar–H), 7.30 (s, 1H, Ar–H)), 6.95(s, 2H, Ar–H)), 4.34–4.29 (m, 2H, NCH 2), 4.13–4.10 (m, 2H, NCH 2), 1.37 (s, 9H,CH3), 1.26(s, 9H, CH3)。HRESI-MS: m/z cacld. C25H30N2O3[M-H]-; 405.2175, found:405.2173.
from the above characterization results, the obtained product is the ligand of formula (A) in which R is tert-butyl.
Preparation of aluminum complexes (I) from ligand A
The aluminum complex shown in the formula (I) is formed by a ligand A and trimethylaluminum through an alkyl elimination and alkyl addition reaction, and the reaction formula is as follows.
Example 5
The structural formula of the ligand is shown as the formula (A), wherein R is hydrogen, and the reaction process is as follows: dissolving 0.21 g of ligand A in 8 mL of dry toluene under nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.0 time of that of the ligand A at the temperature of-10 ℃, heating to 100 ℃ after the reaction temperature naturally rises to room temperature for reaction for 1 hour, vacuumizing the solvent after the reaction is finished, adding dry n-hexane, filtering, washing with the dry n-hexane, filtering, collecting, drying and weighing to obtain 0.22 g of solid with the yield of 88.0%.
The nuclear magnetic information of the obtained product is as follows, and the compound (I) with the hydrogen as R can be successfully synthesized.
1H NMR (400 MHz, CDCl3)8.22 (s, 1H, ArHC=N), 7.61 (d,J= 6.7 Hz,1H, Ar–H), 7.53 (d,J= 6.7 Hz, 1H, Ar–H), 7.41 (t,J= 7.1 Hz, 1H, Ar–H),7.33 (d,J= 6.3 Hz, 1H, Ar–H), 7.08 (d,J= 7.1 Hz, 1H, Ar–H), 6.76–6.62 (m,3H, Ar–H), 4.25–4.20 (m, 2H, NCH 2), 4.13–4.08 (m,2H, NCH 2), 1.65 (s, 3H,CH 3),–0.50(s, 3H, AlCH3). Anal. Calcd for C19H19AlN2O3: C 65.14, H 5.47, N 8.00.Found: C 65.16, H 5.49, N 8.05.
Example 6
The structural formula of the ligand is shown as the formula (A), wherein R is methyl, and the reaction process is as follows: under nitrogen atmosphere, 0.41 g of ligand A is dissolved in 12 mL of dry cyclohexane, 1.05 times of the molar weight of trimethylaluminum of the ligand A is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 60 ℃ for reaction for 4 hours, after the reaction is finished, the solvent is pumped out in vacuum, dried n-hexane is added for filtration and washing by the dried n-hexane, the filtration, the collection, the drying and the weighing are carried out, 0.39 g of solid is obtained, and the yield is 81.2%.
The nuclear magnetic information of the obtained product is as follows, and the compound (I) with the methyl R is successfully synthesized.
1H NMR (400 MHz, CDCl3)8.17 (s, 1H, ArHC=N), 7.68 (s, 1H, Ar–H),7.61–7.57 (m, 2H, Ar–H), 7.13 (s, 1H, Ar–H), 6.30 (s, 1H, Ar–H), 4.32 (m, 2H,NCH2), 4.13 (m, 2H, NCH2), 2.14–2.10 (m, 2H, CH2CH 2), 2.10 (s, 3H, ArCH 3),2.08 (s, 3H, ArCH 3), 1.67 (s, 3H, CCH 3), –0.50 (s, 3H, AlCH 3). Anal. Calcd forC21H23AlN2O3: C 66.66, H 6.13, N 7.40. Found: C 66.61, H 6.18, N 7.45.
Example 7
The structural formula of the ligand is shown as the formula (A), wherein R is bromine, and the reaction process is as follows: under nitrogen atmosphere, 0.24g of ligand A is dissolved in 10 mL of dry toluene, 1.1 times of the molar weight of trimethylaluminum of the ligand A is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 50 ℃ for reaction for 5 hours, after the reaction is finished, the solvent is pumped out in vacuum, dried n-hexane is added for filtration and washing by the dried n-hexane, the filtration is carried out, the collection, the drying and the weighing are carried out, 0.24g of solid is obtained, and the yield is 88.9%.
The nuclear magnetic information of the obtained product is shown below, from which it can be seen that the synthesis of compound (I) in which R is bromine was successful.
