Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Catechol derivative as well as synthesis and application of biomimetic polymer of catechol derivative

A catechol polyurethane and catechol technology, which is applied in the field of polymer biomaterials and functional materials, can solve the problems of difficult purification, difficult synthesis of catechol derivatives, and single reaction method, and achieve excellent formation Coating ability, easy to expand production, simple equipment requirements

Active Publication Date: 2018-06-19
HUAZHONG NORMAL UNIV
View PDF8 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In these synthetic methods, adopt dopamine and dopamine to carry out derivation or grafting, the source of raw material is limited, the price is expensive, and reaction method is single; Adopt the synthetic method of (3,4-dimethoxy)benzene derivative, synthetic route is long , requiring cumbersome protection and deprotection of phenolic hydroxyl groups, etc.
In addition, the synthesis of pyrocatechol derivatives is also very difficult, and the method for the synthesis of pyrocatechol derivatives reported in the literature at present mainly takes phenol as starting material, and obtains through steps such as formylation and redox (CN103265391 , CN102653506, CN 106278825), these methods have poor selectivity, complex products, and difficult purification; transition metal catalysis can also be used to synthesize catechol derivatives (Angew.Chem.Int.Ed.2013,52,5398-5401.) , this method requires additional directed groups, the source of raw materials is limited and the synthesis cost is expensive; it is also reported that catechol derivatives are obtained through oxidation from cyclohexanone (CN105801381), although this method has good selectivity, but Limited by the substrate cyclohexanone derivatives, the obtained catechol compounds cannot be used in the synthesis of biomimetic polymers

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
  • Catechol derivative as well as synthesis and application of biomimetic polymer of catechol derivative
  • Catechol derivative as well as synthesis and application of biomimetic polymer of catechol derivative
  • Catechol derivative as well as synthesis and application of biomimetic polymer of catechol derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The synthesis of embodiment 1 pyrocatechol derivatives

[0027] The general method for the synthesis of catechol derivatives: add secondary amine (0.03mol), formaldehyde solution (37% solution, 0.03mol), 50mL water in a 150mL flask, stir and react for 30min at 25°C, N 2 Under atmosphere, an aqueous solution (10 mL) of catechol (0.03 mol) was slowly added, and the reaction was continued for 3 h, and the end point of the reaction was monitored by TLC. Dilute hydrochloric acid (1 mol / L) was added to the reaction solution to adjust the pH value of the reaction solution to about 2, and the raw material of catechol was recovered by extraction with ether, and the water phase was retained. Add NaOH solution to adjust the pH value of the aqueous phase to about 8, extract 3 to 5 times with 100 mL ethyl acetate, and remove the organic phase with anhydrous Na 2 SO 4 Drying, precipitation, recrystallization from an appropriate amount of acetonitrile to obtain the 4-substituted cat...

Embodiment 2

[0039] Synthesis of embodiment 2 polyurethane biomimetic polymer (CPU)

[0040] In a 100mL three-necked flask, add polyethylene glycol (molecular weight 1000, 4.0g, 4mmol) and 20mL N,N-dimethylformamide (DMF, anhydrous) that were dewatered under vacuum at 100°C, and heat up to 70°C. N 2 With mechanical stirring, slowly add isophorone diisocyanate (1.78g, 8mmol) dropwise, react for 2h, control -NCO content at 5.8% of theoretical value (use di-n-butylamine method for titration, bromophenol blue as indicator) , cooled to room temperature, slowly added dropwise 5 mL of a DMF solution containing 4-(N,N-bis(2-hydroxyethyl)aminomethyl)catechol (II-c) (0.91g, 4mmol), 60°C Reaction 2h. Cool to room temperature, add anhydrous diethyl ether to precipitate, centrifuge to obtain a yellow thick or jelly, and vacuum dry at 40°C for 48 hours to obtain catechol-containing biomimetic polyurethane CPU with a yield of 85%.

