CN114438780A - Preparation method of environment-friendly long-acting antibacterial fiber - Google Patents

Preparation method of environment-friendly long-acting antibacterial fiber Download PDF

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CN114438780A
CN114438780A CN202210094405.0A CN202210094405A CN114438780A CN 114438780 A CN114438780 A CN 114438780A CN 202210094405 A CN202210094405 A CN 202210094405A CN 114438780 A CN114438780 A CN 114438780A
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fiber
polyhexamethylene guanidine
putting
antibacterial fiber
water
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王娟
刘俊雅
李飞
吴玉娇
王帅
刘子晴
魏超月
陈新乐
马思怡
黄玲玲
张敏
张伟亮
贾鹏飞
葛凤燕
刘占旗
邢云立
章柏宁
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Shijiazhuang University
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Shijiazhuang University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/123—Polyaldehydes; Polyketones
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    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract

The invention discloses a preparation method of an environment-friendly long-acting antibacterial fiber, belonging to the technical field of fibers; the preparation method of the antibacterial fiber comprises the following steps: 1) alcohol treatment; 2) alkali treatment; 3) and (4) preparing the antibacterial fiber. The preparation method has simple process, safe and low-toxicity preparation raw materials, environmental protection, and long bacteriostatic effect of the prepared product, conforms to the green development concept, improves the application range of the fiber, and has outstanding practical effect and application prospect.

Description

Preparation method of environment-friendly long-acting antibacterial fiber
Technical Field
The invention relates to the technical field of fibers, in particular to a preparation method of an environment-friendly long-acting antibacterial fiber.
Background
For a long time, the infectious diseases bring great troubles to our lives, and the factors inducing the infectious diseases are complicated. For example, in daily life, cleaning articles such as towels are usually placed in a toilet, air is not circulated, ventilation and air permeability are poor, direct sunlight is lacked, and temperature and humidity are suitable for the proliferation of bacteria and fungi. Therefore, the development of textiles with durable antibacterial properties is of great significance in various fields such as daily life, safe home furnishing, medical environments and the like.
At present, polyester and nylon blended polyester-nylon composite fibers are widely applied to various aspects of life, medicine and the like. But the terylene composite fiber with bacteriostatic function faces the bottleneck of difficult grafting with the disinfectant. Polyester in the polyester-nylon composite fiber: nylon is about 7.5: 2.5, the chemical name of terylene is polyethylene terephthalate, the chemical name of chinlon is polyamide, and the chemical structure of the main component terylene has few active groups, and generally, the reaction is not easy to occur, so the ester group needs to be hydrolyzed for the chemical reaction. And the problem of difficult grafting of the disinfectant with the textile is existed.
Polytrimethylene terephthalate (PTT for short) is used as a novel polyester material, and the fiber prepared from the Polytrimethylene terephthalate has excellent elastic recovery, stain resistance and dyeing property, and is widely applied to various aspects of life, medicine and the like. Therefore, the development of textiles having durable antibacterial properties under daily visible light is of great significance in various fields such as daily life, safe home furnishing, medical environments and the like. But PTT fibers with bacteriostatic functionality also face the bottleneck of difficult grafting with disinfectants.
Disclosure of Invention
In order to solve the problems, the invention uses glutaraldehyde, titanium dioxide, copper ions and silver ions, and adds bacteriostatic to increase the antibacterial performance of the fiber, and the method is simple and low in toxicity, and has very outstanding practical effect and application prospect.
The invention provides a preparation method of environment-friendly long-acting antibacterial fiber, which comprises the following steps:
1) alcohol treatment: pouring absolute ethyl alcohol into the container until the fibers are immersed, ultrasonically cleaning for 25-45min, and after cleaning, putting the fibers into a clean place to be naturally dried;
2) alkali treatment: putting 8-12% w/w sodium hydroxide solution and magnetons into a reaction container, heating to 75-85 ℃, adding the fiber treated by the alcohol in the step (1), stirring for 25-35min, taking out the fiber, washing the fiber with distilled water to be neutral, and drying for later use;
3) preparing antibacterial fibers: and (3) putting the substance A, the bacteriostatic agent, the water and the fiber subjected to alkali treatment in the step (2) into a reaction container to prepare the antibacterial fiber.
Ultrasonic cleaning is carried out for 30min in the alcohol treatment, the concentration of a sodium hydroxide solution is 10% in the alkali treatment, and the treatment is carried out for 30 min.
