Medical dressing as well as preparation method and application thereof

Abstract

The invention provides a medical dressing and a preparation method and application thereof, the medical dressing comprises a polydisulfide and a drug, the polydisulfide comprises polylipoic acid and / or polylipoic acid amide and / or poly (lipoic acid-lipoic acid amide); the polylipoic acid is obtained by carrying out cation ring-opening polymerization reaction on a lipoic acid monomer. The invention solves the problems that the dressing synthesized by polydisulfide in the prior art cannot control the molecular weight and molecular chain structure or contains other incompletely degradable components, so that the dressing needs to be removed after being used by a patient, and secondary injury to wounds is easily caused; according to the medical dressing, the technical problems that due to the fact that polydisulfide is not completely degraded, the effects of removing and controlling medicine slow release cannot be achieved at the same time are solved, the medical dressing provided by the invention does not contain components which cannot be completely degraded, removal-free of the medical dressing is achieved, the medicine is gradually released along with degradation of the polydisulfide in the use process of the dressing, and therefore the technical effect of controlling medicine slow release is achieved.

Description

Technical Field

[0001] This invention relates to the field of medical materials technology, and more specifically, to a medical dressing, its preparation method, and its application. Background Technology

[0002] Wound dressings serve as a physical barrier, replacing normal skin to effectively resist the invasion of external microorganisms. Their properties are crucial, including providing a favorable healing microenvironment, closing the wound, achieving timely hemostasis, and accommodating wound movement. Traditional wound dressings, such as gauze, cotton, and sponges, cannot effectively close the wound or stop bleeding in a timely manner, while surgical sutures and staples are not effectively used before hospitalization. During patient movement, the wound site also moves frequently, and traditional hydrogel wound dressings, due to insufficient tissue adhesion and mechanical properties, cannot meet the needs of wound movement, often resulting in breakage or displacement, thus causing wound infection.

[0003] Thioctic acid (TA) is a naturally occurring cyclic disulfide found in plants and animals, possessing antioxidant properties. Its molecular structure contains cyclic disulfide bonds and carboxyl groups. Thioctic acid can be synthesized through ring-opening polymerization into poly(thioctic acid) (PTA), a linear polydisulfide with a dynamic disulfide bond in the main chain and carboxyl groups in the side groups. This polydisulfide can depolymerize in dilute sodium hydroxide solution, reverting back to thioctic acid monomers, enabling chemical closed-loop recycling and thus exhibiting regenerative properties. The degradation products of poly(thioctic acid) through disulfide bond reduction are biocompatible small molecules, thus possessing biodegradability. The carboxyl side groups in poly(thioctic acid) can form coordination bonds, hydrogen bonds, etc., and can also serve as crosslinking points to prepare crosslinked polymers. The unique chemical structure of poly(thioctic acid) endows it with many excellent properties, such as cell permeability, processability, ductility, and adhesion, making it promising for applications in biomedical materials, smart materials, self-healing materials, recyclable materials, adhesives, and electronic devices. Furthermore, thioctinamide is also present in the human body's metabolic processes. Applying polydisulfide to wound dressings, however, minimizes displacement, and its flexibility can reduce secondary injury caused by movement, thus addressing the aforementioned issues. However, a problem exists: existing polydisulfide dressings, due to the inability to control molecular weight and chain structure or the presence of other non-degradable components, require regular removal and replacement by patients, potentially causing secondary damage to the wound. Therefore, they cannot simultaneously achieve the effects of no removal and controlled drug release. Summary of the Invention

[0004] This invention solves the technical problem that existing dressings synthesized from polydisulfide cannot control molecular weight and molecular chain structure or contain other non-degradable components. These dressings require regular removal and replacement after use, which can easily cause secondary damage to the wound. Therefore, they cannot simultaneously achieve the effects of no removal and controlled drug release. The medical dressing provided by this invention does not contain non-degradable components. Polydisulfide can depolymerize in environments with excessive reactive oxygen species, thiol-containing proteins such as glutathione, strong acids, and alkaline substances. This achieves the goal of no removal of the medical dressing, and the drug is gradually released as the polydisulfide degrades during dressing use, thus achieving the technical effect of controlled drug release.

[0005] To address the above problems, the present invention provides a medical dressing comprising: a polydisulfide and a drug, wherein the polydisulfide comprises polythioctic acid and / or polythiocamide and / or poly(thioctic acid-thiocamide); The polythioctic acid is obtained by cationic ring-opening polymerization of thioctic acid monomer; The preparation method of the polythioctinamide includes the following steps: After the polythioctic acid and isocyanate are mixed, a catalyst is added, and the mixture undergoes a condensation reaction at 40-160 °C for 0.5-4 h to obtain the polythioctic amide. Wherein, the molar ratio of the polythiooctanoic acid to the isocyanate is 1:(1.1-1.5) based on the ratio of carboxyl groups to isocyanate groups; or Thioctyl amide monomer is added to the first organic solvent at a set molar ratio to obtain thiocyl amide reaction component. The thiocyl amide monomer is dissolved in the first organic solvent to obtain thiocyl amide monomer solution. An initiator is added to the thiocamide reaction component at a set molar ratio, and the initiator initiates the cationic ring-opening polymerization reaction of the thiocamide monomer. A reaction terminator is added to the thiocamide reaction component after the initiator is added to obtain the polythiocamide.

