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Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof

A technology of bidentate amino groups and aluminum complexes, which is applied in the application field of catalytic lactone ring-opening polymerization, can solve the problems of low catalytic activity and difficulty in industrial production, and achieve high catalytic activity, narrow molecular weight distribution, and easy preparation Effect

Inactive Publication Date: 2014-11-05
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2010, Mountford et al. reported that aluminum ethyl complexes of bidentate and claw-shaped ligands containing nitrogen-coordinating atoms showed catalytic activity for lactide ring-opening polymerization, and had the characteristics of active polymerization in the catalytic process, but The study found that the catalytic activity of this type of catalyst is very low when there is no alcohol initiation
Due to the higher requirements and restrictions on the accuracy of the amount of alcohol added, this has brought greater difficulties to industrial production

Method used

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  • Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof
  • Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof
  • Heterocycle substituted bidentate amino ligand aluminium complex as well as preparation method thereof and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Synthesis of Ligand Compound L1

[0042] To 2-piperidinylbenzaldehyde (20mL, 20mmol) in N,N-dimethylformamide solution, add 2-chloroaniline (21mL, 20mmol) and anhydrous K 2 CO 3(3g, 22mmol), refluxed for 4h. Add 50mL of water, extract with dichloromethane, and extract by anhydrous MgSO 4 Dry and filter. After the filtrate was distilled off the solvent under reduced pressure, it was dissolved in 20 mL of absolute ethanol, NaBH4 (240 mmol) was added, refluxed, and water was added to neutralize the remaining NaBH 4 , dichloromethane extraction, anhydrous MgSO 4 Dry and purify by recrystallization with ethanol-water at -20°C to obtain a white solid (3.48g, yield: 58%), the structural formula is as follows:

[0043]

[0044] mp 73°C; δ H (400MHz, CDCl 3 , 25°C): 7.34(d, J=7.5Hz, 1H, Ar-H), 7.26-7.21(m, 2H, Ar-H), 7.18-6.98(m, 3H, Ar-H), 6.71(d , J=7.2Hz, 1H, Ar-H), 6.60(td, J=7.7, 1.3Hz, 1H, Ar-H), 5.21(br, 1H, -NH), 4.44(d, J=3.8Hz, 2H, Ar-CH 2 -), 3.01-2.80 (m...

Embodiment 2

[0046] Synthetic Ligand Compound L2

[0047] To a solution of 2-piperidinylbenzaldehyde (20mL, 20mmol) in N,N-dimethylformamide, add p-cymeniline (21mL, 20mmol), and anhydrous K 2 CO 3 (3g, 22mmol), refluxed for 4h, added 50mL of water, extracted with dichloromethane, and the extract was made of anhydrous MgSO 4 Dry and filter. After the filtrate was distilled off the solvent under reduced pressure, it was dissolved in 20 mL of absolute ethanol, and NaBH 4 (240mmol), reflux, add water and residual NaBH 4 , dichloromethane extraction, anhydrous MgSO 4 Dry and purify by recrystallization with ethanol-water at -20°C to obtain a white solid (4.13g, yield: 67%), the structural formula is as follows:

[0048]

[0049] mp 68°C; δ H (400MHz, CDCl 3 , 25°C): 7.36(d, J=7.5Hz, 1H, Ar-H), 7.22(t, J=7.2Hz, 1H, Ar-H), 7.10(dd, J=7.9, 0.8Hz, 1H, Ar-H), 7.06-7.01(m, 3H, Ar-H), 6.61(d, J=7.5Hz, 2H, Ar-H), 4.50(br, 1H, -NH), 4.35(s, 2H, Ar-CH 2 -), 2.90-2.81 (m, 4H, -NCH 2 -), 2.7...

Embodiment 3

[0051] Synthetic Ligand Compound L3

[0052] To 2-piperidinylbenzaldehyde (20mL, 20mmol) in N,N-dimethylformamide solution, add aniline (21mL, 20mmol), and anhydrous K 2 CO 3 (3g, 22mmol), refluxed for 4h, added 50mL of water, extracted with dichloromethane, and the extract was made of anhydrous MgSO 4 Dry and filter. After the filtrate was distilled off the solvent under reduced pressure, it was dissolved in 20 mL of absolute ethanol, and NaBH 4 (240mmol), reflux, add water and remaining NaBH 4 , dichloromethane extraction, anhydrous MgSO 4 Dry, and purify by recrystallization with ethanol-water at -20°C to obtain a white solid (3.40 g, yield: 64%), the structural formula is as follows:

[0053]

[0054] mp 64°C; δ H (400MHz, CDCl 3 , 25°C): 7.35(d, J=7.5Hz, 1H, Ar-H), 7.25(d, J=7.2Hz, 1H, Ar-H), 7.18-7.14(m, 2H, Ar-H), 7.11(d, J=7.9Hz, 1H, Ar-H), 7.03(t, J=7.5Hz, 1H, Ar-H), 6.70-6.63(m, 3H, Ar-H), 4.60(br, 1H , -NH), 4.37(s, 2H, Ar-CH 2 -), 3.02-2.79 (m, 4H, -NC...

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Abstract

The invention discloses a heterocycle substituted bidentate amino ligand aluminum complex as well as a preparation method thereof and an application thereof in catalyzing lactone polymerization. The preparation method comprises the following steps of: directly reacting heterocycle substituted bidentate amino ligand and aluminum alkyl; and then obtaining a target compound from a reactant through filtering, concentrating and recrystallization steps. The heterocycle substituted bidentate amino ligand aluminum complex disclosed by the invention is a high-efficiency lactone ring-opening polymerization catalyst, which can be used for polymerization reaction of lactide, epsilon-caprolactone and the like. The novel aluminum complex disclosed by the invention has very obvious advantages of easily obtained raw material, simple synthesis route, high product yield, comparatively stable property, higher catalytic activity and narrow molecular weight distribution; polylactide with high molecular weight and polycaprolactone with high molecular weight can be obtained; and requirements of industrial departments can be satisfied. The structural formulas of the ligand and the complex are shown in the specification.

Description

technical field [0001] The invention relates to a class of heterocyclic substituted bidentate amino ligand aluminum metal complex and its application in catalyzing lactone ring-opening polymerization. Background technique [0002] Cyclic lactone compounds, among which the more important ones are ε-caprolactone (ε-CL) and lactide (LA), etc., can be ring-opened and polymerized under the action of a catalyst to obtain polylactone compounds, which is also the preparation of polylactone compounds. Important method for lactone materials. With the development of society, people's requirements for the environmental performance of materials are also increasing. Because polylactone materials have excellent biodegradability, excellent biocompatibility, plasticity, and good mechanical processing properties, they are regarded as the most promising materials. It has huge application potential in the fields of packaging materials, medicine and hygiene, medical equipment, and clothing. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/06C07D295/135C08G63/08C08G63/84
Inventor 马海燕刘峻鹏
Owner EAST CHINA UNIV OF SCI & TECH