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WO2021037269A1 - 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 - Google Patents

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 Download PDF

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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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polyvinyl alcohol
polyethyleneimine
solvent
functional group
acid functional
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French (fr)
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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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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

本发明公开了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。本发明以聚乙烯亚胺，聚乙烯醇，含苯硼酸官能团分子为原料，制备了聚乙烯亚胺-聚乙烯醇水凝胶。其中，含苯硼酸官能团分子相当于桥接剂，将两种亲水性聚合物交联在一起。聚乙烯亚胺的氨基可与含苯硼酸官能团分子的醛基或羰基反应，生成动态可逆的亚胺键；而聚乙烯醇的醇羟基又可与含苯硼酸官能团分子的硼酸基团反应生成动态可逆硼酯键；同时聚乙烯亚胺与聚乙烯醇分子之间又存在氢键作用。通过以上协同作用，制备了可快速自愈合的水凝胶，并且该水凝胶无需额外刺激，便可实现优异的自愈合性能。

Description

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 技术领域
本发明属于高分子聚合物技术领域，具体涉及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。
背景技术
自愈合水凝胶指材料经外力破坏后，经过一定时间仍可恢复其初始性能及形貌的凝胶。由于其具备可靠性，耐久性等特点，被广泛应用于生物医学领域(组织粘附剂、药物控释等)、电化学领域(软机器人，传感器，人造皮肤等)。
自愈合水凝胶按照愈合条件又可分为自动自愈合水凝胶和非自动自愈合水凝胶。自动自愈合水凝胶，即无需额外刺激，比如光、电、pH、温度等刺激，便可实现自愈合。这使得自愈合过程简单化，既减少了能源的消耗，又利于凝胶的实际应用。尤其在生物医学应用方面，光、电等额外刺激会对细胞造成损伤，因此自动自愈合的水凝胶具有更大的优势。
对于自愈合水凝胶的构建，主要有两种方法：一是物理交联，比如利用氢键，离子键，超疏水作用，主客体作用等进行构建；二是化学交联，该法则是通过动态共价键构建自愈合水凝胶，例如，亚胺键、硼酯键、二硫键、酰腙键等。
Yixi Wang等[Wang Y,Niu J,Hou J,et al.A novel design strategy for triple-network structure hydrogels with high-strength,tough and self-healing properties[J].Polymer,2018,135:16-24.]构建了PAA/Agar/PVA三网络水凝胶，该凝胶体系由于存在配位作用以及氢键作用，使得该凝胶具备自愈合能力，其应变自愈合效率达84％。
Christopher C.Deng等[Deng C C,Brooks W L A,Abboud K A,et al.Boronic Acid-Based Hydrogels Undergo Self-Healing at Neutral and Acidic pH[J].Acs Macro Letters,2015,4(2):220-224.]以含硼酸的嵌段共聚物和PVA为原料，通过动态硼酯键以及氢键作用反应交联，获得具有室温自愈合的水凝胶，该水凝胶在60min内实现完全自愈合。
Bin Yan等[Yan B,Huang J,Han L,et al.Duplicating Dynamic Strain-Stiffening Behavior and Nanomechanics of Biological Tissues in A Synthetic Self-Healing Flexible Network Hydrogel[J].ACS Nano,2017:acsnano.7b05109.]以醛基封端的聚乙二醇和聚 乙烯亚胺为原料，通过动态亚胺键以及氢键作用构建自愈合水凝胶，该水凝胶具有应变硬化及优异的室温自动自愈合能力。
发明内容
本发明的目的在于克服现有技术缺陷，提供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。
本发明的原理如下：
本发明以聚乙烯亚胺，聚乙烯醇，含苯硼酸官能团分子为原料，制备了聚乙烯亚胺-聚乙烯醇水凝胶。其中，含苯硼酸官能团分子相当于桥接剂，将两种亲水性聚合物交联在一起。聚乙烯亚胺的氨基可与含苯硼酸官能团分子的醛基或羰基反应，生成动态可逆的亚胺键；而聚乙烯醇的醇羟基又可与含苯硼酸官能团分子的硼酸基团反应生成动态可逆硼酯键；同时聚乙烯亚胺与聚乙烯醇分子之间又存在氢键作用。通过以上协同作用，制备了可快速自愈合的水凝胶，并且该水凝胶无需额外刺激，便可实现优异的自愈合性能。
本发明的技术方案如下：
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，其特征在于：包括如下步骤：
(1)将聚乙烯醇与溶剂于70-98℃充分混合溶解；
(2)将聚乙烯亚胺与溶剂在室温下混合后，超声处理至澄清；
(3)将含苯硼酸官能团单体与溶剂在室温下混合后，超声处理至澄清；
(4)将步骤(3)所得的物料于室温下与步骤(2)所得的物料混合，超声处理至澄清；
(5)将步骤(4)所得的物料于70～90℃以0.5-2滴/s的速度滴入步骤(1)所得的物料中，滴加结束后，保温反应4-8h，再于50～90℃下热处理0～9h，冷却即得所述具有自愈合性能的聚乙烯亚胺-聚乙烯醇水凝胶；
上述溶剂由去离子水与有机溶剂以1.5-2.5:0.8-1.2的体积比混合而成，其中有机溶剂为乙醇、甲醇或DMF；上述含苯硼酸官能团单体为4-甲酰基苯硼酸，2-甲酰基苯硼酸和4-乙酰基苯硼酸中的至少一种。
在本发明的一个优选实施方案中，所述聚乙烯醇为聚乙烯醇1799型，醇解度99.8～100％。
在本发明的一个优选实施方案中，所述聚乙烯亚胺的分子量为600-70000。
在本发明的一个优选实施方案中，所述溶剂由去离子水与有机溶剂以2:1的体积比混合而成
在本发明的一个优选实施方案中，所述聚乙烯亚胺与聚乙烯醇的质量比为0.5-2:1。
在本发明的一个优选实施方案中，所述聚乙烯亚胺的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的1.0-7.0wt％。
在本发明的一个优选实施方案中，所述聚乙烯醇的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的3.0-3.5wt％。
在本发明的一个优选实施方案中，所述含苯硼酸官能团单体的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的0-1.0wt％。
在本发明的一个优选实施方案中，所述溶剂的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的88.5-96wt％。
在本发明的一个优选实施方案中，所述聚乙烯亚胺的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的1.0-7.0wt％，所述聚乙烯醇的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的3.0-3.5wt％，所述含苯硼酸官能团单体的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的0-1.0wt％，所述溶剂的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的88.5-96wt％。
本发明的有益效果是：
1、本发明采用的聚乙烯醇具有良好的生物相容性，生物可降解性，以及无毒性；而低分子量的支化聚乙烯亚胺是一种高阳离子性水溶性聚合物，毒性低，含有大量氨基基团，易于交联，并且在已有文献报道中也多次表明其具备高载药能力。
2、本发明中的凝胶体系中存在的硼酯键是动态可逆的，并且对葡萄糖具有响应性，苯硼酸基团会优先与小分子葡萄糖的邻二羟基反应，因此可用于胰岛素药物释放；
3、本发明的凝胶中含有的活性基团(比如氨基，醛基等)也具有载药功能。
4、本发明的凝胶不仅具备优异的生物相容性，生物可降解性，还具备快速的自愈合性能，在药物控释等方面具有潜在应用。
5、本发明的合成方法工艺简单，易于操作，反应条件较为温和。所合成的水凝 胶具有快速的室温自愈合功能，在2min内其应变自愈合效率最高可达100％
附图说明
图1为本发明实施例1～9制得的聚乙烯亚胺-聚乙烯醇水凝胶的的制备的反应方程式。
图2为本发明实施例2制得的聚乙烯亚胺-聚乙烯醇水凝胶的光学图片；
图3为本发明实施例2制得的聚乙烯亚胺-聚乙烯醇水凝胶的红外光谱图。
图4为本发明实施例2制得的聚乙烯亚胺-聚乙烯醇水凝胶的SEM图，其中，a为横截面200倍下的SEM图，b为横截面500倍下的SEM图。
图5为本发明实施例5制得的聚乙烯亚胺-聚乙烯醇水凝胶愈合前后的应力-应变曲线。
图6为本发明实施例1制得的聚乙烯亚胺-聚乙烯醇水凝胶的自愈合过程图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例的反应原理如图1所示，聚乙烯醇为聚乙烯醇1799型，醇解度99.8～100％。
实施例1：
称取2g聚乙烯醇(PVA)溶于40mL去离子水中，90℃下溶解3.5h；2g聚乙烯亚胺(PEI1800)溶于10mL乙醇中，超声40min；称取0.15g4-甲酰基苯硼酸溶于10mL乙醇中，超声2min；将4-甲酰基苯硼酸于室温下加入PEI溶液中，混合超声30min后，于80℃下滴入聚乙烯醇溶液中，反应6h，获得均一黏稠状溶液，再将其倒入烧杯中，60℃下热处理5h，冷却即得水凝胶PEI-PVA-1。
