Antistatic fabric containing polylactic acid fibers and preparation method thereof

Abstract

The invention discloses an antistatic fabric containing polylactic acid fibers and a preparation method thereof, and belongs to the technical field of fabrics. The invention discloses an antistatic fabric containing polylactic acid fibers. The antistatic fabric is prepared from the following raw materials in parts by weight: 78-92 parts of modified polyester fibers and 8-22 parts of cotton fibers. The prepared polylactic acid antistatic fabric is comfortable in skin feeling, environment-friendly and degradable, and the raw materials are renewable, environment-friendly and safe; the polylactic acid fiber is used as a main raw material, moisture absorption and sweat releasing are achieved, the breathability is good, the skin feeling is good, the raw material is renewable and blended with the cotton fiber, and the moisture absorption and breathability of the fabric are remarkably improved; the assistant is designed and synthesized, so that the fabric is endowed with lasting antibacterial property and remarkable antistatic property, the hygroscopicity of the fabric can be further improved, and the fabric is long in property and not easy to fall off. Therefore, the prepared antistatic fabric has stable and efficient antibacterial property and antistatic property, is comfortable and soft, is safe and environment-friendly, and has important application value in the technical field of fabrics.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fabric preparation, and particularly relates to an antistatic fabric containing polylactic acid fibers and a preparation method thereof. BACKGROUND

[0002] Polylactic acid (PLA) fibers become an environmentally friendly alternative to replace traditional synthetic fibers due to their biodegradability and good biocompatibility. The fabric made of PLA fibers has good skin feeling, draping property, ultraviolet resistance, excellent processing performance, and is suitable for various fashion, home textile and medical and sanitary products, and has broad application prospects. However, the surface resistivity of PLA fibers is high, and static electricity and dust are easily accumulated, which limits the application and development of PLA fibers. In addition, PLA fibers themselves have no antibacterial activity and are easy to become a breeding medium for microorganisms, resulting in odor and hygiene problems.

[0003] Therefore, it is necessary to invent an antistatic fabric with antibacterial property and moisture absorption and ventilation, which can be worn for a long time, and has important application value in the technical field of fabric. SUMMARY

[0004] The application aims to overcome the defects of the prior art and provide an antistatic fabric containing polylactic acid fibers and a preparation method thereof.

[0005] The object of the application can be achieved by the following technical solutions. A preparation method of an antistatic fabric containing polylactic acid fibers, comprising the following steps: Step 1, polylactic acid particles are placed in a vacuum drying box and dried for 12 hours, then mixed with an auxiliary agent, added into a twin-screw extruder, and melt-blended and spun to obtain modified polylactic acid fibers; Step 2, the modified polylactic acid fibers and cotton fibers are combined on a drawing frame to form roving, and then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to form blended yarn, and then a polylactic acid fabric is prepared by using a weft knitting method of a circular knitting machine.

[0006] A preparation method of an antistatic fabric containing polylactic acid fibers, comprising the following raw materials according to weight fractions: 85-95 parts of polylactic acid particles, 5-15 parts of an auxiliary agent, 78-92 parts of modified polylactic acid fibers, and 8-22 parts of cotton fibers.

