CN108239261B - Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups - Google Patents

Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups Download PDF

Info

Publication number
CN108239261B
CN108239261B CN201711315746.1A CN201711315746A CN108239261B CN 108239261 B CN108239261 B CN 108239261B CN 201711315746 A CN201711315746 A CN 201711315746A CN 108239261 B CN108239261 B CN 108239261B
Authority
CN
China
Prior art keywords
reaction
catalyst
ligand
glycolide
aluminum complex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711315746.1A
Other languages
Chinese (zh)
Other versions
CN108239261A (en
Inventor
姚伟
高爱红
张永芳
王洪宾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201711315746.1A priority Critical patent/CN108239261B/en
Publication of CN108239261A publication Critical patent/CN108239261A/en
Application granted granted Critical
Publication of CN108239261B publication Critical patent/CN108239261B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • 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)
    • 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 a method for catalyzing glycolide polymerization by using an aluminum complex containing salicylaldehyde groups, which comprises the following steps: mixing a catalyst, an organic solvent, a benzyl alcohol cocatalyst and glycolide, carrying out ring-opening polymerization reaction under the conditions of no water and no oxygen and inert gas protection, and treating reactants after reaction to obtain polyglycolide; the catalyst is an aluminum complex containing salicylaldehyde. The method takes the self-developed aluminum complex containing the salicylaldehyde group as the catalyst to carry out the glycolide ring-opening polymerization reaction, the catalyst is simple in preparation method, low in cost and diverse in structure variation, the divalent N, N, O and O of the metal center aluminum and the ligand are coordinated, the catalytic activity is high, the stereoselectivity is high, the reaction rate is high, the obtained polymer is a benzyloxy-terminated polymer, the molecular weight distribution is narrow, the molecular weight is controllable, the yield is high, and the market demand is met. When the asymmetric tetradentate nitrogen oxygen aluminum compound is used as a catalyst to carry out the ring opening polymerization reaction of glycolide, the obtained product has controllable molecular weight and high yield.