1H NMR (400 MHz, CDCl3)8.21 (s, 1H, ArHC=N), 7.84 (d, J = 6.7 Hz,1H, Ar–H), 7.66 (s, 2H, Ar–H), 7.64–7.55 (m, 2H, Ar–H), 7.40–7.33 (m, 1H, Ar–H), 4.27 (m, 2H, NCH 2), 4.10–4.06 (m, 2H, NCH 2), 1.67 (s, 1H, CCH 3), –0.50 (s,3H, AlCH 3). Anal. Calcd for C19H17AlBr2N2O3: C 44.91, H 3.37, N 5.51. Found: C44.93, H 3.41, N 5.55.
Example 8
The structural formula of the ligand is shown as the formula (A), wherein R is tert-butyl, and the reaction process is as follows: under nitrogen atmosphere, 0.23 g of ligand A is dissolved in 10 mL of dry n-hexane, 1.0 time of molar weight of trimethylaluminum of the ligand A is added at-10 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 40 ℃ for reaction for 12 hours, the filter cake is filtered and washed by the dry n-hexane, and the solid is collected, dried and weighed to obtain 0.24g of solid with the yield of 92.3 percent.
The nuclear magnetic information of the obtained product is shown below, from which it can be seen that the synthesis of the compound (I) in which R is tert-butyl is successful.
1H NMR (400 MHz, CDCl3)8.17 (s, 1H, ArHC=N), 7.80 (d, J = 6.7 Hz,1H, Ar–H), 7.67 (s, 2H, Ar–H), 7.60–7.53 (m, 2H, Ar–H), 7.41–7.32 (m, 1H, Ar–H), 4.33–4.29 (m, 2H, NCH 2), 3.93–3.86 (m, 2H, NCH 2), 1.66 (s, 3H, CCH 3), 1.31(s, 9H, CH3), 1.24(s, 9H, CH3), –0.52 (s, 3H, AlCH 3). Anal. Calcd forC27H35AlN2O3: C 70.11, H 7.63, N 6.06. Found: C 70.12, H 7.65, N 6.12.
Preparation of aluminum Complex (I) from ligand II
Example 9
And (3) synthesizing a ligand II with R as hydrogen: dissolving 0.30 g of ligand A (R is hydrogen) in 10 mL of dry toluene under the nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.0 time of that of the ligand A at the temperature of-10 ℃, heating to 60 ℃ after the reaction temperature naturally rises to the room temperature, reacting for 4 hours, adding 55 microliters of water after the reaction is finished, stopping the reaction, separating liquid, collecting an organic phase, drying by anhydrous sodium sulfate, spin-drying the solvent to obtain a crude product, and recrystallizing the crude product by methanol to obtain 0.27 g of a pure product with the yield of 84.4%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.85 (s, 1H, OH), 8.31 (s, 1H, CH=N), 7.61(d, J = 7.5 Hz, 1H, Ar–H), 7.55–7.47 (m, 4H, Ar–H), 7.15 (d, J = 7.4 Hz, 1H,Ar–H), 6.88 (d, J = 8.2 Hz, 1H, Ar–H), 6.65 (t, J = 7.4 Hz, 1H, Ar–H), 4.41–4.32 (m, 2H, NCH 2), 4.16–4.10 (m, 2H, NCH), 1.61 (s, 3H, CH3).
HRESI-MS: m/z cacld. C18H18N2O3[M-H]-; 309.1238, found: 309.1236.
from the above characterization results, the obtained product is the ligand of formula (II) above in which R is hydrogen.
The structural formula of the ligand is shown as the formula (II), wherein R is hydrogen, and the reaction process is as follows: dissolving 0.30 g of ligand II in 10 mL of dry cyclohexane under nitrogen atmosphere, adding trimethylaluminum with the molar weight being 1.2 times that of the ligand II at-10 ℃, heating to 40 ℃ after the reaction temperature naturally rises to room temperature for reaction for 6 hours, filtering after the reaction is finished, washing by using dry n-hexane, filtering, collecting, drying and weighing to obtain 0.29 g of solid with the yield of 85.3%. The structural formula of the product is shown as formula I, and R is hydrogen.
