Shading ultraviolet-proof tarpaulin material and preparation method thereof

Abstract

The invention relates to a shading ultraviolet-proof tarpaulin material and a preparation method thereof, and belongs to the technical field of tarpaulin materials, and the shading ultraviolet-proof tarpaulin material is prepared by the following steps: combining thiazolopyridine dicarboxylic acid with gallic acid, and then grafting polypropylene glycol monomethyl ether to obtain a plasticizing material; phosphonitrilic chloride trimer is combined with the plasticizing material, and the flame-retardant plasticizing material is obtained; graphene oxide is combined with a flame-retardant plasticizing material, so that an anti-ultraviolet auxiliary agent is obtained; the preparation method comprises the following steps: mixing an anti-ultraviolet auxiliary agent and polyvinyl chloride, melting, plasticizing and extruding, coating the mixture on the upper and lower surfaces of base cloth through curtain coating, cooling, sizing and coiling to finally prepare the shading and anti-ultraviolet tarpaulin material. According to the technical scheme, after the phosphonitrilic chloride trimer is combined with the plasticizing material, the graphene oxide is combined, and the prepared anti-ultraviolet auxiliary agent is added into the polyvinyl chloride, so that the mechanical property and the anti-ultraviolet property of a polyvinyl chloride matrix are improved, the flame retardant property of the polyvinyl chloride matrix is also improved, and the comprehensive performance of the tarpaulin material is overall improved.

Description

Technical Field

[0001] The invention belongs to the technical field of tarpaulin materials, and in particular, relates to a light-shielding and ultraviolet-proof tarpaulin material and a preparation method thereof. Background Art

[0002] Tarpaulin, also known as coated fabric, is a waterproof product made of polymer coated on the base fabric. It is mainly used in places that require waterproofing, dustproofing and barrier. An important use of tarpaulin is to cover and shield, such as covering automobile transportation and open-air warehouses. Therefore, in order to adapt to changing weather conditions and protect the covered objects from damage caused by sunlight, especially exposure to ultraviolet rays of various bands, it is necessary to improve the anti-ultraviolet and sun-resistant properties of tarpaulin, so that the covered objects can maintain their quality and not be damaged under long-term, high-intensity outdoor exposure. In order to enhance the anti-ultraviolet ability of tarpaulin, a layer of anti-ultraviolet coating is usually applied to the outer surface of the tarpaulin to reduce the effects of sunlight exposure and rain erosion.

[0003] Anti-UV additives are often used in anti-UV coatings to enhance the anti-UV performance. Commonly used anti-UV additives include silica, zinc oxide, aluminum oxide, etc. Although these inorganic materials have anti-UV properties, they usually require a higher amount of addition to achieve the ideal anti-UV effect, which will seriously affect the weight of the material itself. In addition, the commonly used matrix in anti-UV coatings is polyvinyl chloride. Due to the poor compatibility of these inorganic materials with the polyvinyl chloride matrix, it will also cause the mechanical properties of polyvinyl chloride to decline, thereby shortening the service life of the polyvinyl chloride tarpaulin. Summary of the invention

[0004] The object of the present invention is to provide a light-shielding and UV-proof tarpaulin material and a preparation method thereof. Thiazolopyridine dicarboxylic acid is combined with gallic acid, and then grafted with polypropylene glycol monomethyl ether to obtain a plasticizer. Thiazolopyridine dicarboxylic acid improves the UV protection and plasticization of polyvinyl chloride, and polypropylene glycol monomethyl ether increases the interface compatibility between polyvinyl chloride and the plasticizer. Hexachlorocyclotriphosphazene is combined with the plasticizer to obtain a flame-retardant plasticizer. The hexachlorocyclotriphosphazene not only improves the flame-retardant performance of polyvinyl chloride, but also provides a reaction for subsequent combination with graphene oxide. site; by combining graphene oxide with flame retardant plasticizer, an anti-UV agent is obtained, which improves the mechanical properties of polyvinyl chloride and has a synergistic anti-UV effect with the flame retardant plasticizer; after the anti-UV agent and polyvinyl chloride are mixed, they are melt-plasticized and extruded, and then coated on the upper and lower surfaces of the base fabric by casting, cooled and shaped, and wound up to finally obtain a light-shielding and anti-UV tarpaulin material. The anti-UV agent improves the mechanical properties, flame retardant properties and anti-UV properties of the polyvinyl chloride tarpaulin, thereby improving the comprehensive performance of the tarpaulin material as a whole and extending the service life of the tarpaulin.

