Preparation method of waterproof antifouling wall cloth

Abstract

The invention discloses a preparation method of waterproof antifouling wall cloth, and relates to the field of fiber fabrics. When the waterproof and antifouling wall cloth is prepared, tetramethylcyclotetrasiloxane and dihydroxyl silicone oil react to prepare modified silicone oil; the preparation method comprises the following steps: reacting hydrotalcite with gamma-aminopropyltriethoxysilane, and then reacting with 3-thiophenecarbonyl chloride, thiophene and 3-vinyl thiophene to prepare modified hydrotalcite; uniformly mixing the modified hydrotalcite, perfluorohexyl ethylene, chloroplatinic acid, methyl iodide and deionized water to prepare an after-finishing solution; 1, 3-propylene glycol, N-propyl diethanol amine, dimethyl terephthalate, the modified silicone oil and tetrabutyl titanate are subjected to a reaction, and modified polyester is prepared; the modified polyester is subjected to melt spinning to be woven into fabric, and then the fabric is subjected to padding treatment through the after-finishing liquid to prepare the waterproof and antifouling wall cloth. The prepared waterproof and antifouling wall cloth has good waterproof and antifouling performance, flame retardant performance, antibacterial performance, antistatic performance and wear-resisting performance.

Description

Technical Field

[0001] The invention relates to the field of fiber fabrics, and in particular to a method for preparing a waterproof and anti-fouling wall cloth. Background Art

[0002] Wall cloth, also known as "wall cloth", is a fabric used for wall papering. Cotton cloth is often used as the base cloth, and printed or embossed on the base cloth. There are also large jacquard weaves, and the patterns used are mostly geometric and floral patterns. As one of the three major synthetic fibers in the world, polyester fiber is mainly composed of polyethylene terephthalate. There are benzene rings on the long chain of macromolecules, and the benzene rings and the carbonyl plane are almost parallel to the fiber axis, which makes the polyester fiber have high geometric regularity, strong intermolecular forces, and weak reactivity. Therefore, it has excellent physical and chemical properties, such as resistance to organic solvents and oxidants, high breaking strength, high elastic modulus, and good optical resistance. At the same time, its synthetic processing technology is simple and the price is relatively cheap. Polyester fiber fabrics are strong and durable, easy to wash and dry quickly, and are widely used in various fields of production and life.

[0003] Polyester itself has a certain degree of hydrophobicity, fiber molecules are bonded by covalent bonds, and there are few polar groups, which are not easy to ionize, and electrons are not easy to transfer, resulting in charge accumulation and static electricity, so it is easy to be contaminated. The waterproof and antifouling wall cloth prepared by the present invention has good waterproof and antifouling properties, flame retardant properties, antibacterial properties, antistatic properties and wear resistance, and has broad market prospects. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a waterproof and anti-fouling wall cloth to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A waterproof and antifouling wall cloth is prepared by reacting tetramethylcyclotetrasiloxane and dihydroxy silicone oil to obtain modified silicone oil; reacting hydrotalcite and γ-aminopropyltriethoxysilane and then reacting with 3-thiophenecarbonyl chloride, thiophene and 3-vinylthiophene to obtain modified hydrotalcite; mixing the modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water to obtain a finishing liquid; reacting 1,3-propylene glycol, N-propyldiethanolamine, dimethyl terephthalate, modified silicone oil and tetrabutyl titanate to obtain modified polyester; melt-spinning the modified polyester into fabric, and then padding the fabric with the finishing liquid to obtain the waterproof and antifouling wall cloth.

[0007] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0008] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide are mixed, nitrogen is passed for 10 to 20 minutes, stirred at 80 to 90° C. and 100 to 200 r / min for 2 to 3 hours, the temperature is raised to 130 to 140° C. and stirring is continued for 40 to 50 minutes, and distilled under vacuum for 1 to 2 hours to obtain modified silicone oil;

[0009] (2) Mix magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea, add deionized water 25 to 30 times the mass of magnesium nitrate hexahydrate, react at 105 to 115° C. in a sealed environment for 20 to 24 hours, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol to remove carbon dioxide for 3 to 5 times, and dry at 80 to 90° C. for 4 to 6 hours to obtain hydrotalcite; mix hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane in a mass ratio of 1: (0.4 to 0.6): (40 to 60), react at 65 to 75° C. for 5 to 7 hours, cool to room temperature, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol for 3 to 5 times, and dry at 80 to 90° C. for 4 to 6 hours to obtain pretreated hydrotalcite;

[0010] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride and N,N-dimethylformamide were mixed and reacted at room temperature at 300-400 r / min for 2-3 hours. Thiophene (0.04-0.06 times the mass of the pretreated hydrotalcite), 3-vinylthiophene (0.04-0.06 times the mass of the pretreated hydrotalcite) and anhydrous ferric chloride (0.3-0.5 times the mass of the pretreated hydrotalcite) were added under a nitrogen atmosphere, and the mixture was reacted at 0°C for 2-4 hours. The mixture was then reacted at room temperature for 2-3 days. Methanol (0.8-1.2 times the mass of N,N-dimethylformamide) was added, and the mixture was allowed to stand for 1-2 hours. The precipitate was separated by centrifugation, washed with methanol for 3-5 times, and vacuum dried at 50-60°C for 4-6 hours to obtain modified hydrotalcite.