[0006] Compared with existing technologies, the technical advantages achieved by this solution include: the cationic polymerization system offers diverse initiator selection; the polymerization activity of monomers can be controlled by factors such as the initiator, polymerization temperature, and solvent polarity; and it features extremely fast reaction rates and non-terminating chain kinetics. Under the presence of an initiating system, efficient ring-opening polymerization of thiocic acid and thiocamide can be achieved to synthesize polythiocic acid and polythiocamide. Alternatively, polythiocamide can be obtained through the condensation reaction of the carboxyl group of polythiocic acid with isocyanate to generate amide groups, simultaneously releasing carbon dioxide gas. The medical dressing provided by this invention utilizes the skin adhesion of polydisulfide to effectively seal wounds and stop bleeding; its flexibility reduces discomfort at the wound site during patient movement; its biodegradability allows for dressing removal without causing secondary damage or medical waste; the small molecules of lipoic acid or lipoamide generated after degradation have antioxidant effects, clearing excess reactive oxygen species, reducing intracellular oxidative stress, and accelerating the healing process of chronic wounds, such as diabetic wounds; simultaneously, lipoic acid and lipoamide, as functional small molecules naturally present in the human body, can play a certain anti-inflammatory role without side effects. Furthermore, polydisulfide can serve as a dressing base, loading antibacterial, anti-inflammatory, and hemostatic drugs and combining them through physical and chemical interactions. During dressing use, these drugs are gradually released as the polydisulfide degrades, thus providing a sustained-release function. The duration of this sustained-release effect can be controlled by adjusting the molecular weight of the polydisulfide.

[0007] In one embodiment of the present invention, the preparation method of poly(lipoic acid-lipoamide) includes the following steps: after mixing polylipoic acid and isocyanate, a catalyst is added, and a condensation reaction is carried out at 40-160 °C for 0.5-4 h to obtain poly(lipoic acid-lipoamide); wherein, the ratio of polylipoic acid to isocyanate is 200:(1-200) based on the molar ratio of carboxyl groups to isocyanate groups.

[0008] Compared with existing technologies, the technical advantages achieved by this solution are as follows: Amide groups are generated through the condensation reaction of the carboxyl groups of polythioctic acid and the ester groups of isocyanate, while simultaneously releasing carbon dioxide gas. This yields polythiocamide or poly(thioctic acid-thiocamide).

[0009] In one embodiment of the invention, the catalyst comprises N,N -Dimethylcyclohexylamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N' -Tetramethylalkylene diamine, Triethylamine, N,N - Dimethylbenzylamine, solidamine, N -Ethylmorpholine, N -Methylmorpholine, N,N'Diethylpiperazine, dibutyltin dilaurate, dioctyltin dilaurate, stannous octanoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin dithiol, dioctyltin thiol, organobismuth, triazine trimerizing catalyst, bis(dimethylaminomethyl)benzene, triethanolamine N,N Dimethylethanolamine (DMEA), pyridine, N,N' At least one of dimethylpyridine.

[0010] Compared with existing technologies, the technical effects achieved by this technical solution are: the catalyst can improve the reaction rate, selectivity and yield, thereby improving the preparation efficiency.

[0011] In one embodiment of the present invention, the preparation method of poly(lipoic acid-lipoamide) includes the following steps: adding lipoic acid monomer and lipoamide monomer to a second organic solvent at a set molar ratio to obtain a lipoic acid-lipoamide reaction component; dissolving the lipoic acid monomer and lipoamide monomer in the second organic solvent to obtain a lipoic acid-lipoamide monomer solution; adding an initiator to the lipoic acid-lipoamide reaction component at a set molar ratio; the initiator initiating a cationic ring-opening polymerization reaction between the lipoic acid monomer and the lipoamide monomer; and adding a reaction terminator to the lipoic acid-lipoamide reaction component after adding the initiator to obtain poly(lipoic acid-lipoamide).

[0012] Compared with existing technologies, the technical effects achieved by this technical solution are as follows: under the action of an initiator, it can realize the efficient ring-opening polymerization of lipoic acid and lipoamide to synthesize poly(lipoic acid-lipoamide), with fast reaction speed and high synthesis efficiency.

