CN109224118B - Medical operation suture line - Google Patents

Medical operation suture line Download PDF

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Publication number
CN109224118B
CN109224118B CN201811111447.0A CN201811111447A CN109224118B CN 109224118 B CN109224118 B CN 109224118B CN 201811111447 A CN201811111447 A CN 201811111447A CN 109224118 B CN109224118 B CN 109224118B
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acid modified
medical
suture
polyethylene glycol
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CN109224118A (en
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邓生卫
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HANGZHOU HUAWEI MEDICAL APPLIANCE CO.,LTD.
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Hunan Bojun Biomedicine Co ltd
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Priority to CN202011306603.6A priority Critical patent/CN112480420A/en
Priority to CN202011311148.9A priority patent/CN112430292A/en
Priority to CN201811111447.0A priority patent/CN109224118B/en
Priority to CN202011306632.2A priority patent/CN112336911A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/005Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • A61L17/10At least partially resorbable materials containing macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • A61L17/10At least partially resorbable materials containing macromolecular materials
    • A61L17/105Polyesters not covered by A61L17/12
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • A61L17/10At least partially resorbable materials containing macromolecular materials
    • A61L17/12Homopolymers or copolymers of glycolic acid or lactic acid
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/14Post-treatment to improve physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/204Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/41Anti-inflammatory agents, e.g. NSAIDs
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/04Materials for stopping bleeding

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Abstract

The invention discloses a medical operation suture line which comprises the following components in parts by mass: 20-30 parts of 5-hydantoin acetic acid modified polylysine, 10-20 parts of polyethylene glycol hydroxy acid modified polylactic acid, 45-55 parts of sodium alginate-based polycaprolactone copolymer, 10-20 parts of gamma-cyclodextrin and 5-10 parts of hydroxybutyl methyl cellulose. The medical operation suture disclosed by the invention has the advantages of complete absorption, high tensile strength, good biocompatibility, capability of promoting cell growth, and effects of sterilization, inflammation diminishing and hemostasis.

Description

Medical operation suture line
Technical Field
The invention relates to the technical field of medical supplies, in particular to a medical operation suture and a preparation method thereof.
Background
The medical operation suture line is a special line used for ligation hemostasis, suture hemostasis and tissue suture in surgical operation or trauma treatment, and has an important effect on the initial healing of wounds. Generally, the suture can be divided into two types, namely an absorbable suture and a non-absorbable suture, wherein the non-absorbable suture is not degraded in vivo, and if the non-absorbable suture is not taken out, the non-absorbable suture is left in tissues as a body foreign body, so that the tissue infection is easily caused; the absorbable suture line is degraded in body tissues under the action of acid, alkali or enzyme, the degradation speed depends on the temperature and the pH value of the tissues and the liquid environment around the suture line, and the degraded products are converted into metabolites and excrement of a human body and are non-toxic and harmless. Therefore, the absorbable surgical suture line is a development trend of the medical surgical suture line and has important application prospect.
Common absorbable suture lines in the prior art can be divided into the following parts according to different materials and absorption degrees: catgut, chemically synthesized suture, and pure natural collagen suture. The absorbable suture lines have some defects, and the catgut is easy to cause calculus and has poor absorbability; the slow absorption of the chemical synthetic thread is not beneficial to accelerating the recovery speed of the wound; the pure natural collagen suture line has difficult material obtaining and high cost, and is not suitable for large-scale use.
Chinese patent publication No. CN1051510A proposes a method for preparing a collagen-polyvinyl alcohol absorbable surgical suture, but because the collagen suture is degraded in vivo, it is dissolved and swelled first, and then degraded, so that the suture is easily expanded to a greater extent, resulting in weak ligation. Patent publication No. CN102573935A reports a preparation method of chitosan absorbable suture, and chitosan generally used for spinning suture must have higher viscosity, so that the requirement for raw materials is higher; in addition, the chitosan is derived from animals, is influenced by raw materials, and has poor product performance stability.
