Flame-retardant tarpaulin material and preparation method thereof

Abstract

The invention discloses a flame-retardant tarpaulin material and a preparation method thereof, and belongs to the technical field of tarpaulin material preparation. The flame-retardant tarpaulin material comprises a lining layer, flame-retardant ultraviolet-resistant layers and a waterproof layer, the flame-retardant ultraviolet-resistant layers are uniformly covered on two sides of the lining layer, the waterproof layer is uniformly covered on the surfaces of the flame-retardant ultraviolet-resistant layers, the lining layer is made of a polyethylene film, and the polyethylene film is made of a plastic film. The material of the flame-retardant ultraviolet-resistant layer is prepared from nanowires, diethyl phosphite, 1-chloromethyl benzotriazole, p-aminobenzaldehyde and acrylic resin, and the material of the waterproof layer is prepared from 3-aminodiphenyl ether, perfluorooctyl ethyl iodide, heptafluorobutyric anhydride and phthaloyl chloride. The tarpaulin material prepared by the method has excellent flame retardant property, waterproof property and aging resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of tarpaulin material preparation, and particularly relates to a flame-retardant tarpaulin material and a preparation method thereof. Background Art

[0002] With the acceleration of industrialization and the improvement of urbanization, the demand for tarpaulins in various buildings and industrial facilities is increasing. In these occasions, tarpaulins not only need to have good basic properties such as waterproof, sun-proof, and weather-resistant, but also need to have excellent flame retardant properties to ensure that they can effectively prevent the spread of fire and protect the safety of people and property in emergencies such as fire. Secondly, the rapid development of the transportation and logistics industries has also put forward higher performance requirements for tarpaulin materials. During long-distance transportation and warehousing, tarpaulins need to withstand various harsh environmental conditions, such as high temperature, low temperature, rain, wind and sand, etc. At the same time, due to the possible fire risks during transportation and warehousing, the flame retardant properties of tarpaulins have also become one of the important criteria for measuring their quality. Therefore, research and development of tarpaulin materials with excellent flame retardant properties is of great significance to improving the safety and efficiency of the transportation and warehousing industries. Summary of the invention

[0003] The object of the present invention is to provide a flame retardant tarpaulin material and a preparation method thereof, so as to solve the technical problems of poor flame retardancy, aging resistance and waterproof performance of tarpaulin materials in the prior art.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: The invention provides a flame-retardant tarpaulin material. The flame-retardant tarpaulin material comprises an inner layer, a flame-retardant UV-resistant layer and a waterproof layer. Both sides of the inner layer are evenly covered with the flame-retardant UV-resistant layer, and the surface of the flame-retardant UV-resistant layer is evenly covered with the waterproof layer. The inner layer material is composed of a polyethylene film, the flame-retardant UV-resistant layer material is prepared from nanosilk, diethyl phosphite, 1-chloromethylbenzotriazole, p-aminobenzaldehyde and acrylic resin, and the waterproof layer material is prepared from 3-aminodiphenyl ether, perfluorooctyl ethyl iodide, heptafluorobutyric anhydride and phthaloyl chloride.

[0005] Preferably, the method for preparing the flame retardant and UV resistant layer material comprises the following steps: Q1: Add sodium wire to a container containing tetrahydrofuran, slowly drop diethyl phosphite under argon atmosphere, heat and stir until the sodium wire is completely dissolved, slowly drop tetrahydrofuran containing 1-chloromethylbenzotriazole into the container after stirring, heat to react after the addition is complete, add distilled water to quench the reaction after the reaction is complete, extract, combine the organic phases, wash, dry, distill under reduced pressure, and purify by column chromatography to obtain compound 1; Q2: Compound 1 is added to a container containing tetrahydrofuran under low temperature, and sodium methoxide is slowly added to the container under argon atmosphere. After the addition is completed, react at low temperature, and then tetrahydrofuran dissolved with p-aminobenzaldehyde is slowly added dropwise to the container, heated under reflux for reaction, and after the reaction is completed, the temperature is lowered, distilled water is added to quench the reaction, extraction, washing, drying, vacuum distillation, and column chromatography purification are performed to obtain a flame retardant and UV-resistant agent; Q3: Add acrylic resin, flame retardant and UV resistant agent, tetrahydrofuran, leveling agent, defoaming agent and antioxidant into a container, stir and mix evenly to obtain a flame retardant and UV resistant layer material.

[0006] In the above process, the synthetic reaction formula of the flame retardant and UV resistant agent is as follows:

[0007] The results of mass spectrometry analysis of compound 1 were: m / z: 269.09 (100.0%), 270.10 (12.2%), 271.10(1.3%), 270.09 (1.1%); the results of mass spectrometry analysis of flame retardant and UV resistant agent were: m / z: 236.11 (100.0%), 237.11 (15.3%), 237.10 (1.5%), 238.11 (1.3%).