[0013] In one embodiment of the present invention, the initiator is a single-component initiator or a two-component initiator. The single-component initiator is a strong organic acid or an anhydride or ester corresponding to a strong organic acid. The two-component initiator includes a first initiator and a second initiator. The first initiator is a small molecule initiator with an active initiation site. The second initiator is a salt or Lewis acid corresponding to a strong organic acid. The small molecule initiator is selected from allyl chloride, allyl bromide, methyl allyl chloride, methyl allyl bromide, benzyl chloride, benzyl bromide, etc. α,α -Dimethylbenzyl chloride, α,αAt least one of dimethylbenzyl bromide, 1,3-di(chloromethyl)benzene, 1,3-di(bromomethyl)benzene, 1,4-di(chloromethyl)benzene, 1,4-di(bromomethyl)benzene, 1,3,5-tri(chloromethyl)benzene, and 1,3,5-tri(bromomethyl)benzene. Salts or Lewis acids corresponding to strong organic acids are selected from silver fluorosulfonate, silver trifluoromethanesulfonate, trifluoromethanesulfonates of lanthanides (yttrium, scandium, dysprosium, samarium, gadolinium, and neodymium), silver hexafluorophosphate, silver hexafluoroarsenate, silver hexafluoroantimonate, lithium perchlorate, potassium perchlorate, manganese perchlorate, silver perchlorate, magnesium perchlorate, calcium perchlorate, cesium perchlorate, barium perchlorate, ferric perchlorate, zinc dichloride, cadmium dichloride, mercuric dichloride, aluminum trichloride, aluminum tribromide, gallium trichloride, ferric trichloride, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, vanadium tetrachloride, antimony pentafluoride, antimony pentachloride, antimony hexafluoride, tungsten pentachloride, boron trichloride, boron trifluoride, boron tribromide, and AlR. m X 3-m At least one of Lewis acids, such as (R is alkyl such as methyl or ethyl, and X is halogen).

[0014] Compared with existing technologies, the technical effects achieved by adopting this technical solution are as follows: Initiators have the following functions: starting the reaction, initiators can initiate chemical reactions by providing activation energy or changing the activity of reactants; reducing activation energy, in chemical reactions, initiators can reduce the activation energy required for the reaction, making the reaction easier to occur; increasing the reaction rate, the presence of initiators can increase the rate of chemical reactions, allowing the reaction to reach equilibrium more quickly; controlling the polymerization process, in polymerization reactions, initiators not only initiate the polymerization reaction of monomers, but their type and amount also directly affect the properties of the polymer, such as molecular weight, molecular weight distribution, and polymer morphology.

[0015] In one embodiment of the present invention, the reaction terminator is deionized water, an alkyl alcohol solution, or a thiol solution.

[0016] Compared with existing technologies, the technical effects achieved by this solution are as follows: the reaction terminator can react rapidly with the initiator or growth chain, thereby effectively destroying its activity, controlling the reaction process, and terminating the polymerization reaction. Timely termination of the polymerization reaction can yield high-quality polymer products with uniform molecular weight and stable molecular structure. In addition to terminating the reaction, it also has the function of preventing aging. This is because it can eliminate active centers in the system, preventing further chemical reactions of the polymer during storage and use, thereby extending the polymer's service life.

[0017] In one embodiment of the present invention, the drug is used for antibacterial or anti-inflammatory purposes, and the drug includes at least one of the following: nano-silver, streptomycin, gentamicin, tobramycin, amikacin, tetracycline, doxycycline, minocycline, magnolol, tobramycin, amikacin, benzoyl peroxide, furacilin, magnesium sulfate, clotrimazole, triamcinolone, erythromycin, azithromycin, clarithromycin, fusidic acid, mupirocin, ampicillin, chloramphenicol, sulfamethoxazole, sulfadiazine, ibuprofen, thrombin, tranexamic acid, ethamsylate, aldehyde cellulose, oxidized cellulose, and Yunnan Baiyao.

[0018] Compared with existing technologies, the technical effects achieved by this technical solution are as follows: Polydisulfide can be used as a dressing base, loaded with antibacterial, anti-inflammatory, and hemostatic drugs, and combined with them through physical and chemical reactions. During the use of the dressing, the drugs are gradually released as the polydisulfide degrades, thus having a sustained-release function. The sustained release can be achieved by adjusting the molecular weight of the polydisulfide, and the duration of drug action is controllable.

[0019] In one embodiment of the present invention, the medical dressing is a patch-type medical dressing, a spray-type medical dressing, or a topical medical dressing.

[0020] Compared with existing technologies, the technical effects achieved by adopting this technical solution are: any of the above forms of medical dressings are easy to produce, convenient to use, and not easily displaced.

[0021] The present invention also provides a method for preparing the above-mentioned medical dressing, the method comprising the following steps: dissolving polydisulfide in a solvent to obtain a polydisulfide solution; pouring the polydisulfide solution into a mold to form a patch; brushing or spin-coating a drug onto either side of the patch to obtain a patch-type medical dressing; or dissolving polydisulfide in an ethanol solution, adding a drug, and stirring evenly to obtain a spray-type medical dressing; or dissolving polydisulfide in an ethanol or isopropanol solution, adding a drug, and stirring evenly to obtain a topical medical dressing.

[0022] Compared with existing technologies, the technical effects achieved by this technical solution are as follows: Medical dressings can take the following three forms: (1) Patch form: Polydisulfide film patch, which is directly applied to the wound; (2) Spray form: Polydisulfide ethanol solution spray, which is sprayed onto the wound, and the ethanol evaporates quickly to form a film that adheres to the wound; (3) Brush form: Polydisulfide ethanol or isopropanol application solution, which is applied to the wound after a cotton swab or small brush is dipped in an appropriate amount of liquid, and the ethanol or isopropanol gradually evaporates to form a film that adheres to the wound. Any of the above methods for preparing medical dressings is easy to mass-produce, convenient for patients to use, and not easy to shift, and the drug has a sustained-release effect.

[0023] The present invention also provides an application of any of the above-mentioned medical dressings, which is used to prepare products for hemostasis, anti-inflammatory, antibacterial and repair of skin wounds.