[0011] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate are mixed in a molar ratio of 1:(1-2):1 and added to a reaction kettle. The mixture is heated to 160-170° C. under a nitrogen atmosphere. After dimethyl terephthalate is completely melted, 0.1-0.2 times the mass of dimethyl terephthalate of tetrabutyl titanate is added. The mixture is stirred at a speed of 70-90 r / min for 1-2 h under normal pressure. Then, 0.2-0.4 times the mass of dimethyl terephthalate of polyethylene glycol and 0.05-0.1 times the mass of dimethyl terephthalate of polyethylene glycol are added. 5 times of tetrabutyl titanate, heating to 210-230°C and stirring for 20-40 minutes to obtain prepolyester; mixing prepolyester, modified silicone oil and tetrabutyl titanate in a mass ratio of 1: (0.2-0.3): (0.08-0.12), heating to 215-225°C, stirring at normal pressure for 25-35 minutes under a nitrogen atmosphere, adding antimony oxide 0.001-0.002 times of the mass of the prepolyester, heating to 225-235°C, evacuating, reacting until the climbing pole effect appears and stopping the reaction, and discharging the material to obtain modified polyester;

[0012] (5) The polyester material is dried at 105-115° C. for 10-14 hours, melt-spun, and then woven to obtain fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water are mixed to obtain a finishing solution, the fabric is immersed in the finishing solution, placed at 80-90° C. for 1-2 hours, taken out and then padded, placed at 80-90° C. for 4-6 hours, washed with deionized water for 3-5 times, and dried to obtain a waterproof and anti-fouling wall cloth.

[0013] As an optimization, the mass ratio of tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide siliconate in step (1) is 1: (1.1-1.3): (0.01-0.03).

[0014] As an optimization, the molar ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and urea in step (2) is 2:1:10.

[0015] As an optimization, the mass ratio of the pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide in step (3) is 1: (0.1-0.2): (20-30).

[0016] As an optimization, the molar ratio of 1,3-propylene glycol, N-propyldiethanolamine and dimethyl terephthalate in step (4) is 1:(1-2):1.

[0017] As an optimization, the mass ratio of the modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water in step (5) is 1:0.3:0.08:0.2:50.

[0018] As an optimization, the padding treatment process parameters in step (5) are: two dips and two paddings, with a padding rate of 80%.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] When preparing the waterproof and antifouling wall cloth, the present invention comprises the following steps: tetramethylcyclotetrasiloxane and dihydroxy silicone oil are reacted to obtain modified silicone oil; hydrotalcite and gamma-aminopropyltriethoxysilane are reacted and then reacted with 3-thiophenecarbonyl chloride, thiophene and 3-vinylthiophene to obtain modified hydrotalcite; the modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water are mixed to obtain a finishing liquid; 1,3-propylene glycol, N-propyldiethanolamine, dimethyl terephthalate, modified silicone oil and tetrabutyl titanate are reacted to obtain modified polyester; the modified polyester is melt-spun to form a fabric, and the fabric is then treated by padding with the finishing liquid to obtain the waterproof and antifouling wall cloth.

[0021] Firstly, tetramethylcyclotetrasiloxane and dihydroxy silicone oil are reacted to obtain modified silicone oil, and 1,3-propylene glycol, N-propyldiethanolamine, dimethyl terephthalate, modified silicone oil and tetrabutyl titanate are reacted to obtain modified polyester. Dihydroxy silicone oil introduces silicon chains containing a large amount of silicon-hydrogen structure into polyester. On the one hand, the silicon-hydrogen structure can undergo silicon-hydrogen addition reaction with the double bonds on perfluorohexylethylene and the double bonds introduced by polythiophene on the modified hydrotalcite to form a complex and stable cross-linked network, thereby improving the wear resistance. In addition, the silicon chain will be thermally decomposed under high temperature conditions to form silicon dioxide, which can play an isolating role, blocking the contact between oxygen and combustibles, thereby playing a flame retardant role and improving the flame retardant performance. On the other hand, the presence of the silicon chain can effectively reduce the surface energy, thereby improving the waterproof performance of the waterproof and anti-fouling wall cloth.

[0022] Secondly, hydrotalcite and γ-aminopropyltriethoxysilane react and then react with 3-thiophenecarbonyl chloride, thiophene and 3-vinylthiophene to obtain modified hydrotalcite; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water are mixed to obtain a finishing liquid. The iodomethane in the finishing liquid can react with the tertiary amine structure introduced by N-propyldiethanolamine in the polyester to undergo a quaternary ammonium salt cation, which has a good contact antibacterial effect and effectively improves the antibacterial properties of the waterproof and antifouling wall cloth. After the hydrotalcite reacts with γ-aminopropyltriethoxysilane, it has an amino group and can react with the acyl chloride on 3-thiophenecarbonyl chloride. 3-thiophenecarbonyl chloride, thiophene and 3-vinylthiophene are polymerized on the surface of the hydrotalcite to form polythiophene. The polythiophene has a conjugated structure, and the π electrons can freely jump between the thiophene rings to form a large number of conductive electrons, so that the wall cloth has good conductivity, improves the antistatic performance, and is not easy to generate static electricity, which can reduce the adsorption of dust, thereby improving the antifouling performance of the wall cloth. The hydrotalcite can play a physical barrier role, preventing the escape of combustible gases and the contact between combustibles and oxygen, and the hydrotalcite will decompose and produce carbon dioxide when heated, effectively diluting the oxygen concentration, and escaping with water vapor can also take away a lot of heat, effectively improving the flame retardant properties of the waterproof and antifouling wall cloth. DETAILED DESCRIPTION

[0023] 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 described embodiments 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 work are within the scope of protection of the present invention.