[0041] 1 H NMR (600MHz, DMSO-d6) δ6.6-7.1 (broad peak, benzene ring ...

Embodiment 3

[0042] The synthesis of embodiment 3 polyacrylate biomimetic polymer (CPA)

[0043] First, the methacrylated intermediate II-d (catechol-containing acrylate) was synthesized. 4-(N-(2-hydroxyethyl)--N-methylaminomethyl)catechol (II-d, 1.97g, 10mmol) was dissolved in 50mL of anhydrous tetrahydrofuran, and triethylamine ( 2.02g, 10mmol), slowly dropwise added 10mL of anhydrous tetrahydrofuran solution containing 2-methacrylic anhydride (2.31g, 15mmol) under ice-cooling, and reacted at room temperature for 12h. After column chromatography (eluent: ethyl acetate / petroleum ether, volume ratio 1 / 2), 2-(N-(3,4-dihydroxybenzyl)-N-methylamino)ethylmethyl Acrylate (yellow oil, 1.91 g, yield 72%). 1 H NMR (600MHz, CDCl 3 )δ6.76(s,1H),6.71(d,J=7.9Hz,1H),6.63(d,J=7.5Hz,1H),6.18(s,2H),6.10(s,1H),5.56( s, 1H), 4.31 (t, J = 5.6Hz, 2H), 3.48 (s, 2H), 2.76 (t, J = 5.6Hz, 2H), 2.31 (s, 3H), 1.92 (s, 3H).

[0044] In a three-necked flask, add methacrylation intermediate II-d (1.33g, 5mmol), p...

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 weightaaaaaaaaaa
Login to View More

Abstract

The invention discloses a synthetic method and application of a catechol derivative and a biomimetic polymer, which belongs to the field of macromolecule biological materials and functional materials.Catechol, formaldehyde and secondary amine, which are low in price and easy to acquire, are used as raw materials to obtain 4-amine methyl substituted catechol derivative and 3-amine methyl substituted catechol derivative by virtue of mannich reaction. The biomimetic polymer is the biomimetic polymer comprising catechol polyurethane or the biomimetic polymer comprising catechol polyacrylate, andpolymer monomers are prepared into the biomimetic polymer comprising a catechol structure by virtue of addition polymerization or radical polymerization. The catechol derivative obtained by the methodprovided by the invention can be used for synthesizing the biomimetic polymer comprising the catechol structural unit; and the biomimetic polymer synthesized from the catechol derivative has excellent coating forming capability, protein adsorption resistant capability and hydrogel forming capability and has application value in the aspects such as medical adhesive, medical hydrogel, and coating materials.

Description

technical field [0001] The invention relates to the field of macromolecular biomaterials and functional materials, in particular to a synthesis method and application of a class of catechol derivatives and bionic polymers. Background technique [0002] Catechol units widely exist in biomolecules in nature, and have important diverse biological activities and functions. Among them, mussel silk podoprotein (mfps) containing catechol units has the ability of adhesion and wet adhesion on any surface. Function has received extensive attention in recent years [Science.2007,318,426-430.Nat Mater.2008,7,8-9.]. Inspired by the function of mussel fibropodia, specifically designed catechol-containing polymers have important potential applications [Chem.Rev.2014,114,5057-5115.Chem.Soc.Rev.2011,40,4244- 4258.]. For example, the amphiphilic polymer (mPEG-DOPA) containing catechol structure can form a coating with anti-protein adsorption ability on various surfaces (Langmuir, 2005, 21, 6...

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 Applications(China)
IPC IPC(8): C07C213/02C07C215/50C07C227/18C07C229/16C08G18/32C08F220/36C08F220/28C09D175/04C09D133/14
CPCC07C213/02C07C227/18C08F220/28C08F220/36C08G18/10C09D133/14C09D175/04C08F220/286C07C229/16C07C215/50C08G18/3215
Inventor 张爱东段江涂海洋吴文海
Owner HUAZHONG NORMAL UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com