A long-lasting antibacterial high-elastic shapewear fabric and a preparation method thereof

Abstract

The application discloses a kind of long-lasting antibacterial high-elasticity body-shaping clothes fabric and preparation method thereof, and relates to the technical field of fabric.The long-lasting antibacterial high-elasticity body-shaping clothes fabric is prepared as follows: first, dihydric alcohol and diester are copolymerized to form a pre-modified polyester, which is then reacted with cyano-(3-thiophene propyl) acetate to form a modified polyester;second, pretreated mica sheet, phosphoric acid and propylene oxide are reacted to form a pre-modified mica sheet, which is then reacted with 2-amino-1H-benzimidazole-5-carboxylic acid, and then reacted with 1,3-bis(3-thiophene)-2-propylene-1-ketone to obtain a modified mica sheet;finally, the modified polyester and the modified mica sheet are blended and spun to obtain modified polyester, which is blended and spun with spandex to form a fabric, and the fabric is finished with thiophene to obtain the long-lasting antibacterial high-elasticity body-shaping clothes fabric.The long-lasting antibacterial high-elasticity body-shaping clothes fabric prepared by the application has good antibacterial, anti-aging and anti-static properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fabric, in particular to a high-elasticity shapewear fabric with persistent antibacterial property and a preparation method thereof. BACKGROUND

[0002] Shapewear is a kind of clothing that realizes shaping, supporting or medical functions by closely fitting the human body curve, and its core function depends on the high elasticity and fit of the fabric, so traditional shapewear usually adopts synthetic materials such as spandex, lycra and polyester fiber.

[0003] However, with the expansion of shapewear use scenarios (such as long-term wear, sports scenarios, high-temperature environments, etc.), its functional requirements have shifted from simple physical support to comprehensive performance improvement; due to the tight design of shapewear, it is in close contact with the skin for a long time, especially in sports or high-temperature environments, the user is prone to sweating, and the fabric surface is prone to form a humid environment, providing a breeding ground for bacteria, in addition, medical shapewear (such as postoperative recovery clothes) needs to directly contact wounds or sensitive skin, if the fabric lacks antibacterial property, it may increase the risk of infection, therefore, developing persistent antibacterial function becomes the key to improving the hygiene and safety of shapewear; the synthetic fibers commonly used in high-elasticity fabrics (such as polyester and nylon) have the characteristic of easily generating static electricity, and in dry environments, friction easily leads to static electricity accumulation; in addition, ultraviolet radiation during outdoor sports may cause degradation of the synthetic fibers of shapewear, resulting in a decrease in fabric elasticity and strength, therefore, the combination of antistatic and anti-ultraviolet functions not only improves the wearing comfort, but also prolongs the service life of the fabric; traditional high-elasticity fabrics (such as polyester and polyurethane) are mostly flammable materials that burn quickly when exposed to fire, therefore, the flame-retardant function is also a necessary requirement for shapewear fabrics in specific scenarios, to ensure that the fabric is not easily ignited or delayed in combustion when exposed to fire. The user group of modern shapewear is increasingly diverse, and the demand for health and safety and functionality is constantly increasing, therefore, developing composite fabrics with high elasticity and multiple functions has become an innovative direction in the industry, and ensuring the persistence and comfort of various functions has become the focus of current research. SUMMARY

[0004] The present application aims to provide a high-elasticity shapewear fabric with persistent antibacterial property and a preparation method thereof to solve the problems in the prior art.

[0005] To solve the above technical problems, the present application provides the following technical scheme: a preparation method of a high-elasticity shapewear fabric with persistent antibacterial property, comprising the following preparation steps:

[0006] (1) reacting cyanoacetic acid and 3-(3-thienyl)-1-propanol to obtain cyano-(3-thienylpropyl) acetate;

[0007] (2) mixing 4,4'-carbonylbis(benzoic acid methyl ester), dimethyl terephthalate, 1,4-butanediol, stannous octoate, and then under nitrogen protection, heating to 180-190°C for 2-3h, continuously heating to 240-250°C, and then reacting for 2-3h under 50Pa, stopping heating, and then recovering to normal pressure by introducing nitrogen, to obtain the pre-modified polyester;

[0008] (3) reacting the pre-modified polyester with cyano-(3-thiophene propyl) acetate to obtain the modified polyester;

[0009] (4) mixing the pretreated mica sheet, phosphoric acid, and ethyl acetate, and then adding dropwise propylene oxide to react, to obtain the pre-modified mica sheet;

[0010] (5) reacting the pre-modified mica sheet with 2-amino-1H-benzimidazole-5-carboxylic acid to obtain the benzimidazolyl mica sheet, and then reacting the benzimidazolyl mica sheet with 1,3-bis(3-thiophene)-2-propen-1-one to obtain the modified mica sheet;

[0011] (6) mixing the modified polyester and the modified mica sheet, melt blending in a double-screw extruder, extruding and granulating, melt spinning by a spinning machine to obtain the modified polyester, and then blending the modified polyester with spandex to obtain a composite yarn, and then weaving into a fabric;

[0012] (7) immersing the fabric in a mixed solution of ferric chloride and chloroform for 30-40min, then adding thiophene and stirring, and then immersing in a 1-1.5mol / L hydrochloric acid solution, and then washing with saturated sodium carbonate and pure water, and then drying to obtain the long-lasting antibacterial high-elasticity body-shaping clothing fabric.