[0005] The technical problem to be solved by the present invention is that anti-ultraviolet additives are often used in anti-ultraviolet coatings to enhance the anti-ultraviolet performance. Commonly used anti-ultraviolet additives include silicon dioxide, zinc oxide, aluminum oxide, etc. Although these inorganic materials have anti-ultraviolet performance, they usually require a higher addition amount to achieve the ideal anti-ultraviolet effect, which will seriously affect the weight of the material itself. In addition, the commonly used matrix in anti-ultraviolet coatings is polyvinyl chloride. Due to the poor compatibility of these inorganic materials with the polyvinyl chloride matrix, the mechanical properties of polyvinyl chloride will also be reduced, thereby shortening the service life of the polyvinyl chloride tarpaulin, and therefore it is limited in practical applications.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing a light-shielding and UV-proof tarpaulin material comprises the following steps:

[0008] S1: combining thiazolylpyridine dicarboxylic acid with gallic acid, and then grafting polypropylene glycol monomethyl ether to obtain a plasticized material;

[0009] S2: combining hexachlorocyclotriphosphazene with a plasticizer to obtain a flame retardant plasticizer;

[0010] S3: Obtaining an anti-ultraviolet additive by combining graphene oxide with a flame retardant plasticizer;

[0011] S4: After the anti-ultraviolet additive and polyvinyl chloride are mixed, they are melt-plasticized and extruded, coated on the upper and lower surfaces of the base fabric by casting, cooled and shaped, and rolled up, and finally a light-shielding and anti-ultraviolet tarpaulin material is obtained.

[0012] Further, in step S1, the plasticized material comprises the following steps to be prepared:

[0013] A1: Thiazolopyridinedicarboxylic acid, gallic acid, p-toluenesulfonic acid monohydrate and toluene are mixed, and then heated in an oil bath at 145-155° C. overnight to azeotropically remove water in the esterification reaction, toluene and unreacted gallic acid are removed by rotary evaporation, and the crude product is purified by column chromatography using dichloromethane as an eluent to obtain product A, wherein the amount ratio of thiazolopyridinedicarboxylic acid, gallic acid, p-toluenesulfonic acid monohydrate and toluene is 4.8-4.9 g:7.8-7.9 g:0.05-0.1 g:45-55 mL;

[0014] A2: Product A, polypropylene glycol monomethyl ether, p-toluenesulfonic acid and cyclohexane are mixed, the mixture is stirred evenly and heated at 90-120° C. for 9-11 hours, cyclohexane and excess polypropylene glycol monomethyl ether are removed by reduced pressure distillation, and then the remaining mixture is neutralized with an aqueous NaOH solution to a pH value of 7-7.5, and excess water is removed by reduced pressure distillation to finally obtain a plasticizer, wherein the amount ratio of product A, polypropylene glycol monomethyl ether, p-toluenesulfonic acid and cyclohexane is 8.4-8.6g:36.9-37.1g:0.05-0.1g:3.3-3.5g.

[0015] In the above reaction process, both ends of thiazolylpyridine dicarboxylic acid have carboxyl groups, gallic acid has three hydroxyl groups and one carboxyl group, the carboxyl groups at both ends of thiazolylpyridine dicarboxylic acid are respectively combined with the hydroxyl groups on gallic acid through esterification reaction, and gallic acid is combined with thiazolylpyridine dicarboxylic acid to obtain product A; polypropylene glycol monomethyl ether has a hydroxyl group, the carboxyl group on gallic acid in product A can be combined with the hydroxyl group on polypropylene glycol monomethyl ether, and polypropylene glycol monomethyl ether is grafted onto product A to finally obtain a plasticizer.

[0016] Furthermore, the polypropylene glycol monomethyl ether is one of propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether.

[0017] Furthermore, the thiazolopyridine dicarboxylic acid is prepared by the following steps:

[0018] 19.1 g of citric acid, 12.1 g of L-cysteine ​​and 100 mL of deionized water were mixed. After the citric acid and L-cysteine ​​were completely dissolved, the mixture was dried at 140° C. overnight and cooled at room temperature. The crude product was crushed, washed with 100 mL of deionized water and filtered, and then vacuum dried at 80° C. for 24 h to obtain thiazolylpyridinedicarboxylic acid.

[0019] In the above reaction process, citric acid has a carboxyl group, and L-cysteine ​​has an amino group and a sulfhydryl bond. Under high temperature conditions, citric acid and L-cysteine ​​undergo multiple dehydration to finally obtain thiazolylpyridinedicarboxylic acid with carboxyl groups at both ends.