[0024] Compared with existing technologies, the technical effects achieved by adopting this technical solution are as follows: when the medical dressings of any of the above examples are applied to the preparation of products for hemostasis, anti-inflammatory, antibacterial and repair of skin wounds, the resulting products have all the beneficial effects of medical dressings, which will not be elaborated here. Attached Figure Description Figure 1 This is a schematic diagram of the synthesis path of polydisulfide provided in an embodiment of the present invention.

[0025] Figure 2 The results are from irritation experiments conducted on the skin surface of New Zealand rabbits using PTA (polythiooctanoic acid), NS (physiological saline), and SDS (10% sodium lauryl sulfate), respectively.

[0026] Figure 3 These are the results of the peroxidation damage resistance test of polythioctic acid.

[0027] Figure 4 The therapeutic efficacy of PTA against cellular inflammatory damage is assessed through molecular imprinting detection.

[0028] Figure 5 These are pathological test images of rat wound dressings treated with polythioctic acid, including images of the rat wound, HE staining, and CD31 staining.

[0029] Figure 6 The inhibition zone method was used to test the effect of polythioctic acid on Gram-negative bacteria. E. coli ) and Gram-positive bacteria ( S. aureus The ability to inhibit proliferation.

[0030] Figure 7 This is the release curve of ibuprofen in polythioctic acid in PBS buffer (phosphate-balanced saline pH=7.4). Figure 8 The curves show the release of ibuprofen from polythioctic acid and the depolymerization of polythioctic acid to form thioctic acid in PBS buffer (phosphate-balanced saline, pH=8.0). Detailed Implementation

[0031] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0032] Example 1: The present invention provides a medical dressing comprising: a polydisulfide and a drug, wherein the polydisulfide comprises polythioctic acid and / or polythiocamide and / or poly(thioctic acid-thiocamide); Polythioctic acid is obtained by cationic ring-opening polymerization of thioctic acid monomers; The preparation method of polythioctinamide includes the following steps: Polythioctic acid and isocyanate are mixed, a catalyst is added, and the mixture is subjected to a condensation reaction at 40-160 °C for 0.5-4 h to obtain polythioctic amide; The ratio of polythiooctanoic acid to isocyanate is 200:100 molar ratio of carboxyl groups to isocyanate groups; or Thioctyl amide monomer is added to the first organic solvent according to a set molar ratio to obtain thiocyl amide reaction component. Thioctyl amide monomer is dissolved in the first organic solvent to obtain thiocyl amide monomer solution. An initiator is added to the thiocamide reaction components at a set molar ratio, and the initiator initiates the cationic ring-opening polymerization reaction of the thiocamide monomer. A reaction terminator is added to the thiocamide reaction component after the initiator is added to obtain polythiocamide.

[0033] For details, see Figure 1 This diagram illustrates the synthetic pathways for polythioctic acid, polythiocamide, and poly(thioctic acid-thiocamide) provided by this invention. Cationic polymerization systems offer diverse initiator choices, and the polymerization activity of monomers can be controlled by factors such as the initiator, polymerization temperature, and solvent polarity. They also feature extremely fast reaction rates and non-terminating chain kinetics. In the presence of an initiating system, highly efficient ring-opening polymerization of thiocamide can be achieved to synthesize polythiocamide. Alternatively, polythiocamide can be obtained through the condensation reaction of the carboxyl group of polythioctic acid with isocyanate to generate amide groups, simultaneously releasing carbon dioxide gas. The medical dressing provided by this invention utilizes the skin adhesion of polydisulfide to effectively seal wounds and stop bleeding; its flexibility reduces discomfort at the wound site during patient movement; its biodegradability allows for dressing removal without causing secondary damage or medical waste; the small molecules of lipoic acid or lipoamide generated after degradation have antioxidant effects, clearing excess reactive oxygen species, reducing intracellular oxidative stress, and accelerating the healing process of chronic wounds, such as diabetic wounds; simultaneously, lipoic acid and lipoamide, as functional small molecules naturally present in the human body, can play a certain anti-inflammatory role without side effects. Furthermore, polydisulfide can serve as a dressing base, loading antibacterial and anti-inflammatory drugs and combining them through physical and chemical interactions. During dressing use, these drugs are gradually released as the polydisulfide degrades, thus providing a sustained-release function. The duration of this sustained-release effect can be controlled by adjusting the molecular weight of the polydisulfide.

[0034] Specifically, the preparation method of polythioctic acid includes the following steps: Lipoic acid monomers are added to an organic solvent at a set molar ratio to obtain lipoic acid reaction components. The lipoic acid monomers are dissolved in the organic solvent to obtain a lipoic acid monomer solution. An initiator is added to the lipoic acid reaction components according to a set molar ratio. The initiator initiates the cationic ring-opening polymerization reaction of the lipoic acid monomer. A reaction terminator is added to the thioctic acid reaction component after the initiator is added to obtain polythioctic acid.

[0035] Furthermore, the preparation method of poly(lipoic acid-lipoamide) includes the following steps: After mixing polythioctic acid and isocyanate, a catalyst is added, and the mixture undergoes a condensation reaction at 40-160 °C for 0.5-4 h to obtain poly(thioctic acid-thiocamide). The ratio of polythioctic acid to isocyanate is 200:100 based on the molar ratio of carboxyl groups to isocyanate groups.

[0036] Specifically, an amide group is generated through the condensation reaction of the carboxyl group of polythioctic acid and the ester group of isocyanate, while releasing carbon dioxide gas. This yields polythiocamide or poly(thioctic acid-thiocamide).

[0037] Furthermore, the catalyst includes N,N -Dimethylcyclohexylamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N' -Tetramethylalkylene diamine, Triethylamine, N,N - Dimethylbenzylamine, solidamine, N -Ethylmorpholine, N -Methylmorpholine, N,N' -Diethylpiperazine, dibutyltin dilaurate, dioctyltin dilaurate, stannous octanoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin dithiol, dioctyltin thiol, organobismuth, triazine trimerizing catalyst, bis(dimethylaminomethyl)benzene, triethanolamine N,N -Dimethylethanolamine (DMEA), pyridine, N,N' At least one of dimethylpyridine.

[0038] Specifically, catalysts can improve reaction rates, selectivity, and yields, thereby increasing preparation efficiency.

[0039] Furthermore, the preparation method of poly(lipoic acid-lipoamide) includes the following steps: Lipoic acid monomer and lipoamide monomer are added to the second organic solvent according to a set molar ratio to obtain lipoic acid-lipoamide reaction component. The lipoic acid monomer and lipoamide monomer are dissolved in the second organic solvent to obtain lipoic acid-lipoamide monomer solution. An initiator is added to the lipoic acid-lipoamide reaction component according to a set molar ratio. The initiator initiates a cationic ring-opening polymerization reaction between the lipoic acid monomer and the lipoamide monomer. Adding a reaction terminator to the lipoic acid-lipoamide reaction component after adding the initiator yields poly(lipoic acid-lipoamide).

[0040] Specifically, under the action of an initiator, efficient ring-opening polymerization of lipoic acid and lipoamide can be achieved to synthesize poly(lipoic acid-lipoamide), with fast reaction speed and high synthesis efficiency.

[0041] Furthermore, the initiator is a single-component initiator or a two-component initiator. The single-component initiator is a strong organic acid or its corresponding anhydride or ester. The two-component initiator includes a first initiator and a second initiator. The first initiator is a small molecule initiator with an active initiation site, and the second initiator is a salt or Lewis acid corresponding to a strong organic acid. The small molecule initiator is selected from allyl chloride, allyl bromide, methyl allyl chloride, methyl allyl bromide, benzyl chloride, benzyl bromide, etc. α,α -Dimethylbenzyl chloride, α,α At least one of dimethylbenzyl bromide, 1,3-di(chloromethyl)benzene, 1,3-di(bromomethyl)benzene, 1,4-di(chloromethyl)benzene, 1,4-di(bromomethyl)benzene, 1,3,5-tri(chloromethyl)benzene, and 1,3,5-tri(bromomethyl)benzene. Salts or Lewis acids corresponding to strong organic acids are selected from silver fluorosulfonate, silver trifluoromethanesulfonate, trifluoromethanesulfonates of lanthanides (yttrium, scandium, dysprosium, samarium, gadolinium, and neodymium), silver hexafluorophosphate, silver hexafluoroarsenate, silver hexafluoroantimonate, lithium perchlorate, potassium perchlorate, manganese perchlorate, silver perchlorate, magnesium perchlorate, calcium perchlorate, cesium perchlorate, barium perchlorate, ferric perchlorate, zinc dichloride, cadmium dichloride, mercuric dichloride, aluminum trichloride, aluminum tribromide, gallium trichloride, ferric trichloride, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, vanadium tetrachloride, antimony pentafluoride, antimony pentachloride, antimony hexafluoride, tungsten pentachloride, boron trichloride, boron trifluoride, boron tribromide, and AlR. m X 3-m At least one of Lewis acids, such as (R is alkyl such as methyl or ethyl, and X is halogen).

[0042] Specifically, initiators have the following functions: initiating reactions, as they can initiate chemical reactions by providing activation energy or altering the activity of reactants; lowering activation energy, as initiators can reduce the activation energy required for a chemical reaction, making the reaction easier to occur; increasing reaction rates, as the presence of initiators can increase the rate of chemical reactions, allowing them to reach equilibrium more quickly; and controlling the polymerization process, as initiators not only initiate the polymerization of monomers but also directly affect the properties of the polymer, such as molecular weight, molecular weight distribution, and polymer morphology, depending on their type and amount.

[0043] Furthermore, the reaction terminator is deionized water, an alkyl alcohol solution, or a thiol solution.

[0044] Specifically, reaction terminators can react rapidly with initiators or growth chains, effectively destroying their activity, controlling the reaction process, and terminating the polymerization reaction. Timely termination of the polymerization reaction yields high-quality polymer products with uniform molecular weight and stable molecular structure. In addition to terminating the reaction, they also prevent aging. This is because they eliminate active centers in the system, preventing further chemical reactions during storage and use, thereby extending the polymer's lifespan.

