CN113026367B - Medical silver-carrying gauze and preparation method thereof - Google Patents
Medical silver-carrying gauze and preparation method thereof Download PDFInfo
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- CN113026367B CN113026367B CN202110220868.2A CN202110220868A CN113026367B CN 113026367 B CN113026367 B CN 113026367B CN 202110220868 A CN202110220868 A CN 202110220868A CN 113026367 B CN113026367 B CN 113026367B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract
The invention discloses a medical silver-carrying gauze, wherein modified polyamide complex silver is loaded in the gauze; the modified polyamide complexed silver is mainly formed by complexing silver ions and amino groups of the modified polyamide, and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide. Silver ions are wrapped inside the modified polyamide and are tightly combined with the gauze without falling off, so that the silver ions can be released in a fixed and micro-scale manner and are released stably; the release duration of the silver ions reaches more than 8 days, and the release is lasting; the antibacterial performance is excellent; and the adopted nano silver has no stimulation, sensitization, acute and chronic systemic toxicity, genetic toxicity and good biocompatibility. The invention also discloses a preparation method of the medical silver-loaded gauze, which is simple to operate, low in cost, environment-friendly, high in safety performance and free of introducing new impurity elements.
Description
Technical Field
The invention belongs to the field of medical materials, and particularly relates to medical silver-carrying gauze and a preparation method thereof.
Background
The silver-containing dressing is a dressing for changing the medicine of chronic and difficult-to-heal wounds. At present, the dressing containing silver has the characteristics of easy oxidation and the like, so that the dressing is easy to discolor and lose the antibacterial effect, the silver release is uncontrollable, the silver deposition is easy to cause, and the antibacterial effect is not lasting.
In order to solve the problem that silver ions are easy to oxidize and uncontrollable in release, a cationic nano-silver aqueous solution with a closed space network structure and stable polyamide dendrimer polymer is designed in the prior art and is combined with gauze in an infiltration manner. However, nano silver can enter cells in the form of particles through an endocytic pathway and continuously release silver ions. Therefore, the nano silver can not only directly damage cell membranes through silver ions released from the surface of the nano silver, but also play a role in cells, has definite antibacterial property and cytotoxicity and is not suitable for wound surfaces.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, provide a medical silver-carrying gauze which is not nano-silver and has no shedding of silver ions and the gauze which are tightly combined, and provide a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a medical silver-carrying gauze is characterized in that modified polyamide complex silver is loaded in the gauze; the modified polyamide complexed silver is mainly formed by complexing silver ions and amino groups of modified polyamide, and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide.
Preferably, the molar ratio of the amino groups to the silver ions is 3-50: 1 (more preferably 3:1), and the structural formula of the modified polyamide is as follows:
preferably, the gauze is one or more of absorbent cotton gauze, full cotton gauze and blended gauze.
The gauze takes cellulose as a main component, and hydroxyl groups rich in the cellulose can generate ionization in aqueous solution water and carry certain negative charges. The amino contained in the modified polyamide is only present in the interior of a molecular structure, so that silver ions are wrapped in the modified polyamide, redundant amino is protonated in an aqueous solution to enable the surface of the modified polyamide to be rich in positive charges, and the surface of the redundant amino has the effects of electrostatic adsorption with hydroxyl in cellulose, hydrogen bond generation and the like, so that polyamide molecules have good dispersion uniformity, adhesion stability and a determined proportional relation on cellulose gauze, and the polyamide complexed silver and the gauze are tightly combined without falling off and maintain excellent antibacterial performance.
Experiments prove that the silver ions in the silver-loaded gauze can be released in a fixed trace manner and are released stably; the release duration of the silver ions reaches more than 7 days, and the release is lasting; the bacteriostatic rate on escherichia coli, staphylococcus aureus, agrobacterium virens, candida albicans and the like reaches more than 99.9 percent, and the bacteriostatic performance is excellent; and has no irritation, sensitization, acute and chronic systemic toxicity, genetic toxicity and biocompatibility.