Example 10
And (3) synthesizing a ligand II with R being methyl: under nitrogen atmosphere, 0.40 g of ligand A (R is methyl) is dissolved in 10 mL of dry cyclohexane, trimethylaluminum with the molar weight being 1.05 times of that of the ligand A is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 40 ℃ for reaction for 6 hours, 67 microliters of water is added after the reaction to stop the reaction, the organic phase is separated and collected, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode to obtain a crude product, and the crude product is recrystallized by methanol to obtain 0.36 g of a pure product with the yield of 85.7%.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)13.01 (s, 1H，OH), 8.27 (s, 1H, CH=N), 7.64(d, J = 7.4 Hz, 1H, Ar–H), 7.55–7.44 (m, 3H, Ar–H), 6.98–6.88 (m, 1H, Ar–H),6.81–6.72 (m, 1H, Ar–H), 4.38–4.31 (m, 2H, NCH2), 4.18–4.09 (m, 2H, NCH2),2.21 (s, 6H, ArCH3), 1.61 (s, 3H, CH3). HRESI-MS: m/z cacld. C20H22N2O3[M-H]-;337.1553, found: 337.1556.
from the above characterization results, the obtained product is the ligand of formula (II) above in which R is methyl.
The structural formula of the ligand is shown as the formula (II), wherein R is methyl, and the reaction process is as follows: under nitrogen atmosphere, 0.25 g of ligand II is dissolved in 10 mL of dry toluene, 1.1 times of the molar weight of trimethylaluminum of the ligand II is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the reaction temperature is heated to 110 ℃ for reaction for 1 hour, after the reaction is finished, the solvent is pumped out in vacuum, dried n-hexane is added for filtration and is washed by the dried n-hexane, the filtration is carried out, the collection, the drying and the weighing are carried out, 0.20 g of solid is obtained, and the yield is 71.4%. The structural formula of the product is shown as formula I, and R is methyl.
Example 11
And (3) synthesizing a ligand II with R being bromine: under nitrogen atmosphere, 0.30 g of ligand A (R is bromine) is dissolved in 10 mL of dry toluene, trimethylaluminum with the molar weight 1.1 times of that of the ligand A is added at the temperature of minus 5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 110 ℃ for reaction for 1 hour, 36 microliters of water is added after the reaction is finished to stop the reaction, the organic phase is separated and collected, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode to obtain a crude product, and the crude product is recrystallized by ethanol to obtain 0.26 g of a pure product with the yield of 83.9 percent.
The obtained product was characterized with the following results:
1H NMR (400 MHz, CDCl3)12.56 (s, 1H，OH), 8.27 (s, 1H, CH=N), 7.63–7.58 (m, 2H, Ar–H), 7.41–7.30 (m, 2H, Ar–H), 7.16 (d, J = 7.2 Hz, 1H, Ar–H),7.12 (d, J = 7.2 Hz, 1H, Ar–H), 4.45–4.32 (m, 2H, NCH 2), 4.23–4.14 (m, 2H,NCH 2), 1.60 (s, 3H, CH3).
HRESI-MS: m/z cacld. C18H16Br2N2O3[M-H]-; 464.9448, found: 464.9452.
from the above characterization results, the obtained product is the ligand of formula (II) above in which R is bromine.
The structural formula of the ligand is shown as the formula (II), wherein R is bromine, and the reaction process is as follows: 0.45 g of ligand II is dissolved in 15 mL of dry hexane under nitrogen atmosphere, 1.0 time molar amount of trimethylaluminum of ligand II is added at-5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 60 ℃ for reaction for 3 hours, and after the reaction is finished, the mixture is filtered, washed by dry n-hexane, filtered, collected, dried and weighed, and 0.41 g of solid is obtained with the yield of 83.7%. The structural formula of the product is shown as formula I, and R is bromine.
Example 12
And (3) synthesizing a ligand II with R being tert-butyl: under nitrogen atmosphere, 0.20 g of ligand A (R is tert-butyl) is dissolved in 8 mL of dry n-hexane, trimethylaluminum with the molar weight 1.3 times that of the ligand A is added at minus 5 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 30 ℃ for reaction for 8 hours, 27 microliters of water is added after the reaction to stop the reaction, liquid is separated to collect an organic phase, anhydrous sodium sulfate is dried, the solvent is dried in a spinning mode to obtain a crude product, and the crude product is recrystallized by methanol to obtain 0.17 g of a pure product with the yield of 81.0%.
The obtained product was characterized with the following results:
1H NMR (300 MHz, CDCl3)13.02 (s, 1H，OH), 8.24 (s, 1H, CH=N), 7.76–7.65 (m, 1H, Ar–H), 7.63–7.52 (m, 3H, Ar–H), 7.50–7.42(m, 1H, Ar–H), 7.40 (d,J = 7.2 Hz, 1H, Ar–H), 7.18 (d, J = 7.0 Hz, 1H, Ar–H), 7.08–7.00 (m, 1H, Ar–H), 4.35–4.21 (m, 2H, NCH 2), 4.14–4.06 (m, 2H, NCH 2), 1.62(s, 3H, CH3), 1.38(s, 9H, CH3), 1.24 (s, 9H, CH3).