[0008] Preferably, in Q1, the amount ratio of nanosilk, tetrahydrofuran, diethyl phosphite, 1-chloromethylbenzotriazole, tetrahydrofuran in which 1-chloromethylbenzotriazole is dissolved, and distilled water is (0.3-0.62) g: (8-12) mL: (0.21-0.35) g: (0.32-0.37) g: (9-12) mL: (45-55) mL, the heating and stirring temperature is 60-70°C, the heating reaction temperature is 60-70°C, the reaction time is 7-10 h, the product is extracted with dichloromethane 3-5 times, washed with saturated sodium chloride solution 2-4 times, and dried with anhydrous sodium sulfate. During the purification process, a mixed solution of dichloromethane and methanol in a volume ratio of (18-20): (0.8-1.2) is used as the eluent.

[0009] Preferably, in Q2, the amount ratio of compound 1, tetrahydrofuran, sodium methoxide, p-aminobenzaldehyde, tetrahydrofuran for dissolving p-aminobenzaldehyde and distilled water is (0.51-0.566) g: (18-22) mL: (0.098-0.118) g: (0.12-0.17) g: (4-6) mL: (45-55) mL, the low temperature environment temperature is 0-1°C, the low temperature reaction temperature is 0-1°C, the reaction time is 30-45 min, the heating reflux reaction temperature is 50-70°C, the reaction time is 8-12 h, the temperature is lowered to 28-32°C, extracted with dichloromethane, washed with saturated sodium chloride, and dried with anhydrous sodium sulfate. During the purification process, a mixed solution of petroleum ether and ethyl acetate in a volume ratio of (4.5-5.2): (0.9-1.3) is used as the eluent.

[0010] Preferably, in Q3, the usage ratio of acrylic resin, flame retardant and UV resistant agent, tetrahydrofuran, leveling agent, defoaming agent and antioxidant is (50-70) g: (8-14) g: (20-25) mL: (1-1.3) g: (2-2.6) g: (1.3-2.1) g, the stirring speed is 800-1100 rpm, and the mixing time is 30-45 min.

[0011] Preferably, the method for preparing the waterproof layer material comprises the following steps: S1: Add 3-aminodiphenyl ether and perfluorooctyl ethyl iodide into a container, mix well, heat and magnetically stir to reflux for reaction, add dichloromethane after the reaction is completed, wash, dry the organic layer, rotary evaporate, separate and purify to obtain intermediate A; S2: Under low temperature conditions, add intermediate A to a container filled with dichloromethane, stir to dissolve, then add pyridine, continue stirring, then slowly drop dichloromethane dissolved with heptafluorobutyric anhydride into the container, control the dropping speed, after the dropwise addition is completed, stir at room temperature for reaction, after the reaction is completed, wash, extract, dry, filter, and rotary evaporate to obtain intermediate B; S3: Under low temperature conditions, add the intermediate B to a container filled with dichloromethane, then add anhydrous aluminum chloride and stir, then slowly drop dichloromethane dissolved with phthaloyl chloride, control the dropping speed, and after the dropping is completed, stir and react at room temperature. After the reaction is completed, wash and purify to obtain a waterproofing agent; S4: Add the waterproofing agent to N,N-dimethylacetamide, stir at room temperature, and perform vacuum degassing to obtain a waterproof layer material.

[0012] In the above process, the synthetic reaction formula of the waterproofing agent is as follows:

[0013] The results of mass spectrometry analysis of intermediate A were: m / z: 631.08 (100.0%), 632.08 (24.2%), 633.09(2.7%); the results of mass spectrometry analysis of intermediate B were: m / z: 827.06 (100.0%), 828.06 (28.3%), 829.06(4.3%); the results of mass spectrometry analysis of waterproofing agent were: m / z: 1784.12 (100.0%), 1785.12 (66.2%), 1786.12(22.4%), 1787.13 (5.2%), 1788.13 (1.0%).

[0014] Preferably, in S1, the molar ratio of 3-aminodiphenyl ether to perfluorooctylethyl iodide is (0.8-1.1): (0.9-1.2), the temperature of the heated magnetic stirring reflux reaction is 140-150°C, the reaction time is 14-18h, the reaction is washed with deionized water for 3-5 times, and the reaction is dried with anhydrous magnesium sulfate. During the separation and purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 is used as an eluent; in S2, the low temperature environment temperature is 0-2°C, the molar ratio of the intermediate A to heptafluorobutyric anhydride is (1-1.2): (2.8-3.5), the stirring time is continued for 10-15min, the dripping speed is controlled to 30-40 drops / min, the stirring reaction time is 10-12h, the reaction is washed with deionized water, and the reaction is dried with anhydrous magnesium sulfate.

[0015] Preferably, in S3, the low temperature environment temperature is 2-5°C, the molar ratio of intermediate B, anhydrous aluminum chloride and phthaloyl chloride is (0.95-1.2): (2.4-2.6): (0.48-0.52), the dripping speed is controlled to 20-30 drops / min, the reaction temperature is stirred at room temperature for 10-12h, first washed with 0.5mol / L hydrochloric acid 3-5 times, and then washed with deionized water 3-5 times, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 is used as an eluent during the purification process.

[0016] Preferably, in S4, the usage ratio of the waterproofing agent to N,N-dimethylacetamide is (10-16) g: (6-8) mL, the stirring time at room temperature is 10-12 h, and the vacuum degassing time is 8-12 h.

[0017] Preferably, the method for preparing a flame retardant tarpaulin material comprises the following steps: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

[0018] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. The present invention first uses nanosilk, diethyl phosphite, 1-chloromethylbenzotriazole, p-aminobenzaldehyde and acrylic resin as raw materials to prepare a flame retardant and UV-resistant layer material, and then uses 3-aminodiphenyl ether, perfluorooctyl ethyl iodide, heptafluorobutyric anhydride and phthaloyl chloride as raw materials to prepare a waterproof layer material. The two are applied to the tarpaulin material to effectively improve its flame retardant performance, aging resistance and waterproof performance.

[0019] 2. The flame retardant and UV-resistant layer material prepared by the present invention is added into the preparation process of the tarpaulin material, which can effectively improve the flame retardant and aging resistance of the material. The triazole ring structure contained in the flame retardant and UV-resistant agent is an effective UV absorption group. When ultraviolet rays are irradiated to the surface of the flame retardant and UV-resistant agent, the light energy causes the electron density to change, the electron density of the oxygen atom turns to the nitrogen atom, the electron density of the nitrogen atom increases, and the electron density of the oxygen atom decreases, forming a tautomer. The tautomer releases the energy of the excited state in the form of thermal energy, thereby returning to a stable state. In this process, the ultraviolet light energy is continuously converted into thermal energy to achieve the effect of ultraviolet absorption, thereby improving the aging resistance of the tarpaulin; the triazole ring structure contained in it can release non-combustible gases such as nitrogen in a high temperature environment, thereby diluting the oxygen concentration in the air and inhibiting the combustion of the flame. It can also form a stable carbonized layer during the combustion process, thereby blocking the transfer of oxygen and heat and slowing down the combustion process. The amino group contained in it can quickly decompose when encountering a fire source, absorb a large amount of heat, and reduce the temperature of the material surface. The generated gas can also dilute the oxygen concentration in the flame area, further inhibiting the combustion of the flame, thereby improving the flame retardant performance of the material.

[0020] 3. The present invention adds the prepared waterproof layer material to the tarpaulin material, which can effectively improve the waterproof performance of the material. The fluorine ions contained in the waterproof agent have extremely low surface energy, so that the waterproof agent can form a dense waterproof film on the surface of the tarpaulin, effectively preventing the penetration of water molecules and improving its waterproof performance. The carbonyl and ether bonds contained in the waterproof agent are polar groups, which can interact with the groups on the surface of the tarpaulin to form strong chemical bonds and hydrogen bonds, thereby enhancing the adhesion of the waterproof layer, so that the waterproof layer can be firmly attached to the surface of the tarpaulin. The amide bonds contained in the waterproof agent ensure that the waterproof layer is evenly distributed on the surface of the tarpaulin to form a continuous waterproof film, so that the tarpaulin can still maintain the stability and durability of its waterproof performance in harsh environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0022] Figure 1 A schematic structural diagram of the flame retardant tarpaulin material prepared by the present invention.

[0023] Description of the drawings: 1. Inner layer, 2. Flame retardant and UV resistant layer, 3. Waterproof layer. DETAILED DESCRIPTION

[0024] The following will be combined with the drawings in 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 creative work are within the scope of protection of the present invention.

[0025] Example 1: See Figure 1 As shown, a flame retardant tarpaulin material includes an inner layer 1, a flame retardant and UV resistant layer 2 and a waterproof layer 3. Both sides of the inner layer 1 are evenly covered with the flame retardant and UV resistant layer 2, and the surface of the flame retardant and UV resistant layer 2 is evenly covered with the waterproof layer 3.