[0020] Further, in step S2, the flame retardant plasticized material is prepared by the following steps:

[0021] The plasticizer, hexachlorocyclotriphosphazene and benzyltriethylammonium chloride are mixed and reacted at 95-105°C for 3-5h, then cooled to 25-35°C, and then an aqueous NaOH solution is added and the reaction is continued for 0.5-1.5h. The mixture is washed with deionized water until the pH value is 7-7.5, and the excess hexachlorocyclotriphosphazene and water are removed by reduced pressure distillation to obtain a flame retardant plasticizer, wherein the amount ratio of the plasticizer, hexachlorocyclotriphosphazene, benzyltriethylammonium chloride and the aqueous NaOH solution is 1.5-2g:18-18.5g:0.9-1.1g:150-170mL.

[0022] In the above reaction process, hexachlorocyclotriphosphazene has six chlorine atoms, and the chlorine atoms on the hexachlorocyclotriphosphazene can combine with the hydroxyl groups on the gallic acid in the plasticizer through a substitution reaction, so that the hexachlorocyclotriphosphazene is grafted onto the plasticizer, and finally a flame-retardant plasticizer is obtained.

[0023] Furthermore, in step S3, the anti-ultraviolet auxiliary agent is prepared by the following steps:

[0024] Graphene oxide and a flame retardant plasticizer are mixed and dispersed in tetrahydrofuran, and then NaOH dispersed in tetrahydrofuran is added, the mixture is dispersed in an ultrasonic water bath for 1.5-2.5 hours, refluxed in an oil bath at 65-75° C. and in a dry nitrogen atmosphere for 22-24 hours, filtered, washed with tetrahydrofuran and acetone in sequence to remove unreacted flame retardant plasticizer, and then vacuum dried at 75-85° C. to finally obtain an anti-ultraviolet additive, wherein the amount ratio of graphene oxide, flame retardant plasticizer and NaOH is 0.9-1.1 g: 0.9-1.1 g: 0.4-0.6 g.

[0025] During the above reaction process, graphene oxide has hydroxyl groups and carboxyl groups, and the chlorine atoms on the hexachlorocyclotriphosphazene in the flame retardant plasticizer can combine with the carboxyl groups on the graphene oxide through a substitution reaction, so that the graphene oxide and the flame retardant plasticizer are combined together, and finally an anti-ultraviolet additive is obtained, thereby improving the anti-ultraviolet performance of polyvinyl chloride.

[0026] Furthermore, in step S4, the light-shielding and UV-proof tarpaulin material is prepared by the following steps:

[0027] After the polyvinyl chloride and the anti-ultraviolet additive are mixed, they are melt-plasticized and extruded, and then cast on the upper and lower surfaces of the base fabric at a melt temperature of 190-230°C, and then cooled and shaped at 70-120°C, and rolled up, and finally the light-shielding and anti-ultraviolet tarpaulin material is obtained.

[0028] Furthermore, the base fabric is made of polyester fiber woven fabric, which is formed by interweaving warp yarns and weft yarns.

[0029] Furthermore, the warp yarns and weft yarns are both made of polyester filaments.

[0030] Beneficial effects of the present invention:

[0031] (1) In the technical scheme of the present invention, thiazolylpyridine dicarboxylic acid is combined with gallic acid, and then grafted with polypropylene glycol monomethyl ether to obtain a plasticizer; thiazolylpyridine dicarboxylic acid is obtained by multiple dehydration of citric acid and cysteine. Due to its thiazolylpyridine conjugated structure, it has a strong ultraviolet absorption ability, which can improve the ultraviolet protection performance of polyvinyl chloride. Thiazolopyridine dicarboxylic acid can also be used as a plasticizer to plasticize polyvinyl chloride and enhance its thermal stability and migration resistance. Combining gallic acid and thiazolylpyridine dicarboxylic acid can not only enhance its mechanical properties and thermal stability, but also provide a carboxyl group for grafting polypropylene glycol monomethyl ether. Polypropylene glycol monomethyl ether is grafted onto gallic acid. The methylethoxy unit in polypropylene glycol monomethyl ether can improve the plasticization and migration resistance of polyvinyl chloride, and can increase the strong interaction with the polyvinyl chloride skeleton, thereby improving the compatibility between the plasticizer and polyvinyl chloride. Hexachlorocyclotriphosphazene is combined with a plasticizer to obtain a flame-retardant plasticizer. Hexachlorocyclotriphosphazene, as a flame retardant, combined with a plasticizer can further improve the flame retardant properties of polyvinyl chloride and enhance the thermal stability of polyvinyl chloride. It also provides a reaction site for subsequent combination with graphene oxide. The plasticizer also increases the interface compatibility between hexachlorocyclotriphosphazene and polyvinyl chloride.