Therefore, the medical operation suture line which is simple to prepare, good in biocompatibility, sufficient in absorption and excellent in mechanical property and has the sterilization and inflammation diminishing effects is developed, meets the market demand and has wide market value and application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a medical operation suture line and a preparation method thereof. The prepared medical operation suture overcomes the defects of low tensile strength and elongation, poor suture effect, poor biocompatibility, incomplete absorption and easy generation of calculus of more or less traditional operation sutures in the prior art, and has the advantages of complete absorption, high tensile strength, good biocompatibility, capability of promoting cell growth, sterilization, inflammation diminishing and bleeding stopping.
In order to achieve the aim, the invention adopts the technical scheme that the medical operation suture consists of the following components in parts by mass: 20-30 parts of 5-hydantoin acetic acid modified polylysine, 10-20 parts of polyethylene glycol hydroxy acid modified polylactic acid, 45-55 parts of sodium alginate-based polycaprolactone copolymer, 10-20 parts of gamma-cyclodextrin and 5-10 parts of hydroxybutyl methyl cellulose.
Preferably, the preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 5-hydantoin acetic acid in an organic solvent to form a solution, adding polylysine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1-hydroxybenzotriazole into the solution, stirring and reacting at 60-80 ℃ for 6-8 hours, then performing rotary evaporation to remove the solvent, washing with ethanol and water for 3-5 times respectively, and then placing in a vacuum drying oven for drying for 15-20 hours to obtain the 5-hydantoin acetic acid modified polylysine.
Preferably, the mass ratio of the 5-hydantoin acetic acid, the organic solvent, the polylysine, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the 1-hydroxybenzotriazole is 1 (10-15) to (3-5) to 0.5 to 0.3.
Preferably, the organic solvent is selected from one of dichloromethane, ethyl acetate and dimethyl sulfoxide.
Preferably, the preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding polyethylene glycol hydroxy acid and polylactic acid into dioxane, adding concentrated sulfuric acid into the dioxane, carrying out reflux reaction at 170-180 ℃ for 8-10 hours, then carrying out rotary evaporation to remove the dioxane, and adding water for washing until the eluate is close to neutral, thereby obtaining the polyethylene glycol hydroxy acid modified polylactic acid.
Preferably, the mass ratio of the polyethylene glycol hydroxy acid to the polylactic acid to the dioxane to the concentrated sulfuric acid is 1:2 (10-15): 0.3.
Preferably, the preparation method of the sodium alginate-based polycaprolactone copolymer comprises the following steps: adding maleimide terminal group polycaprolactone, allyl hydantoin, food-grade sodium alginate, silver methacrylate, 5-vinyl-2-thiazolamine, an initiator and an emulsifier into a mixed solvent, stirring and reacting for 4-6 hours at 80-90 ℃ in a nitrogen or inert gas atmosphere, and then removing the solvent by rotary evaporation to obtain the polycaprolactone copolymer based on sodium alginate.
Preferably, the maleimide-terminated polycaprolactone is prepared beforehand, the preparation method referring to: zhang, m.j.; liu, h.h.; shao, w.; miao, k.; zhao, y.l. synthesis and properties of multiclearable ampiphilic polymeric compositions and topoothbrik polymeric compositions compatible alteration PEG and PCL grafts, macromolecules,2013,46, 1325-.
Preferably, the mass ratio of the maleimide end group polycaprolactone to the allyl hydantoin to the food-grade sodium alginate to the silver methacrylate to the 5-vinyl-2-thiazolamine to the initiator to the emulsifier to the mixed solvent is 2:1:1:0.5:0.2 (0.03-0.05) to 0.04 (20-25).
Preferably, the initiator is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the emulsifier is one or more selected from sodium dodecyl sulfate salt, sodium dodecyl sulfonate salt, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether and sorbitan fatty acid ester.
Preferably, the mixed solvent is a mixture of N, N-dimethylformamide and water in a mass ratio of 1: 1.
Preferably, the inert gas is selected from one of helium, neon and argon.
Preferably, a method for preparing a surgical suture for medical use comprises the steps of: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 20-30 minutes at the rotating speed of 70-90r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.02-0.05 mm; and then putting the silk thread into medical alcohol for disinfection for 2-3h, and finally carrying out vacuum drying to obtain the medical operation suture.
