CN117618624A - Medical polymer bandage convenient for biodegradation and preparation method thereof - Google Patents
Medical polymer bandage convenient for biodegradation and preparation method thereof Download PDFInfo
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- CN117618624A CN117618624A CN202311515147.XA CN202311515147A CN117618624A CN 117618624 A CN117618624 A CN 117618624A CN 202311515147 A CN202311515147 A CN 202311515147A CN 117618624 A CN117618624 A CN 117618624A
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- polylactic acid
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- biodegradation
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- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006065 biodegradation reaction Methods 0.000 title claims description 25
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 95
- 239000004626 polylactic acid Substances 0.000 claims abstract description 95
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 51
- 229920001661 Chitosan Polymers 0.000 claims abstract description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 108
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 44
- 239000007795 chemical reaction product Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 22
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 15
- KUBWXQUHENSKGC-UHFFFAOYSA-N 2-chloroacetic acid;ethanol Chemical compound CCO.OC(=O)CCl KUBWXQUHENSKGC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- 229940106681 chloroacetic acid Drugs 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 2
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 6
- 230000000840 anti-viral effect Effects 0.000 abstract description 5
- 230000021164 cell adhesion Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 239000002906 medical waste Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000001266 bandaging Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically 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
- A61L2300/208—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/23—Carbohydrates
- A61L2300/232—Monosaccharides, disaccharides, polysaccharides, lipopolysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—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
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—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
- A61L2300/45—Mixtures of two or more drugs, e.g. synergistic mixtures
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Hematology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Medical Uses (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the field of medical supplies, in particular to a medical polymer bandage convenient to biodegrade and a preparation method thereof, which solve the problems that the surface of the existing PLA medical polymer bandage lacks active groups, has poor adhesion capability to cells, has poor antibacterial and bacteriostatic properties and has insufficient antibacterial and antiviral effects; the antibacterial skin-friendly polylactic acid is prepared by reacting carboxyl modified chitosan, epoxy quaternary ammonium salt and hydrophilic modified polylactic acid, and the carboxyl modified chitosan and the epoxy quaternary ammonium salt are used for modifying the hydrophilic modified polylactic acid, so that the three are connected in a chemical bond mode, the crosslinking degree of the three is improved, the mechanical property of the three is improved, active groups are increased, the cell adhesion capacity is improved, the antibacterial and antibacterial properties of the medical high-molecular bandage are improved, the antibacterial and antiviral effects are excellent, the biodegradability is excellent, and great contribution is made to environmental protection.
Description
Technical Field
The invention relates to the field of medical supplies, in particular to a medical polymer bandage convenient to biodegrade and a preparation method thereof.
Background
The bandage is a common medical product for bandaging wounds and affected parts, and is mainly made of gauze, cotton cloth or synthetic fibers, and the disposable medical product of the bandage can be burnt, buried or piled in open air as medical waste after the use is completed. The incineration of medical waste can generate a large amount of harmful gas to pollute the atmosphere, and the direct landfill can influence the stability of soil environment because of the low degradation rate, thereby threatening the survival of animals and microorganisms in the soil, and the open-air stacking can cause the waste of land resources.
PLA is a green polymer material prepared by grains, has the advantages of biocompatibility, natural degradability and the like, can be degraded into carbon dioxide and water by microorganisms in the natural world, and based on the advantages, a non-woven material taking PLA as a main body is one of materials for preparing medical polymer bandages, but the PLA non-woven material contains a large amount of ester groups, so that the PLA non-woven material shows high hydrophobicity, lacks active groups on the surface, has poor cell adhesion capability, has poor antibacterial and bacteriostatic properties and insufficient antibacterial and antiviral effects, and limits the application of PLA in the field of medical and health.
How to improve the existing PLA medical polymer bandages that the surface lacks active groups, has poor cell adhesion capability and poor antibacterial and bacteriostatic properties, and the insufficient antibacterial and antiviral effects are key of the invention, so that a medical polymer bandage convenient for biodegradation and a preparation method thereof are needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a medical polymer bandage convenient for biodegradation and a preparation method thereof: the medical polymer bandage convenient for biodegradation is obtained by uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture, adding the mixture into an extruder for melt extrusion, spinning through a spinneret plate to form a nonwoven material, and then cutting and rolling, so that the problems that the surface of the existing PLA medical polymer bandage lacks active groups, the cell adhesion capability is poor, the antibacterial and antibacterial properties are poor, and the antibacterial and antiviral effects are insufficient are solved.
The aim of the invention can be achieved by the following technical scheme:
a medical polymer bandage convenient for biodegradation comprises the following components in parts by weight:
50-60 parts of antibacterial skin-friendly polylactic acid, 8-10 parts of nano titanium dioxide, 2-6 parts of talcum powder, 1-5 parts of silane coupling agent and 10-15 parts of absolute ethyl alcohol.
As a further scheme of the invention: the antibacterial skin-friendly polylactic acid is prepared by the following steps:
step I: adding polylactic acid and 1, 4-dioxane into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 25-45min under the conditions of 60-65 ℃ and stirring speed of 400-500r/min, then adding 2-hydroxyethylamine solution dropwise while stirring, controlling the dropping speed to be 1-2 drops/s, continuing stirring and reacting for 2-3h after the dripping is finished, cooling a reaction product to room temperature after the reaction is finished, rotationally evaporating to remove a solvent, washing for 3-5 times with distilled water, then placing in a vacuum drying box, and drying for 3-5h under the conditions of 60-65 ℃ to obtain hydrophilic modified polylactic acid;
step II: adding sodium hydroxide and deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at a temperature of 25-30 ℃ and a stirring rate of 400-500r/min for reacting for 15-20min, adding chitosan, continuously stirring for reacting for 2-3h, adding chloroacetic acid-ethanol solution dropwise while stirring, controlling the dropping rate to be 1-2 drops/s, continuously stirring for reacting for 30-40min after the dropping is finished, heating to 60-65 ℃ for continuously stirring for reacting for 4-5h, cooling a reaction product to room temperature after the reaction is finished, adjusting the pH value to 7-7.5 with acetic acid solution, performing vacuum suction filtration, washing a filter cake with ethanol solution for 3-5 times, then placing the filter cake in a vacuum drying box, and drying at a temperature of 50-55 ℃ for 8-10h to obtain carboxyl modified chitosan;
step III: adding epichlorohydrin and anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 15-20min under the conditions of the temperature of-5-0 ℃ and the stirring rate of 400-500r/min, then adding triethylamine dropwise while stirring, controlling the dropping rate to be 1-2 drops/s, heating to 25-30 ℃ after the dropping is finished, continuing stirring and reacting for 2.5-3h, vacuum filtering a reaction product after the reaction is finished, washing a filter cake with acetone for 3-5 times, then placing in a vacuum drying box, and drying for 4-5h under the conditions of the temperature of 50-55 ℃ to obtain epoxy quaternary ammonium salt;
step IV: adding hydrophilic modified polylactic acid, carboxyl modified chitosan, p-toluenesulfonic acid, deionized water and methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 30-40min under the conditions of 25-30 ℃ and stirring speed of 400-500r/min, adding epoxy quaternary ammonium salt, continuously stirring and reacting for 20-25min, heating to 60-65 ℃ and continuously stirring and reacting for 20-30h, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into absolute ethyl alcohol, centrifuging, placing the centrifuged product into a vacuum drying box, and drying for 8-10h under the conditions of 50-55 ℃ to obtain the antibacterial skin-friendly polylactic acid.
As a further scheme of the invention: the dosage ratio of the polylactic acid to the 1, 4-dioxane to the 2-hydroxyethylamine solution in the step I is 3g:55-65mL:8-12mL, the relative molecular weight of the polylactic acid is 10 5 The mass fraction of the 2-hydroxyethylamine solution is 10-15%.
As a further scheme of the invention: the dosage ratio of the sodium hydroxide, deionized water, chitosan and chloroacetic acid-ethanol solution in the step II is 4-5g:20-25mL:2g:10-15mL, wherein the viscosity of the chitosan is 20-50 mPa.s, and the chloroacetic acid-ethanol solution is prepared from 13-15g of chloroacetic acid: 100mL of the solution formed by dissolving the solution in absolute ethyl alcohol, the volume fraction of the acetic acid solution is 15-20%, and the volume fraction of the ethanol solution is 70-75%.
As a further scheme of the invention: the dosage ratio of the epichlorohydrin to the anhydrous tetrahydrofuran to the triethylamine in the step III is 0.3 to 0.35mol:50-55mL:0.1mol.
As a further scheme of the invention: the dosage ratio of the hydrophilic modified polylactic acid to the carboxyl modified chitosan to the p-toluenesulfonic acid to the deionized water to the dichloromethane to the epoxy quaternary ammonium salt in the step IV is 10g:1-10g:0.01-0.03g:80-100mL:80-100mL:0.1-0.5g.
As a further scheme of the invention: a preparation method of medical polymer bandages convenient for biodegradation comprises the following steps:
step one: weighing 50-60 parts of antibacterial skin-friendly polylactic acid, 8-10 parts of nano titanium dioxide, 2-6 parts of talcum powder, 1-5 parts of silane coupling agent and 10-15 parts of absolute ethyl alcohol according to parts by weight for standby;
step two: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step three: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 40-60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
As a further scheme of the invention: the silane coupling agent is one of a silane coupling agent KH-550, a silane coupling agent KH-792 and a silane coupling agent KH-560.
The invention has the beneficial effects that:
according to the medical polymer bandage convenient to biodegrade and the preparation method thereof, antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol are uniformly mixed to obtain a mixture, the mixture is added into an extruder to be melted and extruded, and is subjected to spinneret spinning to form a nonwoven material, and then the nonwoven material is cut and rolled to obtain the medical polymer bandage convenient to biodegrade; in the process of preparing the medical polymer bandage, firstly, a bacteriostatic skin-friendly polylactic acid is prepared, firstly, 2-hydroxyethylamine is used for modifying the polylactic acid, the 2-hydroxyethylamine has hydrophilic amino groups and hydrophilic hydroxyl groups, the amino groups of ethanolamine are used for attacking ester groups in the polylactic acid to form amide bonds by means of ammonolysis reaction, hydrophilic hydroxyl groups are introduced to enhance the hydrophilicity of the polylactic acid, so that hydrophilic modified polylactic acid is obtained, then sodium hydroxide and chloroacetic acid are used for modifying chitosan, and the chitosan generates living organisms under alkaline conditionsSex center, this will destroy its hydrogen bond to a certain extent, thus provide more reaction sites for chloroacetic acid, active center generated after chitosan alkalization will undergo carboxymethylation nucleophilic substitution reaction with chloroacetic acid, the reaction will undergo substitution reaction at three reaction sites, respectively C 2 Amino group and C 3 、C 6 The carboxyl group on the carboxyl modified chitosan is subjected to esterification reaction with the hydroxyl group on the hydrophilic modified polylactic acid, the epoxy group on the epoxy quaternary ammonium salt can be subjected to reaction with the carboxyl group on the carboxyl modified chitosan or the hydroxyl group on the hydrophilic modified polylactic acid, and finally, the three are connected in a chemical bond mode, so that the crosslinking degree of the carboxyl modified polylactic acid is improved, the mechanical property and the hydrophilic property of the hydrophilic modified polylactic acid are improved, the cell adhesion capability is improved, the application range of PLA in the medical and sanitary field is enlarged, the antibacterial property of the hydrophilic modified polylactic acid is improved, the infection of bacteria on wounds is prevented, and the medical and anti-bacterial antibacterial medical bandage is endowed with good biological degradation effect under the effect of the carboxyl modified polylactic acid.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of a method for preparing a medical polymer bandage of the present invention for facilitating biodegradation.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
referring to fig. 1, the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 55mL of 1, 4-dioxane into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 25min at the temperature of 60 ℃ under the condition of the stirring rate of 400r/min, then adding 8mL of 2-hydroxy ethylamine solution with the mass fraction of 10% dropwise while stirring, controlling the dropping rate to be 1 drop/s, continuing stirring and reacting for 2h after the dripping is finished, cooling a reaction product to room temperature after the reaction is finished, rotationally evaporating to remove a solvent, washing with distilled water for 3 times, then placing in a vacuum drying box, and drying for 3h at the temperature of 60 ℃ to obtain the hydrophilic modified polylactic acid;
step II: adding 4g of sodium hydroxide and 20mL of deionized water into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 15min at the temperature of 25 ℃ and the stirring rate of 400r/min, adding 2g of chitosan with the viscosity of 20 mPas, continuously stirring and reacting for 2h, and adding 10mL of chloroacetic acid dropwise while stirring according to 13g:100mL of chloroacetic acid-ethanol solution formed by dissolving the mixture in absolute ethanol, controlling the dropping speed to be 1 drop/s, continuing to stir and react for 30min after the dropping is finished, then heating to 60 ℃, continuing to stir and react for 4h, cooling the reaction product to room temperature after the reaction is finished, then adjusting the pH value to 7 by using acetic acid solution with the volume fraction of 15%, then carrying out vacuum filtration, washing a filter cake by using ethanol solution with the volume fraction of 70% for 3 times, then placing the filter cake in a vacuum drying box, and drying for 8h at the temperature of 50 ℃ to obtain carboxyl modified chitosan;
step III: adding 0.3 mol of epichlorohydrin and 50mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 15min under the condition that the temperature is-5 ℃ and the stirring speed is 400r/min, then adding 0.1mol of triethylamine dropwise while stirring, controlling the dropping speed to be 1 drop/s, continuously stirring and reacting for 2.5h under the condition that the temperature is raised to 25 ℃ after the dropping is finished, vacuum filtering a reaction product after the reaction is finished, washing a filter cake with acetone for 3 times, and then placing in a vacuum drying box, and drying for 4h under the condition that the temperature is 50 ℃ to obtain epoxy quaternary ammonium salt;
step IV: adding 10g of hydrophilic modified polylactic acid, 1g of carboxyl modified chitosan, 0.01g of p-toluenesulfonic acid, 80mL of deionized water and 80mL of methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 30min at the temperature of 25 ℃ and the stirring rate of 400r/min, adding 0.1g of epoxy quaternary ammonium salt, continuing stirring and reacting for 20min, heating to 60 ℃ and continuing stirring and reacting for 20h, cooling the reaction product to room temperature after the reaction is finished, adding the reaction product into absolute ethyl alcohol, centrifuging, placing the centrifugal product into a vacuum drying oven, and drying for 8h at the temperature of 50 ℃ to obtain antibacterial skin-friendly polylactic acid;
step V: weighing 50 parts of antibacterial skin-friendly polylactic acid, 8 parts of nano titanium dioxide, 2 parts of talcum powder, 1 part of silane coupling agent and 10 parts of absolute ethyl alcohol according to parts by weight for standby; the silane coupling agent is a silane coupling agent KH-550;
step VI: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step VII: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 40g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 2:
referring to fig. 1, the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 60ml1, 4-dioxane into AnStirring and reacting for 35min at 62 ℃ under the condition of stirring speed of 450r/min in a three-neck flask with a stirrer, a thermometer and a constant-pressure dropping funnel, then dropwise adding 10mL of 2-hydroxyethylamine solution with the mass fraction of 12% while stirring, controlling the dropping speed to be 1 drop/s, continuing stirring and reacting for 2.5h after the dropping is finished, cooling a reaction product to room temperature after the reaction is finished, rotationally evaporating to remove a solvent, washing for 4 times with distilled water, then placing in a vacuum drying box, and drying for 4h under the condition of 62 ℃ to obtain hydrophilic modified polylactic acid;
step II: 4.5g of sodium hydroxide and 22mL of deionized water are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at the temperature of 28 ℃ and the stirring rate of 450r/min for reaction for 18min, then 2g of chitosan with the viscosity of 35 mPas is added for continuous stirring reaction for 2.5h, and then 12mL of chloroacetic acid is added dropwise while stirring according to 14g:100mL of chloroacetic acid-ethanol solution formed by dissolving the mixture in absolute ethanol is controlled to have the dropping speed of 2 drops/s, stirring is continued for reaction for 35min after the dropping is finished, then stirring is continued for reaction for 4.5h under the condition of heating to 62 ℃, the reaction product is cooled to room temperature after the reaction is finished, then the pH value is regulated to 7.3 by using acetic acid solution with the volume fraction of 18%, then vacuum filtration is carried out, a filter cake is washed for 4 times by using ethanol solution with the volume fraction of 72%, and then the filter cake is placed in a vacuum drying box and dried for 9h under the condition of 52 ℃ to obtain carboxyl modified chitosan;
step III: adding 0.32 mol of epichlorohydrin and 52mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 18min under the condition that the temperature is-3 ℃ and the stirring speed is 450r/min, then adding 0.1mol of triethylamine dropwise while stirring, controlling the dropping speed to be 1 drop/s, continuously stirring and reacting for 2.8h under the condition that the temperature is raised to 28 ℃ after the dropping is finished, vacuum filtering a reaction product after the reaction is finished, washing a filter cake with acetone for 4 times, and then placing in a vacuum drying box, and drying for 4.5h under the condition that the temperature is 52 ℃ to obtain epoxy quaternary ammonium salt;
step IV: adding 10g of hydrophilic modified polylactic acid, 5.5g of carboxyl modified chitosan, 0.02g of p-toluenesulfonic acid, 90mL of deionized water and 90mL of dichloromethane into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 35min at the temperature of 28 ℃ and the stirring rate of 450r/min, adding 0.3g of epoxy quaternary ammonium salt, continuously stirring and reacting for 22min, heating to 62 ℃ and continuously stirring and reacting for 25h, cooling the reaction product to room temperature after the reaction is finished, adding the reaction product into absolute ethyl alcohol, centrifuging, placing the centrifugal product into a vacuum drying oven, and drying for 9h at the temperature of 52 ℃ to obtain antibacterial skin-friendly polylactic acid;
step V: 55 parts of antibacterial skin-friendly polylactic acid, 9 parts of nano titanium dioxide, 4 parts of talcum powder, 3 parts of silane coupling agent and 12 parts of absolute ethyl alcohol are weighed according to parts by weight for standby; the silane coupling agent is a silane coupling agent KH-792;
step VI: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step VII: adding the mixture into an extruder for melt extrusion, and spraying through a spinneret plate to form a fiber with the surface density of 50g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 3:
referring to fig. 1, the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 65mL of 1, 4-dioxane into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 45min at the temperature of 65 ℃ and the stirring rate of 500r/min, then adding 12mL of 2-hydroxy ethylamine solution with the mass fraction of 15% dropwise while stirring, controlling the dropping rate to be 2 drops/s, continuing stirring and reacting for 3h after the dripping is finished, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, washing with distilled water for 5 times, then placing in a vacuum drying box, and drying for 5h at the temperature of 65 ℃ to obtain the hydrophilic modified polylactic acid;
step II: 5g of sodium hydroxide and 25mL of deionized water are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring is carried out for 20min at the temperature of 30 ℃ and the stirring rate of 500r/min, then 2g of chitosan with the viscosity of 50 mPas is added for continuous stirring reaction for 3h, and then 15mL of chloroacetic acid is added dropwise while stirring according to 15g:100mL of chloroacetic acid-ethanol solution formed by dissolving the mixture in absolute ethanol, controlling the dropping speed to be 2 drops/s, continuing to stir and react for 40min after the dropping is finished, then heating to 65 ℃ and continuing to stir and react for 5h, cooling the reaction product to room temperature after the reaction is finished, then regulating the pH value to 7.5 by using 20% of acetic acid solution, then carrying out vacuum suction filtration, washing a filter cake for 5 times by using 75% of ethanol solution, then placing the filter cake in a vacuum drying oven, and drying for 10h at the temperature of 55 ℃ to obtain carboxyl modified chitosan;
step III: adding 0.35mol of epichlorohydrin and 55mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring and reacting for 20min under the condition that the temperature is 0 ℃ and the stirring speed is 500r/min, then adding 0.1mol of triethylamine dropwise while stirring, controlling the dropping speed to be 2 drops/s, continuously stirring and reacting for 3h under the condition that the temperature is raised to 30 ℃ after the dropping is finished, vacuum-filtering a reaction product after the reaction is finished, washing a filter cake with acetone for 5 times, and then placing in a vacuum drying oven, and drying for 5h under the condition that the temperature is 55 ℃ to obtain epoxy quaternary ammonium salt;
step IV: adding 10g of hydrophilic modified polylactic acid, 10g of carboxyl modified chitosan, 0.03g of p-toluenesulfonic acid, 100mL of deionized water and 100mL of methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 40min at the temperature of 30 ℃ and the stirring rate of 500r/min, adding 0.5g of epoxy quaternary ammonium salt, continuing stirring and reacting for 25min, heating to 65 ℃ and continuing stirring and reacting for 30h, cooling the reaction product to room temperature after the reaction is finished, adding into absolute ethyl alcohol, centrifuging, placing the centrifugal product into a vacuum drying oven, and drying for 10h at the temperature of 55 ℃ to obtain antibacterial skin-friendly polylactic acid;
step V: weighing 60 parts of antibacterial skin-friendly polylactic acid, 10 parts of nano titanium dioxide, 6 parts of talcum powder, 5 parts of silane coupling agent and 15 parts of absolute ethyl alcohol according to parts by weight for standby; the silane coupling agent is a silane coupling agent KH-560;
step VI: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step VII: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 4:
the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: weighing the components with relative molecular weight of 10 according to weight parts 5 60 parts of polylactic acid, 10 parts of nano titanium dioxide, 6 parts of talcum powder, 5 parts of silane coupling agent and 15 parts of absolute ethyl alcohol for standby; the silane coupling agent is a silane coupling agent KH-560;
step II: uniformly mixing polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step III: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 5:
the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 65mL of 1, 4-dioxane into a three-neck flask with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 45min at 65 ℃ and a stirring rate of 500r/min, and then dropwise adding 12mL of 2-hydroxyethylamine with a mass fraction of 15% while stirringControlling the dropping speed of the solution to be 2 drops/s, continuing stirring and reacting for 3 hours after the dropping, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing with distilled water for 5 times, and then placing in a vacuum drying oven and drying for 5 hours at the temperature of 65 ℃ to obtain the hydrophilic modified polylactic acid;
step II: weighing 60 parts of hydrophilic modified polylactic acid, 10 parts of nano titanium dioxide, 6 parts of talcum powder, 5 parts of silane coupling agent and 15 parts of absolute ethyl alcohol according to parts by weight for later use; the silane coupling agent is a silane coupling agent KH-560;
step III: uniformly mixing hydrophilic modified polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step IV: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 6:
the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 65mL of 1, 4-dioxane into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 45min at the temperature of 65 ℃ and the stirring rate of 500r/min, then adding 12mL of 2-hydroxy ethylamine solution with the mass fraction of 15% dropwise while stirring, controlling the dropping rate to be 2 drops/s, continuing stirring and reacting for 3h after the dripping is finished, cooling the reaction product to room temperature after the reaction is finished, rotationally evaporating to remove the solvent, washing with distilled water for 5 times, then placing in a vacuum drying box, and drying for 5h at the temperature of 65 ℃ to obtain the hydrophilic modified polylactic acid;
step II: adding 0.35mol of epichlorohydrin and 55mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring and reacting for 20min under the condition that the temperature is 0 ℃ and the stirring speed is 500r/min, then adding 0.1mol of triethylamine dropwise while stirring, controlling the dropping speed to be 2 drops/s, continuously stirring and reacting for 3h under the condition that the temperature is raised to 30 ℃ after the dropping is finished, vacuum-filtering a reaction product after the reaction is finished, washing a filter cake with acetone for 5 times, and then placing in a vacuum drying oven, and drying for 5h under the condition that the temperature is 55 ℃ to obtain epoxy quaternary ammonium salt;
step III: adding 10g of hydrophilic modified polylactic acid, 100mL of deionized water and 100mL of methylene dichloride into a three-neck flask with a stirrer and a thermometer, stirring and reacting for 40min at the temperature of 30 ℃ and the stirring speed of 500r/min, adding 0.5g of epoxy quaternary ammonium salt, continuously stirring and reacting for 25min, heating to 65 ℃ and continuously stirring and reacting for 30h, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into absolute ethyl alcohol, centrifuging, placing the centrifuged product in a vacuum drying oven, and drying for 10h at the temperature of 55 ℃ to obtain bacteriostatic skin-friendly polylactic acid;
step IV: weighing 60 parts of antibacterial skin-friendly polylactic acid, 10 parts of nano titanium dioxide, 6 parts of talcum powder, 5 parts of silane coupling agent and 15 parts of absolute ethyl alcohol according to parts by weight for standby; the silane coupling agent is a silane coupling agent KH-560;
step V: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step VI: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
Example 7:
the embodiment is a preparation method of antibacterial skin-friendly polylactic acid, which comprises the following steps:
step I: 3g of the polymer having a relative molecular mass of 10 5 Adding polylactic acid and 65mL1, 4-dioxane into a three-neck flask with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 45min at 65 ℃ and stirring speed of 500r/min, and then dropwise adding 12mL while stirring2-hydroxy ethylamine solution with the fraction of 15 percent is controlled to have the dropping rate of 2 drops/s, the reaction is continuously stirred for 3 hours after the dropping, the reaction product is cooled to the room temperature after the reaction is finished, then the solvent is removed by rotary evaporation, the solution is washed for 5 times by distilled water, and then the solution is placed in a vacuum drying oven and dried for 5 hours at the temperature of 65 ℃ to obtain the hydrophilic modified polylactic acid;
step II: 5g of sodium hydroxide and 25mL of deionized water are added into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring is carried out for 20min at the temperature of 30 ℃ and the stirring rate of 500r/min, then 2g of chitosan with the viscosity of 50 mPas is added for continuous stirring reaction for 3h, and then 15mL of chloroacetic acid is added dropwise while stirring according to 15g:100mL of chloroacetic acid-ethanol solution formed by dissolving the mixture in absolute ethanol, controlling the dropping speed to be 2 drops/s, continuing to stir and react for 40min after the dropping is finished, then heating to 65 ℃ and continuing to stir and react for 5h, cooling the reaction product to room temperature after the reaction is finished, then regulating the pH value to 7.5 by using 20% of acetic acid solution, then carrying out vacuum suction filtration, washing a filter cake for 5 times by using 75% of ethanol solution, then placing the filter cake in a vacuum drying oven, and drying for 10h at the temperature of 55 ℃ to obtain carboxyl modified chitosan;
step III: adding 10g of hydrophilic modified polylactic acid, 10g of carboxyl modified chitosan, 0.03g of p-toluenesulfonic acid, 100mL of deionized water and 100mL of methylene dichloride into a three-neck flask provided with a stirrer and a thermometer, stirring and reacting for 40min under the condition of 30 ℃ and 500r/min of stirring rate, heating to 65 ℃ and continuing stirring and reacting for 30h, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into absolute ethyl alcohol, centrifuging, placing the centrifuged product into a vacuum drying oven, and drying for 10h under the condition of 55 ℃ to obtain bacteriostatic skin-friendly polylactic acid;
step IV: weighing 60 parts of antibacterial skin-friendly polylactic acid, 10 parts of nano titanium dioxide, 6 parts of talcum powder, 5 parts of silane coupling agent and 15 parts of absolute ethyl alcohol according to parts by weight for standby; the silane coupling agent is a silane coupling agent KH-560;
step V: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step VI: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
The properties of the medical polymer bandages of examples 1 to 7, which are convenient for biodegradation, were tested, and the test results are shown in the following table:
the bacteriostasis rate adopts escherichia coli as a test strain, the degradation rate adopts the steps of weighing, burying the strain into soil, sampling after 60 days, and recording the mass loss.
Referring to the above table data, according to the comparison between examples 1 to 7, it can be known that the degradation rate of the hydrophilically modified polylactic acid is improved after hydrophilization modification, and the degradation performance of the hydrophilically modified polylactic acid can be further improved by adding the carboxyl modified chitosan, and meanwhile, the mechanical performance and the antibacterial performance of the hydrophilically modified polylactic acid are greatly improved, and the antibacterial performance of the hydrophilically modified polylactic acid is improved more obviously by adding the epoxy quaternary ammonium salt, so that the medical polymer bandage which is convenient to biodegrade and is prepared by hydrophilically modifying the polylactic acid, adding the carboxyl modified chitosan and adding the epoxy quaternary ammonium salt is excellent in mechanical performance, antibacterial performance and degradation performance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. The medical polymer bandage convenient for biodegradation is characterized by comprising the following components in parts by weight:
50-60 parts of antibacterial skin-friendly polylactic acid, 8-10 parts of nano titanium dioxide, 2-6 parts of talcum powder, 1-5 parts of silane coupling agent and 10-15 parts of absolute ethyl alcohol;
wherein, the antibacterial skin-friendly polylactic acid is prepared by the following steps:
step I: adding polylactic acid and 1, 4-dioxane into a three-neck flask, stirring for reaction, then dropwise adding 2-hydroxyethylamine solution while stirring, continuing stirring for reaction after the dropwise adding is finished, cooling a reaction product after the reaction is finished, performing rotary evaporation, washing and drying to obtain hydrophilic modified polylactic acid;
step II: adding sodium hydroxide and deionized water into a three-neck flask, stirring for reaction, adding chitosan, continuously stirring for reaction, dropwise adding chloroacetic acid-ethanol solution while stirring, continuously stirring for reaction after the dropwise addition is finished, cooling a reaction product after the reaction is finished, adjusting the pH value, performing vacuum filtration, washing a filter cake, and drying to obtain carboxyl modified chitosan;
step III: adding epichlorohydrin and anhydrous tetrahydrofuran into a three-neck flask, stirring for reaction, then adding triethylamine dropwise while stirring, continuing stirring for reaction after the dripping is finished, vacuum-filtering a reaction product after the reaction is finished, and washing and drying a filter cake to obtain epoxy quaternary ammonium salt;
step IV: adding hydrophilic modified polylactic acid, carboxyl modified chitosan, p-toluenesulfonic acid, deionized water and methylene dichloride into a three-neck flask for stirring reaction, then adding epoxy quaternary ammonium salt for continuous stirring reaction, cooling a reaction product after the reaction is finished, then adding the reaction product into absolute ethyl alcohol, centrifuging, and drying a centrifugal product to obtain the antibacterial skin-friendly polylactic acid.
2. The medical polymer bandage convenient for biodegradation as claimed in claim 1, wherein the dosage ratio of the polylactic acid, the 1, 4-dioxane and the 2-hydroxyethylamine solution in the step i is 3g:55-65mL:8-12mL, the relative molecular weight of the polylactic acid is 10 5 The mass fraction of the 2-hydroxyethylamine solution is 10-15%.
3. The medical polymer bandage convenient for biodegradation as claimed in claim 1, wherein the dosage ratio of the sodium hydroxide, deionized water, chitosan and chloroacetic acid-ethanol solution in the step ii is 4-5g:20-25mL:2g:10-15mL, wherein the viscosity of the chitosan is 20-50 mPa.s, and the chloroacetic acid-ethanol solution is prepared from 13-15g of chloroacetic acid: 100mL of the solution was dissolved in absolute ethanol.
4. The medical polymer bandage convenient for biodegradation as claimed in claim 1, wherein the usage ratio of epichlorohydrin, anhydrous tetrahydrofuran and triethylamine in the step iii is 0.3-0.35mol:50-55mL:0.1mol.
5. The medical polymer bandage convenient for biodegradation as claimed in claim 1, wherein the dosage ratio of the hydrophilic modified polylactic acid, the carboxyl modified chitosan, the p-toluenesulfonic acid, the deionized water, the methylene dichloride and the epoxy quaternary ammonium salt in the step IV is 10g:1-10g:0.01-0.03g:80-100mL:80-100mL:0.1-0.5g.
6. The preparation method of the medical polymer bandage convenient for biodegradation is characterized by comprising the following steps of:
step one: weighing 50-60 parts of antibacterial skin-friendly polylactic acid, 8-10 parts of nano titanium dioxide, 2-6 parts of talcum powder, 1-5 parts of silane coupling agent and 10-15 parts of absolute ethyl alcohol according to parts by weight for standby;
step two: uniformly mixing antibacterial skin-friendly polylactic acid, nano titanium dioxide, talcum powder, silane coupling agent and absolute ethyl alcohol to obtain a mixture;
step three: adding the mixture into an extruder for melt extrusion, and performing spinneret spinning to form a fiber with an areal density of 40-60g/m 2 And then cutting and rolling the nonwoven material to obtain the medical polymer bandage convenient for biodegradation.
7. The method for preparing a medical polymer bandage convenient for biodegradation as claimed in claim 6, wherein said silane coupling agent is one of silane coupling agent KH-550, silane coupling agent KH-792 and silane coupling agent KH-560.
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| CN118454487A (en) * | 2024-05-20 | 2024-08-09 | 上海乐纯生物技术股份有限公司 | A method for preparing hydrophilic modified polyvinylidene fluoride filter membrane |
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| CN118454487A (en) * | 2024-05-20 | 2024-08-09 | 上海乐纯生物技术股份有限公司 | A method for preparing hydrophilic modified polyvinylidene fluoride filter membrane |
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| CN118931136A (en) * | 2024-09-05 | 2024-11-12 | 江苏省产品质量监督检验研究院 | A bio-based antibacterial packaging material and preparation method thereof |
| CN118931136B (en) * | 2024-09-05 | 2025-06-13 | 江苏省产品质量监督检验研究院 | A bio-based antibacterial packaging material and preparation method thereof |
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