CN115304792A - 一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 - Google Patents
一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 Download PDFInfo
- Publication number
- CN115304792A CN115304792A CN202211033479.XA CN202211033479A CN115304792A CN 115304792 A CN115304792 A CN 115304792A CN 202211033479 A CN202211033479 A CN 202211033479A CN 115304792 A CN115304792 A CN 115304792A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- hydrogel
- polydopamine
- tannic acid
- urea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/7024—Esters of saccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- 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
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/16—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing nitrogen, e.g. nitro-, nitroso-, azo-compounds, nitriles, cyanates
- A61K47/18—Amines; Amides; Ureas; Quaternary ammonium compounds; Amino acids; Oligopeptides having up to five amino acids
-
- 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
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/0066—Medicaments; Biocides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
-
- 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
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/23—Carbohydrates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- 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
- 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
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Communicable Diseases (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
- Oncology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种改性聚乙烯醇多功能水凝胶及其制备方法、应用。首先,合成聚多巴胺,接着,配制聚乙烯醇/聚多巴胺分散液,再加入尿素和单宁酸进行交联反应,最终得到多功能水凝胶产品。测试结果表明,该水凝胶同时具有抗菌、粘附、抗氧化、抗溶胀、自愈、光热和可塑性等多重功能,并且光热性还有助于进一步提升水凝胶的抗菌效果,起到了协同增效的作用。本发明制备方法简单、易于实现,通过对部分工艺参数的调控,还能够灵活调节水凝胶的各种性能,从而丰富了水凝胶产品的类型和用途。
Description
技术领域
本发明涉及生物医用材料技术领域,具体涉及一种改性聚乙烯醇多功能水凝胶及其制备方法、应用。
背景技术
