CN113318268A - Porous self-heating modified polyacrylamide gel dressing - Google Patents
Porous self-heating modified polyacrylamide gel dressing Download PDFInfo
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- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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Abstract
The invention relates to the field of functional materials, and discloses a porous self-heating modified polyacrylamide gel dressing, which comprises the following steps: (1) preparing modified polyacrylamide; (2) a supported foaming agent; (3) electrostatic spinning; (4) foaming and crosslinking. The dressing takes the modified polyacrylamide gel as a raw material, has a developed porous structure inside, and is strong in water absorption; meanwhile, the dressing also contains moisture-retaining self-heating particles, so that self-heating can be realized after water absorption, the skin pore relaxation is further promoted, and the absorption of functional substances in the dressing by the skin is accelerated.
Description
Technical Field
The invention relates to the field of functional materials, in particular to a porous self-heating modified polyacrylamide gel dressing.
Background
The medical dressings comprise natural gauze, synthetic fiber dressings, polymeric film dressings, foaming polymeric dressings, alginate dressings, hydrogel dressings and the like according to different product forms. The medical dressings can be divided into dressings with different purposes according to different functional substances contained in the dressings, for example, the dressing containing the substance for promoting wound healing can be used for wrapping wounds, the dressing containing the hemostatic substance can be used for hemostasis, the dressing containing the antibacterial substance can be used for antibiosis and antiphlogosis, and the dressing containing the antipyretic substance can be used for antipyresis and the like.
The gel dressing is mainly made of polyacrylate, polyacrylamide and the like. However, the conventional dressing has the following disadvantages: (1) the porosity is low: the dressing needs a long time to be applied on the skin surface to play a moistening role, and the dressing with low porosity has poor water absorption and is also airtight, so that the use experience is poor. (2) The functionality is single: existing dressings often contain only one primary function, such as antimicrobial, hemostatic, wound healing, and the like; and the achievement of these functions generally requires a better absorption of the corresponding functional substance by the skin. Under normal conditions, the skin absorbs the functional substances slowly and poorly, so that the effect is slow and poor.
Therefore, in order to increase the porosity of the existing dressing and to promote the absorption of functional substances, it is necessary to develop a new dressing product.
Disclosure of Invention
In order to solve the technical problems, the invention provides a porous self-heating modified polyacrylamide gel dressing. The dressing takes the modified polyacrylamide gel as a raw material, has a developed porous structure inside, and is strong in water absorption; meanwhile, the dressing also contains moisture-retaining self-heating particles, so that self-heating can be realized after water absorption, the skin pore relaxation is further promoted, and the absorption of functional substances in the dressing by the skin is accelerated.
The specific technical scheme of the invention is as follows: a porous self-heating modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparing modified polyacrylamide: adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating in an inert atmosphere in the presence of an initiator to perform free radical polymerization; and after the reaction is finished, cooling to room temperature, dialyzing in water, and freeze-drying to obtain the modified polyacrylamide.
(2) Loading a foaming agent: adding the modified polyacrylamide into a 4-azidoaniline foaming agent aqueous solution for oscillation and dispersion treatment; filtering and drying to obtain the modified polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde, moisturizing self-heating particles and functional active substances into N, N-dimethylformamide, uniformly mixing to obtain spinning solution, and preparing the unfoamed and uncrosslinked dressing through electrostatic spinning.