HRESI-MS: m/z cacld. C26H34N2O3[M-H]-; 421.2492, found: 421.2487.
as can be seen from the above characterization results, the obtained product is the ligand of formula (II) above in which R is tert-butyl.
The structural formula of the ligand is shown as the formula (II), wherein R is tert-butyl, and the reaction process is as follows: under nitrogen atmosphere, 0.40 g of ligand II is dissolved in 12 mL of dry toluene, 1.1 times of the molar amount of trimethylaluminum of the ligand II is added at 0 ℃, after the reaction temperature naturally rises to room temperature, the mixture is heated to 60 ℃ for reaction for 2 hours, and after the reaction is finished, the mixture is filtered, washed by dry n-hexane, filtered, collected, dried and weighed, so that 0.40 g of solid is obtained, and the yield is 90.9%. The structural formula of the product is shown as formula I, and R is tert-butyl.
Preparation of polyglycolide
Example 13
Under the protection of anhydrous oxygen-free and inert gasPerforming reaction, namely firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 100 mu mol of benzyl alcohol, 20 mL of toluene and 10mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then placing the ampoule in a container of 110oAnd C, in an oil bath, after reacting for 12 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.09 g of a product, wherein the yield is 94.0 percent, and the molecular weight is 2.2 ten thousand.
Example 14
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex represented by formula I, and R is methyl. The mass of the product obtained after 14 minutes of reaction was 1.10 g, the yield was 94.8%, and the molecular weight was 2.3 ten thousand.
Example 15
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex shown as a formula I, and R is bromine. The mass of the product obtained after 7 minutes of reaction was 1.12 g, the yield was 96.6%, and the molecular weight was 2.1 ten thousand.
Example 16
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used is an aluminum complex represented by formula I, and R is tert-butyl. After 15 minutes of reaction, the obtained product had a mass of 1.10 g, a yield of 94.8% and a molecular weight of 2.0 ten thousand.
Example 17
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (an aluminum complex shown as a formula I, R is bromine), 100 mu mol of benzyl alcohol, 20 mL of toluene and 10mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then respectively adding the mixture into a reactor at 20 mu moloC、40oC、60oC、80oC and 100oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein the reaction is carried out for 18 hours at 20 ℃ to obtain 1.10 g of product, the yield is 94.8 percent, and the molecular weight is 2.1 ten thousand.
The reaction was carried out at 40 ℃ for 9 hours to give 1.11 g of a product, 95.7% yield, 2.3 ten thousand molecular weight.
The reaction was carried out at 60 ℃ for 5 hours to give 1.09 g of product, 94.0% yield, 2.0 ten thousand molecular weight.
The reaction was carried out at 80 ℃ for 40 minutes to obtain 1.10 g of a product, the yield was 94.8%, and the molecular weight was 2.2 ten thousand.
The reaction was carried out at 100 ℃ for 15 minutes to obtain 1.11 g of a product, the yield was 95.7%, and the molecular weight was 2.1 ten thousand.
Example 18
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 30 mu mol of benzyl alcohol, 10 mL of tetrahydrofuran and 15mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then 30 mu mol of benzyl alcohol, 10 mL of tetrahydrofuran and 15mmol of glycolideoC, after reacting for 16 hours, adding a small amount of water to terminate the reaction, precipitating and washing the product for a plurality of times by using methanol, and drying the product in vacuum at room temperature to obtain 1.68 g of a product, wherein the yield is 96.6 percent, and the molecular weight is 13.3 ten thousand.
Example 19
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (aluminum complex shown in formula I, R methyl), 20 mu mol of benzyl alcohol, 20 mL of tetrahydrofuran and 10mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then placing the ampoule in a 50-degree nitrogen atmosphereoC, in an oil bath, after 8 hours of reaction, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.10 g of a product, wherein the yield is 94.8 percent, and the molecular weight is 14.0 ten thousand.
Example 20
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 200 mu mol of catalyst (aluminum complex shown as formula I, R is tertiary butyl), 200 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen, and then placing the ampoule in a 70-degree reactoroAnd C, in an oil bath, after reacting for 4 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction for a plurality of times by using methanol, and drying the reaction in vacuum at room temperature to obtain 1.10 g of a product, wherein the yield is 94.8 percent, and the molecular weight is 1.1 ten thousand.