[0045] Furthermore, the drug is used for antibacterial, anti-inflammatory, or hemostatic purposes, and includes at least one of the following: nano-silver, streptomycin, gentamicin, tobramycin, amikacin, tetracycline, doxycycline, minocycline, magnolol, tobramycin, amikacin, benzoyl peroxide, furacilin, magnesium sulfate, clotrimazole, triamcinolone, erythromycin, azithromycin, clarithromycin, fusidic acid, mupirocin, ampicillin, chloramphenicol, sulfamethoxazole, sulfadiazine, ibuprofen, thrombin, tranexamic acid, ethamsylate, aldehyde cellulose, oxidized cellulose, and Yunnan Baiyao.

[0046] Specifically, polydisulfide can be used as a dressing base to load antibacterial, anti-inflammatory, and hemostatic drugs and combine them through physical and chemical interactions. During the use of the dressing, the drugs are gradually released as the polydisulfide degrades, thus providing a sustained-release function. The sustained release can be achieved by adjusting the molecular weight of the polydisulfide, and the duration of drug action can be controlled.

[0047] Furthermore, the medical dressing is a patch-type medical dressing, a spray-type medical dressing, or a topical medical dressing.

[0048] Specifically, any of the above-mentioned forms of medical dressings are easy to manufacture, convenient to use, and not easily displaced.

[0049] Example 2: This embodiment provides a method for preparing the traditional Chinese medicine dressing described above. The preparation method includes the following steps: The polydisulfide is dissolved in a solvent to obtain a polydisulfide solution; Pour the polydisulfide solution into a mold to form a patch; Apply medication by brushing or swirl to either side of the patch to obtain a patch-type medical dressing; or After dissolving the polydisulfide in an ethanol solution, the drug is added and stirred until homogeneous to obtain a spray-type medical dressing; or After dissolving the polydisulfide in an ethanol or isopropanol solution, the drug is added and stirred evenly to obtain a topical medical dressing.

[0050] Specifically, medical dressings can take the following three forms: (1) patch form: polydisulfide film patch, which is directly applied to the wound; (2) spray form: polydisulfide ethanol solution spray, which is sprayed onto the wound, and the ethanol evaporates quickly to form a film that adheres to the wound; (3) brush form: polydisulfide isopropanol varnish, which is applied to the wound with a cotton swab or small brush after being dipped in an appropriate amount of liquid, and the ethanol or isopropanol gradually evaporates to form a film that adheres to the wound. Any of the above methods of preparing medical dressings is easy to mass-produce, convenient for patients to use, and not easy to shift, and the drug has a sustained-release effect.

[0051] Example 3: This embodiment provides an application of the traditional Chinese medicine dressing described above, which is used to prepare products for hemostasis, anti-inflammation, antibacterial repair of skin wounds.

[0052] Test Results Figure 2 The results are from skin irritation experiments conducted on New Zealand rabbits using PTA (polythiooctanoic acid), NS (physiological saline), and SDS (10% sodium lauryl sulfate), respectively. Figure 2 The results showed that after 72 hours, no irritation reactions such as erythema, edema, desquamation or ulceration were observed at the PTA site, which was consistent with the control group (physiological saline), indicating that polythioctic acid is non-irritating to the skin. Figure 3 These are the results of the peroxidation damage resistance test of polythioctic acid. Based on the fluorescence intensity, it is shown that the material has antioxidant properties and can effectively alleviate oxidative stress. Figure 4 The therapeutic effect of PTA on cellular inflammatory damage was evaluated using molecular imprinting assays. The results showed that polythioctic acid can inhibit IL-6 and IL-1. β TNF- α The expression of the protein can reduce inflammatory damage caused by bacterial lipopolysaccharide. Figure 5 This is a rat wound image obtained by applying polythioctic acid to a wound dressing, along with pathological images showing HE staining and CD31 staining. After 12 days, the repair effect in the sample group was better than that in the control group. Pathological examination of the wound using HE staining and CD31 staining showed that polythioctic acid dressing applied to the wound can promote skin and blood vessel regeneration and accelerate wound healing. Figure 6 The inhibition zone method was used to test the effect of polythioctic acid on Gram-negative bacteria. E. coli ) and Gram-positive bacteria ( S. aureus Inhibition of proliferation. It exhibits significant antibacterial activity on agar plates containing *Escherichia coli* and *Staphylococcus aureus*, forming clearly defined circular inhibition zones.