(4) Foaming and crosslinking: and (3) carrying out foaming crosslinking on the obtained dressing under ultraviolet irradiation and heating conditions, washing with absolute ethyl alcohol, and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
The dressing is a porous dry dressing prepared from modified polyacrylamide serving as a raw material, and functional substances and moisturizing self-heating particles are loaded in the dressing. When in use, only water is needed to be added for wetting. In order to improve the porosity of the dressing, the invention carries out a series of modification treatments in the polyacrylamide synthesis stage, so that a developed porous structure is generated in the dressing, and the water absorption and the air permeability of the dressing can be improved. In addition, the dressing is loaded with moisture-keeping self-heating particles, and the moisture-keeping self-heating particles are porous silica gel particles loaded with calcium oxide. The calcium oxide can generate heat after absorbing water, and can promote pore relaxation and more dissolution of functional substances after the dressing is wetted and applied on the surface of the skin, so that the functional substances are accelerated to be absorbed by the skin. The porous silica gel particles are used as carriers of calcium oxide, and are used as delaying mediums for moisture and heat transfer, so that excessive heat generated by severe reaction of large-area calcium oxide in contact with water in a short time is prevented, and local skin burns are avoided. Meanwhile, the porous silica gel can also play a moisturizing effect as a hydrophilic substance. In addition, the hydrophilicity of the polyacrylamide can be improved after the temperature of the dressing is increased, and effective moisture preservation can be realized. Specifically, the method comprises the following steps:
in the step (1), when the polyacrylamide is synthesized, acrylamide and acrylonitrile are adopted, a modified monomer, namely sodium allylsulfonate, is added, and sufficient anionic groups are distributed in the molecular chain of the synthesized modified polyacrylamide, so that the modified polyacrylamide is negatively charged.
In the step (2), after the modified polyacrylamide is immersed in the 4-azidoaniline foaming agent aqueous solution, the 4-azidoaniline can quickly and uniformly permeate and adsorb to the inside and the surface of the polyacrylamide under the electrostatic adsorption effect because the 4-azidoaniline is positively charged.
In the step (3), the unfoamed and uncrosslinked dressing can be prepared by using the modified polyacrylamide foaming material, glutaraldehyde, the moisturizing self-heating particles and the functional active substance as raw materials through an electrostatic spinning process.
In the step (4), because the 4-azidoaniline is an ultraviolet light-excited azide foaming agent, nitrogen can be removed from the dressing after the dressing is excited by ultraviolet light to form a porous structure, so that the water absorption and air permeability of the dressing are improved. Because the electrostatic adsorption mode in the step (2) can ensure that the 4-azidoaniline is uniformly distributed on the modified polyacrylamide, a more uniform porous structure can be formed in the dressing after foaming, and the water absorption of all parts of the dressing is more uniform. And the heated glutaraldehyde can be fully crosslinked with the polyacrylamide, so that the polyacrylamide can be prevented from being incapable of being molded due to insufficient crosslinking degree after water is added subsequently.
Further, in the step (1), the molar ratio of the acrylamide to the acrylonitrile to the sodium allylsulfonate is (50-70): (10-20): (20-30).
Further, in the step (1), the initiator is azobisisobutyronitrile, and the using amount of the initiator is 0.5-3% of the total mass of the monomers.
Further, in the step (1), the reaction temperature is 50-70 ℃, and the reaction time is 4-8 h.
Further, in the step (2), the concentration of the 4-azidoaniline foaming agent aqueous solution is 140-160 g/L; the dosage ratio of the modified polyacrylamide to the 4-azidoaniline foaming agent aqueous solution is 400-600 g/L.
Further, in the step (3), the concentrations of the materials in the spinning solution are as follows: 5-10 wt% of modified polyacrylamide foaming material, 1-5 wt% of glutaraldehyde, 0.1-0.5 wt% of moisture-retaining self-heating particles and 0.1-0.5 wt% of functional active substance.
Further, in the step (3), the preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: (5-15) mixing calcium hydroxide with the average particle size of 40-60nm and rhamnolipid with the average particle size of 10-20nm, and then carrying out ball-milling coating under the protection of inert gas to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 85-95 deg.C, performing ultrasonic dispersion, and filtering to remove insoluble substances to obtain clarified liquid; soaking 300-500nm porous silica gel particles in clear liquid according to the solid-to-liquid ratio of 10-20g/100mL, performing microwave treatment for 5-15min at the temperature of 85-95 ℃ under vacuum, taking out, drying, and repeating soaking-microwave-drying for at least 2 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; the nano calcium oxide @ porous silica gel particles are obtained by firstly carrying out aerobic roasting for 2-4h at the temperature of 300-400 ℃, and then carrying out anaerobic roasting activation for 1-2h at the temperature of 650-750 ℃, namely the nano calcium oxide @ porous silica gel particles, namely the moisturizing self-heating particles, and sealing for later use.