[0007] As a further technical solution, the blending temperature is 120-150 DEG C. As a further technical solution, the auxiliary agent is prepared by the following steps: S1, in a three-necked flask equipped with a stirring device, first mix PEG400, bromoacetylene and tetrahydrofuran, and start the stirrer, then add the catalyst potassium butoxide, heat to 30℃ in water bath, keep the temperature for 24h, after the reaction is completed, extract and separate, wash with water, and vacuum dry to obtain the intermediate 1; As a further technical solution, the amount ratio of PEG400, bromoacetylene, tetrahydrofuran and potassium butoxide in step S1 is 30g:17.7g:200mL:13.4g Under the catalysis of potassium butoxide, the hydroxyl group at the end of PEG400 is activated to generate PEG-O-; the generated PEG-O- and bromoacetylene undergo nucleophilic substitution to obtain the intermediate 1; the specific reaction is shown as follows: S2, place 4-methyl-5-hydroxyethylthiazole, methanesulfonyl chloride, anhydrous DCM and triethylamine in a three-necked flask, and introduce nitrogen as a protective gas, and then cool to 0℃ in an ice water bath, and stir at this temperature for 5h; after the reaction is completed, rotary evaporation is carried out at room temperature, and vacuum drying is carried out for 2h to obtain the intermediate 2; As a further technical solution, the amount ratio of 4-methyl-5-hydroxyethylthiazole, methanesulfonyl chloride, triethylamine and anhydrous DCM in step S2 is 14.3g:12.5g:13.1g:300mL; This reaction is a typical formylation reaction of hydroxyl group, the -OH oxygen atom in 4-methyl-5-hydroxyethylthiazole acts as a nucleophile to attack the sulfur atom of the methanesulfonyl group to form an -OMs bond, by controlling the molar ratio of the two to be close to 1:1.2, and the methanesulfonyl chloride is slightly excessive, and the triethylamine removes the generated HCl, and the specific reaction process is shown as follows: S3, mix the intermediate 2 and anhydrous DMF in a three-necked flask equipped with a stirring device, add NaN3 to the DMF solution to prepare a NaN3 DMF solution, and then add the NaN3 DMF solution to the three-necked flask while stirring, and dropwise add within 10min, and react at 70℃ for 4h; after the reaction is completed, first remove most of the solvent by rotary evaporation, and then purify by column chromatography (the eluent is a mixed solvent of ethyl acetate / petroleum ether, and the volume ratio of the two is 1:3), and then remove the eluent by rotary evaporation to obtain the intermediate 3; As a further technical solution, the amount ratio of the intermediate 2, DMF and NaN3 is 11.0g:150mL:8.1g; As a further technical solution, the amount ratio of NaN3 and DMF in the NaN3 DMF solution is 1g:5mL.

[0008] In the reaction, -OMs on the intermediate 2 acts as an excellent leaving group, which is easy to participate in nucleophilic substitution reaction with azide ion on NaN3. By controlling the molar ratio of the two to be close to 1:2.5 and the excess of NaN3, -OMs on the intermediate 2 is allowed to participate in the reaction as much as possible to obtain the intermediate 3. The specific reaction process is shown as follows: S4, the intermediate 1 is dissolved in a mixture of PBS buffer and tert-butyl alcohol in a three-neck flask equipped with a stirring device at room temperature under nitrogen protection, and ultrasonic treatment is performed for 5 min until complete dissolution. The intermediate 3 is dissolved in DMSO and added to the three-neck flask and stirred uniformly, followed by the addition of PMDETA and CuCl, and the reaction is carried out at room temperature for 2 h, and then the product fraction is collected by passing through a Sephadex LH-20 column eluted with methanol to obtain the intermediate 4; As a further technical solution, the molar ratio of the intermediate 1, the intermediate 3 and CuCl is close to 1:1.2:0.1.

[0009] As a further technical solution, the ratio of the amount of PBS buffer and tert-butyl alcohol is 1:2.

[0010] As a further technical solution, the PMDETA is N,N,N',N'',N''-pentamethyl diethylene triamine, and the molar ratio of PMDETA and CuCl is 1:1.

[0011] Under the catalysis of Cu(I), the intermediate 1 and the intermediate 3 undergo click chemistry to introduce a triazole structure group, and by controlling the molar ratio of the intermediate 1, the intermediate 3 and CuCl to be close to 1:1.2:0.2 and the intermediate 3 to be slightly excessive, the intermediate 4 is obtained. The specific reaction process is shown as follows: S5, the intermediate 4, iodomethane and anhydrous DMF are mixed and stirred uniformly in a three-neck flask equipped with a stirring device, and the reaction temperature is controlled at 95℃, and the reaction is carried out for 12 h. After sufficient reaction, part of the solvent is removed by rotary evaporation, and then the product is purified by column chromatography and dried to obtain the additive. As a further technical solution, the molar ratio of the intermediate 4 and iodomethane is 1:5. As a further technical solution, the ratio of the amount of the intermediate 4 and anhydrous DMF is 1g:25mL.

[0012] The quaternary ammonium reaction is carried out by adding excess iodomethane to make the reaction sufficient to obtain the additive. The structure of the additive is shown as follows: The prepared additive contains PEG ether chains, triazoles, thiazoles, and quaternary ammonium salt ions. The PEG ether chains effectively enhance hydrophilicity, and the flexibility of the PEG chains reduces fiber rigidity, thus improving the matrix's flexibility and reducing the coefficient of friction. Furthermore, the additive contains multiple triazole groups, which significantly improve its water solubility, allowing its performance to be fully realized. Additionally, the introduced quaternary ammonium salt ions adsorb onto the bacterial cell membrane surface, altering cell membrane permeability and causing leakage of enzymes, proteins, and other substances from within the bacteria. This interferes with bacterial metabolic processes, achieving a bactericidal and antibacterial effect, thus giving the matrix a certain degree of antibacterial properties. Moreover, the cations (N⁺) and counterions (such as I⁻) of the quaternary ammonium salt... - This forms a dynamic charge migration network, enhancing the antistatic properties of the substrate.

[0013] It should be added that in the textile field, the higher the hydrophilicity, the better the antistatic properties. Therefore, auxiliaries can significantly enhance both the hydrophilicity and antistatic properties of the matrix.

[0014] The beneficial effects of this invention are: 1. The polylactic acid antistatic fabric prepared by this invention is not only comfortable against the skin and environmentally friendly and biodegradable, but also uses renewable raw materials, reducing environmental pollution and making it a sustainable and environmentally friendly choice. 2. Using polylactic acid as the main raw material, it has excellent moisture absorption and perspiration wicking, breathability, and skin feel. The raw material is also renewable and blended with cotton fibers, which significantly improves the moisture absorption and breathability of the fabric. 3. Design and synthesize an auxiliary agent to give the fabric lasting antibacterial and significant antistatic properties, further improve the fabric's moisture absorption, and have good washability.

[0015] Therefore, the resulting antistatic fabric has stable and efficient antibacterial and antistatic properties, is comfortable and soft, and is also safe and environmentally friendly, making it of great application value in the field of fabric technology. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 Preparation aids: S1, in a three-necked flask equipped with a stirring device, 100 mL of PEG400, 17.7 g of propargyl bromide and 200 mL of tetrahydrofuran were mixed, and the stirrer was started, then 13.4 g of potassium butoxide was added, and the water bath was heated to 30℃, and the reaction was kept for 24 h, and after the reaction was completed, extraction separation, water washing and vacuum drying were carried out, and then the intermediate product 1 was obtained; S2, 14.3 g of 4-methyl-5-hydroxyethylthiazole, 12.5 g of methanesulfonyl chloride, 300 mL of anhydrous DCM and 13.1 g of triethylamine were placed in a three-necked flask, nitrogen was introduced as a protective gas, and an ice water bath was used to cool the temperature to 0℃, and the stirring reaction was carried out at this temperature for 5 h; after the reaction was completed, rotary evaporation was carried out at room temperature, and vacuum drying was carried out for 2 h to obtain the intermediate 2; S3, in a three-necked flask equipped with a stirring device, 11.0 g of intermediate 2 and 150 mL of anhydrous DMF were mixed; 8.1 g of NaN3 was added to 40 mL of DMF solution to prepare a NaN3 DMF solution, and the prepared NaN3 DMF solution was slowly added to the three-necked flask while stirring, and the dropping was completed within 10 min, and the reaction was carried out at 70℃ for 4 h; after the reaction was completed, most of the solvent was removed by rotary evaporation, and then column chromatography was used for purification (the eluent was a mixture of ethyl acetate and petroleum ether, and the volume ratio of the two was 1:3), the eluent was removed by rotary evaporation, and the intermediate 3 was obtained; S4, at room temperature and under nitrogen protection, 42.4 g of intermediate 1 was dissolved in a mixture of 30 mL of PBS buffer and 60 mL of tert-butyl alcohol in a three-necked flask equipped with a stirring device, and ultrasonic treatment was carried out for 5 min until complete dissolution. 20.16 g of intermediate 3 was dissolved in 100 mL of DMSO, and then added to the three-necked flask and stirred uniformly, followed by the addition of 1 g of PMDETA and 1 g of CuCl, and the reaction was carried out at room temperature for 2 h, and then the Sephadex LH-20 column was used for elution with methanol, and the product fraction was collected to obtain the intermediate 4; S5, in a three-necked flask equipped with a stirring device, 81.2 g of intermediate 4, 70.90 g of iodomethane and 500 mL of DMF were mixed and stirred uniformly, and the reaction temperature was controlled at 95℃, and the reaction was carried out for 12 h; after sufficient reaction, part of the solvent was removed by rotary evaporation, and then column chromatography was used for purification, and the product was dried to obtain the additive; Example 2 Step 1, 95 parts of polylactic acid particles were placed in a vacuum drying box and dried for 12 h, then taken out and mixed with 5 parts of the additive prepared in Example 1, and then added to a twin-screw extruder for melt blending and spinning, and the temperature was 120℃, and then a modified polylactic acid fiber was obtained; Step 2, 92 parts of the modified polylactic acid fiber and 8 parts of cotton fiber were combined on a drawing frame to make a roving, and then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make a blended yarn, and then a polylactic acid fabric was prepared by using a circular knitting machine for weft knitting.

[0018] Example 3 Step 1, 90 parts of polylactic acid particles were placed in a vacuum drying oven and dried for 12 h, then mixed with 10 parts of the auxiliary prepared in Example 1, and added into a twin-screw extruder for melt blending and spinning at a temperature of 120℃, to obtain modified polylactic acid fibers; Step 2, 78 parts of modified polyester fibers and 22 parts of cotton fibers were combined on a drawing frame to make roving, and then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make blended yarn, and a polylactic acid fabric was prepared by weft knitting method on a circular knitting machine.

[0019] Example 4 Step 1, 85 parts of polylactic acid particles were placed in a vacuum drying oven and dried for 12 h, then mixed with 15 parts of the auxiliary prepared in Example 1, and added into a twin-screw extruder for melt blending and spinning at a temperature of 120℃, to obtain modified polylactic acid fibers; Step 2, 85 parts of modified polyester fibers and 15 parts of cotton fibers were combined on a drawing frame to make roving, and then drawn and twisted on a roving frame, and finally further drawn and twisted on a spinning frame to make blended yarn, and a polylactic acid fabric was prepared by weft knitting method on a circular knitting machine.

[0020] Comparative Example 1 No auxiliary was added, and the remaining steps were the same as Example 4.

[0021] Comparative Example 2 A commercially available octadecyl trimethyl ammonium bromide produced by Shanghai Jizhisheng Chemical Technology Co., Ltd. was used as the auxiliary, and the remaining steps were the same as Example 4.

[0022] The fabrics obtained in Examples 2-4 and Comparative Examples 1-2 were tested for the following properties according to different test standards, and the test results are shown in Tables 1 and 2: The static half-life (s) and friction voltage (kV) of the fabric were determined according to the national standard GB / T 12703.1-2021 "Evaluation of Static Electricity Performance of Textiles Part 1: Corona Charging Method", so as to test the antistatic performance (the shorter the static half-life time, the better the antistatic performance; the lower the voltage, the better the antistatic performance); The wicking height was determined according to the national standard GB / T 21655.1-2008 "Evaluation of Moisture Absorption and Quick Drying of Textiles Part 1: Single Combination Test Method"; The Escherichia coli and Staphylococcus aureus inhibition rates before and after 30 times of washing were tested according to the national standard GB / T 20944.3-2008 "Evaluation of Antibacterial Performance of Textiles Part 3: Oscillation Method", and the washing method was carried out on a washing fastness tester, and the washing conditions were as follows: washing powder 3.5 g / L, mass ratio of fabric to washing liquid 1:35, temperature 30℃, and washing time 15 min.

[0023] Table 1: Anti-static test results Table 2: Anti-bacterial test and moisture absorption test From the data in the above table 1, the anti-static fabric prepared by the application has a friction voltage lower than 1kV, effectively preventing static electricity accumulation on the surface of the fabric; in addition, table 2 shows that the anti-static fabric of the application has excellent antibacterial property and washing resistance.

[0024] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0025] The above is only an example and description of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as it does not deviate from the application or exceed the scope defined by the claims, which shall belong to the protection scope of the application.

Claims

1. A method for preparing an antistatic fabric containing polylactic acid fibers, characterized in that, Includes the following steps: Step 1: Place polylactic acid granules in a vacuum drying oven and dry for 12 hours. After drying, remove them and mix them with the additives. Add them to a twin-screw extruder and melt-blend and spin to obtain modified polylactic acid fibers. Step 2: Combine modified polylactic acid fiber and cotton fiber on a drawing frame to make roving. Draft and twist the roving on a roving frame, and finally further draft and twist it on a spinning frame to make blended yarn. Use a circular knitting machine to weft knit polylactic acid fabric.

2. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 1, characterized in that, The raw materials in step 1 are as follows by weight: 85-95 parts polylactic acid granules, 5-15 parts additives.

3. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 1, characterized in that, The raw materials in step 2 are as follows by weight: 78-92 parts modified polyester fiber, 8-22 parts cotton fiber.

4. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 1, characterized in that, The auxiliary agent is prepared by the following steps: S1. Mix PEG400, propyne bromide and tetrahydrofuran, stir well, add potassium butoxide catalyst, heat in a water bath to 30°C, keep the reaction at this temperature for 24 hours, after the reaction is complete, extract and separate, wash with water, and vacuum dry to obtain intermediate product 1. S2. Place 4-methyl-5-hydroxyethylthiazole, methanesulfonyl chloride, anhydrous DCM, and triethylamine in a three-necked flask, purge with nitrogen as a protective gas, and heat in an ice-water bath to 0°C. Stir the reaction at this temperature for 5 hours. After the reaction is complete, rotary evaporate at room temperature and vacuum dry for 2 hours to obtain intermediate 2. S3. Mix intermediate 2, anhydrous DMF, and NaN3, and react at 70°C for 4 hours. After the reaction is complete, remove most of the solvent by rotary evaporation at room temperature, and then purify by column chromatography. Remove the eluent by rotary evaporation to obtain intermediate 3. S4. Intermediate 1, dissolved in a mixture of PBS buffer and tert-butanol, and intermediate 3, dissolved in DMSO, are mixed thoroughly. Then PMDETA and CuCl are added, and the mixture is reacted at room temperature for 2 hours. The product fraction is then collected by passing the mixture through a Sephadex LH-20 column and eluting with methanol to obtain intermediate 4. S5. Mix intermediate 4, iodomethane and anhydrous DMF evenly, control the reaction temperature at 95℃, react for 12h, remove solvent by rotary evaporation, purify by column chromatography, rotary evaporation, and allow to stand and dry to obtain the auxiliary agent.

5. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 4, characterized in that, In step S1, the ratio of PEG400, propyne bromide, tetrahydrofuran, and potassium butoxide is 30g:17.7g:200mL:13.4g.

6. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 4, characterized in that, In step S2, the ratio of 4-methyl-5-hydroxyethylthiazole, methanesulfonyl chloride, triethylamine, and anhydrous DCM is 14.3 g: 12.5 g: 13.1 g: 300 mL.

7. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 4, characterized in that, In step S3, the ratio of intermediate 2, DMF, and NaN3 is 11.0g:150mL:8.1g.

8. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 4, characterized in that, In step S4, the molar ratio of intermediate 1, intermediate 3 and CuCl is approximately 1:1.2:0.1, the ratio of PBS buffer to tert-butanol is 1:2, and the molar ratio of PMDETA to CuCl is 1:

1.

9. The method for preparing an antistatic fabric containing polylactic acid fiber according to claim 4, characterized in that, In step S5, the molar ratio of intermediate 4 to iodomethane is 1:5; and the ratio of intermediate 4 to anhydrous DMF is 1 g: 25 mL.

10. An antistatic fabric containing polylactic acid fibers, characterized in that, Prepared according to the method according to any one of claims 1-9.

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