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Pyrrolidyl amino bidentate ligand aluminum complex and preparation method and application thereof

A technology of pyrrolidinylamine and bidentate ligand is applied to the application field of lactone ring-opening polymerization, which can solve the difficulty of industrial production, ε-caprolactone does not have any catalytic activity, and the catalytic activity and selectivity are relatively affected. It can achieve the effect of highly controllable molecular weight, stable properties and simple preparation method.

Inactive Publication Date: 2011-09-28
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2008, Mu Ying's group reported the aluminum methyl complexes of bridged aniline tetradentate ligands, and found that the catalyst can catalyze the polymerization of ε-caprolactone with high activity under the trigger of benzyl alcohol, but when benzyl alcohol is not added, Does not have any catalytic activity for ε-caprolactone (Dalton Trans., 2008, 3199-3206)
However, as the industry has higher and higher requirements for the activity and selectivity of catalysts, there are also higher requirements for the difficulty of catalyst synthesis, cost and operation. It can be seen from the research report that nitrogen Most Al catalysts with ligands need to be initiated by adding alcohol compounds in an accurate and quantitative manner, and the catalytic activity and selectivity are greatly affected by the amount of alcohol added, which brings great difficulties to industrial production.

Method used

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  • Pyrrolidyl amino bidentate ligand aluminum complex and preparation method and application thereof
  • Pyrrolidyl amino bidentate ligand aluminum complex and preparation method and application thereof
  • Pyrrolidyl amino bidentate ligand aluminum complex and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Synthesis of complex C1

[0034] To a solution of 2,6-dimethyl-N-(2-pyrrolidinyl-benzyl)-aniline (10 mL, 4 mmol) in n-hexane at room temperature, slowly add a solution of trimethylaluminum in toluene (2 mL, 4 mmol) , stirred at room temperature for 20h. The solvent was removed by filtration, and the remaining solid was crystallized from a mixed solution of dichloromethane and n-hexane to obtain 0.457 g of colorless crystals (yield: 34%).

[0035]

[0036] 1 H NMR (400MHz, CDCl 3 ): δ7.20-7.12(t, J=6.7Hz, 1H, Ar-H), 7.04(d, J=8.3Hz, 1H, Ar-H), 6.90(m, 3H, Ar-H), 6.83 (d, J=1.6Hz, 1H, Ar-H), 6.79-6.70 (d, J=7.6Hz, 1H, Ar-H), 4.44 (br, 2H, phenyl-CH 2 ), 3.18(br, 4H, N(CH 2 )), 2.22 (br, 6H, phenyl-CH 3 ), 1.98 (br, 4H, CH 2 ), -0.94(s, 6H, Al-CH 3 ). 13 C NMR (100MHz, CDCl 3 ): δ153.16(Ar-C), 149.99(Ar-C), 132.02(Ar-C), 132.22(Ar-C), 131.83(Ar-C), 130.24(Ar-C), 129.84(Ar-C C), 129.49(Ar-C), 128.50(Ar-C), 125.27(Ar-C), 125.18(Ar-C), 123.84(Ar-C), 122.10(Ar-C), ...

Embodiment 2

[0038] Synthesis of complex C2

[0039] To a solution of 4-chloro-N-(2-pyrrolidinyl-benzyl)-aniline (10 mL, 4 mmol) in n-hexane at room temperature, trimethylaluminum toluene solution (2 mL, 4 mmol) was slowly added, and stirred at room temperature for 20 h. The solvent was removed by filtration, and the remaining solid was crystallized from a mixed solution of dichloromethane and n-hexane to obtain 0.561 g of colorless crystals (yield: 41%).

[0040]

[0041] 1 H NMR (400MHz, CDCl 3 ): δ7.27 (t, J=5.3, 1H, Ar-H), 7.21 (d, J=7.1, 1H, Ar-H), 7.16 (t, J=4.7, 1H, Ar-H), 7.09 (d, J=1.2Hz, 1H, Ar-H), 7.03-7.00 (d, J=7.6, 2H, Ar-H), 6.54-6.52 (d, J=7.4, 2H, Ar-H), 4.31 (s, 2H, phenyl-CH 2 ), 3.44(m, 4H, N(CH 2 )), 1.97(m, 4H, CH 2 ), -0.98(s, 6H, Al-CH 3 ). 13 C NMR (100MHz, CDCl 3 ): δ152.88(Ar-C), 144.80(Ar-C), 134.13(Ar-C), 132.11(Ar-C), 128.46(Ar-C), 128.12(Ar-C), 127.22(Ar-C C), 119.05(Ar-C), 119.00(Ar-C), 115.34(Ar-C), 54.16(phenyl-CH 2 ), 53.62 (N (CH 2 )), 23....