[0024] Embodiment 1:

[0025] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0026] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.1:0.01, nitrogen was passed for 10 minutes, stirred at 80°C and 100 r / min for 2 hours, heated to 130°C and continued to stir for 40 minutes, and distilled under vacuum for 1 hour to obtain modified silicone oil;

[0027] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 25 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 105°C for 20 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed three times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 80°C for 4 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.4:40, and the mixture was reacted at 65°C for 5 hours, cooled to room temperature, and the solid was separated by centrifugation. The solid was washed three times with deionized water and anhydrous ethanol, and dried at 80°C for 4 hours to obtain pretreated hydrotalcite;

[0028] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.1:20, reacted at 300 r / min at room temperature for 2 h, and added with 0.04 times the mass of thiophene, 0.04 times the mass of 3-vinylthiophene, and 0.3 times the mass of anhydrous ferric chloride under a nitrogen atmosphere, reacted at 0°C for 2 h, and then reacted at room temperature for 2 days, and added with 0.8 times the mass of N,N-dimethylformamide methanol, and allowed to stand for 1 h. The precipitate was separated by centrifugation, washed with methanol 3 times, and vacuum dried at 50°C for 4 h to obtain modified hydrotalcite;

[0029] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1:1. The temperature was raised to 160°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate in an amount 0.1 times the mass of dimethyl terephthalate was added. The mixture was stirred at a speed of 70 r / min for 1 h under normal pressure. Polyethylene glycol and dimethyl terephthalate in an amount 0.2 times the mass of dimethyl terephthalate were added. 0.05 times the mass of tetrabutyl titanate, heating to 210°C and stirring for 20 minutes to obtain prepolyester; prepolyester, modified silicone oil and tetrabutyl titanate are mixed in a mass ratio of 1:0.2:0.08, heated to 215°C, stirred at normal pressure for 25 minutes under a nitrogen atmosphere, antimony oxide 0.001 times the mass of the prepolyester is added, the temperature is raised to 225°C, vacuumed, reacted until the climbing pole effect appears and the reaction is stopped, and the modified polyester is obtained;

[0030] (5) The polyester material was dried at 105°C for 10 hours and then melt-spun at a spinning temperature of 275°C and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, the fabric was immersed in the finishing liquid, and placed at 80°C for 1 hour, taken out, immersed and rolled twice, with a rolling rate of 80%, and allowed to stand at 80°C for 4 hours, washed three times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0031] Embodiment 2:

[0032] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0033] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0034] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0035] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.15:25, reacted at room temperature at 350 r / min for 2.5 h, and added with 0.05 times the mass of thiophene, 0.05 times the mass of 3-vinylthiophene, and 0.4 times the mass of anhydrous ferric chloride under a nitrogen atmosphere, reacted at 0°C for 3 h, and then reacted at room temperature for 2.5 days, and added with methanol equal to the mass of N,N-dimethylformamide, and allowed to stand for 1.5 h, centrifuged to separate the precipitate, washed with methanol 4 times, and vacuum dried at 55°C for 5 h to obtain modified hydrotalcite;

[0036] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.15 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol (0.3 times the mass of dimethyl terephthalate) and dibutyl terephthalate (0.15 times the mass of dimethyl terephthalate) were added. Tetrabutyl titanate with a mass of 0.1 times that of methyl ester was heated to 220°C and stirred for 30 minutes to obtain prepolyester; the prepolyester, modified silicone oil and tetrabutyl titanate were mixed at a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until the climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging;

[0037] (5) The polyester material was dried at 110° C. for 12 h and then melt-spun at a spinning temperature of 280° C. and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, the fabric was immersed in the finishing liquid, and placed at 85° C. for 1.5 h, taken out, immersed and rolled twice, with a rolling rate of 80%, and allowed to stand at 85° C. for 5 h, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0038] Embodiment 3:

[0039] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0040] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.3:0.03, nitrogen was passed for 20 minutes, stirred at 90°C and 200 r / min for 3 hours, heated to 140°C and continued to stir for 50 minutes, and distilled under vacuum for 2 hours to obtain modified silicone oil;

[0041] (2) Mix magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea in a molar ratio of 2:1:10, add deionized water 30 times the mass of magnesium nitrate hexahydrate, react at 115°C in a sealed environment for 24 hours, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol to remove carbon dioxide for 5 times, and dry at 90°C for 6 hours to obtain hydrotalcite; mix hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane in a mass ratio of 1:0.6:60, react at 75°C for 7 hours, cool to room temperature, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol for 5 times, and dry at 90°C for 6 hours to obtain pretreated hydrotalcite;