[0032] (2) In the technical solution of the present invention, an anti-ultraviolet additive is obtained by combining graphene oxide with a flame retardant plasticizer; the combination of hexachlorocyclotriphosphazene in the flame retardant plasticizer and graphene oxide can not only further improve the flame retardant properties of polyvinyl chloride, but also improve the mechanical properties of polyvinyl chloride. Hexachlorocyclotriphosphazene also increases the dispersibility of graphene oxide, improves its compatibility with polyvinyl chloride, and graphene oxide, as an inorganic material for ultraviolet absorption, also has good anti-ultraviolet ability. Graphene oxide and thiazolylpyridine dicarboxylic acid play a synergistic role in improving the anti-ultraviolet performance of polyvinyl chloride. After the anti-ultraviolet additive and polyvinyl chloride are mixed, they are melt-plasticized and extruded, and coated on the upper and lower surfaces of the base fabric by casting, cooled and shaped, and rolled up, and finally a light-shielding and anti-ultraviolet tarpaulin material is obtained; the anti-ultraviolet additive is added to polyvinyl chloride, has good dispersibility, improves its interface compatibility with polyvinyl chloride, and enhances the anti-ultraviolet performance of the polyvinyl chloride tarpaulin.

[0033] (3) In the technical scheme of the present invention, thiazolylpyridine dicarboxylic acid is combined with gallic acid, then grafted with polypropylene glycol monomethyl ether, then combined with hexachlorocyclotriphosphazene, and finally combined with graphene oxide to obtain an anti-ultraviolet additive. After mixing with polyvinyl chloride, it is coated on a base fabric by cast film, cooled and shaped, and rolled up to finally obtain a light-shielding and anti-ultraviolet tarpaulin material. The anti-ultraviolet additive improves the anti-ultraviolet performance, mechanical properties and flame retardant properties of the polyvinyl chloride tarpaulin, thereby improving the overall performance of the tarpaulin material, extending the service life of the tarpaulin, and expanding its application range. DETAILED DESCRIPTION

[0034] 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 creative work are within the scope of protection of the present invention.

[0035] The specific parameters of the raw materials used in the present invention are as follows:

[0036] The polyester fiber woven fabric has a warp and weft specification of 30 tex, a warp density of 280 yarns / 10 cm, and a weft density of 200 yarns / 10 cm; the average polymerization degree of polyvinyl chloride is 500-800, the apparent density is 0.27 g / mL, the volatility is 0.2%, and the whiteness is 85% (160°C, 8 min), which was purchased from Qianxian Chemical Co., Ltd.

[0037] Thiazolopyridinedicarboxylic acid comprises the following steps to prepare:

[0038] 19.1 g of citric acid, 12.1 g of L-cysteine ​​and 100 mL of deionized water were mixed. After the citric acid and L-cysteine ​​were completely dissolved, the mixture was dried at 140° C. overnight and cooled at room temperature. The crude product was crushed, washed with 100 mL of deionized water and filtered, and then vacuum dried at 80° C. for 24 h to obtain thiazolylpyridinedicarboxylic acid.

[0039] Example 1

[0040] The plasticized material comprises the following steps to prepare:

[0041] A1: 4.8 g of thiazolopyridinedicarboxylic acid, 7.8 g of gallic acid, 0.05 g of p-toluenesulfonic acid monohydrate and 45 mL of toluene were mixed, and then heated in an oil bath at 145° C. overnight to azeotropically remove water in the esterification reaction, toluene and unreacted gallic acid were removed by rotary evaporation, and the crude product was purified by column chromatography using 50 mL of dichloromethane as an eluent (flow rate of 5 mL / min) to obtain product A;

[0042] A2: 8.4 g of product A, 36.9 g of propylene glycol monomethyl ether, 0.05 g of p-toluenesulfonic acid and 3.3 g of cyclohexane were mixed, the mixture was stirred evenly and heated at 90°C for 9 hours, cyclohexane and excess polypropylene glycol monomethyl ether were removed by reduced pressure distillation, and then the remaining mixture was neutralized with a NaOH aqueous solution with a mass concentration of 0.1 mol / L to a pH value of 7, and excess water was removed by reduced pressure distillation to finally obtain a plasticized material.