表1 实施例中各组分用量
Figure PCTCN2020112641-appb-000001
Figure PCTCN2020112641-appb-000002
(注：应变自愈合效率是根据凝胶的应力-应变曲线计算而得，即愈合2min后凝胶的最大应变与初始凝胶样品最大应变的比值。)
对照组：称取2g聚乙烯醇(PVA)溶于40mL去离子水中，95℃下溶解1.5h；2g聚乙烯亚胺(PEI1800)溶于20mL乙醇中，超声30min；于80℃下将聚乙烯亚胺溶液滴入聚乙烯醇溶液中，反应6h，获得透明溶液，再将其倒入烧杯中，70℃下热处理8h，冷却并未形成水凝胶。
通过此对照试验，可以发现4-甲酰基苯硼酸对于水凝胶的形成有促进作用，说明该体系仅依靠氢键作用，并不能形成凝胶。借助小分子交联剂与聚合物之间动态共价键的生成，促进了两种聚合物之间的交联。
实施例2：
称取2g聚乙烯醇(PVA)溶于40mL去离子水中，90℃下溶解3.5h；2g聚乙烯亚胺(PEI1800)溶于10mL乙醇中，超声40min；称取0.30g4-甲酰基苯硼酸溶于10mL乙醇中，超声2min；将4-甲酰基苯硼酸于室温下加入PEI溶液中，混合超声30min后，于80℃下滴入聚乙烯醇溶液中，反应6h，获得均一黏稠状溶液，再将其倒入烧杯中，60℃下热处理3h，冷却即得水凝胶PEI-PVA-2，见图2。
实施例3：
称取2g聚乙烯醇(PVA)溶于40mL去离子水中，90℃下溶解3.5h；2g聚乙烯亚胺(PEI1800)溶于10mL乙醇中，超声30min；称取0.45g4-甲酰基苯硼酸溶于10mL乙醇中，超声2min；将4-甲酰基苯硼酸于室温下加入PEI溶液中，混合超声20min后，于80℃下滴入聚乙烯醇溶液中，反应5h，获得均一黏稠状溶液，再将其倒入烧杯中，60℃下热处理1h，冷却即得水凝胶PEI-PVA-3。
实施例4：
称取2g聚乙烯醇(PVA)溶于40mL去离子水中，90℃下溶解3.5h；2g聚乙烯亚胺(PEI600)溶于10mL乙醇中，超声40min；称取0.15g4-甲酰基苯硼酸溶于10mL乙醇中，超声2min；将4-甲酰基苯硼酸于室温下加入PEI溶液中，混合超声30min后，于80℃下滴入聚乙烯醇溶液中，反应6h，获得均一黏稠状溶液，再将其倒入烧杯中，80℃下热处理7h，冷却即得水凝胶PEI-PVA-4。
实施例5：
称取2g聚乙烯醇(PVA)溶于40mL去离子水中，90℃下溶解3.5h；2g聚乙烯亚胺(PEI10000)溶于10mL乙醇中，超声60min；称取0.15g4-甲酰基苯硼酸溶于10mL乙醇中，超声2min；将4-甲酰基苯硼酸于室温下加入PEI溶液中，混合超声30min后，于80℃下滴入聚乙烯醇溶液中，反应6h，获得均一黏稠状溶液，再将其倒入烧杯中，60℃下热处理4h，冷却即得水凝胶PEI-PVA-5。
实施例6～11步骤同实施例1，各组分用量及其应变自愈合效率见表1。
图3为实施例2制备的聚乙烯亚胺-聚乙烯醇水凝胶的红外光谱图。该谱图表明：3275cm -1为-OH、-NH2的振动吸收峰，2918，2829cm -1为亚甲基的振动吸收峰，上述说明聚乙烯亚胺以及聚乙烯醇的存在。1568，1454cm -1为苯环骨架的特征吸收峰，811cm -1为对二取代芳基C-H面外弯曲振动峰，以上说明4-甲酰基苯硼酸分子的引入。 1645cm -1处为C＝N键的特征吸收峰，说明聚乙烯亚胺的氨基与4-甲酰基苯硼酸分子的醛基发生了反应；此外，1371cm -1为B-O-C键的特征峰，说明硼酯键的生成。
图4为实施例2制备的聚乙烯亚胺-聚乙烯醇水凝胶的SEM图。从SEM图可见，所制备的水凝胶为传统的三维网络状结构(图4a)；并且其具有微米级孔洞结构，大小10μm左右(图4b)。水凝胶体系具备的多孔结构也利于药物的承载与控释。
图5为实施例5制备的聚乙烯亚胺-聚乙烯醇水凝胶愈合前后的拉伸应力-应变曲线。从图中可得，黑线为初始样品的应力-应变曲线，其强度约为60kPa，断裂伸长率可达1400％；红线为愈合2min后样品的应力-应变曲线，其与初始样品的曲线基本吻合。根据相应计算，该水凝胶的应变自愈合效率可达100％，说明其具备优异的室温自愈合能力。
图6为实施例1制备的聚乙烯亚胺-聚乙烯醇水凝胶的自愈合过程图。首先将水凝胶做成3个小球状，并把其中一个球状凝胶进行染色；然后将3个球状凝胶接触在一起，经过2min后，可用镊子将其提起，说明该水凝胶可承受自重，并且进一步表现了其快速自愈合的行为。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明公开了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。本发明以聚乙烯亚胺，聚乙烯醇，含苯硼酸官能团分子为原料，制备了聚乙烯亚胺-聚乙烯醇水凝胶。其中，含苯硼酸官能团分子相当于桥接剂，将两种亲水性聚合物交联在一起。聚乙烯亚胺的氨基可与含苯硼酸官能团分子的醛基或羰基反应，生成动态可逆的亚胺键；而聚乙烯醇的醇羟基又可与含苯硼酸官能团分子的硼酸基团反应生成动态可逆硼酯键；同时聚乙烯亚胺与聚乙烯醇分子之间又存在氢键作用。通过以上协同作用，制备了可快速自愈合的水凝胶，并且该水凝胶无需额外刺激，便可实现优异的自愈合性能,具有工业实用性。

