Water and oil repellent fabric and method for making the same

Abstract

The application 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 grey cloth for immersion pretreatment, washing with hot water, washing with warm water, washing with cold water, and airing; immersing the pretreated fabric grey cloth in a finishing liquid, twice immersion and twice pressing, pre-drying, baking, washing, and drying, so that the water-repellent and oil-repellent fabric is obtained; the finishing liquid comprises: a finishing agent, which is mainly prepared from a short-chain fluorine-containing acrylate polymer with raw materials of a double-side symmetrical fluorine-containing acrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate and 5-hydroxyamyl acrylate; and a finishing auxiliary agent, which comprises a starch grafted carbon nanotube, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, a hydrochloric acid solution and a mixed solution of epichlorohydrin; the surface of the fabric is treated by preparing the finishing liquid, so that the water-repellent and oil-repellent effect of the fabric is enhanced.

Description

Technical Field

[0001] This invention relates to the field of fabric finishing technology, specifically to a water-repellent and oil-repellent fabric and its preparation method. Background Technology

[0002] In today's era, the demand for functional textiles has far surpassed the traditional pursuit of basic properties such as softness, comfort, moisture absorption, and breathability. Consumers and industries are now paying more attention to advanced functions such as antibacterial and hygienic properties, water, oil, and stain resistance, wrinkle-free and non-iron effects, radiation and UV protection, flame retardancy, and medical protective properties. With the continuous research and application of new fiber materials and the ongoing innovation of new processes and technologies, these diverse needs are gradually being realized and met. Functional finishing technology, as a key technology in textile processing, is being strongly driven by the growing demand for high technology and high added value. In particular, three-proof finishing technology, namely water-repellent, oil-repellent, and stain-resistant finishing technology, has become an important development direction in the field of textile finishing. Three-proof finishing agents are a class of textile finishing agents specifically used for fabrics such as cotton, wool, silk, chemical fibers, and blended fibers. They alter the surface properties of the fabric, giving it strong water and oil repellency, thereby effectively preventing water and common oil stains from wetting or staining it. While water- and oil-repellent fiber products currently on the market have high water and oil repellency in the initial stage, their water and oil repellency often decreases after repeated washing and rubbing. This is a technical problem that urgently needs to be solved in the field of functional textiles. Summary of the Invention

[0003] The purpose of this invention is to provide a water-repellent and oil-repellent fabric and its preparation method, which solves the problem that the water-repellent and oil-repellent properties of fabrics in the prior art are poor in durability and that the water-repellent and oil-repellent properties of fabrics are easily reduced after washing and rubbing.

[0004] The objective of this invention can be achieved through the following technical solutions:

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

[0006] S1. Immerse the fabric in the pretreatment solution, take it out and wash it in hot water, warm water and cold water in sequence, and then dry it.

[0007] S2. The pretreated fabric is immersed in the finishing solution, dipped and tied twice, pre-dried, baked, washed and dried to obtain the water-repellent and oil-repellent fabric.

[0008] The finishing solution includes:

[0009] Finishing agent, mainly made from short-chain fluoroacrylate polymers of bilaterally symmetrical fluoroacrylate monomers, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate.

[0010] Finishing aids include a mixture of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin.

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

[0012] As a further aspect of the present invention, the method for preparing the bilaterally symmetrical fluoroacrylate monomer includes 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 and transparent liquid reaction material.

[0014] A2. Under a nitrogen atmosphere, the reactants, triethylamine, and tetrahydrofuran are mixed and stirred. Acryloyl chloride is added in an ice-water bath and stirred at room temperature to purify and obtain the bilaterally symmetrical fluoroacrylate monomer.

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

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

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

[0018] As a further embodiment of the present invention, the mass ratio of the bilaterally symmetrical fluoroacrylate 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 aspect of the present invention, in step S2, the baking refers to baking at 150-180℃ for 3-5 minutes.

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

[0021] Water-repellent and oil-repellent fabrics were prepared using the above-described method.

