A kind of aminophenol ligand magnesium, zinc complex and its preparation method and application

A technology of aminophenols and complexes, applied in the application field of lactone ring-opening polymerization, can solve the problem of low catalytic activity, achieve high catalytic activity, stable properties, and simple synthetic routes

Inactive Publication Date: 2016-07-06
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2014, the Du group reported the chiral oxazole β-diimine zinc complex, which catalyzed the ring-opening polymerization of racemic lactide to obtain high isotactic polylactide (P m =0.91), but the catalytic activity is very low (Acs.Macro.Lett.2014,3:689-692)
However, in terms of catalyzing the stereoselective polymerization of racemic lactide, magnesium and zinc catalysts with high activity and high selectivity are still rarely reported, so a lot of research work needs to be further carried out

Method used

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  • A kind of aminophenol ligand magnesium, zinc complex and its preparation method and application
  • A kind of aminophenol ligand magnesium, zinc complex and its preparation method and application
  • A kind of aminophenol ligand magnesium, zinc complex and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Synthesis of Ligand L1

[0043] Into a 500mL three-neck flask, add NH 4 Cl (7.865g, 147mmol), 30mLH 2 O, 300mL ethanol, Zn powder (19.160g, 294mmol), 2-nitro-2'-(N,N-dimethylamino)biphenyl (11.845g, 48.9mmol), heated to reflux under stirring. Suction filtration, the filtrate was collected, and the ethanol was removed by rotary evaporation, then 100 mL of water was added to the residue, and the 2 Cl 2 Multiple extractions, organic phase with anhydrous Na 2 SO 4 After drying, filtering, and removing the solvent, the target product 2-amino-2'-(N,N-dimethylamino)biphenyl was obtained as 10.281 g of a colorless liquid with a yield of 99%. 1 HNMR (400MHz, CDCl 3 ):δ7.33(td,J=8.6,J=1.7Hz,1H,Ar-H),7.23–7.16(m,3H,Ar-H),7.12–7.03(m,2H,Ar-H), 6.92(t, J=7.5Hz, 1H, Ar-H), 6.82(d, J=7.9Hz, 1H, Ar-H), 2.64(s, 6H, -N(CH 3 ) 2 ).

[0044] To a 500mL single-necked flask, add glacial acetic acid (43mL, 484mmol), 200mL CH 2 Cl 2 , 2-amino-2'-(N,N-dimethylamino)-biphenyl (10.281...

Embodiment 2

[0050] Synthesis of Ligand L2

[0051] Add 2-(N-ethylamino)-2'-(N,N-dimethylamino)biphenyl (0.961g, 4.0mmol) and 15mL THF to a 100mL single-necked flask, stir at room temperature, add dropwise 20mL of 2 , 4-Dichloro-6-bromomethylphenol (1.54g, 4.0mmol) in THF was added dropwise with Et 3 N (0.84mL, 6.0mmol), reacted for 1.5h, separated by column to obtain 1.06g of white solid, yield 64.1%.

[0052]

[0053] 1 HNMR (400MHz, CDCl 3 ):δ7.43–7.25(m,5H),7.17(d,J=2.3Hz,1H,Ar-H),7.12–7.00(m,3H),6.85(d,J=2.2Hz,1H,Ar -H), 4.34(d, J=14.1Hz, 1H, Ar-CH 2 ), 4.03 (d, J=14.2Hz, 1H, Ar-CH 2 ),2.84–2.75(m,1H,-CH 2 CH 3 ),2.74–2.65(m,1H,-CH 2 CH 3 ),2.45(s,6H,-N(CH 3 ) 2 ),0.75(t,J=7.1Hz,3H,-CH 2 CH 3 ). 13 CNMR (CDCl 3 ,100MHz):δ152.04,151.13,147.14,139.80,133.32,132.42,131.53,128.59,128.22,128.16,126.73,126.67,125.78,124.16,122.83,122.22,121.70,121.16,118.50(AllAr-C),58.93(Ar -CH 2 ),47.46(-CH 2 CH 3 ),43.53(-N(CH 3 ) 2 ),43.50(-N(CH 3 ) 2 ),11.30(-CH 2 CH 3 ).Ana...

Embodiment 3

[0055] Synthesis of Ligand L3

[0056] Add 2-(N-ethylamino)-2'-(N,N-dimethylamino)biphenyl (0.961g, 4.0mmol) and 15mL THF to a 100mL single-necked flask, stir at room temperature, add dropwise 20mL of 2 , 4-dibromo-6-bromomethylphenol (1.37g, 4.0mmol) in THF was added dropwise with Et 3 N (0.84mL, 6.0mmol), reacted for 1.5h, separated by column to obtain 1.35g of white solid, yield 53.5%.

[0057]

[0058] 1 HNMR (300MHz, CDCl 3 ):δ7.46(d,J=2.0Hz,1H,Ar-H),7.34(m,5H,Ar-H),7.11–7.00(m,4H,Ar-H),4.33(d,J= 14.1Hz, 1H, Ar-CH 2 ), 4.02 (d, J=14.1Hz, 1H, Ar-CH 2 ),2.85-2.75(m,1H,-CH 2 CH 3 ),2.73-2.64(m,1H,-CH 2 CH 3 ),2.45(s,6H,-N(CH 3 ) 2 ),0.75(t,J=7.1Hz,3H,-CH 2 CH 3 ). 13 CNMR (CDCl 3 ,100MHz):δ153.43,151.05,146.98,139.66,133.63,133.58,133.20,132.41,131.51,130.21,130.15,128.54,128.11,125.71,124.53,122.14,121.62,118.42,110.66,110.01(AllAr-C),58.72 (Ar-CH 2 ),47.37(-CH 2 CH 3 ),43.50(-N(CH 3 ) 2 ),43.47(-N(CH 3 ) 2 ),11.19(-CH 2 CH 3 ).Anal.Calcd.ForC 2...

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Abstract

The invention discloses a biphenyl or binaphthyl aminophenol ligand magnesium and zinc complex, a preparation method thereof and an application in catalyzing the ring-opening polymerization of lactone and cyclic carbonate. The preparation method comprises the following steps: directly reacting biphenyl or binaphthyl skeleton aminophenol ligand (I) with metal raw material compounds of magnesium and zinc in an organic solvent, and obtaining the target magnesium, Zinc complex (II). The magnesium and zinc complex compound of the invention is a high-efficiency catalyst for ring-opening polymerization of lactone and cyclic carbonate, and can be used for the polymerization reaction of lactide, ε-caprolactone, cyclic carbonate and the like. The advantages of the magnesium and zinc complexes of the present invention are very obvious: the raw materials are easy to obtain, the synthetic route is simple, the yield is high, the properties are relatively stable, and it has high catalytic activity at the same time, and can obtain high molecular weight polyester and polycarbonate, and can Meet the needs of the industrial sector. The structural formulas of biphenyl or binaphthyl aminophenol ligands and their magnesium and zinc complexes are as follows: .

Description

technical field [0001] The invention relates to a novel biphenyl or binaphthyl aminophenol ligand magnesium and zinc complexes and the application of such compounds in lactone ring-opening polymerization. Background technique [0002] In many respects, aliphatic polyesters have properties comparable to polyolefin polymer materials such as polyethylene and polystyrene, which use fossil energy as raw materials, but have incomparable advantages over polyolefin polymer materials. On the one hand, the carbon-heterobond contained in aliphatic polyester makes it have excellent biodegradability, biocompatibility and other characteristics, so it can be widely used in environment-friendly daily necessities, agricultural films, drug controllable release carriers and the production of biomedical materials. On the other hand, from the source of raw materials, aliphatic polyesters represented by polylactic acid can be prepared from the fermentation products of renewable crops such as whe...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C215/50C07C213/02C07F19/00C08G63/08C08G63/83C08G64/02C08G64/30
Inventor 马海燕黄淼
Owner EAST CHINA UNIV OF SCI & TECH
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