Based on a general inventive concept, the invention also provides a preparation method of the medical silver-loaded gauze, which comprises the following steps:
(1) performing polycondensation reaction on polyamino monomers and olefin substances to synthesize hyperbranched polyamino polymer, and then modifying the hyperbranched polyamino polymer through acid anhydride substances or alkylene oxide substances to obtain modified polyamide;
(2) respectively dissolving the modified polyamide and the silver-containing compound in a purified water solution, slowly dripping the silver-containing compound solution into the modified polyamide solution for complex reaction, and heating and volatilizing to obtain a polyamide complex silver solution;
(3) and (3) soaking the gauze in the polyamide complex silver solution, and drying to obtain the polyamide complex silver gauze.
Through modification of polyamide, amino originally positioned at the tail end is amidated and transferred to the interior of a molecular structure, no amino exists at the molecular tail end, and the amino positioned in the interior of the molecular structure is in coordination complexing with silver ions in an aqueous solution, so that the silver ions are wrapped in the modified polyamide, the stability of the complexed silver ions is improved, and the aims of reducing the toxicity, improving the biocompatibility and subsequently controlling the slow release of the modified polyamide are fulfilled. Meanwhile, due to the optimized tail structure, stable electrolytic balance is formed by silver ions in a solution or water immersion environment, so that the silver ions have good diffusivity and slow release. Heating and volatilizing can remove redundant water and nitrate/acetate ions, so that the solution is neutral and meets the safety requirement.
Preferably, the polyamino monomer is any one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine, the olefinic substance is any one or more of acrylic acid, methyl acrylate, methyl methacrylate and ethyl acrylate, the anhydride substance is any one or more of succinic anhydride and maleic anhydride, and the alkylene oxide substance is any one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, dodecane oxide and 1, 2-hexadecane oxide; the molar ratio of the polyamino monomer to the olefin substance is 1: 1-6, the molar ratio of the hyperbranched polyamino polymer to the acid anhydride substance is 1: 3-200, and the molar ratio of the hyperbranched polyamino polymer to the alkylene oxide substance is 1: 3-200.
Preferably, the silver-containing compound is silver nitrate or silver acetate. The silver source adopts analytically pure silver nitrate or silver acetate, nitrate ions can be removed through heating volatilization, and new impurity elements cannot be introduced; the acetate is good in biocompatibility and can be easily removed without heating treatment.
Preferably, cooling polyamino monomer to 5-10 ℃ in ice water bath, then dropwise adding olefin substance, reacting for 1-4h at normal temperature after dropwise adding to generate a light yellow intermediate, placing the intermediate on a rotary evaporator, reducing the vacuum degree to 0.1-1000Pa, removing unreacted monomer and other solvents, heating to 80-170 ℃, and reacting for 2-48h under reduced pressure to obtain the polyamino hyperbranched polymer.
Preferably, the reaction conditions for the modification are: decompression at 100-160 deg.c of 10Pa-10 5 Pa, and the reaction time is 1-24 h.
Preferably, the reaction temperature of the complex reaction is 50-100 ℃, and the reaction time is 5-60 min; in the polyamide complex silver solution, the molar ratio of amino to silver ions is 3-50: 1. The molar number of the amino groups is far more than that of silver ions, the silver space size is large, the amino groups are generally more than that of silver, the redundant amino groups are favorable for being combined with hydroxyl groups in cellulose to form hydrogen bonds, and then the silver-containing complex is firmly combined with the cellulose in the cotton substrate, so that the silver-containing polymer is not easy to fall off from gauze, and the stable, controllable and long-term release of silver is achieved.
Preferably, the heating temperature for heating volatilization is 80-95 ℃, and the heating time is 30-120 min.
Compared with the prior art, the invention has the following beneficial effects:
1. in the silver-carrying gauze, silver ions are wrapped in the modified polyamide and are tightly combined with the gauze without falling off, so that the silver ions can be released in a fixed and micro-scale manner and are stably released; the release duration of the silver ions reaches more than 8 days, and the release is lasting; the antibacterial rate of the antibacterial agent on escherichia coli, staphylococcus aureus, agrobacterium virens, candida albicans and the like is more than 99.9%, and the antibacterial performance is excellent; and the adopted nano silver has no irritation, sensitization, acute and chronic systemic toxicity, genetic toxicity and good biocompatibility.