Description

Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups
Technical Field
The invention relates to a method for catalyzing glycolide polymerization, in particular to a method for catalyzing glycolide polymerization by using an aluminum complex containing salicylaldehyde groups.
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 a method for catalyzing glycolide polymerization by using an aluminum complex containing salicylaldehyde groups, which is simple to operate, good in reaction controllability by using a self-developed aluminum complex containing salicylaldehyde groups as a catalyst, and high in yield, and the molecular weight of the obtained polyglycolide is controllable.
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 invention provides a salicylaldehyde-containing aluminum complex catalyst with a special structure, which has a structural formula shown as the following formula (I):
Figure 105355DEST_PATH_IMAGE001
。
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. Further, the catalytic activity is best when R is bromine.
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 bromine;
Figure 296296DEST_PATH_IMAGE002
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 ethylenediamine protected by phthalic anhydride into dichloromethane, slowly dropwise adding a saturated sodium bicarbonate aqueous solution to react 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 ethylenediamine protected by unilateral phthalic anhydride;
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;
Figure 428200DEST_PATH_IMAGE004
。
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 compound a, and the C = O double bond becomes 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, is subjected to liquid separation, organic phase collection and solvent recovery treatment, and is recrystallized to obtain the compound shown in the formula II. Therefore, the preparation of the aluminum compound 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.
Figure 1
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, the stereoselectivity is high, and the catalyst is a good catalyst for the ring-opening polymerization reaction of the cyclic lactone.
When the aluminum complex containing salicylaldehyde groups is used as a catalyst for ring-opening polymerization reaction of cyclic lactone, the ring-opening polymerization of glycolide can be catalyzed to obtain a series of polyglycolide. The invention specifically provides a method for catalyzing glycolide polymerization by using the aluminum complex containing salicylaldehyde groups, which comprises the following steps: mixing the salicylaldehyde-containing aluminum complex catalyst, an organic solvent, a benzyl alcohol cocatalyst and glycolide, carrying out ring-opening polymerization reaction under the protection of anhydrous and oxygen-free inert gases, and treating reactants after reaction to obtain polyglycolide.
When the aluminum complex containing salicylaldehyde groups is used as a catalyst for the ring-opening polymerization reaction of glycolide, the catalytic activity is optimal when R is bromine.
In the ring-opening polymerization reaction, the molar ratio of glycolide 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 ℃. With the increase of the polymerization temperature, the stereoselectivity of the catalyst tends to decrease, and the catalytic activity tends to increase.
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, 300 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 molecular weight of the obtained polyglycolide has high controllability and can be adjusted within the range of 1-13.5 ten thousand.
The method takes the self-developed aluminum complex containing the salicylaldehyde group as the catalyst to carry out the glycolide ring-opening polymerization reaction, the preparation method of the aluminum complex containing the salicylaldehyde group catalyst is simple, the cost is low, the product yield is high, the catalyst structure is varied, the divalent N, N, O and O coordination of the metal center aluminum and the ligand is high, the catalytic activity is high, the stereoselectivity is high, the reaction rate is high, the obtained polymer is a benzyloxy-terminated polymer, the molecular weight distribution is narrow, the molecular weight is controllable, the yield is high, and the market demand is met. When the asymmetric tetradentate nitrogen oxygen aluminum compound is used as a catalyst to carry out the ring opening polymerization reaction of glycolide, the obtained product has controllable molecular weight and high yield.
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 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%.
Figure 577214DEST_PATH_IMAGE006
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.
Figure 871930DEST_PATH_IMAGE007
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= 5.5 Hz, 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.
Figure 174735DEST_PATH_IMAGE002
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
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 glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then placing the ampoule in a position of 110 mu moloAnd 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
The reaction is carried out under the protection of anhydrous oxygen-free and inert gas, and 100 mu mol of catalyst (aluminum complex shown in formula I, R is bromine) is firstly added in sequence into an ampoule after being washed and baked by high-purity nitrogen gas100 μmol benzyl alcohol, 20 mL toluene, and 10mmol glycolide, respectively, then 20oC、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 15 mmol 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 15 mmol 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
Reacting under the protection of anhydrous oxygen-free inert gas, firstly adding into an ampoule after being washed and baked by high-purity nitrogen gasAdding 200 mu mol of catalyst (aluminum complex shown in formula I, R is tertiary butyl), 200 mu mol of benzyl alcohol, 10 mL of toluene and 10mmol of glycolide, and placing the mixture in a reactor at 70oAnd 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
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), 20 mu mol of benzyl alcohol, 15 mL of toluene and 5 mmol of glycolide into an ampoule after being washed and baked by high-purity nitrogen gas, and then sequentially adding 90 mu mol of catalyst, 20 mu mol of benzyl alcohol, 15 mL of toluene and 5 mmol of glycolideoC, 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.
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.
Figure 407264DEST_PATH_IMAGE008
Polyglycolide was prepared according to the method of example 13 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 0.24g, the yield is 20.7 percent, and the molecular weight is 1.1 ten thousand. The nickel catalyst has too low activity for polymerization of glycolide 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: dissolving 0.20 g of ligand in 10 mL of toluene under the protection of anhydrous oxygen-free inert gas, and adding at-5 DEG CAdding trimethylaluminum with the molar weight being 1.0 time of that of the ligand, slowly heating to room temperature, heating to 80 ℃ for reaction for 12 hours, concentrating the solvent in vacuum after the reaction is finished, adding dry hexane to precipitate solid, filtering, washing with hexane, and drying to obtain the aluminum catalyst, wherein the structural formula of the aluminum catalyst is LAlMe shown in the specification.
Figure 86507DEST_PATH_IMAGE009
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used was the aluminum catalyst. After reacting for 1 hour, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain 0.91 g, yield 78.4%, and molecular weight 1.8 ten thousand.
Comparative example 3
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used was the catalyst used in example 10 of patent 201410609375.8. After reacting for 1h, adding a small amount of water to terminate the reaction, precipitating with ethanol, washing for several times, and vacuum drying at room temperature to obtain polyglycolide with a mass of 0.96g, a yield of 82.8% and a molecular weight of 1.9 ten thousand.
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
Polyglycolide was prepared according to the method of example 13 except that: the catalyst is an aluminum complex shown as a formula I, and R is methoxy. After 12min of reaction, the mass of the obtained product was 0.98 g, the yield was 84.5%, and the molecular weight was 2.0 ten thousand.
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）。
Polyglycolide was prepared according to the method of example 13 except that: the catalyst used was the aluminum catalyst. The mass of the product obtained after the reaction was 0.43 g, the yield was 37.1%, and the molecular weight was 1.4 ten thousand.
Figure 252041DEST_PATH_IMAGE010

Claims (14)

