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Biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound and preparation method and application thereof

A technology of aminophenoloxy binuclear zinc and aminophenol, which is applied in the field of magnesium complexes and biphenyl skeleton chiral aminophenoloxy binuclear zinc, can solve the problem of binuclear zinc and magnesium complexes with few reports and external problems. Racemic lactide has low polymerization activity and no isotactic selectivity, achieving stable properties, high stereoselectivity, and convenient preparation

Inactive Publication Date: 2016-03-02
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2006, Lin's group synthesized NNO-type double ligand dinuclear or benzyloxy bridged zinc complexes, in CH 2 Cl 2 In solvents, it can catalyze the polymerization of racemic lactide to obtain heterotactic polymers, but the activity is not high, [rac-LA] 0 / [cat.] 0 = 200, the conversion rate reaches 97% within 4 hours, and the heterogeneity can reach 0.91 after lowering the temperature to -55°C (Macromolecules, 2006, 39, 3745)
In 2012, Otero reported a chiral heteroheterocrab-type zinc complex, which has active polymerization characteristics for racemic lactide, but only polymers with low heterotacticity were obtained (Organometallics, 2012, 31, 4191)
In 2013, the Otero group reported a chiral heteroscorpion-type zinc complex containing a phenocene ligand, which catalyzed the polymerization of racemic lactide with low activity and obtained a moderately isotactic polymer (P m =0.77) (Organometallics, 2013, 32, 3437)
[0005] In summary, although the heterozygous metal zinc and magnesium complexes with a single initiator group have shown high activity and stereoselectivity in catalyzing the ring-opening polymerization of lactide, the binuclear zinc and magnesium complexes There are few reports and no obvious isotactic selectivity

Method used

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  • Biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound and preparation method and application thereof
  • Biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound and preparation method and application thereof
  • Biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Synthesis of Ligand L1

[0048] (1) Synthesis of 5,5'-dimethyl-3,3'-dibromomethyl-2,2'-biphenol

[0049]

[0050] Add 5,5'-dimethyl-2,2'-biphenol (7.05g, 33.0mmol), paraformaldehyde (3.00g, 100mmol) and 30mL hydrobromic acetic acid solution (30%) into a 100mL three-necked flask , stirred at room temperature for 10 min and then heated to 70 ° C for 2 h. A large amount of white solids precipitated, filtered, washed with petroleum ether, and dried to obtain 8.08 g of white powdery solids, with a yield of 61.2%. 1 HNMR (400MHz, CDCl 3 ): δ7.20(s,2H),7.03(s,2H),5.49(brs,2H),4.60(s,4H),2.31(s,6H).

[0051] (2) Synthesis of Ligand L1

[0052]

[0053] Under the protection of argon, the toluene solution of 5,5'-dimethyl-3,3'-dibromomethyl-2,2'-biphenol (2.80g, 7.00mmol) was slowly dropped into (S)-N -Methylene-[2-(1-ethyltetrahydropyrrolyl)]benzylamine (3.06g, 14.0mmol) and potassium hydroxide (1.57g, 28.0mmol) in toluene solution, heated to 70°C for overnight reacti...

Embodiment 2

[0056] Synthesis of Ligand L2

[0057]

[0058]In addition to raw materials, 5,5'-dimethyl-3,3'-dibromomethyl-2,2'-biphenol (5.00g, 12.5mmol), (S)-N-methylene-[2 -(1-n-butyltetrahydropyrrolyl)] benzylamine (6.16g, 25.0mmol) and potassium hydroxide (2.81g, 50.0mmol), the rest of the operation steps are the same as in Example 1, to obtain a light yellow viscous substance 3.91 g, yield 42.8%.