2. The preparation method disclosed by the invention is simple to operate, low in cost, environment-friendly and high in safety performance, and new impurity elements cannot be introduced.
3. According to the preparation method, the silver solution obtained after the complexing reaction is a complexing silver aqueous solution and a non-nano silver aqueous solution, the microcosmic physical size of silver ions is smaller than that of nano silver, and the aqueous solution has better stability and better dispersibility compared with the nano silver solution (the nano silver solution is easy to agglomerate and precipitate due to the surface effect).
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of the structure of a modified polyamide.
FIG. 2 shows the valence state of silver in the silver-loaded gauze of example 1.
Figure 3 is a release profile of silver from the silver loaded gauze of example 1.
Fig. 4 shows the valence state of silver in the silver-loaded gauze of example 2.
Figure 5 is a release profile of silver from the silver loaded gauze of example 2.
FIG. 6 shows the valence state of silver in the silver-loaded gauze of example 3.
Figure 7 is a release profile of silver from the silver loaded gauze of example 3.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to medical silver-loaded gauze, which is characterized in that polyamide complex silver is loaded in absorbent gauze; the modified polyamide complexed silver is formed by complexing silver ions with amino groups of the modified polyamide (see fig. 1), and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide.
The medical silver-loaded gauze of the embodiment is prepared by the following method:
(1) synthesizing and modifying polyamide: performing polycondensation reaction on a polyamino monomer (triethylene tetramine) and an olefin acid substance (acrylic acid); cooling triethylene tetramine to 5-10 ℃ in ice water bath, then slowly dripping acrylic acid into the cooled triethylene tetramine by using a funnel, reacting for 4 hours at normal temperature after dripping is finished to generate a light yellow intermediate, placing the intermediate on a rotary evaporator, removing unreacted monomers and other solvents by reducing pressure, and heating to 120-140 ℃ for reduced pressure reaction for 2-4 hours to obtain polyamino hyperbranched polymer; then, modifying the hyperbranched polyamino polymer by acid anhydride (succinic anhydride) (specifically, continuously reducing the pressure at 140-150 ℃ for 10-100Pa, wherein the reaction time is 1-4h) to amidate the terminal amino group and transfer the terminal amino group to the interior of the molecular structure, so as to obtain modified polyamide; the molar ratio of the polyamino monomer to the olefin substance is 1:2, and the molar ratio of the hyperbranched polyamino polymer to the acid anhydride substance is 1: 30;
(2) complexing silver ions: respectively dissolving 20g of modified polyamide and 10g of silver nitrate in 1000mL of purified water solution, slowly dropwise adding the silver nitrate solution into the modified polyamide solution for complex reaction (50 ℃, 200 r/min, 20min), heating to 95 ℃ for volatilization (30min), and obtaining a polyamide complex silver solution (the molar ratio of amino to silver ions is 3: 1);
(3) dip dyeing and curing: at normal temperature, the absorbent gauze is dipped and dyed in the polyamide complex silver solution for 2-3s, and is baked and dried at 110 ℃ to obtain the final silver-loaded gauze.
The valence test result of silver element in silver-loaded gauze is shown in fig. 2. As shown in FIG. 2, Ag 3d 3/2 And Ag 3d 5/2 The maximum binding energies were 373.84eV and 367.79eV, respectively. Inquiring the standard spectrum manual of XPS, and determining that the silver element in the silver-carrying gauze is Ag by comparing the standard spectrum of Ag + And no elemental silver is generated. Because the silver-carrying gauze is non-nano silver, the silver-carrying gauze has no stimulation, no sensitization, no acute and chronic systemic toxicity, no genetic toxicity and good biocompatibility.
