Antibacterial medical composite bandage and preparation method thereof
By introducing antibacterial modified graphene oxide and chitosan powder into the bandage, a multi-layer composite fiber network is prepared to form an all-round antibacterial system, which solves the problem of insufficient antibacterial performance of traditional bandages, achieves excellent antibacterial effect, and reduces the risk of wound infection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGDAO LI KANG YUAN MEDICAL DEVICE
- Filing Date
- 2025-12-17
- Publication Date
- 2026-06-23
AI Technical Summary
Traditional medical bandages have limited ability to protect against bacteria, making it difficult to effectively inhibit wound infection and affect wound healing.
Antibacterial fibers are prepared using antibacterial modified graphene oxide and chitosan powder, and combined with multi-layer composite fiber webs and antibacterial materials to form a multi-layer, all-round antibacterial system. The antibacterial effect is enhanced by destroying bacterial cell membranes through electrostatic attraction and physical cutting.
It achieves excellent antibacterial properties of the bandage, improves its ability to protect against bacteria, reduces the risk of wound infection, and forms a synergistic antibacterial and long-lasting stable antibacterial effect.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of bandage technology, specifically to an antibacterial medical composite bandage and its preparation method. Background Technology
[0002] In modern healthcare systems, medical bandages, seemingly simple medical supplies, play an irreplaceable and vital role. Medical bandages excel in limb immobilization and support. For patients with fractures, sprains, or strains, bandages can immobilize the limb, restrict movement of the injured area, reduce secondary injury caused by movement, and provide a stable environment for tissue repair. During the rehabilitation phase, they also provide support, helping patients gradually regain limb function and reducing pain and discomfort. Furthermore, compared to some advanced medical equipment and complex treatment methods, bandages are readily available and can be widely used in various medical settings. Whether in the emergency room of a large hospital, a primary healthcare unit, or a home medicine cabinet, medical bandages can be found at any time. They are simple to use, requiring no specialized technicians to apply, and can quickly provide timely treatment in emergencies.
[0003] However, wound infection is a common and challenging problem in medical practice. When wounds are exposed to the external environment, they are highly susceptible to invasion by various bacteria, fungi, and other microorganisms. While traditional medical bandages provide some physical isolation, their ability to protect against bacteria is limited. Therefore, it is necessary to improve the antibacterial properties of bandages to effectively inhibit microbial growth, reduce the risk of wound infection, and provide a safer environment for wound healing.
[0004] To overcome the shortcomings of the prior art, the present invention provides an antibacterial medical composite bandage and its preparation method. Summary of the Invention
[0005] The purpose of this invention is to provide an antibacterial medical composite bandage 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:
[0007] A method for preparing an antibacterial medical composite bandage includes the following steps:
[0008] Step 1: Add antibacterial modified graphene oxide to deionized water and disperse it evenly by ultrasonication to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise. After the addition is completed, continue stirring for 3-4 hours to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers.
[0009] Step 2: Obtain an antibacterial fiber layer by carding the antibacterial fiber, then stack the antibacterial fiber layer with nonwoven fabric in layers and cross-lay it to obtain a multi-layer composite fiber web; prepare the base material by needle punching the multi-layer composite fiber web; impregnate the base material in the antibacterial material for 15-20 minutes, and dry it at 25-30℃ for 15-20 hours after impregnation to obtain the finished product.
[0010] In a more optimized manner, the mass-to-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is (0.05-0.07) g: 5 g: 100 mL: 9 mL; the carding process is as follows: cylinder speed 13-15 Hz, doffer speed 12-14 Hz, and feed rate 7-8 Hz; the mass of the antibacterial fiber layer is 30-40% of the mass of the nonwoven fabric.
[0011] In a more optimized manner, the preparation process of antibacterial modified graphene oxide in step one is as follows:
[0012] Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred until homogeneous, and then heated to 110-120℃. 6-chloro-1-hexanol was then added dropwise. After the addition was complete, the reaction continued for 25-30 hours. After the reaction was completed, the hydroxylated quaternary phosphorus salt was obtained by vacuum distillation, cooling, washing, separation, and drying.
[0013] Step S2: Under a nitrogen atmosphere, hexaisophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring each mixture thoroughly, the latter was added dropwise to the former. The mixture was refluxed at 58-60℃ for 2.0-2.5 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt.
[0014] Step S3: Add graphene oxide to N,N-dimethylformamide, disperse it evenly by ultrasonication, then add isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate. After vacuuming, purge with nitrogen and stir at 80-85℃ for 20-25 hours. After the reaction is completed, centrifuge, wash, vacuum dry and grind to obtain antibacterial modified graphene oxide.