Example 21
Reacting under the protection of anhydrous oxygen-free inert gas, and sequentially washing with high-purity nitrogen gas in an ampoule after bakingAdding 10 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 20 mu mol of benzyl alcohol, 15 mL of toluene and 5mmol of glycolide, and then adding 90 mu mol of catalystoC, after reacting for 5 hours, adding a small amount of water to terminate the reaction, precipitating and washing the product for a plurality of times by using methanol, and drying the product in vacuum at room temperature to obtain 0.54 g of a product, wherein the yield is 93.1 percent, and the molecular weight is 6.7 ten thousand.
Preparation of poly-caprolactone
Example 22
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 100 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of caprolactone in an ampoule after being washed and baked by high-purity nitrogen, and then placing the mixture in a 110 mu mol flaskoAnd C, in an oil bath, after reacting for 5 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.11 g of a product, wherein the yield is 97.4 percent, and the molecular weight is 2.4 ten thousand.
Example 23
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex represented by formula I, and R is methyl. After 6 minutes of the reaction, the obtained product had a mass of 1.10 g, a yield of 96.5% and a molecular weight of 2.0 ten thousand.
Example 24
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex shown as a formula I, and R is bromine. The mass of the product obtained after 1.5 minutes of reaction was 1.12 g, the yield was 98.2%, and the molecular weight was 2.2 ten thousand.
Example 25
Polycaprolactone was prepared according to the method of example 22 except that: the catalyst used is an aluminum complex represented by formula I, and R is tert-butyl. The mass of the product obtained after 7 minutes of reaction was 1.10 g, the yield was 96.5%, and the molecular weight was 2.3 ten thousand.
Example 26
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown in formula I, R is bromine), 100 mu mol of benzyl alcohol, 10 mL of toluene and 10mm of catalyst in an ampoule after being washed and baked by high-purity nitrogen gasol caprolactone, then 20 respectivelyoC、40oC、60oC、80oC and 100oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, the reaction is carried out for 35 minutes at 20 ℃ to obtain 1.10 g of product, the yield is 96.5 percent, and the molecular weight is 2.0 ten thousand.
The reaction was carried out at 40 ℃ for 18 minutes to obtain 1.10 g of a product, the yield was 96.5%, and the molecular weight was 2.3 ten thousand.
The reaction was carried out at 60 ℃ for 12 minutes to obtain 1.11 g of a product, the yield was 97.4%, and the molecular weight was 2.1 ten thousand.
The reaction was carried out at 80 ℃ for 9 minutes to obtain 1.11 g of a product, the yield was 97.4%, and the molecular weight was 2.2 ten thousand.
The reaction was carried out at 100 ℃ for 3 minutes to obtain 1.12 g of a product, the yield was 98.2%, and the molecular weight was 2.4 ten thousand.
Example 27
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 30 mu mol of benzyl alcohol, 10 mL of tetrahydrofuran and 5mmol of-caprolactone in an ampoule after being washed and baked by high-purity nitrogen, and then 30 mu mol of benzyl alcohol, 10 mL of tetrahydrofuran and 5mmol of-caprolactoneoC, after reacting for 50 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and drying in vacuum at room temperature to obtain 0.54 g of a product, wherein the yield is 94.7 percent, and the molecular weight is 5.8 ten thousand.
Example 28
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (an aluminum complex shown as a formula I, wherein R is methyl), 30 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of caprolactone in an ampoule after being washed and baked by high-purity nitrogen, and then 50 mu mol of catalyst, 30 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of caprolactoneoC, after reacting for 20 minutes, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for a plurality of times, and drying in vacuum at room temperature to obtain 1.12 g of a product, wherein the yield is 98.2 percent, and the molecular weight is 7.4 ten thousand.
Example 29
The reaction is carried out under the conditions of no water and no oxygen and the protection of inert gas, and firstly, 10 mu mol of catalyst (aluminum complex shown as formula I, R is tertiary butyl) is sequentially added into an ampoule after being washed and baked by high-purity nitrogen gas20 μmol benzyl alcohol, 15 mL toluene and 15mmol caprolactone, then placed at 90oAnd C, in an oil bath, after reacting for 9 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 1.63 g of a product, wherein the yield is 95.3 percent, and the molecular weight is 15.8 ten thousand.
Example 30
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 100 mu mol of benzyl alcohol, 10 mL of toluene and 5mmol of caprolactone in an ampoule after being washed and baked by high-purity nitrogen, and then placing the mixture in a 70-degree atmosphereoAnd C, in an oil bath, after reacting for 11 minutes, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 0.55 g of a product, wherein the yield is 96.5 percent, and the molecular weight is 1.0 ten thousand.