The silver-carrying gauze takes conventional PBS (phosphate buffer solution) which simulates body fluid of 100mL as a soaking medium, and the release conditions of silver ions in different time periods are researched by different liquid changing modes (100 mL of soaking liquid is taken out and then 100mL of new PBS is supplemented for group A, 10mL of soaking liquid is taken out and then 10mL of new PBS is supplemented for group B). The result is shown in fig. 3, it can be seen that the silver-loaded gauze can maintain a relatively fixed concentration in the simulated body fluid PBS, the silver-loaded gauze of the simulated body fluid PBS can continuously and stably release silver ions without changing the silver-loaded gauze, and the silver ions in the silver-loaded gauze can be released in a fixed and micro-amount manner for more than 8 days, and the release is stable.
In addition, the bacteriostatic rate of the antibacterial agent on escherichia coli, staphylococcus aureus, agrobacterium virens, candida albicans and the like is more than 99.9%, and the antibacterial property is excellent.
Example 2:
the invention relates to a medical silver-carrying gauze, which is characterized in that polyamide complex silver is loaded in absorbent gauze; the modified polyamide complexed silver is formed by complexing silver ions with amino groups of the modified polyamide (see fig. 1), and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide.
The medical silver-loaded gauze of the embodiment is prepared by the following method:
(1) polyamide synthesis modification: the polyamino monomer (diethylenetriamine) and the olefin acid substance (methyl acrylate) are subjected to polycondensation reaction; cooling diethylenetriamine to 5-10 ℃ in an ice water bath, then slowly dripping methyl acrylate into the cooled diethylenetriamine by using a funnel, reacting for 4 hours at normal temperature after dripping is finished to generate a light yellow intermediate, placing the intermediate on a rotary evaporator, removing unreacted monomers and other solvents by decompression, and heating to 120-140 ℃ for decompression reaction for 2 hours to obtain the polyamino hyperbranched polymer; then modifying the hyperbranched polyamino polymer by anhydride (succinic anhydride) (specifically, continuously reducing the pressure at 140-150 ℃ for 10-100Pa, and the reaction time is 48h) to amidate the terminal amino group and transfer the terminal amino group to the interior of the molecular structure, so as to obtain modified polyamide; the molar ratio of the polyamino monomer to the olefin substance is 1:1, and the molar ratio of the hyperbranched polyamino polymer to the acid anhydride substance is 1: 20;
(2) complexing silver ions: respectively dissolving 60g of modified polyamide and 1g of silver nitrate in 1000mL of purified water solution, slowly dropwise adding the silver nitrate solution into the modified polyamide solution for complex reaction (100 ℃, 200 r/min, 20min), heating to 80 ℃ for volatilization (30min), and obtaining the polyamide complex silver solution (the molar ratio of amino to silver ions is 50: 1).
(3) Dip dyeing and curing: and (3) at normal temperature, dyeing the absorbent gauze in the polyamide complex silver solution for 2-3s, and baking and drying at 140 ℃ to obtain the final silver-loaded gauze.
The valence state test result of the silver element in the silver-carrying gauze is shown in fig. 4. As shown in FIG. 4, Ag 3d 3/2 And Ag 3d 5/2 The maximum binding energies were 373.91eV and 367.81eV, respectively. Inquiring the standard spectrum manual of XPS, and determining that the silver element in the silver-carrying gauze is Ag by comparing the standard spectrum of Ag + No elemental silver is produced. Because the silver-carrying gauze is non-nano silver, the silver-carrying gauze has no stimulation, no sensitization, no acute and chronic systemic toxicity, no genetic toxicity and good biocompatibility.
The silver-loaded gauze takes conventional PBS (100 mL of simulated body fluid) as a soaking medium, and release conditions of silver ions in different time periods are researched by different liquid changing modes (group A takes out 100mL of soaking liquid and replenishes 100mL of new PBS each time, group B takes out 10mL of soaking liquid and replenishes 10mL of new PBS each time). The result of fig. 5 shows that the silver-loaded gauze can maintain a relatively fixed concentration in the simulated body fluid PBS, the simulated body fluid PBS silver-loaded gauze is continuously replaced to continuously and stably release silver ions, and the silver ions in the silver-loaded gauze can be released in a fixed trace amount for more than 4 days, so that the release is stable.