[0013] As an optimization, the preparation method of the cyano-(3-thiophene propyl) acetate in step (1) is as follows: mixing cyanoacetic acid, 3-(3-thiophenyl)-1-propanol, and concentrated sulfuric acid according to a mass ratio of 1:(2.5-3.0):(0.05-0.06), heating to 110-120°C for 6-8h, cooling to room temperature, distilling under reduced pressure, adjusting the pH to 7 with saturated sodium carbonate, separating, washing with saturated sodium chloride solution, drying with anhydrous magnesium sulfate, and then distilling under reduced pressure to obtain the cyano-(3-thiophene propyl) acetate.

[0014] As an optimization, the molar ratio of 4,4'-carbonylbis(benzoic acid methyl ester), dimethyl terephthalate, 1,4-butanediol, and stannous octoate in step (2) is 1:(4-5):(5.5-6.0):(0.005-0.006).

[0015] As an optimization, the preparation method of the modified polyester in step (3) is as follows: the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, and toluene-n-heptane solution are mixed, and half of the p-toluenesulfonic acid solution is added under nitrogen protection. The mixture is stirred for 30-40 min, heated to 100-110℃ and refluxed for 2-3 h. The remaining p-toluenesulfonic acid solution is added, and the reaction is continued for 5-6 h. The mixture is precipitated by ice water, filtered, washed and dried to obtain the modified polyester. The mass ratio of the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution and p-toluenesulfonic acid solution is 1:(0.6-0.7):(10-12):(1-1.2).

[0016] As an optimization, the toluene-n-heptane solution is obtained by mixing toluene and n-heptane in a volume ratio of (3-4):1; the p-toluenesulfonic acid solution is obtained by mixing p-toluenesulfonic acid and ethanol in a volume ratio of 1:(9-10).

[0017] As an optimization, the preparation method of the pre-modified mica sheet in step (4) is as follows: Mica sheet and 1M hydrochloric acid are ultrasonically mixed at a mass ratio of 1:(10-12) for 30-40 min, filtered, washed, and dried to obtain activated mica sheet; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and pure water are mixed at a mass ratio of 1:(4-5), the pH is adjusted to 4-5 using glacial acetic acid, stirred at 35-45℃ for 1-2 h, and distilled under reduced pressure at 40℃ for 20 min to obtain hydrolyzed siloxane; activated mica sheet, hydrolyzed siloxane, and isopropanol are mixed at a mass ratio of 1:(0.5-0.7). ): (50-60) Sonicate for 20 min, adjust pH to 10 with 28wt% ammonia, react at 70-80℃ for 5-6 h, filter, wash and dry to obtain pretreated mica sheets; mix pretreated mica sheets, phosphoric acid and ethyl acetate in a mass ratio of 1:(4-5):(30-40) sonicate for 20-30 min, add 1.5-2 times the mass of phosphoric acid propylene oxide at a dropping rate of 0.6 mL / min at 20-25℃, after the addition is completed, raise the temperature to 80-90℃ and react for 3-4 h, filter, wash and dry to obtain premodified mica sheets.

[0018] As an optimization, the preparation method of the modified mica sheet in step (5) is as follows: pre-modified mica sheet, 2-amino-1H-benzimidazole-5-carboxylic acid, p-toluenesulfonic acid, and N,N-dimethylformamide are mixed in a mass ratio of 1:(2-3):(0.4-0.5):(20-30), heated to 100-110℃ and reacted for 7-8h, and then filtered, washed and dried to obtain benzimidazole mica sheet; benzimidazole mica sheet, 1,3-bis(3-thiophene)-2-propen-1-one, ethanol, and glacial acetic acid are mixed in a mass ratio of 1:(1.5-2.0):(40-50):(0.003-0.005), heated to 80-90℃ and reacted for 10-12h, then 3-4 times the volume of ethanol in ice water is added, and then filtered, washed and dried to obtain modified mica sheet.

[0019] As an optimization, the fabric preparation method in step (6) is as follows: modified polyester and modified mica sheets are mixed at a mass ratio of 1:(0.03-0.05), melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun by a spinning machine to obtain modified polyester. The spinning temperature is 240-250℃, the winding speed is 700-800m / min, the draw ratio is 1.5-2.0 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of (80-85):(15-20). The fabric is woven by a double-sided circular weft machine. The fabric weight is 150-160g / m².

