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WO2021037269A1 - Procédé de préparation d'un hydrogel de polyéthylèneimine-alcool polyvinylique présentant des propriétés d'auto-cicatrisation - Google Patents

Procédé de préparation d'un hydrogel de polyéthylèneimine-alcool polyvinylique présentant des propriétés d'auto-cicatrisation Download PDF

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Publication number
WO2021037269A1
WO2021037269A1 PCT/CN2020/112641 CN2020112641W WO2021037269A1 WO 2021037269 A1 WO2021037269 A1 WO 2021037269A1 CN 2020112641 W CN2020112641 W CN 2020112641W WO 2021037269 A1 WO2021037269 A1 WO 2021037269A1
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Prior art keywords
polyvinyl alcohol
polyethyleneimine
solvent
functional group
acid functional
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Ceased
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PCT/CN2020/112641
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English (en)
Chinese (zh)
Inventor
袁丛辉
柳君
戴李宗
杨杰
黄俊文
蔡其鹏
杨羽歆
陈国荣
申应军
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Xiamen University
Jinyoung Xiamen Advanced Materials Technology Co Ltd
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Xiamen University
Jinyoung Xiamen Advanced Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K38/00—Medicinal preparations containing peptides
    • A61K38/16—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • A61K38/17—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • A61K38/22—Hormones
    • A61K38/28—Insulins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds

Definitions

  • the invention belongs to the technical field of high molecular polymers, and specifically relates to a preparation method of a polyethyleneimine-polyvinyl alcohol hydrogel with self-healing properties.
  • Self-healing hydrogel refers to a gel that can recover its original performance and appearance after a certain period of time after the material is destroyed by external force. Because of its reliability and durability, it is widely used in the fields of biomedicine (tissue adhesives, controlled drug release, etc.) and electrochemistry (soft robots, sensors, artificial skin, etc.).
  • self-healing hydrogels can be divided into self-healing hydrogels and non-self-healing hydrogels.
  • Automatic self-healing hydrogel that is, without additional stimulation, such as light, electricity, pH, temperature and other stimuli, self-healing can be achieved. This simplifies the self-healing process, which not only reduces energy consumption, but also facilitates the practical application of the gel.
  • additional stimuli such as light and electricity can cause damage to cells, so the self-healing hydrogel has greater advantages.
  • Self-healing hydrogels are constructed by dynamic covalent bonds, such as imine bonds, boronic ester bonds, disulfide bonds, acylhydrazone bonds, etc.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a polyethyleneimine-polyvinyl alcohol hydrogel with self-healing properties.
  • the invention uses polyethyleneimine, polyvinyl alcohol, and molecules containing phenylboronic acid functional groups as raw materials to prepare polyethyleneimine-polyvinyl alcohol hydrogel.
  • the molecule containing phenylboronic acid functional group is equivalent to a bridging agent, which cross-links two hydrophilic polymers together.
  • the amino group of polyethyleneimine can react with the aldehyde group or carbonyl group of the molecule containing phenylboronic acid functional group to form a dynamic reversible imine bond; while the alcoholic hydroxyl group of polyvinyl alcohol can react with the boronic acid group of the molecule containing phenylboronic acid functional group to generate dynamic Reversible boron ester bond; at the same time, there is a hydrogen bond between polyethyleneimine and polyvinyl alcohol molecules.
  • a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing properties which is characterized in that it comprises the following steps:
  • step (4) Drop the material obtained in step (4) into the material obtained in step (1) at a rate of 0.5-2 drops/s at 70-90°C. After the addition is completed, heat the reaction for 4-8 hours, and then at 50 Heat treatment at ⁇ 90°C for 0-9h and cool to obtain the self-healing polyethyleneimine-polyvinyl alcohol hydrogel;
  • the above-mentioned solvent is made by mixing deionized water and organic solvent in a volume ratio of 1.5-2.5:0.8-1.2, wherein the organic solvent is ethanol, methanol or DMF; the above-mentioned phenylboronic acid functional group monomer is 4-formylphenylboronic acid, 2 -At least one of formylphenylboronic acid and 4-acetylphenylboronic acid.
  • the polyvinyl alcohol is polyvinyl alcohol 1799 type, with a degree of alcoholysis of 99.8-100%.
  • the molecular weight of the polyethyleneimine is 600-70,000.
  • the solvent is formed by mixing deionized water and organic solvent in a volume ratio of 2:1
  • the mass ratio of the polyethyleneimine to polyvinyl alcohol is 0.5-2:1.
  • the amount of polyethyleneimine used is 1.0-7.0wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
  • the amount of the polyvinyl alcohol is 3.0-3.5 wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
  • the amount of the monomer containing phenylboronic acid functional group is 0-1.0wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
  • the amount of the solvent is 88.5-96% by weight of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
  • the amount of polyethyleneimine is 1.0-7.0wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent.
  • the amount used is 3.0-3.5wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and solvent, and the amount of the phenylboronic acid functional group-containing monomer is polyethyleneimine, polyvinyl alcohol, benzene
  • the total amount of the boric acid functional group monomer and the solvent is 0-1.0 wt%, and the amount of the solvent is 88.5-96 wt% of the total amount of polyethyleneimine, polyvinyl alcohol, phenylboronic acid functional group monomer and the solvent.
  • the polyvinyl alcohol used in the present invention has good biocompatibility, biodegradability, and non-toxicity; and the low-molecular-weight branched polyethyleneimine is a highly cationic water-soluble polymer with low toxicity. It contains a large number of amino groups and is easy to cross-link, and it has been repeatedly shown in the literature to have high drug-carrying capacity.
  • the boronic ester bond in the gel system of the present invention is dynamically reversible and responsive to glucose.
  • the phenylboronic acid group will preferentially react with the o-dihydroxyl group of small molecule glucose, so it can be used for insulin drug release;
  • the active groups (such as amino groups, aldehyde groups, etc.) contained in the gel of the present invention also have a drug-carrying function.
  • the gel of the present invention not only has excellent biocompatibility and biodegradability, but also has rapid self-healing properties, and has potential applications in controlled drug release and the like.
  • the synthesis method of the present invention has simple process, easy operation, and relatively mild reaction conditions.
  • the synthesized hydrogel has a rapid room temperature self-healing function, and its strain self-healing efficiency can reach 100% within 2 minutes.
  • Figure 1 is a reaction equation for the preparation of polyethyleneimine-polyvinyl alcohol hydrogels prepared in Examples 1-9 of the present invention.
  • Figure 2 is an optical picture of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 2 of the present invention
  • Fig. 3 is an infrared spectrum diagram of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 2 of the present invention.
  • Example 4 is an SEM image of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 2 of the present invention, where a is an SEM image at 200 times the cross section, and b is an SEM image at 500 times the cross section.
  • Fig. 5 is the stress-strain curve of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 5 of the present invention before and after healing.
  • Example 6 is a diagram of the self-healing process of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 1 of the present invention.
  • the reaction principle of the following examples is shown in Figure 1.
  • the polyvinyl alcohol is polyvinyl alcohol type 1799, and the degree of alcoholysis is 99.8-100%.
  • the strain self-healing efficiency is calculated based on the stress-strain curve of the gel, that is, the ratio of the maximum strain of the gel after 2 minutes of healing to the maximum strain of the initial gel sample.
  • Control group Weigh 2g polyvinyl alcohol (PVA) and dissolve it in 40mL deionized water, dissolve it at 95°C for 1.5h; dissolve 2g polyethyleneimine (PEI1800) in 20mL ethanol, ultrasound for 30min; dissolve the polyethylene at 80°C
  • PVA polyvinyl alcohol
  • PEI1800 polyethyleneimine
  • the imine solution was dropped into the polyvinyl alcohol solution and reacted for 6 hours to obtain a transparent solution. Then it was poured into a beaker and heat-treated at 70° C. for 8 hours. After cooling, no hydrogel was formed.
  • Example 6-11 The steps in Examples 6-11 are the same as in Example 1, and the dosage of each component and its strain self-healing efficiency are shown in Table 1.
  • FIG. 3 is an infrared spectrum diagram of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 2.
  • the spectra show: -1 -OH, -NH2 vibration absorption peak of 3275cm, 2918,2829cm -1 vibration absorption peak of methylene group, the presence of polyvinyl alcohol and polyethyleneimine described above.
  • 1568, 1454 cm -1 is the characteristic absorption peak of the benzene ring skeleton, and 811 cm -1 is the out-of-plane bending vibration peak of the p-disubstituted aryl CH.
  • the introduction of 4-formylphenylboronic acid molecules is explained above.
  • FIG. 4 is an SEM image of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 2. It can be seen from the SEM image that the prepared hydrogel has a traditional three-dimensional network structure (Figure 4a); and it has a micron-scale pore structure with a size of about 10 ⁇ m ( Figure 4b). The porous structure of the hydrogel system is also conducive to drug loading and controlled release.
  • Fig. 5 is the tensile stress-strain curve of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 5 before and after healing.
  • the black line is the stress-strain curve of the initial sample, its strength is about 60kPa, and the elongation at break can reach 1400%;
  • the red line is the stress-strain curve of the sample after 2 minutes of healing, which is the curve of the initial sample Basically agree.
  • the strain self-healing efficiency of the hydrogel can reach 100%, indicating that it has excellent room temperature self-healing ability.
  • FIG. 6 is a diagram of the self-healing process of the polyethyleneimine-polyvinyl alcohol hydrogel prepared in Example 1. Firstly, the hydrogel is made into 3 small balls, and one of the spherical gels is dyed; then the 3 spherical gels are brought into contact with each other, and after 2 minutes, they can be lifted with tweezers, indicating that the hydrogel can withstand Self-respect, and further demonstrated its rapid self-healing behavior.
  • the invention discloses a preparation method of polyethyleneimine-polyvinyl alcohol hydrogel with self-healing properties.
  • polyethyleneimine, polyvinyl alcohol, and molecules containing phenylboronic acid functional groups are used as raw materials to prepare polyethyleneimine-polyvinyl alcohol hydrogel.
  • the molecule containing phenylboronic acid functional group is equivalent to a bridging agent, which cross-links two hydrophilic polymers together.
  • the amino group of polyethyleneimine can react with the aldehyde group or carbonyl group of the molecule containing phenylboronic acid functional group to form a dynamic reversible imine bond; while the alcoholic hydroxyl group of polyvinyl alcohol can react with the boronic acid group of the molecule containing phenylboronic acid functional group to generate dynamic Reversible boron ester bond; at the same time, there is a hydrogen bond between polyethyleneimine and polyvinyl alcohol molecules.