Because calcium oxide can not be added with water to prepare a solution and then loaded on the porous silica gel particles, the solubility of calcium hydroxide in water is very low. Therefore, the rhamnolipid with high surface activity is coated on the surface of calcium hydroxide through a mechanical ball milling process, so that the surface activity of the calcium hydroxide can be obviously improved, and the solubility of the calcium hydroxide in water is further increased. After the clarified liquid is obtained, the porous silica gel is immersed in the clarified liquid and subjected to vacuum microwave treatment, so that the modified calcium hydroxide can be promoted to fully permeate into the internal pore channels of the porous silica gel, and the loading capacity is improved. After the rhamnolipid coated modified calcium hydroxide @ porous silica gel particles are obtained, in order to obtain calcium oxide, low-temperature aerobic roasting is firstly carried out to remove organic matters (rhamnolipid) on the surface of the calcium hydroxide, the phenomenon that the coating of the organic matters layer hinders water absorption in use is avoided, then high-temperature anaerobic roasting is carried out, the calcium hydroxide is decomposed at the temperature of more than 600 ℃ and is converted into calcium oxide, and finally the moisturizing self-heating particles (calcium oxide @ porous silica gel) are obtained. The moisture-keeping self-heating particles can use moisture absorbed in pore passages of the dressing as a heat-generating raw material to realize self-heating.
Further, in the step (3), the electrostatic spinning process conditions are as follows: the diameter of the spinning is 2-4 microns, the spinning speed is 0.5-1.0mL/h, the spinning distance is 15-20cm, the voltage is 15-20kV, the temperature is 25-35 ℃, and the humidity is 40-60%.
Further, in the step (3), the functional active substance comprises one or more of epidermal growth factor, bletilla striata extract, aloe extract, seaweed extract, hyaluronic acid, tartaric acid and snake oil.
Further, in the step (4), the wavelength of the ultraviolet irradiation is 365nm, the heating condition is 80-120 ℃, and the time is 30-90 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the dressing disclosed by the invention takes modified polyacrylamide as a raw material, has a developed porous structure inside, and is strong in water absorption and good in air permeability.
(2) The dressing contains the moisture-retaining self-heating particles, and can absorb water and then self-heat, so that the skin pores are promoted to relax, and the absorption of functional substances in the dressing by the skin is accelerated.
(3) According to the invention, glutaraldehyde is added and thermal crosslinking is carried out in the preparation process of the dressing, so that the condition that the polyacrylamide cannot be molded due to insufficient crosslinking degree after subsequent water addition can be prevented.
Detailed Description
Example 1: a porous self-heating modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparing modified polyacrylamide: according to a molar ratio of 60: 15: 25 adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating to 60 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (2% of the total mass of the monomers) to perform free radical polymerization for 6 hours; and after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48 hours, and freeze-drying to obtain the modified polyacrylamide.
(2) Loading a foaming agent: adding the modified polyacrylamide into 150g/L of 4-azidoaniline foaming agent aqueous solution according to the solid-to-liquid ratio of 500g/L, and carrying out oscillation dispersion treatment; filtering and drying to obtain the modified polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde, moisture-retaining self-heating particles and functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 8 wt% of the modified polyacrylamide foaming material, 3 wt% of the glutaraldehyde, 0.3 wt% of the moisture-retaining self-heating particles and 0.3 wt% of the functional active substances (equivalent epidermal growth factors and aloe extracts), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 3 microns, the spinning speed is 0.5mL/h, the spinning distance is 20cm, the voltage is 18kV, the temperature is 30 ℃, and the humidity is 50%; an unfoamed and uncrosslinked dressing was prepared.
The preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: 10, mixing calcium hydroxide with the average particle size of 50nm and rhamnolipid with the average particle size of 15nm, and then carrying out ball-milling coating under the protection of nitrogen to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 90 deg.C, ultrasonically dispersing for 30min, filtering to remove insoluble substances to obtain clarified solution; soaking 400nm porous silica gel particles in clear liquid according to a solid-to-liquid ratio of 15g/100mL, performing microwave treatment for 15min at 90 ℃ under a vacuum condition, taking out, drying, and repeating soaking-microwave-drying for 3 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; roasting the mixture at 350 ℃ for 3h in air, then roasting and activating the mixture at 800 ℃ for 1.5h in anaerobic environment to obtain nano-scale moisturizing self-heating particles, and sealing the particles for later use.