[0015] In a more optimized manner, in step S1, the molar ratio of triphenylphosphine to 6-chloro-1-hexanol is (1.0-1.1):1; in step S2, the molar ratio of hexaisophorone diisocyanate to hydroxylated quaternary phosphonium salt is (1.0-1.1):1; in step S3, the mass ratio of graphene oxide to isocyanated quaternary phosphonium salt is 1:(3-4), and the amount of dibutyltin dilaurate in the reaction system is 0.5-0.8 wt%.
[0016] In a more optimized manner, the preparation process of the antibacterial material in step two is as follows:
[0017] Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran, stirred until homogeneous, and then triethylamine was added. Acryloyl chloride was then added at 0-2℃. After the addition was complete, the mixture was stirred at 25-30℃ for 5-7 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran, stirred until homogeneous, and then refluxed at 68-70℃ for 13-15 hours. After the reaction was completed, the mixture was precipitated and dried under vacuum to obtain antibacterial modified siloxane.
[0018] Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 5-6 hours. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane.
[0019] Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 60-65℃ for 1.5-2.0 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 60-65℃ to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 60-65℃ for 7-8 h. After the reaction is complete, nano zinc oxide sol is obtained.
[0020] Step S4: Add the antibacterial modified siloxane and quaternary phosphonium salt modified siloxane to the solvent, stir for 1.0-1.5 h, and then slowly add 0.10-0.12 mol / L hydrochloric acid. After the addition is complete, stir and react at 30-35℃ for 20-22 h. After the reaction is complete, add nano zinc oxide sol and continue stirring for 20-30 min to obtain the antibacterial material.
[0021] In a more optimized manner, in step S1, the reaction molar ratio of 2-aminobenzothiazole to acryloyl chloride is (1.1-1.2):1; the reaction molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane is (1.2-1.3):1.
[0022] In a more optimized manner, in step S2, the molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane is (1.2-1.3):1.
[0023] In a more optimized manner, in step S3, the reaction mass ratio of zinc acetate dihydrate to sodium hydroxide is (10-11):4.
[0024] In a more optimized manner, in step S4, the solvent includes tetrahydrofuran and isopropanol; the content of each component of the antibacterial material is as follows: by mass parts, 2-3 parts antibacterial modified siloxane, 1-2 parts quaternary phosphonium salt modified siloxane, 2.5-3.0 parts tetrahydrofuran, 2.5-3.0 parts isopropanol, 1.5-1.7 parts hydrochloric acid, and 3.5-4.0 parts nano zinc oxide sol.
[0025] The beneficial effects of this invention are:
[0026] The key feature of this invention is that a nucleophilic substitution reaction is initiated by adding triphenylphosphine and 6-chloro-1-hexanol to obtain a hydroxylated quaternary phosphonium salt. Further addition of the hydroxylated quaternary phosphonium salt and hexaisophorone diisocyanate leads to a nucleophilic addition reaction, yielding an isocyanate-modified quaternary phosphonium salt. Then, graphene oxide, the isocyanate-modified quaternary phosphonium salt, and dibutyltin dilaurate are mixed, and the oxygen-containing functional groups on the graphene oxide surface and the isocyanate groups in the isocyanate-modified quaternary phosphonium salt undergo a nucleophilic addition reaction to obtain antibacterial modified graphene oxide. Quaternary phosphonium salts are compounds with excellent antibacterial properties. The phosphorus atoms of the quaternary phosphonium salt carry a positive charge, which allows them to electrostatically attract negatively charged components on the bacterial cell membrane surface, disrupting the structure and function of the bacterial cell membrane, thereby exerting an antibacterial effect. Graphene oxide has a sharp, sheet-like structure and a large specific surface area, which can physically cut the cell membrane of bacteria, causing leakage of cell contents and thus killing the bacteria, thus possessing a certain degree of antibacterial properties. Therefore, introducing quaternary phosphonium salt groups into the surface of graphene oxide results in antibacterial modified graphene oxide with excellent antibacterial properties.
[0027] Furthermore, antibacterial modified graphene oxide and chitosan powder are mixed to prepare a spinning solution, ultimately producing antibacterial fibers. Chitosan, a natural high-molecular-weight polysaccharide, possesses excellent antibacterial properties. In this composite system of antibacterial fibers, both quaternary phosphonium salts and chitosan carry a positive charge, allowing them to work together to target bacterial cell membranes and enhance their disruptive effect. The physical cleaving action of graphene oxide combined with the chemical disruptive action of quaternary phosphonium salts and chitosan attacks bacteria from multiple angles, synergistically improving the antibacterial effect.
