CN110862481A - Self-healing hydrogel based on hydrophobic effect and preparation method thereof - Google Patents

Self-healing hydrogel based on hydrophobic effect and preparation method thereof Download PDF

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Publication number
CN110862481A
CN110862481A CN201911197590.0A CN201911197590A CN110862481A CN 110862481 A CN110862481 A CN 110862481A CN 201911197590 A CN201911197590 A CN 201911197590A CN 110862481 A CN110862481 A CN 110862481A
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self
healing
nacl
stirring
gel
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贺晓凌
杨雨晴
孟红艳
邓时煜
贺婷婷
魏东盛
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The invention relates to a self-healing hydrogel based on hydrophobic effect and a preparation method thereof, belonging to the technical field of biomedical materials. Can be prepared by the following method: with 96% octadecyl methacrylate (C)18) As a hydrophobing agent, C18Dissolving in a NaCl-surfactant system, taking N-isopropylacrylamide (NIPA) and acrylamide (AAm) as raw materials, taking N, N, N ', N' -Tetramethylethylenediamine (TEMED) as a coagulant and Ammonium Persulfate (APS) as an initiator, and preparing the self-healing hydrogel by a micelle copolymerization method. The hydrogel has good mechanical property, biocompatibility and biodegradability and excellent self-healing capability, and can be used as a material in the field of biomedicine.

Description

Self-healing hydrogel based on hydrophobic effect and preparation method thereof
Technical Field
The invention relates to a preparation method of self-healing hydrogel, belonging to the technical field of biomedical materials.
Background
The hydrogel is a material with good biocompatibility and can be endowed with multiple functions (such as degradable stimulation responsiveness and the like), can guide the functional expression of cells through the interaction with the cells and further form new tissues, and can store and release drugs, so that the hydrogel has great potential application value in the fields of tissue adhesives, controlled storage and release of the drugs and the like. However, the traditional hydrogel has the problems of incapability of self-healing after being damaged, poor mechanical strength and the like, so that the application of the hydrogel in the biomedical field is greatly limited. Self-healing materials are intelligent materials with inherent automatic injury repair capacity, two healing modes exist in the prior art, one mode is that a healing process is self-triggered by external factors such as light, heat, pH or a catalyst, but the process not only consumes a lot of energy, but also has complex healing process, and particularly in the aspect of the biomedical field, the application of self-healing hydrogel is greatly limited; the other is that self-healing hydrogel can be self-repaired without external force after being damaged, and the self-healing hydrogel becomes one of the research hotspots of the current intelligent materials. With the development of science and technology, scientists have made a great deal of research on the blocking of self-healing hydrogels in various aspects, but from the current research situation, in order to make self-healing hydrogels meet the needs in the biomedical field, the self-healing hydrogels need to have good biocompatibility, biodegradability and nontoxicity, and self-healing without external force.
Self-healing hydrogels that heal without external force can be classified into physical self-healing hydrogels and chemical self-healing hydrogels, where chemical self-healing hydrogels heal themselves typically through reversible covalent bonds, and physical self-healing hydrogels heal themselves typically through hydrogen bonds, electrostatic interactions, hydrophobic interactions. The self-healing mechanism is based on the reversible action of dynamic chemical bonds, complex chemical reaction is required, the preparation process is complicated, and organic solvents are mostly used as reaction systems, so that the problems of environmental pollution, difficult waste liquid treatment and the like are easily caused. Physical-action self-healing hydrogels can overcome these disadvantages, with the cross-linking points being transient in nature and in a dynamic equilibrium between cross-linking and de-cross-linking, and the internal stresses of the gel being relaxed during this dynamic equilibrium, and physical-type gels having the greater advantage in the preparation of gels with self-healing properties.
Disclosure of Invention
The invention aims to provide a self-healing hydrogel based on hydrophobic effect, which has good mechanical strength, biocompatibility and biodegradability and excellent self-healing capability. The self-healing hydrogel based on the hydrophobic effect provided by the invention can be prepared by the following method:
a certain amount of NaCl (0.7M) and a surfactant were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
The invention also aims to provide a preparation method of the self-healing hydrogel based on the hydrophobic effect, which comprises the following steps:
a certain amount of NaCl (0.7M) and a surfactant were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g of N-isopropylacrylamide (NIPA) and 0.5g of acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Advantageous effects
The self-healing hydrogel based on the hydrophobic effect provided by the invention has good mechanical property, biocompatibility and biodegradability and excellent self-healing capability, and can be applied to the field of biomedicine.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following specific embodiments.
Example 1:
NaCl (0.7M) and Sodium Dodecyl Sulfate (SDS) (0.17M) were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Example 2:
NaCl (0.7M) and cetyltrimethylammonium chloride (CTAC) (0.24M) were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C)18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Example 3:
NaCl (0.7M) and Tween 80(TW80) (0.31M) were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Example 4:
NaCl (0.7M) and sodium oleate (NAOL) (0.17M) were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Example 5:
NaCl (0.7M) and Sodium Dodecyl Sulfate (SDS) (0.24M) were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.
Example 6:
measuring NaCl (0.7M) and cetyltrimethylammonium chloride (CTAC) (0.31M) at 25 deg.C, dissolving in 9.8mL of distilled water, and stirring with a stirrer to obtainAfter the solution was clear, 88uL of 96% octadecyl methacrylate (C)18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation. Wait for C18After dissolution, 0.5g N-isopropyl acrylamide (NIPA) and 0.5g acrylamide (AAm) were added and reacted for 0.5 h. 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) were added to the reaction solution, and stirred well. Pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent the volatilization of the moisture of the gel.

