Antibacterial polyester ultrafine fiber and preparation method thereof

Abstract

The present application provides an antibacterial polyester ultrafine fiber and a preparation method thereof. The preparation includes the following steps: preparing an antibacterial agent: using water / isopropanol with a volume ratio of 1:(5-8) as a solvent, adding an Mo source, an S source, and a doping element Bi source into the solvent, mixing evenly and then transferring it into a high-pressure reaction kettle for reaction; dissolving the prepared Bi-MoS2 in deionized water, adding a Ce source and urea, mixing evenly and transferring it into a high-pressure kettle for microwave hydrothermal reaction to obtain a Bi-MoS2 / CeO2 antibacterial agent; dissolving polyester in an organic solvent, mixing evenly, and then adding the antibacterial agent and mixing evenly to obtain a mixed solution; electrospinning the mixed solution to obtain an antibacterial polyester ultrafine fiber. The present application carefully designs antibacterial materials from four aspects: material composition, morphology regulation, doping ions, and constructing heterostructures. By compounding with polyester through electrospinning, while effectively improving antibacterial properties, the shedding of antibacterial agents is avoided, and it has excellent stability.

Description

Technical Field

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

[0002] As a polyester fiber with special functions, antibacterial polyester fiber can effectively prevent bacteria and other microorganisms from growing and multiplying on the surface of clothing, household items and other items by adding antibacterial agents, thereby ensuring that clothing, household items, etc. remain clean and hygienic for a long time, greatly reducing the odor problem caused by bacteria. In addition, the soft and skin-friendly properties of this fiber make the product more comfortable to the touch and improve the user's overall wearing or use experience. More importantly, antibacterial polyester fiber can resist the erosion of microorganisms on items, thereby significantly extending the service life of the product. In terms of hygiene and safety, it provides users with a safer and healthier use environment. Therefore, antibacterial polyester fiber, with its multiple advantages, plays an important role in many fields such as textiles, clothing, and home furnishings, and comprehensively improves the performance and use experience of the product.

[0003] Photocatalytic antibacterial materials are materials that use photocatalytic reactions to generate active oxygen to kill bacteria, viruses, fungi and other microorganisms. Due to their high antibacterial properties, they are currently widely used in textiles. For example, patent application CN119082916A discloses a method for preparing photodynamic antibacterial fibers, which couples n-type, direct bandgap semiconductor Bi2S3 with tight bandgap energy, excellent photosensitivity and good absorption capacity in a wide wavelength with MXene with excellent conductivity, strong light absorption conversion ability and good biocompatibility to form Bi2S3 / MXene composite materials, which can effectively improve the electron-hole separation efficiency and light absorption capacity of semiconductors, and construct photodynamic antibacterial agent Bi2S3 / MXene composite materials with good light response activity in ultraviolet-visible-infrared, full-band photodynamic antibacterial and high ROS yield, thereby improving the antibacterial properties of fabrics made of fibers made of Bi2S3 / MXene composite materials, and overcoming the serious defects of Bi2S3 in photogenerated carrier recombination, low specific surface area and low reduction potential. At present, the photocatalytic antibacterial agents used in polyester fibers still have technical problems such as poor antibacterial performance, easy shedding, low spectrum utilization, and complex preparation process. Summary of the invention

[0004] In order to solve the above problems, the present invention provides an antibacterial polyester ultrafine fiber and a preparation method thereof, wherein the preparation method comprises the following steps:

[0005] S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent:

[0006] Using water / isopropanol with a volume ratio of 1: (5-8) as solvent, add Mo source, S source and doping element Bi source into the solvent, mix well and transfer into a high pressure reactor, react at 200-220°C for 24-48h;

[0007] The prepared Bi-MoS2 was dissolved in deionized water, Ce source and urea were added, and the mixture was evenly mixed and then transferred into an autoclave for microwave hydrothermal reaction to obtain a Bi-MoS2 / CeO2 antibacterial agent;

[0008] S2: Preparation of antibacterial polyester microfiber:

[0009] Dissolve polyester in an organic solvent, mix well, add the antibacterial agent prepared in step S1, continue to mix well, and obtain a mixed solution; electrospin the mixed solution to obtain antibacterial polyester ultrafine fibers;

[0010] Further, the Mo source is selected from sodium molybdate dihydrate or ammonium molybdate, and the sulfur source is selected from thioacetamide or thiourea;

[0011] Further, the Ce source is cerium nitrate; the Bi source is bismuth nitrate;

[0012] Further, the molar ratio of the Mo source, the S source and the doping element Bi source is 1:2:(0.01-0.08);

[0013] Further, the molar ratio of Ce source and urea is 1:(2-2.5);

[0014] Furthermore, the power of microwave hydrothermal is 350-450w; the temperature is 160-200°C, and the reaction time is 0.5-2h;

[0015] Further, the conditions of the electrospinning process are: spinning voltage 20-25 kV, receiving distance 13-17 cm, injection speed 3-5 ml / h;

[0016] Further, the organic solvent is phenol or hexafluoroisopropanol;

[0017] The technical effects achieved by this application are:

[0018] The Bi-MoS2 prepared in the present application has a flower-like structure that refracts light multiple times, thereby improving the utilization rate of light; the huge specific surface area can fully expose the active reaction points and improve the antibacterial property; through Bi doping, the electrons of MoS2 can be transferred from the conduction band to the Bi ions, increasing the delocalization degree of MoS2 electrons, reducing the recombination rate of electrons and holes, and thus improving the antibacterial property; through recombination with CeO2, a heterojunction is easily formed between the two, which broadens the range of visible light response, improves the utilization rate of light, and thus improves the antibacterial property.

[0019] The antibacterial properties are improved by comprehensively designing antibacterial materials from four perspectives: material composition, morphology regulation, ion doping, and heterogeneous structure construction. The antibacterial properties are directly compounded with polyester through electrospinning, which effectively improves the antibacterial properties while avoiding the shedding of the antibacterial agent and has excellent stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the SEM image of the Bi-MoS2 / CeO2 antibacterial agent prepared in this application.

[0021] Figure 2 This is the TEM image of the Bi-MoS2 / CeO2 antibacterial agent prepared in this application. DETAILED DESCRIPTION

[0022] Example 1

[0023] S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent:

[0024] 10 ml of water and 60 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate, 20 mmol of thioacetamide and 0.2 mmol of doping element bismuth nitrate were added to the solvent, mixed evenly and transferred to a high-pressure reactor, and reacted at 200° C. for 24 h;

[0025] The prepared Bi-MoS2 was dissolved in 50 ml of deionized water, 1 mmol of cerium nitrate and 2 mmol of urea were added, the mixture was evenly mixed and transferred into an autoclave for microwave hydrothermal reaction. The power of the microwave hydrothermal reaction was 350 W, the temperature was 180 ° C, and the reaction time was 1 h. The Bi-MoS2 / CeO2 antibacterial agent was obtained.

[0026] S2: Preparation of antibacterial polyester microfiber:

[0027] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:6, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is subjected to electrospinning, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, injection speed 3 ml / h, and subsequent drying to obtain antibacterial polyester ultrafine fibers.

[0028] Example 2

[0029] S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent:

[0030] 10 ml of water and 70 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate, 20 mmol of thioacetamide and 0.2 mmol of doping element bismuth nitrate were added to the solvent, mixed evenly and transferred to a high-pressure reactor, and reacted at 200° C. for 36 hours;

[0031] The prepared Bi-MoS2 was dissolved in 50 ml of deionized water, 1 mmol of cerium nitrate and 2 mmol of urea were added, the mixture was evenly mixed and then transferred into an autoclave for microwave hydrothermal reaction. The power of microwave hydrothermal reaction was controlled to be 400 W, the temperature was 180 ° C, and the reaction time was 1 h. Bi-MoS2 / CeO2 antibacterial agent was obtained.

