Water-repellent and oil-repellent fabric and preparation method thereof

Abstract

The invention discloses a water-repellent and oil-repellent fabric and a preparation method thereof, and belongs to the technical field of fabric finishing. The preparation method of the water-repellent and oil-repellent fabric comprises the following steps: taking fabric gray cloth, carrying out dipping pretreatment, washing with hot water, washing with warm water, washing with cold water, and airing; soaking the pre-treated gray fabric in the finishing liquid, soaking twice and rolling twice, pre-drying, baking, washing and drying to obtain the water-repellent and oil-repellent fabric, the finishing liquid comprises a finishing agent and a solvent, wherein the finishing agent is a short-chain fluorine-based acrylate polymer mainly prepared from double-side symmetric fluorine-based acrylate monomers, octadecyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid-2-hydroxyethyl ester and 5-hydroxyl amyl acrylate as raw materials; the finishing aid comprises a mixed solution of starch grafted carbon nanotubes, tetrabutyl ammonium hydroxide, deionized water, glycerol, calcium chloride, a hydrochloric acid solution and epichlorohydrin; the surface of the fabric is treated by preparing the finishing liquid, so that the water-repellent and oil-repellent effects of the fabric are enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of fabric finishing, and in particular to a water-repellent and oil-repellent fabric and a preparation method thereof. Background Art

[0002] Today, the demand for functional textiles has far surpassed the traditional pursuit of basic properties such as softness, comfort, moisture absorption, and breathability. Consumers and industry are now more focused on advanced features such as antibacterial and hygienic properties, water, oil, and stain resistance, wrinkle-free application, radiation and UV protection, flame retardancy, and medical protection. With the continuous development and application of new fiber materials and the continuous innovation of new processes and technologies, these diverse demands are gradually being realized and met. Functional finishing technology, a key technology in textile processing, is being strongly driven by the growing demand for high-tech and high-value-added products. In particular, triple-proofing finishing technologies—multifunctional finishing technologies that offer water, oil, and stain repellency—have become a key development direction in the textile finishing field. Triple-proofing finishing agents are a type of textile finishing agent specifically designed for fabrics made from cotton, wool, silk, chemical fibers, and blended fibers. They modify the surface properties of fabrics, imparting strong water and oil repellency, thereby effectively preventing wetting or contamination by water, common oils, and stains. The water- and oil-repellent fiber products currently on the market have high water- and oil-repellent properties in the initial stage, but after repeated washing and friction, their oil- and water-repellent properties often decrease. This is a technical problem that urgently needs to be solved in the current field of functional textiles. Summary of the Invention

[0003] The present invention aims to provide a water-repellent and oil-repellent fabric and a preparation method thereof, so as to solve the problem in the prior art that the water-repellent and oil-repellent properties of the fabric are poorly durable and easily degraded after washing and friction.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a water-repellent and oil-repellent fabric, comprising the following steps:

[0006] S1. Take the fabric and immerse it in the pretreatment solution. After taking it out, wash it with hot water, warm water, and cold water in sequence, and dry it;

[0007] S2, dipping the pretreated fabric in a finishing solution, dipping and tying twice, pre-drying, baking, washing, and drying to obtain the water- and oil-repellent fabric;

[0008] The finishing liquid comprises:

[0009] The finishing agent is mainly a short-chain fluorine-based acrylate polymer prepared from bilaterally symmetrical fluorine-based acrylate monomers, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate;

[0010] The finishing auxiliary agent comprises a mixed solution of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution and epichlorohydrin.

[0011] As a further solution of the present invention, the mass ratio of the finishing agent to the finishing auxiliary agent is 32-44:3.4-5.2.

[0012] As a further embodiment of the present invention, the method for preparing the bilaterally symmetrical fluorinated acrylate monomer comprises the following steps:

[0013] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, add epichlorohydrin, stir, heat and stir, and separate to obtain a colorless transparent liquid reaction mass;

[0014] A2. In a nitrogen atmosphere, the reaction materials, triethylamine, and tetrahydrofuran were mixed and stirred, acryloyl chloride was added in an ice-water bath, and the mixture was stirred at room temperature. Purification was performed to obtain the bilaterally symmetrical fluorinated acrylate monomer.

[0015] As a further embodiment of the present invention, in step A1, the dosage ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 26-28 g: 5.5-5.8 g: 0.12-0.15 g: 150 mL: 11-13 g.

[0016] As a further embodiment of the present invention, in step A2, the ratio of the reaction material, triethylamine, tetrahydrofuran, and acryloyl chloride is 14-15 g: 3.2-3.5 g: 50 mL: 3-3.2 g.

[0017] As a further embodiment of the present invention, the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin are prepared in a ratio of 6-8 g: 0.8-1.2 g: 50 mL: 3-4 mL: 0.8-1.2 g: 80-100 mL: 2-3 mL.

[0018] As a further embodiment of the present invention, the mass ratio of the bilaterally symmetrical fluorine-based acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate is 5.8-6.2:3-4:2-3:2-3:0.8-1.2:0.6-0.8.

[0019] As a further solution of the present invention, in step S2, the baking refers to baking at 150-180° C. for 3-5 minutes.

[0020] As a further solution of the present invention, in step S2, the pre-baking refers to pre-baking at 75° C. for 1-2 minutes.

[0021] The water-repellent and oil-repellent fabric is prepared by the above preparation method.

[0022] Beneficial effects of the present invention:

[0023] The water- and oil-repellent fabric and the preparation method thereof disclosed in the present invention use short-chain bilaterally symmetrical fluorine-based acrylate monomers to prepare a polyacrylate finishing agent, which has good water- and oil-repellent properties.

[0024] Furthermore, by adding starch-grafted multi-walled carbon nanotubes that are firmly attached to the fabric surface, the hydroxyl groups of amylose are multiple-crosslinked with the hydroxyl groups of polyacrylate and the fabric fiber surface, thereby improving the durability of the fabric's ammonium water oil repellency. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be further described below with reference to the accompanying drawings.

[0026] Figure 1 This is a schematic diagram showing the water-repellent and oil-repellent properties of the water-repellent and oil-repellent fabric prepared in Example 2 of the present invention after finishing. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0028] Example 1

[0029] A water-repellent and oil-repellent fabric and a preparation method thereof, comprising the following steps:

[0030] S1. Take a 20cm×20cm (warp×weft) pure cotton fabric and immerse it in a pretreatment solution for 50 minutes. After taking it out, wash it with 80℃ hot water for 1 minute, 60℃ warm water for 5 minutes, and 20℃ cold water for 10 minutes, and dry it. The pretreatment solution is composed of 10g sodium hydroxide, 8g sodium bicarbonate, and 500mL deionized water.

[0031] S2, take 500mL ethyl acetate, add 40g finishing liquid, stir evenly; the pretreated fabric cloth was immersed in the above material for 25min, two dips and two rolls, the rolling rate was 80%, pre-baked at 75°C for 1min, baked at 150°C for 3min, washed, and dried to obtain the water- and oil-repellent fabric;

[0032] The finishing liquid is composed of a finishing agent and a finishing auxiliary agent in a mass ratio of 32:3.4;

[0033] The preparation method of the finishing agent comprises the following steps:

[0034] Ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water were mixed and stirred for 10 minutes to obtain material A; the mass ratio of ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water was 0.2:0.4:0.7:50;

[0035] A bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate were mixed and stirred for 30 minutes to obtain material B; the mass ratio of the bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate was 5.8:3:2:2:0.8:0.6;

[0036] The material A and the material B were mixed, ultrasonically stirred for 30 minutes, stirred in a nitrogen atmosphere at 70°C water bath for 4 hours, cooled to room temperature, adjusted to pH 7.5 with ammonia water, filtered, and discharged to obtain the finishing agent;

[0037] The preparation method of the bilaterally symmetrical fluorine-based acrylate monomer comprises the following steps:

[0038] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 30 minutes, add epichlorohydrin, stir for 20 minutes, stir at 70°C for 12 hours, wash the mixture with 500 mL of deionized water, let it stand for separation, dehydrate the organic phase with anhydrous sodium sulfate and then filter, remove toluene by vacuum distillation, and separate the reaction mass by column chromatography (petroleum ether:ethyl acetate, volume ratio of 10:1) to obtain a colorless, transparent liquid reaction mass; the ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 26 g:5.5 g:0.12 g:150 mL:11 g;

[0039] A2. In a nitrogen atmosphere, the reaction material, triethylamine, and tetrahydrofuran were mixed and stirred for 10 minutes. Acryloyl chloride was added to an ice-water bath and stirred at room temperature for 10 hours. The tetrahydrofuran was removed by distillation under reduced pressure, 50 mL of dichloromethane was added, and the mixture was washed with a 5% sodium bicarbonate solution to a pH of 8. The mixture was allowed to stand for separation. The organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. The dichloromethane was removed by distillation under reduced pressure to obtain a light yellow liquid, which was purified by column chromatography (petroleum ether:ethyl acetate, volume ratio 8:1) to obtain the bilaterally symmetrical fluorinated acrylate monomer; the ratio of the reaction material, triethylamine, tetrahydrofuran, and acryloyl chloride was 14 g:3.2 g:50 mL:3 g;

[0040] The preparation method of the finishing aid comprises the following steps:

[0041] Multi-walled carbon nanotubes (purchased from Shanghai Yien Chemical Technology Co., Ltd.) and mixed acid were mixed, ultrasonically stirred for 4 hours, potassium permanganate was added, stirring was continued for 2 hours, centrifuged, the solid phase was washed, and dried to obtain modified carbon nanotubes with hydroxyl and carboxyl groups grafted on the surface; the carbon nanotubes, mixed acid, and potassium permanganate were prepared in a ratio of 1.8 g:50 mL:2.8 g; the mixed acid was a mixture of 98% by mass sulfuric acid and 68% by mass nitric acid in a volume ratio of 3:1;

[0042] The modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed, refluxed and stirred at 70°C for 20 hours, thionyl chloride was removed by reduced pressure distillation, and vacuum dried to obtain chlorinated carbon nanotubes; the modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were prepared in a ratio of 0.8 g:30 mL:1 mL;

[0043] The chlorinated carbon nanotubes and N,N-dimethylformamide were mixed, and amylose (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and pyridine were added. The mixture was stirred at 110°C for 20 hours, centrifuged, and the solid phase was washed and dried to obtain starch-grafted carbon nanotubes. The ratio of the chlorinated carbon nanotubes, N,N-dimethylformamide, amylose, and pyridine was 0.4 g:30 mL:0.1 g:1 mL.

[0044] The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, and deionized water are mixed, ultrasonically dispersed for 15 seconds, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin are added, and stirred for 4 minutes to obtain the finishing agent; the dosage ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 6g:0.8g:50mL:3mL:0.8g:80mL:2mL; the mass fraction of the hydrochloric acid solution is 0.5%.

[0045] Example 2

[0046] A water-repellent and oil-repellent fabric and a preparation method thereof, comprising the following steps:

[0047] S1. Take a 20cm×20cm (warp×weft) pure cotton fabric and immerse it in a pretreatment solution for 65 minutes. After taking it out, wash it with 80℃ hot water for 1 minute, 60℃ warm water for 5 minutes, and 20℃ cold water for 10 minutes, and dry it. The pretreatment solution is composed of 10g sodium hydroxide, 8g sodium bicarbonate, and 500mL deionized water.

[0048] S2, take 500mL ethyl acetate, add 40g finishing liquid, stir evenly; the pretreated fabric cloth was immersed in the above material for 30min, double dip and double roll, the rolling rate was 80%, pre-baked at 75 ° C for 1.5min, baked at 165 ° C for 4min, washed, and dried to obtain the water-repellent and oil-repellent fabric; Figure 1 As shown in the figure, the cotton fabric treated with the finishing liquid has good water-repellent and oil-repellent properties.

[0049] The finishing liquid is composed of a finishing agent and a finishing auxiliary agent in a mass ratio of 38:4.3;

[0050] The preparation method of the finishing agent comprises the following steps:

[0051] Ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water were mixed and stirred for 15 minutes to obtain material A; the mass ratio of ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water was 0.25:0.45:0.8:50;

[0052] Mix a bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate, and stir for 35 minutes to obtain material B; the mass ratio of the bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate is 6.0:3.5:2.5:2.5:1.0:0.7;

[0053] The material A and the material B were mixed, ultrasonically stirred for 35 minutes, stirred in a nitrogen atmosphere at 75°C water bath for 5 hours, cooled to room temperature, adjusted to pH 7.5 with ammonia water, filtered, and discharged to obtain the finishing agent;

[0054] The preparation method of the bilaterally symmetrical fluorine-based acrylate monomer comprises the following steps:

[0055] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 35 minutes, add epichlorohydrin, stir for 25 minutes, stir at 73°C for 13 hours, wash the mixture with 500 mL of deionized water, let it stand for separation, dehydrate the organic phase with anhydrous sodium sulfate and then filter, remove toluene by vacuum distillation, and separate the reaction mass by column chromatography (petroleum ether:ethyl acetate, volume ratio of 10:1) to obtain a colorless, transparent liquid reaction mass; the ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 27 g:5.7 g:0.14 g:150 mL:12 g;

[0056] A2. In a nitrogen atmosphere, the reaction material, triethylamine, and tetrahydrofuran were mixed and stirred for 12 minutes. Acryloyl chloride was added to an ice-water bath and stirred at room temperature for 12 hours. The tetrahydrofuran was removed by distillation under reduced pressure, 50 mL of dichloromethane was added, and the mixture was washed with a 5% sodium bicarbonate solution by mass until the pH was 8. The mixture was allowed to stand for separation. The organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. The dichloromethane was removed by distillation under reduced pressure to obtain a light yellow liquid, which was purified by column chromatography (petroleum ether: ethyl acetate volume ratio of 8:1) to obtain the bilaterally symmetrical fluorinated acrylate monomer; the ratio of the reaction material, triethylamine, tetrahydrofuran, and acryloyl chloride was 14.5 g:3.4 g:50 mL:3.1 g;

[0057] The preparation method of the finishing aid comprises the following steps:

[0058] Multi-walled carbon nanotubes and mixed acid were mixed and ultrasonically stirred for 4.5 hours. Potassium permanganate was added and stirred for another 2.5 hours. The mixture was centrifuged, and the solid phase was washed and dried to obtain modified carbon nanotubes with surface grafted hydroxyl and carboxyl groups. The carbon nanotubes, mixed acid, and potassium permanganate were prepared in a ratio of 2.1 g:52 mL:3.0 g. The mixed acid was a mixture of 98% by mass sulfuric acid and 68% by mass nitric acid in a volume ratio of 3:1.

[0059] The modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed, refluxed and stirred at 70° C. for 25 h, thionyl chloride was removed by reduced pressure distillation, and vacuum dried to obtain acyl chloride carbon nanotubes; the modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were prepared in a ratio of 0.9 g:30 mL:1 mL;

[0060] The chlorinated carbon nanotubes and N,N-dimethylformamide were mixed, and amylose and pyridine were added. The mixture was stirred at 110° C. for 25 h, centrifuged, and the solid phase was washed and dried to obtain starch-grafted carbon nanotubes. The ratio of the chlorinated carbon nanotubes, N,N-dimethylformamide, amylose, and pyridine was 0.45 g:35 mL:0.15 g:1.1 mL.

[0061] The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, and deionized water are mixed, ultrasonically dispersed for 20 seconds, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin are added, and stirred for 4.5 minutes to obtain the finishing agent; the dosage ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 7g:1.0g:50mL:3.5mL:1.0g:90mL:2.5mL; the mass fraction of the hydrochloric acid solution is 0.5%.

[0062] Example 3

[0063] A water-repellent and oil-repellent fabric and a preparation method thereof, comprising the following steps:

[0064] S1. Take a 20cm×20cm (warp×weft) pure cotton fabric and immerse it in a pretreatment solution for 80 minutes. After taking it out, wash it with 80℃ hot water for 1 minute, 60℃ warm water for 5 minutes, and 20℃ cold water for 10 minutes, and dry it. The pretreatment solution is composed of 10g sodium hydroxide, 8g sodium bicarbonate, and 500mL deionized water.

[0065] S2, take 500mL ethyl acetate, add 40g finishing liquid, stir evenly; the pretreated fabric cloth was immersed in the above material for 35min, two dips and two rolls, the rolling rate was 80%, pre-baked at 75°C for 2min, baked at 180°C for 5min, washed, and dried to obtain the water- and oil-repellent fabric;

[0066] The finishing liquid is composed of a finishing agent and a finishing auxiliary agent in a mass ratio of 44:5.2;

[0067] The preparation method of the finishing agent comprises the following steps:

[0068] Ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water were mixed and stirred for 20 minutes to obtain material A; the mass ratio of ammonium persulfate, sodium lauryl sulfate, emulsifier OP-10, and deionized water was 0.3:0.5:0.9:50;

[0069] Mix a bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate, and stir for 40 minutes to obtain material B; the mass ratio of the bilaterally symmetrical fluorinated acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate is 6.2:4:3:3:1.2:0.8;

[0070] The material A and the material B were mixed, ultrasonically stirred for 40 minutes, stirred in a nitrogen atmosphere at 80°C water bath for 6 hours, cooled to room temperature, adjusted to pH 7.5 with ammonia water, filtered, and discharged to obtain the finishing agent;

[0071] The preparation method of the bilaterally symmetrical fluorine-based acrylate monomer comprises the following steps:

[0072] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 40 minutes, add epichlorohydrin, stir for 30 minutes, stir at 75°C for 14 hours, wash the mixture with 500 mL of deionized water, let it stand for separation, dehydrate the organic phase with anhydrous sodium sulfate and then filter, remove toluene by vacuum distillation, and separate the reaction mass by column chromatography (petroleum ether:ethyl acetate, volume ratio of 10:1) to obtain a colorless, transparent liquid reaction mass; the ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 28 g:5.8 g:0.15 g:150 mL:13 g;

[0073] A2. In a nitrogen atmosphere, the reaction material, triethylamine, and tetrahydrofuran were mixed and stirred for 15 minutes. Acryloyl chloride was added to an ice-water bath and stirred at room temperature for 15 hours. The tetrahydrofuran was removed by distillation under reduced pressure, 50 mL of dichloromethane was added, and the mixture was washed with a 5% sodium bicarbonate solution to a pH of 8. The mixture was allowed to stand for separation. The organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. The dichloromethane was removed by distillation under reduced pressure to obtain a light yellow liquid, which was purified by column chromatography (petroleum ether: ethyl acetate, volume ratio 8:1) to obtain the bilaterally symmetrical fluorinated acrylate monomer; the ratio of the reaction material, triethylamine, tetrahydrofuran, and acryloyl chloride was 15 g:3.5 g:50 mL:3.2 g;

[0074] The preparation method of the finishing aid comprises the following steps:

[0075] Multi-walled carbon nanotubes and mixed acid are mixed and ultrasonically stirred for 4-5 hours. Potassium permanganate is added and stirred for 3 hours. The mixture is centrifuged, and the solid phase is washed and dried to obtain modified carbon nanotubes with surface grafted hydroxyl and carboxyl groups. The carbon nanotubes, mixed acid, and potassium permanganate are prepared in a ratio of 2.4 g:55 mL:3.2 g. The mixed acid is a mixture of 98% by mass sulfuric acid and 68% by mass nitric acid in a volume ratio of 3:1.

[0076] The modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed, refluxed and stirred at 70°C for 30 hours, thionyl chloride was removed by reduced pressure distillation, and vacuum dried to obtain acyl chloride carbon nanotubes; the modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were prepared in a ratio of 1 g: 30 mL: 1 mL;

[0077] The chlorinated carbon nanotubes and N,N-dimethylformamide were mixed, and amylose and pyridine were added. The mixture was stirred at 110° C. for 30 h, centrifuged, and the solid phase was washed and dried to obtain starch-grafted carbon nanotubes. The ratio of the chlorinated carbon nanotubes, N,N-dimethylformamide, amylose, and pyridine was 0.5 g:40 mL:0.2 g:1.2 mL.

[0078] The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, and deionized water are mixed, ultrasonically dispersed for 25 seconds, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin are added, and stirred for 5 minutes to obtain the finishing agent; the dosage ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 8g:1.2g:50mL:4mL:1.2g:100mL:3mL; the mass fraction of the hydrochloric acid solution is 0.5%.

[0079] Comparative Example 1

[0080] The difference from Example 2 is that the fluorine-containing acrylate monomer is selected differently. The fluorine-containing acrylate monomer in Comparative Example 1 is tridecafluorooctyl acrylate.

[0081] Comparative Example 2

[0082] The difference from Example 2 is that the fluorine-containing acrylate monomer is selected differently. The fluorine-containing acrylate monomer in Comparative Example 2 is 2-(perfluorobutyl)ethyl acrylate.

[0083] Comparative Example 3

[0084] The difference from Example 2 is that no finishing aid is added to the finishing liquid.

[0085] Comparative Example 4

[0086] The difference from Example 2 is that the preparation method of the finishing auxiliary agent includes the following steps:

[0087] Multi-walled carbon nanotubes and mixed acid are mixed, ultrasonically stirred for 4.5 hours, potassium permanganate is added, stirring is continued for 2.5 hours, centrifuged, the solid phase is washed, and dried to obtain modified carbon nanotubes with surface grafted hydroxyl and carboxyl groups; the carbon nanotubes, mixed acid, and potassium permanganate are prepared in a ratio of 2.1 g:52 mL:3.0 g; the mixed acid is a mixture of 98% by mass sulfuric acid and 68% by mass nitric acid in a volume ratio of 3:1.

[0088] Comparative Example 5

[0089] The difference from Example 2 is that during the preparation of the finishing agent:

[0090] The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, and deionized water are mixed, ultrasonically dispersed for 20 seconds, glycerol, hydrochloric acid solution, and epichlorohydrin are added, and stirred for 4.5 minutes to obtain the finishing agent; the dosage ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 7g:1.0g:50mL:3.5mL:90mL:2.5mL; the mass fraction of the hydrochloric acid solution is 0.5%.

[0091] Comparative Example 6

[0092] The difference from Example 2 is that during the preparation of the finishing agent:

[0093] The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, and deionized water are mixed, ultrasonically dispersed for 20 seconds, glycerol, calcium chloride, and hydrochloric acid solution are added, and stirred for 4.5 minutes to obtain the finishing agent; the dosage ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 7g:1.0g:50mL:3.5mL:1.0g:90mL; the mass fraction of the hydrochloric acid solution is 0.5%.

[0094] Performance Testing

[0095] The cotton fabrics prepared in Examples 1-3 and Comparative Examples 1-6 after being treated by the finishing process were tested for water-repellency and oil-repellency. The test results are shown in Table 1 below.

[0096] Table 1

[0097]

[0098]

[0099] As can be seen from Table 1, Examples 1-3 of the present application have good water and oil repellency, wherein the water and oil repellency of the fabric after finishing with the finishing liquid made by adding more raw materials in Example 3 is slightly lower than that of Examples 1-2, but it still has lasting water and oil repellency after multiple washings; in Comparative Example 1, a polyacrylate is prepared by using a unilateral fluorine-containing short chain and a finishing aid, and its water and oil repellency is slightly lower than that of Example 2, but it still exhibits lasting water and oil repellency; in Comparative Example 2, a perfluorinated monomer is used to prepare polyacrylate, which proves that the polyacrylate obtained by polymerization of the bilaterally symmetrical fluorine-based acrylate monomer prepared in this application has good water and oil repellency, and is more environmentally friendly than the perfluorinated monomer; no finishing aid is added in Comparative Example 3, resulting in a significant decrease in water and oil repellency; although multi-walled carbon nanotubes are added in Comparative Example 4 to increase the surface roughness of the fabric, its chrysanthemum water oil repellency and durability are decreased compared to Example 2; in Comparative Examples 5-6, only a single cross-linked cross-linking agent is added, resulting in a decrease in the durability of its chrysanthemum water oil repellency.

[0100] The above describes some embodiments of the present invention in detail, but the contents described are only preferred embodiments of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing a water-repellent and oil-repellent fabric, characterized in that: The preparation method of the water- and oil-repellent fabric comprises the following steps: S1. Take the fabric and immerse it in the pretreatment solution. After taking it out, wash it with hot water, warm water, and cold water in sequence, and dry it; S2, dipping the pretreated fabric in a finishing solution, dipping and tying twice, pre-drying, baking, washing, and drying to obtain the water- and oil-repellent fabric; The finishing liquid comprises: The finishing agent is mainly a short-chain fluorine-based acrylate polymer prepared from bilaterally symmetrical fluorine-based acrylate monomers, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate; The finishing auxiliary agent comprises a mixed solution of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution and epichlorohydrin.

2. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: The mass ratio of the finishing agent to the finishing auxiliary agent is 32-44:3.4-5.

2.

3. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: The preparation method of the bilaterally symmetrical fluorine-based acrylate monomer comprises the following steps: A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, add epichlorohydrin, stir, heat and stir, and separate to obtain a colorless transparent liquid reaction mass; A2. In a nitrogen atmosphere, the reaction materials, triethylamine, and tetrahydrofuran were mixed and stirred, acryloyl chloride was added in an ice-water bath, and the mixture was stirred at room temperature. Purification was performed to obtain the bilaterally symmetrical fluorinated acrylate monomer.

4. The method for preparing a water- and oil-repellent fabric according to claim 3, wherein: In step A1, the dosage ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 26-28 g: 5.5-5.8 g: 0.12-0.15 g: 150 mL: 11-13 g.

5. The method for preparing a water-repellent and oil-repellent fabric according to claim 3, wherein: In step A2, the ratio of the reaction material, triethylamine, tetrahydrofuran, and acryloyl chloride is 14-15 g: 3.2-3.5 g: 50 mL: 3-3.2 g.

6. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: The starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin have a dosage ratio of 6-8 g: 0.8-1.2 g: 50 mL: 3-4 mL: 0.8-1.2 g: 80-100 mL: 2-3 mL.

7. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: The mass ratio of the bilaterally symmetrical fluorine-based acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate is 5.8-6.2:3-4:2-3:2-3:0.8-1.2:0.6-0.

8.

8. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: In step S2, the baking refers to baking at 150-180° C. for 3-5 minutes.

9. The method for preparing a water- and oil-repellent fabric according to claim 1, wherein: In step S2, the pre-baking refers to pre-baking at 75° C. for 1-2 minutes.

10. A water-repellent and oil-repellent fabric produced by the preparation method according to any one of claims 1 to 9.

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