Preparation method of biological organic carbon enhanced magnetic antibacterial master batch

Abstract

The invention relates to a preparation method of a biological organic carbon enhanced magnetic antibacterial master batch. The magnetic antibacterial master batch is loaded with silver through a ZIF-67 (at) Biomass complex, and the silver loading step comprises the following components by mass: 0.1 to 0.3 mL of an AgNO3 aqueous solution with the concentration of 75.75 to 80.75 mg / mL, and 500 to 700 [mu] L of a newly prepared NaBH4 aqueous solution with the concentration of 20 to 30 mg / mL, so as to prepare the Ag-ZIF-67 (at) Biomass complex; then, the Ag-ZIF-67 (at) Biomass complex and natural biomass materials (corn straw, peanut shells and bagasse) are fired to obtain Ag-ZBC powder, and finally, the Ag-ZBC powder and polyester are fused to prepare the Ag-ZBC magnetic antibacterial master batch. The magnetic antibacterial master batch prepared by the invention has obvious magnetic health-care effect and antibacterial property, is healthy, environment-friendly and non-toxic, and can be widely applied to the field of fabric spinning.

Description

Technical Field

[0001] The invention relates to a method for preparing biological organic carbon-enhanced magnetic antibacterial masterbatch. Background Art

[0002] With the gradual promotion of magnetic materials in the medical and healthcare fields, the concept of magnetic health care has gained wider recognition and understanding. The technical principle of magnetic health care is generally defined as follows: magnetic fields promote fluid circulation, reduce viscosity, activate enzymes, and influence hemoglobin movement, resulting in anti-inflammatory and analgesic effects, sleep enhancement, scar repair, swelling reduction, and mood improvement. This treatment method is currently considered non-toxic, harmless, non-invasive, and safe. Generally speaking, magnetic health care utilizes this biomagnetic effect within the human body to adjust and restore various imbalances or abnormal functional states to achieve therapeutic purposes. Magnetic health care is primarily suitable for treating conditions such as hypertension, hyperlipidemia, neuralgic headaches, neurasthenia, hemifacial spasm, bronchitis, enteritis, ulcers, cervical spondylosis, low back and leg pain, acute lumbar sprains, lumbar muscle strain, biliary colic, biliary stones, urinary stones, rhinitis, dermatitis, and phlebitis.

[0003] The development of magnetic fabrics is based on the principle that applying a magnetic field to the external environment of the human body affects the human nervous system and body fluid circulation, causing changes in molecular structure and charge potential, and then affecting the physiological and biochemical functions of the human body, thereby improving body functions and enhancing disease resistance. Therefore, magnetic fabrics have a bright market prospect in the field of medical and health care.

[0004] Magnetic fiber masterbatch is the technical core of magnetic fabrics. In order to meet the design requirements of magnetic fabrics for underwear, antibacterial properties must be taken into account. In the specific implementation process, magnetic masterbatch and antibacterial masterbatch are respectively combined with fibers to make antibacterial fabrics with magnetic health effects. The magnetic strength of existing functional masterbatch and fiber blending spinning is difficult to control. In particular, when small-particle magnetic powder is used as functional masterbatch to meet the requirements of blending spinning, the magnetic powder has a larger specific surface area and is more likely to lose effectiveness due to contact with air and water, becoming a bottleneck that prevents the masterbatch and fiber blending spinning processing and manufacturing. At present, most magnetic fabrics have the problem of incompatibility between magnetism and antibacterial properties, which greatly affects the use scenarios and application range of magnetic fabrics.

[0005] While this method of controlling the magnetic strength of fibers by controlling the magnetic powder content can produce magnetic fibers, it has drawbacks: if the magnetic powder content in the fiber is high, the addition of antimicrobial masterbatch will reduce the fiber's strength, leading to increased brittleness. When preparing functional nylon fibers, when the masterbatch content reaches 15%, the fiber's strength drops to approximately 50% of its original strength (breaking strength of approximately 1.8 CN / dtex). Therefore, the amount of masterbatch used in functional fibers produced by co-spinning is a major constraint on the development of multifunctional fabrics.

[0006] To address the above constraints, we have developed a multifunctional masterbatch that combines magnetism and antibacterial properties. The magnetic antibacterial masterbatch provided by the present invention has both excellent antibacterial properties and adjustable magnetic strength, and through the synergistic effect of the two functions, it meets the wide demand for magnetic health-care fabrics. Summary of the Invention

[0007] In view of the problems existing in the prior art, the purpose of the present invention is to provide a technical solution for the preparation of a magnetic antibacterial masterbatch enhanced with bio-organic carbon.

[0008] The method for preparing the bio-organic carbon-enhanced magnetic antibacterial masterbatch comprises the following steps: Step S1. Preparation of ZIF-67@Biomass complex: Co(NO3)2·6H2O was weighed and dissolved in methanol (containing sugarcane bagasse, peanut shells, and corn straw powder) and shaken on a shaker for 1-3 hours to form solution A. 2-Methylimidazole was weighed and dissolved in methanol to form solution B. Solution B was quickly poured into solution A to form solution C. Solution C was stirred at room temperature for 12-24 hours, washed three times with methanol, and vacuum dried for 12-24 hours to obtain the ZIF-67@Biomass complex. Step S2. Preparation of Ag-ZIF-67@Biomass complex: ZIF-67@Biomass was dispersed in n-hexane, and the mixed solution was sonicated for 10 to 30 minutes. An AgNO3 aqueous solution was added to the above solution, and the mixed solution was stirred at room temperature for 2 to 4 hours. The supernatant was removed and dried overnight. The resulting product was dispersed in methanol, and a certain amount of freshly prepared NaBH4 aqueous solution was added dropwise and rapidly stirred for 20 to 40 minutes. The mixture was centrifuged through methanol three times and dried overnight to obtain a deep purple-red product, the Ag-ZIF-67@Biomass complex. Step S3. Preparation of Ag-ZBC powder: Under nitrogen protection, the Ag-ZIF-67@Biomass complex was heated to 800 °C and maintained for 2 hours. The resulting black powder was immersed in hydrochloric acid solution for 3 to 6 hours to remove unstable Co particles and CoOx The acid-washed product was washed three times with methanol and deionized water, and vacuum-dried overnight to obtain Ag-ZBC powder; Step S4. Preparation of Ag-ZBC magnetic antibacterial masterbatch: 50 mg of polyester was heated and melted at 260 ° C. After it was melted, 50 mg (mass fraction 50%) of Ag-ZBC powder was added. After stirring evenly, it was cooled and solidified to obtain bio-organic carbon enhanced Ag-ZBC magnetic antibacterial masterbatch.

[0009] Preferably, in step S1, the amount of Co(NO3)2·6H2O is 0.19 g to 0.39 g, the shaker temperature is controlled at 20 to 40°C, the amount of 2-methylimidazole is 0.556 g to 0.756 g, and the amount of methanol is 10 to 30 mL. The methanol contains 5 to 15 mg / mL of bio-organic powder, and the bio-organic powder includes sugarcane bagasse, peanut shells, and corn straw powder. The vacuum drying needs to maintain a constant temperature of 40 to 80°C.

[0010] Preferably, in step S2, the amount of ZIF-67@Biomass is 450-600 mg, the amount of n-hexane is 30-50 mL, the amount of AgNO3 aqueous solution is 0.1-0.3 mL, and the concentration thereof is 75.75-80.75 mg / mL. The temperature should be maintained at 55-75°C during drying overnight.

[0011] Preferably, in step S2, the amount of methanol is 100-150 mL, the amount of the newly prepared NaBH4 aqueous solution is 500-700 μL, the concentration of which is 20-30 mg / mL, and the temperature needs to be maintained at 60-80° C. for drying overnight.