[0053] Example 4: This embodiment provides an application of the traditional Chinese medicine dressing material described in the above example for the sustained release of ibuprofen, an anti-inflammatory drug. First, polythioctic acid is fully dissolved in anhydrous ethanol and stirred at room temperature until completely dissolved, forming a homogeneous and transparent polymer solution. Then, twice the mass of ibuprofen relative to the polythioctic acid is added to this solution, and stirring is continued to ensure thorough mixing. After homogeneity, the resulting mixture is placed in an oven to remove the ethanol solvent, allowing the system to gradually solidify. Finally, an ibuprofen-loaded polythioctic acid solid is obtained. The obtained ibuprofen-loaded polythioctic acid solid material is pulverized and sieved to obtain a sample with uniform particle size. A certain amount of sample is accurately weighed and placed in a sealed dialysis bag, then immersed in a quantitative amount of phosphate-buffered saline (PBS, pH=7.4), and stirred at a constant rate at 37 °C to simulate the in vivo release environment. At preset time intervals (e.g., 0.5 h, 1 h, 2 h, 4 h, 8 h, 12 h, 24 h, 48 h…), a quantitative volume of release medium was aspirated, and an equal volume of fresh PBS buffer was simultaneously added at the same temperature to maintain a constant volume of the release system. The absorbance of the sample solution was measured at the characteristic absorption wavelength of ibuprofen using a UV-Vis spectrophotometer. The drug concentration in the release medium at each time point was calculated based on a pre-plotted ibuprofen standard curve, and the release rate and amount of ibuprofen were then cumulatively calculated. By plotting the release rate-time curve, the loading and sustained-release effect of the polythiooctanoic acid material on ibuprofen can be systematically evaluated. Figure 7 This is the release curve of ibuprofen in polythioctic acid in PBS buffer (phosphate-balanced saline pH=7.4).

[0054] Test Results Under pH 7.4 conditions, timed UV monitoring of the release medium revealed that ibuprofen loaded with polythioctic acid exhibited a clear sustained-release characteristic. In the initial release phase (0-6 hours), the drug showed a certain burst release effect, with a cumulative release rate of approximately 15%. Subsequently, the drug release entered a stable sustained-release phase, with the release rate significantly slowing down. Over a release period of up to 7 days (168 hours), the drug was continuously and stably released from the polymer matrix, ultimately achieving a cumulative release rate of 43%. This drug release curve demonstrates that polythioctic acid, as a drug carrier, can effectively control the diffusion and dissolution of ibuprofen.

[0055] Example 5: This embodiment provides an application of the above-mentioned TCM dressing material for the simultaneous sustained release of ibuprofen anti-inflammatory drug and thioctic acid antioxidant. The specific steps are described in Example 4, except that phosphate buffered saline (PBS, pH=8.0) is used. Figure 8 The curves show the release of ibuprofen from polythioctic acid and the depolymerization of polythioctic acid to form thioctic acid in PBS buffer (phosphate-balanced saline, pH=8.0).

[0056] Test Results Under pH 8.0 conditions, timed UV detection of the release medium revealed a clear sustained-release characteristic of ibuprofen loaded in polythioctic acid (PPA) and the lipoic acid monomers gradually depolymerized from PPA. In the initial release phase (0-6 hours), the cumulative release rate of ibuprofen was approximately 6%, while PPA did not depolymerize. Subsequently, PPA began to depolymerize, releasing lipoic acid molecules. Within 12 hours, PPA depolymerization was slow, with a cumulative release rate of only 2%. Afterward, the release rate of ibuprofen slowed slightly but remained relatively constant, reaching a cumulative release rate of 32% within 2 days (48 hours), after which the release rate significantly decreased. Within 24 hours, the cumulative release rate of lipoic acid generated from the depolymerization of PPA reached 17%. Over a release period of up to 6 days (144 hours), the cumulative release rate of ibuprofen reached 75%, and the cumulative release rate of lipoic acid reached 67%, with sustained release still ongoing. The drug release curve shows that the polythioctic acid carrier gradually depolymerizes, which to some extent improves the release rate and utilization rate of ibuprofen. Furthermore, polythioctic acid, as a drug carrier, can gradually decompose under certain conditions, thus achieving the effect of eliminating the need for removal.

[0057] Specifically, applying the medical dressings described above to the preparation of products for hemostasis, anti-inflammatory, antibacterial, and repair of skin wounds yields products that possess all the beneficial effects of medical dressings, which will not be elaborated further here. Although the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. A medical dressing, characterized in that, include: Polydisulfide and pharmaceuticals, said polydisulfide comprising polythioctic acid and / or polythiocamide and / or poly(thioctic acid-thiocamide); The polythioctic acid is obtained by cationic ring-opening polymerization of thioctic acid monomer; The preparation method of the polythiooctamide includes the following steps: After the polythioctic acid and isocyanate are mixed, a catalyst is added, and the mixture undergoes a condensation reaction at 40-160 °C for 0.5-4 h to obtain the polythioctic amide. Wherein, the molar ratio of the polythioctic acid to the isocyanate is 1:(1.1-1.5) based on the ratio of carboxyl groups to isocyanate groups; or Thioctyl amide monomer is added to the first organic solvent at a set molar ratio to obtain thiocyl amide reaction component. The thiocyl amide monomer is dissolved in the first organic solvent to obtain thiocyl amide monomer solution. An initiator is added to the thiocamide reaction component at a set molar ratio, and the initiator initiates the cationic ring-opening polymerization reaction of the thiocamide monomer. A reaction terminator is added to the thiocamide reaction component after the initiator is added to obtain the polythiocamide.

2. The medical dressing according to claim 1, characterized in that, The preparation method of the poly(lipoic acid-lipoamide) includes the following steps: After the polythioctic acid and isocyanate are mixed, a catalyst is added, and the mixture undergoes a condensation reaction at 40-160 °C for 0.5-4 h to obtain the poly(thioctic acid-thiocamide). The molar ratio of the polythioctic acid to the isocyanate is 200:(1-200) based on the ratio of carboxyl groups to isocyanate groups.