[0022] The beneficial effects of this invention are:

[0023] The present invention discloses a water- and oil-repellent fabric and its preparation method, which prepares a polyacrylate finishing agent by using short-chain, bilaterally symmetrical fluoroacrylate monomers, and has good water- and oil-repellent properties.

[0024] Furthermore, by adding starch-grafted multi-walled carbon nanotubes that firmly adhere to the fabric surface, multiple cross-linking occurs between the hydroxyl groups of the linear starch and the polyacrylate and the hydroxyl groups on the fabric fiber surface, thereby improving the durability of the fabric's chrysanthemum water-repellent properties. Attached Figure Description

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

[0026] Figure 1 This is a schematic diagram showing the water and oil repellency performance of the water-repellent and oil-repellent fabric obtained in Embodiment 2 of the present invention after finishing. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1

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

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

[0031] S2. Take 500 mL of ethyl acetate, add 40 g of finishing solution, and stir evenly; immerse the pretreated fabric in the above material for 25 min, dip and roll twice, with a roll-off rate of 80%, pre-dry at 75℃ for 1 min, bake at 150℃ for 3 min, wash, and dry to obtain the water-repellent and oil-repellent fabric.

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

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

[0034] Ammonium persulfate, sodium dodecyl 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 dodecyl sulfate, emulsifier OP-10, and deionized water was 0.2:0.4:0.7:50.

[0035] Mix the bilaterally symmetrical fluoroacrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate, and stir for 30 min to obtain material B; the mass ratio of the bilaterally symmetrical fluoroacrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate is 5.8:3:2:2:0.8:0.6.

[0036] Mix materials A and B, ultrasonically stir for 30 minutes, stir in a nitrogen atmosphere and a 70°C water bath for 4 hours, cool to room temperature, adjust the pH to 7.5 with ammonia, filter, and discharge to obtain the finishing agent.

[0037] The preparation method of the bilaterally symmetrical fluoroacrylate monomer includes the following steps:

[0038] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 30 min, add epichlorohydrin, stir for 20 min, stir at 70℃ for 12 h, wash the mixture with 500 mL of deionized water, allow to stand and separate, remove water from the organic phase with anhydrous sodium sulfate, filter, remove toluene by vacuum distillation, and separate by column chromatography TLC (petroleum ether and ethyl acetate volume ratio 10:1) to obtain a colorless and transparent liquid reactant; the molar 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. Under a nitrogen atmosphere, the reactants, triethylamine, and tetrahydrofuran were mixed and stirred for 10 min. Acryloyl chloride was added in an ice-water bath, and the mixture was stirred at room temperature for 10 h. Tetrahydrofuran was removed by vacuum distillation. 50 mL of dichloromethane was added, and the mixture was washed with 5% sodium bicarbonate solution until the pH reached 8. After standing and separating the liquids, the organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. Dichloromethane was removed by vacuum distillation to obtain a pale yellow liquid. The bilateral fluoroacrylate monomer was purified by column chromatography (petroleum ether: ethyl acetate volume ratio 8:1). The mass ratio of the reactants, triethylamine, tetrahydrofuran, and acryloyl chloride was 14 g: 3.2 g: 50 mL: 3 g.

[0040] The preparation method of the finishing agent includes the following steps:

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

[0042] The modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed and refluxed at 70°C for 20 h. The thionyl chloride was removed by vacuum distillation and then dried under vacuum to obtain acyl chloride carbon nanotubes. The ratio of the modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide was 0.8 g: 30 mL: 1 mL.

[0043] The acyl chloride carbon nanotubes and N,N-dimethylformamide were mixed, and then amyl starch (purchased from Shanghai Maclean Biochemical Technology Co., Ltd.) and pyridine were added. The mixture was stirred at 110℃ for 20 h, centrifuged, and the solid phase was washed and dried to obtain starch-grafted carbon nanotubes. The ratio of acyl chloride carbon nanotubes, N,N-dimethylformamide, amyl starch and pyridine was 0.4 g: 30 mL: 0.1 g: 1 mL.

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

[0045] Example 2

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

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

[0048] S2. Take 500 mL of ethyl acetate, add 40 g of finishing solution, and stir evenly; immerse the pretreated fabric in the above material for 30 min, repeat the two-dip, two-roll process, with a pick-up rate of 80%, pre-dry at 75℃ for 1.5 min, bake at 165℃ for 4 min, wash, and dry to obtain the water-repellent and oil-repellent fabric; Figure 1 As shown, cotton fabrics treated with finishing solution have good water and oil repellency properties.

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

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

[0051] Ammonium persulfate, sodium dodecyl 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 dodecyl sulfate, emulsifier OP-10, and deionized water was 0.25:0.45:0.8:50.

[0052] Mix the bilaterally symmetrical fluoroacrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate, and stir for 35 min to obtain material B; the mass ratio of the bilaterally symmetrical fluoroacrylate 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] Mix materials A and B, ultrasonically stir for 35 minutes, stir in a nitrogen atmosphere and a 75°C water bath for 5 hours, cool to room temperature, adjust the pH to 7.5 with ammonia, filter, and discharge to obtain the finishing agent.

[0054] The preparation method of the bilaterally symmetrical fluoroacrylate monomer includes the following steps:

[0055] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 35 min, add epichlorohydrin, stir for 25 min, stir at 73℃ for 13 h, wash the mixture with 500 mL of deionized water, allow to stand and separate, remove water from the organic phase with anhydrous sodium sulfate, filter, remove toluene by vacuum distillation, and separate by column chromatography (TLC) (petroleum ether and ethyl acetate volume ratio 10:1) to obtain a colorless and transparent liquid reactant; 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. Under a nitrogen atmosphere, the reactants, triethylamine, and tetrahydrofuran were mixed and stirred for 12 min. Acryloyl chloride was added in an ice-water bath, and the mixture was stirred at room temperature for 12 h. Tetrahydrofuran was removed by vacuum distillation. 50 mL of dichloromethane was added, and the mixture was washed with 5% sodium bicarbonate solution until the pH reached 8. After standing and separation, the organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. Dichloromethane was removed by vacuum distillation to obtain a pale yellow liquid. The bilateral fluoroacrylate monomer was purified by column chromatography (petroleum ether: ethyl acetate volume ratio 8:1). The molar ratio of the reactants, triethylamine, tetrahydrofuran, and acryloyl chloride was 14.5 g: 3.4 g: 50 mL: 3.1 g.

[0057] The preparation method of the finishing agent includes the following steps:

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

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

[0060] The acyl chloride carbon nanotubes and N,N-dimethylformamide were mixed, and then amyl starch 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 acyl chloride carbon nanotubes, N,N-dimethylformamide, amyl starch 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 were mixed and ultrasonically dispersed for 20 seconds. Glycerin, calcium chloride, hydrochloric acid solution, and epichlorohydrin were then added and stirred for 4.5 minutes to obtain the finishing agent. The ratio of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerin, calcium chloride, hydrochloric acid solution, and epichlorohydrin was 7g:1.0g:50mL:3.5mL:1.0g:90mL:2.5mL. The mass fraction of the hydrochloric acid solution was 0.5%.

[0062] Example 3

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

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

[0065] S2. Take 500 mL of ethyl acetate, add 40 g of finishing solution, and stir evenly; immerse the pretreated fabric in the above material for 35 min, dip and roll twice, with a roll-off rate of 80%, pre-dry at 75℃ for 2 min, bake at 180℃ for 5 min, wash, and dry to obtain the water-repellent and oil-repellent fabric.

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

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

[0068] Ammonium persulfate, sodium dodecyl 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 dodecyl sulfate, emulsifier OP-10, and deionized water was 0.3:0.5:0.9:50.

[0069] Mix the bilaterally symmetrical fluoroacrylate monomer, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate, and stir for 40 min to obtain material B; the mass ratio of the bilaterally symmetrical fluoroacrylate 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] Mix materials A and B, ultrasonically stir for 40 minutes, stir in a nitrogen atmosphere and 80°C water bath for 6 hours, cool to room temperature, adjust the pH to 7.5 with ammonia, filter, and discharge to obtain the finishing agent.

[0071] The preparation method of the bilaterally symmetrical fluoroacrylate monomer includes the following steps:

[0072] A1. Mix 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, and toluene, stir for 40 min, add epichlorohydrin, stir for 30 min, stir at 75℃ for 14 h, wash the mixture with 500 mL of deionized water, allow to stand and separate, remove water from the organic phase with anhydrous sodium sulfate, filter, remove toluene by vacuum distillation, and separate by column chromatography TLC (petroleum ether and ethyl acetate volume ratio 10:1) to obtain a colorless and transparent liquid reactant; 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. Under a nitrogen atmosphere, the reactants, triethylamine, and tetrahydrofuran were mixed and stirred for 15 min. Acryloyl chloride was added in an ice-water bath, and the mixture was stirred at room temperature for 15 h. Tetrahydrofuran was removed by vacuum distillation. 50 mL of dichloromethane was added, and the mixture was washed with 5% sodium bicarbonate solution until the pH reached 8. After standing and separating the liquids, the organic phase was first dehydrated with anhydrous sodium sulfate and then filtered. Dichloromethane was removed by vacuum distillation to obtain a pale yellow liquid. The bilateral fluoroacrylate monomer was purified by column chromatography (petroleum ether and ethyl acetate in a volume ratio of 8:1). The ratio of reactants, triethylamine, tetrahydrofuran, and acryloyl chloride was 15 g: 3.5 g: 50 mL: 3.2 g.

[0074] The preparation method of the finishing agent includes the following steps:

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

[0076] The modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide were mixed and refluxed at 70°C for 30 h. The thionyl chloride was removed by vacuum distillation and then dried under vacuum to obtain acyl chloride carbon nanotubes. The ratio of the modified carbon nanotubes, thionyl chloride, and N,N-dimethylformamide was 1 g: 30 mL: 1 mL.

[0077] The acyl chloride carbon nanotubes and N,N-dimethylformamide were mixed, and then amyl starch 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 acyl chloride carbon nanotubes, N,N-dimethylformamide, amyl starch 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 were mixed and ultrasonically dispersed for 25 seconds. Glycerin, calcium chloride, hydrochloric acid solution, and epichlorohydrin were then added and stirred for 5 minutes to obtain the finishing agent. The ratio of the starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerin, calcium chloride, hydrochloric acid solution, and epichlorohydrin was 8 g: 1.2 g: 50 mL: 4 mL: 1.2 g: 100 mL: 3 mL. The mass fraction of the hydrochloric acid solution was 0.5%.

[0079] Comparative Example 1

[0080] The difference from Example 2 is that the fluorinated acrylate monomer is different; in Comparative Example 1, the fluorinated acrylate monomer is tridecafluorooctyl acrylate.

[0081] Comparative Example 2

[0082] The difference from Example 2 is that the fluorinated acrylate monomer is different; the fluorinated 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 agent is added to the finishing solution.

[0085] Comparative Example 4

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

[0087] Multi-walled carbon nanotubes and mixed acid were mixed and ultrasonically stirred for 4.5 h. Potassium permanganate was added and stirring was continued for 2.5 h. After centrifugation, the solid phase was washed and dried to obtain modified carbon nanotubes with hydroxyl and carboxyl groups grafted onto the surface. The ratio of carbon nanotubes, mixed acid, and potassium permanganate was 2.1 g: 52 mL: 3.0 g. The mixed acid was a mixture of 98% sulfuric acid and 68% nitric acid at a volume ratio of 3:1.

[0088] Comparative Example 5

[0089] The difference from Example 2 lies in the preparation process of the finishing agent:

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

[0091] Comparative Example 6

[0092] The difference from Example 2 lies in the preparation process of the finishing agent:

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

[0094] Performance testing

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

[0096] Table 1

[0097]

[0098]

[0099] As shown in Table 1, Examples 1-3 of this application exhibit good water and oil repellency. In Example 3, the water and oil repellency of the fabric treated with a finishing solution containing more raw materials is slightly lower than that of Examples 1-2, but it still maintains durable water and oil repellency after multiple washes. In Comparative Example 1, a polyacrylate prepared using a single-sided fluorinated short chain combined with a finishing agent exhibits slightly lower water and oil repellency than that of Example 2, but still demonstrates durable water and oil repellency. In Comparative Example 2, a polyacrylate prepared using a perfluorinated monomer demonstrates that the polyacrylate obtained by polymerizing the double-sided symmetrical fluorinated acrylate monomer prepared in this application has good water and oil repellency and is more environmentally friendly than perfluorinated monomers. In Comparative Example 3, no finishing agent was added, resulting in a significant decrease in water and oil repellency. In Comparative Example 4, although multi-walled carbon nanotubes were added to increase the surface roughness of the fabric, its water and oil repellency and durability decreased compared to Example 2. In Comparative Examples 5-6, only a single crosslinking agent was added, leading to a decrease in the durability of its water and oil repellency.

[0100] The foregoing has described some embodiments of the present invention in detail, but the content described is only a preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A method for preparing a water-repellent and oil-repellent fabric, characterized in that, The method for preparing the water-repellent and oil-repellent fabric includes the following steps: S1. Immerse the fabric in the pretreatment solution, take it out and wash it in hot water, warm water and cold water in sequence, and then dry it. S2. The pretreated fabric is immersed in the finishing solution, dipped and tied twice, pre-dried, baked, washed and dried to obtain the water-repellent and oil-repellent fabric. The finishing solution includes: Finishing agent, mainly made from short-chain fluoroacrylate polymers of bilaterally symmetrical fluoroacrylate monomers, octadecyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and 5-hydroxypentyl acrylate. Finishing aids include a mixture of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin; The mass ratio of the finishing agent to the finishing aid is 32-44:3.4-5.2; The ratio of starch-grafted carbon nanotubes, tetrabutylammonium hydroxide, deionized water, glycerol, calcium chloride, hydrochloric acid solution, and epichlorohydrin is 6-8g: 0.8-1.2g: 50mL: 3-4mL: 0.8-1.2g: 80-100mL: 2-3mL; The mass ratio of the bilaterally symmetrical fluoroacrylate 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.

2. The method for preparing a water-repellent and oil-repellent fabric according to claim 1, characterized in that, The preparation method of the bilaterally symmetrical fluoroacrylate monomer includes 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 and transparent liquid reaction material. A2. Under a nitrogen atmosphere, the reactants, triethylamine, and tetrahydrofuran are mixed and stirred. Acryloyl chloride is added in an ice-water bath and stirred at room temperature to purify and obtain the bilaterally symmetrical fluoroacrylate monomer.

3. The method for preparing a water-repellent and oil-repellent fabric according to claim 2, characterized in that, In step A1, the ratio of 1H,1H,5H-octafluoropentane-1-ol, sodium hydroxide, tetrabutylammonium bromide, toluene, and epichlorohydrin is 26-28g: 5.5-5.8g: 0.12-0.15g: 150mL: 11-13g.

4. The method for preparing a water-repellent and oil-repellent fabric according to claim 2, characterized in that, In step A2, the ratio of the reactants, triethylamine, tetrahydrofuran, and acryloyl chloride is 14-15g: 3.2-3.5g: 50mL: 3-3.2g.

5. The method for preparing a water-repellent and oil-repellent fabric according to claim 1, characterized in that, In step S2, baking refers to baking at 150-180℃ for 3-5 minutes.

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

7. A water-repellent and oil-repellent fabric prepared by the preparation method according to any one of claims 1-6.

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