CN110862481A - A kind of self-healing hydrogel based on hydrophobic interaction and preparation method thereof - Google Patents
A kind of self-healing hydrogel based on hydrophobic interaction and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种基于疏水作用自愈合水凝胶及其制备方法,属于生物医学材料技术领域。可由下述方法制得:以96%的甲基丙烯酸十八烷基酯(C18)作为疏水剂,将C18溶解在NaCl‑表面活性剂体系中,以N‑异丙基丙烯酰胺(NIPA)和丙烯酰胺(AAm)作为原料,以N,N,N’,N’‑四甲基乙二胺(TEMED)作为促凝剂,过硫酸铵(APS)作为引发剂,通过胶束共聚法制备自愈合水凝胶。该水凝胶具有良好的力学性能、生物相容性和生物降解性,优良的自愈合能力,可作为生物医药领域的材料使用。The invention relates to a self-healing hydrogel based on hydrophobic interaction and a preparation method thereof, belonging to the technical field of biomedical materials. It can be prepared by the following method: with 96% octadecyl methacrylate (C 18 ) as hydrophobic agent, C 18 is dissolved in NaCl-surfactant system, and N-isopropylacrylamide (NIPA ) and acrylamide (AAm) as raw materials, with N,N,N',N'-tetramethylethylenediamine (TEMED) as coagulant and ammonium persulfate (APS) as initiator, by micellar copolymerization method Preparation of self-healing hydrogels. The hydrogel has good mechanical properties, biocompatibility and biodegradability, and excellent self-healing ability, and can be used as a material in the field of biomedicine.
Description
技术领域technical field
本发明涉及一种自愈合水凝胶的制备方法,属于生物医学材料技术领域。The invention relates to a preparation method of a self-healing hydrogel, belonging to the technical field of biomedical materials.
背景技术Background technique
水凝胶作为一种具有良好的生物相容性、可被赋予多种功能(如可降解性刺激响应性等)的材料,它可以通过与细胞的相互作用从而引导细胞功能表达并进一步形成新生组织,它还可以储存并释放药物,因而它在组织粘合剂、药物控制储存与释放等领域拥有重大的潜在应用价值。但传统的水凝胶存在在受损后不能自愈合且力学强度差等问题,所以极大地限制了其在生物医学领域的应用。自愈合材料是一类具有内在自动损伤修复能力的智能材料,现有愈合方式有两种,一种是通过光、热、pH或催化剂等外界因素自触发愈合过程,但这一过程不仅消耗许多能量,而且它们的愈合过程较为复杂,尤其是在生物医学领域方面,这大大限制了自愈合水凝胶的应用;另一种是自愈合水凝胶受损后,不通过外力作用,进行自我修复,现已成为目前智能材料的研究热点之一。随着科学技术的发展,科学家们在自愈合水凝胶的堵多方面已经做了大量的研究,但从目前的研究情况来看,要使自愈合水凝胶满足生物医学领域方面的需要,这就需要它们具有良好生物相容性、生物可降解性和无毒性,无需外力作用而进行自修复。As a material with good biocompatibility, hydrogel can be endowed with a variety of functions (such as degradability, stimuli responsiveness, etc.), it can interact with cells to guide the expression of cell functions and further form new It can also store and release drugs, so it has great potential application value in the fields of tissue adhesives, drug controlled storage and release, etc. However, traditional hydrogels have problems such as inability to self-heal after damage and poor mechanical strength, which greatly limits their application in the biomedical field. Self-healing materials are a class of smart materials with inherent automatic damage repair capabilities. There are two existing healing methods. One is to self-trigger the healing process through external factors such as light, heat, pH or catalysts, but this process not only consumes Many energies, and their healing process is complex, especially in the field of biomedicine, which greatly limits the application of self-healing hydrogels; , self-healing has become one of the current research hotspots of smart materials. With the development of science and technology, scientists have done a lot of research on the blocking of self-healing hydrogels, but from the current research situation, it is necessary to make self-healing hydrogels meet the requirements of the biomedical field. required, which requires them to have good biocompatibility, biodegradability and non-toxicity, and self-repair without external force.
不通过外力进行愈合的自愈合水凝胶可分为物理自愈合水凝胶和化学自愈合水凝胶,化学自愈合水凝胶通常通过可逆共价键自愈合,物理自愈合水凝胶一般通过氢键、静电作用、疏水作用进行自愈合。自愈合机理基于动态化学键的可逆作用,需要进行复杂的化学反应,制备过程繁琐,且多以有机溶剂为反应体系,容易产生环境污染,废液难处理等问题。物理作用自愈合水凝胶可克服这些缺点,其交联点均具有瞬态特征,处于交联与解交联的动态平衡过程中,而凝胶的内应力也在这一动态平衡过程中得到松她,物理型凝胶在制备具有自愈合性能的凝胶中具有更大优势。Self-healing hydrogels that heal without external force can be divided into physical self-healing hydrogels and chemical self-healing hydrogels. Chemical self-healing hydrogels usually self-heal through reversible covalent bonds, and physical self-healing hydrogels. Healing hydrogels generally self-heal through hydrogen bonds, electrostatic interactions, and hydrophobic interactions. The self-healing mechanism is based on the reversible action of dynamic chemical bonds, which requires complex chemical reactions, and the preparation process is cumbersome, and most of them use organic solvents as the reaction system, which is prone to environmental pollution and difficult disposal of waste liquids. Physically acting self-healing hydrogels can overcome these shortcomings, and their cross-linking points have transient characteristics and are in the dynamic equilibrium process of cross-linking and de-cross-linking, and the internal stress of the gel is also in this dynamic equilibrium process. Obtaining Songshe, the physical gel has a greater advantage in the preparation of gels with self-healing properties.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种基于疏水作用自愈合水凝胶,该凝胶具有良好的力学强度、生物相容性和生物降解性,以及优良的自愈合能力。本发明所提供的基于疏水作用自愈合水凝胶可由以下方法制得:The object of the present invention is to provide a self-healing hydrogel based on hydrophobic interaction, which has good mechanical strength, biocompatibility and biodegradability, and excellent self-healing ability. The self-healing hydrogel based on hydrophobic interaction provided by the present invention can be prepared by the following methods:
在25℃下量取一定量NaCl(0.7M)和表面活性剂溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve a certain amount of NaCl (0.7M) and surfactant in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% octadecyl methacrylate (C 18 ) Dissolve in NaCl-surfactant system, continue to stir for 2h, and seal with plastic wrap to prevent water evaporation during stirring. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
本发明的另一目的在于提供一种基于疏水作用自愈合水凝胶的制备方法,制备方法包括以下步骤:Another object of the present invention is to provide a preparation method of self-healing hydrogel based on hydrophobic interaction, the preparation method comprising the following steps:
在25℃下量取一定量NaCl(0.7M)和表面活性剂溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5gN-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve a certain amount of NaCl (0.7M) and surfactant in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% octadecyl methacrylate (C 18 ) Dissolve in NaCl-surfactant system, continue to stir for 2h, and seal with plastic wrap to prevent water evaporation during stirring. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
有益效果beneficial effect
本发明所提供的基于疏水作用自愈合水凝胶具有良好的力学性能、生物相容性和生物降解性,优良的自愈合能力,可应用于生物医药领域。The self-healing hydrogel based on the hydrophobic interaction provided by the present invention has good mechanical properties, biocompatibility, biodegradability, and excellent self-healing ability, and can be applied to the field of biomedicine.
具体实施方式Detailed ways
下面通过具体实施方式对本发明的技术方案进行进一步说明和描述。The technical solutions of the present invention will be further illustrated and described below through specific embodiments.
实施例1:Example 1:
在25℃下量取NaCl(0.7M)和十二烷基硫酸钠(SDS)(0.17M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and sodium dodecyl sulfate (SDS) (0.17M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a clear solution, take 88uL of 96% methacrylic acid The octaalkyl ester (C 18 ) was dissolved in the NaCl-surfactant system, and the stirring was continued for 2 h. During the stirring, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
实施例2:Example 2:
在25℃下量取NaCl(0.7M)和十六烷基三甲基氯化铵(CTAC)(0.24M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and cetyltrimethylammonium chloride (CTAC) (0.24M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% Octadecyl methacrylate (C 18 ) was dissolved in the NaCl-surfactant system, stirring was continued for 2 h, and during the stirring period, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
实施例3:Example 3:
在25℃下量取NaCl(0.7M)和吐温80(TW80)(0.31M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and Tween 80 (TW80) (0.31M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% octadecyl methacrylate The ester (C 18 ) was dissolved in the NaCl-surfactant system, stirring was continued for 2 h, and during stirring, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
实施例4:Example 4:
在25℃下量取NaCl(0.7M)和油酸钠(NAOL)(0.17M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and sodium oleate (NAOL) (0.17M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% octadecyl methacrylate The ester (C 18 ) was dissolved in the NaCl-surfactant system, stirring was continued for 2 h, and during stirring, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
实施例5:Example 5:
在25℃下量取NaCl(0.7M)和十二烷基硫酸钠(SDS)(0.24M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and sodium dodecyl sulfate (SDS) (0.24M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a clear solution, take 88uL of 96% methacrylic acid ten The octaalkyl ester (C 18 ) was dissolved in the NaCl-surfactant system, and the stirring was continued for 2 h. During the stirring, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
实施例6:Example 6:
在25℃下量取NaCl(0.7M)和十六烷基三甲基氯化铵(CTAC)(0.31M)溶于9.8mL蒸馏水中,用搅拌器搅拌获得透明溶液后,取88uL 96%的甲基丙烯酸十八烷基酯(C18)溶解在NaCl-表面活性剂体系中,继续搅拌2h,搅拌期间用保鲜膜封口防止水分蒸发。待C18溶解后,加入0.5g N-异丙基丙烯酰胺(NIPA)和0.5g丙烯酰胺(AAm)反应0.5h。将25uL N,N,N’,N’-四甲基乙二胺(TEMED)和0.1mL过硫酸铵(APS)(0.08g/mL)添加到反应溶液中,搅拌均匀。将所得溶液倒入玻璃板中,静置24h,制得的凝胶放置在保鲜膜内保存,以防止凝胶水分的挥发。Dissolve NaCl (0.7M) and cetyltrimethylammonium chloride (CTAC) (0.31M) in 9.8mL of distilled water at 25°C, stir with a stirrer to obtain a transparent solution, take 88uL of 96% Octadecyl methacrylate (C 18 ) was dissolved in the NaCl-surfactant system, and stirring was continued for 2 h. During stirring, the seal was sealed with plastic wrap to prevent water evaporation. After C 18 was dissolved, 0.5 g of N-isopropylacrylamide (NIPA) and 0.5 g of acrylamide (AAm) were added to react for 0.5 h. 25uL of N,N,N',N'-tetramethylethylenediamine (TEMED) and 0.1 mL of ammonium persulfate (APS) (0.08 g/mL) were added to the reaction solution and stirred well. The obtained solution was poured into a glass plate, and allowed to stand for 24 hours, and the obtained gel was placed in a plastic wrap to prevent volatilization of the gel moisture.
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CN113201153A (en) * | 2021-05-10 | 2021-08-03 | 海南大学 | Super-elastic heat-resistant anti-freezing composite hydrogel and preparation method thereof |
CN114957538A (en) * | 2022-04-06 | 2022-08-30 | 大连海事大学 | Self-healing gel based on dynamic non-covalent bond effect and preparation method and application thereof |
CN115160489A (en) * | 2022-08-03 | 2022-10-11 | 浙江大学 | Preparation method and application of hydrogel composite thermochromic material |
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CN113201153A (en) * | 2021-05-10 | 2021-08-03 | 海南大学 | Super-elastic heat-resistant anti-freezing composite hydrogel and preparation method thereof |
CN113201153B (en) * | 2021-05-10 | 2022-05-31 | 海南大学 | A kind of superelasticity heat-resistant and antifreeze composite hydrogel and preparation method thereof |
CN114957538A (en) * | 2022-04-06 | 2022-08-30 | 大连海事大学 | Self-healing gel based on dynamic non-covalent bond effect and preparation method and application thereof |
CN114957538B (en) * | 2022-04-06 | 2024-05-10 | 大连海事大学 | A self-healing gel based on dynamic non-covalent bond action and its preparation method and application |
CN115160489A (en) * | 2022-08-03 | 2022-10-11 | 浙江大学 | Preparation method and application of hydrogel composite thermochromic material |
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