[0043] Example 2

[0044] The plasticized material comprises the following steps to prepare:

[0045] A1: 4.85 g of thiazolopyridinedicarboxylic acid, 7.85 g of gallic acid, 0.08 g of p-toluenesulfonic acid monohydrate and 50 mL of toluene were mixed, and then heated in an oil bath at 150° C. overnight to azeotropically remove water in the esterification reaction, toluene and unreacted gallic acid were removed by rotary evaporation, and the crude product was purified by column chromatography using 50 mL of dichloromethane as an eluent (flow rate of 5 mL / min) to obtain product A;

[0046] A2: 8.5 g of product A, 37 g of tripropylene glycol monomethyl ether, 0.08 g of p-toluenesulfonic acid and 3.4 g of cyclohexane were mixed, the mixture was stirred evenly and heated at 110°C for 10 h, cyclohexane and excess polypropylene glycol monomethyl ether were removed by reduced pressure distillation, and then the remaining mixture was neutralized with a NaOH aqueous solution with a mass concentration of 0.1 mol / L to a pH value of 7.3, and excess water was removed by reduced pressure distillation to finally obtain a plasticized material.

[0047] Example 3

[0048] The plasticized material comprises the following steps to prepare:

[0049] A1: 4.9 g of thiazolopyridinedicarboxylic acid, 7.9 g of gallic acid, 0.1 g of p-toluenesulfonic acid monohydrate and 55 mL of toluene were mixed, and then heated in an oil bath at 155° C. overnight to azeotropically remove water in the esterification reaction, toluene and unreacted gallic acid were removed by rotary evaporation, and the crude product was purified by column chromatography using 50 mL of dichloromethane as eluent (flow rate of 5 mL / min) to obtain product A;

[0050] A2: 8.6 g of product A, 37.1 g of dipropylene glycol monomethyl ether, 0.1 g of p-toluenesulfonic acid and 3.5 g of cyclohexane were mixed, the mixture was stirred evenly and heated at 120°C for 11 hours, cyclohexane and excess polypropylene glycol monomethyl ether were removed by reduced pressure distillation, and then the remaining mixture was neutralized with a NaOH aqueous solution with a mass concentration of 0.1 mol / L to a pH value of 7.5, and excess water was removed by reduced pressure distillation to finally obtain a plasticized material.

[0051] Example 4

[0052] The flame retardant plasticized material comprises the following steps:

[0053] 1.5 g of the plasticizer prepared in Example 1, 18 g of hexachlorocyclotriphosphazene and 0.9 g of benzyltriethylammonium chloride were mixed and reacted at 95° C. for 3 h, then cooled to 25° C., 150 mL of a 0.1 mol / L NaOH aqueous solution was added, and the reaction was continued for 0.5 h. The mixture was washed with deionized water until the pH value was 7, and the excess hexachlorocyclotriphosphazene and water were removed by reduced pressure distillation to obtain a flame retardant plasticizer.

[0054] Example 5

[0055] The flame retardant plasticized material comprises the following steps:

[0056] 1.8 g of the plasticizer prepared in Example 2, 18.4 g of hexachlorocyclotriphosphazene and 1 g of benzyltriethylammonium chloride were mixed and reacted at 100° C. for 4 h, then cooled to 30° C., 160 mL of a 0.1 mol / L NaOH aqueous solution was added, and the reaction was continued for 1 h. The mixture was washed with deionized water until the pH value was 7.3, and the excess hexachlorocyclotriphosphazene and water were removed by reduced pressure distillation to obtain a flame retardant plasticizer.

[0057] Example 6

[0058] The flame retardant plasticized material comprises the following steps:

[0059] 2 g of the plasticizer prepared in Example 3, 18.5 g of hexachlorocyclotriphosphazene and 1.1 g of benzyltriethylammonium chloride were mixed and reacted at 105° C. for 5 h, then cooled to 35° C., 170 mL of a 0.1 mol / L NaOH aqueous solution was added, and the reaction was continued for 1.5 h. The mixture was washed with deionized water until the pH value was 7.5, and the excess hexachlorocyclotriphosphazene and water were removed by reduced pressure distillation to obtain a flame retardant plasticizer.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 6 is that the plasticized material prepared in Example 3 is replaced by the product A obtained in step A1 of Example 3, and the remaining steps and raw materials are the same as those in Example 6.

[0062] Comparative Example 2

[0063] The difference between this comparative example and Example 6 is that the plasticizer prepared in Example 3 is replaced by the thiazolyl pyridine dicarboxylic acid in step A1 of Example 3, and the remaining steps and raw materials are the same as those in Example 6.

[0064] Comparative Example 3

[0065] The difference between this comparative example and Example 6 is that the mass of the plasticizer prepared in Example 3 is replaced by gallic acid in step A1 of Example 3, and the remaining steps and raw materials are the same as those in Example 6.

