Photopolymerized antibacterial hydrogel patch and preparation method thereof
The antibacterial hydrogel dressing prepared by photopolymerization utilizes the core-shell structure of modified chitosan and antibacterial siloxane reinforcing materials, which overcomes the shortcomings of hydrogel dressings in terms of antibacterial and mechanical properties, and achieves long-lasting protection of the wound.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU NEWVALUE MEDICAL PROD CO LTD
- Filing Date
- 2026-05-12
- Publication Date
- 2026-06-09
AI Technical Summary
Existing hydrogel dressings are inadequate in terms of antibacterial properties, mechanical properties, and durability, making them difficult to effectively address infections in both chronic and acute wounds.
Antibacterial hydrogel patches were prepared by photopolymerization. Modified chitosan and antibacterial siloxane reinforcing materials were used to form a core-shell structure. Combined with UV-induced free radical copolymerization, chemical bonding between chitosan and acryloyloxyethyltrimethylammonium chloride was achieved, which improved the antibacterial properties. Antibacterial siloxane reinforcing materials were prepared by modifying nano-zinc oxide with γ-methacryloyloxypropyltrimethoxysilane and reacting with Schiff bases, which enhanced the mechanical properties.
It improves the antibacterial durability and mechanical properties of hydrogel dressings, providing effective protection for wounds and is suitable for the treatment of both chronic and acute wounds.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of medical materials technology, specifically to a photopolymerized antibacterial hydrogel dressing and its preparation method. Background Technology
[0002] Hydrogel dressings, as a high-water-content material, provide crucial physiological conditions for wound repair. The high water content not only dissolves necrotic tissue and provides continuous, gentle debridement, but also effectively prevents new granulation tissue from adhering to the dressing. This allows for painless and non-invasive removal during dressing changes, greatly improving patient experience and compliance. The value of modern hydrogel dressings extends beyond basic physical coverage and absorption. Through molecular design, hydrogel networks can achieve controlled release of different active ingredients, enabling synergistic therapeutic effects such as antibacterial, anti-inflammatory, and angiogenesis promotion.
[0003] However, the number of patients with chronic wounds (such as diabetic foot, pressure injuries, and venous ulcers) worldwide is enormous, and infections of acute wounds (such as trauma and surgical incisions) also account for a considerable proportion. Wound infections significantly prolong hospital stays, increase the frequency of dressing changes and antibiotic use, and consume substantial medical resources. Repairing infected wounds remains a challenge in clinical practice. Traditional antibacterial methods still have many drawbacks, such as narrow application areas, poor antibacterial performance, lack of durability, and no healing-promoting effects. Therefore, further improving the antibacterial capabilities of dressings is crucial. Furthermore, dressings must possess sufficient mechanical strength and resilience to withstand friction, pressure, and traction during daily activities, providing a durable and intact physical barrier for fragile wounds.
[0004] To overcome the shortcomings of the prior art, the present invention provides a photopolymerized antibacterial hydrogel patch and its preparation method. Summary of the Invention
[0005] The purpose of this invention is to provide a photopolymerized antibacterial hydrogel patch and its preparation method, so as to solve the problems raised in the prior art.
[0006] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a photopolymerizable antibacterial hydrogel patch includes the following steps: Step 1: Under normal temperature and light-protected conditions, mix acrylic monomer, hydroxyethyl methacrylate, antibacterial monomer, crosslinking agent, photoinitiator, and solvent, stir to dissolve, then add reinforcing material, thickener, and humectant in sequence, stir to dissolve, and obtain prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:(1.3-1.5); the reinforcing materials include antibacterial polysiloxane reinforcing materials and antibacterial siloxane reinforcing materials, wherein the mass ratio of antibacterial polysiloxane reinforcing materials to antibacterial siloxane reinforcing materials is 2:(1.0-1.2). Step 2: Pour the prepolymer solution between two layers of PET release film, and irradiate with ultraviolet light to obtain an antibacterial hydrogel dressing.