[0012] Preferably, in step S3, the temperature is raised to 800° C. under nitrogen protection at a heating rate of 5-15° C. / min; the concentration of the hydrochloric acid solution is 0.5-1.5 mol / L, and the vacuum drying needs to be maintained at a constant temperature of 40-80° C.

[0013] Preferably, a bio-organic carbon-enhanced magnetic antibacterial masterbatch is prepared by the method of any one of claims 1 to 5, comprising 50% by mass of Ag-ZBC composite powder and a polyester carrier.

[0014] Preferably, a magnetic antibacterial fiber is made by blending the masterbatch according to claim 6 with polyester.

[0015] The present invention aims to overcome the shortcomings of existing magnetic masterbatches, addressing the problems of limited functionality and difficulty controlling magnetic strength. This invention provides a method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch, which combines magnetic health benefits with antibacterial properties. The masterbatch enhances magnetic strength by adding organic carbon. The required carbon source can be a wide range of biomass materials, including bamboo charcoal, corn stalks, sugarcane bagasse, and peanut shells. Furthermore, the masterbatch is healthy, environmentally friendly, and non-toxic, making it suitable for widespread use in the field of health-care fabric textiles.

[0016] The fabric obtained by blending the bio-organic carbon-enhanced magnetic antibacterial masterbatch provided by the present invention with fibers has the characteristics of moisture absorption and breathability, antibacterial and antibacterial, and green environmental protection. Compared with the magnetic bamboo charcoal fabric currently on the market, it has better antibacterial performance on the basis of other advantages, and has the outstanding characteristics of energy saving, carbon fixation and emission reduction during the production process. DETAILED DESCRIPTION

[0017] The magnetic antibacterial masterbatch of the present invention is loaded with silver through a ZIF-67@Biomass complex. The silver loading step includes the following components by mass: 0.1-0.3 mL of an AgNO3 aqueous solution with a concentration of 75.75-80.75 mg / mL and 500-700 μL of a newly prepared NaBH4 aqueous solution with a concentration of 20-30 mg / mL to prepare an Ag-ZIF-67@Biomass complex; then, the Ag-ZIF-67@Biomass complex is fired with natural biomass materials (corn straw, peanut shells, and sugarcane bagasse) to obtain Ag-ZBC powder, which is finally melted with polyester to prepare an Ag-ZBC magnetic antibacterial masterbatch. The firing process includes: after adding Ag-ZIF-67@Biomass, controlling the temperature to rise from 25°C to 800°C, and controlling the heating rate to be 5-15°C / minute; the purpose of the firing process is to adjust the magnetic strength through biochar dilution, so that the finally prepared Ag-ZBC magnetic antibacterial masterbatch can exert a magnetic health effect within a reasonable magnetic range; the magnetic antibacterial masterbatch prepared by the present invention has obvious magnetic health effect and antibacterial performance, is healthy, environmentally friendly and non-toxic, and can be widely used in the field of fabric textiles.

[0018] A bio-organic carbon-enhanced magnetic antibacterial masterbatch comprises 50% by mass of Ag-ZBC composite powder and a polyester carrier.

[0019] The invention discloses a magnetic antibacterial fiber, which is made by spinning a blend of masterbatch and polyester. Example

[0020] Preparation of bio-organic carbon-enhanced Ag-ZBC magnetic antibacterial masterbatch: (1) Preparation of ZIF-67@Biomass complex: 0.291 g of Co(NO3)2·6H2O was dissolved in 20 mL of methanol (containing 10 mg / mL of bio-organic matter powder) and shaken at 30°C for 2 h to form solution A. 0.656 g of 2-methylimidazole was dissolved in 20 mL of methanol to form solution B. Solution B was quickly poured into solution A to form solution C. Solution C was stirred at room temperature for 24 h, washed three times with methanol, and dried in vacuo at 60°C for 12 h to obtain the ZIF-67@Biomass complex.