[0028] The invention is characterized by the following steps: An olefinically modified benzothiazole is obtained by adding 2-aminobenzothiazole and acryloyl chloride to induce a nucleophilic substitution reaction; the olefinically modified benzothiazole is then mixed with 3-mercaptopropyltrimethoxysilane to induce a mercapto-olefin click reaction, yielding an antibacterial modified siloxane. Allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone are mixed and subjected to a mercapto-olefin click reaction under ultraviolet light irradiation to obtain a quaternary phosphonium salt modified siloxane. The antibacterial modified siloxane, the quaternary phosphonium salt modified siloxane, and a solvent are mixed and stirred until homogeneous. Hydrochloric acid is then slowly added dropwise. As the reaction proceeds, hydrolysis and condensation reactions continuously occur, forming a three-dimensional network siloxane polymer structure. After the reaction is complete, nano-zinc oxide sol is added, and stirring continues to yield the antibacterial material.
[0029] The benzothiazole ring in the antibacterial modified siloxane possesses inherent biological activity. The structure of benzothiazole can interfere with bacterial metabolic processes, affecting bacterial growth and reproduction. Quaternary phosphonium salt-modified siloxanes can act on bacterial cell membranes, disrupting their structure. Therefore, when antibacterial modified siloxanes and quaternary phosphonium salt-modified siloxanes undergo hydrolysis and condensation reactions under hydrochloric acid, the benzothiazole and quaternary phosphonium salt groups integrate into a polymer network, enabling the two antibacterial components to work synergistically and improving overall antibacterial efficiency. Furthermore, the polymer network can encapsulate and slow-release benzothiazole and quaternary phosphonium salts, allowing them to be slowly released into the surrounding environment, prolonging the duration of the antibacterial effect. Moreover, after forming the siloxane polymer network, nano-zinc oxide sol is added and stirred, ensuring the nano-zinc oxide particles are uniformly dispersed within the siloxane polymer network. The nano-zinc oxide, together with the benzothiazole and quaternary phosphonium salts in the siloxane polymer network, exerts a combined antibacterial effect. The antibacterial mechanism of nano zinc oxide differs from that of benzothiazole and quaternary phosphonium salts; they can complement each other to further enhance antibacterial properties.
[0030] Finally, the antibacterial fibers are carded to obtain an antibacterial fiber layer, which is then layered and interwoven with nonwoven fabric to form a multi-layered composite fiber web. This multi-layered composite fiber web is then needle-punched to obtain the base material. The base material is impregnated with the antibacterial material, and after impregnation, it is dried to obtain the finished bandage. This structural design gives the bandage a larger specific surface area, increasing the opportunity for contact with bacteria. Simultaneously, the various antibacterial components in the antibacterial fibers and antibacterial material work synergistically to form a multi-layered, comprehensive antibacterial system, resulting in excellent antibacterial properties in the finished bandage. In summary, this finished bandage forms a synergistic, long-lasting, and stable antibacterial system, which, combined with its unique structural design, ultimately exhibits excellent antibacterial performance. Detailed Implementation
[0031] 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.
[0032] Raw material source:
[0033] Graphene oxide, provided by Beijing Meiston Technology Development Co., Ltd., model number SY-GO-S; chitosan powder, provided by Qingdao Bozhi Huili Biotechnology Co., Ltd., with a degree of deacetylation of 86.5%; non-woven fabric, provided by Suzhou Guoyao New Materials Co., Ltd., made of polypropylene, grade PP H7914; by mass, one part is 1g.
[0034] Example 1: Step 1: Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred until homogeneous, and then heated to 120°C. 6-chloro-1-hexanol was then added dropwise. After the addition was complete, the reaction continued for 30 hours. After the reaction was completed, the product was distilled under reduced pressure, cooled, washed, separated, and dried to obtain a hydroxylated quaternary phosphonium salt. The molar ratio of triphenylphosphine to 6-chloro-1-hexanol was 1.05:1.
[0035] Step S2: Under a nitrogen atmosphere, hexaisophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring thoroughly, the latter was added dropwise to the former, and the mixture was refluxed at 60°C for 2.5 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt. The molar ratio of hexaisophorone diisocyanate to hydroxylated quaternary phosphonium salt was 1.05:1.