水凝胶是以水作为分散介质,通过物理或化学交联的三维聚合物,其同时具有固体和液体的性质。由于类似软组织的含水结构和一定的力学性能(柔韧性和可拉伸性等),水凝胶已成为组织工程支架、伤口敷料与新型给药系统的理想材料,在生物医学领域应用广泛。
采用化学修饰和复合等技术可以设计与构建各种结构的功能型水凝胶,例如高强度水凝胶、抗菌水凝胶和可注射水凝胶等,然而在不同的应用环境中往往对水凝胶提出了多功能的要求,所以,需要研发出同时具有多种功能的水凝胶新材料。
聚乙烯醇是一种常见的合成高分子,由聚醋酸乙烯醇解得到。由于聚乙烯醇分子链中存在众多亲水性羟基,因此,很容易制成水凝胶,具体的制备方法包括循环冷冻—解冻和硼砂交联法。虽然聚乙烯醇水凝胶的生物相容性、力学性能较为优异,但是由于聚乙烯醇分子结构中不含功能性基团,导致水凝胶的抗菌和粘附等性能明显不足,无法满足多功能的应用需求,因此,有必要对其进行功能化修饰。
发明内容
本发明的目的在于克服现有技术存在的上述问题和不足,提供一种全新的改性聚乙烯醇多功能水凝胶及其制备方法和应用。本发明将聚乙烯醇、单宁酸、聚多巴胺和尿素复合得到改性聚乙烯醇多功能水凝胶,其中,单宁酸的加入提高了水凝胶的粘附性能和抗氧化性能,聚多巴胺则同时提高了水凝胶的粘附性能、抗菌性能和光热性能。为实现上述目的,本发明所采用的技术方案如下:
一种改性聚乙烯醇多功能水凝胶的制备方法,具体包括以下步骤:首先,合成聚多巴胺,接着,配制聚乙烯醇/聚多巴胺复合分散液,再加入尿素、单宁酸,反应得到改性聚乙烯醇多功能水凝胶。
进一步的,反应所需聚乙烯醇、聚多巴胺、尿素、单宁酸的质量比为1:0.02~0.1:3~15:1.5。
进一步的,聚多巴胺的合成方法具体如下:称取一定量多巴胺粉末加入到乙醇溶液中,用NaOH溶液调节混合液的pH至9,搅拌反应16小时后离心分离,所得固体烘干即为聚多巴胺。
进一步的,聚乙烯醇/聚多巴胺分散液的配制方法如下:按比例将聚多巴胺、聚乙烯醇投入容器中,再加入去离子水并升温至85~95℃,在此温度下充分搅拌(约1~2小时),使聚乙烯醇完全溶解,同时,聚多巴胺分散均匀即可。
进一步的,聚乙烯醇/聚多巴胺分散液中聚乙烯醇的质量百分浓度为6%~15%。
进一步的,原料中的尿素以尿素水溶液的形式引入。尿素主要起到调控聚乙烯醇和单宁酸成胶的作用,单纯的聚乙烯醇和单宁酸交联程度过于紧密,并不利于多酚基团的暴露,适当性的加入尿素可以降低水凝胶的交联程度,让更多多酚基团暴露出来,从而提高水凝胶的粘附性能。
更进一步的,尿素的质量百分浓度为37.5%。
进一步的,原料单宁酸以单宁酸水溶液的形式引入。
更进一步的,单宁酸的质量百分浓度为15%。
进一步的,加入单宁酸后在室温下搅拌反应1~5分钟。
本发明的另一重目的在于提供一种改性聚乙烯醇多功能水凝胶,该水凝胶同时表现出优异的抗菌、粘附、抗氧化、抗溶胀、自愈、光热和可塑性。
本发明的第三重目的在于提供上述改性聚乙烯醇多功能水凝胶在生物医药和个人卫生材料方面的应用。
本发明改性聚乙烯醇多功能水凝胶的制备机理如下:通过复合单宁酸,使其与聚乙烯醇的交联更紧密,同时暴露出更多的邻苯多酚结构,由此显著增强了水凝胶的粘附性能,并且保留了单宁酸原有的抗氧化性和抗菌性。聚多巴胺的引入则能够同时提高水凝胶的粘附、抗菌和光热性能。该水凝胶通过单宁酸对聚乙烯醇进行交联,尿素也参与交联,起到调控交联结构的作用。聚多巴胺主要以小颗粒形式存在于体系中,形成双重粘附网络结构,即单宁酸以及聚多巴胺的粘附作用。这两种粘附作用之间并非相互独立存在,而是协同作用,通过氢键作用交联在一起,聚多巴胺也以氢键负载于水凝胶之中,共同赋予水凝胶多功能性。
与现有技术相比,本发明的有益效果主要体现在以下几个方面:
(1)本发明提供的水凝胶同时具有优异的抗菌、粘附、抗氧化、抗溶胀、自愈、光热和可塑性等多重功能,可以满足综合性能要求较高的应用场景;
(2)本发明提供的水凝胶采用纯物理交联,无化学交联剂添加,因而生物相容性好;
(3)本发明提供的水凝胶对各种物体(如玻璃、金属、橡胶和皮肤组织等)都具有突出的粘附性;
(4)随着聚多巴胺的加入,本发明提供的改性聚乙烯醇多功能水凝胶的粘附性能显著提升,能够稳定的粘附在皮肤表面;
(5)本发明提供的水凝胶具有良好的光热性能;
(6)本发明提供的水凝胶对金黄色葡萄球菌和大肠杆菌均具有良好的抗菌性,聚多巴胺的加入使抗菌性明显增强,并且光热性还有助于进一步提升水凝胶的抗菌效果;
(7)本发明中尿素的加入可显著增强水凝胶的粘附性能;
(8)本发明提供的水凝胶具有优异的双重粘附和双重抗菌能力,而这均源于单宁酸、聚多巴胺和尿素的作用;
(9)本发明提供的水凝胶具有突出的抗溶胀性,在应用环境中溶胀小、结构稳定,粘附等性能也能够保持稳定;