[0007] In a more optimized manner, the prepolymer solution is poured into the space between two PET release films at a rate of 150-450 mL / min, and then irradiated with ultraviolet light for 3-6 minutes to obtain an antibacterial hydrogel dressing.
[0008] In a more optimized manner, the content of each component in the prepolymer liquid is as follows: by mass parts, 20-30 parts acrylic monomer, 10-15 parts hydroxyethyl methacrylate, 7-10 parts antibacterial monomer, 0.1-0.3 parts crosslinking agent, 0.5-1.0 parts photoinitiator, 60-70 parts solvent, 1.5-2.5 parts reinforcing material, 1-2 parts thickener, and 8-15 parts humectant.
[0009] In a more optimized manner, the acrylic monomer is any one of hydroxybutyl vinyl ether, N-vinylpyrrolidone, acrylamide, vinylcaprolactam, N,N-dimethylacrylamide, dipropylene glycol diacrylate, laurate acrylate, methyl methacrylate, and sodium 2-acrylamido-2-methylpropanesulfonate; the crosslinking agent is any one of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, polyethylene glycol diacrylate, ethoxypentaerythritol tetraacrylate, and N,N'-methylenebisacrylamide; the photoinitiator is any one of photoinitiator 6976, photoinitiator 1173, photoinitiator 369, photoinitiator 2959, and photoinitiator BDK; the thickener is any one of carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyoxyethylene, sodium polyacrylate, and gelatin; the humectant is any one of glycerin, propylene glycol, butylene glycol, D-panthenol, and urea; and the solvent is deionized water.
[0010] A more optimized preparation process for modified chitosan is as follows: chitosan powder is added to a 2.0-2.5 wt% aqueous acetic acid solution and stirred at 27-35℃ for 4.5-5.0 h to dissolve, thus obtaining a chitosan reaction solution; hydrochloric acid is added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.5-3.7, and then allyl alcohol glycidyl ether is added dropwise. The mixture is stirred at 65-70℃ for 25-30 h. After stirring, the mixture is precipitated, filtered, washed, and dried to obtain modified chitosan.
[0011] The optimal reaction mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether is 2:(98-100):(0.45-0.50).
[0012] In a more optimized manner, the reinforcing materials include antibacterial polysiloxane reinforcing materials and antibacterial siloxane reinforcing materials. The specific addition steps are as follows: under normal temperature and light-protected conditions, acrylic monomer, hydroxyethyl methacrylate, antibacterial monomer, crosslinking agent, photoinitiator, and solvent are mixed and stirred to dissolve. Then, antibacterial siloxane reinforcing materials are added and stirred for 10-15 minutes. After stirring to dissolve, antibacterial polysiloxane reinforcing materials are added and stirred to dissolve. Thickener and humectant are added in sequence and stirred to dissolve to obtain a prepolymer solution.
[0013] The optimized preparation process of antibacterial polysiloxane reinforced materials is as follows: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.0-3.2, then add γ-methacryloyloxypropyltrimethoxysilane, and sonicate at 25-30℃ for 1.5-2.0h. Then add nano zinc oxide, disperse it evenly, and reflux at 80-85℃ for 4-5h. After the reaction is completed, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 55-60℃, then add chloroplatinic acid catalyst, and heat to 95-100℃ and keep the temperature for 3.5-4.0h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material.
[0014] In a more optimized manner, the volume ratio of anhydrous ethanol to deionized water in the mixed solution is (9-10):1; the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane to nano zinc oxide is 1:(10-12); and the reaction mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is (6.0-6.5):1.
[0015] A more optimized preparation process for antibacterial siloxane-reinforced materials is as follows: γ-aminopropyltriethoxysilane is added to anhydrous ethanol under nitrogen atmosphere, ultrasonically dispersed, and then cinnamaldehyde is added. The mixture is stirred and reacted at 60-65℃ for 4-5 hours. After the reaction is completed, the mixture is centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material.