Embodiment 3

[0043] Synthesis of complex C3

[0044] To a solution of 4-isopropyl-N-(2-pyrrolidinyl-benzyl)-aniline (10 mL, 4 mmol) in n-hexane at room temperature, slowly add trimethylaluminum toluene solution (2 mL, 4 mmol), and stir at room temperature 20h. The solvent was removed by filtration, and the remaining solid was crystallized from a mixed solution of dichloromethane and n-hexane to obtain 0.462 g of colorless crystals (yield: 33%).

[0045]

[0046] 1 H NMR (400MHz, CDCl 3 ): δ7.28-7.25(d, J=7.8Hz, 1H, Ar-H), 7.20-7.18(t, J=5.3Hz, 1H, Ar-H), 7.16-7.12(t, J=4.7Hz , 1H, Ar-H), 7.08 (d, J=6.8Hz, 1H, Ar-H), 6.99-6.96 (d, J=8.2Hz, 2H, Ar-H), 6.59 (d, J=6.5, 2H, Ar-H), 4.37(s, 2H, phenyl-CH 2 ), 3.44(m, 4H, N(CH 2 )), 2.72(h, J=1.1Hz, 1H, CH(CH 3 ) 2 ), 1.97 (m, 4H, CH 2 ), 1.14(d, J=6.9Hz, 6H, CH(CH 3 ) 2 ), -0.97(s, 6H, Al-CH 3 ). 13 C NMR (100MHz, CDCl 3 ): δ152.20(Ar-C), 144.92(Ar-C), 134.74(Ar-C), 134.70(Ar-C), 132.02(Ar-C), 127.80(Ar-C), 127.06(Ar-C C), 126.6...

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Abstract

The invention discloses a pyrrolidyl amino bidentate ligand aluminum complex, a preparation method thereof and application thereof in catalyzing polymerization of lactone. The preparation method comprises the following steps of: directly reacting a neutral pyrrolidyl amino bidentate ligand with an alkyl aluminum compound; and filtering, concentrating and recrystallizing to obtain the target compound from reaction products. The pyrrolidyl amino bidentate ligand aluminum complex is a high-efficiency catalyst for ring-opening polymerization of the lactone, can be used for polymerization reaction of lactide, epsilon-caprolactone and the like. The pyrrolidyl amino bidentate ligand aluminum complex has the obvious advantages that: raw materials are readily available; the synthetic route is simple; the product has high yield, stable properties and higher catalytic activity; poly(L-lactide) and poly(epsilon-caprolactone) with high molecular weight and narrow molecular weight distribution can be obtained; and the requirement of the industrial department can be met. The structural formula of the complex is shown as the description.

Description

technical field [0001] The invention relates to a novel pyrrolidinyl amino bidentate ligand aluminum metal complex and the application of the compound in lactone ring-opening polymerization. Background technique [0002] Due to their good biodegradability, biocompatibility and mechanical processing properties, polylactide, polycaprolactone and their copolymers are widely used in medical and health fields such as drugs, drug sustained-release materials, tissue scaffolds, and gene antibody carriers. It has a wide range of uses, and its potential application value as a substitute for polyolefin products is increasingly emerging (Adv. Mater. 1996, 8, 305-313). The preparation of polylactide, polycaprolactone and other aliphatic polyesters by ring-opening polymerization of lactones catalyzed by metal-organic complexes has the characteristics of high catalytic activity, controllable molecular weight and three-dimensional structure of polymers, and has a strong position in the fiel...

Claims

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Application Information

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IPC IPC(8): C07F5/06B01J31/22C08G63/08C08G63/84
Inventor 马海燕刘峻鹏
Owner EAST CHINA UNIV OF SCI & TECH
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