Preparation of polylactide
Example 31
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 100 mu mol of benzyl alcohol, 20 mL of toluene and 10mmol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then 20 mmol of racemic lactideoC, reacting for 21 hours, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and drying in vacuum at room temperature to obtain 1.34 g of a product with the yield of 93.1%. The product obtained was isotactic polylactide having a molecular weight of 2.8 ten thousand and an isotactic stereoselectivityP m= 0.77。
Example 32
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex represented by formula I, and R is methyl. After 22 hours of reaction, a small amount of water is added to terminate the reaction, ethanol is used for precipitation, washing is carried out for a plurality of times, and vacuum drying is carried out at room temperature. The obtained product had a mass of 1.36 g, a yield of 94.4%, a molecular weight of 2.9 ten thousand, and an isotactic stereoselectivityP m=0.81。
Example 33
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex shown as the formula IAnd R is bromine. After reacting for 20 hours, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum-drying at room temperature. The obtained product had a mass of 1.42 g, a yield of 98.6%, a molecular weight of 2.6 ten thousand, and an isotactic stereoselectivityP m=0.80。
Example 34
Polylactide was prepared according to the method of example 31, except that: the catalyst used is an aluminum complex represented by formula I, and R is tert-butyl. After 24 hours of reaction, a small amount of water is added to stop the reaction, ethanol is used for precipitation, washing is carried out for a plurality of times, and vacuum drying is carried out at room temperature. The obtained product had a mass of 1.40 g, a yield of 97.2%, a molecular weight of 2.7 ten thousand, and an isotactic stereoselectivityP m=0.83。
Example 35
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst (aluminum complex shown as formula I, R is tertiary butyl), 100 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen, and then respectively adding the mixture into a reactor at 40 DEG CoC、60oC and 80oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, the reaction is carried out for 21 hours at 40 ℃ to obtain 1.40 g of product, the yield is 97.2 percent, the molecular weight is 2.8 ten thousand,P m= 0.78。
reacting at 60 ℃ for 17 hours to obtain 1.41 g of product, wherein the yield is 97.9 percent, the molecular weight is 2.6 ten thousand,P m= 0.71。
reacting at 80 ℃ for 14 hours to obtain 1.41 g of product, wherein the yield is 97.9 percent, the molecular weight is 2.7 ten thousand,P m= 0.64。
example 36
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 200 mu mol of catalyst (aluminum complex shown in formula I, R is hydrogen), 200 mu mol of benzyl alcohol, 20 mL of tetrahydrofuran and 10mmol of L-lactide into an ampoule after being washed and baked by high-purity nitrogen, and then 30 mol of L-lactideoC, after reacting for 20 hours, adding a small amount of water to stop the reaction, precipitating with ethanol, and washingSeveral times, vacuum drying at room temperature to obtain 1.40 g of product, yield 97.2%, molecular weight 1.1 ten thousand.
Example 37
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (an aluminum complex shown as a formula I, wherein R is methyl), 10 mu mol of benzyl alcohol, 10 mL of tetrahydrofuran and 5mmol of meso-lactide into an ampoule after being washed and baked by high-purity nitrogen, and then placing the ampoule in a 50-degree nitrogen washing furnaceoAnd C, in an oil bath, after reacting for 17 hours, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 0.66 g of a product, wherein the yield is 91.7 percent, and the molecular weight is 11.2 ten thousand.
Example 38
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (an aluminum complex shown as a formula I, wherein R is bromine), 30 mu mol of benzyl alcohol, 20 mL of toluene and 10mmol of levorotatory lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then 90 mu mol of catalyst, 30 mu mol of benzyl alcohol, 20 mL of toluene and 10mmol of levorotatory lactideoC, after reacting for 2 hours, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for a plurality of times, and drying in vacuum at room temperature to obtain 1.40 g of a product, wherein the yield is 97.2 percent, and the molecular weight is 7.8 ten thousand.
Example 39
Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 10 mu mol of catalyst (an aluminum complex shown as a formula I, R is bromine), 20 mu mol of benzyl alcohol, 20 mL of toluene and 15mmol of levorotatory lactide into an ampoule after being washed and baked by high-purity nitrogen, and then placing the ampoule in a 110-degree reactoroAnd C, in an oil bath, after reacting for 1 hour, adding a small amount of water to terminate the reaction, precipitating and washing the reaction by using ethanol for a plurality of times, and drying the reaction in vacuum at room temperature to obtain 2.11 g of a product, wherein the yield is 97.7 percent, and the molecular weight is 17.3 ten thousand.