[0066] Example 7

[0067] The anti-ultraviolet auxiliary agent comprises the following steps to prepare:

[0068] 0.9 g of graphene oxide and 0.9 g of the flame retardant plasticizer prepared in Example 4 were mixed and dispersed in 190 mL of tetrahydrofuran, and then 0.4 g of NaOH dispersed in 90 mL of tetrahydrofuran was added, and the mixture was dispersed in an ultrasonic water bath for 1.5 h (the power of the ultrasonic wave was 150 W and the frequency was 20 kHz), refluxed in an oil bath at 65 ° C and a dry nitrogen atmosphere for 22 h, filtered, washed with 50 mL of tetrahydrofuran and 50 mL of acetone in turn to remove unreacted flame retardant plasticizer, and then vacuum dried at 75 ° C to finally obtain an anti-UV additive.

[0069] Example 8

[0070] The anti-ultraviolet auxiliary agent comprises the following steps to prepare:

[0071] 1 g of graphene oxide and 1 g of the flame retardant plasticizer prepared in Example 5 were mixed and dispersed in 200 mL of tetrahydrofuran, and then 0.5 g of NaOH dispersed in 100 mL of tetrahydrofuran was added, and the mixture was dispersed in an ultrasonic water bath for 2 h (the power of the ultrasonic wave was 150 W and the frequency was 20 kHz), refluxed in an oil bath at 70° C. and in a dry nitrogen atmosphere for 23 h, filtered, washed with 50 mL of tetrahydrofuran and 50 mL of acetone in turn to remove unreacted flame retardant plasticizer, and then vacuum dried at 80° C. to finally obtain an anti-UV additive.

[0072] Example 9

[0073] The anti-ultraviolet auxiliary agent comprises the following steps to prepare:

[0074] 1.1 g of graphene oxide and 1.1 g of the flame retardant plasticizer prepared in Example 6 were mixed and dispersed in 210 mL of tetrahydrofuran, and then 0.6 g of NaOH dispersed in 110 mL of tetrahydrofuran was added, and the mixture was dispersed in an ultrasonic water bath for 2.5 h (the power of the ultrasonic wave was 150 W and the frequency was 20 kHz), refluxed in an oil bath at 75 ° C and a dry nitrogen atmosphere for 24 h, filtered, washed with 50 mL of tetrahydrofuran and 50 mL of acetone in turn to remove unreacted flame retardant plasticizer, and then vacuum dried at 85 ° C to finally obtain an anti-UV additive.

[0075] Comparative Example 4

[0076] The difference between this comparative example and Example 9 is that the flame retardant plasticized material prepared in Example 6 is replaced by the material prepared in Comparative Example 1, and the remaining steps and raw materials are the same as those in Example 9.

[0077] Comparative Example 5

[0078] The difference between this comparative example and Example 9 is that the flame retardant plasticized material prepared in Example 6 is replaced by the material prepared in Comparative Example 2, and the remaining steps and raw materials are the same as those in Example 9.

[0079] Comparative Example 6

[0080] The difference between this comparative example and Example 9 is that the flame retardant plasticized material prepared in Example 6 is replaced by the material prepared in Comparative Example 3, and the remaining steps and raw materials are the same as those in Example 9.

[0081] Comparative Example 7

[0082] The difference between this comparative example and Example 9 is that the flame retardant plasticized material prepared in Example 6 is replaced by the plasticized material prepared in Example 3, and the remaining steps and raw materials are the same as those in Example 9.

[0083] Example 10

[0084] The light-shielding and UV-proof tarpaulin material is prepared by the following steps:

[0085] 80g of polyvinyl chloride and 20g of the anti-ultraviolet additive prepared in Example 7 were mixed, melt-plasticized and extruded, and cast on the upper and lower surfaces of the polyester fiber woven fabric at a melt temperature of 190°C, and then cooled and shaped with a cooling roller at 70°C and wound up to finally obtain a light-shielding and anti-ultraviolet tarpaulin material.

[0086] Embodiment 11

[0087] The light-shielding and UV-proof tarpaulin material is prepared by the following steps:

[0088] 90g of polyvinyl chloride and 25g of the anti-ultraviolet additive prepared in Example 8 were mixed, melt-plasticized and extruded, and cast on the upper and lower surfaces of the polyester base cloth at a melt temperature of 210°C. Then, the mixture was cooled and shaped with a cooling roller at 90°C, and then rolled up to obtain a light-shielding and anti-ultraviolet tarpaulin material.

[0089] Example 12

[0090] The light-shielding and UV-proof tarpaulin material is prepared by the following steps:

[0091] 100g of polyvinyl chloride and 30g of the anti-ultraviolet additive prepared in Example 9 were mixed, melt-plasticized and extruded, and cast on the upper and lower surfaces of the polyester base cloth at a melt temperature of 235°C. Then, the mixture was cooled and shaped with a cooling roller at 120°C, and then rolled up to obtain a light-shielding and anti-ultraviolet tarpaulin material.