(4) Foaming and crosslinking: and (3) carrying out foaming and crosslinking on the obtained dressing for 60min under 365nm ultraviolet irradiation and at 100 ℃, washing with absolute ethyl alcohol and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
Example 2: a porous self-heating modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparing modified polyacrylamide: according to the molar ratio of 50: 20: 30 adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating to 70 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (2% of the total mass of the monomers) to perform free radical polymerization for 4 hours; and after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48 hours, and freeze-drying to obtain the modified polyacrylamide.
(2) Loading a foaming agent: adding the modified polyacrylamide into 160g/L of 4-azidoaniline foaming agent aqueous solution according to the solid-to-liquid ratio of 400g/L, and carrying out oscillation dispersion treatment; filtering and drying to obtain the modified polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde, moisture-retaining self-heating particles and functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 10 wt% of the modified polyacrylamide foaming material, 5 wt% of the glutaraldehyde, 0.5 wt% of the moisture-retaining self-heating particles and 0.5 wt% of the functional active substances (equal amounts of aloe extract and snake oil), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 4 microns, the spinning speed is 1.0mL/h, the spinning distance is 15cm, the voltage is 15kV, the temperature is 25 ℃, and the humidity is 40%; an unfoamed and uncrosslinked dressing was prepared.
The preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: 10, mixing calcium hydroxide with the average particle size of 60nm and rhamnolipid with the average particle size of 20nm, and then carrying out ball-milling coating under the protection of nitrogen to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 95 deg.C, ultrasonically dispersing for 30min, filtering to remove insoluble substances to obtain clarified solution; soaking 500nm porous silica gel particles in clear liquid according to a solid-to-liquid ratio of 15g/100mL, performing microwave treatment for 10min at 95 ℃ under vacuum, taking out, drying, and repeating soaking-microwave-drying for 2 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; roasting the mixture at 350 ℃ for 3h in air, then roasting the mixture at 800 ℃ in anaerobic environment for 2h for activation to obtain nano-scale moisturizing self-heating particles, and sealing the particles for later use.
(4) Foaming and crosslinking: and (3) carrying out foaming and crosslinking on the obtained dressing for 30min under 365nm ultraviolet irradiation and at 120 ℃, washing with absolute ethyl alcohol and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
Example 3: a porous self-heating modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparing modified polyacrylamide: according to the molar ratio of 70: 10: 20, adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating to 50 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (3% of the total mass of monomers) to perform free radical polymerization for 8 hours; and after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48 hours, and freeze-drying to obtain the modified polyacrylamide.
(2) Loading a foaming agent: adding the modified polyacrylamide into 140g/L of 4-azidoaniline foaming agent aqueous solution according to the solid-to-liquid ratio of 600g/L, and carrying out oscillation dispersion treatment; filtering and drying to obtain the modified polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde, moisture-retaining self-heating particles and functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 5 wt% of the modified polyacrylamide foaming material, 1 wt% of the glutaraldehyde, 0.1 wt% of the moisture-retaining self-heating particles and 0.1 wt% of the functional active substances (seaweed extracts), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 2 microns, the spinning speed is 0.5mL/h, the spinning distance is 15cm, the voltage is 20kV, the temperature is 35 ℃, and the humidity is 60%; an unfoamed and uncrosslinked dressing was prepared.
The preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: 10, mixing calcium hydroxide with the average particle size of 40nm and rhamnolipid with the average particle size of 10nm, and then carrying out ball-milling coating under the protection of nitrogen to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 95 deg.C, ultrasonically dispersing for 30min, filtering to remove insoluble substances to obtain clarified solution; soaking 300nm porous silica gel particles in clear liquid according to a solid-to-liquid ratio of 15g/100mL, performing microwave treatment for 10min at 95 ℃ under vacuum, taking out, drying, and repeating soaking-microwave-drying for 2 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; roasting the mixture at 350 ℃ for 3h in air, then roasting the mixture at 800 ℃ in anaerobic environment for 2h for activation to obtain nano-scale moisturizing self-heating particles, and sealing the particles for later use.