Claims (10)

  1. 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，其特征在于：包括如下步骤：
    (1)将聚乙烯醇与溶剂于70-98℃充分混合溶解；
    (2)将聚乙烯亚胺与溶剂在室温下混合后，超声处理至澄清；
    (3)将含苯硼酸官能团单体与溶剂在室温下混合后，超声处理至澄清；
    (4)将步骤(3)所得的物料于室温下与步骤(2)所得的物料混合，超声处理至澄清；
    (5)将步骤(4)所得的物料于70～90℃以0.5-2滴/s的速度滴入步骤(1)所得的物料中，滴加结束后，保温反应4-8h，再于50～90℃下热处理0～9h，冷却即得所述具有自愈合性能的聚乙烯亚胺-聚乙烯醇水凝胶；
    上述溶剂由去离子水与有机溶剂以1.5-2.5:0.8-1.2的体积比混合而成，其中有机溶剂为乙醇、甲醇或DMF；上述含苯硼酸官能团单体为4-甲酰基苯硼酸，2-甲酰基苯硼酸和4-乙酰基苯硼酸中的至少一种。
  2. 如权利要求1所述的制备方法，其特征在于：所述聚乙烯醇为聚乙烯醇1799型，醇解度99.8～100％。
  3. 如权利要求1所述的制备方法，其特征在于：所述聚乙烯亚胺的分子量为600-70000。
  4. 如权利要求1所述的制备方法，其特征在于：所述溶剂由去离子水与有机溶剂以2:1的体积比混合而成
  5. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述聚乙烯亚胺与聚乙烯醇的质量比为0.5-2:1。
  6. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述聚乙烯亚胺的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的1.0-7.0wt％。
  7. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述聚乙烯醇的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的3.0-3.5wt％。
  8. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述含苯硼酸官能团单体的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的 0-1.0wt％。
  9. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述溶剂的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的88.5-96wt％。
  10. 如权利要求1至4中任一权利要求所述的制备方法，其特征在于：所述聚乙烯亚胺的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的1.0-7.0wt％，所述聚乙烯醇的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的3.0-3.5wt％，所述含苯硼酸官能团单体的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的0-1.0wt％，所述溶剂的用量为聚乙烯亚胺、聚乙烯醇、苯硼酸官能团单体和溶剂的总量的88.5-96wt％。
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