[0026] Embodiment 2: This embodiment discloses a method for preparing a flame retardant and UV-resistant layer material, comprising the following steps: Q1: 0.46 g of sodium silk was added to a container containing 10 mL of tetrahydrofuran. Under an argon atmosphere, 0.28 g of diethyl phosphite was slowly added dropwise. The mixture was heated and stirred at 65°C until the sodium silk was completely dissolved. After the stirring, 10.5 mL of tetrahydrofuran containing 0.34 g of 1-chloromethyl-benzotriazole was slowly added dropwise to the container. After the addition was completed, the mixture was heated at 65°C for 10 h. After the reaction was completed, 50 mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane three times. The organic phases were combined, washed with saturated sodium chloride solution four times, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of dichloromethane and methanol with a volume ratio of 20:1 was used as an eluent to obtain compound 1. Q2: 0.538g of compound 1 was added to a container containing 20mL of tetrahydrofuran at 1°C. Under an argon atmosphere, 0.108g of sodium methoxide was slowly added to the container. After the addition was completed, the reaction was carried out at a low temperature of 1°C for 30min. Then, 5mL of tetrahydrofuran dissolved with 0.14g of p-aminobenzaldehyde was slowly added dropwise to the container. The reaction was heated to reflux at 60°C for 12h. After the reaction was completed, the temperature was lowered to 28°C. 50mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a flame retardant and UV-resistant agent. Q3: 60 g of acrylic resin, 11 g of flame retardant and UV resistant agent, 22.5 mL of tetrahydrofuran, 1.15 g of leveling agent, 2.3 g of defoaming agent and 1.7 g of antioxidant were added into a container, and stirred at 1000 rpm for 45 min to obtain a flame retardant and UV resistant layer material.

[0027] This embodiment discloses a method for preparing a waterproof layer material, comprising the following steps: S1: 8.79 g of 3-aminodiphenyl ether and 30.14 g of perfluorooctyl ethyl iodide were added to a container, mixed evenly, heated to 140°C and refluxed with magnetic stirring for 16 h. After the reaction, dichloromethane was added, washed with deionized water for 3 times, the organic layer was dried with anhydrous magnesium sulfate, rotary evaporated, separated and purified, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 was used as an eluent to obtain intermediate A; S2: Under 2°C, add 11.21g of intermediate A to a container containing 30mL of dichloromethane, stir to dissolve, add 2.54mL of pyridine, continue stirring for 15min, then slowly drop 30mL of dichloromethane containing 18.45g of heptafluorobutyric anhydride into the container, control the dropping speed to 30 drops / min, after the dropwise addition is completed, stir at room temperature for 12h, after the reaction is completed, wash with deionized water, extract, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain intermediate B; S3: Under 5°C, 11.52g of intermediate B was added to a container containing 20mL of dichloromethane, and then 4.155g of anhydrous aluminum chloride was added for stirring, followed by slow dripping of 10mL of dichloromethane containing 1.17g of phthaloyl chloride, and the dripping speed was controlled to be 20 drops / min. After the dripping was completed, the mixture was stirred at room temperature for 12h. After the reaction was completed, the mixture was first washed 3 times with 0.5mol / L hydrochloric acid, and then washed 5 times with deionized water for purification. During the purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a waterproofing agent. S4: Add 13 g of waterproofing agent to 7 mL of N,N-dimethylacetamide, stir at room temperature for 12 h, and vacuum degas for 12 h to obtain a waterproof layer material.

[0028] This embodiment discloses a method for preparing a flame retardant tarpaulin material, which is characterized by comprising the following steps: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

[0029] Embodiment 3: This embodiment discloses a method for preparing a flame retardant and UV-resistant layer material, comprising the following steps: Q1: 0.3 g of sodium silk was added to a container containing 8 mL of tetrahydrofuran. Under an argon atmosphere, 0.21 g of diethyl phosphite was slowly added dropwise. The mixture was heated and stirred at 65°C until the sodium silk was completely dissolved. After the stirring, 12 mL of tetrahydrofuran containing 0.32 g of 1-chloromethyl-benzotriazole was slowly added dropwise to the container. After the addition was completed, the mixture was heated at 65°C for 10 h. After the reaction was completed, 45 mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane three times. The organic phases were combined, washed with saturated sodium chloride solution four times, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of dichloromethane and methanol with a volume ratio of 20:1 was used as an eluent to obtain compound 1. Q2: 0.51g of compound 1 was added to a container containing 22mL of tetrahydrofuran at 1°C. Under an argon atmosphere, 0.118g of sodium methoxide was slowly added to the container. After the addition was completed, the reaction was carried out at a low temperature of 1°C for 30min. Then, 4mL of tetrahydrofuran dissolved with 0.12g of p-aminobenzaldehyde was slowly added dropwise to the container. The reaction was heated to reflux at 60°C for 12h. After the reaction was completed, the temperature was lowered to 28°C. 45mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a flame retardant and UV-resistant agent. Q3: 50 g of acrylic resin, 8 g of flame retardant and UV resistant agent, 20 mL of tetrahydrofuran, 1.3 g of leveling agent, 2 g of defoaming agent and 1.3 g of antioxidant were added into a container, and stirred at 1000 rpm for 45 min to obtain a flame retardant and UV resistant layer material.

[0030] This embodiment discloses a method for preparing a waterproof layer material, comprising the following steps: S1: 7.4 g of 3-aminodiphenyl ether and 25.83 g of perfluorooctyl ethyl iodide were added to a container, mixed evenly, heated to 140°C and refluxed with magnetic stirring for 16 h. After the reaction was completed, dichloromethane was added, washed with deionized water for 3 times, the organic layer was dried with anhydrous magnesium sulfate, rotary evaporated, separated and purified, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 was used as an eluent to obtain intermediate A; S2: Under 2°C, add 10.19g of intermediate A to a container containing 30mL of dichloromethane, stir to dissolve, add 2.54mL of pyridine, continue stirring for 15min, then slowly drop 30mL of dichloromethane containing 16.4g of heptafluorobutyric anhydride into the container, control the dropping speed to 30 drops / min, after the dropwise addition is completed, stir at room temperature for 12h, after the reaction is completed, wash with deionized water, extract, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain intermediate B; S3: Under 5°C, 10.18g of intermediate B was added to a container containing 20mL of dichloromethane, and then 3.99g of anhydrous aluminum chloride was added for stirring, followed by slow dripping of 10mL of dichloromethane containing 1.015g of phthaloyl chloride, and the dripping speed was controlled to be 20 drops / min. After the dripping was completed, the mixture was stirred at room temperature for 12h. After the reaction was completed, the mixture was first washed 3 times with 0.5mol / L hydrochloric acid, and then washed 5 times with deionized water for purification. During the purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a waterproofing agent. S4: Add 10 g of waterproofing agent to 6 mL of N,N-dimethylacetamide, stir at room temperature for 12 h, and vacuum degas for 12 h to obtain a waterproof layer material.

[0031] This embodiment discloses a method for preparing a flame retardant tarpaulin material, which is characterized by comprising the following steps: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

[0032] Embodiment 4: This embodiment discloses a method for preparing a flame retardant and UV-resistant layer material, comprising the following steps: Q1: 0.62 g of sodium silk was added to a container containing 12 mL of tetrahydrofuran. Under an argon atmosphere, 0.35 g of diethyl phosphite was slowly added dropwise. The mixture was heated and stirred at 65°C until the sodium silk was completely dissolved. After the stirring, 9 mL of tetrahydrofuran containing 0.37 g of 1-chloromethyl-benzotriazole was slowly added dropwise to the container. After the addition was completed, the mixture was heated at 65°C for 10 h. After the reaction was completed, 55 mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane three times. The organic phases were combined, washed with saturated sodium chloride solution four times, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of dichloromethane and methanol with a volume ratio of 20:1 was used as an eluent to obtain compound 1. Q2: 0.566g of compound 1 was added to a container containing 18mL of tetrahydrofuran at 1°C. Under an argon atmosphere, 0.098g of sodium methoxide was slowly added to the container. After the addition was completed, the reaction was carried out at a low temperature of 1°C for 30min. Then, 6mL of tetrahydrofuran dissolved with 0.17g of p-aminobenzaldehyde was slowly added dropwise to the container. The reaction was heated to reflux at 60°C for 12h. After the reaction was completed, the temperature was lowered to 28°C. 55mL of distilled water was added to quench the reaction. The reaction was extracted with dichloromethane, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a flame retardant and UV-resistant agent. Q3: 70 g of acrylic resin, 14 g of flame retardant and UV resistant agent, 25 mL of tetrahydrofuran, 1 g of leveling agent, 2.6 g of defoaming agent and 2.1 g of antioxidant were added into a container, and stirred at 1000 rpm for 45 min to obtain a flame retardant and UV resistant layer material.

[0033] This embodiment discloses a method for preparing a waterproof layer material, comprising the following steps: S1: 10.18 g of 3-aminodiphenyl ether and 34.44 g of perfluorooctyl ethyl iodide were added to a container, mixed evenly, heated to 140°C and refluxed with magnetic stirring for 16 h. After the reaction, dichloromethane was added, washed with deionized water for 3 times, the organic layer was dried with anhydrous magnesium sulfate, rotary evaporated, separated and purified, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 was used as an eluent to obtain intermediate A; S2: Under 2°C, add 12.22g of intermediate A to a container containing 30mL of dichloromethane, stir to dissolve, add 2.54mL of pyridine, continue stirring for 15min, then slowly drop 30mL of dichloromethane containing 20.5g of heptafluorobutyric anhydride into the container, control the dropping speed to 30 drops / min, after the dropwise addition is completed, stir at room temperature for 12h, after the reaction is completed, wash with deionized water, extract, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain intermediate B; S3: Under 5°C, 12.86g of intermediate B was added to a container containing 20mL of dichloromethane, and then 4.32g of anhydrous aluminum chloride was added for stirring, followed by slow dripping of 10mL of dichloromethane containing 1.32g of phthaloyl chloride, and the dripping speed was controlled to be 20 drops / min. After the dripping was completed, the mixture was stirred at room temperature for 12h. After the reaction was completed, the mixture was first washed 3 times with 0.5mol / L hydrochloric acid, and then washed 5 times with deionized water for purification. During the purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a waterproofing agent. S4: Add 16 g of waterproofing agent to 8 mL of N,N-dimethylacetamide, stir at room temperature for 12 h, and vacuum degas for 12 h to obtain a waterproof layer material.

[0034] This embodiment discloses a method for preparing a flame retardant tarpaulin material, which is characterized by comprising the following steps: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

[0035] Embodiment 5: This embodiment discloses a method for preparing a flame retardant and UV-resistant layer material, comprising the following steps: Q1: 0.35 g of sodium silk was added to a container containing 9 mL of tetrahydrofuran. Under an argon atmosphere, 0.24 g of diethyl phosphite was slowly added dropwise. The mixture was heated and stirred at 65°C until the sodium silk was completely dissolved. After the stirring, 10 mL of tetrahydrofuran containing 0.35 g of 1-chloromethyl-benzotriazole was slowly added dropwise to the container. After the addition was completed, the mixture was heated at 65°C for 10 h. After the reaction was completed, 48 mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane three times. The organic phases were combined, washed with saturated sodium chloride solution four times, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of dichloromethane and methanol with a volume ratio of 20:1 was used as an eluent to obtain compound 1. Q2: 0.523g of compound 1 was added to a container containing 19mL of tetrahydrofuran at 1°C. Under an argon atmosphere, 0.101g of sodium methoxide was slowly added to the container. After the addition was completed, the reaction was carried out at a low temperature of 1°C for 30min. Then, 4.5mL of tetrahydrofuran dissolved with 0.13g of p-aminobenzaldehyde was slowly added dropwise to the container. The mixture was heated to reflux at 60°C for 12h. After the reaction was completed, the temperature was lowered to 28°C. 48mL of distilled water was added to quench the reaction. The mixture was extracted with dichloromethane, washed with saturated sodium chloride, dried with anhydrous sodium sulfate, distilled under reduced pressure, and purified by column chromatography. During the purification process, a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a flame retardant and UV-resistant agent. Q3: 55 g of acrylic resin, 9 g of flame retardant and UV resistant agent, 21 mL of tetrahydrofuran, 1.2 g of leveling agent, 2.1 g of defoaming agent and 1.5 g of antioxidant were added into a container, and stirred at 1000 rpm for 45 min to obtain a flame retardant and UV resistant layer material.

[0036] This embodiment discloses a method for preparing a waterproof layer material, comprising the following steps: S1: 7.92 g of 3-aminodiphenyl ether and 27.75 g of perfluorooctyl ethyl iodide were added to a container, mixed evenly, heated to 140°C and refluxed with magnetic stirring for 16 h. After the reaction was completed, dichloromethane was added, washed with deionized water for 3 times, the organic layer was dried with anhydrous magnesium sulfate, rotary evaporated, separated and purified, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 was used as an eluent to obtain intermediate A; S2: Under 2°C, add 10.83g of intermediate A to a container containing 30mL of dichloromethane, stir to dissolve, add 2.54mL of pyridine, continue stirring for 15min, then slowly drop 30mL of dichloromethane containing 17.3g of heptafluorobutyric anhydride into the container, control the dropping speed to 30 drops / min, after the dropwise addition is completed, stir at room temperature for 12h, after the reaction is completed, wash with deionized water, extract, dry with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain intermediate B; S3: Under 5°C, 10.93g of intermediate B was added to a container containing 20mL of dichloromethane, and then 4.03g of anhydrous aluminum chloride was added for stirring, followed by slow dripping of 10mL of dichloromethane containing 1.087g of phthaloyl chloride, and the dripping speed was controlled to be 20 drops / min. After the dripping was completed, the mixture was stirred at room temperature for 12h. After the reaction was completed, the mixture was first washed 3 times with 0.5mol / L hydrochloric acid, and then washed 5 times with deionized water for purification. During the purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 was used as an eluent to obtain a waterproofing agent. S4: Add 11 g of waterproofing agent to 7 mL of N,N-dimethylacetamide, stir at room temperature for 12 h, and vacuum degas for 12 h to obtain a waterproof layer material.

[0037] This embodiment discloses a method for preparing a flame retardant tarpaulin material, which is characterized by comprising the following steps: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

[0038] Comparative Example 1: Compared with Example 2, in Comparative Example 1, no flame retardant and UV resistant agent is added during the preparation of the flame retardant and UV resistant layer material, and other conditions remain unchanged.

[0039] Comparative Example 2: Compared with Example 2, in Comparative Example 2, no waterproofing agent is added during the preparation of the waterproof layer material, and other conditions remain unchanged.

[0040] Experimental Example: The samples prepared in Examples 2-5 and Comparative Examples 1-2 were subjected to performance tests. The waterproof performance of the samples was tested according to GB / T 4745-2012, the flame retardant performance of the samples was tested according to GB / T 5455-2014, and the aging resistance of the samples was tested according to GB / T 16422.2-2014. The test results are shown in Table 1: Table 1

[0041] When the water level is 0, it means that the entire sample surface is completely soaked; when the water level is 1, it means that the showered surface is completely wetted; when the water level is 1-2, it means that the sample surface is wetted beyond the spray point, and the wetting area exceeds half of the showered surface; when the water level is 2, it means that the sample surface is wetted beyond the spray point, and the wetting area is about half of the showered surface; when the water level is 2-3, it means that the sample surface is wetted beyond the spray point, and the wetting area is less than half of the showered surface; when the water level is 3, the sample surface is wetted at the spray point; when the water level is 3-4, the sample surface is wetted at equal to or less than half of the spray points; when the water level is 4, the sample surface is wetted at sporadic spray points; when the water level is 4-5, the sample surface is not wetted, but there are a small amount of water droplets; when the water level is 5, there are no water droplets or wetting on the sample surface. The higher the water level, the better the waterproof effect of the sample. From the test results in Table 1, it can be seen that the tarpaulins prepared in Examples 2-5 of the present invention have excellent waterproof performance, flame retardant performance and aging resistance. From the comparison between Comparative Example 1 and Examples 2-5, it can be seen that adding a flame retardant and UV-resistant agent can effectively improve the flame retardant and aging resistance of the tarpaulin; from the comparison between Comparative Example 2 and Examples 2-5, it can be seen that adding a waterproofing agent can effectively improve the waterproof performance of the tarpaulin.

[0042] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0043] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flame retardant tarpaulin material, characterized in that: The flame retardant tarpaulin material comprises an inner layer, a flame retardant UV resistant layer and a waterproof layer. The flame retardant UV resistant layer is evenly covered on both sides of the inner layer, and the surface of the flame retardant UV resistant layer is evenly covered with the waterproof layer. The inner layer material is composed of a polyethylene film, the flame retardant UV resistant layer material is prepared from nanosilk, diethyl phosphite, 1-chloromethylbenzotriazole, p-aminobenzaldehyde and acrylic resin, and the waterproof layer material is prepared from 3-aminodiphenyl ether, perfluorooctyl ethyl iodide, heptafluorobutyric anhydride and phthaloyl chloride.

2. The flame retardant tarpaulin material according to claim 1, characterized in that: The method for preparing the flame retardant and UV-resistant layer material comprises the following steps: Q1: Add sodium wire to a container containing tetrahydrofuran, slowly drop diethyl phosphite under argon atmosphere, heat and stir until the sodium wire is completely dissolved, slowly drop tetrahydrofuran containing 1-chloromethylbenzotriazole into the container after stirring, heat to react after the addition is complete, add distilled water to quench the reaction after the reaction is complete, extract, combine the organic phases, wash, dry, distill under reduced pressure, and purify by column chromatography to obtain compound 1; Q2: Compound 1 is added to a container containing tetrahydrofuran under low temperature, and sodium methoxide is slowly added to the container under argon atmosphere. After the addition is completed, react at low temperature, and then tetrahydrofuran dissolved with p-aminobenzaldehyde is slowly added dropwise to the container, heated under reflux for reaction, and after the reaction is completed, the temperature is lowered, distilled water is added to quench the reaction, extraction, washing, drying, vacuum distillation, and column chromatography purification are performed to obtain a flame retardant and UV-resistant agent; Q3: Add acrylic resin, flame retardant and UV resistant agent, tetrahydrofuran, leveling agent, defoaming agent and antioxidant into a container, stir and mix evenly to obtain a flame retardant and UV resistant layer material.

3. The flame retardant tarpaulin material according to claim 2, characterized in that: In the Q1, the dosage ratio of nanosilk, tetrahydrofuran, diethyl phosphite, 1-chloromethylbenzotriazole, tetrahydrofuran in which 1-chloromethylbenzotriazole is dissolved, and distilled water is (0.3-0.62) g: (8-12) mL: (0.21-0.35) g: (0.32-0.37) g: (9-12) mL: (45-55) mL, the heating and stirring temperature is 60-70°C, the heating reaction temperature is 60-70°C, the reaction time is 7-10 h, the product is extracted with dichloromethane 3-5 times, washed with saturated sodium chloride solution 2-4 times, and dried with anhydrous sodium sulfate. During the purification process, a mixed solution of dichloromethane and methanol in a volume ratio of (18-20): (0.8-1.2) is used as the eluent.