(4) Foaming and crosslinking: and (3) carrying out foaming and crosslinking on the obtained dressing for 90min under 365nm ultraviolet irradiation and at 80 ℃, washing with absolute ethyl alcohol and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
Comparative example 1: a self-heating modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparation of polyacrylamide: according to a molar ratio of 80: 20, adding acrylamide and acrylonitrile into a dimethyl sulfoxide solution, and heating to 60 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (2% of the total mass of the monomers) to perform free radical polymerization for 6 hours; after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48h, and freeze-drying to obtain the polyacrylamide.
(2) Loading a foaming agent: adding polyacrylamide into 150g/L of 4-azidoaniline foaming agent aqueous solution according to the solid-to-liquid ratio of 500g/L, and carrying out oscillation dispersion treatment; filtering and drying to obtain the polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the polyacrylamide foaming material, glutaraldehyde, the moisturizing self-heating particles and the functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 8 wt% of the modified polyacrylamide foaming material, 3 wt% of glutaraldehyde, 0.3 wt% of the moisturizing self-heating particles and 0.3 wt% of the functional active substances (equivalent epidermal growth factor and aloe extract), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 3 microns, the spinning speed is 0.5mL/h, the spinning distance is 20cm, the voltage is 18kV, the temperature is 30 ℃, and the humidity is 50%; an unfoamed and uncrosslinked dressing was prepared.
The preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: 10, mixing calcium hydroxide with the average particle size of 50nm and rhamnolipid with the average particle size of 15nm, and then carrying out ball-milling coating under the protection of nitrogen to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 90 deg.C, ultrasonically dispersing for 30min, filtering to remove insoluble substances to obtain clarified solution; soaking 400nm porous silica gel particles in clear liquid according to a solid-to-liquid ratio of 15g/100mL, performing microwave treatment for 15min at 90 ℃ under a vacuum condition, taking out, drying, and repeating soaking-microwave-drying for 3 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; roasting the mixture at 350 ℃ for 3h in air, then roasting and activating the mixture at 800 ℃ for 1.5h in anaerobic environment to obtain nano-scale moisturizing self-heating particles, and sealing the particles for later use.
(4) Foaming and crosslinking: and (3) carrying out foaming and crosslinking on the obtained dressing for 60min under 365nm ultraviolet irradiation and at 100 ℃, washing with absolute ethyl alcohol and drying to obtain the self-heating polyacrylamide gel dressing.
Comparative example 2: a porous modified polyacrylamide gel dressing is prepared by the following steps:
(1) preparing modified polyacrylamide: according to a molar ratio of 60: 15: 25 adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating to 60 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (2% of the total mass of the monomers) to perform free radical polymerization for 6 hours; and after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48 hours, and freeze-drying to obtain the modified polyacrylamide.
(2) Loading a foaming agent: adding the modified polyacrylamide into 150g/L of 4-azidoaniline foaming agent aqueous solution according to the solid-to-liquid ratio of 500g/L, and carrying out oscillation dispersion treatment; filtering and drying to obtain the modified polyacrylamide foaming material adsorbed with the 4-azidoaniline.
(3) Electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde and functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 8 wt% of the modified polyacrylamide foaming material, 3 wt% of glutaraldehyde and 0.3 wt% of functional active substances (equivalent epidermal growth factor and aloe extract), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 3 microns, the spinning speed is 0.5mL/h, the spinning distance is 20cm, the voltage is 18kV, the temperature is 30 ℃, and the humidity is 50%; an unfoamed and uncrosslinked dressing was prepared.
(4) Foaming and crosslinking: and (3) carrying out foaming and crosslinking on the obtained dressing for 60min under 365nm ultraviolet irradiation and at 100 ℃, washing with absolute ethyl alcohol and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
Comparative example 3: a self-heating polyacrylamide gel dressing is prepared by the following steps:
(1) preparation of polyacrylamide: according to a molar ratio of 80: 20, adding acrylamide and acrylonitrile into a dimethyl sulfoxide solution, and heating to 60 ℃ in a nitrogen atmosphere in the presence of an initiator azobisisobutyronitrile (2% of the total mass of the monomers) to perform free radical polymerization for 6 hours; after the reaction is finished, cooling to room temperature, dialyzing in deionized water for 48h, and freeze-drying to obtain the polyacrylamide.