[0042] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.2:30, reacted at room temperature at 400 r / min for 3 h, and added with 0.06 times the mass of thiophene, 0.06 times the mass of 3-vinylthiophene, and 0.5 times the mass of anhydrous ferric chloride under a nitrogen atmosphere, reacted at 0°C for 4 h, and then reacted at room temperature for 3 days, and added with 1.2 times the mass of N,N-dimethylformamide methanol, and allowed to stand for 2 h. The precipitate was separated by centrifugation, washed with methanol 5 times, and vacuum dried at 60°C for 6 h to obtain modified hydrotalcite;

[0043] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:2:1. The temperature was raised to 170°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.2 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 90 r / min for 2 h under normal pressure. Polyethylene glycol (0.4 times the mass of dimethyl terephthalate) and dimethyl terephthalate (0.4 times the mass of dimethyl terephthalate) were added. 0.15 times the mass of tetrabutyl titanate, heating to 230°C and stirring for 40 minutes to obtain prepolyester; prepolyester, modified silicone oil and tetrabutyl titanate are mixed in a mass ratio of 1:0.3:0.12, heated to 225°C, stirred at normal pressure for 35 minutes under a nitrogen atmosphere, antimony oxide 0.002 times the mass of the prepolyester is added, the temperature is raised to 235°C, vacuumed, reacted until the climbing pole effect appears and the reaction is stopped, and the modified polyester is obtained;

[0044] (5) The polyester material was dried at 115°C for 14 hours and then melt-spun at a spinning temperature of 285°C and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, the fabric was immersed in the finishing liquid, placed at 90°C for 2 hours, taken out, immersed and rolled twice, with a rolling rate of 80%, and allowed to stand at 90°C for 6 hours, washed with deionized water 5 times, and dried to obtain a waterproof and anti-fouling wall cloth.

[0045] Comparative Example 1:

[0046] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0047] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0048] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0049] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.15:25, reacted at room temperature at 350 r / min for 2.5 h, and added with 0.05 times the mass of thiophene, 0.05 times the mass of 3-vinylthiophene, and 0.4 times the mass of anhydrous ferric chloride under a nitrogen atmosphere, reacted at 0°C for 3 h, and then reacted at room temperature for 2.5 days, and added with methanol equal to the mass of N,N-dimethylformamide, and allowed to stand for 1.5 h, centrifuged to separate the precipitate, washed with methanol 4 times, and vacuum dried at 55°C for 5 h to obtain modified hydrotalcite;

[0050] (4) 1,3-propylene glycol and dimethyl terephthalate were added into a reactor in a molar ratio of 2.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, 0.15 times the mass of dimethyl terephthalate of tetrabutyl titanate was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. 0.3 times the mass of dimethyl terephthalate of polyethylene glycol and 0.5 times the mass of dimethyl terephthalate of tetrabutyl titanate were added. .1 times of tetrabutyl titanate, heating to 220°C and stirring for 30 minutes to obtain prepolyester; prepolyester, modified silicone oil and tetrabutyl titanate are mixed in a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide 0.0015 times of the mass of the prepolyester is added, the temperature is raised to 230°C, vacuumed, reacted until the climbing pole effect appears and the reaction is stopped, and the modified polyester is obtained;

[0051] (5) The polyester material was dried at 110°C for 12 hours and then melt-spun at a spinning temperature of 280°C and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, and deionized water were mixed at a mass ratio of 1:0.3:0.08:50 to obtain a finishing liquid, and the fabric was immersed in the finishing liquid and placed at 85°C for 1.5 hours. After being taken out, it was immersed and rolled twice, with a rolling rate of 80%, and then allowed to stand at 85°C for 5 hours, washed with deionized water 4 times, and dried to obtain a waterproof and anti-fouling wall cloth.

[0052] Comparative Example 2:

[0053] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0054] (1) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0055] (2) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.15:25, reacted at room temperature at 350 r / min for 2.5 h, and added with 0.05 times the mass of thiophene, 0.05 times the mass of 3-vinylthiophene, and 0.4 times the mass of anhydrous ferric chloride under a nitrogen atmosphere, reacted at 0°C for 3 h, and then reacted at room temperature for 2.5 days, and added with methanol equal to the mass of N,N-dimethylformamide, and allowed to stand for 1.5 h, centrifuged to separate the precipitate, washed with methanol 4 times, and vacuum dried at 55°C for 5 h to obtain modified hydrotalcite;

[0056] (3) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, 0.15 times the mass of dimethyl terephthalate of tetrabutyl titanate was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol and 0.3 times the mass of dimethyl terephthalate were added. Tetrabutyl titanate with a mass of 0.1 times that of dimethyl phthalate was heated to 220°C and stirred for 30 minutes to obtain a prepolyester; the prepolyester and tetrabutyl titanate were mixed at a mass ratio of 1:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until a climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging the material;

[0057] (4) The polyester material was dried at 110° C. for 12 h and then melt-spun at a spinning temperature of 280° C. and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, and the fabric was immersed in the finishing liquid and placed at 85° C. for 1.5 h. After being taken out, it was immersed and rolled twice, with a rolling rate of 80%, and then allowed to stand at 85° C. for 5 h, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0058] Comparative Example 3:

[0059] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0060] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0061] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0062] (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride, and N,N-dimethylformamide were mixed in a mass ratio of 1:0.15:25, reacted at room temperature at 350 r / min for 2.5 h, added with 0.05 times the mass of thiophene and 0.4 times the mass of anhydrous ferric chloride of the pretreated hydrotalcite under a nitrogen atmosphere, reacted at 0°C for 3 h, and then reacted at room temperature for 2.5 days, added with methanol equal to the mass of N,N-dimethylformamide, allowed to stand for 1.5 h, centrifuged to separate the precipitate, washed with methanol 4 times, and vacuum dried at 55°C for 5 h to obtain modified hydrotalcite;

[0063] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.15 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol (0.3 times the mass of dimethyl terephthalate) and dibutyl terephthalate (0.15 times the mass of dimethyl terephthalate) were added. Tetrabutyl titanate with a mass of 0.1 times that of methyl ester was heated to 220°C and stirred for 30 minutes to obtain prepolyester; the prepolyester, modified silicone oil and tetrabutyl titanate were mixed at a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until the climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging;

[0064] (5) The polyester material was dried at 110° C. for 12 h and then melt-spun at a spinning temperature of 280° C. and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, the fabric was immersed in the finishing liquid, and placed at 85° C. for 1.5 h, taken out, immersed and rolled twice, with a rolling rate of 80%, and allowed to stand at 85° C. for 5 h, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0065] Comparative Example 4:

[0066] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0067] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0068] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0069] (3) Pretreated hydrotalcite and N,N-dimethylformamide were mixed at a mass ratio of 1:25, and 0.05 times the mass of thiophene, 0.05 times the mass of 3-vinylthiophene and 0.4 times the mass of anhydrous ferric chloride were added under a nitrogen atmosphere, and the mixture was reacted at 0°C for 3 hours, and then reacted at room temperature for 2.5 days. Methanol with an equal mass of N,N-dimethylformamide was added, and the mixture was allowed to stand for 1.5 hours. The precipitate was separated by centrifugation, washed with methanol for 4 times, and vacuum dried at 55°C for 5 hours to obtain modified hydrotalcite.

[0070] (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.15 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol (0.3 times the mass of dimethyl terephthalate) and dibutyl terephthalate (0.15 times the mass of dimethyl terephthalate) were added. Tetrabutyl titanate with a mass of 0.1 times that of methyl ester was heated to 220°C and stirred for 30 minutes to obtain prepolyester; the prepolyester, modified silicone oil and tetrabutyl titanate were mixed at a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until the climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging;

[0071] (5) The polyester material was dried at 110° C. for 12 h and then melt-spun at a spinning temperature of 280° C. and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, the fabric was immersed in the finishing liquid, and placed at 85° C. for 1.5 h, taken out, immersed and rolled twice, with a rolling rate of 80%, and allowed to stand at 85° C. for 5 h, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0072] Comparative Example 5:

[0073] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0074] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0075] (2) Magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea were mixed in a molar ratio of 2:1:10, deionized water 27.5 times the mass of magnesium nitrate hexahydrate was added, and the mixture was reacted at 110°C for 22 hours in a sealed environment, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol from which carbon dioxide was removed, and dried at 85°C for 5 hours to obtain hydrotalcite; hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane were mixed in a mass ratio of 1:0.5:50, and the mixture was reacted at 70°C for 6 hours, and cooled to room temperature, and the solid was separated by centrifugation. The solid was washed 4 times with deionized water and anhydrous ethanol, and dried at 85°C for 5 hours to obtain pretreated hydrotalcite;

[0076] (3) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.15 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol (0.3 times the mass of dimethyl terephthalate) and dibutyl terephthalate (0.15 times the mass of dimethyl terephthalate) were added. Tetrabutyl titanate with a mass of 0.1 times that of methyl ester was heated to 220°C and stirred for 30 minutes to obtain prepolyester; the prepolyester, modified silicone oil and tetrabutyl titanate were mixed at a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until the climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging;

[0077] (4) The polyester material was dried at 110° C. for 12 h and then melt-spun at a spinning temperature of 280° C. and a spinning rate of 3000 m / min, and then woven to obtain a fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing liquid, and the fabric was immersed in the finishing liquid and placed at 85° C. for 1.5 h. After being taken out, it was immersed and rolled twice, with a rolling rate of 80%, and then allowed to stand at 85° C. for 5 h, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0078] Comparative Example 6:

[0079] A method for preparing a waterproof and anti-fouling wall cloth comprises the following preparation steps:

[0080] (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide were mixed in a mass ratio of 1:1.2:0.02, nitrogen was passed for 15 minutes, stirred at 85°C and 150 r / min for 2.5 hours, heated to 135°C and continued to stir for 45 minutes, and distilled under vacuum for 1.5 hours to obtain modified silicone oil;

[0081] (2) 3-thiophenecarbonyl chloride, thiophene, 3-vinylthiophene, and N,N-dimethylformamide were mixed in a mass ratio of 1::3:1:25, reacted at 0°C for 3 hours under a nitrogen atmosphere, and then reacted at room temperature for 2.5 days, and methanol with an equal mass of N,N-dimethylformamide was added, and the mixture was allowed to stand for 1.5 hours. The precipitate was separated by centrifugation, washed with methanol for 4 times, and vacuum dried at 55°C for 5 hours to obtain polythiophene;

[0082] (3) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate were added to a reactor in a molar ratio of 1:1.5:1. The temperature was raised to 165°C under a nitrogen atmosphere. After dimethyl terephthalate was completely melted, tetrabutyl titanate (0.15 times the mass of dimethyl terephthalate) was added. The mixture was stirred at a speed of 80 r / min for 1.5 h under normal pressure. Polyethylene glycol (0.3 times the mass of dimethyl terephthalate) and dibutyl terephthalate (0.15 times the mass of dimethyl terephthalate) were added. Tetrabutyl titanate with a mass of 0.1 times that of methyl ester was heated to 220°C and stirred for 30 minutes to obtain prepolyester; the prepolyester, modified silicone oil and tetrabutyl titanate were mixed at a mass ratio of 1:0.25:0.1, heated to 220°C, stirred at normal pressure for 30 minutes under a nitrogen atmosphere, antimony oxide with a mass of 0.0015 times that of the prepolyester was added, the temperature was raised to 230°C, vacuumed, reacted until the climbing pole effect appeared and the reaction was stopped, and the modified polyester was obtained by discharging;

[0083] (4) The polyester material was dried at 110°C for 12 hours and then melt-spun at a spinning temperature of 280°C and a spinning rate of 3000 m / min, and then woven to obtain a fabric; polythiophene, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water were mixed at a mass ratio of 1:0.3:0.08:0.2:50 to obtain a finishing solution, and the fabric was immersed in the finishing solution and placed at 85°C for 1.5 hours. After being taken out, it was immersed and rolled twice, with a rolling rate of 80%, and then allowed to stand at 85°C for 5 hours, washed 4 times with deionized water, and dried to obtain a waterproof and anti-fouling wall cloth.

[0084] Test Example 1:

[0085] Waterproof performance test: According to GB / T31906-2015 "Test for the repellency of aqueous solutions and water-alcohol solutions of textiles", the static contact angle of the fabric to water was measured on a JC2000C contact angle tester. The droplet size was 5μL. Each test was measured 10 times with an interval of at least 1cm, and the final average value was calculated. The results are shown in Table 1.

[0086] Table 1

[0087]

[0088]

[0089] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 1, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good waterproof performance.

[0090] By comparison, the static contact angles of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that the dihydroxy silicone oil participates in the copolymerization of polyester and introduces silicon-containing segments into the polyester, which effectively reduces the surface energy and improves the waterproof performance of the waterproof and antifouling wall cloth.

[0091] Test Example 2:

[0092] Antifouling performance test: Refer to GB / T30159.1-2013 "Testing and evaluating the antifouling performance of textiles Part 1: Antifouling" to test the antifouling performance of fabrics. Use the liquid stain method to prepare the fabric sample to be tested. The size can meet the test. Place it horizontally with the front side facing up and filter paper at the bottom. Drop soy sauce on the surface of the sample. Drop three drops of 0.05mL on different parts of each sample with an interval of more than 50mm. After 30s, observe the droplets from a 45° direction and rate them. The results are shown in Table 2.

[0093] Table 2

[0094]

[0095]

[0096] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 2, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good antifouling performance.

[0097] By comparison, the antifouling levels of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that the dihydroxy silicone oil participates in the copolymerization of polyester, and the silicon-containing chain segments are introduced into the polyester, which effectively reduces the surface energy, thereby effectively improving the antifouling performance of the waterproof and antifouling wall cloth; the antifouling levels of Examples 1 to 3 are greater than that of Comparative Example 5, indicating that polythiophene is coated on the surface of the modified hydrotalcite, and polythiophene has a conjugated structure, and π electrons can freely jump between thiophene rings to form a large number of conductive electrons, so that the wall cloth has good conductivity, is not easy to generate static electricity, can reduce the adsorption of dust, and thus improve the antifouling performance of the wall cloth.

[0098] Test Example 3:

[0099] Antibacterial performance test: The antibacterial rate of each embodiment and comparative example against Staphylococcus aureus was tested according to the Quine test method. The results are shown in Table 3.

[0100] Table 3

[0101]

[0102]

[0103] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 3, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good antibacterial properties.

[0104] By comparison, the antibacterial rates of Examples 1 to 3 are significantly greater than that of Comparative Example 1, indicating that N-propyldiethanolamine introduces a tertiary amine structure during the preparation of polyester, and iodomethane quaternization is used during post-finishing to give it a quaternary ammonium salt cation, which has a good contact antibacterial effect and effectively improves the antibacterial properties of the waterproof and antifouling wall cloth.

[0105] Test Example 4:

[0106] Flame retardant performance test: The waterproof and antifouling wall coverings obtained in the embodiments and test examples were prepared into samples according to GB / T2406 and tested for limiting oxygen index. The results are shown in Table 4.

[0107] Table 4

[0108] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 31.2 Comparative Example 1 30.1 Example 2 30.9 Comparative Example 2 23.6 Example 3 30.8 Comparative Example 3 31.4 Comparative Example 4 30.2 Comparative Example 5 30.7 Comparative Example 6 21.3

[0109] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 4, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good flame retardant properties.