[0092] Comparative Example 8

[0093] The difference between this comparative example and Example 12 is that the anti-ultraviolet additive prepared in Example 9 is replaced by the substance prepared in Comparative Example 4, and the remaining steps and raw materials are the same as Example 12.

[0094] Comparative Example 9

[0095] The difference between this comparative example and Example 12 is that the anti-ultraviolet auxiliary agent prepared in Example 9 is replaced by the substance prepared in Comparative Example 5, and the remaining steps and raw materials are synchronized with Example 12.

[0096] Comparative Example 10

[0097] The difference between this comparative example and Example 12 is that the anti-ultraviolet auxiliary agent prepared in Example 9 is replaced by the substance prepared in Comparative Example 6, and the remaining steps and raw materials are synchronized with Example 12.

[0098] Comparative Example 11

[0099] The difference between this comparative example and Example 12 is that the anti-ultraviolet auxiliary agent prepared in Example 9 is replaced by the substance prepared in Comparative Example 7, and the remaining steps and raw materials are synchronized with Example 12.

[0100] Comparative Example 12

[0101] The difference between this comparative example and Example 12 is that the anti-ultraviolet additive prepared in Example 9 is replaced by the flame retardant plasticizer in Example 6, and the remaining steps and raw materials are the same as Example 12.

[0102] The light-shielding and UV-proof tarpaulin materials prepared in Examples 10-12 and Comparative Examples 8-12 were tested for UV protection, flame retardancy and tear strength, wherein the tear strength was measured using the GB / T3917.3-2009 standard; the flame retardancy was measured using the UL 94 test method; the UV protection was tested using an ultraviolet aging experiment in accordance with IEC 61646:2008, with the UVB (280-320nm) energy in the metal halide lamp accounting for 3-10% of the total energy, and the lamp irradiance being 180W / m 2 The light-shielding and UV-proof tarpaulin materials prepared in Examples 10-12 and Comparative Examples 8-12 were made into samples of certain sizes and placed in an UV metal halide lamp aging box for UV irradiation. The total irradiation energy was 30, 90, 150, and 180 kWh / m 2After the sample aging is completed, the yellow index test is performed. The test results are shown in Tables 1 and 2 below:

[0103] Table 1

[0104]

[0105]

[0106] Table 2

[0107]

[0108]

[0109] It can be seen from the data in Table 1 and Table 2 above that, by comparing Comparative Examples 8-10 with Example 12, it can be seen that the test results of the light-shielding and UV-proof tarpaulin material prepared without adding polypropylene glycol monomethyl ether or gallic acid or without adding thiazolyl pyridine dicarboxylic acid are worse than those of Example 12, indicating that after combining thiazolyl pyridine dicarboxylic acid with gallic acid and then grafting polypropylene glycol monomethyl ether, the compatibility between the plasticizer and polyvinyl chloride can be increased, and the UV protection and mechanical properties of polyvinyl chloride can be further improved;

[0110] From the comparison between Comparative Example 11 and Example 12, it can be seen that the light-shielding and UV-proof tarpaulin material is prepared by using a plasticizer without grafting hexachlorocyclotriphosphazene, which indicates that grafting hexachlorocyclotriphosphazene onto the plasticizer can increase the compatibility between the plasticizer and polyvinyl chloride, and further improve the flame retardant properties and mechanical properties of polyvinyl chloride.

[0111] By comparing Comparative Example 12 and Example 12, it can be seen that the light-shielding and UV-proof tarpaulin material is prepared by using a flame-retardant plasticizer that is not combined with graphene oxide, which indicates that combining graphene oxide with a flame-retardant plasticizer can better disperse graphene oxide and increase the compatibility between graphene oxide and polyvinyl chloride, and that graphene oxide and thiazolylpyridine dicarboxylic acid have a synergistic effect on the UV protection performance of polyvinyl chloride, thereby further improving the mechanical properties, flame retardant properties and UV protection performance of the polyvinyl chloride tarpaulin.

[0112] It can be seen from Table 1 and Table 2 above that the light-shielding and UV-proof tarpaulin materials prepared in Examples 10-12 are compared with Comparative Examples 8-12. The anti-ultraviolet additive is obtained by combining thiazolylpyridine dicarboxylic acid with gallic acid, then grafting polypropylene glycol monomethyl ether, then combining with hexachlorocyclotriphosphazene, and finally combining with graphene oxide. The anti-ultraviolet additive is mixed with polyvinyl chloride, and then coated on the base fabric by cast coating, cooled and shaped, and rolled up to finally obtain the light-shielding and UV-proof tarpaulin material. The mechanical properties, flame retardant properties and UV protection properties of the tarpaulin material are improved as a whole, and the test performance requirements are met. The light-shielding and UV-proof tarpaulin materials prepared in Comparative Examples 8-12 do not meet the performance requirements. The light-shielding and UV-proof tarpaulin material prepared by the present invention not only has good mechanical properties and UV protection properties, but also has good flame retardant properties, improves the comprehensive performance of the tarpaulin material, and extends the service life of the tarpaulin.

[0113] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0114] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing a light-shielding and UV-proof tarpaulin material, characterized in that: The following steps are involved: S1: combining thiazolylpyridine dicarboxylic acid with gallic acid, and then grafting polypropylene glycol monomethyl ether to obtain a plasticized material; S2: combining hexachlorocyclotriphosphazene with a plasticizer to obtain a flame retardant plasticizer; S3: Obtaining an anti-ultraviolet additive by combining graphene oxide with a flame retardant plasticizer; S4: After the anti-ultraviolet additive and polyvinyl chloride are mixed, they are melt-plasticized and extruded, coated on the upper and lower surfaces of the base fabric by casting, cooled and shaped, and rolled up, and finally a light-shielding and anti-ultraviolet tarpaulin material is obtained.

2. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 1, characterized in that: Step S1 is specifically: A1: Thiazolopyridinedicarboxylic acid, gallic acid, p-toluenesulfonic acid monohydrate and toluene were mixed, and then heated in an oil bath at 145-155° C. overnight. After rotary evaporation, the crude product was purified with dichloromethane to obtain product A; A2: Product A, polypropylene glycol monomethyl ether, p-toluenesulfonic acid and cyclohexane are mixed, the mixture is stirred evenly and heated at 90-120° C. for 9-11 hours, and after vacuum distillation, the remaining mixture is neutralized with an aqueous NaOH solution to a pH value of 7-7.5, and excess water is removed by vacuum distillation to obtain a plasticized material.

3. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 2, characterized in that: In step A1, the usage ratio of thiazolyl pyridine dicarboxylic acid, gallic acid, p-toluenesulfonic acid monohydrate and toluene is 4.8-4.9 g: 7.8-7.9 g: 0.05-0.1 g: 45-55 mL; in step A2, the usage ratio of product A, polypropylene glycol monomethyl ether, p-toluenesulfonic acid and cyclohexane is 8.4-8.6 g: 36.9-37.1 g: 0.05-0.1 g: 3.3-3.5 g.

4. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 1, characterized in that: Step S2 is specifically as follows: The plasticizer, hexachlorocyclotriphosphazene and benzyltriethylammonium chloride are mixed and reacted at 95-105°C for 3-5h, then cooled to 25-35°C, and then an aqueous NaOH solution is added and the reaction is continued for 0.5-1.5h. The mixture is washed with deionized water until the pH value is 7-7.5, and finally a flame retardant plasticizer is obtained by vacuum distillation.

5. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 4, characterized in that: The usage ratio of the plasticizer, hexachlorocyclotriphosphazene, benzyltriethylammonium chloride and NaOH aqueous solution is 1.5-2g:18-18.5g:0.9-1.1g:150-170mL.

6. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 1, characterized in that: Step S3 is specifically as follows: The graphene oxide and the flame retardant plasticizer are mixed and dispersed in tetrahydrofuran, and then NaOH dispersed in tetrahydrofuran is added, the mixture is dispersed in an ultrasonic water bath for 1.5-2.5 hours, refluxed in an oil bath under a dry nitrogen atmosphere at 65-75° C. for 22-24 hours, filtered, washed with tetrahydrofuran and acetone in sequence, and then vacuum dried at 75-85° C. to finally obtain an anti-ultraviolet additive.

7. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 6, characterized in that: The usage ratio of graphene oxide, flame retardant plasticizer and NaOH is 0.9-1.1g: 0.9-1.1g: 0.4-0.6g.

8. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 1, characterized in that: Step S4 is specifically as follows: After the polyvinyl chloride and the anti-ultraviolet additive are mixed, they are melt-plasticized and extruded, and then cast on the upper and lower surfaces of the base fabric at a melt temperature of 190-230°C, and then cooled and shaped at 70-120°C, and rolled up, and finally the light-shielding and anti-ultraviolet tarpaulin material is obtained.

9. The method for preparing a light-shielding and UV-proof tarpaulin material according to claim 8, characterized in that: The base fabric is made of polyester fiber woven fabric, which is formed by interweaving warp yarns and weft yarns.

10. A light-shielding and UV-proof tarpaulin material prepared by the preparation method according to any one of claims 1 to 9.

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