CN116874886A - Silver-loaded chitosan nanoparticle modified by oligomeric lactic acid and antibacterial polylactic acid material - Google Patents
Silver-loaded chitosan nanoparticle modified by oligomeric lactic acid and antibacterial polylactic acid material Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 47
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 41
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- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses an oligomeric lactic acid modified silver-loaded chitosan nanoparticle and an antibacterial polylactic acid material, and relates to the technical field of functional polylactic acid materials, wherein the preparation method of the oligomeric lactic acid modified silver-loaded chitosan nanoparticle comprises the following steps: s1, preparing chitosan nanoparticles; s2, preparing silver-loaded chitosan nanoparticles; s3, preparing the silver-loaded chitosan nano particles modified by the polylactic acid. According to the invention, the chitosan nanoparticle is prepared through an ion gelation mechanism, the antibacterial effect of the chitosan nanoparticle is improved through silver loading, and then the silver-loaded chitosan nanoparticle is subjected to surface modification by adopting the low polylactic acid, so that the compatibility of the antibacterial agent and the polylactic acid is effectively improved, and the obtained polylactic acid material has excellent antibacterial performance and physical and mechanical properties.
Description
Technical field:
the invention relates to the technical field of functional polylactic acid materials, in particular to an oligomeric polylactic acid modified silver-loaded chitosan nanoparticle and an antibacterial polylactic acid material.
The background technology is as follows:
polylactic acid (PLA) fiber is an ecological and environment-friendly fiber that has both the basic characteristics of synthetic fiber and the biocompatibility and degradability of natural fiber, and is more competitive in many respects than various textile products that use petroleum as a raw material. The research on the antibacterial polylactic acid material is an important aspect for improving the added value of the polylactic acid, and can further promote the application of polylactic acid fibers in the fields of environmental protection, medical and health, clothing home textile and the like.
Chitosan is a biopolymer whose antibacterial properties are well known. The chitosan has low antibacterial efficiency, and generally needs higher dosage to obtain ideal antibacterial effect, which is common in the industry; and chitosan does not have the antibacterial property, and the antibacterial effect of chitosan is also influenced. In the prior art, chitosan is combined with other antibacterial components, such as organic antibacterial agents such as chitosan grafted quaternary ammonium salt, etc., plant essential oil antibacterial agents coated with chitosan microcapsules, nano metal particle antibacterial agents coated with chitosan microcapsules, etc. Although the antibacterial effect of chitosan is effectively enhanced by the technical means, some preparation methods are complex, and the applicability of the chitosan on different polymers is different due to different application matrixes.
The preparation of the antibacterial polylactic acid material by adopting the blending method is a common method, but two major problems to be solved are the antibacterial efficiency of the antibacterial agent and the compatibility of the antibacterial agent and polylactic acid.
The invention comprises the following steps:
aiming at the problems existing in the prior art, the invention provides an antibacterial agent which does not influence the degradation performance of polylactic acid, has excellent antibacterial performance and good compatibility with polylactic acid, a preparation method thereof and an antibacterial polylactic acid material prepared from the antibacterial agent.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the invention aims at providing a preparation method of silver-loaded chitosan nanoparticles modified by oligomeric lactic acid, which comprises the following steps:
s1, preparing chitosan nano particles
(1) Dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan solution;
(2) Dissolving sodium tripolyphosphate in deionized water to obtain sodium tripolyphosphate solution;
(3) Slowly dripping the sodium tripolyphosphate solution into the chitosan solution, stirring while dripping, and continuing stirring after dripping is finished to obtain a chitosan nanoparticle suspension;
s2, preparing silver-loaded chitosan nano particles
(1) Dissolving silver nitrate in deionized water to obtain a silver nitrate solution;
(2) Dropwise adding a silver nitrate solution into the chitosan nanoparticle suspension, and continuously stirring after the dropwise adding is finished to obtain a silver-loaded chitosan nanoparticle suspension;
(3) Centrifugally separating, washing and drying the silver-loaded chitosan nanoparticle suspension to obtain silver-loaded chitosan nanoparticles;
s3, preparing the silver-loaded chitosan nano particles modified by the polylactic acid
Stirring and dispersing silver-loaded chitosan nano particles in dimethyl sulfoxide, then adding L-lactide and a catalyst, heating while stirring, carrying out heat preservation reaction, cooling after the reaction is finished, precipitating with acetone, filtering, washing and vacuum drying to obtain the low polylactic acid modified silver-loaded chitosan nano particles.
In the step S1, the volume fraction of acetic acid in the acetic acid aqueous solution is 1-2%; the mass fraction of chitosan in the chitosan solution is 0.5-2%; the molecular weight of the chitosan is 8-10 ten thousand, and the deacetylation degree is 75-95%; the mass fraction of sodium tripolyphosphate in the sodium tripolyphosphate solution is 0.5-2%; the mass ratio of the sodium tripolyphosphate to the chitosan is 1 (1-5). The preparation of the chitosan nanoparticle adopts an ion gel method, sodium tripolyphosphate is added into chitosan acetic acid solution, and the chitosan is subjected to ion-induced gelation by utilizing the sodium tripolyphosphate to prepare the chitosan nanoparticle.
In the step S2, the mass fraction of silver nitrate in the silver nitrate solution is 0.1-0.2%; the mass ratio of the silver nitrate to the chitosan nano particles is 1 (10-20); the rotational speed of the centrifugal separation is 5000-8000 r/min, the time is 30-60 min; the washing is carried out by deionized water, and the washing times are 1-3 times; the drying is freeze drying. During the preparation of silver-loaded chitosan nano-particles, ag + On the one hand, the free amino group is attached to the chitosan nanoparticle by forming a coordination bond with the lone pair electron of the free amino group on the chitosan nanoparticle, and on the other hand, the phosphate ion with negative electricity and the Ag with positive electricity + And ionic bond combination is formed between the silver-loaded chitosan nanoparticles.
In the step S3, the mass ratio of the silver-loaded chitosan nano particles to the dimethyl sulfoxide is (2-5) 100; the catalyst is Sn (OCt) 2 、Ti(OBu) 4 At least one of (a) and (b); the mass ratio of the L-lactide to the silver-loaded chitosan nano particles is (1-5): 1; the temperature of the heat preservation reaction is 70-90 ℃ and the time is 24-48 h; the washing is carried out by using ethyl acetate, and the washing times are 1-3 times; the temperature of the vacuum drying is 40-60 ℃ and the time is 12-24 h. And initiating lactide ring-opening polymerization through amino, hydroxyl and other active groups in chitosan to obtain the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid.
The second purpose of the invention is to provide the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid prepared by the preparation method.
The invention further provides application of the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid in a polylactic acid material.
The invention provides an antibacterial polylactic acid material, which comprises polylactic acid and the above-mentioned low polylactic acid modified silver-loaded chitosan nano particles.
The invention aims to provide a preparation method of an antibacterial polylactic acid material, which comprises the steps of uniformly mixing polylactic acid and the low polylactic acid modified silver-loaded chitosan nano particles, and spinning by a micro spinning machine to obtain the antibacterial polylactic acid material.
Preferably, the mass ratio of the silver-loaded chitosan nano particles modified by the oligomeric lactic acid to the polylactic acid is (0.5-3) 100.
Preferably, the spinning temperature is 180-210 ℃, the screw rotating speed is 20-70 rpm, and the winding speed is 300-500 m/min.
According to the invention, the chitosan nanoparticle is prepared through an ion gelation mechanism, the antibacterial effect of the chitosan nanoparticle is improved through silver loading, and then the silver-loaded chitosan nanoparticle is subjected to surface modification by adopting the low polylactic acid, so that the compatibility of the antibacterial agent and the polylactic acid is effectively improved.
The beneficial effects of the invention are as follows:
1. according to the invention, the chitosan nanoparticle is prepared by a simple ion gelation mechanism, the preparation method is simple, and the chitosan nanoparticle has better antibacterial property than chitosan and is more convenient for subsequent silver-carrying modification.
2. According to the invention, the antibacterial performance of the nano chitosan particles is further enhanced by silver loading, so that the antibacterial effect of the nano chitosan particles on the polylactic acid material is improved. The chitosan itself is used as a stabilizer and a reducing agent, so that the problem of color change caused by oxidation of Ag+ into silver simple substance can be prevented.
3. According to the invention, through modification of the low polylactic acid, the compatibility of the antibacterial agent and the polylactic acid is effectively improved, and the obtained polylactic acid material has excellent antibacterial performance and physical and mechanical properties.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1
200mL of 1% acetic acid aqueous solution was added to a three-necked flask, and chitosan (molecular weight: 8 ten thousand, degree of deacetylation: 90%) was further added thereto, followed by stirring at 30℃to dissolve, thereby preparing a 1% chitosan solution. 200mL of a 1% by mass aqueous sodium tripolyphosphate solution was prepared. Slowly dropwise adding the sodium tripolyphosphate aqueous solution into the chitosan solution, stirring while dropwise adding, keeping the temperature at 30 ℃, and continuing stirring for reaction for 10min after the dropwise adding is finished to obtain the chitosan nanoparticle suspension.
Preparing 100mL of silver nitrate aqueous solution with the mass fraction of 0.1%, dripping the silver nitrate aqueous solution into the chitosan nanoparticle suspension, and stirring for reaction for 30min after the dripping is finished. And (3) centrifugally separating the obtained silver-loaded chitosan nanoparticle suspension, washing with deionized water, and freeze-drying to obtain the silver-loaded chitosan nanoparticle.
2g of silver-loaded chitosan nanoparticles and 100g of dimethyl sulfoxide are added into a three-necked flask, stirred and dispersed, and purged with nitrogen for 30min. Into a three-necked flask, 2g L-lactide and 0.02g of catalyst Sn (OCt) were successively introduced under nitrogen atmosphere 2 The reaction mixture was stirred while heating to 90℃and reacted at constant temperature for 24 hours. After the reaction, naturally cooling to room temperature, precipitating the mixture in ice acetone, and filtering. Washing the filter cake with ethyl acetate for 2 times, and vacuum drying at 40 ℃ for 24 hours to obtain the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid.
Uniformly mixing 100g of polylactic acid resin particles with 0.5g of silver-loaded chitosan nano particles modified by oligomeric lactic acid, and spinning by a micro spinning machine at 180 ℃ at a screw speed of 20rpm and a winding speed of 300m/min to obtain the antibacterial polylactic acid fiber.
Example 2
250mL of 2% acetic acid aqueous solution was added to a three-necked flask, and chitosan (molecular weight: 8 ten thousand, degree of deacetylation: 90%) was further added thereto, followed by stirring and dissolution at 50℃to prepare a 2% mass fraction chitosan solution. 100mL of a 1% by mass aqueous solution of sodium tripolyphosphate was prepared. Slowly dropwise adding the sodium tripolyphosphate aqueous solution into the chitosan solution, stirring while dropwise adding, keeping the temperature at 40 ℃, and continuing stirring for reaction for 10min after the dropwise adding is finished to obtain the chitosan nanoparticle suspension.
250mL of silver nitrate aqueous solution with the mass concentration of 0.2% is prepared, and is dripped into the chitosan nanoparticle suspension, and the reaction is stirred for 30min after the dripping is finished. And (3) centrifugally separating the obtained silver-loaded chitosan nanoparticle suspension, washing with deionized water, and freeze-drying to obtain the silver-loaded chitosan nanoparticle.
5g of silver-loaded chitosan nanoparticles and 100g of dimethyl sulfoxide were added to a three-necked flask, stirred for dispersion, and purged with nitrogen for 30min. Into a three-necked flask, 25g L-lactide and 0.05g of Ti (OBu) as a catalyst were successively introduced under nitrogen atmosphere 4 Mixing the reactionThe mixture is stirred and heated to 90 ℃ for reaction for 24 hours under heat preservation. After the reaction, naturally cooling to room temperature, precipitating the mixture in ice acetone, and filtering. Washing the filter cake with ethyl acetate for 2 times, and vacuum drying at 40 ℃ for 24 hours to obtain the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid.
100g of polylactic acid resin particles and 3g of the silver-loaded chitosan nano particles modified by the polylactic acid are uniformly mixed and then are spun by a micro spinning machine, the spinning temperature is 210 ℃, the screw rotating speed is 70rpm, and the winding speed is 400m/min, so that the antibacterial polylactic acid fiber is obtained.
Example 3
400mL of 1% acetic acid aqueous solution was added to the three-necked flask, and chitosan (molecular weight: 8 ten thousand, degree of deacetylation: 90%) was further added thereto, followed by stirring at 30℃to dissolve, thereby preparing a 0.5% mass fraction chitosan solution. Another 50mL of a 2% mass fraction aqueous sodium tripolyphosphate solution was prepared. Slowly dropwise adding the sodium tripolyphosphate aqueous solution into the chitosan solution, stirring while dropwise adding, keeping the temperature at 50 ℃, and continuing stirring for reaction for 30min after the dropwise adding is finished to obtain the chitosan nanoparticle suspension.
Preparing 100mL of silver nitrate aqueous solution with the mass concentration of 0.15%, dripping the silver nitrate aqueous solution into the chitosan nanoparticle suspension, and stirring for reaction for 30min after the dripping is finished. And (3) centrifugally separating the obtained silver-loaded chitosan nanoparticle suspension, washing with deionized water, and freeze-drying to obtain the silver-loaded chitosan nanoparticle.
2g of silver-loaded chitosan nanoparticles and 100g of dimethyl sulfoxide are added into a three-necked flask, stirred and dispersed, and purged with nitrogen for 30min. 6g L-lactide and 0.03g of catalyst Ti (OBu) were added in sequence to a three-necked flask under nitrogen protection 4 The reaction mixture was stirred and heated to 70℃for 48h with thermal insulation. After the reaction, naturally cooling to room temperature, precipitating the mixture in ice acetone, and filtering. Washing the filter cake with ethyl acetate for 2 times, and vacuum drying at 40 ℃ for 24 hours to obtain the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid.
100g of polylactic acid resin particles and 1g of the silver-loaded chitosan nano particles modified by the polylactic acid are uniformly mixed and then are spun by a micro spinning machine, the spinning temperature is 190 ℃, the screw rotating speed is 50rpm, and the winding speed is 500m/min, so that the antibacterial polylactic acid fiber is obtained.
Example 4
400mL of 1% acetic acid aqueous solution was added to a three-necked flask, and chitosan (molecular weight: 8 ten thousand, degree of deacetylation: 90%) was further added thereto, followed by stirring at 30℃to dissolve, thereby preparing a 1% chitosan solution. 100mL of a sodium tripolyphosphate aqueous solution with a mass fraction of 2% was prepared. Slowly dropwise adding the sodium tripolyphosphate aqueous solution into the chitosan solution, stirring while dropwise adding, keeping the temperature at 30 ℃, and continuing stirring for reaction for 30min after the dropwise adding is finished to obtain the chitosan nanoparticle suspension.
Preparing 150mL of silver nitrate aqueous solution with mass concentration of 0.2%, dripping the silver nitrate aqueous solution into the chitosan nanoparticle suspension, and stirring for reaction for 60min after dripping. And (3) centrifugally separating the obtained silver-loaded chitosan nanoparticle suspension, washing with deionized water, and freeze-drying to obtain the silver-loaded chitosan nanoparticle.
3g of silver-loaded chitosan nanoparticles and 100g of dimethyl sulfoxide are added into a three-necked flask, stirred and dispersed, and purged with nitrogen for 30min. Into a three-necked flask, 10-g L-lactide and 0.03g of Ti (OBu) as a catalyst were successively introduced under nitrogen atmosphere 4 The reaction mixture was stirred while heating to 80℃and incubated for 24h. After the reaction, naturally cooling to room temperature, precipitating the mixture in ice acetone, and filtering. Washing the filter cake with ethyl acetate for 2 times, and vacuum drying at 40 ℃ for 24 hours to obtain the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid.
100g of polylactic acid resin particles and 2g of silver-loaded chitosan nano particles modified by oligomeric lactic acid are uniformly mixed and then spun by a micro spinning machine, wherein the spinning temperature is 190 ℃, the screw rotation speed is 50rpm, and the winding speed is 500m/min, so that the antibacterial polylactic acid fiber is obtained.
Example 5
The preparation method of the silver-loaded chitosan nanoparticle modified by the polylactic acid is the same as that of example 4.
100g of polylactic acid resin particles and 1g of the silver-loaded chitosan nano particles modified by the polylactic acid are uniformly mixed and then are spun by a micro spinning machine, the spinning temperature is 190 ℃, the screw rotating speed is 50rpm, and the winding speed is 500m/min, so that the antibacterial polylactic acid fiber is obtained.
Example 6
The preparation method of the silver-loaded chitosan nanoparticle modified by the polylactic acid is the same as that of example 4.
100g of polylactic acid resin particles and 3g of the silver-loaded chitosan nano particles modified by the polylactic acid are uniformly mixed and then are spun by a micro spinning machine, the spinning temperature is 190 ℃, the screw rotating speed is 50rpm, and the winding speed is 500m/min, so that the antibacterial polylactic acid fiber is obtained.
Comparative example 1
The chitosan nanoparticle was prepared in the same manner as in example 4.
100g of polylactic acid resin particles and 2g of chitosan nanoparticles are uniformly mixed and then spun by a micro spinning machine, wherein the spinning temperature is 190 ℃, the screw rotation speed is 50rpm, and the winding speed is 500m/min, so as to obtain the polylactic acid fiber.
Comparative example 2
Silver-loaded chitosan nanoparticles were prepared in the same manner as in example 4.
And uniformly mixing 100g of polylactic acid resin particles with 2g of silver-loaded chitosan nanoparticles, and spinning by a micro spinning machine at the spinning temperature of 190 ℃ and the screw rotating speed of 50rpm and the winding speed of 500m/min to obtain the polylactic acid fiber.
Comparative example 3
And directly spinning the polylactic acid resin particles on a micro spinning machine to obtain the polylactic acid fiber.
Performance testing
Antibacterial performance test: evaluation of antimicrobial Properties of textiles according to GB/T20944-2008 part 3: vibration method, and determining the antibacterial rate of polylactic acid fiber to colibacillus and staphylococcus aureus.
Mechanical property test: according to GB/T14344-2008 'method for testing tensile Property of chemical fiber filament', the breaking strength of polylactic acid fiber is tested by adopting YG061M single yarn strength tester.
Table 1 shows the antibacterial properties and mechanical properties of the polylactic acid fibers obtained in examples 1 to 6 and comparative examples 1 to 3.
TABLE 1
As shown in Table 1, when the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid prepared by the invention is used as an antibacterial agent, and the mass ratio of the antibacterial agent to the polylactic acid is 0.5%, the antibacterial rates to escherichia coli and staphylococcus aureus are 82.3% and 85.6%, respectively. When the mass ratio of the antibacterial agent to the polylactic acid is 2%, the antibacterial rate of 99.99% can be achieved, and the antibacterial effect is excellent; the breaking strength and the breaking extension degree of the polylactic acid fiber are improved, which shows that the obtained antibacterial fiber has good physical and mechanical properties, thereby showing that the prepared low polylactic acid modified silver-loaded chitosan nanoparticle has good compatibility with polylactic acid. As is clear from comparative example 1, the obtained polylactic acid fiber has a limited antibacterial effect when only chitosan is used. As is clear from comparative example 2, the antibacterial effect of the polylactic acid fiber can be effectively improved by silver-carrying, but the antibacterial effect is slightly lower than that of the silver-carrying chitosan nanoparticle modified by the oligomeric lactic acid with the same addition, which indicates that the silver-carrying chitosan nanoparticle influences the dispersibility of the nanoparticle in the polylactic acid matrix due to the compatibility problem when the silver-carrying chitosan nanoparticle is blended with the polylactic acid without being modified by the oligomeric lactic acid, thereby influencing the play of the antibacterial effect. The decrease in the fiber breaking strength and elongation at break of comparative example 1 and comparative example 2 was also due to poor compatibility of the additive with polylactic acid. The results show that the silver-loaded chitosan nanoparticle modified by the low polylactic acid prepared by the method effectively improves the antibacterial performance of the antibacterial agent and the compatibility with polylactic acid through chitosan nanocrystallization, silver loading and low polylactic acid modification.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of an oligomeric lactic acid modified silver-loaded chitosan nanoparticle is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing chitosan nano particles
(1) Dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan solution;
(2) Dissolving sodium tripolyphosphate in deionized water to obtain sodium tripolyphosphate solution;
(3) Slowly dripping the sodium tripolyphosphate solution into the chitosan solution, stirring while dripping, and continuing stirring after dripping is finished to obtain a chitosan nanoparticle suspension;
s2, preparing silver-loaded chitosan nano particles
(1) Dissolving silver nitrate in deionized water to obtain a silver nitrate solution;
(2) Dropwise adding a silver nitrate solution into the chitosan nanoparticle suspension, and continuously stirring after the dropwise adding is finished to obtain a silver-loaded chitosan nanoparticle suspension;
(3) Centrifugally separating, washing and drying the silver-loaded chitosan nanoparticle suspension to obtain silver-loaded chitosan nanoparticles;
s3, preparing the silver-loaded chitosan nano particles modified by the polylactic acid
Stirring and dispersing silver-loaded chitosan nano particles in dimethyl sulfoxide, then adding L-lactide and a catalyst, heating while stirring, carrying out heat preservation reaction, cooling after the reaction is finished, precipitating with acetone, filtering, washing and vacuum drying to obtain the low polylactic acid modified silver-loaded chitosan nano particles.
2. The method of manufacturing according to claim 1, wherein: in the step S1, the volume ratio of acetic acid to water in the acetic acid aqueous solution is (1-2): 100; the mass fraction of chitosan in the chitosan solution is 0.5-2%; the molecular weight of the chitosan is 8-10 ten thousand, and the deacetylation degree is 75-95%; the mass fraction of sodium tripolyphosphate in the sodium tripolyphosphate solution is 0.5-2%; the mass ratio of the sodium tripolyphosphate to the chitosan is 1 (1-5).
3. The method of manufacturing according to claim 1, wherein: in the step S2, the mass fraction of silver nitrate in the silver nitrate solution is 0.1-0.2%; the mass ratio of the silver nitrate to the chitosan nano particles is 1 (10-20); the rotational speed of the centrifugal separation is 5000-8000 r/min, and the time is 30-60 min; the washing is carried out by deionized water, and the washing times are 1-3 times; the drying is freeze drying.
4. The method of manufacturing according to claim 1, wherein: in the step S3, the mass ratio of the silver-loaded chitosan nano particles to the dimethyl sulfoxide is (2-5) 100; the catalyst is Sn (OCt) 2 、Ti(OBu) 4 At least one of (a) and (b); the mass ratio of the L-lactide to the silver-loaded chitosan nano particles is (1-5): 1; the temperature of the heat preservation reaction is 70-90 ℃ and the time is 24-48 h; the washing is carried out by using ethyl acetate, and the washing times are 1-3 times; the temperature of the vacuum drying is 40-60 ℃ and the time is 12-24 h.
5. The silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the silver-loaded chitosan nanoparticle modified by the oligomeric lactic acid in a polylactic acid material.
7. An antibacterial polylactic acid material comprising polylactic acid and the oligolactic acid modified silver-loaded chitosan nanoparticle of claim 5.
8. A preparation method of an antibacterial polylactic acid material is characterized by comprising the following steps: uniformly mixing polylactic acid and the low polylactic acid modified silver-loaded chitosan nano particles according to claim 5, and spinning by a micro spinning machine to obtain the antibacterial polylactic acid material.
9. The method of preparing as claimed in claim 8, wherein: the mass ratio of the silver-loaded chitosan nano particles modified by the oligomeric lactic acid to the polylactic acid is (0.5-3) 100.
10. The method of preparing as claimed in claim 8, wherein: the spinning temperature is 180-210 ℃, the screw rotating speed is 20-70 rpm, and the winding speed is 300-500 m/min.
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