[0036] Step S3: Graphene oxide was added to N,N-dimethylformamide and ultrasonically dispersed until uniform. Then, isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate were added. After evacuation, nitrogen gas was introduced and the mixture was stirred at 85°C for 25 hours. After the reaction, the mixture was centrifuged, washed, vacuum dried, and ground to obtain antibacterial modified graphene oxide. The mass ratio of graphene oxide to isocyanate-modified quaternary phosphonium salt was 1:3.5, and the amount of dibutyltin dilaurate in the reaction system was 0.6 wt%.
[0037] Step S4: Add antibacterial modified graphene oxide to deionized water and ultrasonically disperse it evenly to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise, and continue stirring for 4 hours after the addition is completed to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers; the mass-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is 0.06g:5g:100mL:9mL;
[0038] Step 2: Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran, stirred until homogeneous, and then triethylamine was added. Acryloyl chloride was then added at 2°C. After the addition was complete, the mixture was stirred at 30°C for 7 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran, stirred until homogeneous, and then refluxed at 70°C for 15 hours. After the reaction was completed, the mixture was precipitated and vacuum dried to obtain antibacterial modified siloxane. The molar ratio of 2-aminobenzothiazole to acryloyl chloride was 1.15:1; the molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0039] Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 6 hours. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane. The molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0040] Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 65°C for 2.0 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 65°C to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 65°C for 8 h. After the reaction is complete, nano-zinc oxide sol is obtained; the mass ratio of zinc acetate dihydrate to sodium hydroxide is 10.5:4.
[0041] Step S4: Add 2g of antibacterial modified siloxane and 1g of quaternary phosphonium salt modified siloxane to a solvent consisting of 2.5g of tetrahydrofuran and 2.5g of isopropanol. After stirring for 1.5h, slowly add 1.5g of 0.10mol / L hydrochloric acid. After the addition is complete, stir and react at 35℃ for 22h. After the reaction is complete, add 3.5g of nano zinc oxide sol and continue stirring for 30min to obtain the antibacterial material.
[0042] Step S5: Obtain an antibacterial fiber layer by carding the antibacterial fiber through a carding process. Then, stack the antibacterial fiber layer with the nonwoven fabric in layers and cross-lay it to obtain a multi-layer composite fiber web. Prepare the base material by needle punching the multi-layer composite fiber web. Impregnate the base material with the antibacterial material for 20 minutes. After impregnation, dry it at 30°C for 20 hours to obtain the finished product. Carding process: cylinder speed 15Hz, doffer speed 14Hz, feed speed 8Hz. The mass of the antibacterial fiber layer is 40% of the mass of the nonwoven fabric.
[0043] Example 2: Step 1: Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred until homogeneous, and then heated to 115°C. 6-chloro-1-hexanol was then added dropwise. After the addition was complete, the reaction continued for 27 hours. After the reaction was completed, the product was distilled under reduced pressure, cooled, washed, separated, and dried to obtain a hydroxylated quaternary phosphonium salt. The molar ratio of triphenylphosphine to 6-chloro-1-hexanol was 1.05:1.
[0044] Step S2: Under a nitrogen atmosphere, hexaisophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring thoroughly, the latter was added dropwise to the former, and the mixture was refluxed at 59°C for 2.3 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt. The molar ratio of hexaisophorone diisocyanate to hydroxylated quaternary phosphonium salt was 1.05:1.
[0045] Step S3: Graphene oxide was added to N,N-dimethylformamide and ultrasonically dispersed until uniform. Then, isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate were added. After evacuation, nitrogen gas was introduced and the mixture was stirred at 83°C for 23 hours. After the reaction, the mixture was centrifuged, washed, vacuum dried, and ground to obtain antibacterial modified graphene oxide. The mass ratio of graphene oxide to isocyanate-modified quaternary phosphonium salt was 1:3.5, and the amount of dibutyltin dilaurate in the reaction system was 0.6 wt%.
[0046] Step S4: Add antibacterial modified graphene oxide to deionized water and ultrasonically disperse it evenly to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise, and continue stirring for 3.5 hours after the addition is completed to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers; the mass-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is 0.06g:5g:100mL:9mL;
[0047] Step 2: Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran, stirred until homogeneous, and then triethylamine was added. Acryloyl chloride was then added at 1°C. After the addition was complete, the mixture was stirred at 27°C for 6 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran, stirred until homogeneous, and then refluxed at 69°C for 14 hours. After the reaction was completed, the mixture was precipitated and vacuum dried to obtain antibacterial modified siloxane. The molar ratio of 2-aminobenzothiazole to acryloyl chloride was 1.15:1; the molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0048] Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 5.5 h. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane. The molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0049] Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 63°C for 1.7 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 63°C to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 63°C for 7.5 h. After the reaction is complete, nano-zinc oxide sol is obtained; the mass ratio of zinc acetate dihydrate to sodium hydroxide is 10.5:4.