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Abstract

L'invention concerne un procédé de préparation d'un hydrogel de polyéthylèneimine-alcool polyvinylique présentant des propriétés d'auto-cicatrisation. Selon la présente invention, l'hydrogel de polyéthylèneimine-alcool polyvinylique est préparé à l'aide de polyéthylèneimine, d'alcool polyvinylique et d'une molécule contenant un groupe fonctionnel acide borique benzène en tant que matières premières, la molécule contenant un groupe fonctionnel acide borique benzène étant équivalente à un agent de pontage et réticulant deux polymères hydrophiles ensemble. Le groupe amino de la polyéthylèneimine peut réagir avec le groupe aldéhyde ou le groupe carbonyle de la molécule contenant un groupe fonctionnel acide borique benzène en vue de produire une liaison imine réversible dynamique ; de plus, le groupe hydroxyle alcoolique de l'alcool polyvinylique peut en outre réagir avec le groupe acide borique de la molécule contenant un groupe fonctionnel acide borique benzène en vue de produire une liaison ester d'acide borique réversible dynamique ; de plus, une interaction de liaison à l'hydrogène est également présente entre la molécule de polyéthylèneimine et la molécule d'alcool polyvinylique. Au moyen de l'effet synergique ci-dessus, un hydrogel qui peut rapidement auto-cicatriser est préparé, et l'hydrogel peut réaliser d'excellentes propriétés d'auto-cicatrisation sans nécessiter une stimulation supplémentaire.
PCT/CN2020/112641 2019-08-30 2020-08-31 Procédé de préparation d'un hydrogel de polyéthylèneimine-alcool polyvinylique présentant des propriétés d'auto-cicatrisation Ceased WO2021037269A1 (fr)

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CN201910822216.9A CN110698697B (zh) 2019-08-30 2019-08-30 一种具有自愈合性能的聚乙烯亚胺-聚乙烯醇水凝胶的制备方法

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CN120154570A (zh) * 2025-05-20 2025-06-17 浙江大学医学院附属邵逸夫医院 可注射响应性多功能水凝胶及其用途

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CN119219944B (zh) * 2024-09-29 2025-06-24 山东大学 一种聚乙烯醇-聚乙烯亚胺复合荧光水凝胶及其制备方法
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