The fiber is polyester-nylon composite fiber or polytrimethylene terephthalate fiber.
The substance A is any one of glutaraldehyde, titanium dioxide, silver ions or copper ions.
When the substance A is glutaraldehyde, the preparation method of the antibacterial fiber comprises the steps of putting 0.8-1.2% of glutaraldehyde, 0.6-0.9% of bacteriostatic agent, 98-98.5% of water and magnetons into a reactor according to parts by weight, heating and stirring, putting the fiber subjected to alkali treatment in the step 2 when the rotation number of the magnetons is 800r/min, reacting at 90 ℃ for 3 hours, taking out the fiber, and drying at 70 ℃ for 1 hour.
When the substance A is titanium dioxide, the preparation method of the antibacterial fiber comprises the steps of putting 0.8-1.2% of titanium dioxide, 1.5-3% of bacteriostatic agent, 96-97.5% of water and magnetons into a reactor according to parts by weight, stirring for 1 hour at normal temperature, putting the fiber subjected to alkali treatment in the step 2 into the reactor, reacting for 2 hours at normal temperature, taking out the fiber, and drying for 1 hour at normal temperature.
When the substance A is silver ions, the preparation method of the antibacterial fiber comprises the steps of putting 0.03-0.2% of silver nitrate, 0.8-1.4% of bacteriostatic agent, 98.5-99% of water and magnetons into a reactor according to parts by weight, stirring for 2 hours at normal temperature at the rotation speed of 750r/min in a manner of keeping out of the sun at the outer layer of the reactor, then adding 0.08g/100ml of sodium borohydride solution, wherein the volume ratio of the sodium borohydride solution to the water is 1:18-22, stirring for 5 hours at normal temperature, then putting the fiber subjected to alkali treatment in the step 2, reacting for 2 hours, taking out the fiber, and drying for 1 hour at normal temperature.
When the substance A is copper ions, the preparation method of the antibacterial fiber comprises the steps of putting 4-6% of copper sulfate solid, 0.8-1.2% of bacteriostatic agent, 93-95% of water and magnetons into a reactor according to parts by weight, heating and stirring, starting to react for 5 hours at the temperature of 80 ℃, putting the fiber subjected to alkali treatment in the step 2 into the reactor, reacting for 2 hours at the temperature of 80 ℃, taking out the fiber, and drying for 1 hour at the temperature of 70 ℃.
The bacteriostatic agent is any one of polyhexamethylene guanidine and thiourea graft, polyhexamethylene guanidine and chitosan graft, and polyhexamethylene guanidine and maleic anhydride graft.
When the bacteriostatic agent is a polyhexamethylene guanidine (PHGC) and thiourea graft, the grafting method comprises the following steps: dissolving polyhexamethylene guanidine into a mixed solution of ethanol and water in a volume ratio of 1.5-3:1, adding thiourea into the mixed solution after dissolving, wherein the mass ratio of the thiourea to the polyhexamethylene guanidine is 0.06-1: 1, reacting the mixture at 100 ℃ for 1.5h, carrying out rotary evaporation on the obtained product at 85 ℃ for 15-30min, and drying the product at room temperature in vacuum for 12h to obtain the polyhexamethylene guanidine and thiourea graft.
When the bacteriostatic agent is a polyhexamethylene guanidine and maleic anhydride graft, the grafting method comprises the following steps: dissolving polyhexamethylene guanidine into a mixed solution of ethanol and water in a volume ratio of 1.5-3:1, adding maleic anhydride after dissolving, wherein the molar ratio of the polyhexamethylene guanidine to the polyhexamethylene guanidine is 1-1.5: 1, reacting the mixture at 40 ℃ for 10-30h, carrying out rotary evaporation on the obtained product at 40 ℃ for 15-30min, settling the product by using acetone, filtering supernatant, repeating the operation for 3 times, and carrying out vacuum drying at room temperature for 12h to obtain the polyhexamethylene guanidine and maleic anhydride graft.
When the bacteriostatic agent is a polyhexamethylene guanidine and chitosan grafting object, the grafting method comprises the following steps: polyhexamethylene guanidine was dissolved in ethanol: acetone: the volume ratio of water is 1-3: 0.5-1.5: 1, adding glycidyl methacrylate into the solution of the formula 1, wherein the molar ratio of the glycidyl methacrylate to the polyhexamethylene guanidine is 1:1, carrying out reaction for 6h in a nitrogen atmosphere at the temperature of 40-45 ℃, and carrying out rotary evaporation to obtain a product, namely polyhexamethylene guanidine hydrochloride derivative (PHGH); dissolving chitosan in an acetic acid solution with the concentration of 1%, introducing nitrogen, fully stirring for 20-40min, adding a polyhexamethylene guanidine hydrochloride derivative and ceric ammonium nitrate, adjusting the pH value of the suspension to 5-6 by using 0.2mol/L nitric acid, placing a reactor in a water bath with the temperature of 50-55 ℃ for 3h under the nitrogen atmosphere, then using acetone for settling, and filtering to obtain a crude grafting product, wherein the mass ratio of the polyhexamethylene guanidine to the chitosan is 4-6: 3, the mass ratio of the polyhexamethylene guanidine hydrochloride derivative to the ceric ammonium nitrate is (40-50): 1; extracting with ethanol for 8h, vacuum drying, and grinding to obtain pure graft product.
Compared with the prior art, the invention has the following advantages:
1. after the alcohol treatment and the alkali treatment, the fiber of the invention can better loosen the surface structure of the fiber, and can not greatly destroy the tensile strength and the breaking strength of the fiber, thereby being very beneficial to the reaction of the fiber and the bacteriostatic agent.
2. The antibacterial fiber has good antibacterial performance.
3. The preparation method disclosed by the invention is simple in process, the preparation raw materials are safe and low in toxicity, the environment is protected, the prepared product has a long antibacterial effect, the green development concept is met, the application range of the fiber is improved, and the preparation method has an outstanding practical effect and an application prospect.
Drawings
Fig. 1 is a control picture of the bacteriostatic performance of the antibacterial fiber of example 1 (washed 0, 10, 30, 50 times) and the antibacterial fiber of the comparative example.
Fig. 2 is a control picture of the bacteriostatic performance of the antibacterial fiber of example 2 (washed 0, 10, 30, 50 times) and the antibacterial fiber of the comparative example.
Fig. 3 is a control picture of the bacteriostatic performance of the antibacterial fiber of example 3 (washed 0, 10, 30, 50 times) and the antibacterial fiber of the comparative example.
Fig. 4 is a control picture of the bacteriostatic performance of the antibacterial fiber of example 4 (washed 0, 10, 30, 50 times) and the antibacterial fiber of the comparative example.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood by those skilled in the art that the specific examples of the present invention are not intended to limit the present invention in any way, and any equivalents based on the present invention are within the scope of the present invention.
Example 1:
1) alcohol treatment: putting 4.8g of the polyester-nylon composite fiber into a beaker, pouring absolute ethyl alcohol until the polyester-nylon composite fiber is immersed, carrying out ultrasonic cleaning for 30min, and putting the polyester-nylon composite fiber into a clean place after cleaning is finished, and naturally airing the polyester-nylon composite fiber.
2) Alkali treatment: weighing 10g of NaOH and 90ml of distilled water to prepare a 10% sodium hydroxide solution, putting the 10% sodium hydroxide solution into a wide-mouth bottle, putting a magneton into the wide-mouth bottle, putting the wide-mouth bottle into a water bath kettle, adding the alcohol-treated polyester-polyamide composite fiber obtained in the step 1 when the internal temperature of the wide-mouth bottle is 80 ℃, and stirring for 30 min. (keeping the internal temperature of the wide-mouth bottle at 80 ℃ during the reaction), taking out the polyester-nylon composite fiber, washing the polyester-nylon composite fiber to be neutral by using distilled water, and drying the polyester-nylon composite fiber in an air-blast drying oven for 1h at 70 ℃ for later use.
3) Preparing a bacteriostatic agent: dissolve 5g phgc in ethanol: acetone: adding the same mole of Glycidyl Methacrylate (GMA) into a solution with the water volume ratio of 2:1:1, reacting for 6 hours at the temperature of 40-45 ℃ in a nitrogen atmosphere, and performing rotary evaporation to obtain a product, namely polyhexamethylene guanidine hydrochloride derivative (PHGH); 3g of chitosan was dissolved in a 1% acetic acid solution, added together with nitrogen gas to a three-necked flask and stirred well for 30min, and then PHGH and Cerium Ammonium Nitrate (CAN) (0.015 g of CAN per 0.7g of PHGH) were added to the flask, and the pH of the suspension was adjusted to 5-6 with 0.2mol/L nitric acid, and the flask was placed in a water bath at 50-55 ℃ for 180min under nitrogen atmosphere. Then acetone is used for settling, and a crude grafting product is obtained by filtering; extracting with ethanol for 8h, vacuum drying, and grinding to obtain pure polyhexamethylene guanidine (PHMG) and chitosan graft product.