In addition, the bacteriostatic rate of the antibacterial agent on escherichia coli, staphylococcus aureus, agrobacterium virens, candida albicans and the like reaches more than 99.9%, and the antibacterial agent has excellent bacteriostatic performance.
Example 3:
the invention relates to medical silver-loaded gauze, which is characterized in that polyamide complex silver is loaded in absorbent gauze; the modified polyamide complexed silver is formed by complexing silver ions with amino groups of the modified polyamide (see fig. 1), and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide.
The medical silver-loaded gauze of the embodiment is prepared by the following method:
(1) synthesizing and modifying polyamide: performing polycondensation reaction on a polyamino monomer (mixed solution of diethylenetriamine and tetraethylenepentamine) and an olefin acid substance (methyl acrylate); cooling a mixed solution of diethylenetriamine and tetraethylenepentamine at a ratio of 1:1 to 5-10 ℃ in an ice water bath, then slowly dropwise adding methyl methacrylate into the mixed solution by using a funnel, reacting for 4 hours at normal temperature after dropwise adding to generate a light yellow intermediate, placing the intermediate on a rotary evaporator, reducing pressure to remove unreacted monomers and other solvents, heating to 120-140 ℃, and carrying out reduced pressure reaction for 2 hours to obtain a polyamino hyperbranched polymer; then modifying the hyperbranched polyamino polymer by anhydride (maleic anhydride) (specifically, continuously reducing the pressure at 140-150 ℃ for 10-100Pa, wherein the reaction time is 12h) to amidate the terminal amino group and transfer the terminal amino group to the interior of the molecular structure, so as to obtain modified polyamide; the molar ratio of the polyamino monomer to the olefin substance is 1:1, and the molar ratio of the hyperbranched polyamino polymer to the acid anhydride substance is 1: 100;
(2) complexing silver ions: respectively dissolving 30g of modified polyamide and 1g of silver nitrate in 1000mL of purified water solution, slowly dropwise adding the silver nitrate solution into the modified polyamide solution for complex reaction (50 ℃, 200 rpm/min, 60min), heating to 100 ℃ for volatilization (20min), and obtaining the polyamide complex silver solution (the molar ratio of amino to silver ions is 3: 1).
(3) Dip dyeing and curing: at normal temperature, the absorbent gauze is dipped and dyed in the polyamide complex silver solution for 2 to 3 seconds, and is baked and dried at 150 ℃ to obtain the final silver-loaded gauze.
The valence test result of silver element in the silver-loaded gauze is shown in fig. 6. As shown in FIG. 6, Ag 3d 3/2 And Ag 3d 5/2 The maximum binding energies were 373.91eV and 368.00eV, respectively. Inquiring the standard spectrum manual of XPS, and determining that the silver element in the silver-carrying gauze is Ag by comparing the standard spectrum of Ag + No elemental silver is produced. Because the non-nano silver is adopted, the silver-loaded gauze has no stimulation, no sensitization, no acute and chronic systemic toxicity, no genetic toxicity and good biocompatibility.
The silver-carrying gauze takes conventional PBS (phosphate buffer solution) which simulates body fluid of 100mL as a soaking medium, and the release conditions of silver ions in different time periods are researched by different liquid changing modes (100 mL of soaking liquid is taken out and then 100mL of new PBS is supplemented for group A, 10mL of soaking liquid is taken out and then 10mL of new PBS is supplemented for group B). The result is shown in fig. 7, the silver-loaded gauze can maintain a relatively fixed concentration in the simulated body fluid PBS, the silver-loaded gauze of the simulated body fluid PBS can continuously and stably release silver ions without changing the silver-loaded gauze, and the silver ions in the silver-loaded gauze can be released in a fixed and micro-amount manner for more than 4 days, so that the release is stable.
In addition, the bacteriostatic rate of the antibacterial agent on escherichia coli, staphylococcus aureus, agrobacterium virens, candida albicans and the like reaches more than 99.9%, and the antibacterial agent has excellent bacteriostatic performance.