(3) Electrostatic spinning: adding polyacrylamide, glutaraldehyde and functional active substances into N, N-dimethylformamide, and uniformly mixing to obtain a spinning solution containing 8 wt% of polyacrylamide foaming material, 3 wt% of glutaraldehyde, 0.3 wt% of moisturizing self-heating particles and 0.3 wt% of functional active substances (equivalent epidermal growth factor and aloe extract), and performing electrostatic spinning, wherein the process conditions are as follows: the spinning diameter is 3 microns, the spinning speed is 0.5mL/h, the spinning distance is 20cm, the voltage is 18kV, the temperature is 30 ℃, and the humidity is 50%; an unfoamed and uncrosslinked dressing was prepared.
The preparation method of the moisturizing self-heating particles comprises the following steps: according to the mass ratio of 100: 10, mixing calcium hydroxide with the average particle size of 50nm and rhamnolipid with the average particle size of 15nm, and then carrying out ball-milling coating under the protection of nitrogen to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 90 deg.C, ultrasonically dispersing for 30min, filtering to remove insoluble substances to obtain clarified solution; soaking 400nm porous silica gel particles in clear liquid according to a solid-to-liquid ratio of 15g/100mL, performing microwave treatment for 15min at 90 ℃ under a vacuum condition, taking out, drying, and repeating soaking-microwave-drying for 3 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; roasting the mixture at 350 ℃ for 3h in air, then roasting and activating the mixture at 800 ℃ for 1.5h in anaerobic environment to obtain nano-scale moisturizing self-heating particles, and sealing the particles for later use.
(4) Heating and crosslinking: crosslinking the obtained dressing at 100 ℃ for 60min, washing with absolute ethyl alcohol and drying to obtain the self-heating polyacrylamide gel dressing.
The dressings prepared in example 1 and comparative examples 1 to 3 were subjected to various performance tests.
The water absorption detection method comprises the following steps: at 37 ℃, 100g of dressing (the thickness is 2mm) is flatly laid and immersed in a tray containing 1L of water, stands, soaks and absorbs water, is taken out after 2 hours, drains until no water drips and maintains constant weight, and is weighed; set 10 parallel groups and take the average. Water uptake (weight of dressing after water uptake-dry weight of dressing) 100%/dry weight of dressing.
The self-heating test method comprises the following steps: randomly selecting 20 adult testers, adding water to moisten the dressing, then applying the dressing on the back of the arm, performing questionnaire survey after 10min, and counting the number of people who feel spontaneous heating.
The results are shown in the following table:
the comparative analysis of the data in the table shows that:
compared with the example 1, the difference of the comparative example 1 is that the modified monomer sodium propylene 2-sulfonate is not doped in the synthetic process of the polyacrylamide in the comparative example 1, so that the polyacrylamide obtained in the comparative example 1 does not contain enough anionic groups, cannot generate sufficient electrostatic adsorption with the positively charged 4-azidoaniline, and the foaming agent content in the polyacrylamide foaming material is low, so that the prepared dressing has low porosity and poor water absorption.
Comparative example 2 compared with example 1, the difference is that comparative example 2 does not add moisture-retaining self-heating particles in the polyacrylamide electrostatic spinning process, so that the self-heating effect cannot be sensed after the finally obtained dressing is laid by adding water.
Comparative example 3 compared with comparative example 1, the difference is that the polyacrylamide of comparative example 3 has no adsorbed foaming agent and is subjected to ultraviolet irradiation to promote foaming after electrospinning. The dressing obtained in comparative example 3 is therefore less porous and less absorbent.