[0016] The optimal reaction molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde is (1.1-1.2):1.
[0017] The beneficial effects of this invention are: The key feature of this invention is that chitosan powder is dissolved in an aqueous acetic acid solution, and then allyl alcohol glycidyl ether is added to initiate a ring-opening reaction to obtain modified chitosan. Acryloyloxyethyltrimethylammonium chloride and modified chitosan are then mixed to obtain an antibacterial monomer, which is added to the prepolymer solution during preparation, effectively enhancing the antibacterial properties of the hydrogel dressing. Chitosan possesses broad-spectrum antibacterial activity. Through chemical grafting of allyl groups, the modified chitosan can undergo free radical copolymerization, firmly anchoring itself in the hydrogel network with chemical bonds, effectively preventing chitosan loss. Furthermore, acryloyloxyethyltrimethylammonium chloride, with a strong positive charge, is mixed with the modified chitosan. Under ultraviolet light initiation, they, along with monomers such as N-vinylpyrrolidone and hydroxyethyl methacrylate in the system, participate in a free radical copolymerization reaction. This allows both chitosan and acryloyloxyethyltrimethylammonium chloride to covalently become part of the three-dimensional hydrogel network, jointly enhancing the antibacterial effect and overcoming the shortcomings of traditional additive antibacterial agents, such as easy migration and rapid deterioration.
[0018] The key feature of this invention is the surface modification of nano-zinc oxide by adding γ-methacryloxypropyltrimethoxysilane to obtain pretreated zinc oxide. This step effectively improves the agglomeration of nano-zinc oxide and introduces carbon-carbon double bonds to undergo a hydrosilylation reaction with low-hydrogen silicone oil, resulting in an antibacterial polysiloxane-reinforced material. In this material, ZnO nanoparticles are covalently linked by multiple flexible polysiloxane chains (derived from low-hydrogen silicone oil), forming a core-shell structure with ZnO as the hard core and polysiloxane as the soft shell. The covalent bonding effectively prevents ZnO leaching and loss, resulting in a more durable antibacterial function. Furthermore, the polysiloxane shell acts as a flexible interface layer, effectively buffering external stress and facilitating efficient stress transfer between the polymer network of the hydrogel and the rigid ZnO core, thus enhancing mechanical properties.
[0019] The key feature of this invention is the mixing of γ-aminopropyltriethoxysilane and cinnamaldehyde, followed by a Schiff base reaction, to obtain an antibacterial material with a siloxane structure, namely, an antibacterial siloxane-reinforced material. Cinnamaldehyde is a natural plant essential oil component with broad-spectrum antibacterial activity. Cinnamaldehyde is linked to the siloxane backbone via stable imine bonds, achieving chemically bonded immobilization and providing a long-lasting antibacterial effect. Furthermore, the siloxane structure introduced into the antibacterial siloxane-reinforced material allows the silanol groups generated during hydrolysis to undergo condensation reactions with other components during subsequent hydrogel curing, enhancing the interfacial bonding between the reinforcing material and the hydrogel matrix, reducing stress concentration points, and contributing to a uniform improvement in mechanical properties.