[0050] Step S4: Add 2g of antibacterial modified siloxane and 1g of quaternary phosphonium salt modified siloxane to a solvent consisting of 2.5g of tetrahydrofuran and 2.5g of isopropanol. After stirring for 1.3h, slowly add 1.5g of 0.10mol / L hydrochloric acid. After the addition is complete, stir and react at 32℃ for 21h. After the reaction is complete, add 3.5g of nano zinc oxide sol and continue stirring for 25min to obtain the antibacterial material.
[0051] Step S5: Obtain an antibacterial fiber layer by carding the antibacterial fiber through a carding process. Then, stack the antibacterial fiber layer with the nonwoven fabric in layers and cross-lay it to obtain a multi-layer composite fiber web. Prepare the base material by needle punching the multi-layer composite fiber web. Impregnate the base material with the antibacterial material for 17 minutes. After impregnation, dry it at 27°C for 17 hours to obtain the finished product. Carding process: cylinder speed 14Hz, doffer speed 13Hz, feed rate 7.5Hz. The mass of the antibacterial fiber layer is 40% of the mass of the nonwoven fabric.
[0052] Example 3: Step 1: Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred until homogeneous, and then heated to 110°C. 6-chloro-1-hexanol was then added dropwise. After the addition was complete, the reaction continued for 25 hours. After the reaction was completed, the product was distilled under reduced pressure, cooled, washed, separated, and dried to obtain a hydroxylated quaternary phosphonium salt. The molar ratio of triphenylphosphine to 6-chloro-1-hexanol was 1.05:1.
[0053] Step S2: Under a nitrogen atmosphere, hexaisophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring thoroughly, the latter was added dropwise to the former, and the mixture was refluxed at 58°C for 2.0 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt. The molar ratio of hexaisophorone diisocyanate to hydroxylated quaternary phosphonium salt was 1.05:1.
[0054] Step S3: Graphene oxide was added to N,N-dimethylformamide and ultrasonically dispersed until uniform. Then, isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate were added. After evacuation, nitrogen gas was introduced and the mixture was stirred at 80°C for 20 hours. After the reaction, the mixture was centrifuged, washed, vacuum dried, and ground to obtain antibacterial modified graphene oxide. The mass ratio of graphene oxide to isocyanate-modified quaternary phosphonium salt was 1:3.5, and the amount of dibutyltin dilaurate in the reaction system was 0.6 wt%.
[0055] Step S4: Add antibacterial modified graphene oxide to deionized water and ultrasonically disperse it evenly to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise, and continue stirring for 3 hours after the addition is completed to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers; the mass-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is 0.06g:5g:100mL:9mL;
[0056] Step 2: Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran, stirred until homogeneous, and then triethylamine was added. Acryloyl chloride was then added at 0°C. After the addition was complete, the mixture was stirred at 25°C for 5 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran, stirred until homogeneous, and then refluxed at 68°C for 13 hours. After the reaction was completed, the mixture was precipitated and vacuum dried to obtain antibacterial modified siloxane. The molar ratio of 2-aminobenzothiazole to acryloyl chloride was 1.15:1; the molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0057] Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 5-6 hours. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane. The molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0058] Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 60°C for 1.5 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 60°C to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 60°C for 7 h. After the reaction is complete, nano-zinc oxide sol is obtained; the mass ratio of zinc acetate dihydrate to sodium hydroxide is 10.5:4.
[0059] Step S4: Add 2g of antibacterial modified siloxane and 1g of quaternary phosphonium salt modified siloxane to a solvent consisting of 2.5g of tetrahydrofuran and 2.5g of isopropanol. After stirring for 1 hour, slowly add 1.5g of 0.10mol / L hydrochloric acid. After the addition is complete, stir and react at 30℃ for 20 hours. After the reaction is complete, add 3.5g of nano zinc oxide sol and continue stirring for 20 minutes to obtain the antibacterial material.