1. A method for catalyzing glycolide polymerization by using an aluminum complex containing salicylaldehyde groups is characterized by comprising the following steps: mixing a catalyst, an organic solvent, a benzyl alcohol cocatalyst and glycolide, carrying out ring-opening polymerization reaction under the conditions of no water and no oxygen and inert gas protection, and treating reactants after reaction to obtain polyglycolide; the catalyst is an aluminum complex containing salicylaldehyde, and the structural formula of the aluminum complex is shown as the following formula I, wherein R is hydrogen, C1-C4 alkyl or halogen;
Figure DEST_PATH_IMAGE001
。
2. the method of claim 1, further comprising: r is bromine.
3. The method of claim 1, further comprising: the preparation method of the catalyst comprises 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, alkyl of C1-C4 or halogen;
Figure 372810DEST_PATH_IMAGE002
。
4. the method of claim 3, wherein: in the structural formulas of the ligand A and the ligand II, R is bromine.
5. The method of claim 3, wherein: in the preparation process of the catalyst, the molar ratio of the ligand A or the ligand II to the trimethylaluminum is 1: 1 to 1.3.
6. The method of claim 5, wherein: in the preparation process of the catalyst, 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: in the preparation process of the catalyst, the organic solvent is one or two of dry hexane, toluene and cyclohexane; the dosage of the organic solvent is 5-40 times of the total mass of the reaction raw materials.
8. The method of claim 3, wherein: in the preparation process of the catalyst, after the temperature is raised to the room temperature, the temperature is raised to 30-110 DEGoC, reacting for 1-12 hours.
9. The method of claim 8, wherein: in the preparation process of the catalyst, after the temperature is raised to the room temperature, the temperature is raised to 40-60 DEGoC, reacting for 3-6 hours.
10. The method of claim 3, wherein: in the preparation process of the catalyst, the reaction is carried out under the protection of inert gas.
11. The method according to any of claims 1-10, characterized by: during the ring-opening polymerization reaction, the molar ratio of glycolide to the catalyst is 50-1500: 1.
12. the method according to any of claims 1-10, characterized by: during ring-opening polymerization reaction, the molar ratio of the benzyl alcohol cocatalyst to the catalyst is 1-3: 1.
13. the method according to any of claims 1-10, characterized by: and during the ring-opening polymerization reaction, the organic solvent is toluene or tetrahydrofuran.
14. The method according to any of claims 1-10, characterized by: during the ring-opening polymerization reaction, the reaction temperature is 20-110 ℃, and the reaction time is 1-1440 minutes.
CN201711315746.1A 2017-12-12 2017-12-12 Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups Active CN108239261B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711315746.1A CN108239261B (en) 2017-12-12 2017-12-12 Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711315746.1A CN108239261B (en) 2017-12-12 2017-12-12 Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups

Publications (2)

Publication Number Publication Date
CN108239261A CN108239261A (en) 2018-07-03
CN108239261B true CN108239261B (en) 2020-09-08

Family

ID=62700667

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711315746.1A Active CN108239261B (en) 2017-12-12 2017-12-12 Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups

Country Status (1)

Country Link
CN (1) CN108239261B (en)

Also Published As

Publication number Publication date
CN108239261A (en) 2018-07-03

Similar Documents

Publication Publication Date Title
CN108239102B (en) Aluminum complex containing salicylaldehyde group and preparation method and application thereof
CN108569993B (en) Tetradentate nitrogen-oxygen symmetric ligand containing chiral cyclohexanediamine and preparation method and application thereof
CN108570066B (en) Aluminum compound containing chiral cyclohexanediamine and preparation method and application thereof
CN108239263B (en) Method for catalyzing caprolactone polymerization by using salicylaldehyde-containing aluminum complex
CN108570143B (en) Method for catalyzing polymerization of glycolide by using aluminum compound containing chiral cyclohexanediamine
CN108503812B (en) Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing o-phenylenediamine group
CN108503801B (en) Method for catalyzing lactide polymerization by using o-phenylenediamine-containing asymmetric aluminum complex
CN108239017B (en) Ligand containing salicylaldehyde group and preparation method and application thereof
CN108503661B (en) Asymmetric aluminum complex containing o-phenylenediamine group, and preparation method and application thereof
CN108003087B (en) Chiral asymmetric nitrogen-oxygen ligand containing salicylaldehyde group and preparation method and application thereof
CN108084218B (en) Chiral asymmetric aluminum complex containing salicylaldehyde group and preparation method and application thereof
CN108503576B (en) Asymmetric ligand containing o-phenylenediamine group, preparation method and application thereof
CN108084411B (en) Method for catalyzing glycolide polymerization by using chiral aluminum complex containing acetylacetone derivative
CN108239261B (en) Method for catalyzing polymerization of glycolide by using aluminum complex containing salicylaldehyde groups
CN107955030B (en) Chiral aluminum complex containing acetylacetone derivative, and preparation method and application thereof
CN108239264B (en) Method for catalyzing lactide polymerization by using aluminum complex containing salicylaldehyde group
CN108003183B (en) Method for catalyzing caprolactone polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound
CN108503802B (en) Method for catalyzing glycolide polymerization by using asymmetric aluminum complex containing o-phenylenediamine group
CN108003336B (en) Method for catalyzing caprolactone polymerization by using chiral asymmetric aluminum complex containing salicylaldehyde group
CN108003335B (en) Method for catalyzing polymerization of glycolide by using chiral asymmetric aluminum complex containing salicylaldehyde groups
CN108084410B (en) Method for catalyzing lactide polymerization by using chiral asymmetric aluminum complex containing salicylaldehyde group
CN108047432B (en) Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing acetylacetone derivative
CN107936238B (en) Method for catalyzing glycolide polymerization by using asymmetric aluminum complex containing acetylacetone derivative
CN108017777B (en) Method for catalyzing caprolactone polymerization by using chiral aluminum complex containing acetylacetone derivative
CN107955146B (en) Method for catalyzing lactide polymerization by using chiral aluminum complex containing acetylacetone derivative

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant