Antibacterial seaweed composite fiber and preparation method thereof

Abstract

The invention discloses an antibacterial seaweed composite fiber and a preparation method thereof, and relates to the technical field of seaweed fibers.The antibacterial seaweed composite fiber is prepared from, by weight, 50-60 parts of alginate, 10-20 parts of silk fibroin, 10-20 parts of polyvinyl alcohol and 1-3 parts of nano-silver-loaded porous gelatin microspheres; the mass ratio of the nano-silver to the porous gelatin microspheres in the nano-silver-loaded porous gelatin microspheres is 1: (60-70). The composite fiber can effectively improve the mechanical property and antibacterial property of the alginate fiber.

Description

Technical Field

[0001] The present invention relates to the technical field of seaweed fibers, and in particular to an antibacterial seaweed composite fiber and a preparation method thereof. Background Art

[0002] Seaweed fiber refers to a fiber prepared from alginic acid extracted from some marine algae plants, and is a new type of biodegradable and renewable fiber. Its raw material resources are rich, and the prepared seaweed fiber can be used as the surface layer of sanitary products, and has special functions such as good biocompatibility and biodegradable absorbability. However, single seaweed fiber has problems of insufficient mechanical properties and antibacterial properties. Summary of the Invention

[0003] Aiming at the defects existing in the above-mentioned prior art, the purpose of the present invention is to provide an antibacterial seaweed composite fiber and a preparation method thereof, which can effectively improve the mechanical properties and antibacterial properties of seaweed fibers.

[0004] One of the purposes of the present invention is achieved by adopting the following technical scheme:

[0005] An antibacterial seaweed composite fiber, comprising the following components in parts by weight: 50-60 parts of alginate, 10-20 parts of silk fibroin, 10-20 parts of polyvinyl alcohol, and 1-3 parts of porous gelatin microspheres loaded with nano silver; the mass ratio of nano silver to porous gelatin microspheres in the porous gelatin microspheres loaded with nano silver is 1:(60-70).

[0006] Preferably, the preparation method of the porous gelatin microspheres loaded with nano silver comprises the following preparation steps:

[0007] (1) Dissolve silver nitrate in deionized water, add polyvinyl alcohol and polyvinylpyrrolidone to the silver nitrate solution, and stir evenly to obtain a first mixed solution; add gelatin particles to water, stir evenly under a water bath at 50-60 °C, and add the gelatin solution to the first mixed solution to obtain a second mixed solution;

[0008] (2) Add Span-80 to paraffin and stir, add it to the second mixed solution and stir evenly, then cool to room temperature, add 25% glutaraldehyde and continue to stir. During the stirring process, dropwise add a reducing solution, and the reducing solution is a mixed solution of glucose and sodium hydroxide. Let it stand, pour off the supernatant to obtain a mixture;

[0009] (3) Under a water bath ultrasound at 30-35 °C, wash the mixture with absolute ethanol multiple times, then wash the mixture with glycine solution multiple times, and wash the mixture with absolute ethanol multiple times again until the oil phase is removed to obtain gelatin microspheres loaded with nano silver;

[0010] (4) Perform freeze-drying treatment on the gelatin microspheres loaded with nano silver to obtain porous gelatin microspheres loaded with nano silver.

[0011] Preferably, the mass ratio of silver nitrate, polyvinylpyrrolidone and sodium hydroxide is 1:(20 - 30):(0.1 - 0.25).

[0012] Preferably, the mass ratio of gelatin and polyvinyl alcohol is 1:(1 - 2).

[0013] Preferably, the particle size of the porous gelatin microspheres loaded with silver nanoparticles is less than 20 μm.

[0014] One of the purposes of the present invention is achieved by the following technical solutions:

[0015] A preparation method of an antibacterial seaweed composite fiber as described above, comprising the following steps:

[0016] S1: Dissolve polyvinyl alcohol in water at 50 - 60 °C, add the porous gelatin microspheres loaded with silver nanoparticles to the polyvinyl alcohol aqueous solution, and ultrasonically disperse evenly to obtain a polyvinyl alcohol mixed solution;

[0017] S2: Dissolve silk fibroin in water, add the silk fibroin aqueous solution to the polyvinyl alcohol mixed solution, and stir evenly to obtain a silk fibroin / polyvinyl alcohol mixed solution;

[0018] S3: Add sodium alginate to the silk fibroin / polyvinyl alcohol mixed solution, and stir evenly at 35 - 40 °C to obtain a composite spinning solution;

[0019] S4: Subject the composite spinning solution to wet spinning through a coagulation bath at 25 - 30 °C, and then through stretching, winding, washing with water and drying to obtain the antibacterial seaweed composite fiber.

[0020] Preferably, in step S4, the spinning solution is coagulated through two coagulation baths. The first coagulation bath uses an aqueous calcium chloride solution, and the second coagulation bath uses a 70 - 80% ethanol aqueous solution.

[0021] Preferably, the mass percentage of the polyvinyl alcohol aqueous solution is 10 - 20%; the mass percentage of the silk fibroin aqueous solution is 10 - 20%.

[0022] Preferably, the mass ratio of silk fibroin and polyvinyl alcohol in the silk fibroin / polyvinyl alcohol mixed solution is 1:(1:1.5).

[0023] The beneficial effects of the present invention are:

[0024] (1) Combining silk fibroin, polyvinyl alcohol and alginate to prepare a composite fiber can effectively improve the mechanical properties of seaweed fiber. Adding silver nanoparticles in the form of porous microspheres to the composite fiber makes the silver nanoparticles more evenly mixed, avoids agglomeration, ensures the success rate of spinning, and increases the antibacterial property of the composite fiber;

[0025] (2) Alginate, polyvinyl alcohol, silk fibroin and gelatin all have a certain water absorption capacity, making them more suitable for sanitary products. Moreover, alginate, polyvinyl alcohol, silk fibroin and gelatin all have good biocompatibility and are more skin-friendly when applied to sanitary products.

[0026] (3) Adding polyvinyl alcohol during the preparation of microspheres can increase the stability of the preparation system, prevent the aggregation of silver nanoparticles in the system, and make the silver nanoparticles uniformly mixed in the microspheres. When dropping the reduction solution while crosslinking and forming the microspheres, silver nanoparticles are generated while the microspheres are being formed. The silver nanoparticles are wrapped inside the microspheres. The silver nanoparticles have a certain influence on the forming process of the microspheres. Under the condition of stirring, the obtained microspheres show an irregular circular structure, which is beneficial for screening microspheres with appropriate particle sizes and facilitating the next spinning process.

[0027] (4) When preparing the composite fiber, first ultrasonically mix the silver-nanoparticle-loaded porous gelatin microspheres in the polyvinyl alcohol aqueous solution. The microspheres are uniformly suspended in the polyvinyl alcohol aqueous solution. Mixing silk fibroin with the polyvinyl alcohol aqueous solution can eliminate some hydrogen bonds on the silk fibroin and increase the mechanical strength during the spinning of silk fibroin. Specific Embodiments

[0028] In order to make the technical problems, technical solutions and beneficial effects solved by the invention clearer, the following further describes the invention in combination with examples and comparative examples.

[0029] Example 1

[0030] This example provides an antibacterial seaweed composite fiber, which includes the following components in parts by weight: 50 parts of alginate, 10 parts of silk fibroin, 12 parts of polyvinyl alcohol and 1 part of silver-nanoparticle-loaded porous gelatin microspheres; the mass ratio of silver nanoparticles to porous gelatin microspheres in the silver-nanoparticle-loaded porous gelatin microspheres is 1:60.

[0031] Example 2

[0032] This example provides an antibacterial seaweed composite fiber, which includes the following components in parts by weight: 60 parts of alginate, 20 parts of silk fibroin, 20 parts of polyvinyl alcohol and 3 parts of silver-nanoparticle-loaded porous gelatin microspheres; the mass ratio of silver nanoparticles to porous gelatin microspheres in the silver-nanoparticle-loaded porous gelatin microspheres is 1:65.

[0033] Example 3

[0034] This example provides an antibacterial seaweed composite fiber, which includes the following components in parts by weight: 56 parts of alginate, 15 parts of silk fibroin, 15 parts of polyvinyl alcohol and 2 parts of silver-nanoparticle-loaded porous gelatin microspheres; the mass ratio of silver nanoparticles to porous gelatin microspheres in the silver-nanoparticle-loaded porous gelatin microspheres is 1:70.

[0035] Example 4

[0036] This example provides an antibacterial seaweed composite fiber, which includes the following components in parts by weight: This example provides an antibacterial seaweed composite fiber, which includes the following components in parts by weight: 50 parts of alginate, 10 parts of silk fibroin, 15 parts of polyvinyl alcohol, and 2 parts of porous gelatin microspheres loaded with nano silver; the mass ratio of nano silver to porous gelatin microspheres in the porous gelatin microspheres loaded with nano silver is 1:70.

[0037] Specifically, the preparation method of the porous gelatin microspheres loaded with nano silver in Examples 1-4 includes the following preparation steps: (1) Dissolve silver nitrate in deionized water, add polyvinyl alcohol and polyvinylpyrrolidone to the silver nitrate solution, and stir evenly to obtain a first mixed solution; add gelatin particles to water, and under a water bath at 50-60 °C, stir evenly, and add the gelatin solution to the first mixed solution to obtain a second mixed solution; (2) Add Span-80 to paraffin and stir, add it to the second mixed solution and stir evenly, then cool to room temperature, add 25% glutaraldehyde and continue to stir. During the second half of the stirring process, dropwise add a reducing solution, which is a mixed solution of glucose and sodium hydroxide, let it stand, pour out the supernatant to obtain a mixture; (3) Under a water bath ultrasound at 30-35 °C, wash the mixture with absolute ethanol multiple times, then wash the mixture with glycine solution multiple times, and wash the mixture with absolute ethanol multiple times again until the oil phase is removed to obtain gelatin microspheres loaded with nano silver; (4) Freeze-dry the gelatin microspheres loaded with nano silver to obtain porous gelatin microspheres loaded with nano silver. The mass ratio of silver nitrate, polyvinylpyrrolidone, and sodium hydroxide is 1:23:0.2; the mass ratio of gelatin to polyvinyl alcohol is 1:1.5; the particle size of the porous gelatin microspheres loaded with nano silver is screened to be less than 20 μm.

[0038] Specifically, the preparation method of the antibacterial seaweed composite fiber in Examples 1-4 includes the following steps: S1: Dissolve polyvinyl alcohol in water at 50-60 °C, and at 35 °C, add the porous gelatin microspheres loaded with nano silver to the polyvinyl alcohol aqueous solution and disperse evenly by ultrasound to obtain a polyvinyl alcohol mixed solution; S2: Dissolve silk fibroin in water, add the silk fibroin aqueous solution to the polyvinyl alcohol mixed solution, and stir evenly to obtain a silk fibroin / polyvinyl alcohol mixed solution; S3: Add sodium alginate to the silk fibroin / polyvinyl alcohol mixed solution and stir evenly at 35-40 °C to obtain a composite spinning solution; S4: Wet-spin the composite spinning solution through two coagulation baths at 25-30 °C. The first coagulation bath uses an aqueous calcium chloride solution, and the second coagulation bath uses a 70-80% ethanol aqueous solution. After stretching, winding, washing with water, and drying, an antibacterial seaweed composite fiber is obtained. The mass percentage of the polyvinyl alcohol aqueous solution is 13%, and the mass percentage of the silk fibroin aqueous solution is 15%.

[0039] Comparative Example 1

[0040] The difference between Comparative Example 1 and Example 1 is that the porous gelatin microspheres loaded with silver nanoparticles are not added in Comparative Example 1.

[0041] Comparative Example 2

[0042] The difference from Example 1 is that silk fibroin is not added in Comparative Example 2.

[0043] Comparative Example 3

[0044] The difference from Example 1 is that polyvinyl alcohol is not added in Comparative Example 3.

[0045] Comparative Example 4

[0046] The difference from Example 1 is that neither silk fibroin nor polyvinyl alcohol is added in Comparative Example 4.

[0047] Comparative Example 5

[0048] The difference from Example 1 is that the porous gelatin microspheres loaded with silver nanoparticles are replaced with silver nanoparticles in Comparative Example 5, and the content of silver nanoparticles is the same as that in the porous gelatin microspheres loaded with silver nanoparticles in Example 1.

[0049] Comparative Example 6

[0050] The difference from Example 1 is that when preparing the antibacterial seaweed composite fiber in Comparative Example 6, the spinning solution is only coagulated with an aqueous calcium chloride solution once.

[0051] The mechanical properties, moisture absorption, antibacterial properties, etc. of the antibacterial seaweed composite fibers of Examples 1-4 and Comparative Examples 1-6 were tested. Specifically, the moisture absorption was measured by the following method: The sample was cut into a size of 10 cm × 10 cm, and the dry weight W0 of each piece was measured. The sample was immersed in deionized water, taken out after 30 seconds of immersion, and hung for 60 seconds, and the wet weight W1 of the sample was measured. The liquid absorption rate = (W1 - W0) / W0; The antibacterial property of the sample was determined according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", and the bacterial strains selected were Staphylococcus aureus and Escherichia coli.