[0020] Furthermore, under ambient temperature and light-protected conditions, acrylic monomers, hydroxyethyl methacrylate, antibacterial monomers, crosslinking agents, photoinitiators, and solvents are mixed and stirred until dissolved. Then, antibacterial siloxane reinforcing material is added, and the mixture is stirred for 10-15 minutes. Next, antibacterial polysiloxane reinforcing material is added, and the mixture is stirred until dissolved. Thickeners and humectants are then added sequentially, and the mixture is stirred until dissolved to obtain a prepolymer solution. By adding the antibacterial siloxane reinforcing material first, reaction conditions are provided for the initial hydrolysis and pre-crosslinking of the siloxane structure, improving the overall uniformity and initial viscosity of the prepolymer solution, and providing a stable medium for adding larger particles of material in the next step. Then, larger-sized antibacterial polysiloxane reinforcing material and other additives are added to obtain the prepolymer solution. The prepolymer solution is poured between two layers of PET release film and irradiated with ultraviolet light to obtain an antibacterial hydrogel dressing. In summary, the antibacterial hydrogel prepared by this invention has good antibacterial properties and mechanical properties, and therefore has broad application prospects in the field of medical materials technology. Detailed Implementation
[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] Raw material source: Chitosan powder, provided by Henan Huachi Biotechnology Co., Ltd., has an effective ingredient content of 99%; low-hydrogen silicone oil, provided by Shandong Juneng Chemical Co., Ltd., model JN-202; nano zinc oxide, provided by Beijing Deco Island Gold Technology Co., Ltd., specification 30nm; hydroxyethyl cellulose, provided by Guangzhou Daojun Biotechnology Co., Ltd., model DJ-10W; by mass, one part is 1g.
[0023] Example 1: Step 1: Chitosan powder was added to a 2.3wt% aqueous acetic acid solution and stirred at 35°C for 5.0 h to dissolve, thus obtaining a chitosan reaction solution; hydrochloric acid was added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.7, and then allyl alcohol glycidyl ether was added dropwise. The mixture was stirred at 70°C for 30 h. After stirring, the mixture was precipitated, filtered, washed, and dried to obtain modified chitosan; the reaction mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether was 2:99:0.47. Step 2: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.2, then add γ-methacryloxypropyltrimethoxysilane and sonicate at 30℃ for 2.0 h. Then add nano zinc oxide, disperse it evenly, and reflux at 85℃ for 5 h. After the reaction is complete, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. The volume ratio of anhydrous ethanol to deionized water in the mixed solution is 9.5:1; the mass ratio of γ-methacryloxypropyltrimethoxysilane to nano zinc oxide is 1:11. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 60°C, then add chloroplatinic acid catalyst, and heat to 100°C and keep the reaction for 4.0 h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material; the mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is 6.3:1. Step S3: Under nitrogen atmosphere, γ-aminopropyltriethoxysilane was added to anhydrous ethanol, ultrasonically dispersed, and then cinnamaldehyde was added. The mixture was stirred at 65°C for 5 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde was 1.15:1. Step 3: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 9g antibacterial monomer, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 0.7g antibacterial siloxane reinforcing material, stir for 15 minutes, then add 1.3g antibacterial polysiloxane reinforcing material, then add 1.5g hydroxyethyl cellulose and 10g glycerol in sequence, stir to dissolve, and obtain the prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:1.4; Step 4: Pour the prepolymer solution into the space between two PET release films at a rate of 450 mL / min, and irradiate with a UV lamp for 6 minutes to obtain an antibacterial hydrogel dressing.
[0024] Example 2: Step 1: Chitosan powder was added to a 2.3wt% aqueous acetic acid solution and stirred at 30°C for 4.7 h to dissolve, thus obtaining a chitosan reaction solution; hydrochloric acid was added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.6, and then allyl alcohol glycidyl ether was added dropwise. The mixture was stirred at 67°C for 27 h. After stirring, the mixture was precipitated, filtered, washed, and dried to obtain modified chitosan; the reaction mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether was 2:99:0.47. Step 2: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.1, then add γ-methacryloxypropyltrimethoxysilane, and sonicate at 27°C for 1.7 h. Then add nano-zinc oxide, disperse it evenly, and reflux at 82°C for 4.5 h. After the reaction is complete, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. The volume ratio of anhydrous ethanol to deionized water in the mixed solution is 9.5:1; the mass ratio of γ-methacryloxypropyltrimethoxysilane to nano-zinc oxide is 1:11. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 57°C, then add chloroplatinic acid catalyst, and heat to 97°C and keep the reaction for 3.7 h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material; the mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is 6.3:1. Step S3: Under nitrogen atmosphere, γ-aminopropyltriethoxysilane was added to anhydrous ethanol, ultrasonically dispersed, and then cinnamaldehyde was added. The mixture was stirred at 63°C for 4.5 h. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde was 1.15:1. Step 3: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 9g antibacterial monomer, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 0.7g antibacterial siloxane reinforcing material, stir for 12 minutes, then add 1.3g antibacterial polysiloxane reinforcing material, then add 1.5g hydroxyethyl cellulose and 10g glycerol in sequence, stir to dissolve, and obtain the prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:1.4; Step 4: Pour the prepolymer solution into the space between two PET release films at a rate of 250 mL / min, and irradiate with a UV lamp for 4 minutes to obtain an antibacterial hydrogel dressing.
[0025] Example 3: Step 1: Chitosan powder was added to a 2.3wt% aqueous acetic acid solution and stirred at 27°C for 4.5 hours to dissolve, thus obtaining a chitosan reaction solution; hydrochloric acid was added dropwise to the chitosan reaction solution to adjust the pH to 3.5, and then allyl alcohol glycidyl ether was added dropwise. The mixture was stirred at 65°C for 25 hours. After stirring, the mixture was precipitated, filtered, washed, and dried to obtain modified chitosan; the mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether was 2:99:0.47. Step 2: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.0, then add γ-methacryloxypropyltrimethoxysilane and sonicate at 25°C for 1.5 h. Then add nano zinc oxide, disperse evenly, and reflux at 80°C for 4 h. After the reaction is complete, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. The volume ratio of anhydrous ethanol to deionized water in the mixed solution is 9.5:1; the mass ratio of γ-methacryloxypropyltrimethoxysilane to nano zinc oxide is 1:11. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 55°C, then add chloroplatinic acid catalyst, and heat to 95°C and keep the reaction for 3.5 hours. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material; the mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is 6.3:1. Step S3: Under nitrogen atmosphere, γ-aminopropyltriethoxysilane was added to anhydrous ethanol, ultrasonically dispersed, and then cinnamaldehyde was added. The mixture was stirred at 60°C for 4 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde was 1.15:1. Step 3: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 9g antibacterial monomer, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 0.7g antibacterial siloxane reinforcing material, stir for 10 minutes, then add 1.3g antibacterial polysiloxane reinforcing material, then add 1.5g hydroxyethyl cellulose and 10g glycerol in sequence, stir to dissolve, and obtain the prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:1.4; Step 4: Pour the prepolymer solution into the space between two PET release films at a rate of 150 mL / min, and irradiate with a UV lamp for 3 minutes to obtain an antibacterial hydrogel dressing.
[0026] Comparative Example 1: The antibacterial monomer was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Step S1: Hydrochloric acid was added to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.2. Then γ-methacryloyloxypropyltrimethoxysilane was added, and the mixture was ultrasonically reacted at 30°C for 2.0 h. Then nano zinc oxide was added, and after being dispersed evenly, the temperature was raised to 85°C and refluxed for 5 h. After the reaction was completed, the mixture was washed with alcohol, filtered, and dried to obtain pretreated zinc oxide. The volume ratio of anhydrous ethanol to deionized water in the mixed solution was 9.5:1; the mass ratio of γ-methacryloyloxypropyltrimethoxysilane to nano zinc oxide was 1:11. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 60°C, then add chloroplatinic acid catalyst, and heat to 100°C and keep the reaction for 4.0 h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material; the mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is 6.3:1. Step S3: Under nitrogen atmosphere, γ-aminopropyltriethoxysilane was added to anhydrous ethanol, ultrasonically dispersed, and then cinnamaldehyde was added. The mixture was stirred at 65°C for 5 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde was 1.15:1. Step 2: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 0.7g antibacterial siloxane reinforcing material, stir for 15 minutes, then add 1.3g antibacterial polysiloxane reinforcing material, then add 1.5g hydroxyethyl cellulose and 10g glycerol in sequence, stir to dissolve, and obtain the prepolymer solution; Step 3: Pour the prepolymer solution into the space between two PET release films at a rate of 450 mL / min, and irradiate with a UV lamp for 6 minutes to obtain an antibacterial hydrogel dressing.
[0027] Comparative Example 2: The antibacterial polysiloxane reinforcing material was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Chitosan powder was added to a 2.3wt% aqueous acetic acid solution and stirred at 35°C for 5.0 h to obtain a chitosan reaction solution; hydrochloric acid was added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.7, and then allyl alcohol glycidyl ether was added dropwise. The mixture was stirred at 70°C for 30 h. After stirring, the mixture was precipitated, filtered, washed, and dried to obtain modified chitosan; the reaction mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether was 2:99:0.47. Step 2: Under nitrogen atmosphere, γ-aminopropyltriethoxysilane was added to anhydrous ethanol, ultrasonically dispersed, and then cinnamaldehyde was added. The mixture was stirred at 65°C for 5 hours. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the antibacterial siloxane-reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde was 1.15:1. Step 3: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 9g antibacterial monomer, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 0.7g antibacterial siloxane reinforcing material, stir for 15 minutes, then add 1.5g hydroxyethyl cellulose and 10g glycerol in sequence, stir to dissolve, and obtain the prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:1.4; Step 4: Pour the prepolymer solution into the space between two PET release films at a rate of 450 mL / min, and irradiate with a UV lamp for 6 minutes to obtain an antibacterial hydrogel dressing.
[0028] Comparative Example 3: The antibacterial siloxane reinforcing material was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Chitosan powder was added to a 2.3wt% aqueous acetic acid solution and stirred at 35°C for 5.0 h to obtain a chitosan reaction solution; hydrochloric acid was added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.7, and then allyl alcohol glycidyl ether was added dropwise. The mixture was stirred at 70°C for 30 h. After stirring, the mixture was precipitated, filtered, washed, and dried to obtain modified chitosan; the reaction mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether was 2:99:0.47. Step 2: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.2, then add γ-methacryloxypropyltrimethoxysilane and sonicate at 30℃ for 2.0 h. Then add nano zinc oxide, disperse it evenly, and reflux at 85℃ for 5 h. After the reaction is complete, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. The volume ratio of anhydrous ethanol to deionized water in the mixed solution is 9.5:1; the mass ratio of γ-methacryloxypropyltrimethoxysilane to nano zinc oxide is 1:11. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 60°C, then add chloroplatinic acid catalyst, and heat to 100°C and keep the reaction for 4.0 h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material; the mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is 6.3:1. Step 3: Under light-protected conditions, mix 25g N-vinylpyrrolidone, 13g hydroxyethyl methacrylate, 9g antibacterial monomer, 0.2g N,N'-methylenebisacrylamide, 0.7g photoinitiator 2959, and 65g solvent, stir to dissolve, then add 1.3g antibacterial polysiloxane reinforcing material, followed by 1.5g hydroxyethyl cellulose and 10g glycerol, stir to dissolve, and obtain the prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:1.4; Step 4: Pour the prepolymer solution into the space between two PET release films at a rate of 450 mL / min, and irradiate with a UV lamp for 6 minutes to obtain an antibacterial hydrogel dressing.
[0029] Testing and experimentation: Mechanical property testing: The prepolymer solutions prepared in the embodiments and comparative examples of this invention were irradiated with ultraviolet light to obtain hydrogel samples of 15mm×40mm×5mm. The tensile strength and elongation at break of the samples were tested by stretching the samples at a rate of 10mm / min using a tensile testing machine.