Preferably, the temperature of the double-screw extruder is 220-250 ℃, and the screw rotating speed is 1100-1300 r/min.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the medical operation suture provided by the invention has the advantages of simple and feasible preparation method, easily available raw materials and low price, and is suitable for large-scale production.
2) The medical operation suture line provided by the invention overcomes the defects of low tensile strength and elongation, poor suture effect, poor biocompatibility, incomplete absorption and easy generation of calculus of more or less traditional operation suture lines in the prior art, and has the advantages of complete absorption, high tensile strength, good biocompatibility, capability of promoting cell growth, sterilization, inflammation diminishing and bleeding stopping.
3) According to the medical surgical suture provided by the invention, the hydrophilicity and the surface wetting degree of the polylactic acid are improved by using the polyethylene glycol hydroxy acid modified polylactic acid, so that the medical surgical suture has better effects of absorbing blood, absorbing moisture and keeping moisture, is favorable for healing of wounds, relieves the pain of patients, reduces the inflammation probability and improves the success rate of surgery; the main chain is copolymerized by maleimide end group polycaprolactone, allyl hydantoin, food grade sodium alginate, silver methacrylate and 5-vinyl-2-thiazolamine, and the synergistic effect is achieved, so that the biocompatibility and the antibacterial property of the suture line are improved, and the broad-spectrum property is achieved; through copolymerization, the proportion of each part is favorably adjusted, so that a more reasonable structure is designed according to the requirement; the food-grade sodium alginate is introduced into a molecular chain in a comonomer form, is more stable and more uniform in dispersion than the food-grade sodium alginate directly added or introduced through ionic bonds, and is beneficial to improving the performance stability of the suture line; the structures of thiazolyl, silver ions, hydantoin and polylysine are synergistic, so that the antibacterial performance of the material can be improved; the cyclodextrin with a special structure is added, so that the comprehensive performance of the suture line is improved; the polylactic acid and the polycaprolactone are added to facilitate biodegradation, so that the use is safe, harmless, sanitary and environment-friendly; the raw materials have synergistic effect, so that the comprehensive performance of the suture is excellent.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The maleimide-terminated polycaprolactone used in the following examples of the invention was prepared in advance, with reference to the preparation method: zhang, m.j.; liu, h.h.; shao, w.; miao, k.; zhao, y.l. synthesis and properties of multiclearable ampiphilic polymeric compositions and topoothbrisk polymeric compositions compatible alteration PEG and PCL grafts, macromolecules,2013,46,1325 and 1336; other raw materials were purchased from the national pharmaceutical group chemical reagents, ltd.
Example 1
A medical operation suture line comprises the following components in parts by mass: 20 parts of 5-hydantoin acetic acid modified polylysine, 10 parts of polyethylene glycol hydroxy acid modified polylactic acid, 45 parts of sodium alginate-based polycaprolactone copolymer, 10 parts of gamma-cyclodextrin and 5 parts of hydroxybutyl methyl cellulose.
The preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 10g of 5-hydantoin acetic acid in 100g of dichloromethane to form a solution, adding 30g of polylysine, 5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 3g of 1-hydroxybenzotriazole into the solution, stirring at 60 ℃ for reaction for 6 hours, then carrying out rotary evaporation to remove the solvent, washing with ethanol and water for 3 times respectively in sequence, and then placing in a vacuum drying oven for drying for 15 hours to obtain the 5-hydantoin acetic acid modified polylysine.
The preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding 10g of polyethylene glycol hydroxy acid and 20g of polylactic acid into 100g of dioxane, adding 3g of concentrated sulfuric acid into the mixture, carrying out reflux reaction at 170 ℃ for 8 hours, carrying out rotary evaporation to remove the dioxane, adding water into the mixture, and washing until the eluate is nearly neutral to obtain the polyethylene glycol hydroxy acid modified polylactic acid.
The preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding 20g of maleimide end group polycaprolactone, 10g of allyl hydantoin, 10g of food-grade sodium alginate, 5g of silver methacrylate, 2g of 5-vinyl-2-thiazolamine, 0.3g of potassium persulfate and 0.4g of sodium dodecyl sulfate into 200g of mixed solvent, stirring and reacting for 4 hours at 80 ℃ in a nitrogen atmosphere, and then carrying out rotary evaporation to remove the solvent, thus obtaining the sodium alginate-based polycaprolactone copolymer.
The mixed solvent is a mixture formed by mixing N, N-dimethylformamide and water according to the mass ratio of 1: 1.
A preparation method of a medical surgical suture comprises the following steps: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 20 minutes at the rotating speed of 70r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.02 mm; and then putting the silk thread into medical alcohol for disinfection for 2 hours, and finally carrying out vacuum drying to obtain the medical operation suture.
The temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 1100 r/min.
Example 2
A medical operation suture line comprises the following components in parts by mass: 23 parts of 5-hydantoin acetic acid modified polylysine, 13 parts of polyethylene glycol hydroxy acid modified polylactic acid, 48 parts of sodium alginate-based polycaprolactone copolymer, 13 parts of gamma-cyclodextrin and 6 parts of hydroxybutyl methyl cellulose.
The preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 10g of 5-hydantoin acetic acid in 115g of ethyl acetate to form a solution, adding 35g of polylysine, 5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 3g of 1-hydroxybenzotriazole into the solution, stirring and reacting at 65 ℃ for 6.5 hours, then performing rotary evaporation to remove the solvent, washing with ethanol and water for 4 times respectively, and placing in a vacuum drying oven for drying for 16 hours to obtain the 5-hydantoin acetic acid modified polylysine.
The preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding 10g of polyethylene glycol hydroxy acid and 20g of polylactic acid into 115g of dioxane, adding 3g of concentrated sulfuric acid into the mixture, carrying out reflux reaction at 173 ℃ for 8.5 hours, then carrying out rotary evaporation to remove the dioxane, adding water into the mixture for washing until the eluate is nearly neutral, and thus obtaining the polyethylene glycol hydroxy acid modified polylactic acid.
The preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding 20g of maleimide end group polycaprolactone, 10g of allyl hydantoin, 10g of food-grade sodium alginate, 5g of silver methacrylate, 2g of 5-vinyl-2-thiazolamine, 0.35g of sodium persulfate and 0.4g of sodium dodecyl sulfonate into 215g of mixed solvent, stirring and reacting for 4.5 hours at 83 ℃ in helium atmosphere, and then removing the solvent by rotary evaporation to obtain the polycaprolactone copolymer based on sodium alginate.
The mixed solvent is a mixture formed by mixing N, N-dimethylformamide and water according to the mass ratio of 1: 1.
A preparation method of a medical surgical suture comprises the following steps: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 23 minutes at the rotating speed of 75r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.03 mm; and then putting the silk thread into medical alcohol for disinfection for 2.3h, and finally carrying out vacuum drying to obtain the medical operation suture.
The temperature of the double-screw extruder is 230 ℃, and the rotating speed of the screw is 1150 r/min.
Example 3
A medical operation suture line comprises the following components in parts by mass: 25 parts of 5-hydantoin acetic acid modified polylysine, 15 parts of polyethylene glycol hydroxy acid modified polylactic acid, 50 parts of sodium alginate-based polycaprolactone copolymer, 15 parts of gamma-cyclodextrin and 7 parts of hydroxybutyl methyl cellulose.
The preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 10g of 5-hydantoin acetic acid in 130g of dimethyl sulfoxide to form a solution, adding 40g of polylysine, 5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 3g of 1-hydroxybenzotriazole into the solution, stirring and reacting for 7 hours at 70 ℃, removing the solvent by rotary evaporation, washing with ethanol and water for 4 times respectively in sequence, and placing in a vacuum drying oven for drying for 17 hours to obtain the 5-hydantoin acetic acid modified polylysine.
The preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding 10g of polyethylene glycol hydroxy acid and 20g of polylactic acid into 135g of dioxane, adding 3g of concentrated sulfuric acid, carrying out reflux reaction at 175 ℃ for 9 hours, carrying out rotary evaporation to remove dioxane, adding water for washing until eluate is nearly neutral, and thus obtaining the polyethylene glycol hydroxy acid modified polylactic acid.
The preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding 20g of maleimide end group polycaprolactone, 10g of allyl hydantoin, 10g of food-grade sodium alginate, 5g of silver methacrylate, 2g of 5-vinyl-2-thiazolamine, 0.4g of ammonium persulfate and 0.4g of fatty alcohol-polyoxyethylene ether into 230g of mixed solvent, stirring and reacting for 5 hours at 85 ℃ in a neon atmosphere, and then removing the solvent by rotary evaporation to obtain the sodium alginate-based polycaprolactone copolymer.
The mixed solvent is a mixture formed by mixing N, N-dimethylformamide and water according to the mass ratio of 1: 1.
A preparation method of a medical surgical suture comprises the following steps: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 25 minutes at the rotating speed of 80r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.04 mm; and then putting the silk thread into medical alcohol for disinfection for 2.5h, and finally carrying out vacuum drying to obtain the medical operation suture.
The temperature of the double-screw extruder is 240 ℃, and the rotating speed of the screw is 1200 r/min.
Example 4
A medical operation suture line comprises the following components in parts by mass: 28 parts of 5-hydantoin acetic acid modified polylysine, 18 parts of polyethylene glycol hydroxy acid modified polylactic acid, 53 parts of sodium alginate-based polycaprolactone copolymer, 18 parts of gamma-cyclodextrin and 9 parts of hydroxybutyl methyl cellulose.
The preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 10g of 5-hydantoin acetic acid in 145g of dichloromethane to form a solution, adding 45g of polylysine, 5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 3g of 1-hydroxybenzotriazole into the solution, stirring and reacting at 78 ℃ for 7.8 hours, then performing rotary evaporation to remove the solvent, washing with ethanol and water for 5 times respectively in sequence, and then placing in a vacuum drying oven to dry for 19 hours to obtain the 5-hydantoin acetic acid modified polylysine.
The preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding 10g of polyethylene glycol hydroxy acid and 20g of polylactic acid into 145g of dioxane, adding 3g of concentrated sulfuric acid into the mixture, carrying out reflux reaction at 177 ℃ for 9.5 hours, then carrying out rotary evaporation to remove the dioxane, adding water into the mixture for washing until the eluate is nearly neutral, and thus obtaining the polyethylene glycol hydroxy acid modified polylactic acid.
The preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding 20g of maleimide end group polycaprolactone, 10g of allyl hydantoin, 10g of food-grade sodium alginate, 5g of silver methacrylate, 2g of 5-vinyl-2-thiazolamine, 0.45g of initiator and 0.4g of emulsifier into 245g of mixed solvent, stirring and reacting for 5.5 hours at 88 ℃ in argon atmosphere, and then carrying out rotary evaporation to remove the solvent, thus obtaining the sodium alginate-based polycaprolactone copolymer.
The initiator is a mixture formed by mixing potassium persulfate, sodium persulfate and ammonium persulfate according to the mass ratio of 2:3: 1.
The emulsifier is a mixture formed by mixing sodium dodecyl sulfate, sodium dodecyl sulfonate, fatty alcohol-polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether and sorbitan fatty acid ester according to the mass ratio of 1:1:2:1: 3.
The mixed solvent is a mixture formed by mixing N, N-dimethylformamide and water according to the mass ratio of 1: 1.
A preparation method of a medical surgical suture comprises the following steps: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 28 minutes at the rotating speed of 88r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.045 mm; and then putting the silk thread into medical alcohol for disinfection for 2.8h, and finally carrying out vacuum drying to obtain the medical operation suture.
The temperature of the double-screw extruder is 245 ℃, and the rotating speed of the screw is 1250 r/min.
Example 5
A medical operation suture line comprises the following components in parts by mass: 30 parts of 5-hydantoin acetic acid modified polylysine, 20 parts of polyethylene glycol hydroxy acid modified polylactic acid, 55 parts of sodium alginate-based polycaprolactone copolymer, 20 parts of gamma-cyclodextrin and 10 parts of hydroxybutyl methyl cellulose.
The preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 10g of 5-hydantoin acetic acid in 150g of dimethyl sulfoxide to form a solution, adding 50g of polylysine, 5g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 3g of 1-hydroxybenzotriazole into the solution, stirring at 80 ℃ for reacting for 8 hours, then performing rotary evaporation to remove the solvent, washing with ethanol and water for 5 times respectively in sequence, and then placing in a vacuum drying oven for drying for 20 hours to obtain the 5-hydantoin acetic acid modified polylysine.
The preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding 10g of polyethylene glycol hydroxy acid and 20g of polylactic acid into 150g of dioxane, adding 3g of concentrated sulfuric acid, carrying out reflux reaction at 180 ℃ for 10 hours, carrying out rotary evaporation to remove dioxane, adding water for washing until eluate is nearly neutral, and thus obtaining the polyethylene glycol hydroxy acid modified polylactic acid.
The preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding 20g of maleimide end group polycaprolactone, 10g of allyl hydantoin, 10g of food-grade sodium alginate, 5g of silver methacrylate, 2g of 5-vinyl-2-thiazolamine, 0.5g of sodium persulfate and 0.4g of sorbitan fatty acid ester into 250g of mixed solvent, stirring and reacting for 6 hours at 90 ℃ in a nitrogen atmosphere, and then carrying out rotary evaporation to remove the solvent, thus obtaining the polycaprolactone copolymer based on the sodium alginate.
The mixed solvent is a mixture formed by mixing N, N-dimethylformamide and water according to the mass ratio of 1: 1.
A preparation method of a medical surgical suture comprises the following steps: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 30 minutes at the rotating speed of 90r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.05 mm; and then putting the silk thread into medical alcohol for disinfection for 3h, and finally carrying out vacuum drying to obtain the medical operation suture.
The temperature of the double-screw extruder is 250 ℃, and the rotating speed of the screw is 1300 r/min.
Comparative example
An absorbable surgical suture is prepared according to the formula and the preparation method of the embodiment I of the Chinese invention patent CN 105133088B.
The medical operation suture prepared in the embodiments 1 to 5 of the invention and the operation suture of the comparative example are subjected to performance test, and the test standards and results are shown in table 1.
TABLE 1
Figure BDA0001809229990000131
Figure BDA0001809229990000141
As can be seen from Table 1, the medical surgical suture prepared by the embodiment of the invention has more excellent mechanical property, biocompatibility and bactericidal and antibacterial properties, and has good absorbability.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. The medical operation suture is characterized by comprising the following components in parts by mass: 20-30 parts of 5-hydantoin acetic acid modified polylysine, 10-20 parts of polyethylene glycol hydroxy acid modified polylactic acid, 45-55 parts of sodium alginate-based polycaprolactone copolymer, 10-20 parts of gamma-cyclodextrin and 5-10 parts of hydroxybutyl methyl cellulose;
the preparation method of the 5-hydantoin acetic acid modified polylysine comprises the following steps: dissolving 5-hydantoin acetic acid in an organic solvent to form a solution, adding polylysine, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1-hydroxybenzotriazole into the solution, stirring and reacting at 60-80 ℃ for 6-8 hours, then performing rotary evaporation to remove the solvent, washing with ethanol and water for 3-5 times respectively in sequence, and then placing in a vacuum drying oven for drying for 15-20 hours to obtain 5-hydantoin acetic acid modified polylysine;
the preparation method of the polyethylene glycol hydroxy acid modified polylactic acid comprises the following steps: adding polyethylene glycol hydroxy acid and polylactic acid into dioxane, adding concentrated sulfuric acid into the dioxane, carrying out reflux reaction at the temperature of 170-180 ℃ for 8-10 hours, then carrying out rotary evaporation to remove the dioxane, and adding water for washing until the eluate is close to neutral to obtain polyethylene glycol hydroxy acid modified polylactic acid;
the preparation method of the polycaprolactone copolymer based on sodium alginate comprises the following steps: adding maleimide terminal group polycaprolactone, allyl hydantoin, food-grade sodium alginate, silver methacrylate, 5-vinyl-2-thiazolamine, an initiator and an emulsifier into a mixed solvent, stirring and reacting for 4-6 hours at 80-90 ℃ in a nitrogen or inert gas atmosphere, and then removing the solvent by rotary evaporation to obtain the polycaprolactone copolymer based on sodium alginate.
2. The medical surgical suture of claim 1, wherein the organic solvent is one selected from dichloromethane, ethyl acetate, and dimethylsulfoxide.
3. The medical surgical suture of claim 1, wherein the initiator is selected from one or more of potassium persulfate, sodium persulfate, and ammonium persulfate.
4. The medical surgical suture of claim 1, wherein the emulsifier is one or more selected from sodium dodecyl sulfate, sodium dodecyl sulfonate, fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, and sorbitan fatty acid ester.
5. The medical surgical suture according to claim 1, wherein the mixed solvent is a mixture of N, N-dimethylformamide and water in a mass ratio of 1: 1.
6. The medical surgical suture according to any one of claims 1 to 5, wherein the method for preparing the medical surgical suture comprises the steps of: adding the raw materials into a high-speed mixer according to the mass ratio, and mixing for 20-30 minutes at the rotating speed of 70-90r/min to obtain a mixture; then feeding the mixture into a double-screw extruder for granulation, cooling, drying and cutting to obtain master batches; then melting and spinning the master batch into a silk thread with the diameter of 0.02-0.05 mm; and then putting the silk thread into medical alcohol for disinfection for 2-3h, and finally carrying out vacuum drying to obtain the medical operation suture.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004238745A (en) * 2003-02-04 2004-08-26 Teijin Ltd Yarn composed of in vivo bioabsorbable polymer
CN101700418A (en) * 2009-10-30 2010-05-05 上海锦葵医疗器械有限公司 Developed degradable polymer composites and preparation method thereof
CN101721739A (en) * 2008-10-10 2010-06-09 陈东 Polymer composite fiber surgical suture line capable of sustaining and controlling release of therapeutic medicaments and preparation method thereof
CN105079869A (en) * 2015-08-11 2015-11-25 安徽省康宁医疗用品有限公司 Absorbable medical suture line with good mechanical performance
CN105561376A (en) * 2015-12-17 2016-05-11 张德信 Medical suture line for promoting wound healing and preparation method thereof
WO2017156531A1 (en) * 2016-03-11 2017-09-14 The Johns Hopkins University Ultra-thin, high strength, drug-loaded sutures and coatings thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004238745A (en) * 2003-02-04 2004-08-26 Teijin Ltd Yarn composed of in vivo bioabsorbable polymer
CN101721739A (en) * 2008-10-10 2010-06-09 陈东 Polymer composite fiber surgical suture line capable of sustaining and controlling release of therapeutic medicaments and preparation method thereof
CN101700418A (en) * 2009-10-30 2010-05-05 上海锦葵医疗器械有限公司 Developed degradable polymer composites and preparation method thereof
CN105079869A (en) * 2015-08-11 2015-11-25 安徽省康宁医疗用品有限公司 Absorbable medical suture line with good mechanical performance
CN105561376A (en) * 2015-12-17 2016-05-11 张德信 Medical suture line for promoting wound healing and preparation method thereof
WO2017156531A1 (en) * 2016-03-11 2017-09-14 The Johns Hopkins University Ultra-thin, high strength, drug-loaded sutures and coatings thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Antimicrobial Treatment of Nylon;JIAN LIN 等;《JOURNAL OF APPLIED POLYMER SCIENCE》;20011231;第81卷(第4期);第943-947页 *
海因改性N-季铵化壳聚糖衍生物的合成及其抗菌性能;陈燕燕;《化工进展》;20151231;第34卷(第1期);第188-192、233页 *

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