[0060] Step S5: Obtain an antibacterial fiber layer by carding the antibacterial fiber through a carding process. Then, stack the antibacterial fiber layer with the nonwoven fabric in layers and cross-lay it to obtain a multi-layer composite fiber web. Prepare the base material by needle punching the multi-layer composite fiber web. Impregnate the base material with the antibacterial material for 15 minutes. After impregnation, dry it at 25°C for 15 hours to obtain the finished product. Carding process: cylinder speed 13Hz, doffer speed 12Hz, feed speed 7Hz. The mass of the antibacterial fiber layer is 40% of the mass of the nonwoven fabric.
[0061] Comparative Example 1: The antibacterial fiber was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran. After stirring evenly, triethylamine was added, and then acryloyl chloride was added at 2°C. After the addition was completed, the mixture was stirred at 30°C for 7 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran. After stirring evenly, the mixture was refluxed at 70°C for 15 hours. After the reaction was completed, the mixture was precipitated and vacuum dried to obtain antibacterial modified siloxane. The molar ratio of 2-aminobenzothiazole to acryloyl chloride was 1.15:1; the molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0062] Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 6 hours. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane. The molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane was 1.25:1.
[0063] Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 65°C for 2.0 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 65°C to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 65°C for 8 h. After the reaction is complete, nano-zinc oxide sol is obtained; the mass ratio of zinc acetate dihydrate to sodium hydroxide is 10.5:4.
[0064] Step S4: Add 2g of antibacterial modified siloxane and 1g of quaternary phosphonium salt modified siloxane to a solvent consisting of 2.5g of tetrahydrofuran and 2.5g of isopropanol. After stirring for 1.5h, slowly add 1.5g of 0.10mol / L hydrochloric acid. After the addition is complete, stir and react at 35℃ for 22h. After the reaction is complete, add 3.5g of nano zinc oxide sol and continue stirring for 30min to obtain the antibacterial material.
[0065] Step S5: Immerse the non-woven fabric in antibacterial material for 20 minutes, and dry it at 30°C for 20 hours after immersion to obtain the finished product.
[0066] Comparative Example 2: The antibacterial material was removed, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred evenly, and then heated to 120°C. 6-chloro-1-hexanol was then added dropwise. After the addition was completed, the reaction continued for 30 hours. After the reaction was completed, the product was distilled under reduced pressure, cooled, washed, separated, and dried to obtain hydroxylated quaternary phosphonium salt. The molar ratio of triphenylphosphine to 6-chloro-1-hexanol was 1.05:1.
[0067] Step S2: Under a nitrogen atmosphere, hexaisophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring thoroughly, the latter was added dropwise to the former, and the mixture was refluxed at 60°C for 2.5 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt. The molar ratio of hexaisophorone diisocyanate to hydroxylated quaternary phosphonium salt was 1.05:1.
[0068] Step S3: Graphene oxide was added to N,N-dimethylformamide and ultrasonically dispersed until uniform. Then, isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate were added. After evacuation, nitrogen gas was introduced and the mixture was stirred at 85°C for 25 hours. After the reaction, the mixture was centrifuged, washed, vacuum dried, and ground to obtain antibacterial modified graphene oxide. The mass ratio of graphene oxide to isocyanate-modified quaternary phosphonium salt was 1:3.5, and the amount of dibutyltin dilaurate in the reaction system was 0.6 wt%.
[0069] Step S4: Add antibacterial modified graphene oxide to deionized water and ultrasonically disperse it evenly to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise, and continue stirring for 4 hours after the addition is completed to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers; the mass-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is 0.06g:5g:100mL:9mL;
[0070] Step 2: Obtain an antibacterial fiber layer by carding the antibacterial fiber through a carding process. Then, stack the antibacterial fiber layer with the nonwoven fabric in layers and cross-lay it to obtain a multi-layer composite fiber web. Prepare the finished product by needle punching the multi-layer composite fiber web. Carding process: cylinder speed 15Hz, doffer speed 14Hz, feed speed 8Hz. The mass of the antibacterial fiber layer is 40% of the mass of the nonwoven fabric.
[0071] Testing and experimentation:
[0072] Antibacterial rate test: The finished product prepared according to this invention was cut into samples. Using *E. coli* as a model bacterium, *E. coli* was inoculated into LB medium and cultured at 35°C for 15 hours. After culture, the samples were centrifuged, and the centrifuged bacterial solution was diluted with PBS buffer to obtain 10... 7 A bacterial suspension of CFU / mL was prepared. The sample was immersed in the bacterial suspension for 15 hours at 35°C. After incubation, the sample was diluted and incubated again (35°C, 15 hours). The bacterial count was then observed using the plate count method to obtain the bacterial count of the experimental group, denoted as A1. A similar procedure was then performed using non-woven fabric as a control group, and the bacterial count of the control group was observed, denoted as A0. The data were then used in the inhibition rate calculation: (A0 - A1) / A0.
