Anti-aging textile fabric and preparation method thereof

Abstract

The invention discloses an anti-aging textile fabric and a preparation method thereof, and relates to the field of fiber fabrics. When the anti-aging textile fabric is prepared, microcrystalline cellulose sequentially reacts with thionyl chloride, sodium azide, 3-ethynyl benzene sulfonyl chloride and 2, 2 '-4-trihydroxy benzophenone, and then is complexed with zinc ions to prepare functional cellulose; the preparation method comprises the following steps: reacting tetramethylcyclotetrasiloxane with diethyl allyl phosphate, and polymerizing with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane, so as to obtain modified polysiloxane; the preparation method comprises the following steps: mixing functional cellulose and polyethylene glycol terephthalate, carrying out melt spinning to prepare a fabric, and finally, carrying out surface treatment on one side of the fabric by utilizing modified polysiloxane to prepare the anti-aging textile fabric. The anti-aging textile fabric prepared by the invention has the capabilities of flame retardance, one-way moisture conduction and antibiosis.

Description

Technical Field

[0001] The invention relates to the field of fiber fabrics, in particular to an aging-resistant textile fabric and a preparation method thereof. Background Art

[0002] Textile fabrics are textile raw materials made from fibers through textile technology. According to the source of raw materials, they can be divided into three categories: natural fibers, chemical fibers and blended fabrics. Natural fibers include cotton, linen, silk, wool, etc., chemical fibers include synthetic materials such as polyester, nylon, spandex, etc., and blended fabrics combine the advantages of natural and chemical fibers. The fabric properties are determined by the fiber type, weaving process and finishing technology, and are widely used in clothing, home furnishing and industrial fields.

[0003] With the rapid development of outdoor sports, industrial protection and medical textiles, fabrics need to maintain functional stability in complex environments (such as high-intensity ultraviolet rays, alternating humidity and heat, and mechanical wear). Outdoor textiles are often exposed to sunlight, and ultraviolet radiation may cause chemical bond breakage and fiber embrittlement in polymer materials. Therefore, this application introduces an aging-resistant textile fabric with unidirectional moisture conduction ability and a preparation method thereof. Summary of the Invention

[0004] The purpose of the present invention is to provide an aging-resistant textile fabric and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] An aging-resistant textile fabric is prepared by mixing functionalized cellulose and polyethylene terephthalate, melt-spinning the mixture, and then surface-treating one side of the fabric with modified polysiloxane.

[0006] The functionalized cellulose is prepared by reacting microcrystalline cellulose with thionyl chloride, sodium azide, 3-ethynylbenzenesulfonyl chloride and 2,2'-4-trihydroxybenzophenone in sequence, and then complexing with zinc ions.

[0007] The modified polysiloxane is prepared by reacting tetramethylcyclotetrasiloxane and allyl diethyl phosphate, and then polymerizing the resulting mixture with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane.

[0008] A method for preparing an aging-resistant textile fabric, the method mainly comprising the following preparation steps:

[0009] (1) 2,2'-4-trihydroxybenzophenone, dichloromethane and triethylamine were mixed in a molar ratio of 1:18-22:1.4-1.6, stirred at 0-4°C, 200-300 r / min, under nitrogen protection for 8-12 minutes, and modified cellulose with a mass of 7-9 times that of 2,2'-4-trihydroxybenzophenone was added at a uniform rate within 8-12 minutes, heated to room temperature, and stirred for 1.8-2.2 hours. The mixture was filtered and immersed in a 0.1 mol / L zinc acetate aqueous solution at 50-60°C for 22-26 hours, washed with ethanol 3-5 times, and vacuum dried at 30-40°C for 11-13 hours to obtain functionalized cellulose.

[0010] (2) Modified siloxane, octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane and trifluoromethanesulfonic acid are mixed in a mass ratio of 9-11:24-26:4-6:0.11-0.13, stirred at room temperature, 200-300 r / min, under nitrogen protection for 22-26 hours, anhydrous sodium bicarbonate is added to adjust the pH to 7-8, and vacuum dried at 40-50° C. for 22-26 hours to obtain modified polysiloxane;

[0011] (3) 9 to 11 composite fibers are combined and twisted into single yarns, which are then woven into fabrics; an initiator solution is applied to one side of the fabric, the fabric is allowed to stand for 12 to 16 minutes, and the fabric is exposed to light in a UV box for 4 to 6 minutes. The surface treatment liquid is evenly applied to the fabric without any droplets falling, and the fabric is exposed to light in a UV box for 55 to 65 minutes to obtain an aging-resistant fabric.

[0012] As an optimization, the modified cellulose in step (1) is prepared by mixing pre-modified cellulose, 3-ethynylbenzenesulfonyl chloride, and copper bromide in a mass ratio of 7-9:1:0.28-0.32, and adding tetrahydrofuran (4-6 times the mass of 3-ethynylbenzenesulfonyl chloride) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.35-0.37 times the molar amount of 3-ethynylbenzenesulfonyl chloride) in sequence at a uniform rate of 200-300 r / min over 14-16 minutes under nitrogen protection. The mixture is stirred at room temperature for 9-11 hours, poured into methanol, allowed to stand for 14-16 minutes, filtered, washed with methanol 3-5 times, and vacuum dried at 30-40°C for 11-13 hours.

[0013] As an optimization, the pre-modified cellulose is prepared by mixing chlorocellulose, sodium azide, and tetra-n-octylammonium bromide in a mass ratio of 1:0.6-0.8:0.24-0.26, adding tetrahydrofuran (4.8-5.2 times the mass of the chlorocellulose) at a uniform rate of 200-300 r / min over 12-14 minutes, heating to 60-64°C, continuing stirring for 11-13 hours, pouring tetrahydrofuran (11-13 times the mass of the chlorocellulose) and allowing it to stand for 1.5-2.5 hours, pouring it into deionized water and allowing it to stand for 20-30 minutes, filtering it, washing it with deionized water for 3-5 times, vacuum drying it at 30-40°C for 11-13 hours, and crushing it to a particle size of 0.3-0.5 mm.

[0014] As an optimization, the chlorocellulose is prepared by mixing microcrystalline cellulose and N,N-dimethylformamide in a mass ratio of 1:18.5-19, stirring at 85-95°C and 250-350 r / min for 14-16 minutes, adding thionyl chloride in an amount 0.17-0.18 times the volume of N,N-dimethylformamide at a uniform rate within 16-20 minutes, continuing stirring for 2-3 hours, pouring into deionized water, stirring at 600-800 r / min for 20-30 minutes, filtering, washing with deionized water for 8-10 times, vacuum drying at 45-55°C for 11-13 hours, and crushing to a particle size of 0.3-0.5 mm.

[0015] As an optimization, the modified siloxane in step (2) is prepared by mixing tetramethylcyclotetrasiloxane and diethyl allyl phosphate in a molar ratio of 1:3.4 to 3.8, adding a catalyst in an amount of 0.005 to 0.007 times the volume of tetramethylcyclotetrasiloxane, stirring at 60 to 70°C and 200 to 300 r / min for 4.5 to 5.5 hours, cooling to room temperature, and vacuum drying at -10 to 0°C for 22 to 26 hours.

[0016] As an optimization, the catalyst is prepared by uniformly mixing chloroplatinic acid and isopropyl alcohol in a mass ratio of 1:76-80.

[0017] As an optimization, the composite fiber in step (3) is prepared by mixing functionalized cellulose and polyethylene terephthalate in a mass ratio of 1:4 to 4.4, stirring at 266 to 270°C and 50 to 70 r / min for 6 to 8 minutes, setting the twin-screw extrusion temperature to 260 to 270°C, the spinning speed to 2700 to 2900 m / min, winding, and pulling, setting the hot roller temperature of the parallel drawing machine to 55 to 65°C, the hot plate temperature to 115 to 125°C, and the stretching ratio to 1.8 to 2.2.

[0018] As an optimization, the polyethylene terephthalate is purchased from Shanghai Huifei Chemical Co., Ltd.

[0019] As an optimization, the initiator solution in step (3) is prepared by uniformly mixing benzophenone and carbon tetrachloride in a molar ratio of 1:26-30.

[0020] As an optimization, the surface treatment liquid in step (3) is prepared by uniformly mixing carbon tetrachloride and modified polysiloxane at a mass ratio of 3.5 to 4.5:1 at 50 to 60°C.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] When preparing the aging-resistant textile fabric, the present invention comprises the following steps: reacting microcrystalline cellulose with thionyl chloride, sodium azide, 3-ethynylbenzenesulfonyl chloride and 2,2'-4-trihydroxybenzophenone in sequence, and then complexing with zinc ions to obtain functionalized cellulose; reacting tetramethylcyclotetrasiloxane and diethyl allyl phosphate, and then polymerizing with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane to obtain modified polysiloxane; mixing the functionalized cellulose with polyethylene terephthalate, and melt-spinning the mixture to obtain the fabric; and finally surface treating one side of the fabric with the modified polysiloxane to obtain the aging-resistant textile fabric.

[0023] First, microcrystalline cellulose is reacted with thionyl chloride, sodium azide, 3-ethynylbenzenesulfonyl chloride and 2,2'-4-trihydroxybenzophenone in sequence, and then complexed with zinc ions to obtain functionalized cellulose; microcrystalline cellulose is reacted with thionyl chloride, sodium azide and 3-ethynylbenzenesulfonyl chloride in sequence to form a triazole structure, which can complex zinc ions well. Since zinc ions have redox properties, they can react with organic matter (sulfide, carboxyl, hydroxyl) and combine with bacterial cell membranes and membrane proteins, thereby destroying their structure. When it enters the cell, it will break the enzymes in the electron transport system and react with DNA, thereby achieving the antibacterial purpose. , improve the antibacterial ability of the fabric; then react with 2,2'-4-trihydroxybenzophenone to form an o-hydroxybenzophenone structure, which has a strong absorption capacity for ultraviolet radiation. It can convert the absorbed radiation energy into less harmful heat energy through the photophysical process of ground state molecules and excited state molecules, and prevent adverse photooxidation and photodegradation caused by sunlight. However, as a commonly used ultraviolet absorber, o-hydroxybenzophenone has low photostability and is easily oxidized to turn the product yellow. By grafting sulfonyl groups onto cellulose, o-hydroxybenzophenone is not easy to volatilize or lose, and its compatibility with the material is further enhanced, the disadvantage of easy yellowing is improved, and the aging resistance of the material is effectively enhanced in the long term.

[0024] Secondly, tetramethylcyclotetrasiloxane and allyl diethyl phosphate are reacted, and then polymerized with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane to obtain modified polysiloxane; functionalized cellulose is mixed with polyethylene terephthalate, melt-spun to make fabric, and finally the fabric is surface-treated on one side with modified polysiloxane to obtain aging-resistant textile fabric; tetramethylcyclotetrasiloxane and allyl diethyl phosphate are reacted, and then polymerized with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane to obtain modified polysiloxane. Introducing phosphate into polysiloxane can promote the dehydration of polymer carbon when the material burns. The unilateral modification of the fabric makes one side hydrophilic and the other side hydrophobic, so that moisture will be transferred from the small hydrophilic area of the hydrophobic inner layer to the hydrophilic outer layer, where it will quickly diffuse and evaporate, thus achieving the effect of unilateral moisture conduction. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0026] Example 1:

[0027] A method for preparing an aging-resistant textile fabric mainly comprises the following preparation steps:

[0028] (1) Microcrystalline cellulose and N,N-dimethylformamide were mixed in a mass ratio of 1:18.5, stirred at 85°C and 250 r / min for 14 min, and 0.17 times the volume of thionyl chloride of N,N-dimethylformamide was added at a constant rate within 16 min. The mixture was stirred for 2 h, poured into deionized water, stirred at 600 r / min for 20 min, filtered, washed with deionized water 8 times, vacuum dried at 45°C for 11 h, and crushed to a particle size of 0.3 mm to obtain chlorocellulose;

[0029] Chlorocellulose, sodium azide, and tetra-n-octylammonium bromide were mixed in a mass ratio of 1:0.6:0.24, and tetrahydrofuran (4.8 times the mass of the chlorocellulose) was uniformly added at 200 r / min over 12 minutes. The mixture was heated to 60°C and stirred for 11 hours. Tetrahydrofuran (11 times the mass of the chlorocellulose) was poured in and allowed to stand for 1.5 hours. The mixture was poured into deionized water and allowed to stand for 20 minutes. The mixture was filtered, washed with deionized water for three times, and vacuum-dried at 30°C for 11 hours. The mixture was crushed to a particle size of 0.3 mm to obtain pre-modified cellulose.

[0030] Pre-modified cellulose, 3-ethynylbenzenesulfonyl chloride, and copper bromide were mixed in a mass ratio of 7:1:0.28. Under nitrogen protection, tetrahydrofuran (4 times the mass of 3-ethynylbenzenesulfonyl chloride) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.35 times the molar mass of 3-ethynylbenzenesulfonyl chloride) were added successively at a constant rate of 200 r / min over 14 minutes. The mixture was stirred at room temperature for 9 hours, poured into methanol, allowed to stand for 14 minutes, filtered, washed with methanol three times, and dried in vacuo at 30°C for 11 hours to obtain modified cellulose.

[0031] 2,2'-4-trihydroxybenzophenone, dichloromethane and triethylamine were mixed in a molar ratio of 1:18:1.4, stirred at 0°C, 200 r / min and nitrogen protection for 8 minutes, and modified cellulose with a mass 7 times that of 2,2'-4-trihydroxybenzophenone was added at a uniform rate within 8 minutes. The mixture was heated to room temperature and stirred for 1.8 hours. The mixture was filtered and immersed in a 0.1 mol / L zinc acetate aqueous solution at 50°C for 22 hours. The mixture was washed with ethanol three times and dried in vacuum at 30°C for 11 hours to obtain functionalized cellulose.

[0032] (2) Chloroplatinic acid and isopropanol were mixed uniformly in a mass ratio of 1:76 to prepare a catalyst; tetramethylcyclotetrasiloxane and diethyl allyl phosphate were mixed in a molar ratio of 1:3.4, 0.005 times the volume of tetramethylcyclotetrasiloxane was added as the catalyst, and the mixture was stirred at 60°C and 200 r / min for 4.5 hours, cooled to room temperature, and vacuum dried at -10°C for 22 hours to prepare a modified siloxane;

[0033] Modified siloxane, octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane and trifluoromethanesulfonic acid were mixed in a mass ratio of 9:24:4:0.11, stirred at room temperature, 200 r / min, under nitrogen protection for 22 hours, anhydrous sodium bicarbonate was added to adjust the pH to 7, and vacuum dried at 40°C for 22 hours to prepare modified polysiloxane;

[0034] (3) Functionalized cellulose and polyethylene terephthalate were mixed in a mass ratio of 1:4, stirred at 266°C and 50 r / min for 6 min, the twin-screw extruder temperature was set to 260°C, the spinning speed was set to 2700 m / min, winding and pulling were performed, the hot roller temperature of the parallel drawing machine was set to 55°C, the hot plate temperature was set to 115°C, and the stretching ratio was set to 1.8 to obtain a composite fiber;

[0035] Nine composite fibers were combined and twisted into single yarn, which was then woven into a fabric; benzophenone and carbon tetrachloride were evenly mixed in a molar ratio of 1:26 to prepare an initiator solution; carbon tetrachloride and modified polysiloxane were evenly mixed in a mass ratio of 3.5:1 at 50°C to prepare a surface treatment liquid; the initiator solution was coated on one side of the fabric, allowed to stand for 12 minutes, and exposed to UV light for 4 minutes, and the surface treatment liquid was evenly coated on this side without dripping, and the fabric was exposed to UV light for 55 minutes to prepare an aging-resistant fabric.

[0036] Example 2:

[0037] A method for preparing an aging-resistant textile fabric mainly comprises the following preparation steps:

[0038] (1) Microcrystalline cellulose and N,N-dimethylformamide were mixed in a mass ratio of 1:18.75, stirred at 90°C and 300 r / min for 15 min, and 0.175 times the volume of thionyl chloride of N,N-dimethylformamide was added at a constant rate within 18 min. The mixture was stirred for 2.5 h, poured into deionized water, stirred at 700 r / min for 25 min, filtered, washed with deionized water for 9 times, vacuum dried at 50°C for 12 h, and crushed to a particle size of 0.4 mm to obtain chlorocellulose;

[0039] Chlorocellulose, sodium azide, and tetra-n-octylammonium bromide were mixed in a mass ratio of 1:0.7:0.25, and tetrahydrofuran (5 times the mass of the chlorocellulose) was added at a constant rate of 250 r / min over 13 minutes. The mixture was heated to 62°C and stirred for 12 hours. The mixture was then poured into tetrahydrofuran (12 times the mass of the chlorocellulose) and allowed to stand for 2 hours. The mixture was then poured into deionized water and allowed to stand for 25 minutes. The mixture was filtered, washed with deionized water for 4 times, and vacuum-dried at 35°C for 12 hours. The mixture was crushed to a particle size of 0.4 mm to obtain pre-modified cellulose.

[0040] Pre-modified cellulose, 3-ethynylbenzenesulfonyl chloride, and copper bromide were mixed in a mass ratio of 8:1:0.3. Under nitrogen protection, tetrahydrofuran (5 times the mass of 3-ethynylbenzenesulfonyl chloride) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.36 times the molar mass of 3-ethynylbenzenesulfonyl chloride) were added successively at a constant rate of 250 r / min over 15 minutes. The mixture was stirred at room temperature for 10 hours, poured into methanol, allowed to stand for 15 minutes, filtered, washed with methanol 4 times, and dried in vacuo at 35°C for 12 hours to obtain modified cellulose.

[0041] 2,2'-4-trihydroxybenzophenone, dichloromethane and triethylamine were mixed in a molar ratio of 1:20:1.5, stirred at 2°C, 250 r / min and nitrogen protection for 10 minutes, and modified cellulose with a mass 8 times that of 2,2'-4-trihydroxybenzophenone was added at a uniform rate within 10 minutes. The mixture was heated to room temperature and stirred for 2 hours. The mixture was filtered and immersed in a 0.1 mol / L zinc acetate aqueous solution at 55°C for 24 hours. The mixture was washed with ethanol 4 times and dried in a vacuum at 5°C for 12 hours to obtain functionalized cellulose.

[0042] (2) Chloroplatinic acid and isopropanol were mixed uniformly in a mass ratio of 1:78 to prepare a catalyst; tetramethylcyclotetrasiloxane and diethyl allyl phosphate were mixed in a molar ratio of 1:3.6, 0.006 times the volume of tetramethylcyclotetrasiloxane was added as a catalyst, and the mixture was stirred at 65°C and 250 r / min for 5 hours, cooled to room temperature, and vacuum dried at -5°C for 24 hours to prepare a modified siloxane;

[0043] Modified siloxane, octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane and trifluoromethanesulfonic acid were mixed in a mass ratio of 10:25:5:0.12, stirred at room temperature, 250 r / min, under nitrogen protection for 24 hours, anhydrous sodium bicarbonate was added to adjust the pH to 7.5, and vacuum dried at 45°C for 24 hours to prepare modified polysiloxane;

[0044] (3) Functionalized cellulose and polyethylene terephthalate were mixed in a mass ratio of 1:4.2, stirred at 268°C and 60 r / min for 7 min, the twin-screw extruder temperature was set to 265°C, the spinning speed was set to 2800 m / min, winding and pulling were performed, the hot roller temperature of the parallel drawing machine was set to 60°C, the hot plate temperature was set to 120°C, and the stretching ratio was set to 2 to obtain a composite fiber;

[0045] Ten composite fibers were combined and twisted into single yarn, which was then woven into a fabric; benzophenone and carbon tetrachloride were evenly mixed in a molar ratio of 1:28 to prepare an initiator solution; carbon tetrachloride and modified polysiloxane were evenly mixed in a mass ratio of 4:1 at 55°C to prepare a surface treatment liquid; the initiator solution was coated on one side of the fabric, allowed to stand for 14 minutes, and exposed to UV light for 5 minutes, and the surface treatment liquid was evenly coated on this side without dripping, and the fabric was exposed to UV light for 60 minutes to prepare an aging-resistant fabric.

[0046] Example 3:

[0047] A method for preparing an aging-resistant textile fabric mainly comprises the following preparation steps:

[0048] (1) Microcrystalline cellulose and N,N-dimethylformamide were mixed in a mass ratio of 1:19, stirred at 95°C and 350 r / min for 16 min, and 0.18 times the volume of thionyl chloride of N,N-dimethylformamide was added at a constant rate within 20 min. The mixture was stirred for 3 h, poured into deionized water, stirred at 800 r / min for 30 min, filtered, washed with deionized water 10 times, vacuum dried at 55°C for 13 h, and crushed to a particle size of 0.5 mm to obtain chlorocellulose;

[0049] Chlorocellulose, sodium azide, and tetra-n-octylammonium bromide were mixed in a mass ratio of 1:0.8:0.26, and tetrahydrofuran (5.2 times the mass of the chlorocellulose) was added at a constant rate of 300 r / min over 14 minutes. The temperature was raised to 64°C and stirred for 13 hours. Tetrahydrofuran (13 times the mass of the chlorocellulose) was poured in and allowed to stand for 2.5 hours. The mixture was poured into deionized water and allowed to stand for 30 minutes. The mixture was filtered, washed with deionized water for 5 times, and vacuum dried at 40°C for 13 hours. The mixture was crushed to a particle size of 0.5 mm to obtain pre-modified cellulose.

[0050] Pre-modified cellulose, 3-ethynylbenzenesulfonyl chloride, and copper bromide were mixed in a mass ratio of 9:1:0.32. Under nitrogen protection, tetrahydrofuran (6 times the mass of 3-ethynylbenzenesulfonyl chloride) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.37 times the molar mass of 3-ethynylbenzenesulfonyl chloride) were added successively at a constant speed of 300 r / min over 16 minutes. The mixture was stirred at room temperature for 11 hours, poured into methanol, allowed to stand for 16 minutes, filtered, washed with methanol 5 times, and dried in vacuo at 40°C for 13 hours to obtain modified cellulose.

[0051] 2,2'-4-trihydroxybenzophenone, dichloromethane and triethylamine were mixed in a molar ratio of 1:22:1.6, stirred at 4°C, 300 r / min under nitrogen protection for 12 minutes, and modified cellulose with a mass of 9 times that of 2,2'-4-trihydroxybenzophenone was added at a uniform rate within 12 minutes. The mixture was heated to room temperature and stirred for 2.2 hours. The mixture was filtered and immersed in a 0.1 mol / L zinc acetate aqueous solution at 60°C for 26 hours. The mixture was washed with ethanol 5 times and dried in vacuum at 40°C for 13 hours to obtain functionalized cellulose.

[0052] (2) Chloroplatinic acid and isopropanol were mixed uniformly in a mass ratio of 1:80 to prepare a catalyst; tetramethylcyclotetrasiloxane and diethyl allyl phosphate were mixed in a molar ratio of 1:3.8, 0.007 times the volume of tetramethylcyclotetrasiloxane was added as the catalyst, and the mixture was stirred at 70°C and 300 r / min for 5.5 h, cooled to room temperature, and vacuum dried at 0°C for 26 h to prepare a modified siloxane;

[0053] Modified siloxane, octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane and trifluoromethanesulfonic acid were mixed in a mass ratio of 11:26:6:0.13, stirred at room temperature, 300 r / min, under nitrogen protection for 26 hours, anhydrous sodium bicarbonate was added to adjust the pH to 8, and vacuum dried at 50°C for 26 hours to prepare modified polysiloxane;

[0054] (3) Functionalized cellulose and polyethylene terephthalate were mixed in a mass ratio of 1:4.4, stirred at 270°C and 70 r / min for 8 min, the twin-screw extruder temperature was set to 270°C, the spinning speed was set to 2900 m / min, winding and pulling were performed, the hot roller temperature of the parallel drawing machine was set to 65°C, the hot plate temperature was set to 125°C, and the stretching ratio was set to 2.2 to obtain a composite fiber;

[0055] Eleven composite fibers were combined and twisted into single yarns, which were then woven into fabrics; benzophenone and carbon tetrachloride were evenly mixed in a molar ratio of 1:30 to prepare an initiator solution; carbon tetrachloride and modified polysiloxane were evenly mixed in a mass ratio of 4.5:1 at 60°C to prepare a surface treatment liquid; the initiator solution was coated on one side of the fabric, allowed to stand for 16 minutes, and exposed to UV light for 6 minutes, and the surface treatment liquid was evenly coated on this side without dripping, and the fabric was exposed to UV light for 65 minutes to prepare an aging-resistant fabric.

[0056] Comparative Example 1:

[0057] The difference between the preparation method of the aging-resistant textile fabric of Comparative Example 1 and Example 2 lies in the difference in step (1). Step (1) is modified as follows: microcrystalline cellulose and N,N-dimethylformamide are mixed in a mass ratio of 1:18.75, stirred at 90°C and 300 r / min for 15 min, thionyl chloride with a volume of 0.175 times that of N,N-dimethylformamide is added at a uniform rate within 18 min, stirring is continued for 2.5 h, poured into deionized water, stirred at 700 r / min for 25 min, filtered, washed with deionized water 9 times, vacuum dried at 50°C for 12 h, and crushed to a particle size of 0.4 mm to obtain chlorocellulose;

[0058] Chlorocellulose, sodium azide, and tetra-n-octylammonium bromide were mixed in a mass ratio of 1:0.7:0.25, and tetrahydrofuran (5 times the mass of the chlorocellulose) was added at a constant rate of 250 r / min over 13 minutes. The mixture was heated to 62°C and stirred for 12 hours. The mixture was then poured into tetrahydrofuran (12 times the mass of the chlorocellulose) and allowed to stand for 2 hours. The mixture was then poured into deionized water and allowed to stand for 25 minutes. The mixture was filtered, washed with deionized water for 4 times, and vacuum-dried at 35°C for 12 hours. The mixture was crushed to a particle size of 0.4 mm to obtain pre-modified cellulose.

[0059] Pre-modified cellulose, phenylacetylene, and copper bromide were mixed in a mass ratio of 8:1:0.3. Under nitrogen protection, tetrahydrofuran (5 times the mass of phenylacetylene) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.36 times the molar mass of phenylacetylene) were added sequentially at a rate of 250 r / min over 15 minutes. Stirring was continued at room temperature for 10 hours. The mixture was poured into methanol, allowed to stand for 15 minutes, filtered, and immersed in a 0.1 mol / L zinc acetate aqueous solution at 55°C for 24 hours. The mixture was washed four times with methanol and vacuum dried at 35°C for 12 hours to produce functionalized cellulose. The remaining steps were the same as in Example 2.

[0060] Comparative Example 2:

[0061] The preparation method of the aging-resistant textile fabric of Comparative Example 2 differs from that of Example 2 in that the microcrystalline cellulose is not modified. The remaining steps are the same as those of Example 2.

[0062] Comparative Example 3:

[0063] The preparation method of the aging-resistant textile fabric of Comparative Example 3 differs from that of Example 2 in step (2). Step (2) is modified as follows: octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane, and trifluoromethanesulfonic acid are mixed in a mass ratio of 37:6:0.13, stirred at room temperature, 300 r / min, under nitrogen protection for 26 hours, anhydrous sodium bicarbonate is added to adjust the pH to 8, and vacuum dried at 50° C. for 26 hours to obtain a modified polysiloxane. The remaining steps are the same as those of Example 2.

[0064] Comparative Example 4:

[0065] The method for preparing the aging-resistant textile fabric of Comparative Example 4 differs from that of Example 2 in that step (2) is omitted and step (3) is modified as follows: functionalized cellulose and polyethylene terephthalate are mixed in a mass ratio of 1:4.2, stirred at 268°C and 60 rpm for 7 min, the twin-screw extruder temperature is set to 265°C, the spinning speed is set to 2800 m / min, winding and pulling are performed, the heated roller temperature of the parallel drawing machine is set to 60°C, the heated plate temperature is set to 120°C, and the stretching ratio is set to 2, to obtain a composite fiber; 10 composite fibers are combined and twisted into a single yarn, which is then woven into a fabric to obtain an aging-resistant fabric. The remaining steps are the same as those of Example 2.

[0066] Test Example 1:

[0067] Flame retardant and antibacterial testing:

[0068] Antibacterial test method: The test was carried out in accordance with GB / T20944.3-2008, with the selected bacteria species being Staphylococcus aureus and Escherichia coli;

[0069] Flame retardant test method: Test the limiting oxygen index according to GB / T5454-1997 test standard. The results are shown in Table 1.

[0070] Table 1

[0071]

[0072]

[0073] From the comparison of the experimental data in Table 1, it can be found that the aging-resistant textile fabric prepared by the present invention has good antibacterial and flame-retardant capabilities.

[0074] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2 in Table 1, it can be found that Examples 1, 2, and 3 have high antibacterial rates. The difference between Comparative Example 2 and the Example is that no triazole structure is formed on the cellulose, and no zinc ion is complexed. This shows that zinc ions have redox properties and can react with organic matter (sulfide, carboxyl, hydroxyl) and combine with bacterial cell membranes and membrane proteins, thereby destroying their structures. When it enters the cell, it will break the enzymes in the electron transfer system and react with DNA, thereby achieving the antibacterial purpose and improving the antibacterial ability of the fabric.

[0075] Comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 3 shows that the limiting oxygen index of Examples 1, 2, and 3 is high. The difference between Comparative Example 3 and the Examples is that no phosphate ester is introduced into the polysiloxane. This indicates that the phosphate ester can promote the dehydration and carbonization of the polymer during combustion, forming an insulating carbon layer, reducing heat conduction from the flame to the condensed phase, and reducing oxygen diffusion and heat transfer, further inhibiting combustion and achieving a flame retardant effect.

[0076] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4, it can be found that the limiting oxygen index of Examples 1, 2 and 3 is high. The difference between Comparative Example 4 and the Examples is that polysiloxane is not introduced, which shows that by using polysiloxane to finish the fabric on one side, a silicon-containing carbon layer can be formed on the surface of the material. This carbon layer not only insulates heat and oxygen, but also effectively prevents the release of combustible gases, thereby enhancing the flame retardant ability of the material.

[0077] Test Example 2:

[0078] Aging resistance test:

[0079] Testing Method: Single yarns prepared in each example and comparative example were tested for breaking strength according to GB / T 9997-1988, denoted as C0. The samples were then irradiated with UV-A340 fluorescent ultraviolet light for 15 days according to ISO 4892-3. The breaking strength was then retested, denoted as C1, and the retention rate was calculated, where retention rate = C1 / C0 × 100%. The results are shown in Table 2.

[0080] Table 2

[0081] Retention rate Example 1 98.8％ Example 2 98.6％ Example 3 98.5％ Comparative Example 1 95.1％ Comparative Example 2 95.0％ Comparative Example 3 98.7％ Comparative Example 4 98.4％

[0082] From the comparison of the experimental data in Table 2, it can be found that the aging-resistant textile fabric prepared by the present invention has good aging resistance.

[0083] From the comparison of the experimental data of Examples 1, 2, and 3 and Comparative Example 1 in Table 2, it can be found that the retention rates of Examples 1, 2, and 3 are large. The difference between Comparative Example 1 and the Examples is that the o-hydroxybenzophenone structure is not introduced, which shows that o-hydroxybenzophenone has a strong absorption capacity for ultraviolet radiation and can convert the absorbed radiation energy into less harmful heat energy through the photophysical process of ground state molecules and excited state molecules, thereby preventing adverse photooxidation and photodegradation caused by sunlight and enhancing the aging resistance of the material.

[0084] Test Example 3:

[0085] Moisture conductivity test:

[0086] Test method: Refer to AATCC Test Method 79-1979, using a liquid moisture management test system to obtain the following parameters:

[0087] Wetting time (s): After the test starts, when the liquid content gradient on the upper and lower surfaces of the fabric is greater than tgl5.

[0088] The time when the surface starts to get wet;

[0089] Maximum water absorption (%): the maximum water absorption of the upper and lower surfaces of the fabric;

[0090] Maximum wetting radius (mm): The maximum wetting diameter of the upper and lower surfaces of the fabric when the slope of the moisture content curve of the upper and lower surfaces is greater than tgl5.

[0091] Liquid water diffusion rate (mm / s): the speed at which water on the upper and lower surfaces diffuses to the maximum wetting radius;

[0092] Cumulative one-way transfer index: the difference in moisture content between the upper and lower surfaces of the fabric during unit test time;

[0093] The rating standards for each parameter provided by the MMT test system refer to AATCC™ 195-2009. The results are shown in Table 3.

[0094] Table 3

[0095] Fabric Grade Example 1 5 Example 2 5 Example 3 5 Comparative Example 1 5 Comparative Example 2 5 Comparative Example 3 5 Comparative Example 4 4

[0096] From the comparison of the experimental data in Table 3, it can be found that the aging-resistant textile fabric prepared in the present invention has good unidirectional moisture conduction ability.

[0097] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4 in Table 3, it can be found that the fabric grades of Examples 1, 2, and 3 are high. The difference between Comparative Example 4 and the Examples is that the fabric is not unilaterally modified by polysiloxane. This shows that after the polysiloxane treatment, one side of the fabric has hydrophilic properties and the other side has hydrophobic properties. Moisture will be transferred from the small hydrophilic area of the hydrophobic inner layer to the hydrophilic outer layer, where it will quickly diffuse and evaporate, thereby achieving a unidirectional moisture conduction effect.

[0098] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An aging-resistant textile fabric, characterized in that: The aging-resistant textile fabric is prepared by mixing functionalized cellulose and polyethylene terephthalate, melt-spinning the mixture to form the fabric, and finally surface-treating one side of the fabric with modified polysiloxane. The functionalized cellulose is prepared by reacting microcrystalline cellulose with thionyl chloride, sodium azide, 3-ethynylbenzenesulfonyl chloride and 2,2'-4-trihydroxybenzophenone in sequence, and then complexing with zinc ions. The modified polysiloxane is prepared by reacting tetramethylcyclotetrasiloxane and allyl diethyl phosphate, and then polymerizing the resulting mixture with octamethylcyclotetrasiloxane and diallyltetramethyldisiloxane.

2. A method for preparing an aging-resistant textile fabric, characterized in that: The preparation method of the aging-resistant textile fabric mainly comprises the following preparation steps: (1) 2,2'-4-trihydroxybenzophenone, dichloromethane and triethylamine were mixed in a molar ratio of 1:18-22:1.4-1.6, stirred at 0-4°C, 200-300 r / min, under nitrogen protection for 8-12 minutes, and modified cellulose with a mass of 7-9 times that of 2,2'-4-trihydroxybenzophenone was added at a uniform rate within 8-12 minutes, heated to room temperature, and stirred for 1.8-2.2 hours. The mixture was filtered and immersed in a 0.1 mol / L zinc acetate aqueous solution at 50-60°C for 22-26 hours, washed with ethanol 3-5 times, and vacuum dried at 30-40°C for 11-13 hours to obtain functionalized cellulose. (2) Modified siloxane, octamethylcyclotetrasiloxane, diallyltetramethyldisiloxane and trifluoromethanesulfonic acid are mixed in a mass ratio of 9-11:24-26:4-6:0.11-0.13, stirred at room temperature, 200-300 r / min, under nitrogen protection for 22-26 hours, anhydrous sodium bicarbonate is added to adjust the pH to 7-8, and vacuum dried at 40-50° C. for 22-26 hours to obtain modified polysiloxane; (3) 9 to 11 composite fibers are combined and twisted into single yarns, which are then woven into fabrics; an initiator solution is applied to one side of the fabric, the fabric is allowed to stand for 12 to 16 minutes, and the fabric is exposed to light in a UV box for 4 to 6 minutes. The surface treatment liquid is evenly applied to the fabric without any droplets falling, and the fabric is exposed to light in a UV box for 55 to 65 minutes to obtain an aging-resistant fabric.

3. The method for preparing an aging-resistant textile fabric according to claim 2, characterized in that: The modified cellulose in step (1) is prepared by mixing pre-modified cellulose, 3-ethynylbenzenesulfonyl chloride and copper bromide in a mass ratio of 7-9:1:0.28-0.32, adding tetrahydrofuran (4-6 times the mass of 3-ethynylbenzenesulfonyl chloride) and N,N,N',N",N"-pentamethyldiethylenetriamine (0.35-0.37 times the molar amount of 3-ethynylbenzenesulfonyl chloride) in sequence at a uniform rate of 200-300 r / min over 14-16 minutes under nitrogen protection, continuing stirring at room temperature for 9-11 hours, pouring into methanol, standing for 14-16 minutes, filtering, washing with methanol 3-5 times, and vacuum drying at 30-40°C for 11-13 hours.

4. The method for preparing an aging-resistant textile fabric according to claim 3, characterized in that: The pre-modified cellulose is prepared by mixing chlorocellulose, sodium azide and tetra-n-octylammonium bromide in a mass ratio of 1:0.6-0.8:0.24-0.26, adding tetrahydrofuran (4.8-5.2 times the mass of the chlorocellulose) at a uniform speed of 200-300 r / min over 12-14 minutes, heating to 60-64°C, continuously stirring for 11-13 hours, pouring tetrahydrofuran (11-13 times the mass of the chlorocellulose) into the mixture, allowing the mixture to stand for 1.5-2.5 hours, pouring the mixture into deionized water, allowing the mixture to stand for 20-30 minutes, filtering the mixture, washing the mixture with deionized water for 3-5 times, vacuum drying the mixture at 30-40°C for 11-13 hours, and crushing the mixture to a particle size of 0.3-0.5 mm.

5. The method for preparing an aging-resistant textile fabric according to claim 4, characterized in that: The chlorocellulose is prepared by mixing microcrystalline cellulose and N,N-dimethylformamide in a mass ratio of 1:18.5-19, stirring at 85-95°C and 250-350 r / min for 14-16 minutes, adding thionyl chloride in an amount 0.17-0.18 times the volume of N,N-dimethylformamide at a uniform rate within 16-20 minutes, continuing stirring for 2-3 hours, pouring into deionized water, stirring at 600-800 r / min for 20-30 minutes, filtering, washing with deionized water for 8-10 times, vacuum drying at 45-55°C for 11-13 hours, and crushing to a particle size of 0.3-0.5 mm.

6. The method for preparing an aging-resistant textile fabric according to claim 2, characterized in that: The modified siloxane in step (2) is prepared by mixing tetramethylcyclotetrasiloxane and diethyl allyl phosphate in a molar ratio of 1:3.4-3.8, adding a catalyst in an amount of 0.005-0.007 times the volume of tetramethylcyclotetrasiloxane, stirring at 60-70°C and 200-300 r / min for 4.5-5.5 hours, cooling to room temperature, and vacuum drying at -10-0°C for 22-26 hours.

7. The method for preparing an aging-resistant textile fabric according to claim 6, characterized in that: The catalyst is prepared by uniformly mixing chloroplatinic acid and isopropyl alcohol in a mass ratio of 1:76-80.

8. The method for preparing an aging-resistant textile fabric according to claim 2, characterized in that: The composite fiber in step (3) is prepared by mixing functionalized cellulose and polyethylene terephthalate in a mass ratio of 1:4 to 4.4, stirring at 266 to 270°C and 50 to 70 r / min for 6 to 8 minutes, setting the twin-screw extrusion temperature to 260 to 270°C, the spinning speed to 2700 to 2900 m / min, winding, and pulling, setting the hot roller temperature of the parallel drawing machine to 55 to 65°C, the hot plate temperature to 115 to 125°C, and the stretching ratio to 1.8 to 2.

2.

9. The method for preparing an aging-resistant textile fabric according to claim 2, characterized in that: The initiator solution in step (3) is prepared by uniformly mixing benzophenone and carbon tetrachloride in a molar ratio of 1:26-30.

10. The method for preparing an aging-resistant textile fabric according to claim 2, characterized in that: The surface treatment liquid in step (3) is prepared by uniformly mixing carbon tetrachloride and modified polysiloxane in a mass ratio of 3.5 to 4.5:1 at 50 to 60°C.

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