Biphenyl skeleton chiral aminophenoloxy dinuclear zinc, magnesium compound and its preparation method and application

A technology of aminophenoloxy binuclear zinc and aminophenol, which is applied in the field of biphenyl skeleton chiral aminophenoloxy binuclear zinc and magnesium compounds, and can solve the problem of rare reports of binuclear zinc and magnesium complexes and racemization Lactide has low polymerization activity and no isotactic selectivity, achieving stable properties, high stereoselectivity, and convenient preparation

Inactive Publication Date: 2017-07-21
EAST CHINA UNIV OF SCI & TECH
View PDF4 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Biphenyl skeleton chiral aminophenoloxy dinuclear zinc, magnesium compound and its preparation method and application
  • Biphenyl skeleton chiral aminophenoloxy dinuclear zinc, magnesium compound and its preparation method and application
  • Biphenyl skeleton chiral aminophenoloxy dinuclear zinc, magnesium compound and its preparation method and application

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 H NMR (400MHz, CDCl 3 ): δ7.20(s,2H),7.03(s,2H),5.49(br s,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 reac...

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 H NMR (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 C NMR (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. for C 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(br s,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....

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

PropertyMeasurementUnit
molecular weight distributionaaaaaaaaaa
molecular weight distributionaaaaaaaaaa
molecular weight distributionaaaaaaaaaa
Login to view more

Abstract

The invention discloses a biphenyl-skeleton chiral aminophenoloxy dinuclear zinc and magnesium compound, a preparation method thereof and an application in catalyzing lactone ring-opening polymerization. The preparation method comprises the following steps: directly reacting the neutral ligand with the metal raw material compound in an organic medium, and then obtaining the target compound through the steps of filtering and drying. The biphenyl skeleton chiral aminophenoloxy dinuclear zinc and magnesium compound of the present invention is a high-efficiency lactone ring-opening polymerization catalyst, which can be used to catalyze the polymerization of lactones such as lactide; especially for racemic lactone Esters can get polylactic acid with higher isotacticity. The advantages of the biphenyl skeleton chiral aminophenoloxy binuclear zinc and magnesium compounds of the present invention are very obvious: the raw materials are easy to obtain, the synthetic route is simple, the product yield is high, and it has high catalytic activity and stereoselectivity, and can obtain high Regularity, high molecular weight polyester material to meet the needs of the industrial sector. Its structural formula is shown below.

Description

technical field [0001] The invention relates to a class of biphenyl skeleton chiral aminophenoloxy dinuclear zinc and magnesium compounds and the application of the compounds 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Patents(China)
IPC IPC(8): C07F3/06C07F3/02B01J31/22C08G63/08C08G63/83
Inventor 马海燕褚文蕾
Owner EAST CHINA UNIV OF SCI & TECH
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap