CN106757785B - Preparation method of silver-loaded chitosan/polyvinyl alcohol micron belt - Google Patents

Preparation method of silver-loaded chitosan/polyvinyl alcohol micron belt Download PDF

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Publication number
CN106757785B
CN106757785B CN201611078308.3A CN201611078308A CN106757785B CN 106757785 B CN106757785 B CN 106757785B CN 201611078308 A CN201611078308 A CN 201611078308A CN 106757785 B CN106757785 B CN 106757785B
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silver
chitosan
polyvinyl alcohol
belt
micro
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CN106757785A (en
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卢启芳
王东
赵晴
刘莉
邓亚亚
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Chengdu Yishenrui Technology Co ltd
Jiangsu Yitong Biological Technology Co ltd
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Qilu University of Technology
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    • DTEXTILES; PAPER
    • 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
    • DTEXTILES; PAPER
    • 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Materials For Medical Uses (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention relates to a silver-loaded chitosan/polyvinyl alcohol micro-belt and a preparation method and application thereof, wherein the micro-belt is a chitosan/polyvinyl alcohol belt-shaped composite fiber film with silver nano-particles uniformly distributed, the diameter of the micro-belt is 0.3-2 mu m, and the particle size of the silver nano-particles is 5-60 nm. Mixing the polyvinyl alcohol solution and the lactic acid solution of the chitosan, adding ethanol, uniformly stirring, adding silver nitrate, stirring for 40-50h in a dark place to prepare a spinning solution, and then carrying out electrostatic spinning to obtain the silver-loaded chitosan/polyvinyl alcohol micro-belt. The micro-belt of the invention has the advantages of one-dimensional and two-dimensional nano materials, has higher specific surface area, porosity and water absorption, and effectively reduces the phenomena of shedding, agglomeration and the like of nano silver by attaching or embedding nano silver particles in the micro-belt, so that the formed nano silver is more uniformly distributed in the micro-belt, and the lethality of the micro-belt to escherichia coli is 100%.

Description

A kind of preparation method carrying silver-colored chitosan/polyvinyl alcohol micro belt
Technical field
The present invention relates to composite nano-fiber material field, in particular to a kind of load silver chitosan with anti-microbial property/ Polyvinyl alcohol micron band and the preparation method and application thereof.
Background technique
Noble silver is used as high-efficiency antimicrobial material because of its unique photoelectric characteristic, high chemical stability and catalytic activity Material.Nano material has big specific surface area and high catalytic activity, has preferably catalysis and sterilization compared to its block materials Etc. performances.In recent years, people prepare the Argent grain of nanoscale by various means, and this nano silver has superior antibacterial Performance.But it is small-sized due to nano silver, when exclusive use, it is easy to be lost, therefore, generally will in practical application It is carried on carrier material, to play its excellent sterilizing ability.By nano-silver loaded into nanofiber, it can utilize The great specific surface area of nanofiber increases the contact area of nano silver and bacterium, and can be effectively prevented in use process silver-colored Loss, it is more more efficient than many conventional methods.
The good life of design feature and chitosan material that one-dimensional chitosan-based material has large specific surface area, porosity high Object medical performance is a kind of green fiber with good environmental-protecting performance.Since viscosity is higher in an acidic solution, band for chitosan Positive charge and intramolecular and the effect of intermolecular strong chemical bond, cause it to be difficult to move freely during electrostatic spinning, cause Fiber is discontinuous, is broken containing pearl or even spinning.And high-specific surface area, continuous flawless can be made in electrostatic blended spinning technology Nanofiber, the tunica fibrosa than chitosan alone preparation is more tough and tensile durable, and cost of material is also lower.Polyvinyl alcohol 1788 (PVA) with the grease resistance and solvent resistance of good chemical stability and physical mechanical property and brilliance.Further, since PVA has good biocompatibility and degradability, is widely applied frequently as biomimetic material.High-molecular polyvinyl alcohol passes through Hydrogen bond action has more good electrostatic spinning performance in conjunction with chitosan, than other polymer.
Chinese patent document CN104511045A (application number: 201310441908.1) is disclosed a kind of containing nano silver The preparation method of chitosan/polyvinyl alcohol nanofiber film dressing, the nanofiber film dressing are mixed with polyvinyl alcohol and chitosan Conjunction object is substrate, by the way that silver sol is added dropwise, obtains chitosan/polyvinyl alcohol nano fibrous membrane using method of electrostatic spinning, then benefit It is crosslinked to obtain water-resistance anti-bacterial fibre with glutaraldehyde and nano fibrous membrane.
Chinese patent document CN103705969A (application number: 201410001923.9) discloses a kind of chitosan base load silver The preparation method of composite antibacterial type superfine fibre film, specific steps include: step 1: in the acetic acid that mass fraction is 50-90% Silver nitrate powder is added in aqueous solution, stirs to dissolve, weighs chitosan and polyethylene glycol oxide or pva powder is added Into above-mentioned solution, spinning solution is stirred to get;Step 2: electrostatic spinning apparatus is added in spinning solution, voltage be 10-20kV, Spinning solution injects speed 0.1-1.0mL/h, reception distance is 8-30cm, spinning temperature is 20-50 DEG C and relative humidity is 10- Electrostatic spinning is carried out under conditions of 55%, and obtained white nano fibrous membrane is dried in vacuo 12-36h, removes remaining solvent, Obtain chitosan-based silver-loaded composite antimicrobial superfine fiber membrane.
But the absorption of tunica fibrosa specific surface area, porosity, imbibition rate, nano silver that above-mentioned two patent documents obtain Ability and bacteriostasis property are all to be improved.
Monodimension nanometer material is received extensive attention due to its excellent physical and chemical performance, two-dimension nano materials due to Stratiform and the characteristics such as controllable and furtherd investigate.The characteristics of micron carrying material has had both a peacekeeping two-dimension nano materials, is current Forward position material in Nanometer scale science and technology research and development is relatively new knot between a peacekeeping two-dimensional nanostructure Structure has rectangular section, and width-thickness ratio is bigger, there is unique property;This very thin strip nanostructure, neither It is same as the hollow structure of nanotube, and the different solid cylinder structures with nano wire.Micro belt Material Manufacturing Process is easy to control, Material structure can be made unified when mass production, internal structure is perfect, surface is clean smooth and does not have internal flaw, dislocation, Purity is higher, these properties enable it to put into industrial production earlier.
Currently, directly preparing the silver-colored chitosan/polyvinyl alcohol micro belt of load using electrostatic spinning technique, relevant report is had no.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silver-colored chitosan/polyvinyl alcohol micro belt of load and its preparations Mixed liquor, polyvinyl alcohol is added using polyvinyl alcohol and chitosan compound as substrate, by silver nitrate in method and application, the micro belt As reducing agent, chitosan prepares the chitosan/polyvinyl alcohol micro belt containing nano silver as stabilizer.
Technical scheme is as follows:
A kind of silver-colored chitosan/polyvinyl alcohol micro belt of load, the micro belt be evenly distributed with the chitosan of silver nano-grain/ The band-like composite cellulosic membrane of polyvinyl alcohol, micro belt diameter are 0.3-2 μm, and the partial size of silver nano-grain is 5-60nm.
, according to the invention it is preferred to, the micro belt is with a thickness of 100-300nm.
, according to the invention it is preferred to, described 0.5-1.5 μm of micro belt diameter, silver nano-grain partial size is 5-40nm.
According to the present invention, the preparation method of above-mentioned load silver chitosan/polyvinyl alcohol micro belt, comprises the following steps that
Ethyl alcohol is added after the lactic acid solution of poly-vinyl alcohol solution and chitosan is mixed, is stirring evenly and then adding into silver nitrate, It is protected from light stirring 40-50h, is made into spinning solution, then electrostatic spinning obtains carrying silver-colored chitosan/polyvinyl alcohol micro belt.
Preparation method according to the present invention, it is preferred that the mass concentration of the poly-vinyl alcohol solution is 10-20%, institute The lactic acid solution mass concentration for the chitosan stated is 2-8%;
Preferably, the mass ratio of poly-vinyl alcohol solution, the lactic acid solution of chitosan and ethyl alcohol is (90-70): (10-30): (5-10)。
Preparation method according to the present invention, it is preferred that the additional amount of silver nitrate is the 2 of polyvinyl alcohol and chitosan gross mass ~8%.
Preparation method according to the present invention, it is preferred that the condition of electrostatic spinning are as follows:
It is received using aluminium foil, voltage 15-20kV, syringe pump fltting speed is 1.5-3mL/h, and receiving distance is 12- 18cm, temperature are 20-25 DEG C.
According to the present invention, above-mentioned load silver chitosan/polyvinyl alcohol micro belt is preparing the application in medical dressing.
Silver nitrate is added using chitosan as stabilizer using polyvinyl alcohol as the reducing agent of silver ion by the present invention Into chitosan/polyvinyl alcohol mixed liquor, silver ion is made to be reduced into nano silver, the method preparation of this " from bottom to top " is received The problems such as rice Argent grain diameter is smaller, avoids and is unevenly distributed after being directly added into nano-silver powder, and partial size is uneven.Using electrostatic spinning Method can make nano silver once-forming with micro belt, and nano-Ag particles is allowed to adhere to or be embedded in chitosan/polyvinyl alcohol micro belt In, it is effectively reduced phenomena such as falling off and reunite of nano silver, makes the distribution of the nano silver to be formed in micro belt more evenly. Using the broad spectrum antibacterial of nano silver, micro belt prepared by the present invention can be used as medical dressing.Polyvinyl alcohol is water-soluble high score Son can form a large amount of hydrogen bond containing a large amount of hydroxyl with hydrone, and therefore, compound micro belt prepared by the present invention can absorb Moisture can provide the environment of wetting for wound.
Beneficial effects of the present invention:
1, the advantages of load silver chitosan/polyvinyl alcohol micro belt of the invention is with a peacekeeping two-dimension nano materials, both It is different from solid nanofiber again different from nanotube, compared to existing nanofiber, micro belt, which possesses, higher compares table Area, porosity and water absorption rate, nano-Ag particles adhere to or are embedded in chitosan/polyvinyl alcohol micro belt, due to bandwidth Than relatively thin, avoid excessive nano silver and be embedded in inside, be effectively reduced phenomena such as falling off and reunite of nano silver, make shape At distribution of the nano silver in micro belt more evenly.
2, load silver chitosan/polyvinyl alcohol micro belt preparation process of the invention is simpler, using polyvinyl alcohol as Reducing agent, chitosan is as stabilizer, and in-situ reducing is at nano silver.And selected substrate is all degradability and biocompatibility Green material, improve the pattern of film, prepare the chitosan/polyvinyl alcohol micro belt of argentiferous, with broad spectrum antibacterial Feature, the lethality to Escherichia coli are 100%.
Detailed description of the invention
Fig. 1 is that the ultra-violet absorption spectrum for being protected from light stirring different time is added in polyvinyl alcohol in silver nitrate in embodiment 1.
Fig. 2 is the XRD spectra that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.In figure a be chitosan/ The XRD curve of polyvinyl alcohol;B is the XRD curve for carrying silver-colored chitosan/polyvinyl alcohol.
Fig. 3 is the scanning electron microscopic picture that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.
Fig. 4 is that silver-colored chitosan/polyvinyl alcohol micro belt transmission electron microscope picture is carried obtained in embodiment 2.A is low power in figure Transmit photo;B is that high power transmits photo.
Fig. 5 is the fungistatic effect figure that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.A is antibacterial in figure Before;After b is antibacterial.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing, the invention will be further described, but not limited to this.
Chitosan used in embodiment is white or off-white powder, deacetylation > 95%, rank medical grade.It is used Polyvinyl alcohol be white particle, model 1788, molecular weight 44.05MW.
Embodiment 1
It weighs 10g polyvinyl alcohol to be dissolved in 90g water, magnetic agitation dissolves by heating, and being made into 100g mass fraction is 10% Poly-vinyl alcohol solution.It weighs 0.2g chitosan to be dissolved in lactic acid, is made into the chitosan lactic acid solution that 10g mass fraction is 2%.It will After above-mentioned polyvinyl alcohol and chitosan solution are mixed with the mass ratio of 70:30, polyvinyl alcohol and chitosan gross mass 2% is added Silver nitrate, be protected from light stirring 48h after be made into spinning solution.Spinning, voltage 20kV are carried out using electrostatic spinning apparatus, syringe pump pushes away It is 2.26mL/h into speed, is received using aluminium foil, receiving distance is 15cm.Obtain the silver-colored chitosan/polyvinyl alcohol micro belt of load.
Obtained spinning solution is with the increase of mixing time, and UV absorption intensity is as shown in Figure 1, with mixing time Increase, UV absorption intensity gradually increases, it was demonstrated that the reproducibility to silver ion of polyvinyl alcohol.
Embodiment 2
The mass concentration of poly-vinyl alcohol solution is expanded as 20%, other reagents and dosage and process conditions are constant, repeat Embodiment 1 is to get to carrying silver-colored chitosan/polyvinyl alcohol micro belt.The XRD of obtained micro belt is as shown in Fig. 2, 20 ° or so It is the unbodied peak of chitosan, the peak of indexing is the peak of elemental silver, illustrates that the silver in micro belt is elemental silver.Substrate carrier silver The scanning of front and back and transmission photo difference are as shown in Figure 3,4, and obtained composite membrane is ribbon-like fibre, and diameter is 0.6-1 μm, carry Ribbon-like fibre surface has uniformly been covered with silver nano-grain, partial size 5-60nm after silver.
Embodiment 3
The mass concentration of chitosan solution is expanded as 8%, other reagents and dosage and process conditions are constant, repeat to implement Example 1 is to get to carrying silver-colored chitosan/polyvinyl alcohol micro belt.
Test example
The sample of embodiment 2 is tested into its bactericidal property using following methods:
Carry examination of the bactericidal property test of silver-colored chitosan/polyvinyl alcohol micro belt according to Appendix B in GB/T21510-2008 Proved recipe method, test strain are most representative Escherichia coli in gramnegative bacterium.Experiment uses shake-flask method, cut-parts It is affixed on 250mL to be equipped in the conical flask of bacteria suspension, under the conditions of 25 DEG C, after 150r/min vibrates 2min, according to remaining in flask Strain, test its bactericidal property.
Obtained bactericidal effect is survived after sterilization as shown in figure 5, have 504 E. coli clones in flask before sterilizing Bacterium colony be 0, it is known that the sterilizing rate for carrying silver-colored chitosan/polyvinyl alcohol micro belt is 100%.

Claims (3)

1. a kind of preparation method for carrying silver-colored chitosan/polyvinyl alcohol micro belt, the micro belt are to be evenly distributed with silver nano-grain The band-like composite cellulosic membrane of chitosan/polyvinyl alcohol, micro belt diameter is 0.5-1.5 μm, and the partial size of silver nano-grain is 5-60 nm;
It comprises the following steps that
Ethyl alcohol is added after the lactic acid solution of poly-vinyl alcohol solution and chitosan is mixed, is stirring evenly and then adding into silver nitrate, is protected from light 40-50 h is stirred, is made into spinning solution, then electrostatic spinning obtains carrying silver-colored chitosan/polyvinyl alcohol micro belt;The polyethylene The mass concentration of alcoholic solution is 10-20%, and the lactic acid solution mass concentration of the chitosan is 2-8%;Poly-vinyl alcohol solution, shell The lactic acid solution of glycan and the mass ratio of ethyl alcohol are (90-70): (10-30): (5-10);
The condition of electrostatic spinning are as follows:
It is received using aluminium foil, voltage is 15-20 kV, and syringe pump fltting speed is 1.5-3 mL/h, and receiving distance is 12-18 Cm, temperature are 20-25 DEG C.
2. the preparation method according to claim 1 for carrying silver-colored chitosan/polyvinyl alcohol micro belt, which is characterized in that described Micro belt with a thickness of 100-300 nm.
3. the preparation method according to claim 1 for carrying silver-colored chitosan/polyvinyl alcohol micro belt, which is characterized in that nitric acid The additional amount of silver is the 2~8% of polyvinyl alcohol and chitosan gross mass.
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CN107691969B (en) * 2017-09-21 2021-06-01 华南协同创新研究院 Low-molecular chitosan @ silver nanoparticle composite membrane and preparation method and application thereof
CN108633879A (en) * 2018-04-20 2018-10-12 袁杰 A kind of circulating water sterilizing agent
CN109169706A (en) * 2018-07-19 2019-01-11 大美泰康(天津)生态科技有限公司 Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained
CN112962216B (en) * 2021-02-07 2022-02-01 宁波工程学院 Preparation method of nylon 6/chitosan/precious metal nano-fiber
CN116617439B (en) * 2023-06-05 2023-10-20 江苏益通生物科技有限公司 Chitosan composite hemostatic dressing and manufacturing method thereof

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CN103705969A (en) * 2014-01-02 2014-04-09 东华大学 Method for preparing chitosan-based silver-loaded composite antimicrobial superfine fiber membrane
CN104511045A (en) * 2013-09-26 2015-04-15 五邑大学 Polyvinyl alcohol/chitosan nano fiber film dressing containing nano silver and preparation thereof
CN104928848A (en) * 2015-07-13 2015-09-23 山东大学 Macroscopic quantity preparation method for macromolecule-based silver-loaded composite nanofiber membrane
CN103933602B (en) * 2014-04-22 2016-06-08 东华大学 The preparation method of chitosan-based medicine carrying composite antibacterial superfine fibre film

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KR100811205B1 (en) * 2006-08-17 2008-03-07 (주) 아모센스 Antibacterial nano-fibers containing silver nano-particles and preparation method thereof
CN104511045A (en) * 2013-09-26 2015-04-15 五邑大学 Polyvinyl alcohol/chitosan nano fiber film dressing containing nano silver and preparation thereof
CN103705969A (en) * 2014-01-02 2014-04-09 东华大学 Method for preparing chitosan-based silver-loaded composite antimicrobial superfine fiber membrane
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Effective date of registration: 20220511

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