[0110] By comparison, the limiting oxygen index of Examples 1 to 3 is significantly greater than that of Comparative Example 2, indicating that the dihydroxy silicone oil participates in the copolymerization of polyester, and long-chain silicon is introduced into the polyester, which is thermally decomposed under high temperature conditions to form silicon dioxide, which can play an isolating role, blocking the contact between oxygen and combustibles, thereby playing a flame retardant role and improving the flame retardant performance; the limiting oxygen index of Examples 1 to 3 is significantly greater than that of Comparative Example 6, indicating that the hydrotalcite can play a physical barrier role, preventing the escape of combustible gases and the contact between combustibles and oxygen, and the hydrotalcite will decompose when heated to produce carbon dioxide, which effectively dilutes the oxygen concentration, and can also take away a large amount of heat when escaping with water vapor, effectively improving the flame retardant performance of the waterproof and anti-fouling wall cloth.

[0111] Test Example 5:

[0112] Volume resistivity test: The volume resistivity of antistatic wear-resistant polyester fiber was tested using the YG321 fiber resistivity meter produced by Nantong Sansi Electromechanical Technology Co., Ltd. The test was conducted in accordance with GB / T14342-93 "Test Method for Resistivity of Synthetic Staple Fibers". The results are shown in Table 5.

[0113] Table 5

[0114] Volume specific resistance Volume specific resistance Example 1 <![CDATA[1.79×10 6 Ohm cm]]> Comparative Example 1 <![CDATA[2.94×10 6 Ohm cm]]> Example 2 <![CDATA[0.62×10 6 Ohm cm]]> Comparative Example 2 <![CDATA[2.01×10 6 Ohm cm]]> Example 3 <![CDATA[1.33×10 6 Ohm cm]]> Comparative Example 3 <![CDATA[2.55×10 6 Ohm cm]]> Comparative Example 4 <![CDATA[1.59×10 6 Ohm cm]]> Comparative Example 5 <![CDATA[6.52×10 7 Ohm cm]]> Comparative Example 6 <![CDATA[2.27×10 6 Ohm cm]]>

[0115] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 5, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good antistatic performance.

[0116] By comparison, the volume resistivity of Examples 1 to 3 is significantly greater than that of Comparative Example 5, indicating that polythiophene is coated on the surface of the modified hydrotalcite. Polythiophene has a conjugated structure, and π electrons can freely jump between thiophene rings to form a large number of conductive electrons, so that the wall cloth has good conductivity and effectively improves the antistatic performance of the wall cloth.

[0117] Test Example 6:

[0118] Wear resistance: The wear resistance was tested using Nu-Martindale 864 wear tester according to GB / T21196.3-2007. The fabric to be tested was cut into a circle with a diameter of 38±0.5mm, and a standard 600-mesh water sandpaper was used as an abrasive (the abrasive was replaced once the number of times exceeded 5000), the pressure was 9kPa, and the breakage of two independent yarns of the fabric was taken as the end point of wear resistance, and the number of wear resistance was recorded. The results are shown in Table 6.

[0119] Table 6

[0120] Wear times Wear times Example 1 2798 Comparative Example 1 2677 Example 2 2869 Comparative Example 2 1742 Example 3 2817 Comparative Example 3 1806 Comparative Example 4 1904 Comparative Example 5 1579 Comparative Example 6 1989

[0121] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 6, it can be found that the waterproof and antifouling wall cloth prepared by the present invention has good wear resistance.

[0122] By comparison, the wear resistance times of Examples 1 to 3 are significantly greater than that of Comparative Example 2, indicating that the introduction of the silicon-hydrogen structure in the polyester can react with the double bonds on the perfluorohexylethylene and the double bonds introduced by the polythiophene on the modified hydrotalcite to form a complex and stable cross-linked network, thereby improving the wear resistance; the wear resistance times of Examples 1 to 3 are significantly greater than that of Comparative Example 3, indicating that the double bonds introduced by the polythiophene structure on the modified hydrotalcite and the silicon-hydrogen structure on the modified polyester can react with the double bonds introduced by the polythiophene structure on the modified hydrotalcite to form a complex cross-linked network under the catalysis of chloroplatinic acid. The stable chemical crosslinking effectively improves the wear resistance; the wear times of Examples 1 to 3 are significantly greater than that of Comparative Example 4, indicating that the amino groups on the modified hydrotalcite and the acyl chlorides on the polythiophene can react to produce chemical crosslinking, thereby effectively improving the wear resistance; the wear times of Examples 1 to 3 are significantly greater than that of Comparative Example 6, indicating that the hydrotalcite, as an inorganic filler, has a large number of reaction sites after being modified with γ-aminopropyltriethoxysilane and polythiophene, and forms a complex crosslinking network through the hydrosilylation reaction, thereby effectively improving the wear resistance.

[0123] 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. A waterproof and anti-fouling wall cloth, characterized in that: The waterproof and antifouling wall cloth is prepared by reacting 1,3-propylene glycol, N-propyldiethanolamine, dimethyl terephthalate, modified silicone oil, and tetrabutyl titanate to obtain a modified polyester, which is melt-spun into a fabric, and then the fabric is treated with a post-finishing liquid for padding. The modified silicone oil is prepared by reacting tetramethylcyclotetrasiloxane and dihydroxy silicone oil; The post-finishing liquid is prepared by reacting magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and urea to obtain hydrotalcite, reacting hydrotalcite and γ-aminopropyltriethoxysilane to obtain pretreated hydrotalcite, reacting the pretreated hydrotalcite with 3-thenoyl chloride, thiophene and 3-vinylthiophene to obtain modified hydrotalcite, and mixing the modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water.

2. A method for preparing a waterproof and antifouling wall cloth, characterized in that: The method comprises the following preparation steps: (1) Tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide silicon alkoxide are mixed, nitrogen is passed for 10 to 20 minutes, stirred at 80 to 90° C. and 100 to 200 r / min for 2 to 3 hours, the temperature is raised to 130 to 140° C. and stirring is continued for 40 to 50 minutes, and distilled under vacuum for 1 to 2 hours to obtain modified silicone oil; (2) Mix magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, and urea, add deionized water 25 to 30 times the mass of magnesium nitrate hexahydrate, react at 105 to 115° C. in a sealed environment for 20 to 24 hours, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol to remove carbon dioxide for 3 to 5 times, and dry at 80 to 90° C. for 4 to 6 hours to obtain hydrotalcite; mix hydrotalcite, γ-aminopropyltriethoxysilane, and cyclohexane in a mass ratio of 1: (0.4 to 0.6): (40 to 60), react at 65 to 75° C. for 5 to 7 hours, cool to room temperature, centrifuge to separate the solid, wash the solid with deionized water and anhydrous ethanol for 3 to 5 times, and dry at 80 to 90° C. for 4 to 6 hours to obtain pretreated hydrotalcite; (3) Pretreated hydrotalcite, 3-thiophenecarbonyl chloride and N,N-dimethylformamide were mixed and reacted at room temperature at 300-400 r / min for 2-3 hours. Thiophene (0.04-0.06 times the mass of the pretreated hydrotalcite), 3-vinylthiophene (0.04-0.06 times the mass of the pretreated hydrotalcite) and anhydrous ferric chloride (0.3-0.5 times the mass of the pretreated hydrotalcite) were added under a nitrogen atmosphere, and the mixture was reacted at 0°C for 2-4 hours. The mixture was then reacted at room temperature for 2-3 days. Methanol (0.8-1.2 times the mass of N,N-dimethylformamide) was added, and the mixture was allowed to stand for 1-2 hours. The precipitate was separated by centrifugation, washed with methanol for 3-5 times, and vacuum dried at 50-60°C for 4-6 hours to obtain modified hydrotalcite. (4) 1,3-propylene glycol, N-propyldiethanolamine, and dimethyl terephthalate are mixed in a molar ratio of 1:(1-2):1 and added to a reaction kettle. The mixture is heated to 160-170° C. under a nitrogen atmosphere. After dimethyl terephthalate is completely melted, 0.1-0.2 times the mass of dimethyl terephthalate of tetrabutyl titanate is added. The mixture is stirred at a speed of 70-90 r / min for 1-2 h under normal pressure. Then, 0.2-0.4 times the mass of dimethyl terephthalate of polyethylene glycol and 0.05-0.1 times the mass of dimethyl terephthalate of polyethylene glycol are added. 5 times of tetrabutyl titanate, heating to 210-230°C and stirring for 20-40 minutes to obtain prepolyester; mixing prepolyester, modified silicone oil and tetrabutyl titanate in a mass ratio of 1: (0.2-0.3): (0.08-0.12), heating to 215-225°C, stirring at normal pressure for 25-35 minutes under a nitrogen atmosphere, adding antimony oxide 0.001-0.002 times of the mass of the prepolyester, heating to 225-235°C, evacuating, reacting until the climbing pole effect appears and stopping the reaction, and discharging the material to obtain modified polyester; (5) The polyester material is dried at 105-115° C. for 10-14 hours, melt-spun, and then woven to obtain fabric; modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide, and deionized water are mixed to obtain a finishing solution, the fabric is immersed in the finishing solution, placed at 80-90° C. for 1-2 hours, taken out and then padded, placed at 80-90° C. for 4-6 hours, washed with deionized water for 3-5 times, and dried to obtain a waterproof and anti-fouling wall cloth.

3. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: The mass ratio of tetramethylcyclotetrasiloxane, dihydroxy silicone oil and tetramethylammonium hydroxide siliconate in step (1) is 1: (1.1-1.3): (0.01-0.03).

4. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: In step (2), the molar ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and urea is 2:1:

10.

5. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: In step (3), the mass ratio of the pretreated hydrotalcite, 3-thiophenecarbonyl chloride and N,N-dimethylformamide is 1:(0.1-0.2):(20-30).

6. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: In step (4), the molar ratio of 1,3-propylene glycol, N-propyldiethanolamine and dimethyl terephthalate is 1:(1-2):

1.

7. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: The mass ratio of the modified hydrotalcite, perfluorohexylethylene, chloroplatinic acid, methyl iodide and deionized water in step (5) is 1:0.3:0.08:0.2:

50.

8. The method for preparing a waterproof and antifouling wall cloth according to claim 2, characterized in that: The padding treatment process parameters in step (5) are: two dips and two pads, with a padding rate of 80%.

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