Comparative example 1
Preparation of nickel catalyst: the structural formula of the ligand is shown as the formula (II), R is bromine, and the reaction process is as follows: dissolving 0.40 g of ligand in 20 mL of absolute ethyl alcohol, adding nickel acetate with the molar weight being 1.0 time of that of the ligand at room temperature, heating and refluxing for 12 hours, concentrating the solvent in vacuum after the reaction is finished, adding dichloromethane to precipitate a solid, filtering, washing with hexane, and drying to obtain the nickel catalyst, wherein the structural formula of the nickel catalyst is shown as the following.
Polylactide was prepared according to the method of example 39, except that: the catalyst used was the nickel catalyst described above. After 24 hours of reaction, a small amount of water is added to terminate the reaction, methanol is used for precipitation and washing for a plurality of times, and vacuum drying is carried out at room temperature to obtain 0.40 g of product, the yield is 18.5 percent, and the molecular weight is 2.0 ten thousand. The nickel catalyst has too low activity for lactide polymerization and is of no value.
Comparative example 2
Preparation of aluminum catalyst: the ligand has the formula (LH)2) The reaction process is as follows: under the protection of anhydrous oxygen-free and inert gas, 0.20 g of ligand is dissolved in 10 mL of toluene, trimethylaluminum with the molar weight being 1.0 time of that of the ligand is added at the temperature of-5 ℃, the temperature is slowly raised to room temperature, the mixture is heated to 80 ℃ for reaction for 12 hours, after the reaction is finished, the solvent is concentrated in vacuum, dried hexane is added to separate out solid, the solid is filtered and washed by hexane, and the aluminum catalyst is dried to obtain the LAlMe with the structural formula shown in the specification.
Polylactide was prepared according to the method of example 35, except that: the catalyst used was the aluminum catalyst. Carrying out reaction under the protection of anhydrous oxygen-free and inert gas, firstly sequentially adding 100 mu mol of catalyst, 100 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of racemic lactide into an ampoule after being washed and baked by high-purity nitrogen gas, and then respectively adding the mixture into a flask with the volume of 20 mu mol of catalyst, 100 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of racemic lactideoC and 80oC, reaction, adding a small amount of water after the reaction is finished, precipitating with methanol, washing for several times, and vacuum drying at room temperature.
Wherein, no product is generated after the reaction is carried out for 36 hours at 20 ℃, which indicates that the catalyst can not catalyze the polymerization of the lactide at lower temperature.
Reacting at 80 deg.C for 24 hr to obtain 1.15 g product with 79.9% yield, 1.4 ten thousand molecular weight and isotactic stereoselectivityP m= 0.53. Both stereoselectivity and activity were lower compared to the aluminum catalyst of example 35.
Comparative example 3
Polylactide was prepared according to the method of example 31, except that: the catalyst used was the catalyst used in example 10 of patent 201410609375.8. The polylactide obtained after the reaction is non-uniform stereoregular polylactide with the mass of 1.33 g, the yield of 92.4 percent, the molecular weight of 1.7 ten thousand and the non-uniform stereoregular stereoselectivityP rIs 0.71.
Comparative example 4
0.20 g of ligand A (R is tert-butyl) was dissolved in 8 mL of dry n-hexane under a nitrogen atmosphere, triisopropylaluminum in an amount of 1.3 times the molar amount of ligand A was added at-5 ℃ to the reaction mixture, the reaction mixture was heated to 30 ℃ after the reaction temperature naturally increased to room temperature to react for 24 hours, 27. mu.l of water was added to the reaction mixture to stop the reaction, the organic phase was collected by liquid separation, dried over anhydrous sodium sulfate, and the solvent was dried by spinning, whereby it was found that no change was caused in the obtained compound (isopropyl group did not undergo C = O addition reaction). Triisopropylaluminum failed to undergo addition reaction.