[0030] Antibacterial performance test: Escherichia coli was diluted to obtain a concentration of 1×10⁻⁶. 7 CFU / mL bacterial suspension. The bacterial suspension was added to a solid culture medium, and the hydrogel sample was placed in it. After incubation at 37℃ for 20 hours, the colonies were counted. A blank group (without hydrogel sample) was also set up. The colony counts obtained from both groups were substituted into the formula to calculate the antibacterial rate. The results are shown in the table below:
[0031] Conclusion: In Examples 1-3, the dosage remained unchanged, with only some reaction parameters modified. Experimental data showed no significant fluctuations in the performance of the samples.
[0032] Comparative Example 1: The antimicrobial monomer was removed, and the rest was the same as in Example 1. The experimental data showed that the antimicrobial rate was reduced to 83.7% compared with Example 1. The reason for this is that the antimicrobial monomer contains multiple antimicrobial materials that work together to fight bacteria, which can greatly improve the antimicrobial activity and ensure the antimicrobial performance. Therefore, removing it reduces the antimicrobial rate.
[0033] Comparative Example 2: The antibacterial polysiloxane reinforcing material was removed, and the rest was the same as in Example 1. The experimental data showed that compared with Example 1, the tensile strength decreased to 534 kPa, the elongation at break decreased to 514%, and the antibacterial rate decreased to 92.8%. The reason for this is that the antibacterial polysiloxane reinforcing material contains flexible segments and rigid antibacterial materials, thus possessing good antibacterial and mechanical properties. Therefore, removing the antibacterial polysiloxane reinforcing material resulted in a decrease in tensile strength, elongation at break, and antibacterial rate.
[0034] Comparative Example 3: The antibacterial siloxane reinforcing material was removed, and the rest was the same as in Example 1. The experimental data showed that compared with Example 1, the tensile strength decreased to 568 kPa, the elongation at break decreased to 546%, and the antibacterial rate decreased to 95.8%. The reason for this is that the antibacterial siloxane reinforcing material contains siloxane structure and antibacterial cinnamaldehyde. Therefore, removing it reduces the tensile strength, elongation at break, and antibacterial rate.
[0035] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.
[0036] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing a photopolymerized antibacterial hydrogel patch, characterized in that: Includes the following steps: Step 1: Under light-protected conditions, mix acrylic monomer, hydroxyethyl methacrylate, antibacterial monomer, crosslinking agent, photoinitiator, and solvent, stir to dissolve, then add reinforcing material, thickener, and humectant in sequence, stir to dissolve, and obtain prepolymer solution; The antibacterial monomers include acryloyloxyethyltrimethylammonium chloride and modified chitosan, wherein the mass ratio of acryloyloxyethyltrimethylammonium chloride to modified chitosan is 1:(1.3-1.5); the reinforcing materials include antibacterial polysiloxane reinforcing materials and antibacterial siloxane reinforcing materials, wherein the mass ratio of antibacterial polysiloxane reinforcing materials to antibacterial siloxane reinforcing materials is 2:(1.0-1.2). Step 2: Pour the prepolymer solution between two layers of PET release film, and irradiate with ultraviolet light to obtain an antibacterial hydrogel dressing.
2. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 1, characterized in that: The prepolymer solution contains the following components by mass: 20-30 parts acrylic monomer, 10-15 parts hydroxyethyl methacrylate, 7-10 parts antibacterial monomer, 0.1-0.3 parts crosslinking agent, 0.5-1.0 parts photoinitiator, 60-70 parts solvent, 1.5-2.5 parts reinforcing material, 1-2 parts thickener, and 8-15 parts humectant.
3. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 2, characterized in that: The acrylic monomer is any one of hydroxybutyl vinyl ether, N-vinylpyrrolidone, acrylamide, vinylcaprolactam, N,N-dimethylacrylamide, dipropylene glycol diacrylate, laurate acrylate, methyl methacrylate, and sodium 2-acrylamido-2-methylpropanesulfonate; the crosslinking agent is any one of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, polyethylene glycol diacrylate, ethoxypentaerythritol tetraacrylate, and N,N'-methylenebisacrylamide; the photoinitiator is any one of photoinitiator 6976, photoinitiator 1173, photoinitiator 369, photoinitiator 2959, and photoinitiator BDK; the thickener is any one of carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyoxyethylene, sodium polyacrylate, and gelatin; the humectant is any one of glycerin, propylene glycol, butylene glycol, D-panthenol, and urea; and the solvent is deionized water.
4. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 1, characterized in that: The preparation process of modified chitosan is as follows: chitosan powder is added to a 2.0-2.5 wt% aqueous acetic acid solution and stirred at 27-35℃ for 4.5-5.0 h to obtain a chitosan reaction solution; hydrochloric acid is added dropwise to the chitosan reaction solution to adjust the pH of the solution to 3.5-3.7, and then allyl alcohol glycidyl ether is added dropwise. The mixture is stirred at 65-70℃ for 25-30 h. After stirring, the mixture is precipitated, filtered, washed, and dried to obtain modified chitosan.
5. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 4, characterized in that: The mass ratio of chitosan powder, aqueous acetic acid solution, and allyl alcohol glycidyl ether is 2:(98-100):(0.45-0.50).
6. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 1, characterized in that: The reinforcing materials include antibacterial polysiloxane reinforcing materials and antibacterial siloxane reinforcing materials. The specific addition steps are as follows: Under light-protected conditions, acrylic monomer, hydroxyethyl methacrylate, antibacterial monomer, crosslinking agent, photoinitiator, and solvent are mixed and stirred to dissolve. Then, antibacterial siloxane reinforcing materials are added and stirred for 10-15 minutes. After stirring to dissolve, thickener and humectant are added in sequence and stirred to dissolve to obtain a prepolymer solution.
7. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 6, characterized in that: The preparation process of antibacterial polysiloxane reinforced materials is as follows: Step S1: Add hydrochloric acid to a mixed solution of anhydrous ethanol and deionized water to adjust the pH of the solution to 3.0-3.2, then add γ-methacryloyloxypropyltrimethoxysilane, and sonicate at 25-30℃ for 1.5-2.0h. Then add nano zinc oxide, disperse it evenly, and reflux at 80-85℃ for 4-5h. After the reaction is completed, wash with alcohol, filter, and dry to obtain pretreated zinc oxide. Step S2: Add low-hydrogen silicone oil and pretreated zinc oxide to toluene, stir and heat to 55-60℃, then add chloroplatinic acid catalyst, and heat to 95-100℃ and keep the temperature for 3.5-4.0h. After the reaction is completed, remove impurities, wash and dry to obtain antibacterial polysiloxane reinforced material.
8. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 7, characterized in that: The volume ratio of anhydrous ethanol to deionized water in the mixed solution is (9-10):1; the reaction mass ratio of γ-methacryloyloxypropyltrimethoxysilane to nano zinc oxide is 1:(10-12); and the reaction mass ratio of low-hydrogen silicone oil to pretreated zinc oxide is (6.0-6.5):
1.
9. The method for preparing a photopolymerized antibacterial hydrogel patch according to claim 6, characterized in that: The preparation process of the antibacterial siloxane reinforced material is as follows: γ-aminopropyltriethoxysilane is added to anhydrous ethanol under nitrogen atmosphere, and after ultrasonic dispersion, cinnamaldehyde is added. The mixture is stirred and reacted at 60-65℃ for 4-5 hours. After the reaction is completed, the mixture is centrifuged, washed, and dried to obtain the antibacterial siloxane reinforced material. The molar ratio of γ-aminopropyltriethoxysilane to cinnamaldehyde is (1.1-1.2):
1.
10. A photopolymerized antibacterial hydrogel dressing, characterized in that, Prepared by the preparation method according to any one of claims 1-9.