[0073] Bacterial anti-adhesion rate test: The finished product prepared according to this invention was cut into samples. Using *E. coli* as the model bacteria, *E. coli* was inoculated into LB medium and cultured at 35°C for 15 h. After culture, the culture was centrifuged, and the centrifuged bacterial solution was diluted with PBS buffer to obtain 10... 7 A bacterial suspension of CFU / mL was prepared. The sample was immersed in the bacterial suspension for 10 hours at 25°C. After incubation, the sample was stained and washed with PBS buffer to obtain the test sample. The number of bacteria on the surface of the test sample was observed using a fluorescence microscope and recorded as X1. A similar procedure was then performed on a non-woven fabric as a blank control, and the number of bacteria in the blank control was observed and recorded as X0. The data were then substituted into the anti-adhesion rate R = (X0 - X1) / X0.
[0074] The results are shown in the table below:
[0075]
[0076] 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.
[0077] Comparative Example 1: The antibacterial fiber was removed, and the rest was the same as in Example 1. The experimental data showed that, compared with Example 1, the antibacterial rate decreased to 84.6% and the anti-adhesion rate decreased to 82.3%. The reason for this is that the antibacterial modified graphene oxide and chitosan powder contained in the antibacterial fiber both have good antibacterial properties. Different antibacterial components work synergistically to enhance the antibacterial properties. Therefore, after removing the antibacterial fiber, the antibacterial rate and the anti-adhesion rate decreased.
[0078] Comparative Example 2: The antibacterial material was removed, while the rest remained the same as in Example 1. Experimental data showed that, compared to Example 1, the antibacterial rate decreased to 73.7%, and the anti-adhesion rate decreased to 71.8%. The reason for this is that the nano-zinc oxide in the antibacterial material, together with the benzothiazole and quaternary phosphonium salts in the siloxane polymer network, exerted a combined antibacterial effect, complementing each other to obtain an antibacterial material with excellent antibacterial properties. Therefore, removing the antibacterial material reduced both the antibacterial rate and the anti-adhesion rate.
[0079] 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.
[0080] 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 an antibacterial medical composite bandage, characterized in that: Includes the following steps: Step 1: Add antibacterial modified graphene oxide to deionized water and disperse it evenly by ultrasonication to obtain a dispersion; add chitosan powder to the dispersion, stir continuously and add glacial acetic acid dropwise. After the addition is completed, continue stirring for 3-4 hours to obtain a spinning solution; subject the spinning solution to degassing, extrusion, coagulation bath, stretching, and washing until neutral to obtain antibacterial fibers. Step 2: Obtain an antibacterial fiber layer by carding the antibacterial fiber, then layer and overlap the antibacterial fiber layer with nonwoven fabric to obtain a multi-layer composite fiber web; prepare the base material by needle punching the multi-layer composite fiber web; impregnate the base material in the antibacterial material for 15-20 minutes, and dry it at 25-30℃ for 15-20 hours after impregnation to obtain the finished product; The preparation process of the antibacterial material is as follows: Step S1: Under a nitrogen atmosphere, 2-aminobenzothiazole was added to tetrahydrofuran, stirred until homogeneous, and then triethylamine was added. Acryloyl chloride was then added at 0-2℃. After the addition was complete, the mixture was stirred at 25-30℃ for 5-7 hours. After the reaction was completed, the mixture was extracted, washed, dried, filtered, and rotary evaporated to obtain olefinized benzothiazole. Under a nitrogen atmosphere, olefinized benzothiazole, 3-mercaptopropyltrimethoxysilane, and azobisisobutyronitrile were added to tetrahydrofuran, stirred until homogeneous, and then refluxed at 68-70℃ for 13-15 hours. After the reaction was completed, the mixture was precipitated and dried under vacuum to obtain antibacterial modified siloxane. Step S2: Under a nitrogen atmosphere, allyltriphenylphosphonium bromide, 3-mercaptopropyltrimethoxysilane, and 2,2'-dimethoxy-2-phenylacetophenone were added to dichloromethane and reacted under ultraviolet light for 5-6 hours. After the reaction was completed, the mixture was rotary evaporated, washed, and dried to obtain quaternary phosphonium salt modified siloxane. Step S3: Add zinc acetate dihydrate to anhydrous ethanol and react at 60-65℃ for 1.5-2.0 h to obtain a zinc solution; add sodium hydroxide to anhydrous ethanol and stir to dissolve at 60-65℃ to obtain a sodium hydroxide solution; slowly add the sodium hydroxide solution dropwise to the zinc solution and react at 60-65℃ for 7-8 h. After the reaction is complete, nano zinc oxide sol is obtained. Step S4: Add the antibacterial modified siloxane and quaternary phosphonium salt modified siloxane to the solvent, stir for 1.0-1.5 h, and then slowly add 0.10-0.12 mol / L hydrochloric acid. After the addition is complete, stir and react at 30-35℃ for 20-22 h. After the reaction is complete, add nano zinc oxide sol and continue stirring for 20-30 min to obtain the antibacterial material.