Claims (6)

1. A self-healing hydrogel based on hydrophobic effect and a preparation method thereof are characterized by having good mechanical property, biocompatibility and biodegradability and excellent self-healing capability, and the gel can be prepared by the following method:
a certain amount of NaCl (0.7M) and a surfactant were measured at 25 ℃ and dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C) was taken18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation18After dissolution, 0.5g of N-isopropylacrylamide (NIPA) and 0.5g of acrylamide (AAm) were added and reacted for 0.5 h. Adding 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) into the reaction solution, stirring uniformly, pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent volatilization of water in the gel.
2. The hydrogel according to claim 1, which has good mechanical properties, biocompatibility and biodegradability, and excellent self-healing ability, and can be used in the biomedical field.
3. The preparation method of the self-healing hydrogel based on the hydrophobic effect comprises the following steps:
measuring a certain amount of NaCl (0.7M) and NaCl at 25 deg.CThe surfactant was dissolved in 9.8mL of distilled water, and after stirring with a stirrer to obtain a clear solution, 88uL of 96% octadecyl methacrylate (C)18) Dissolving in NaCl-surfactant system, stirring for 2 hr while sealing with preservative film to prevent water evaporation18After dissolution, 0.5g of N-isopropylacrylamide (NIPA) and 0.5g of acrylamide (AAm) were added and reacted for 0.5 h. Adding 25uL of N, N, N ', N' -Tetramethylethylenediamine (TEMED) and 0.1mL of Ammonium Persulfate (APS) (0.08g/mL) into the reaction solution, stirring uniformly, pouring the obtained solution into a glass plate, standing for 24h, and placing the prepared gel in a preservative film for preservation so as to prevent volatilization of water in the gel.
4. The method for preparing a self-healing hydrogel based on hydrophobic interaction as claimed in claim 3, wherein the concentration of NaCl in the step is 0.7M.
5. The method for preparing self-healing hydrogel based on hydrophobic interaction as claimed in claim 3, wherein the surfactant in the step is Sodium Dodecyl Sulfate (SDS), cetyltrimethylammonium chloride (CTAC), sodium oleate (NAOL) Tween 80(TW80), and the concentration is 0.17M-0.31M.
6. The method for preparing self-healing hydrogel based on hydrophobic interaction as claimed in claim 3, wherein the ratio of NIPA to AAm is 1: 1.
CN201911197590.0A 2019-11-29 2019-11-29 Self-healing hydrogel based on hydrophobic effect and preparation method thereof Pending CN110862481A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 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
CN114957538B (en) * 2022-04-06 2024-05-10 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
CN115160489B (en) * 2022-08-03 2023-11-21 浙江大学 Preparation method and application of hydrogel composite thermochromic material

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Application publication date: 20200306