4) Preparing antibacterial fibers: weighing 1g of glutaraldehyde, 0.75g of bacteriostatic agent and 98.25ml of distilled water, putting a magneton into a wide-mouth bottle, heating and stirring, wherein the revolution of the magneton is 500 plus 800r/min, putting the polyester-nylon composite fiber subjected to alkali treatment in the step (2) when the temperature of the solution is 90 ℃, reacting for 3 hours at 90 ℃, taking out the polyester-nylon composite fiber after the reaction is finished, wringing the solution on the polyester-nylon composite fiber, and putting the polyester-nylon composite fiber into a forced air drying oven for drying for 1 hour at 70 ℃.
Example 2:
1) alcohol treatment: putting 4.8g of the polyester-nylon composite fiber into a beaker, pouring absolute ethyl alcohol until the polyester-nylon composite fiber is immersed, ultrasonically cleaning for 30min, and putting the polyester-nylon composite fiber into a clean place after cleaning is finished until the polyester-nylon composite fiber is naturally dried;
2) alkali treatment: weighing 10g of NaOH and 90ml of distilled water to prepare a 10% sodium hydroxide solution, putting the 10% sodium hydroxide solution into a wide-mouth bottle, putting a magneton into the wide-mouth bottle, putting the wide-mouth bottle into a water bath kettle, adding the alcohol-treated polyester-polyamide composite fiber obtained in the step 1 when the internal temperature of the wide-mouth bottle is 80 ℃, and stirring for 30 min. (keeping the internal temperature of the wide-mouth bottle at 80 ℃ during the reaction), taking out the polyester-nylon composite fiber, washing the polyester-nylon composite fiber to be neutral by using distilled water, and drying the polyester-nylon composite fiber in an air-blast drying oven for 1 hour at 70 ℃ for later use.
3) Preparing a bacteriostatic agent: dissolving 4g of PHGC in a mixed solution of water and ethanol in a volume ratio of 1:2 in a three-neck flask, adding maleic anhydride into the three-neck flask, wherein the molar ratio of the maleic anhydride to the PHGC is 1:1.2, inserting a thermometer into one neck of the flask, immersing the thermometer in the solution, placing the three-neck flask in an oil bath pot, reacting for 20 hours at the temperature of 45 ℃ shown by the thermometer, performing rotary evaporation on the obtained light yellow diluted liquid product at 40 ℃ for about 20 minutes after the reaction is finished to remove most of the solvent, settling the product by using acetone, filtering supernatant, repeating for 3 times to obtain milky viscous liquid, and performing vacuum drying for 12 hours at room temperature to obtain light yellow brown viscous liquid polyhexamethylene guanidine (PHMG) and maleic anhydride graft.
4) Preparing antibacterial fibers: weighing 1g of titanium dioxide, 2g of bacteriostatic agent and 97ml of distilled water, putting a magneton into a wide-mouth bottle, stirring for 1h at normal temperature, putting the alkali-treated polyester-polyamide composite fiber obtained in the step 2, reacting for 2h at normal temperature, taking out the polyester-polyamide composite fiber after the reaction is finished, wringing the solution on the polyester-polyamide composite fiber, and putting the polyester-polyamide composite fiber into a blast drying oven for drying at normal temperature for 1 h.
Example 3:
1) alcohol treatment: taking 4.8g of polytrimethylene terephthalate (PTT) fibers, cutting into pieces with the size of 12cm multiplied by 36cm, putting the pieces into a beaker, pouring absolute ethyl alcohol until the polyester-nylon composite fibers are immersed, ultrasonically cleaning for 30min, and putting the PTT fibers in a clean place after cleaning to naturally dry;
2) alkali treatment: weighing 10g of NaOH and 90ml of distilled water to prepare 10% sodium hydroxide solution, putting the 10% sodium hydroxide solution into a wide-mouth bottle, putting a magneton into the wide-mouth bottle, putting the wide-mouth bottle into a water bath kettle, adding the PTT fiber subjected to alcohol treatment in the step 1 when the internal temperature of the wide-mouth bottle is 80 ℃, and stirring for 30 min. (the internal temperature of the jar is kept at 80 ℃ during the reaction), after the reaction is finished, taking out the PTT fiber, washing the PTT fiber to be neutral by using distilled water, and drying the PTT fiber in an air-blast drying oven for later use at 70 ℃ for 1 h.
3) Preparing a bacteriostatic agent: dissolving 4g of PHGC in a mixed solution of water and ethanol in a volume ratio of 1:2 in a three-neck flask, adding 0.32g of thiourea, inserting a thermometer into one neck of the flask, immersing the thermometer in the solution, adding a spherical condensation reflux device, placing the flask in an oil bath pot, reacting for 1.5h at the temperature of 100 ℃ displayed by the thermometer, after the reaction is finished, carrying out rotary evaporation on the obtained light yellow thinner liquid product at 85 ℃ for about 20min to remove most of the solvent, and carrying out vacuum drying on the product at room temperature for 12h to obtain a yellow brown viscous liquid, namely a grafting product of polyhexamethylene guanidine and thiourea.
4) Preparing antibacterial fibers: 0.04g of silver nitrate solid, 1g of bacteriostatic agent and 98.96ml of distilled water are weighed in a wide-mouth bottle, the outer layer of the wide-mouth bottle needs to comprise a layer of newspaper to achieve the purpose of avoiding light, a magneton is put in the wide-mouth bottle, and the rotating speed is 500 plus 750 r/min. Stirring for 2h at normal temperature, then adding 5ml of sodium borohydride solution with the concentration of 0.08g/100ml, stirring for 5h at normal temperature, and then adding the polyester-nylon composite fiber subjected to alkali treatment in the step 2 for reaction for 2 h. And (3) taking out the polyester-nylon composite fiber after the reaction is finished, wringing the solution on the polyester-nylon composite fiber, and drying the polyester-nylon composite fiber in a forced air drying oven at normal temperature for 1 h.
Example 4:
1) alcohol treatment: taking 4.8g of polytrimethylene terephthalate (PTT) fibers, cutting into pieces with the size of 12cm multiplied by 36cm, putting the PTT fibers into a beaker, pouring absolute ethyl alcohol until the polyester-nylon composite fibers are immersed, carrying out ultrasonic cleaning for 30min, and putting the PTT fibers in a clean place after the cleaning is finished until the PTT fibers are naturally dried;
2) alkali treatment: weighing 10g of NaOH and 90ml of distilled water to prepare 10% sodium hydroxide solution, putting the 10% sodium hydroxide solution into a wide-mouth bottle, putting a magneton into the wide-mouth bottle, putting the wide-mouth bottle into a water bath kettle, adding the PTT fiber subjected to alcohol treatment in the step 1 when the internal temperature of the wide-mouth bottle is 80 ℃, and stirring for 30 min. (the internal temperature of the jar is kept at 80 ℃ during the reaction), after the reaction is finished, taking out the PTT fiber, washing the PTT fiber to be neutral by using distilled water, and drying the PTT fiber in an air-blast drying oven for later use at 70 ℃ for 1 h.
3) Preparing a bacteriostatic agent: dissolving 4.5g of PHGC in a mixed solution of water and ethanol in a volume ratio of 1:2 in a three-neck flask, adding 0.32g of thiourea, inserting a thermometer into one neck of the flask, immersing the thermometer in the solution, adding a spherical condensation reflux device, placing the flask in an oil bath pot, reacting for 1.5h at the temperature of 100 ℃ shown by the thermometer, after the reaction is finished, performing rotary evaporation on the obtained light yellow thinner liquid product at 85 ℃ for about 20min to remove most of the solvent, and performing vacuum drying on the product at room temperature for 12h to obtain a yellow brown viscous liquid, namely a grafting product of polyhexamethylene guanidine and thiourea.
4) Preparing antibacterial fibers: weighing 5g of copper sulfate solid, 1g of bacteriostatic agent and 94ml of distilled water into a wide-mouth bottle, adding a magneton, heating and stirring until the temperature of the solution in the wide-mouth bottle is 80 ℃, and timing for 5 hours. And 5h, putting the polyester-nylon composite fiber subjected to alkali treatment in the step 2 into the reaction kettle to react for 2h at the temperature of 80 ℃. And (3) taking out the polyester-nylon composite fiber after the reaction is finished, wringing the solution on the polyester-nylon composite fiber, and drying the polyester-nylon composite fiber in a forced air drying oven at 70 ℃ for 1 h.
Comparative example 1:
a blank of example 1, fiber without any treatment.
Comparative example 2:
a blank of example 2, fiber without any treatment.
Comparative example 3:
a blank of example 3, a fiber without any treatment.
Comparative example 4:
a blank of example 4, fiber without any treatment.
Example 5:
fiber bacteriostatic activity experiment: putting the antibacterial fibers obtained in the embodiments 1 to 4 into distilled water, and putting the antibacterial fibers into an ultrasonic cleaning machine for ultrasonic cleaning for 5min, and marking as cleaning once; according to the steps, cleaning is carried out for 0, 10, 30 and 50 times, detection is carried out on examples 1-4 and comparative examples 1-4 according to an absorption method in China textile industry standard FZ/T73023 and 2006, and verification is carried out by using Escherichia coli. (the results are shown in Table 1 and FIGS. 1-4).
TABLE 1 antibacterial Activity test of antibacterial fibers prepared in comparative example and examples 1-4
Figure BDA0003490255570000091
As can be seen from table 1 and fig. 1 to 4, the fibers grafted with the bacteriostatic agent have a strong bacteriostatic effect on escherichia coli, and the fibers without grafted bacteriostatic agent have no bacteriostatic effect.

Claims (11)

1. A preparation method of environment-friendly long-acting antibacterial fiber is characterized by comprising the following steps:
1) alcohol treatment: pouring absolute ethyl alcohol into the container until the fibers are immersed, ultrasonically cleaning for 25-45min, and after cleaning, putting the fibers into a clean place to be naturally dried;
2) alkali treatment: putting 8-12% w/w sodium hydroxide solution and magnetons into a reaction container, heating to 75-85 ℃, adding the fiber treated by the alcohol in the step (1), stirring for 25-35min, taking out the fiber, washing the fiber with distilled water to be neutral, and drying for later use;
3) preparing antibacterial fibers: and (3) putting the substance A, the bacteriostatic agent, the water and the fiber subjected to alkali treatment in the step (2) into a reaction container for reaction to prepare the antibacterial agent.
2. The preparation method of the environment-friendly long-acting antibacterial fiber according to claim 1, wherein the fiber is a polyester-nylon composite fiber or a polytrimethylene terephthalate fiber.
3. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 1, wherein the substance A is any one of glutaraldehyde, titanium dioxide, silver ions or copper ions.
4. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 3, wherein when the substance A is glutaraldehyde, the antibacterial fiber is prepared by putting 0.8-1.2% of glutaraldehyde, 0.6-0.9% of bacteriostatic agent, 98-98.5% of water and magnetons in parts by weight into a reactor, heating and stirring at a magneton rotation number of 500-800r/min, putting the fiber subjected to alkali treatment in the step 2 when the temperature of the solution is 90 ℃, reacting for 3h at 90 ℃, taking out the fiber, and drying for 1h at 70 ℃.
5. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 3, wherein when the substance A is titanium dioxide, the antibacterial fiber is prepared by putting 0.8-1.2% of titanium dioxide, 1.5-3% of bacteriostatic agent, 96-97.5% of water and magneton into a reactor according to parts by weight, stirring for 1h at normal temperature, putting the fiber subjected to alkali treatment in the step 2, reacting for 2h at normal temperature, taking out the fiber, and drying for 1h at normal temperature.
6. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 3, wherein when the substance A is silver ions, the antibacterial fiber is prepared by putting 0.03-0.2% of silver nitrate, 0.8-1.4% of bacteriostatic agent, 98.5-99% of water and magnetons into a reactor according to parts by weight, stirring for 2 hours at normal temperature at the rotation speed of 500 + 750r/min in a manner that the reactor needs to be protected from light, then adding 0.08g/100ml of sodium borohydride solution, wherein the volume ratio of the sodium borohydride solution to the water is 1:18-22, stirring at normal temperature for 5h, then putting the fibers subjected to alkali treatment in the step 2, reacting for 2h, taking out the fibers, and drying at normal temperature for 1 h.
7. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 3, wherein when the substance A is copper ions, the antibacterial fiber is prepared by putting 4-6% of copper sulfate solid, 0.8-1.2% of bacteriostatic agent, 93-95% of water and magnetons into a reactor according to parts by weight, heating and stirring, starting to react for 5h when the temperature is 80 ℃, putting the fiber subjected to alkali treatment in the step 2 at 80 ℃ for reacting for 2h, taking out the fiber, and drying for 1h at 70 ℃.
8. The method for preparing environment-friendly long-acting antibacterial fiber according to any one of claims 1 to 7, wherein the bacteriostatic agent is any one of polyhexamethylene guanidine and thiourea graft, polyhexamethylene guanidine and chitosan graft, and polyhexamethylene guanidine and maleic anhydride graft.
9. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 8, wherein when the bacteriostatic agent is polyhexamethylene guanidine and thiourea graft, the grafting method is as follows: dissolving polyhexamethylene guanidine in ethanol and water at a volume ratio of 1.5-3:1, adding thiourea into the mixed solution, wherein the mass ratio of thiourea to polyhexamethylene guanidine is (0.06-1): 1, reacting the mixture at 100 ℃ for 1.5h, carrying out rotary evaporation on the obtained product at 85 ℃ for 15-30min, and drying the product at room temperature in vacuum for 12h to obtain the polyhexamethylene guanidine and thiourea graft.
10. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 8, wherein when the bacteriostatic agent is a polyhexamethylene guanidine and maleic anhydride graft, the grafting method comprises the following steps: dissolving polyhexamethylene guanidine into a mixed solution of ethanol and water in a volume ratio of 1.5-3:1, adding maleic anhydride after dissolving, wherein the molar ratio of the maleic anhydride to the polyhexamethylene guanidine is 1-1.5: 1, reacting the mixture at 40 ℃ for 10-30h, carrying out rotary evaporation on the obtained product at 40 ℃ for 15-30min, settling the product by using acetone, filtering supernatant, repeating the operation for 3 times, and carrying out vacuum drying at room temperature for 12h to obtain the polyhexamethylene guanidine and maleic anhydride graft.
11. The method for preparing environment-friendly long-acting antibacterial fiber according to claim 8, wherein when the bacteriostatic agent is polyhexamethylene guanidine and chitosan graft, the grafting method is as follows:
1) polyhexamethylene guanidine was dissolved in ethanol: acetone: the volume ratio of water is 1-3: 0.5-1.5: 1, adding glycidyl methacrylate into the solution of the formula 1, wherein the molar ratio of the glycidyl methacrylate to the polyhexamethylene guanidine is 1:1, carrying out reaction for 6h in a nitrogen atmosphere at the temperature of 40-45 ℃, and carrying out rotary evaporation to obtain a polyhexamethylene guanidine hydrochloride derivative;
2) dissolving chitosan in an acetic acid solution with the concentration of 1%, introducing nitrogen, fully stirring for 20-40min, adding a polyhexamethylene guanidine hydrochloride derivative and ceric ammonium nitrate, adjusting the pH value of the suspension to 5-6 by using 0.2mol/L nitric acid, placing a reactor in a water bath with the temperature of 50-55 ℃ for 3h under the nitrogen atmosphere, then using acetone for settling, and filtering to obtain a crude grafting product, wherein the mass ratio of the polyhexamethylene guanidine to the chitosan is 4-6: 3, the mass ratio of the polyhexamethylene guanidine hydrochloride derivative to the ceric ammonium nitrate is (40-50): 1;
3) extracting with ethanol for 8h, vacuum drying, and grinding to obtain pure graft product.
CN202210094405.0A 2022-01-26 2022-01-26 Preparation method of environment-friendly long-acting antibacterial fiber Pending CN114438780A (en)

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CN112853747A (en) * 2021-02-26 2021-05-28 石家庄学院 Preparation method of long-acting antibacterial polyester fiber based on composite nano silver and special device thereof
CN112970773A (en) * 2021-02-26 2021-06-18 河北佩清科技有限公司 Preparation method and device of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant
CN113026361A (en) * 2021-02-26 2021-06-25 石家庄学院 Method and reaction device for preparing long-acting antibacterial polyester fiber by coupling poly hexamethylene hydrochloride with glutaraldehyde
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CN105061771A (en) * 2015-07-30 2015-11-18 山东惠民力洁生物科技有限公司 Preparation method of disinfecting material namely methyl guanidine chitosan hydrochloride
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