[0032] S2: Preparation of antibacterial polyester microfiber:

[0033] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:5, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is subjected to electrospinning, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, injection speed 3 ml / h, and drying to obtain antibacterial polyester ultrafine fibers.

[0034] Example 3

[0035] S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent:

[0036] 10 ml of water and 60 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate, 20 mmol of thioacetamide and 0.1 mmol of doping element bismuth nitrate were added to the solvent, mixed evenly and transferred to a high-pressure reactor, and reacted at 200° C. for 24 h;

[0037] The prepared Bi-MoS2 was dissolved in 50 ml of deionized water, 1.5 mmol of cerium nitrate and 3 mmol of urea were added, the mixture was evenly mixed and transferred into an autoclave for microwave hydrothermal reaction, the microwave hydrothermal power was controlled to be 350 w, the temperature was 180 ° C, and the reaction time was 0.5 h; the Bi-MoS2 / CeO2 antibacterial agent was obtained;

[0038] S2: Preparation of antibacterial polyester microfiber:

[0039] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol of 1:0.2:6, the polyester is dissolved in phenol, mixed evenly, and the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is electrospun, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, injection speed 4 ml / h, and drying to obtain antibacterial polyester ultrafine fibers.

[0040] Comparative Example 1

[0041] S1: Preparation of Bi-MoS2 antibacterial agent:

[0042] 10 ml of water and 60 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate, 20 mmol of thioacetamide and 0.2 mmol of doped element bismuth nitrate were added to the solvent, the mixture was evenly mixed and then transferred to a high-pressure reactor, and reacted at 200° C. for 24 hours; it was directly used as an antibacterial agent.

[0043] S2: Preparation of antibacterial polyester microfiber:

[0044] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:6, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is subjected to electrospinning, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, injection speed 3 ml / h, and drying to obtain antibacterial polyester ultrafine fibers.

[0045] Comparative Example 2

[0046] S1: Preparation of CeO2 antibacterial agent:

[0047] 1mmol cerium nitrate and 2mmol urea were added to 50ml deionized water, and the system was transferred into an autoclave for microwave hydrothermal reaction. The power of microwave hydrothermal reaction was controlled to be 350w, the temperature was 180℃, and the reaction time was 1h. CeO2 antibacterial agent was obtained.

[0048] S2: Preparation of antibacterial polyester microfiber:

[0049] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:6, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is subjected to electrospinning, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, injection speed 3 ml / h, to obtain antibacterial polyester ultrafine fibers.

[0050] Comparative Example 3

[0051] S1: Preparation of MoS2 / CeO2 antibacterial agent:

[0052] 10 ml of water and 60 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate and 20 mmol of thioacetamide were added to the solvent, mixed evenly, and then transferred to a high-pressure reactor for reaction at 200°C for 24 hours;

[0053] The prepared MoS2 was dissolved in deionized water, 1mmol cerium nitrate and 2mmol urea were added, and the system was transferred into an autoclave for microwave hydrothermal reaction. The power of microwave hydrothermal reaction was controlled to be 350w, the temperature was 180℃, and the reaction time was 1h. MoS2 / CeO2 antibacterial agent was obtained.

[0054] S2: Preparation of antibacterial polyester microfiber:

[0055] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:6, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly mixed to obtain a mixed solution; the mixed solution is electrospun, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, and injection speed 3 ml / h to obtain antibacterial polyester ultrafine fibers.

[0056] Comparative Example 4

[0057] S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent:

[0058] 65 ml of water and 5 ml of isopropanol were measured to form a water / isopropanol solvent, 10 mmol of ammonium molybdate, 20 mmol of thioacetamide and 0.1 mmol of doping element bismuth nitrate were added to the solvent, mixed evenly and transferred to a high-pressure reactor, and reacted at 200° C. for 24 h;

[0059] The prepared Bi-MoS2 was dissolved in deionized water, 1mmol cerium nitrate and 2mmol urea were added, and the system was transferred into an autoclave for microwave hydrothermal reaction. The power of microwave hydrothermal reaction was controlled to be 350w, the temperature was 180℃, and the reaction time was 1h. Bi-MoS2 / CeO2 antibacterial agent was obtained.

[0060] S2: Preparation of antibacterial polyester microfiber:

[0061] According to the mass ratio of polyester: antibacterial agent: hexafluoroisopropanol being 1:0.2:6, the polyester is dissolved in hexafluoroisopropanol, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly mixed to obtain a mixed solution; the mixed solution is electrospun, and the conditions of the electrospinning process are: spinning voltage 20 kV, receiving distance 15 cm, and injection speed 3 ml / h to obtain antibacterial polyester ultrafine fibers.

[0062] According to CB / T 20944.3-2008 standard, the antibacterial rate of antibacterial polyester microfiber against different bacteria and the antibacterial rate after washing 30 times were tested. The results are shown in the following table.

[0063] Table 1

[0064]

[0065] By comparing Example 1 with Comparative Examples 1-2, it can be seen that the antibacterial property of the Bi-MoS2 / CeO2 composite material is significantly better than that of the single Bi-MoS2 and CeO2 materials; by comparing Example 1 with Comparative Example 3, it can be seen that the Bi-doped composite material is better than the undoped MoS2 / CeO2; by comparing Example 1 with Comparative Example 4, it can be seen that by adjusting the ratio of water and isopropanol, the antibacterial property is reduced to a certain extent. This is mainly because after adjusting the solvent ratio, the prepared Bi-MoS2 is not a flower-like structure, but a nanoparticle, and the utilization rate of light is reduced to a certain extent, which directly affects its antibacterial properties.

[0066] The above is only a preferred specific implementation of the present invention; however, the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solution and its improved conception within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A method for preparing antibacterial polyester ultrafine fibers, characterized in that: The steps include: S1: Preparation of Bi-MoS2 / CeO2 antibacterial agent: Using water / isopropanol with a volume ratio of 1: (5-8) as solvent, add Mo source, S source and doping element Bi source into the solvent, mix well and transfer into a high pressure reactor, react at 200-220°C for 24-48h; The prepared Bi-MoS2 was dissolved in deionized water, Ce source and urea were added, and the mixture was evenly mixed and then transferred into an autoclave for microwave hydrothermal reaction to obtain a Bi-MoS2 / CeO2 antibacterial agent; S2: Preparation of antibacterial polyester microfiber: The polyester is dissolved in an organic solvent, and after mixing evenly, the antibacterial agent prepared in step S1 is added, and the mixing is continued to be evenly obtained to obtain a mixed solution; the mixed solution is electrostatically spun to obtain antibacterial polyester ultrafine fibers.

2. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The Mo source is selected from sodium molybdate dihydrate or ammonium molybdate, and the sulfur source is selected from thioacetamide or thiourea.

3. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The Ce source is cerium nitrate; the Bi source is bismuth nitrate.

4. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The molar ratio of the Mo source, the S source and the doping element Bi source is 1:2:(0.01-0.08).

5. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The molar ratio of Ce source to urea is 1:(2-2.5).

6. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The power of microwave hydrothermal is 350-450w; the temperature is 160-200℃, and the reaction time is 0.5-2h.

7. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The conditions of the electrospinning process are: spinning voltage 20-25 kV, receiving distance 13-17 cm, and injection speed 3-5 ml / h.

8. The method for preparing antibacterial polyester ultrafine fiber according to claim 1, characterized in that: The organic solvent is phenol or hexafluoroisopropanol.

9. An antibacterial polyester microfiber, characterized in that: Prepared by the method according to any one of claims 1 to 8.

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