[0021] (2) Preparation of Ag-ZIF-67@Biomass complex: 500 mg of ZIF-67@Biomass was dispersed in 40 mL of n-hexane, and the mixed solution was ultrasonically treated for about 20 minutes; 0.2 mL of AgNO3 (78.75 mg / mL) aqueous solution was added to the above solution, and the mixed solution was stirred at room temperature for 3 hours. The supernatant was removed and dried at 65°C overnight; the resulting product was dispersed in 120 mL of methanol, and 600 μL of freshly prepared NaBH4 aqueous solution (25 mg / mL) was added dropwise and stirred rapidly for 30 minutes. The mixture was centrifuged through methanol three times and dried at 65°C overnight to obtain a deep purple-red product, Ag-ZIF-67@Biomass complex.

[0022] (3) Preparation of Ag-ZBC powder: Under nitrogen protection, the temperature was raised at a rate of 10°C / min and maintained at 800°C for 2 hours. The resulting black powder was immersed in a 1 mol / L hydrochloric acid solution for 4 hours. The acid-washed product was washed three times with methanol and deionized water, and vacuum-dried at 60°C overnight to obtain Ag-ZBC powder.

[0023] (4) Preparation of Ag-ZBC magnetic antibacterial masterbatch: 50 mg of polyester was melted at 260 ° C, and after it was melted, 50 mg (mass fraction 50%) of Ag-ZBC powder was added. After stirring evenly, it was cooled and solidified to obtain bio-organic carbon enhanced Ag-ZBC magnetic antibacterial masterbatch.

[0024] The magnetic properties of Ag-ZBC magnetic antibacterial masterbatch enhanced by bio-organic carbon were tested to verify its specific practical effect.

[0025] The magnetic susceptibility of the bio-organic carbon-enhanced magnetic antibacterial masterbatch prepared above was tested using a Gouy balance and converted into magnetic induction intensity. The results are shown in the following table:

[0026] Note: BA is bagasse, PN is peanut shell, and CS is corn straw.

[0027] Preparation of magnetic antibacterial fiber: The data in the table above demonstrates that this bio-organic carbon-enhanced magnetic antibacterial masterbatch exhibits strong magnetic properties. Based on this data, the Ag-ZBC / BA combination was preferred: 90 mg of polyester was melted at 260°C. Once melted, 10 mg of magnetic masterbatch (10% by mass) was added, stirred evenly, and allowed to cool and solidify. The resulting magnetic induction intensity was 0.17 mT. The magnetic induction intensity obtained from spinning a 10% blend (polyester blend spinning solution) meets the requirements of standard FZT01116-2012, "Testing and Evaluation of Magnetic Properties of Textiles," demonstrating that this masterbatch can be used in the production of magnetic antibacterial fabrics.

[0028] The antibacterial performance of Ag-ZBC magnetic antibacterial masterbatch enhanced by bio-organic carbon was tested to examine its specific antibacterial effect.

[0029] Antibacterial test: (1) Preparation of bacterial liquid: Pour 5 mL of LB liquid culture medium into a test tube, inoculate Staphylococcus aureus (Bacillus subtilis, Escherichia coli) strains, and culture in a constant temperature shaker at 28 °C (200 rpm) for 6 to 8 h.

[0030] (2) Prepare LB medium: Liquid culture medium formula: 20 g tryptone, 10 g yeast extract, 10 g sodium chloride, 1000 mL water; Solid culture medium formula: 20 g tryptone, 10 g yeast extract, 10 g sodium chloride, 1000 mL water, 15 g agar powder; Adjust the pH to 7.2-7.4 and sterilize by autoclave at 121°C for 15 minutes; Pour plates (pour 10 mL of LB solid medium into each plate) and prepare test tubes of liquid medium (pour 5 mL of LB liquid medium into each tube). Prepare 50 plates and 25 test tubes of liquid medium in advance and store at 4°C.

[0031] (3) Bacteria preservation: 6 hours after spreading and culturing, single colonies with good adaptability were selected and stored in test tubes (three for each type, at different positions of the culture medium). After culturing for 6 hours, they were stored at 4°C for future use.

[0032] (4) Formal experiment: Pour 5 mL of LB liquid culture medium into the test tube, inoculate the purified bacteria, and culture in a constant temperature shaker at 28°C (200 rpm) for 6 to 8 hours (this step can be saved after the third step is completed).

[0033] Count the cells using a hemocytometer and dilute the bacterial suspension to 1 × 10 7 cfu / mL and store in a 4°C refrigerator (Note: cfu refers to colony forming unit).

[0034] Preparation of test samples: Grind a certain amount of Ag-ZBC magnetic antibacterial masterbatch to obtain powder, adjust its final concentration to 0.1 g / mL, sterilize it by high pressure at 121 °C for 20 min, and store it in a refrigerator at 4 °C for later use.

[0035] Ag-ZBC magnetic antibacterial masterbatch sensitivity test against pathogenic bacteria: Using the Oxford cup method, 10 mL of LB solid culture medium was poured into each plate and placed on a horizontal table. Once the plate solidified and the culture dish was free of moisture, 100 μL of the bacterial suspension was evenly spread on the plate. Three Oxford cups were placed on each plate, and 200 μL of the Ag-ZBC magnetic antibacterial masterbatch powder dilution was added to each Oxford cup. Three replicates were performed for each concentration. The plates were incubated at 28°C for 12 hours. The diameter of the inhibition zone around the Oxford cup was measured and the average value was taken. An inhibition zone diameter of less than 10 mm was considered resistant (R), 10-15 mm was considered moderately sensitive (M), and 15 mm or greater was considered highly sensitive (S).

[0036] Determination of minimum inhibitory concentration and minimum bactericidal concentration: Minimum inhibitory concentration (MIC): Determine the MIC using the 96-well broth microdilution method. Aseptically, prepare a clean 96-well ELISA plate (12 x 8 wells) and add 180 μL of sterile LB liquid medium to each well (except the first well).

[0037] Add 200 μL of the prepared Ag-ZBC magnetic antibacterial masterbatch powder dilution to the first well of the first column, then dilute it 10 times, blow it thoroughly for more than 3 times, draw 20uL, add it to the second well and blow it thoroughly, repeat to the eighth well, so that the mass concentrations of Ag-ZBC magnetic antibacterial masterbatch in wells 1 to 8 are 1000 mg / mL (1-fold dilution), 100 mg / mL (10-fold dilution), 10 mg / mL (100-fold dilution), 1mg / mL (1000-fold dilution), 0.1mg / mL (10,000-fold dilution), 0.01mg / mL (105-fold dilution), 0.001mg / mL (106-fold dilution), 0.0001mg / mL (107-fold dilution). Use the same method to dilute the samples in columns 2 to 3 by 10 times, add 200uL of diluted bacterial solution to each well, columns 9 to 11 serve as positive controls (add bacterial solution but no sample solution), column 12 serves as a negative control (add only blank culture medium but no bacterial solution). Incubate the whole plate in an upright position at 28°C for 12 hours, take out the plate for observation, and place the incubated 96-well plate in a microplate reader for OD600nm determination.

[0038] Determination of MIC wells: The MIC value is the concentration of the lowest dilution of the antimicrobial drug that produces a well with noticeable turbidity observed by the naked eye. To confirm the accuracy of the visually determined MIC wells, the OD600nm value of each well is measured using a microplate reader.

[0039] Determine the bacterial inhibition rate (%) = (positive control well OD - drug well OD) / (positive control well OD - negative control well OD) Antibacterial performance test results:

[0040] According to the antibacterial rate obtained from the antibacterial performance test, it can be seen that the magnetic antibacterial masterbatch has a good antibacterial effect.

[0041] Note: Ag-ZBC is the bio-organic carbon-enhanced magnetic antibacterial masterbatch described in this patent, where Z: ZIF-67; B: Biomass; C: Carbon.

Claims

1. A method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch, comprising the following steps: Step S1. Preparation of ZIF-67@Biomass complex: Co(NO3)2·6H2O was weighed and dissolved in methanol containing bio-organic powder and shaken on a shaker for 1-3 hours to form solution A. 2-Methylimidazole was weighed and dissolved in methanol to form solution B. Solution B was quickly poured into solution A to form solution C. Solution C was stirred at room temperature for 12-24 hours, washed three times with methanol, and vacuum dried for 12-24 hours to obtain the ZIF-67@Biomass complex. Step S2. Preparation of Ag-ZIF-67@Biomass complex: The ZIF-67@Biomass complex was dispersed in n-hexane, and the mixed solution was ultrasonically treated for 10 to 30 minutes. Then, an AgNO3 aqueous solution was added, and the mixed solution was stirred at room temperature for 2 to 4 hours. The supernatant was removed and dried overnight. The resulting product was dispersed in methanol, and a freshly prepared NaBH4 aqueous solution was added dropwise with rapid stirring for 20 to 40 minutes. The mixture was centrifuged through methanol three times and dried overnight to obtain a deep purple-red product, the Ag-ZIF-67@Biomass complex. Step S3. Preparation of Ag-ZBC powder: Under nitrogen protection, the Ag-ZIF-67@Biomass complex was heated to 800 °C and maintained for 2 hours. The resulting black powder was immersed in hydrochloric acid solution for 3 to 6 hours to remove unstable Co particles and CoO x The finished product after acid washing was washed three times with methanol and deionized water, and vacuum dried overnight to obtain Ag-ZBC powder; Step S4. Preparation of Ag-ZBC magnetic antibacterial masterbatch: 50 mg of polyester was heated and melted at 260° C. After melting, 50 mg of Ag-ZBC powder was added, stirred evenly, and cooled and solidified to obtain bio-organic carbon-enhanced Ag-ZBC magnetic antibacterial masterbatch.

2. The method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch according to claim 1, characterized in that: In step S1, the amount of Co(NO3)2·6H2O is 0.19 g to 0.39 g, the shaker temperature is controlled at 20 to 40°C, the amount of 2-methylimidazole is 0.556 to 0.756 g, the amount of methanol is 10 to 30 mL, and the amount of methanol containing bio-organic powder is 5 to 15 mg / mL. The bio-organic powder includes sugarcane bagasse, peanut shells, and corn straw powder. The vacuum drying needs to maintain a constant temperature of 40 to 80°C.

3. The method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch according to claim 1, characterized in that: In step S2, the amount of ZIF-67@Biomass is 450-600 mg, the amount of n-hexane is 30-50 mL, and the amount of AgNO3 aqueous solution is 0.1-0.3 mL, with a concentration of 75.75-80.75 mg / mL. The temperature should be maintained at 55-75°C for drying overnight.

4. The method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch according to claim 1, characterized in that: In step S2, the amount of methanol is 100-150 mL, the amount of the newly prepared NaBH4 aqueous solution is 500-700 μL, the concentration of which is 20-30 mg / mL, and the temperature needs to be maintained at 60-80°C for drying overnight.

5. The method for preparing a bio-organic carbon-enhanced magnetic antibacterial masterbatch according to claim 1, characterized in that: In step S3, the temperature is raised to 800°C under nitrogen protection at a rate of 5-15°C / min. The concentration of the hydrochloric acid solution is 0.5-1.5 mol / L, and the vacuum drying needs to be maintained at a constant temperature of 40-80°C.

6. A bio-organic carbon-enhanced magnetic antibacterial masterbatch, prepared by the method of any one of claims 1 to 5, comprising 50% by weight of Ag-ZBC composite powder and a polyester carrier.

7. A magnetic antibacterial fiber, comprising the masterbatch according to claim 6 and polyester blended and spun.

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