3. The medical dressing according to claim 2, characterized in that, The catalyst includes N,N -Dimethylcyclohexylamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N' -Tetramethylalkylene diamine, Triethylamine, N,N - Dimethylbenzylamine, solidamine, N -Ethylmorpholine, N -Methylmorpholine, N,N' -Diethylpiperazine, dibutyltin dilaurate, dioctyltin dilaurate, stannous octanoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin dithiol, dioctyltin thiol, organobismuth, triazine trimerizing catalyst, bis(dimethylaminomethyl)benzene, triethanolamine N,N -Dimethylethanolamine (DMEA), pyridine, N,N' At least one of dimethylpyridine.

4. The medical dressing according to claim 1, characterized in that, The preparation method of the poly(lipoic acid-lipoamide) includes the following steps: The lipoic acid monomer and the lipoamide monomer are added to the second organic solvent at a set molar ratio to obtain the lipoic acid-lipoamide reaction component. The lipoic acid monomer and the lipoamide monomer are dissolved in the second organic solvent to obtain the lipoic acid-lipoamide monomer solution. An initiator is added to the lipoic acid-lipoamide reaction component at a set molar ratio, and the initiator initiates a cationic ring-opening polymerization reaction between the lipoic acid monomer and the lipoamide monomer; A reaction terminator is added to the lipoic acid-lipoamide reaction component after the initiator is added to obtain the poly(lipoic acid-lipoamide).

5. The medical dressing according to claim 4, characterized in that, The initiator is a single-component initiator or a two-component initiator. The single-component initiator is a strong organic acid or an anhydride or ester corresponding to a strong organic acid. The two-component initiator includes a first initiator and a second initiator. The first initiator is a small molecule initiator with an active initiation site, and the second initiator is a salt or Lewis acid corresponding to a strong organic acid. The small molecule initiator is selected from allyl chloride, allyl bromide, methyl allyl chloride, methyl allyl bromide, benzyl chloride, benzyl bromide, etc. α , α -Dimethylbenzyl chloride, α , α At least one of dimethylbenzyl bromide, 1,3-di(chloromethyl)benzene, 1,3-di(bromomethyl)benzene, 1,4-di(chloromethyl)benzene, 1,4-di(bromomethyl)benzene, 1,3,5-tri(chloromethyl)benzene, and 1,3,5-tri(bromomethyl)benzene. Salts or Lewis acids corresponding to strong organic acids are selected from silver fluorosulfonate, silver trifluoromethanesulfonate, trifluoromethanesulfonates of lanthanides (yttrium, scandium, dysprosium, samarium, gadolinium, and neodymium), silver hexafluorophosphate, silver hexafluoroarsenate, silver hexafluoroantimonate, lithium perchlorate, potassium perchlorate, manganese perchlorate, silver perchlorate, magnesium perchlorate, calcium perchlorate, cesium perchlorate, barium perchlorate, ferric perchlorate, zinc dichloride, cadmium dichloride, mercuric dichloride, aluminum trichloride, aluminum tribromide, gallium trichloride, ferric trichloride, tin tetrachloride, titanium tetrachloride, zirconium tetrachloride, vanadium tetrachloride, antimony pentafluoride, antimony pentachloride, antimony hexafluoride, tungsten pentachloride, boron trichloride, boron trifluoride, boron tribromide, and AlR. m X 3-m At least one of Lewis acids, such as (R is alkyl such as methyl or ethyl, X is halogen).

6. The medical dressing according to claim 4, characterized in that, The reaction terminator is deionized water, an alkyl alcohol solution, or a thiol solution.

7. The medical dressing according to claim 1, characterized in that, The drug is used for antibacterial, anti-inflammatory, or hemostatic purposes, and includes at least one of the following: nano-silver, streptomycin, gentamicin, tobramycin, amikacin, tetracycline, doxycycline, minocycline, magnolol, tobramycin, amikacin, benzoyl peroxide, furacilin, magnesium sulfate, clotrimazole, triamcinolone, erythromycin, azithromycin, clarithromycin, fusidic acid, mupirocin, ampicillin, chloramphenicol, sulfamethoxazole, sulfadiazine, ibuprofen, thrombin, tranexamic acid, ethamsylate, aldehyde cellulose, oxidized cellulose, and Yunnan Baiyao.

8. The medical dressing according to claim 1, characterized in that, The medical dressing is a patch-type medical dressing, a spray-type medical dressing, or a topical medical dressing.

9. A method for preparing a medical dressing as described in claim 8, characterized in that, The preparation method includes the following steps: The polydisulfide is dissolved in a solvent to obtain a polydisulfide solution; The polydisulfide solution is introduced into a mold to form a patch; The drug is brushed or spun onto either side of the patch to obtain the patch-type medical dressing; or After dissolving the polydisulfide in an ethanol solution, the drug is added and stirred until homogeneous to obtain the spray-type medical dressing; or After dissolving the polydisulfide in an ethanol or isopropanol solution, the drug is added and stirred evenly to obtain the topical medical dressing.

10. An application of a medical dressing as described in any one of claims 1-8, characterized in that, It is used in the preparation of products for hemostasis, anti-inflammation, antibacterial repair of skin wounds.

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