2. The method for preparing an antibacterial medical composite bandage according to claim 1, characterized in that: The mass-to-volume ratio of antibacterial modified graphene oxide, chitosan powder, deionized water, and glacial acetic acid is (0.05-0.07) g: 5 g: 100 mL: 9 mL; the carding process is: cylinder speed 13-15 Hz, doffer speed 12-14 Hz, and feed rate 7-8 Hz; the mass of the antibacterial fiber layer is 30-40% of the mass of the nonwoven fabric.
3. The method for preparing an antibacterial medical composite bandage according to claim 2, characterized in that: In step one, the preparation process of antibacterial modified graphene oxide is as follows: Step S1: Under a nitrogen atmosphere, triphenylphosphine was added to N,N-dimethylformamide, stirred until homogeneous, and then heated to 110-120℃. 6-chloro-1-hexanol was then added dropwise. After the addition was complete, the reaction continued for 25-30 hours. After the reaction was completed, the hydroxylated quaternary phosphorus salt was obtained by vacuum distillation, cooling, washing, separation, and drying. Step S2: Under a nitrogen atmosphere, isophorone diisocyanate was added to anhydrous acetone, and hydroxylated quaternary phosphonium salt was added to anhydrous acetone. After stirring evenly, the latter was added dropwise to the former. The mixture was refluxed at 58-60℃ for 2.0-2.5 h. After the reaction was completed, the mixture was cooled, rotary evaporated, washed, filtered, and dried to obtain isocyanated quaternary phosphonium salt. Step S3: Add graphene oxide to N,N-dimethylformamide, disperse it evenly by ultrasonication, then add isocyanate-modified quaternary phosphonium salt and dibutyltin dilaurate. After vacuuming, purge with nitrogen and stir at 80-85℃ for 20-25 hours. After the reaction is completed, centrifuge, wash, vacuum dry and grind to obtain antibacterial modified graphene oxide.
4. The method for preparing an antibacterial medical composite bandage according to claim 3, characterized in that: In step S1, the molar ratio of triphenylphosphine to 6-chloro-1-hexanol is (1.0-1.1):1; in step S2, the molar ratio of isophorone diisocyanate to hydroxylated quaternary phosphonium salt is (1.0-1.1):1; in step S3, the mass ratio of graphene oxide to isocyanated quaternary phosphonium salt is 1:(3-4), and the amount of dibutyltin dilaurate in the reaction system is 0.5-0.8 wt%.
5. The method for preparing an antibacterial medical composite bandage according to claim 1, characterized in that: In step S1, the molar ratio of 2-aminobenzothiazole to acryloyl chloride is (1.1-1.2):1; the molar ratio of olefinized benzothiazole to 3-mercaptopropyltrimethoxysilane is (1.2-1.3):1; in step S2, the molar ratio of allyltriphenylphosphonium bromide to 3-mercaptopropyltrimethoxysilane is (1.2-1.3):
1.
6. The method for preparing an antibacterial medical composite bandage according to claim 1, characterized in that: In step S3, the reaction mass ratio of zinc acetate dihydrate to sodium hydroxide is (10-11):
4.
7. The method for preparing an antibacterial medical composite bandage according to claim 1, characterized in that: In step S4, the solvent includes tetrahydrofuran and isopropanol; the content of each component of the antibacterial material is as follows (by mass): 2-3 parts antibacterial modified siloxane, 1-2 parts quaternary phosphonium salt modified siloxane, 2.5-3.0 parts tetrahydrofuran, 2.5-3.0 parts isopropanol, 1.5-1.7 parts hydrochloric acid, and 3.5-4.0 parts nano zinc oxide sol.
8. An antibacterial medical composite bandage, characterized in that, Prepared by the preparation method according to any one of claims 1-7.