(10)本发明提供的水凝胶具有显著的抗氧化性;
(11)本发明提供的水凝胶具有良好的可塑性;
(12)本发明提供的水凝胶具有优异的自愈性能;
(13)本发明提供的水凝胶制备方法简单、易于实现,通过对部分工艺参数的调控,还可灵活调节水凝胶的各种性能。
附图说明
图1为改性聚乙烯醇多功能水凝胶的粘附性能测试示意图;
图2为改性聚乙烯醇多功能水凝胶的抗菌性能。
具体实施方式
为使本领域普通技术人员充分理解本发明的技术方案和有益效果,以下结合具体实施例及附图进行进一步说明。
实施例1
1)称取0.5g多巴胺粉末,将其加入到90mL去离子水与40mL乙醇组成的混合溶液中,用1mol·L-1的NaOH溶液调节溶液的pH至9,搅拌反应16小时;
2)将步骤1)的产物离心分离并烘干,得到聚多巴胺粉末;
3)在90℃水浴条件下,将0.5g聚乙烯醇、0.03g聚多巴胺加入到4.5mL去离子水中,搅拌均匀得到聚乙烯醇/聚多巴胺分散液;
4)配制质量百分浓度为37.5%的尿素水溶液备用;
5)量取2.5mL尿素水溶液,将其加入到聚乙烯醇/聚多巴胺分散液中,搅拌均匀得到聚乙烯醇/聚多巴胺/尿素复合分散液;
6)将0.75g单宁酸加入到4.25mL去离子水中,在室温下搅拌使其完全溶解,得到单宁酸溶液;
7)将单宁酸溶液缓慢加入到步骤5)所得聚乙烯醇/聚多巴胺/尿素复合分散液中,室温下搅拌反应5分钟,得到改性聚乙烯醇多功能水凝胶。
参照GB/T 33334-2016胶粘剂单搭接拉伸剪切强度试验方法,在室温下对制得的水凝胶进行了皮肤(猪皮)粘附性能测试,示意图见图1。采用2,2-联苯基-1-苦基肼基清除率(15mg水凝胶用量)评价了水凝胶的抗氧化效果。通过称重法测试了水凝胶的溶胀性能。采用平板计数法研究了水凝胶的抗菌性能。(下同)
测试结果表明,实施例1制得水凝胶同时具有优异的可塑性、自愈性、光热性(0.3W功率、808nm近红外光照射10分钟以内,水凝胶的温度由25℃上升到60℃)、粘附(49.2kPa)、抗氧化(2,2-联苯基-1-苦基肼基清除率为90.6%)、抗溶胀(溶胀度34.6%)、抗菌(金黄色葡萄球菌的抗菌率75.3%,大肠杆菌的抗菌率83.1%)等多重性能。
此外如图2所示,用808nm近红外激光照射该水凝胶10分钟后,两种细菌的抗菌率均达到99.9%。而同等制备工艺条件下,不添加聚多巴胺制得的水凝胶(对照组)对金黄色葡萄球菌的抗菌率仅为51.4%,对大肠杆菌的抗菌率仅为63.4%。这一结果表明,聚多巴胺的引入对水凝胶的抗菌性能提升显著。
实施例2
1)称取0.5g多巴胺粉末,将其加入到90mL去离子水与40mL乙醇组成的混合溶液中,用1mol·L-1的NaOH溶液调节溶液的pH至9,搅拌反应16小时;
2)将步骤1)的产物离心分离并烘干,得到聚多巴胺粉末;
3)在90℃水浴条件下,将0.5g聚乙烯醇、0.03g聚多巴胺加入到4.5mL去离子水中,搅拌均匀得到聚乙烯醇/聚多巴胺分散液;
4)配制质量百分浓度为37.5%的尿素水溶液备用;
5)量取4.16mL尿素水溶液,将其加入到聚乙烯醇/聚多巴胺分散液中,搅拌均匀得到聚乙烯醇/聚多巴胺/尿素复合分散液;
6)将0.75g单宁酸加入到4.25mL去离子水中,在室温下搅拌使其完全溶解,得到单宁酸溶液;
7)将单宁酸溶液缓慢加入到步骤5)所得聚乙烯醇/聚多巴胺/尿素复合分散液中,室温下搅拌反应5分钟,得到改性聚乙烯醇多功能水凝胶。
测试结果表明,实施例2制得水凝胶的抗溶胀、抗氧化和粘附性能同样突出,其中溶胀度为29.8%,抗氧化为90.7%(2,2-联苯基-1-苦基肼基清除率),该水凝胶对皮肤的粘附强度为77.8kPa,此外,其对塑料、橡胶、不锈钢、玻璃和纸张都具有良好的粘附性能。
实施例3
1)称取0.5g多巴胺粉末,将其加入到90mL去离子水与40mL乙醇组成的混合溶液中,用1mol·L-1的NaOH溶液调节溶液的pH至9,搅拌反应16小时;
2)将步骤1)的产物离心分离并烘干,得到聚多巴胺粉末;
3)在90℃水浴条件下,将0.5g聚乙烯醇、0.02g聚多巴胺加入到4.5mL去离子水中,搅拌均匀得到聚乙烯醇/聚多巴胺分散液;
4)配制质量百分浓度为37.5%的尿素水溶液备用;
5)量取2.5mL尿素水溶液,将其加入到聚乙烯醇/聚多巴胺分散液中,搅拌均匀得到聚乙烯醇/聚多巴胺/尿素复合分散液;
6)将0.75g单宁酸加入到4.25mL去离子水中,在室温下搅拌使其完全溶解,得到单宁酸溶液;
7)将单宁酸溶液缓慢加入到步骤5)所得聚乙烯醇/聚多巴胺/尿素复合分散液中,室温下搅拌反应5分钟,得到改性聚乙烯醇多功能水凝胶。