4. The flame retardant tarpaulin material according to claim 2, characterized in that: In Q2, the amount ratio of compound 1, tetrahydrofuran, sodium methoxide, p-aminobenzaldehyde, tetrahydrofuran for dissolving p-aminobenzaldehyde and distilled water is (0.51-0.566) g: (18-22) mL: (0.098-0.118) g: (0.12-0.17) g: (4-6) mL: (45-55) mL, the low temperature environment temperature is 0-1°C, the low temperature reaction temperature is 0-1°C, the reaction time is 30-45 min, the heating reflux reaction temperature is 50-70°C, the reaction time is 8-12 h, the temperature is lowered to 28-32°C, extracted with dichloromethane, washed with saturated sodium chloride, and dried with anhydrous sodium sulfate. During the purification process, a mixed solution of petroleum ether and ethyl acetate in a volume ratio of (4.5-5.2): (0.9-1.3) is used as the eluent.

5. The flame retardant tarpaulin material according to claim 2, characterized in that: In the Q3, the usage ratio of acrylic resin, flame retardant and UV resistant agent, tetrahydrofuran, leveling agent, defoaming agent and antioxidant is (50-70) g: (8-14) g: (20-25) mL: (1-1.3) g: (2-2.6) g: (1.3-2.1) g, the stirring speed is 800-1100 rpm, and the mixing time is 30-45 min.

6. The flame retardant tarpaulin material according to claim 1, characterized in that: The preparation method of the waterproof layer material comprises the following steps: S1: Add 3-aminodiphenyl ether and perfluorooctyl ethyl iodide into a container, mix well, heat and magnetically stir to reflux for reaction, add dichloromethane after the reaction is completed, wash, dry the organic layer, rotary evaporate, separate and purify to obtain intermediate A; S2: Under low temperature conditions, add intermediate A to a container filled with dichloromethane, stir to dissolve, then add pyridine, continue stirring, then slowly drop dichloromethane dissolved with heptafluorobutyric anhydride into the container, control the dropping speed, after the dropwise addition is completed, stir at room temperature for reaction, after the reaction is completed, wash, extract, dry, filter, and rotary evaporate to obtain intermediate B; S3: Under low temperature conditions, add the intermediate B to a container filled with dichloromethane, then add anhydrous aluminum chloride and stir, then slowly drop dichloromethane dissolved with phthaloyl chloride, control the dropping speed, and after the dropping is completed, stir and react at room temperature. After the reaction is completed, wash and purify to obtain a waterproofing agent; S4: Add the waterproofing agent to N,N-dimethylacetamide, stir at room temperature, and perform vacuum degassing to obtain a waterproof layer material.

7. The flame retardant tarpaulin material according to claim 6, characterized in that: In the S1, the molar ratio of 3-aminodiphenyl ether and perfluorooctylethyl iodide is (0.8-1.1): (0.9-1.2), the temperature of the heated magnetic stirring reflux reaction is 140-150°C, the reaction time is 14-18h, the reaction is washed with deionized water for 3-5 times, and the reaction is dried with anhydrous magnesium sulfate. During the separation and purification process, a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 10:1 is used as an eluent; in the S2, the low temperature environment temperature is 0-2°C, the molar ratio of the intermediate A and heptafluorobutyric anhydride is (1-1.2): (2.8-3.5), the stirring time is continued for 10-15min, the dripping speed is controlled to 30-40 drops / min, the stirring reaction time is 10-12h, the reaction is washed with deionized water, and the reaction is dried with anhydrous magnesium sulfate.

8. The flame retardant tarpaulin material according to claim 6, characterized in that: In the S3, the low temperature environment temperature is 2-5°C, the molar ratio of the intermediate B, anhydrous aluminum chloride and phthaloyl chloride is (0.95-1.2): (2.4-2.6): (0.48-0.52), the dripping speed is controlled to 20-30 drops / min, the reaction temperature is stirred at room temperature for 10-12h, first washed with 0.5mol / L hydrochloric acid 3-5 times, and then washed with deionized water 3-5 times, and a mixed solution of cyclohexane and ethyl acetate with a volume ratio of 5:1 is used as an eluent during the purification process.

9. The flame retardant tarpaulin material according to claim 6, characterized in that: In the S4, the usage ratio of the waterproofing agent and N,N-dimethylacetamide is (10-16) g: (6-8) mL, the stirring time at room temperature is 10-12 h, and the vacuum degassing time is 8-12 h.

10. A method for preparing a flame retardant tarpaulin material according to any one of claims 1 to 9, characterized in that: The following steps are involved: Step 1: evenly coating the flame retardant and UV resistant layer material on both sides of the polyethylene film, and drying to obtain a composite layer material; Step 2: Evenly apply the waterproof layer material to both sides of the composite layer material, dry it, and obtain a flame-retardant tarpaulin material.

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