[0020] As an optimization, the preparation method of the durable antibacterial high-elastic shaping garment fabric in step (7) is as follows: mix the fabric, ferric chloride, and chloroform at a mass ratio of 1:(12-15):(110-120) for 30-40 min; add thiophene at 20-30℃ and stir for 20-30 min, then take it out and immerse it in 1 mol / L hydrochloric acid solution and mix for 10-20 min, with a bath ratio of 1:(60-80). After taking it out, wash it with saturated sodium carbonate, wash it with pure water and dry it to obtain the durable antibacterial high-elastic shaping garment fabric; the molar ratio of thiophene to ferric chloride is 1:(4-4.5).

[0021] The present invention also provides a durable antibacterial high elastic shapewear fabric prepared according to the above-described method for preparing durable antibacterial high elastic shapewear fabric.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: In preparing a durable antibacterial high-elasticity shapewear fabric, the present invention first reacts cyanoacetic acid and 3-(3-thienyl)-1-propanol to generate cyano-(3-thienylpropyl)acetate; then copolymerizes 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, and 1,4-butanediol to generate a pre-modified polyester; and finally reacts the pre-modified polyester with cyano-(3-thienylpropyl)acetate to generate a modified polyester. Modified polyester is prepared by reacting pretreated mica sheets, phosphoric acid, and propylene oxide to generate pre-modified mica sheets, which are then reacted with 2-amino-1H-benzimidazole-5-carboxylic acid to generate benzimidazole mica sheets, which are then reacted with 1,3-bis(3-thiophene)-2-propen-1-one to obtain modified mica sheets. Finally, modified polyester and modified mica sheets are blended and spun to obtain modified polyester, which is then blended and spun with spandex and treated with thiophene to obtain a durable antibacterial high-elasticity shapewear fabric.

[0023] First, cyanoacetic acid and 3-(3-thienyl)-1-propanol are transesterified to generate cyano-(3-thienylpropyl)acetate. Then, 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, and 1,4-butanediol are copolymerized to generate a pre-modified polyester, incorporating benzophenone structures into the polyester chain. Through the condensation reaction of benzophenone and cyano-(3-thienylpropyl)acetate, cyanoacrylate structures are generated, and thiophene functional groups are introduced at the end of these structures. The conjugated double bond system of the cyanoacrylate structure can capture free radicals and inhibit photo-oxidative degradation, thus endowing the fabric with anti-photoaging properties. Second, mica sheets, due to their layered structure and high thermal conductivity, can quickly conduct heat from the body surface, giving the fabric a cooling sensation. Mica sheets with epoxy functional groups on their surface undergo a ring-opening reaction with phosphoric acid and propylene oxide to generate hydroxyphosphoric acid. The ester structure provides the fabric with certain flame-retardant properties. Hydroxyphosphate ester and -amino-1H-benzimidazole-5-carboxylic acid are grafted onto the mica surface via transesterification with aminobenzimidazole groups. The aminobenzimidazole groups and 1,3-bis(3-thiophene)-2-propen-1-one containing a chalcone structure undergo an addition cyclization reaction to generate a nitrogen-containing heterocyclic imidazole structure. Through protonation, the fabric is endowed with good antibacterial properties and a thiophene structure is introduced. Finally, modified polyester and modified mica are blended and spun to obtain modified polyester. The modified polyester and spandex are blended and woven, and then treated with thiophene to obtain a durable antibacterial high-elastic shaping garment fabric. The surface of the modified polyester contains a thiophene structure, which can polymerize with thiophene monomers under the action of a catalyst to generate polythiophene with antistatic properties. Polythiophene is chemically bonded to the fabric surface, resulting in superior wash resistance. Detailed Implementation

[0024] 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.

[0025] The parameters of the twin-screw extruder described in the following examples and comparative examples are as follows: Zone 1: 220℃, Zone 2: 240℃, Zone 3: 250℃, Die head: 255℃, Screw speed: 80rpm; The spandex fineness is 4.4tex; The mica sheet has a specification of 6μm and was purchased from Lingshou County Dinghong Mineral Products Processing Plant.

[0026] Example 1

[0027] A method for preparing a durable antibacterial, highly elastic shapewear fabric, the method comprising the following steps:

[0028] (1) Cyanoacetic acid, 3-(3-thienyl)-1-propanol and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:2.5:0.05, heated to 120℃ and reacted for 8h. After cooling to room temperature, the mixture was distilled under reduced pressure. The pH was adjusted to 7 with saturated sodium carbonate. After separation, washing with saturated sodium chloride solution, drying with anhydrous magnesium sulfate, and distilling under reduced pressure, cyano-(3-thienylpropyl)acetic acid ester was obtained.

[0029] (2) 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol and stannous octoate were mixed in a molar ratio of 1:4:5.5:0.005 and heated to 190°C for 3 hours under nitrogen protection. The temperature was then increased to 250°C and reacted at 50 Pa for 3 hours. Heating was stopped and nitrogen was introduced to restore the pressure to normal, thus obtaining the pre-modified polyester.

[0030] (3) The pre-modified polyester, cyano-(3-thiophenepropyl) acetate, and toluene-n-heptane solution were mixed. Under nitrogen protection, half of the p-toluenesulfonic acid solution was added, and the mixture was stirred for 40 min. The mixture was heated to 110 °C and refluxed for 3 h. The reaction was continued for 6 h. The mixture was precipitated by ice water, filtered, washed, and dried to obtain the modified polyester. The mass ratio of the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution, and p-toluenesulfonic acid solution was 1:0.6:10:1. The toluene-n-heptane solution was obtained by mixing toluene and n-heptane in a volume ratio of 3:1. The p-toluenesulfonic acid solution was obtained by mixing p-toluenesulfonic acid and ethanol in a volume ratio of 1:9.

[0031] (4) Mica sheets and 1M hydrochloric acid were ultrasonically mixed at a mass ratio of 1:10 for 40 min, filtered, washed and dried to obtain activated mica sheets; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and pure water were mixed at a mass ratio of 1:4, pH was adjusted to 4 with glacial acetic acid, stirred at 35℃ for 1 h, and distilled under reduced pressure at 40℃ for 20 min to obtain hydrolyzed siloxane; activated mica sheets, hydrolyzed siloxane and isopropanol were ultrasonically mixed at a mass ratio of 1:0.5:50 for 20 min, pH was adjusted to 10 with 28wt% ammonia water, reacted at 80℃ for 6 h, filtered, washed and dried to obtain pretreated mica sheets; pretreated mica sheets, phosphoric acid and ethyl acetate were mixed at a mass ratio of 1:4:30, ultrasonicated for 30 min, and 1.5 times the mass of phosphoric acid propylene oxide was added dropwise at 25℃ at 0.6 mL / min. After the addition was completed, the temperature was raised to 90℃ and reacted for 4 h. Filtered, washed and dried to obtain premodified mica sheets;

[0032] (5) Pre-modified mica sheets, 2-amino-1H-benzimidazole-5-carboxylic acid, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:2:0.4:20, heated to 110℃ and reacted for 8 hours. The mixture was then filtered, washed and dried to obtain benzimidazole mica sheets. Benzimidazole mica sheets, 1,3-bis(3-thiophene)-2-propen-1-one, ethanol and glacial acetic acid were mixed in a mass ratio of 1:1.5:40:0.003, heated to 90℃ and reacted for 12 hours. Four times the volume of ethanol in ice water was added, and the mixture was filtered, washed and dried to obtain modified mica sheets.

[0033] (6) Modified polyester and modified mica sheets are mixed at a mass ratio of 1:0.03, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun on a spinning machine to obtain modified polyester. The spinning temperature is 250℃, the winding speed is 800m / min, the draw ratio is 2.0 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 85:15. The fabric is woven using a double-sided circular weft machine with a fabric weight of 160g / m².

[0034] (7) Mix the fabric, ferric chloride and chloroform at a mass ratio of 1:12:110 for 40 min; add thiophene at 30℃ and stir for 30 min, then take it out and immerse it in 1.5 mol / L hydrochloric acid solution and mix for 20 min. The bath ratio is 1:60. After taking it out, wash it with saturated sodium carbonate, wash it with pure water and dry it to obtain a durable antibacterial high elastic body shaping fabric; the molar ratio of thiophene to ferric chloride is 1:4.

[0035] Example 2

[0036] A method for preparing a durable antibacterial, highly elastic shapewear fabric, the method comprising the following steps:

[0037] (1) Cyanoacetic acid, 3-(3-thienyl)-1-propanol and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:2.6:0.05, heated to 115℃ and reacted for 7h. After cooling to room temperature, the mixture was distilled under reduced pressure, and the pH was adjusted to 7 with saturated sodium carbonate. After separation, the mixture was washed with saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain cyano-(3-thienylpropyl)acetic acid ester.

[0038] (2) Mix 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol, and stannous octoate, and heat to 185°C for 3 hours under nitrogen protection. Then, heat to 245°C and react at 50 Pa for 2.5 hours. Stop heating, introduce nitrogen to restore atmospheric pressure, and obtain pre-modified polyester. The molar ratio of 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol, and stannous octoate is 1:4.5:5.7:0.005.

[0039] (3) The pre-modified polyester, cyano-(3-thiophenepropyl) acetate, and toluene-n-heptane solution were mixed. Under nitrogen protection, half of the p-toluenesulfonic acid solution was added, stirred for 35 min, heated to 105℃ and refluxed for 2.5 h. The remaining p-toluenesulfonic acid solution was added, and the reaction was continued for 5.5 h. After precipitation with ice water, the mixture was filtered, washed and dried to obtain the modified polyester. The mass ratio of the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution and p-toluenesulfonic acid solution was 1:0.65:11:1.1. The toluene-n-heptane solution was obtained by mixing toluene and n-heptane in a volume ratio of 3.5:1. The p-toluenesulfonic acid solution was obtained by mixing p-toluenesulfonic acid and ethanol in a volume ratio of 1:9.5.

[0040] (4) Mica sheets and 1M hydrochloric acid were ultrasonically mixed at a mass ratio of 1:11 for 35 min, filtered, washed and dried to obtain activated mica sheets; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and pure water were mixed at a mass ratio of 1:4.5, the pH was adjusted to 4.5 with glacial acetic acid, stirred at 30℃ for 1.5 h, and distilled under reduced pressure at 40℃ for 20 min to obtain hydrolyzed siloxane; activated mica sheets, hydrolyzed siloxane and isopropanol were ultrasonically mixed at a mass ratio of 1:0.6:55. The mixture was stirred for 20 min, and the pH was adjusted to 10 with 28 wt% ammonia. The reaction was carried out at 75 °C for 5.5 h. After filtration, washing and drying, pretreated mica sheets were obtained. The pretreated mica sheets, phosphoric acid and ethyl acetate were ultrasonically mixed at a mass ratio of 1:4.5:35 for 25 min. At 23 °C, 1.7 times the mass of phosphoric acid propylene oxide was added dropwise at a rate of 0.6 mL / min. After the addition was completed, the temperature was raised to 85 °C and the reaction was carried out for 3.5 h. After filtration, washing and drying, pre-modified mica sheets were obtained.

[0041] (5) Pre-modified mica sheets, 2-amino-1H-benzimidazole-5-carboxylic acid, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:2.5:0.45:25, heated to 107℃ and reacted for 7.5 h. After filtration, washing and drying, benzimidazole mica sheets were obtained. Benzimidazole mica sheets, 1,3-di(3-thiophene)-2-propen-1-one, ethanol and glacial acetic acid were mixed in a mass ratio of 1:1.7:45:0.004, heated to 85℃ and reacted for 11 h. Ice water with a volume of 3.5 times that of ethanol was added. After filtration, washing and drying, modified mica sheets were obtained.

[0042] (6) Modified polyester and modified mica sheets are mixed at a mass ratio of 1:0.04, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun on a spinning machine to obtain modified polyester. The spinning temperature is 245℃, the winding speed is 750m / min, the draw ratio is 1.7 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 83:17. The fabric is woven by a double-sided circular weft machine with a fabric weight of 155g / m².

[0043] (7) Mix the fabric, ferric chloride and chloroform at a mass ratio of 1:13:115 for 35 min; add thiophene at 25℃ and stir for 25 min, then take it out and immerse it in 1.3 mol / L hydrochloric acid solution and mix for 15 min. The bath ratio is 1:70. After taking it out, wash it with saturated sodium carbonate, wash it with pure water and dry it to obtain a durable antibacterial high elastic shaping garment fabric; the molar ratio of thiophene to ferric chloride is 1:4.3.

[0044] Example 3

[0045] A method for preparing a durable antibacterial, highly elastic shapewear fabric, the method comprising the following steps:

[0046] (1) Cyanoacetic acid, 3-(3-thienyl)-1-propanol and 98wt% concentrated sulfuric acid were mixed in a mass ratio of 1:3.0:0.06, heated to 110℃ and reacted for 6h, cooled to room temperature, and distilled under reduced pressure. The pH was adjusted to 7 with saturated sodium carbonate, separated, washed with saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and distilled under reduced pressure to obtain cyano-(3-thienylpropyl)acetic acid ester;

[0047] (2) Mix 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol and stannous octoate, and heat to 180°C for 2 hours under nitrogen protection. Then, heat to 240°C and react at 50 Pa for 2 hours. Stop heating and introduce nitrogen to restore to normal pressure to obtain pre-modified polyester. The molar ratio of 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol and stannous octoate is 1:5:6.0:0.006.

[0048] (3) Mix the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, and toluene-n-heptane solution. Under nitrogen protection, add half of the p-toluenesulfonic acid solution, stir for 30 min, heat to 100℃ and reflux for 2 h, add the remaining p-toluenesulfonic acid solution, and continue the reaction for 5 h. After precipitation with ice water, filter, wash and dry to obtain the modified polyester. The mass ratio of the pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution and p-toluenesulfonic acid solution is 1:0.6:10:1. The toluene-n-heptane solution is obtained by mixing toluene and n-heptane in a volume ratio of 4:1. The p-toluenesulfonic acid solution is obtained by mixing p-toluenesulfonic acid and ethanol in a volume ratio of 1:10.

[0049] (4) Mica sheets and 1M hydrochloric acid were ultrasonically mixed at a mass ratio of 1:12 for 30 min, filtered, washed and dried to obtain activated mica sheets; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and pure water were mixed at a mass ratio of 1:5, the pH was adjusted to 5 with glacial acetic acid, stirred at 35℃ for 1 h, and distilled under reduced pressure at 40℃ for 20 min to obtain hydrolyzed siloxane; activated mica sheets, hydrolyzed siloxane and isopropanol were ultrasonically mixed at a mass ratio of 1:0.7:60. Mix for 20 min, adjust pH to 10 with 28 wt% ammonia, react at 70 °C for 5 h, filter, wash and dry to obtain pretreated mica sheets; mix pretreated mica sheets, phosphoric acid and ethyl acetate in a mass ratio of 1:5:40 ultrasonically for 20 min, add propylene oxide at 0.6 mL / min at 20 °C, raise the temperature to 80 °C and react for 3 h, filter, wash and dry to obtain premodified mica sheets;

[0050] (5) Pre-modified mica sheets, 2-amino-1H-benzimidazole-5-carboxylic acid, p-toluenesulfonic acid, and N,N-dimethylformamide were mixed in a mass ratio of 1:3:0.5:30, heated to 100℃ and reacted for 7 h. After filtration, washing and drying, benzimidazole mica sheets were obtained. Benzimidazole mica sheets, 1,3-di(3-thiophene)-2-propen-1-one, ethanol, and glacial acetic acid were mixed in a mass ratio of 1:2.0:50:0.005, heated to 80℃ and reacted for 10 h. Ice water with a volume of 4 times that of ethanol was added. After filtration, washing and drying, modified mica sheets were obtained.

[0051] (6) Modified polyester and modified mica sheets are mixed at a mass ratio of 1:0.05, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun on a spinning machine to obtain modified polyester. The spinning temperature is 240℃, the winding speed is 700m / min, the draw ratio is 1.5 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 80:20. The fabric is woven by a double-sided circular weft machine with a fabric weight of 150g / m².

[0052] (7) Mix the fabric, ferric chloride and chloroform at a mass ratio of 1:15:120 for 30 min; add thiophene at 20℃ and stir for 20 min, then take it out and immerse it in 1 mol / L hydrochloric acid solution and mix for 10 min. The bath ratio is 1:70. After taking it out, wash it with saturated sodium carbonate, wash it with pure water and dry it to obtain a durable antibacterial high elastic body shaping fabric; the molar ratio of thiophene to ferric chloride is 1:4.5.

[0053] Comparative Example 1:

[0054] The difference between the preparation method of the durable antibacterial high-elastic shapewear fabric of Comparative Example 1 and Example 2 is that the pre-modified polyester is not further modified. Specifically, steps (1) to (2) are omitted, and step (6) is modified as follows: the pre-modified polyester and modified mica sheets are mixed at a mass ratio of 1:0.04, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun on a spinning machine to obtain modified polyester. The spinning temperature is 245℃, the winding speed is 750m / min, the draw ratio is 1.7 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 83:17. The fabric is woven using a double-sided circular weft machine with a fabric weight of 160g / m². The remaining steps are the same as in Example 2.

[0055] Comparative Example 2:

[0056] The difference between the preparation method of the durable antibacterial high-elastic shaping garment fabric of Comparative Example 2 and Example 2 is that the pre-modified mica sheet is not modified. Specifically, step (5) is omitted, and step (6) is modified as follows: the modified polyester and the pre-modified mica sheet are mixed at a mass ratio of 1:0.04, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun on a spinning machine to obtain modified polyester. The spinning temperature is 245℃, the winding speed is 750m / min, the draw ratio is 1.7 times, and the modified polyester fineness is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 83:17. The fabric is woven using a double-sided circular weft machine with a fabric weight of 155g / m². The remaining steps are the same as in Example 2.

[0057] Comparative Example 3:

[0058] The difference between the preparation method of the durable antibacterial high-elastic shaping garment fabric of Comparative Example 3 and Example 2 is that the pre-modified polyester is not modified further and the pre-modified mica sheet is not modified. Specifically, step (6) is modified as follows: the pre-modified polyester and pre-modified mica sheet are mixed at a mass ratio of 1:0.04, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun by a spinning machine to obtain modified polyester. The spinning temperature is 245℃, the winding speed is 750m / min, the draw ratio is 1.7 times, and the fineness of the modified polyester is 16.7tex. The modified polyester and spandex are processed into composite yarn by an air-coated yarn machine at a ratio of 83:17. The fabric is woven by a double-sided circular weft machine with a fabric weight of 150g / m². The durable antibacterial high-elastic shaping garment fabric is obtained.

[0059] Test Example 1:

[0060] Antibacterial performance testing:

[0061] Test method: The antibacterial rate of the fabrics prepared in the examples and comparative examples was tested according to GB / T20944.2-2007. The results are shown in Table 1.

[0062]

[0063] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 1 shows that the fabric prepared by the present invention has good antibacterial properties.

[0064] By comparison, the antibacterial rates of Examples 1-3 were greater than those of Comparative Examples 2-3, indicating that hydroxyphosphate and 2-amino-1H-benzimidazole-5-carboxylic acid graft aminobenzimidazole groups onto the mica sheet surface through transesterification. The aminobenzimidazole groups and 1,3-bis(3-thiophene)-2-propen-1-one containing a chalcone structure undergo an addition reaction to generate an azole structure containing heteroatoms, which imparts good antibacterial properties to the fabric through protonation.

[0065] Test Example 2:

[0066] Antistatic performance testing:

[0067] Test method: The surface charge density of the fabric was measured according to the standard GB / T12703-1991 "Textiles - Electrostatic Test Method". The results are shown in Table 2.

[0068] Water wash resistance test:

[0069] Test method: The fabrics prepared in the examples and comparative examples were machine washed 20 times according to standard GB / T 8629-2017, and after drying, the antistatic properties were tested according to the test method. The results are shown in Table 2.

[0070]

[0071] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 2 shows that the fabric prepared by the present invention has good antistatic properties and durability.

[0072] By comparison, Examples 1-3 showed good antistatic properties, and the washability of Examples 1-3 was better than that of Comparative Examples 1-3. Both Examples and Comparative Examples had antistatic properties before washing, while the antistatic properties of the Comparative Examples decreased to varying degrees after washing. This indicates that modified polyester and modified mica sheets were blended and spun to obtain modified polyester, and modified polyester and spandex were blended and woven, and then treated with thiophene to obtain a durable antibacterial high-elastic shaping garment fabric. The surface of the modified polyester contains thiophene structures, which can polymerize with thiophene monomers under the action of a catalyst to generate polythiophene with antistatic properties. Polythiophene is chemically bonded to the fabric surface, resulting in superior washability.

[0073] Test Example 3:

[0074] Test for resistance to photoaging:

[0075] Test method: Antioxidant performance was tested according to national standard GB / T 16422.3-2022; the samples were irradiated with ultraviolet light at 70℃ with an irradiation intensity of 0.76 W / (m²). 2 The UV lamp power was 40W, and the irradiation time was 7 days. After the irradiation, the tensile strength was tested and the tensile strength retention rate was calculated. The tensile strength was tested using the shear strip method according to the standard ASTM D5035-1995 (2003). The results are shown in Table 3.

[0076]

[0077] A comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 3 shows that the moisture-wicking polyester-ammonia blended antibacterial fabric prepared by the present invention has good anti-photoaging properties.

[0078] By comparison, the anti-photoaging performance of Examples 1-3 is better than that of Comparative Examples 1 and 2. This indicates that by transesterifying cyanoacetic acid and 3-(3-thienyl)-1-propanol to generate cyano-(3-thienylpropyl)acetate, and by copolymerizing 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, and 1,4-butanediol to generate a pre-modified polyester, the polyester chain segments contain benzophenone structures. Through the condensation reaction of benzophenone and cyano-(3-thienylpropyl)acetate, cyanoacrylate structures are generated, and thiophene functional groups are introduced at the end of the structure. The conjugated double bond system of the cyanoacrylate structure can capture free radicals and inhibit photo-oxidative degradation, thus endowing the fabric with anti-photoaging ability.

[0079] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a durable, antibacterial, highly elastic shapewear fabric, characterized in that, The preparation steps include the following: (1) Cyanoacetic acid and 3-(3-thienyl)-1-propanol were reacted to obtain cyano-(3-thienylpropyl)acetic acid ester; (2) Mix 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol and stannous octoate, and heat to 180-190℃ under nitrogen protection for 2-3 hours. Continue heating to 240-250℃ and react at 50 Pa for 2-3 hours. Stop heating, introduce nitrogen to restore to normal pressure, and obtain pre-modified polyester; (3) The pre-modified polyester and cyano-(3-thiophenepropyl)acetic acid ester were reacted to obtain the modified polyester; (4) Pretreated mica sheets, phosphoric acid, and ethyl acetate are mixed, and propylene oxide is added dropwise to react and obtain pre-modified mica sheets; the preparation method of the pre-modified mica sheets is as follows: mica sheets and hydrochloric acid are mixed and reacted at a mass ratio of 1:(10-12) to obtain activated mica sheets; 3-(2,3-epoxypropoxy)propyltrimethoxysilane and pure water are mixed and reacted at a mass ratio of 1:(4-5) at pH 4-5 to obtain hydrolyzed siloxane; activated mica sheets, hydrolyzed siloxane, and isopropanol are mixed and reacted at a mass ratio of 1:(0.5-0.7):(50-60) at pH=10 to obtain pretreated mica sheets; Pretreated mica sheets, phosphoric acid, and ethyl acetate were mixed at a mass ratio of 1:(4-5):(30-40) and reacted for 20-30 minutes. Then, 1.5-2 times the mass of propylene oxide was added dropwise to react and obtain pre-modified mica sheets. (5) The pre-modified mica sheet was reacted with 2-amino-1H-benzimidazole-5-carboxylic acid to obtain benzimidazole mica sheet; the benzimidazole mica sheet was reacted with 1,3-bis(3-thiophene)-2-propen-1-one to obtain modified mica sheet; (6) The modified polyester and modified mica sheets are mixed, melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun by a spinning machine to obtain modified polyester. The modified polyester is then blended with spandex to form a composite yarn and woven into a fabric. (7) Immerse the fabric in a mixture of ferric chloride and chloroform for 30-40 minutes; add thiophene and stir, then remove and immerse in a 1-1.5 mol / L hydrochloric acid solution. After removing, wash with saturated sodium carbonate, wash with pure water and dry to obtain a durable antibacterial high-elasticity shapewear fabric.

2. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The preparation method of cyano-(3-thiophenepropyl)acetic acid ester in step (1) is as follows: cyanoacetic acid, 3-(3-thiophene)-1-propanol and concentrated sulfuric acid are mixed and reacted in a mass ratio of 1:(2.5-3.0):(0.05-0.06) to obtain cyano-(3-thiophenepropyl)acetic acid ester.

3. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The molar ratio of 4,4'-carbonyl di(methyl benzoate), dimethyl terephthalate, 1,4-butanediol, and stannous octoate in step (2) is 1:(4-5):(5.5-6.0):(0.005-0.006).

4. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The modified polyester in step (3) is prepared by mixing and reacting pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution and p-toluenesulfonic acid solution to obtain modified polyester; the mass ratio of pre-modified polyester, cyano-(3-thiophenepropyl) acetate, toluene-n-heptane solution and p-toluenesulfonic acid solution is 1:(0.6-0.7):(10-12):(1-1.2).

5. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The modified mica sheet preparation method in step (5) is as follows: pre-modified mica sheet, 2-amino-1H-benzimidazole-5-carboxylic acid, p-toluenesulfonic acid, and N,N-dimethylformamide are mixed and reacted in a mass ratio of 1:(2-3):(0.4-0.5):(20-30) to obtain benzimidazole mica sheet; benzimidazole mica sheet, 1,3-bis(3-thiophene)-2-propen-1-one, ethanol, and glacial acetic acid are mixed and reacted in a mass ratio of 1:(1.5-2.0):(40-50):(0.003-0.005) to obtain modified mica sheet.

6. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The fabric preparation method in step (6) is as follows: modified polyester and modified mica sheets are mixed at a mass ratio of 1:(0.03-0.05), melt-blended in a twin-screw extruder, extruded and granulated, and melt-spun in a spinning machine to obtain modified polyester. The spinning temperature is 240-250℃, the winding speed is 700-800m / min, the draw ratio is 1.5-2.0 times, and the fineness of the modified polyester is 16.7tex. Modified polyester and spandex are processed into composite yarns at a ratio of (80-85):(15-20) using an air-coated yarn machine; the yarns are woven into fabrics using a double-sided circular weft machine; the fabric weight is 150-160 g / m².

7. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 1, characterized in that, The preparation method of the durable antibacterial high-elastic shaping garment fabric in step (7) is as follows: mix the fabric, ferric chloride, and chloroform at a mass ratio of 1:(12-15):(110-120) for 30-40 min; add thiophene at 20-30℃ and stir for 20-30 min, then take it out and immerse it in 1mol / L hydrochloric acid solution and mix for 10-20 min, with a bath ratio of 1:(60-80). After taking it out, wash it with saturated sodium carbonate, wash it with pure water and dry it to obtain the durable antibacterial high-elastic shaping garment fabric; the molar ratio of thiophene to ferric chloride is 1:(4-4.5).

8. The method for preparing a durable antibacterial, high-elasticity shapewear fabric according to claim 4, characterized in that... The volume ratio of toluene to n-heptane in the toluene-n-heptane solution is (3-4):1; the volume ratio of p-toluenesulfonic acid to ethanol in the p-toluenesulfonic acid solution is 1:(9-10).

9. A durable antibacterial, highly elastic shapewear fabric prepared by a method according to any one of claims 1-8.

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