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In-situ cross-linked hydrogel

An in-situ cross-linking and hydrogel technology, applied in the field of hydrogel, can solve the problems of low reaction efficiency, complex preparation of dienophiles, and large gaps in hydrogel cross-linking structures

Active Publication Date: 2017-11-28
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, first, the dienophile is a macromolecule, and the reactive carbon-carbon double bond is at both ends of the macromolecule. In this way, during the D-A reaction, the carbon-carbon double bond is easily wrapped by the main structure of the macromolecule, PEG, resulting in a D-A reaction. The efficiency is very low; secondly, the cross-linked structure of the hydrogel prepared by the dienophile (PEG-AMI) of macromolecular structure has large gaps and is not compact, so it is not suitable for plugging or hemostasis; thirdly, the amphiphile The preparation of alkenes is complicated. First, N-(isopropanoyl)-maleimide (AMI) is synthesized by maleic anhydride and alanine, and then the amphiphile is prepared by reacting AMI with polyethylene glycol (PEG). Enbody (PEG-AMI); Fourth, the preparation conversion rate of dienophile (PEG-AMI) is low and can only reach 23%
[0007] At the same time, the existing hydrogel products are basically cross-linked in the polymerization stage of the preparation process. The final product is in the form of powder or particles after drying, and becomes a hydrogel after absorbing water, and then further applied. In this state, During the application process, the polymer molecular chains in the hydrogel are always a cross-linked network structure, which does not have fluidity

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Embodiment approach

[0043] According to a preferred embodiment of the present invention, the furan-based monomer is a monomer containing a furan group and a polymerizable double bond.

[0044] In a further preferred embodiment, the furyl monomer is selected from one or more of furfuryl methacrylate, furyl acrylic acid, and furyl acrylonitrile.

[0045] In a further preferred embodiment, the furyl monomer is selected from furfuryl methacrylate and / or furyl acrylic acid.

[0046] Wherein, the water-soluble monomer and the furan-based monomer are copolymerized to obtain the polymer main agent, and the main active site of the polymer main agent is the furan side group produced after the furan-based monomer is polymerized, wherein, the water-soluble monomer is added to carry out The purpose of copolymerization is as follows: first, to reduce the steric hindrance effect of furan-based monomers and improve the polymerization efficiency of the polymer main agent; second, to control the cross-linking dens...

Embodiment 1

[0156] (1) Preparation of polymer main agent

[0157] Weigh 99g of acrylamide, 1g of furfuryl methacrylate, and 900g of butanone as a solvent, and add them to a reactor equipped with a reflux condenser. After stirring to dissolve the monomers, fill with nitrogen and exhaust oxygen for 30 minutes, heat up to 65°C, and add 0.5g Initiator azobisisobutyronitrile, stirred and reacted at constant temperature for 6 hours, added 0.5 g of chain terminator hydroquinone, stirred for 20 minutes, stopped the reaction, cooled and discharged, filtered to obtain polymer filter cake, and dried under reduced pressure to obtain polymer main agent .

[0158] (2) Preparation of crosslinking agent

[0159] Take maleic anhydride 33.0g (0.336mol), (diethylene glycol) 17.0g (0.160mol), add in the reactor that reflux condenser is housed, add 50g (0.861mol) acetone and stir to dissolve reactant, Then add 0.25 g (0.003 mol) of catalyst anhydrous sodium acetate, pass through nitrogen to remove the air, ...

Embodiment 2

[0163] (1) Preparation of polymer main agent

[0164] Weigh 100g of hydroxyethyl acrylate, 4.5g of furyl acrylic acid, and 900g of butanone as a solvent, add them into a reactor equipped with a reflux condenser, stir to dissolve the monomers, fill with nitrogen and exhaust oxygen for 30min, heat up to 75°C, add 0.5 g initiator benzoyl peroxide, after stirring and reacting at constant temperature for 8 hours, add 0.5 g of chain terminator methyl hydroquinone, stop the reaction after stirring for 20 minutes, cool and discharge, filter to obtain polymer filter cake, dry under reduced pressure to obtain polymer main agent.

[0165] (2) Preparation of crosslinking agent

[0166] Take maleic anhydride 31.9g (0.325mol), butanediol 14.7g (0.163mol), add in the reactor that reflux condenser is housed, add 50g (0.861mol) acetone stirring and dissolving reactant, then add 0.5g ( 0.006mol) catalyst anhydrous sodium acetate, pass nitrogen to remove the air, heat up to 50°C, stir at const...

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Abstract

The invention discloses in-situ cross-linked hydrogel which is prepared from a polymer main agent and a cross-linking agent in a water solution through cross-linking, wherein the polymer main agent contains furan groups on a side chain; the cross-linking agent contains more than two carbon-carbon double bonds; and as diene, the polymer main agent is subjected to a Diels-Alder cycloaddition reaction with dienophile of the cross-linking agent in a water solvent, and thus the hydrogel is prepared. The hydrogel is free of organic solvent, and is safe and environment-friendly; no catalyst is needed when the hydrogel is prepared, only an in-situ cross-linking reaction is needed, and cross-linking can be carried out at normal temperature; the hydrogel is large in cross-linking density and rapid in reaction process, and can be applied to leaking stoppage or hemostasis; and meanwhile, when the raw materials (the polymer main agent and the cross-linking agent) of the hydrogel are prepared, the yield is high, preparation processes are simple, and large-scale production and application can be easily achieved.

Description

technical field [0001] The invention relates to the field of hydrogels, in particular to an in-situ cross-linked hydrogel, in particular to an in-situ cross-linked hydrogel for leak plugging or hemostasis. Background technique [0002] As a high water absorption and high water retention material, hydrogel is widely used in many fields, such as: water retention in arable land in arid areas, humectant in antipyretic patches and cosmetic mask products, anti-condensation agent in construction, petrochemical industry Water blocking agent, medical hemostatic material, drug carrier, etc., especially for leak plugging or hemostasis. There are many methods for preparing hydrogels, among which, among many types of chemical reactions, the Diels-Alder cycloaddition reaction (D-A reaction) is a reaction that is very suitable for in-situ crosslinking hydrogels. [0003] Nabendu Pramanik et al. prepared polyfurfuryl methacrylate containing diene furan side groups, using 4,4-diaminobipheny...

Claims

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Application Information

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IPC IPC(8): C08J3/24C08J3/075C08F220/56C08F220/32C08L33/26C08L33/14C08L39/06C08L33/24C08L33/02C08F220/28C08F220/04C08F226/10C08F220/42C08F220/54C08F220/06
CPCC08F220/06C08F220/28C08F220/281C08F220/54C08F220/56C08F226/10C08J3/075C08J3/24C08J2333/02C08J2333/14C08J2333/24C08J2333/26C08J2339/06C08F220/32C08F220/04C08F220/42
Inventor 陈晓农范莉君夏宇正石淑先
Owner BEIJING UNIV OF CHEM TECH
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