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CN115262223A - Polyester/chitosan gel composite fiber membrane and preparation method thereof - Google Patents

Polyester/chitosan gel composite fiber membrane and preparation method thereof Download PDF

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Publication number
CN115262223A
CN115262223A CN202211011134.4A CN202211011134A CN115262223A CN 115262223 A CN115262223 A CN 115262223A CN 202211011134 A CN202211011134 A CN 202211011134A CN 115262223 A CN115262223 A CN 115262223A
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polyester
chitosan
fiber membrane
composite fiber
gel composite
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CN202211011134.4A
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CN115262223B (en
Inventor
徐文华
周芳
陈韶娟
孙世斌
刘伊明
马建伟
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Qingdao University
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Qingdao University
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Priority to ZA2023/02739A priority patent/ZA202302739B/en
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    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
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    • 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
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    • 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/62Compostable, hydrosoluble or hydrodegradable materials
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    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • D04H1/43828Composite fibres sheath-core
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    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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    • D06M10/00Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
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Abstract

The invention belongs to the technical field of composite fiber membranes, and particularly relates to a polyester/chitosan gel composite fiber membrane and a preparation method thereof, wherein the thickness of the polyester/chitosan gel composite fiber membrane is 100-800 mu m, and the polyester/chitosan gel composite fiber membrane is composed of superfine fibers with the diameter of 300-800nm, and the preparation method of the polyester/chitosan gel composite fiber membrane is characterized in that a coaxial electrospinning and photocrosslinking method is adopted, and a core solution formed by dissolving polyester in trifluoroethanol and an outer layer solution formed by dissolving chitosan in a mixed solvent composed of trifluoroethanol and acetic acid with the mass percentage concentration of 2% according to the volume ratio of 1; the preparation method is simple and easy in process, the tensile strength of the prepared polyester/chitosan gel composite fiber membrane loaded with the tannic acid is greater than or equal to 5.4Mpa, the antibacterial rate is greater than or equal to 72%, and the polyester/chitosan gel composite fiber membrane has good biocompatibility, degradability, antibacterial property and mechanical property and can be applied to the technical field of wound dressing.

Description

Polyester/chitosan gel composite fiber membrane and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of composite fiber membranes, and particularly relates to a polyester/chitosan gel composite fiber membrane and a preparation method thereof, which can entrap and release drugs.
The background art comprises the following steps:
the chitosan nano fiber scaffold prepared by the electrostatic spinning technology has the advantages of high specific surface area and simulation of extracellular matrix, and is widely concerned in the field of medical tissue engineering. The chitosan fiber is prepared by deacetylation through concentrated alkali treatment, and has the effects of degradability, good biocompatibility, antibiosis, hemostasis and the like. In order to improve the wet stability and mechanical property of chitosan fiber, covalent cross-linking agents (glutaraldehyde, genipin, acrylamide and the like) are required to participate in a cross-linking reaction when chitosan gel is constructed, but the chemical agents are not environment-friendly and have higher price. Wherein the introduction of the aldehyde cross-linking agent also increases the cytotoxicity of the nanofiber membrane and reduces the biocompatibility of the material (LanGQ, luBT, wangtY, wangLJ, chenJH, yuK, liuJW, daiFYandWuDY. Chitosan/gelatin compatibility and available surfactant. Colloid and surface B-Biointerfaces,2015, 136.
Tannic acid generally refers to tannic acid, is a tannin obtained from gallnut, has wide sources, can sterilize bacteria, and has the advantages of environmental protection, low cost and the like. Meanwhile, the tannin can form hydrogen bonds with hydroxyl and amino of the chitosan to play a role in crosslinking. However, the mechanical properties of chitosan fibers loaded with tannic acid in the prior art are low (KiechelMA, schauercl. Non-covalent cross fibers. Carbohydratepolymers.2013, 95. Therefore, the polyester/chitosan gel composite fiber membrane and the preparation method thereof are researched and designed, and the polyester/chitosan gel composite fiber membrane has economic and social benefits.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs a polyester/chitosan gel composite fiber membrane loaded with tannic acid and having higher mechanical property, antibacterial property and biocompatibility and simple preparation method process and a preparation method thereof.
In order to achieve the above object, the present invention relates to a polyester/chitosan gel composite fiber film having a thickness of 100 to 800 μm and composed of ultrafine fibers having a diameter of 300 to 800nm, wherein the ultrafine fibers are composed of chitosan and polyester in a ratio of 1: (2-5) the content of tannic acid per mg of the microfine fiber is 50-400. Mu.g.
The chitosan related to the invention comprises methacryloylated chitosan, the weight average molecular weight of the chitosan is 150-400kDa, the deacetylation degree is more than 80 percent, and the grafting ratio of the methacryloyl molecules is 20-80 percent; the polyester is degradable polyester, including polycaprolactone, polylactide, polyglycolide and copolymers thereof.
The preparation method of the polyester/chitosan gel composite fiber membrane comprises the following process steps:
1) Dissolving polyester in trifluoroethanol to prepare an inner core solution with the concentration of 100-200 mg/mL;
2) Dissolving chitosan in a mixed solvent to prepare an outer layer solution with the concentration of 20-50 mg/mL;
the mixed solvent is a mixture consisting of trifluoroethanol and 2% acetic acid in a volume ratio of 1;
3) Carrying out electric spinning on the outer layer solution and the inner core solution to obtain a polyester/chitosan fiber membrane with the thickness of 100-800 mu m;
the electrospinning conditions are as follows: the flow rate of the inner core solution is 0.3-0.8mL/h, the flow rate of the outer layer solution is 0.4-1.0mL/h, the spinning voltage is 10-20kV, and the receiving distance is 10-25cm;
4) Immersing the polyester/chitosan fiber film in an ethanol solution containing 1-5% of tannic acid and 1% of 2959 photoinitiator for 1-10min, and irradiating under ultraviolet light (100-200 w) for 1-2min to obtain the tannic acid-loaded polyester/chitosan gel composite fiber film.
Compared with the prior art, the tannin-loaded polyester/chitosan gel composite fiber membrane is obtained by using a coaxial electrospinning and photocrosslinking method and dissolving polyester in trifluoroethanol to form an inner core solution and dissolving chitosan in a mixed solvent of trifluoroethanol and 2% acetic acid in a volume ratio of 1; the preparation method is simple and easy in process, the tensile strength of the prepared polyester/chitosan gel composite fiber membrane loaded with the tannin is more than or equal to 5.4Mpa, the antibacterial rate is more than or equal to 72%, and the polyester/chitosan gel composite fiber membrane has good biocompatibility, degradability, antibacterial property and mechanical property and can be applied to the technical field of wound dressing.
The specific implementation method comprises the following steps:
the present invention will be further described below by way of specific embodiments.
Example 1:
the preparation method of the polyester/chitosan gel composite fiber membrane related to the embodiment comprises the following steps:
dissolving 200mg of polycaprolactone in 1mL of trifluoroethanol to be used as an inner core solution;
dissolving 50mg of methacrylated chitosan in 1mL of a mixed solvent composed of trifluoroethanol and 2% by mass of acetic acid according to a volume ratio of 1;
carrying out electrospinning by a coaxial electrospinning device under the conditions that the flow rate of the inner core solution is 0.4mL/h, the flow rate of the outer shell solution is 0.6mL/h, the spinning voltage is 12kV and the receiving distance is 15cm, collecting superfine fibers with the diameters of 200-800nm, and accumulating to obtain the polyester/chitosan fiber membrane;
the polyester/chitosan fiber membrane was immersed in an ethanol solution containing 1% by weight of 2959 photoinitiator and 3% of tannic acid for 10min, and then irradiated with ultraviolet light (200 w) for 1min to obtain a tannic acid-supported polyester/chitosan gel composite fiber membrane.
As a comparative group:
dissolving 120mg of polycaprolactone in 1mL of trifluoroethanol to be used as an inner core solution;
dissolving 20mg of chitosan (200 kDa) in a mixed solvent of 1mL of trifluoroethanol and 2% by mass of acetic acid according to a volume ratio of 1;
carrying out electrospinning by a coaxial electrospinning device under the conditions that the flow rate of the inner core solution is 0.4mL/h, the flow rate of the outer shell solution is 0.6mL/h, the spinning voltage is 12kV and the receiving distance is 15cm, collecting superfine fibers with the diameters of 200-800nm, and accumulating to obtain the polyester/chitosan composite fiber membrane;
tests prove that the tensile strength of the polyester/chitosan gel composite fiber membrane loaded with the tannin is 6.5Mpa, and the bacteriostasis rate is 80%;
the tensile strength of the polyester/chitosan composite fiber membrane is 4.0Mpa, and the bacteriostatic rate is only 40%;
the mechanical property and the antibacterial property of the polyester/chitosan gel composite fiber membrane loaded with the tannic acid are superior to those of a comparison group;
this advantage is caused by, on the one hand, the modification and photo-crosslinking process of chitosan, which makes the crosslinked network structure of chitosan formed in the fiber, increase the tensile strength of the tannin-loaded polyester/chitosan gel composite fiber membrane, and on the other hand, tannin is combined with chitosan by the action of hydrogen bonds and the like, giving the tannin-loaded polyester/chitosan gel composite fiber membrane more excellent antibacterial properties.
Example 2:
the preparation method of the polyester/chitosan gel composite fiber membrane related to the embodiment comprises the following steps:
dissolving 120mg of polycaprolactone in 1mL of trifluoroethanol to be used as an inner core solution;
dissolving 20mg of methacrylated chitosan (200 kDa) in 1mL of a mixed solvent composed of trifluoroethanol and 2% by mass of acetic acid according to a volume ratio of 1;
carrying out electrospinning by a coaxial electrospinning device under the conditions that the flow rate of the inner core solution is 0.4mL/h, the flow rate of the outer shell solution is 0.6mL/h, the spinning voltage is 12kV and the receiving distance is 15cm, collecting superfine fibers with the diameters of 200-800nm, and accumulating to obtain the polyester/chitosan fiber membrane;
the polyester/chitosan fiber film was immersed in an ethanol solution containing 1% of 2959 photoinitiator and 5% of tannic acid for 5min, and then irradiated under ultraviolet light (200 w) for 1min to obtain a tannic acid-loaded polyester/chitosan gel composite fiber film, and it was confirmed through experiments that the tensile strength of the tannic acid-loaded polyester/chitosan gel composite fiber film was 6.5Mpa and the bacteriostatic ratio was 80%.
Example 3:
the preparation method of the polyester/chitosan gel composite fiber membrane related to the embodiment comprises the following steps:
dissolving 120mg of polycaprolactone in 1mL of trifluoroethanol to be used as an inner core solution;
dissolving 20mg of methacrylated chitosan (200 kDa) in 1mL of a mixed solvent consisting of trifluoroethanol and 2% by mass of acetic acid according to a volume ratio of 1;
carrying out electrospinning by a coaxial electrospinning device under the conditions that the flow rate of the inner core solution is 0.4mL/h, the flow rate of the outer shell solution is 0.6mL/h, the spinning voltage is 12kV and the receiving distance is 15cm, collecting superfine fibers with the diameters of 200-800nm, and accumulating to obtain the polyester/chitosan fiber membrane;
the polyester/chitosan fiber film was immersed in an ethanol solution containing 1% of 2959 photoinitiator and 1% of tannic acid for 1min, and then irradiated under ultraviolet light (100 w) for 2min to obtain a tannic acid-loaded polyester/chitosan gel composite fiber film, and it was confirmed through experiments that the tensile strength of the tannic acid-loaded polyester/chitosan gel composite fiber film was 5.4Mpa and the bacteriostatic ratio was 72%.

Claims (8)

1. A polyester/chitosan gel composite fiber membrane with the thickness of 100-800 μm and the diameter of 300-800nm is characterized in that the superfine fiber is formed by chitosan and polyester according to the ratio of 1: (2-5) the content of tannic acid per mg of the microfine fiber is 50-400. Mu.g.
2. The polyester/chitosan gel composite fiber membrane according to claim 1, wherein the chitosan comprises methacrylated chitosan, the weight average molecular weight of the chitosan is 150-400kDa, the degree of deacetylation is greater than 80%, and the grafting ratio of methacrylated molecules is 20-80%.
3. The polyester/chitosan gel composite fiber membrane according to claim 1 or 2, wherein the polyester is a degradable polyester, including polycaprolactone, polylactide, polyglycolide, and copolymers thereof.
4. A preparation method of a polyester/chitosan gel composite fiber membrane is characterized by comprising the following process steps:
1) Dissolving polyester in trifluoroethanol to prepare an inner core solution;
2) Dissolving chitosan in a mixed solvent to prepare an outer layer solution;
the mixed solvent is a mixture of trifluoroethanol and acetic acid;
3) Carrying out electrospinning on the outer layer solution and the inner core solution to obtain a polyester/chitosan fiber membrane;
4) And (2) immersing the polyester/chitosan fiber membrane into an ethanol solution containing tannic acid and 2959 photoinitiator for 1-10min, and radiating under ultraviolet light to obtain the tannic acid-loaded polyester/chitosan gel composite fiber membrane.
5. The method for preparing a polyester/chitosan gel composite fiber membrane according to claim 4, wherein the concentration of the inner core solution involved in the step 1) is 100-200mg/mL.
6. The preparation method of the polyester/chitosan gel composite fiber membrane according to claim 4, wherein the volume ratio of the trifluoroethanol to the acetic acid in the mixed solvent involved in the step 2) is 1; the concentration of the outer layer solution is 20-50mg/mL.
7. The method for preparing the polyester/chitosan gel composite fiber membrane according to claim 4, wherein the electrospinning conditions involved in the step 3) are as follows: the flow rate of the inner core solution is 0.3-0.8mL/h, the flow rate of the outer layer solution is 0.4-1.0mL/h, the spinning voltage is 10-20kV, and the receiving distance is 10-25cm; the thickness of the polyester/chitosan fiber film is 100-800 μm.
8. The method for preparing a polyester/chitosan gel composite fiber membrane as claimed in claim 4, wherein the ethanol solution involved in the step 4) contains 1-5% of tannic acid and 1% of 2959 photoinitiator; irradiating under 100-200w ultraviolet light for 1-2min.
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