测试结果表明,实施例3制得水凝胶的溶胀度为30%,抗氧化为90.3%(2,2-联苯基-1-苦基肼基清除率),该水凝胶对皮肤的粘附强度为50.1kPa。上述结果表明,该水凝胶确实具有良好的抗溶胀、抗氧化和粘附性能。
实施例4
1)称取0.5g多巴胺粉末,将其加入到90mL去离子水与40mL乙醇组成的混合溶液中,用1mol·L-1的NaOH溶液调节溶液的pH至9,搅拌反应16小时;
2)将步骤1)的产物离心分离并烘干,得到聚多巴胺粉末;
3)在90℃水浴条件下,将0.3g聚乙烯醇、0.03g聚多巴胺加入到4.5mL去离子水中,搅拌均匀得到聚乙烯醇/聚多巴胺分散液;
4)配制质量百分浓度为37.5%的尿素水溶液备用;
5)量取2.5mL尿素水溶液,将其加入到聚乙烯醇/聚多巴胺分散液中,搅拌均匀得到聚乙烯醇/聚多巴胺/尿素复合分散液;
6)将0.75g单宁酸加入到4.25mL去离子水中,在室温下搅拌使其完全溶解,得到单宁酸溶液;
7)将单宁酸溶液缓慢加入到步骤5)所得聚乙烯醇/聚多巴胺/尿素复合分散液中,室温下搅拌反应5分钟,得到改性聚乙烯醇多功能水凝胶。
测试结果表明,实施例4制得水凝胶的溶胀度为24.5%,抗氧化为91.8%(2,2-联苯基-1-苦基肼基清除率),该水凝胶对皮肤的粘附强度为32.5kPa。这一结果表明,该水凝胶具有显著的抗溶胀、抗氧化和粘附性能。
Claims (10)
1.一种改性聚乙烯醇多功能水凝胶的制备方法,其特征在于:该方法包括以下步骤:首先,合成聚多巴胺,接着,配制聚乙烯醇/聚多巴胺分散液,再加入尿素、单宁酸反应即可。
2.如权利要求1所述的方法,其特征在于:聚多巴胺的合成方法包括:将多巴胺加入乙醇水溶液中,再加入NaOH溶液调节溶液的pH至9,搅拌反应16小时后分离、干燥即可。
3.如权利要求1所述的方法,其特征在于:聚乙烯醇、聚多巴胺、尿素、单宁酸的质量比为1:0.02~0.1:3~15:1.5。
4.如权利要求1所述的方法,其特征在于:聚乙烯醇/聚多巴胺分散液的配制方法包括:按比例将聚多巴胺、聚乙烯醇混合,再加入去离子水,所得混合物升温至85~95℃后充分搅拌均匀。
5.如权利要求1或4所述的方法,其特征在于:聚乙烯醇/聚多巴胺分散液中聚乙烯醇的质量百分浓度为6%~15%。
6.如权利要求1所述的方法,其特征在于:尿素以尿素水溶液的形式引入,尿素的质量百分浓度为37.5%。
7.如权利要求1所述的方法,其特征在于:单宁酸以单宁酸水溶液的形式引入,单宁酸的质量百分浓度为15%,加入单宁酸后在室温下搅拌反应。
8.一种改性聚乙烯醇多功能水凝胶,其特征在于:该水凝胶按照权利要求1-7中的任意一种方法制备得到。
9.如权利要求8所述的改性聚乙烯醇多功能水凝胶,其特征在于:该水凝胶具有三维网络结构,能粘附在玻璃、金属、橡胶或皮肤组织上,同时具有抗菌、粘附、抗氧化、抗溶胀、自愈、光热和可塑性。
10.权利要求8或9所述改性聚乙烯醇多功能水凝胶在生物医药和个人卫生材料方面的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211033479.XA CN115304792A (zh) | 2022-08-26 | 2022-08-26 | 一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211033479.XA CN115304792A (zh) | 2022-08-26 | 2022-08-26 | 一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115304792A true CN115304792A (zh) | 2022-11-08 |
Family
ID=83865057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211033479.XA Pending CN115304792A (zh) | 2022-08-26 | 2022-08-26 | 一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115304792A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115894971A (zh) * | 2023-01-09 | 2023-04-04 | 北京科技大学 | 石墨炔/聚合物复合水凝胶及其制备方法 |
CN116327640A (zh) * | 2023-03-08 | 2023-06-27 | 大连理工大学 | 生物粘附型水滑石-聚多巴胺皮肤复合光屏蔽剂及其制备方法 |