[0059] 1 HNMR (400MHz, CDCl 3 ):δ7.35-7.28(m,4H),7.28-7.17(m,6H),7.03(s,2H),6.85(s,2H),4.03(d,J=13.6Hz,2H),3.81( d,J=13.0Hz,2H),3.68(d,J=13.7Hz,2H),3.43(d,J=13.0Hz,2H),2.68-2.42(m,8H),2.29(s,6H), 2.10-1.90(m,6H),1.65-1.50(m,4H),1.47-1.33(m,6H),1.33-1.18(m,6H),0.88(t,J=7.2Hz,6H). 13 CNMR (100MHz, CDCl 3 ): δ152.4, 137.1, 131.4, 129.9, 128.9, 128.3, 127.6, 127.3, 126.0, 122.4, 62.4, 59.2, 58.9, 58.6, 55.2, 54.2, 30.9, 30.4, 22.5, 20.8, 20.5, 14Calcd.0.Anal. forC 48 h 66 N 4 o 2 : C, 78.86; H, 9.10; N, 7.66%. Found: C, 78.56; H, 9.22; N, 7.45%.

Embodiment 3

[0061] Synthesis of Ligand L3

[0062] (1) Synthesis of 5,5'-di-tert-butyl-3,3'-dibromomethyl-2,2'-biphenol

[0063]

[0064] Add 5,5'-di-tert-butyl-2,2'-biphenol (14.9g, 50.0mmol), paraformaldehyde (4.50g, 150mmol) and 80mL hydrobromic acetic acid solution (30% ), stirred at room temperature for 10 min and then heated to 70 °C for 2 h. A large amount of white solids precipitated, filtered, washed with petroleum ether, and dried to obtain 17.2 g of white powdery solids, with a yield of 71.2%. 1 HNMR (400MHz, CDCl 3 ): δ7.40(s,2H),7.23(s,2H),5.51(brs,2H),4.65(s,4H),1.28(s,18H).

[0065] (2) Synthesis of Ligand L3

[0066]

[0067] In addition to raw materials, 5,5'-di-tert-butyl-3,3'-dibromomethyl-2,2'-biphenol (7.26g, 15.0mmol), (S)-N-methylene-[ Except for 2-(1-n-butyltetrahydropyrrolyl)]benzylamine (7.39g, 30.0mmol) and potassium hydroxide (3.36g, 60.0mmol), the remaining operating steps were the same as in Example 1 to obtain a light yellow viscous substance 4.4...

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Abstract

The invention discloses a biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound and a preparation method thereof and application of the compound in lactone ring opening polymerization catalyzing. The preparation method of the compound comprises the following steps that a neutral ligand directly reacts with a metal raw material compound in an organic medium, and then filtration and extraction are performed to obtain the target compound. The biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound is an efficient lactone ring opening polymerization catalyst and can be used for catalyzing a polymerization reaction of lactones such as lactide and particularly can be used for racemizing the lactide to obtain polylactic acid with the higher isotacticity degree. The biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound has the very obvious advantages that the raw materials are easy to obtain, the synthesis route is simple, the product yield is high, the higher catalytic activity and stereoselectivity are achieved, the polyester material with the higher isotacticity degree and the high molecular weight can be obtained, and the requirements of an industrial department can be met. The structural formula of the biphenyl skeleton chiral amino phenol oxyl dual-core zinc-magnesium compound is as followed (please see the structural formula in the specification).

Description

technical field [0001] The invention relates to a class of biphenyl skeleton chiral aminophenoloxy dinuclear zinc and magnesium complexes and the application of the complexes in lactone polymerization. Background technique [0002] In today's society, the extensive application of traditional polyolefin materials has caused energy crisis and environmental pollution that cannot be ignored. Therefore, finding renewable, degradable and environmentally friendly new polymer materials is an important topic in the field of material science. Among them, the aliphatic polyester (polyglycolide PGA, polybutyrolactone PBL, polycaprolactone PCL, polycarbonate PTMC, etc.) polymer materials represented by polylactide (PLA) have good biophase Capacitance, degradability, and reproducibility have attracted widespread attention in the fields of industrial and agricultural production and biomedicine (such as sustained-release materials for drugs, medical suture materials, etc.). PLA can be synt...

Claims

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Application Information

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IPC IPC(8): C07F3/06C07F3/02B01J31/22C08G63/08C08G63/83
Inventor 马海燕褚文蕾
Owner EAST CHINA UNIV OF SCI & TECH
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