Claims (10)
1. A porous self-heating modified polyacrylamide gel dressing is characterized in that: the preparation method comprises the following steps:
(1) preparing modified polyacrylamide: adding acrylamide, acrylonitrile and sodium propylene sulfonate into a dimethyl sulfoxide solution, and heating in an inert atmosphere in the presence of an initiator to perform free radical polymerization; after the reaction is finished, cooling to room temperature, dialyzing in water, and freeze-drying to obtain modified polyacrylamide;
(2) loading a foaming agent: adding the modified polyacrylamide into a 4-azidoaniline foaming agent aqueous solution for oscillation and dispersion treatment; filtering and drying to obtain a modified polyacrylamide foaming material adsorbed with 4-azidoaniline;
(3) electrostatic spinning: adding the modified polyacrylamide foaming material, glutaraldehyde, moisturizing self-heating particles and functional active substances into N, N-dimethylformamide, uniformly mixing to obtain spinning solution, and preparing unfoamed and uncrosslinked dressing through electrostatic spinning;
(4) foaming and crosslinking: and (3) carrying out foaming crosslinking on the obtained dressing under ultraviolet irradiation and heating conditions, washing with absolute ethyl alcohol, and drying to obtain the porous self-heating modified polyacrylamide gel dressing.
2. The gel dressing of claim 1, wherein in step (1), the molar ratio of acrylamide, acrylonitrile and sodium allylsulfonate is (50-70): (10-20): (20-30).
3. The gel dressing of claim 1, wherein in step (1), said initiator is azobisisobutyronitrile and is used in an amount of 0.5 to 3% by weight of the total mass of the monomers.
4. The gel dressing of claim 1, wherein in step (1), the reaction temperature is 50-70 ℃ and the reaction time is 4-8 h.
5. The gel dressing of claim 1, wherein in step (2), the concentration of the aqueous solution of 4-azidoaniline blowing agent is 140-160 g/L; the dosage ratio of the modified polyacrylamide to the 4-azidoaniline foaming agent aqueous solution is 400-600 g/L.
6. The gel dressing of claim 1, wherein in step (3), the concentrations of the substances in the spinning solution are: 5-10 wt% of modified polyacrylamide foaming material, 1-5 wt% of glutaraldehyde, 0.1-0.5 wt% of moisture-retaining self-heating particles and 0.1-0.5 wt% of functional active substance.
7. The gel dressing of claim 1, wherein in step (3), the moisturizing self-heating particles are prepared by: according to the mass ratio of 100: (5-15) mixing calcium hydroxide with the average particle size of 40-60nm and rhamnolipid with the average particle size of 10-20nm, and then carrying out ball-milling coating under the protection of inert gas to obtain rhamnolipid-coated modified calcium hydroxide; adding excessive rhamnolipid coated modified calcium hydroxide into water at 85-95 deg.C, performing ultrasonic dispersion, and filtering to remove insoluble substances to obtain clarified liquid; soaking 300-500nm porous silica gel particles in clear liquid according to the solid-to-liquid ratio of 10-20g/100mL, performing microwave treatment for 5-15min at the temperature of 85-95 ℃ under vacuum, taking out, drying, and repeating soaking-microwave-drying for at least 2 times to obtain rhamnolipid-coated modified calcium hydroxide @ porous silica gel particles; the nano calcium oxide @ porous silica gel particles are obtained by firstly carrying out aerobic roasting for 2-4h at the temperature of 300-400 ℃, and then carrying out anaerobic roasting activation for 1-2h at the temperature of 650-750 ℃, namely the nano calcium oxide @ porous silica gel particles, namely the moisturizing self-heating particles, and sealing for later use.
8. The gel dressing of claim 1, wherein in step (3), the electrospinning process conditions are: the diameter of the spinning is 2-4 microns, the spinning speed is 0.5-1.0mL/h, the spinning distance is 15-20cm, the voltage is 15-20kV, the temperature is 25-35 ℃, and the humidity is 40-60%.
9. The gel dressing of claim 1, wherein in step (3), said functionally active substance comprises one or more of epidermal growth factor, bletilla striata extract, aloe vera extract, seaweed extract, hyaluronic acid, tartaric acid and snake oil.
10. The gel dressing of claim 1, wherein in step (4), said ultraviolet radiation has a wavelength of 365nm, and is heated at 80-120 ℃ for 30-90 min.
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