Claims (5)
1. The medical silver-carrying gauze is characterized in that modified polyamide complex silver is loaded in the gauze; the modified polyamide complexed silver is mainly formed by complexing silver ions and amino groups of modified polyamide, and the amino groups of the modified polyamide exist only in the interior of the molecular structure of the modified polyamide; the molar ratio of the amino group to the silver ion is 3-50: 1, and the structural formula of the modified polyamide is as follows:
2. the medical silver-carrying gauze according to claim 1, wherein the gauze is any one or more of absorbent cotton gauze, full cotton gauze and blended gauze.
3. The method for preparing the medical silver-carrying gauze as claimed in claim 1 or 2, which comprises the following steps:
(1) synthesizing hyperbranched polyamino polymer by performing polycondensation reaction on polyamino monomer and olefin substance, and modifying the hyperbranched polyamino polymer by using anhydride substance or alkylene oxide substance to obtain modified polyamide; the polyamino monomer is any one or more of diethylenetriamine, triethylene tetramine, tetraethylenepentamine and pentaethylene hexamine, the olefin substance is any one or more of acrylic acid, methyl acrylate, methyl methacrylate and ethyl acrylate, the anhydride substance is any one or more of succinic anhydride and maleic anhydride, and the alkylene oxide substance is any one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, dodecane oxide and 1, 2-hexadecane oxide; the molar ratio of the polyamino monomer to the olefin substance is 1: 1-6, the molar ratio of the hyperbranched polyamino polymer to the acid anhydride substance is 1: 20-100, and the molar ratio of the hyperbranched polyamino polymer to the alkylene oxide substance is 1: 3-200;
the operation of the polycondensation reaction comprises the following steps: cooling polyamino monomer to 5-10 ℃ in ice water bath, then dropwise adding olefin substance, reacting for 1-4h at normal temperature after dropwise adding to generate a light yellow intermediate, placing the intermediate on a rotary evaporator, reducing the vacuum degree to 0.1-1000Pa, removing unreacted monomer and other solvents, heating to 80-170 ℃, and carrying out reduced pressure reaction for 2-48h to obtain polyamino hyperbranched polymer; the reaction conditions for the modification are as follows: decompression at the temperature of 100-160 ℃ is 10Pa-10 5 Pa, the reaction time is 1-24 h;
(2) respectively dissolving the modified polyamide and the silver-containing compound in a purified water solution, slowly dripping the silver-containing compound solution into the modified polyamide solution for complexing reaction, and heating and volatilizing to obtain a polyamide complexing silver solution; the reaction temperature of the complex reaction is 50-100 ℃, and the reaction time is 5-60 min; in the polyamide complex silver solution, the molar ratio of amino to silver ions is 3-50: 1; the microcosmic physical size of silver ions of the polyamide complex silver solution obtained after the complexing reaction is less than that of nano silver;
(3) and (3) soaking the gauze in the polyamide complex silver solution, and drying to obtain the polyamide complex silver gauze.
4. The method according to claim 3, wherein the silver-containing compound is silver nitrate or silver acetate.
5. The method according to claim 4, wherein the heating temperature for heating and volatilizing is 80-95 ℃, and the heating time is 30-120 min.
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| CN115120771A (en) * | 2022-06-30 | 2022-09-30 | 长沙海润生物技术有限公司 | Pre-convergent laser sintering gauze dressing and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106421873A (en) * | 2016-11-23 | 2017-02-22 | 长沙海润生物技术有限公司 | Functional medical dressing and preparation method thereof |
| CN106561711A (en) * | 2016-11-23 | 2017-04-19 | 长沙海润生物技术有限公司 | Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof |
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Patent Citations (2)
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| CN106421873A (en) * | 2016-11-23 | 2017-02-22 | 长沙海润生物技术有限公司 | Functional medical dressing and preparation method thereof |
| CN106561711A (en) * | 2016-11-23 | 2017-04-19 | 长沙海润生物技术有限公司 | Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof |
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