[0052] Table 1 Performance measurement results of Examples 1-4 and Comparative Examples 1-6

[0053]

[0054] As can be seen from the above table, without adding silk fibroin and polyvinyl alcohol, the mechanical properties of the fibers will decline. Especially when lacking polyvinyl alcohol, the breaking strength and elongation at break of the fibers will decrease significantly. Without adding porous gelatin microspheres loaded with silver nanoparticles, the mechanical strength of the fibers will be enhanced, but their antibacterial properties are significantly insufficient. Compared with adding silver nanoparticles alone, adding porous gelatin microspheres loaded with silver nanoparticles can improve the mechanical strength of the fibers, especially the elongation at break. Compared with a single coagulation bath, the double coagulation baths of Examples 1-4 can enhance the liquid absorption rate of the fibers and significantly improve the mechanical properties of the fibers.

[0055] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims

1. An antibacterial seaweed composite fiber, characterized in that, It comprises the following components in parts by weight: 50 - 60 parts of alginate, 10 - 20 parts of silk fibroin, 10 - 20 parts of polyvinyl alcohol, and 1 - 3 parts of porous gelatin microspheres loaded with silver nanoparticles; the mass ratio of silver nanoparticles to porous gelatin microspheres in the porous gelatin microspheres loaded with silver nanoparticles is 1:(60 - 70).

2. The antibacterial seaweed composite fiber according to claim 1, wherein The preparation method of the porous gelatin microspheres loaded with silver nanoparticles comprises the following preparation steps: (1) Dissolve silver nitrate in deionized water, add polyvinyl alcohol and polyvinylpyrrolidone to the silver nitrate solution, stir evenly to obtain a first mixed solution; add gelatin particles to water, stir evenly under a water bath at 50 - 60 °C, and add the gelatin solution to the first mixed solution to obtain a second mixed solution; (2) Add Span - 80 to paraffin and stir, add it to the second mixed solution and stir evenly, then cool to room temperature, add 25% glutaraldehyde and continue to stir. During the stirring process, dropwise add a reducing solution, which is a mixed solution of glucose and sodium hydroxide, let it stand, pour out the supernatant to obtain a mixture; (3) Under a water bath ultrasound at 30 - 35 °C, wash the mixture with absolute ethanol multiple times, then wash the mixture with glycine solution multiple times, and wash the mixture with absolute ethanol multiple times again until the oil phase is removed to obtain gelatin microspheres loaded with silver nanoparticles; (4) Perform freeze - drying treatment on the gelatin microspheres loaded with silver nanoparticles to obtain porous gelatin microspheres loaded with silver nanoparticles.

3. The antibacterial seaweed composite fiber according to claim 2, characterized in that, The mass ratio of silver nitrate, polyvinylpyrrolidone, and sodium hydroxide is 1:(20 - 30):(0.1 - 0.25).

4. The antibacterial seaweed composite fiber according to claim 2, wherein The mass ratio of gelatin to polyvinyl alcohol is 1:(1 - 2).

5. An antibacterial seaweed composite fiber according to claim 1, characterized in that The particle size of the porous gelatin microspheres loaded with silver nanoparticles is less than 20 μm.

6. A method for preparing an antibacterial seaweed composite fiber according to any one of claims 1-5, characterized in that, It comprises the following steps: S1: Dissolve polyvinyl alcohol in water at 50 - 60 °C, add the porous gelatin microspheres loaded with silver nanoparticles to the polyvinyl alcohol aqueous solution, and disperse evenly by ultrasound to obtain a polyvinyl alcohol mixed solution; S2: Dissolve silk fibroin in water, add the silk fibroin aqueous solution to the polyvinyl alcohol mixed solution, and stir evenly to obtain a silk fibroin / polyvinyl alcohol mixed solution; S3: Add sodium alginate to the silk fibroin / polyvinyl alcohol mixed solution, and stir evenly at 35 - 40 °C to obtain a composite spinning solution; S4: Perform wet spinning on the composite spinning solution through a coagulation bath at 25 - 30 °C, and then obtain antibacterial seaweed composite fibers after drawing, winding, water washing, and drying.

7. The preparation method of an antibacterial seaweed composite fiber according to claim 6, characterized in that, In step S4, the spinning solution is coagulated by two coagulation baths. The first coagulation bath uses an aqueous calcium chloride solution, and the second coagulation bath uses a 70 - 80% ethanol aqueous solution.

8. The preparation method of an antibacterial seaweed composite fiber according to claim 6, characterized in that, The mass percentage of the polyvinyl alcohol aqueous solution is 10 - 20%; the mass percentage of the silk fibroin aqueous solution is 10 - 20%.

9. The preparation method of an antibacterial seaweed composite fiber according to claim 6, characterized in that, The mass ratio of silk fibroin to polyvinyl alcohol in the silk fibroin / polyvinyl alcohol mixed solution is 1:(1:1.5).

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