Comparative example 5
Polylactide was prepared according to the method of example 31, except that: the catalyst is an aluminum complex shown as a formula I, and R is methoxy. After 36 hours of reaction, the obtained product had a mass of 0.94 g, a yield of 65.3%, a molecular weight of 1.1 ten thousand, and an isotactic stereoselectivityP m= 0.70。
Comparative example 6
Dissolving p-toluenesulfonic acid into xylene, slowly adding 1, 3-propane diamine with equimolar amount of p-toluenesulfonic acid, adding phthalic anhydride with equimolar amount of p-toluenesulfonic acid, heating for reflux reaction, cooling to room temperature after the reaction is finished, filtering the solid, washing, and drying to obtain 1, 3-propane diamine protected by p-toluenesulfonic acid and phthalic anhydride. Dissolving p-toluenesulfonic acid and 1, 3-propanediamine protected by phthalic anhydride in dichloromethane, slowly dripping excessive saturated aqueous solution of sodium bicarbonate at room temperature for reaction to remove the p-toluenesulfonic acid, separating liquid after the reaction is finished, drying with anhydrous magnesium sulfate, and spin-drying the solvent to obtain the 1, 3-propanediamine protected by unilateral phthalic anhydride. Heating and refluxing unilateral phthalic anhydride protected propane diamine and 3, 5-dibromo salicylaldehyde with equal molar quantity in methanol, cooling in a refrigerator after the reaction is finished, separating out a solid, filtering, washing with cold methanol, and drying to obtain a compound LD.
Preparation of aluminum catalyst: dissolving 0.20 g of compound LD in 10 mL of dry toluene under nitrogen atmosphere, adding 1.0 time of trimethylaluminum in the molar amount of the compound LD at-10 ℃, heating to 110 ℃ after the reaction temperature naturally rises to room temperature for reaction for 1 hour, vacuumizing the solvent after the reaction is finished, adding dry n-hexane for washing, filtering and drying to obtain 0.18 g of solid with the yield of 81.8%, and performing mass spectrum characterization after hydrolysis of the aluminum compound to find that the ligand can only perform addition reaction on one side to obtain LDAlMe2（HRESI-MS: m/z cacld. C18H14Br2N2O3[M-H]-; 462.9294, found: 462.9292）。
Polylactide was prepared according to the method of example 31, except that: the catalyst used was the aluminum catalyst. The mass of the product obtained after the reaction is 0.60 g, the yield is 41.7%, the molecular weight is 1.2 ten thousand, and stereoselectivity is avoided.
Claims (13)
1. An aluminum complex containing salicylaldehyde groups, which is characterized in that: the compound has a structural formula shown in a formula I, wherein R is hydrogen, methyl, tert-butyl or bromine;
2. the aluminum complex according to claim 1, characterized in that: r is tert-butyl or bromine.
3. The salicylaldehyde-containing aluminum complex as claimed in claim 1The preparation method of the compound is characterized by comprising the following steps: adding the ligand A or the ligand II into an organic solvent at-10 to 0%oAdding trimethylaluminum under C, naturally raising the reaction temperature to room temperature after the addition is finished, and then raising the temperature to 30-110 DEG CoC, reacting, and then, carrying out vacuum drying on the solvent, washing and filtering to obtain the salicylaldehyde-containing aluminum complex shown in the formula I; the structural formulas of the ligand A and the ligand II are shown as follows, wherein R is hydrogen, methyl, tert-butyl or bromine;
4. the method of claim 3, wherein: in the ligand A and the ligand II, R is tert-butyl or bromine.
5. The method of claim 3, wherein: the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.3.
6. The method according to claim 5, wherein: the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.05.
7. The method of claim 3, wherein: the organic solvent is one or two of dry hexane, toluene and cyclohexane.
8. The method of claim 3, wherein: the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials.
9. The method of claim 3, wherein: after the temperature is raised to the room temperature, the temperature is raised to 30-110 DEGoC, reacting for 1-12 hours.
10. The method of claim 9, wherein: heating to room temperatureThen the temperature is raised to 40-60 DEGoC, reacting for 3-6 hours.
11. The method of claim 3, wherein: the reaction is carried out under the protection of inert gas.
12. Use of the salicylaldehyde-containing aluminum complex as claimed in claim 1 or 2 as a catalyst for ring-opening polymerization of cyclic lactones.
13. Use according to claim 12, characterized in that: the cyclic lactone is levo-lactide, meso-lactide, racemic lactide, caprolactone or glycolide.
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| CN104370951A (en) * | 2014-11-04 | 2015-02-25 | 济南大学 | Methyl aluminum complex of tetradentate nitrogen-oxygen ligand and application thereof |
| CN108239017A (en) * | 2017-12-12 | 2018-07-03 | 济南大学 | Ligand of the aldehyde radical containing bigcatkin willow and its preparation method and application |
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| CN104370951A (en) * | 2014-11-04 | 2015-02-25 | 济南大学 | Methyl aluminum complex of tetradentate nitrogen-oxygen ligand and application thereof |
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