CN117050336A (zh) * | 2023-07-13 | 2023-11-14 | 海南大学 | 聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用 |
-
2022
- 2022-08-26 CN CN202211033479.XA patent/CN115304792A/zh active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115894971A (zh) * | 2023-01-09 | 2023-04-04 | 北京科技大学 | 石墨炔/聚合物复合水凝胶及其制备方法 |
CN116327640A (zh) * | 2023-03-08 | 2023-06-27 | 大连理工大学 | 生物粘附型水滑石-聚多巴胺皮肤复合光屏蔽剂及其制备方法 |
CN116327640B (zh) * | 2023-03-08 | 2024-04-26 | 大连理工大学 | 生物粘附型水滑石-聚多巴胺皮肤复合光屏蔽剂及其制备方法 |
CN117050336A (zh) * | 2023-07-13 | 2023-11-14 | 海南大学 | 聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用 |
CN117050336B (zh) * | 2023-07-13 | 2024-05-24 | 海南大学 | 聚乙烯醇/羧甲基壳聚糖/PDA@EGCG NPs水凝胶及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN115304792A (zh) | 一种改性聚乙烯醇多功能水凝胶及其制备方法、应用 | |
CN102210884B (zh) | 抗菌促愈创伤敷料的制备方法 | |
WO2011018995A1 (ja) | 有機無機複合ヒドロゲルおよびその製造方法 | |
CN115536919B (zh) | 一种改性壳聚糖粘附水凝胶及其制备方法和应用 | |
CN110960724A (zh) | 一种药用水凝胶及其制备方法 | |
CN113698646A (zh) | 一种透明性保湿抗菌可降解包装膜及其制备方法与应用 | |
CN108018620B (zh) | 抗菌性磷酸锆钠银海藻纤维及其制备方法 | |
CN113896930A (zh) | 一种n-卤胺型丙烯酰胺/聚乙烯醇基抗菌水凝胶及其制备方法 | |
KR20160085152A (ko) | 나노셀룰로오스를 포함하는 하이드로겔 복합재 및 이의 제조방법 | |
CN113150302B (zh) | 一种无机复合胍盐聚合物抗有害微生物材料及其制备方法 | |
WO2024087417A1 (zh) | 一种具有近红外光热效应的机械增强型淀粉基膜及其制备方法 | |
CN116585541A (zh) | 一种抗菌止血可吸收外科钉及其制备方法 | |
CN116265032A (zh) | 一种医用水溶性润滑剂及其制备方法 | |
CN107047827B (zh) | 一种充填硅基纳米银系抗菌剂的复合膜及其制备方法和应用 | |
CN107198789B (zh) | 一种纳米铂聚合物及其制备方法和应用 | |
CN113061255B (zh) | 聚氧乙烯聚氧丙烯-壳聚糖嵌段共聚物、骨止血材料及其制备方法 | |
CN111840315B (zh) | 一种纳米硒材料、制备方法及使用方法 | |
CN113881154A (zh) | 抑菌食品包装盒及其生产方法 | |
CN112175337A (zh) | 一种抗菌硅胶材料及其制备方法 | |
CN109867845A (zh) | 一种抗老化防静电的塑料及其制备方法 | |
CN114887111B (zh) | 一种可生物吸收的复合止血材料及其制备方法与应用 | |
CN115181291A (zh) | 一种具有低细胞毒性的自愈合抗菌水凝胶及其制备方法 | |
CN115501248B (zh) | 一种用于胃损伤治疗的水下黏附抑菌水凝胶及其制备与应用 | |
CN113773523B (zh) | 一种温敏可逆水凝胶及其制备方法与应用 | |
KR102340029B1 (ko) | 나노 바이오 세라믹스를 함유한 항균 및 항바이러스 제품 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |