Fireproof and flame-retardant polyester fabric and preparation process thereof

Abstract

The present application relates to the field of textile fabric, in particular to a fireproof and flame-retardant polyester fabric and a preparation process thereof, wherein polyvinyl alcohol, modified hybrid molybdenum disulfide and sodium alginate are used to prepare flame-retardant fibers by electrospinning, the flame-retardant fibers are mixed with polyester fibers, and then impregnation finishing is performed, and modified hybrid molybdenum disulfide and self-repairing water-based polyurethane emulsion are used to prepare a protective finishing solution; hybrid molybdenum disulfide is generated from carbon nanotubes, hexadecyl trimethyl ammonium bromide, molybdenum ammonium sulfate tetrahydrate and thiourea, perylene tetraanhydride is deposited on the surface of the hybrid molybdenum disulfide, and then methylsilicic acid trihydroxymethyl methylamine cage ester is grafted; in the preparation of the self-repairing water-based polyurethane emulsion, 2-amino-5-(2-hydroxyethyl)-6-methyl pyrimidine-4-ol containing multiple hydrogen bonds, polytetrahydrofuran and isophorone diisocyanate are used to prepare a prepolymer, bis(2-hydroxyethyl) disulfide is introduced as a chain extender, and methylsilicic acid trihydroxymethyl methylamine cage ester and perfluoropolyether alcohol are introduced as end-capping agents.

Description

Technical Field

[0001] The invention relates to the field of textile fabrics, in particular to a fire-resistant and flame-retardant polyester fabric and a preparation process thereof. Background Art

[0002] Polyester is the main type of chemical fiber, and its annual output accounts for more than half of the total synthetic fiber. Its chemical composition is polyethylene terephthalate. Due to its high strength, good wear resistance and good elasticity, it is widely used in various fields such as automobiles, industry, and clothing.

[0003] However, polyester fabrics have poor flame retardancy and produce large amounts of smoke and molten droplets when burned, which can cause serious damage, thus limiting their application. In the current market, polyester fabrics are generally treated with flame retardant finishing agents or additives to improve their flame retardancy. However, this functional finishing significantly reduces their strength. Therefore, how to simultaneously enhance the strength, flame retardancy, and water repellency of polyester fabrics is crucial for achieving the protective and multifunctional properties of polyester products. Summary of the Invention

[0004] The purpose of the present invention is to provide a fire-resistant and flame-retardant polyester fabric and a preparation process thereof, so as to solve the problems in the prior art.

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

[0006] A preparation process of a fire-retardant polyester fabric comprises the following steps:

[0007] S1: Electrospinning solution was prepared using polyvinyl alcohol, modified hybrid molybdenum disulfide, sodium alginate, and deionized water, and flame-retardant fibers were obtained by electrospinning.

[0008] S2: blending and weaving the flame retardant fiber with the polyester fiber to obtain a polyester composite fabric;

[0009] S3: Preparation of protective finishing liquid using modified hybrid molybdenum disulfide and self-healing waterborne polyurethane emulsion;

[0010] S4: The polyester composite fabric is twice dipped and twice rolled in a protective finishing liquid, and then pre-baked and baked to obtain a fire-retardant polyester fabric.

[0011] Furthermore, the working conditions of electrospinning are: the propulsion speed of the electrospinning solution is 0.8 mL / h, the receiving distance is 15 cm, the voltage is 23 kV, and the temperature is 18-25°C.

[0012] Furthermore, the working conditions of the double dipping and double rolling are: dipping time is 10-20 minutes, rolling rate is 75%-80%; the working conditions of pre-baking are: keeping warm at 75-80℃ for 3-5 minutes, and the working conditions of baking are: keeping warm at 110-120℃ for 10-12 minutes.

[0013] Furthermore, the mass ratio of polyvinyl alcohol, sodium alginate, and modified hybrid molybdenum disulfide in the electrospinning solution is 4:2:1.

[0014] Furthermore, the blending ratio of the flame retardant fiber to the polyester fiber in the polyester composite fabric is 50:50.

[0015] Furthermore, the mass ratio of the modified hybrid molybdenum disulfide to the self-healing aqueous polyurethane emulsion in the protective impregnation liquid is 4-5%.

[0016] Furthermore, the preparation of the self-repairing waterborne polyurethane emulsion includes the following steps:

[0017] 1) Guanidine carbonate, 2-acetyl-γ-butyrolactone, ethanol, and triethylamine are mixed, heated at 75-80° C. for 10-12 hours, filtered, washed, and dried to obtain 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol;

[0018] 2) Under a nitrogen atmosphere, polytetrahydrofuran is kept at 110°C for 1-2 hours, isophorone diisocyanate, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol, N,N-dimethylacetamide, and dibutyltin dilaurate are added, the temperature is raised to 90-95°C and kept for 1-2 hours, the temperature is lowered to 40-45°C, bis(2-hydroxyethyl) disulfide is added, and the temperature is kept for 1-2 hours. After cooling to 35-40°C, trimethylolmethylamine methylsilicate cage ester is added, and the temperature is continued to be kept for 1-2 hours. Perfluoropolyether alcohol is added and kept for 1-2 hours, the temperature is lowered to 18-25°C, methanol is added, and deionized water is added for emulsification to obtain a self-healing waterborne polyurethane emulsion with a mass fraction of 40-50%.

[0019] Furthermore, the preparation of modified hybrid molybdenum disulfide comprises the following steps:

[0020] (1) mixing carbon nanotubes, hexadecyltrimethylammonium bromide, ammonium molybdate tetrahydrate, thiourea, and deionized water, ultrasonically dispersing for 10-15 minutes, transferring to a hydrothermal reactor, keeping the temperature at 168-172° C. for 9-10 hours, cooling, centrifuging, washing, and drying to obtain hybrid molybdenum disulfide;

[0021] (2) mixing hybrid molybdenum disulfide and isopropyl alcohol, adding a mixture of perylene tetracarboxylic anhydride, chloroform, and deionized water, and ultrasonically treating for 15-20 minutes to obtain composite molybdenum disulfide;

[0022] (3) under the protection of nitrogen, methylsilicic acid trihydroxymethyl methylamine cage ester, dimethyl sulfoxide is mixed, the mixed solution of composite molybdenum disulfide, imidazole, acetone is added, and the temperature is raised to 115-120 DEG C and kept for 5-6h, then cooled, added with anhydrous ethanol, centrifuged, washed and dried to obtain modified hybrid molybdenum disulfide.

[0023] Further, the preparation of methylsilicic acid trihydroxymethyl methylamine cage ester comprises the following steps: under the protection of nitrogen, trihydroxymethyl aminomethyl methane hydrochloride, triethylamine and dioxane are mixed, methyltrichlorosilane is added, and the temperature is kept at 35-40 DEG C for 20-30min, then raised to 68-72 DEG C and kept for 6-7h, hot filtration is carried out, deionized water is added, the pH value is adjusted to 7.9-8.1 with triethylamine, and filtration, washing are carried out to obtain methylsilicic acid trihydroxymethyl methylamine cage ester.

[0024] The beneficial effects of the present application are as follows:

[0025] The present application provides a fireproof and flame-retardant polyester fabric and a preparation process thereof, wherein polyvinyl alcohol and modified hybrid molybdenum disulfide are selected to electrospun to prepare flame-retardant fibers, and the flame-retardant fibers are mixed with polyester fibers and then subjected to impregnation finishing to prepare a fireproof and flame-retardant polyester fabric with a self-repairing super-hydrophobic surface.

[0026] In order to improve the flame retardancy and environmental protection of the fabric, degradable raw material sodium alginate and polyvinyl alcohol are selected to electrospun to prepare flame-retardant fibers, and in order to improve the toughness and flame retardancy of the flame-retardant fibers, modified hybrid molybdenum disulfide is selected as a toughening agent and a flame retardant.

[0027] Hybrid molybdenum disulfide is generated by using carbon nanotubes, cetyltrimethylammonium bromide, molybdate ammonium tetrahydrate and thiourea, and perylene tetracarboxylic anhydride is deposited on the surface of the hybrid molybdenum disulfide by using the strong interaction between perylene tetracarboxylic anhydride and molybdenum disulfide, in order to improve the flame retardancy, methylsilicic acid trihydroxymethyl methylamine cage ester with flame retardancy is synthesized by using trihydroxymethyl aminomethyl methane hydrochloride, triethylamine, dioxane and methyltrichlorosilane, and the anhydride in the perylene tetracarboxylic anhydride on the hybrid molybdenum disulfide reacts with the amino group in the methylsilicic acid trihydroxymethyl methylamine cage ester to graft the methylsilicic acid trihydroxymethyl methylamine cage ester on the hybrid molybdenum disulfide, thereby obtaining halogen-free flame-retardant modified hybrid molybdenum disulfide.

[0028] In order to give the fabric excellent resistance to mechanical damage and enable the fabric to have self-repairing properties at room temperature, modified hybrid molybdenum disulfide and self-repairing waterborne polyurethane emulsion were used to prepare a protective finishing liquid. In the preparation of the self-repairing waterborne polyurethane emulsion, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol containing multiple hydrogen bonds was selected, polytetrahydrofuran, and isophorone diisocyanate to prepare a prepolymer. Bis(2-hydroxyethyl) disulfide was introduced as a chain extender, and trimethylolmethylamine methyl silicate cage ester and perfluoropolyether alcohol were introduced as end-capping agents to synthesize a fluorinated waterborne self-repairing polyurethane containing multiple hydrogen bonds and dynamic disulfide bonds. The self-repairing waterborne polyurethane emulsion was emulsified with deionized water to obtain a self-repairing waterborne polyurethane emulsion. Then, modified hybrid molybdenum disulfide was added as a toughening agent and flame retardant in the protective finishing liquid. By controlling their mass ratio, a fire-retardant polyester fabric with a self-repairing superhydrophobic surface was obtained, thereby greatly improving the self-cleaning property of the fabric and achieving a long-lasting flame retardant effect. DETAILED DESCRIPTION

[0029] 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 embodiments described 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 any creative efforts shall fall within the scope of protection of the present invention.

[0030] It should be noted that if the embodiments of the present invention involve directional indications such as up, down, left, right, front, and back, such directional indications are only used to explain the relative positional relationship and movement of the components in a specific posture. If the specific posture changes, the directional indication will also change accordingly. In addition, the technical solutions of the various embodiments may be combined with each other, but they must be based on the premise that they can be implemented by ordinary technicians in this field. If the combination of technical solutions is mutually inconsistent or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0031] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0032] Example 1: A process for preparing a fire-retardant polyester fabric, comprising the following steps:

[0033] S1: Electrospinning solution was prepared using polyvinyl alcohol, modified hybrid molybdenum disulfide, sodium alginate, and deionized water, and flame-retardant fibers were prepared by electrospinning;

[0034] The working conditions of the electrospinning are as follows: the propulsion speed of the electrospinning solution is 0.8 mL / h, the receiving distance is 15 cm, the voltage is 23 kV, and the temperature is 18°C;

[0035] The preparation of the electrostatic spinning solution comprises the following steps: mixing 4g of polyvinyl alcohol and 400mL of deionized water, stirring to dissolve at 65℃, adding a mixture of 2g of sodium alginate and 100mL of deionized water, vacuumizing and standing for 7h, adding a mixture of 1g of modified hybrid molybdenum disulfide and 100mL of deionized water, ultrasonic dispersion for 1h, to obtain a spinning solution;

[0036] The preparation of the modified hybrid molybdenum disulfide comprises the following steps:

[0037] (1) Mix 2.4g of carbon nanotubes, 0.8g of hexadecyl trimethyl ammonium bromide, 1.6g of ammonium molybdate tetrahydrate, 1.6g of thiourea, and 200mL of deionized water, ultrasonic dispersion for 10min, transfer to an autoclave, heat at 168℃ for 10h, cool, centrifuge, wash, and dry to obtain hybrid molybdenum disulfide;

[0038] (2) Mix 50mg of hybrid molybdenum disulfide and 100mL of isopropanol, add a mixture of 21.4mL of perylene tetraformic anhydride, 100mg of chloroform, and 100mL of deionized water, ultrasonic treatment for 15min, to obtain composite molybdenum disulfide;

[0039] (3) Under nitrogen protection, mix 0.36g of methylsilicic acid trimethylolamine cage ester and 8mL of dimethyl sulfoxide, add a mixture of 1g of composite molybdenum disulfide, 2g of imidazole, and 3mL of acetone, heat to 115℃ for 6h, then cool, add 30mL of anhydrous ethanol, centrifuge, wash, and dry to obtain modified hybrid molybdenum disulfide;

[0040] The preparation of methylsilicic acid trimethylolamine cage ester comprises the following steps: under nitrogen protection, mix 15.2g of trimethylol aminomethyl methane hydrochloride, 12.9g of triethylamine, and 125mL of dioxane, add 21.5g of methyltrichlorosilane, heat at 35℃ for 30min, heat to 68℃ for 7h, hot filtration, add 10mL of deionized water, adjust the pH value to 7.9 with triethylamine, filter, and wash to obtain methylsilicic acid trimethylolamine cage ester;

[0041] S2: blend the flame-retardant fiber with the polyester fiber, and weave to obtain a polyester composite fabric;

[0042] The blending ratio of the flame-retardant fiber to the polyester fiber in the polyester composite fabric is 50:50;

[0043] S3: prepare a protective finishing liquid with the modified hybrid molybdenum disulfide and the self-repairing water-based polyurethane emulsion;

[0044] The mass ratio of the modified hybrid molybdenum disulfide to the self-repairing water-based polyurethane emulsion in the protective impregnating liquid is 4%;

[0045] The preparation of the self-repairing waterborne polyurethane emulsion comprises the following steps:

[0046] 1) Mix 9.9 g guanidine carbonate, 7.2 g 2-acetyl-gamma-butyrolactone, 60 mL ethanol, 15 mL triethylamine, and incubate at 75℃ for 12 h. Filter, wash, and dry to obtain 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol;

[0047] 2) Under a nitrogen atmosphere, incubate 7 g polytetrahydrofuran at 110℃ for 1 h. Add 6.8 g isophorone diisocyanate, 1.5 g 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol, 3.5 mL N,N-dimethylacetamide, 35 mg dibutyltin dilaurate, and incubate at 90℃ for 2 h. Add 0.8 g bis(2-hydroxyethyl) disulfide after the temperature is reduced to 45℃, and incubate for 1 h. Add 0.6 g methylsilicic acid trimethylolmethylamine clathrate after the temperature is reduced to 40℃, and continue to incubate for 1 h. Add 0.25 g perfluoropolyether alcohol and incubate for 1 h. Add 1 mL methanol after the temperature is reduced to 18℃, and spin to evaporate. Add deionized water at a rotation speed of 2500 rpm to emulsify, and prepare a self-repairing waterborne polyurethane emulsion with a mass fraction of 40%;

[0048] S4: dip the polyester composite fabric in the protective finishing liquid twice, and then pre-dry and bake to obtain a fireproof and flame-retardant polyester fabric; the working conditions of the twice dipping and rolling are that the dipping time is 10 min and the rolling rate is 75%; the working conditions of the pre-drying are that the temperature is kept at 75℃ for 5 min; and the working conditions of the baking are that the temperature is kept at 110℃ for 12 min.

[0049] Example 2: a preparation process of a fireproof and flame-retardant polyester fabric, comprising the following steps:

[0050] S1: prepare an electrospinning solution by using polyvinyl alcohol, modified hybrid molybdenum disulfide, sodium alginate, and deionized water, and prepare a flame-retardant fiber by electrospinning;

[0051] The working conditions of the electrospinning are that the propelling speed of the electrospinning solution is 0.8 mL / h, the receiving distance is 15 cm, the voltage is 23 kV, and the temperature is 20℃;

[0052] The preparation of the electrospinning solution comprises the following steps: mix 4 g polyvinyl alcohol and 400 mL deionized water, stir to dissolve at a temperature of 68℃, add a mixed solution of 2 g sodium alginate and 100 mL deionized water, vacuumize and stand for 7.5 h, add a mixed solution of 1 g modified hybrid molybdenum disulfide and 100 mL deionized water, and ultrasonic disperse for 1.5 h to obtain a spinning solution;

[0053] The preparation of the modified hybrid molybdenum disulfide comprises the following steps:

[0054] (1) 2.4 g of carbon nanotubes, 0.8 g of hexadecyltrimethylammonium bromide, 1.6 g of ammonium molybdate tetrahydrate, 1.6 g of thiourea, and 200 mL of deionized water were mixed, ultrasonically dispersed for 12 min, transferred to a hydrothermal autoclave, kept at 170° C. for 9.5 h, cooled, centrifuged, washed, and dried to obtain hybrid molybdenum disulfide;

[0055] (2) 50 mg of hybrid molybdenum disulfide and 100 mL of isopropanol were mixed, and a mixture of 21.4 mL of perylene tetracarboxylic anhydride, 100 mg of chloroform, and 100 mL of deionized water was added, and ultrasonic treatment was performed for 18 min to obtain composite molybdenum disulfide;

[0056] (3) Under nitrogen protection, 0.36 g of tris(hydroxymethyl)methylammonium methyl silicate caged ester and 8 mL of dimethyl sulfoxide were mixed, and a mixture of 1 g of composite molybdenum disulfide, 2 g of imidazole, and 3 mL of acetone was added. The mixture was heated to 118° C. and kept warm for 5.5 h, then cooled, 30 mL of anhydrous ethanol was added, and the mixture was centrifuged, washed, and dried to obtain modified hybrid molybdenum disulfide.

[0057] The preparation of tris(hydroxymethyl)methylammonium methylsilicate caged ester comprises the following steps: under nitrogen protection, 15.2 g of tris(hydroxymethyl)aminomethane hydrochloride, 12.9 g of triethylamine, and 125 mL of dioxane are mixed, 21.5 g of methyltrichlorosilane is added, the mixture is heated at 38° C. for 25 minutes, the temperature is raised to 70° C. and the temperature is maintained for 6.5 hours, the mixture is filtered while hot, 10 mL of deionized water is added, the pH value is adjusted to 8 with triethylamine, the mixture is filtered, and the mixture is washed to obtain tris(hydroxymethyl)methylammonium methylsilicate caged ester;

[0058] S2: blending and weaving the flame retardant fiber with the polyester fiber to obtain a polyester composite fabric;

[0059] The blending ratio of flame retardant fiber to polyester fiber in the polyester composite fabric is 50:50;

[0060] S3: Preparation of protective finishing liquid using modified hybrid molybdenum disulfide and self-healing waterborne polyurethane emulsion;

[0061] The mass ratio of modified hybrid molybdenum disulfide to self-healing waterborne polyurethane emulsion in the protective impregnation liquid is 4.5%;

[0062] The preparation of the self-repairing waterborne polyurethane emulsion includes the following steps:

[0063] 1) 9.9 g of guanidine carbonate, 7.2 g of 2-acetyl-γ-butyrolactone, 60 mL of ethanol, and 15 mL of triethylamine were mixed and incubated at 78°C for 11 h. The mixture was filtered, washed, and dried to obtain 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol.

[0064] 2) Under a nitrogen atmosphere, 7 g of polytetrahydrofuran was kept at 110 ° C for 1.5 h, 6.8 g of isophorone diisocyanate, 1.5 g of 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol, 3.5 mL of N, N-dimethylacetamide, and 35 mg of dibutyltin dilaurate were added, the temperature was raised to 92 ° C and kept for 1.5 h, the temperature was lowered to 45 ° C, 0.8 g of bis(2-hydroxyethyl) disulfide was added, and the temperature was kept for 1.5 h. After cooling to 40 ° C, 0.6 g of trimethylolmethylamine methylsilicate cage ester was added and the temperature was continued to be kept for 1.5 h. 0.25 g of perfluoropolyether alcohol was added and kept for 1.5 h. The temperature was lowered to 20 ° C and 1 mL of methanol was added. The mixture was rotary evaporated and deionized water was added at a speed of 2500 rpm for emulsification to obtain a self-healing waterborne polyurethane emulsion with a mass fraction of 45%;

[0065] S4: The polyester composite fabric is double-dipped and double-rolled in a protective finishing liquid, and then pre-baked and baked to obtain a fire-retardant polyester fabric; the working conditions of the double-dip and double-rolling are: the dipping time is 15 minutes, and the rolling rate is 78%; the working conditions of the pre-baking are: keeping warm at 78°C for 4 minutes, and the working conditions of the baking are: keeping warm at 115°C for 11 minutes.

[0066] Example 3: A process for preparing a fire-retardant polyester fabric, comprising the following steps:

[0067] S1: Electrospinning solution was prepared using polyvinyl alcohol, modified hybrid molybdenum disulfide, sodium alginate, and deionized water, and flame-retardant fibers were prepared by electrospinning;

[0068] The working conditions of the electrospinning are as follows: the propulsion speed of the electrospinning solution is 0.8 mL / h, the receiving distance is 15 cm, the voltage is 23 kV, and the temperature is 25°C;

[0069] The preparation of the electrospinning solution comprises the following steps: mixing 4 g of polyvinyl alcohol and 400 mL of deionized water, heating to 70° C. and stirring until dissolved, adding a mixture of 2 g of sodium alginate and 100 mL of deionized water, evacuating and allowing to stand for 8 hours, adding a mixture of 1 g of modified hybrid molybdenum disulfide and 100 mL of deionized water, and ultrasonically dispersing for 2 hours to obtain a spinning solution;

[0070] The preparation of the modified hybrid molybdenum disulfide comprises the following steps:

[0071] (1) 2.4 g of carbon nanotubes, 0.8 g of hexadecyltrimethylammonium bromide, 1.6 g of ammonium molybdate tetrahydrate, 1.6 g of thiourea, and 200 mL of deionized water were mixed, ultrasonically dispersed for 15 min, transferred to a hydrothermal reactor, kept at 172 ° C for 9 h, cooled, centrifuged, washed, and dried to obtain hybrid molybdenum disulfide;

[0072] (2) 50 mg of hybrid molybdenum disulfide and 100 mL of isopropanol were mixed, and a mixture of 21.4 mL of perylene tetracarboxylic anhydride, 100 mg of chloroform, and 100 mL of deionized water was added, and ultrasonic treatment was performed for 20 min to obtain composite molybdenum disulfide;

[0073] (3) Under nitrogen protection, 0.36 g of tris(hydroxymethyl)methylammonium methyl silicate caged ester and 8 mL of dimethyl sulfoxide were mixed, and a mixture of 1 g of composite molybdenum disulfide, 2 g of imidazole, and 3 mL of acetone was added. The mixture was heated to 120° C. and kept warm for 5 h, then cooled, 30 mL of anhydrous ethanol was added, and the mixture was centrifuged, washed, and dried to obtain modified hybrid molybdenum disulfide.

[0074] The preparation of tris(hydroxymethyl)methylammonium methylsilicate caged ester comprises the following steps: under nitrogen protection, 15.2 g of tris(hydroxymethyl)aminomethane hydrochloride, 12.9 g of triethylamine, and 125 mL of dioxane are mixed, 21.5 g of methyltrichlorosilane is added, the mixture is heated at 40° C. for 20 minutes, the temperature is raised to 72° C. and the temperature is maintained for 6 hours, the mixture is filtered while hot, 10 mL of deionized water is added, the pH value is adjusted to 8.1 with triethylamine, the mixture is filtered, and the mixture is washed to obtain tris(hydroxymethyl)methylammonium methylsilicate caged ester;

[0075] S2: blending and weaving the flame retardant fiber with the polyester fiber to obtain a polyester composite fabric;

[0076] The blending ratio of flame retardant fiber to polyester fiber in the polyester composite fabric is 50:50;

[0077] S3: Preparation of protective finishing liquid using modified hybrid molybdenum disulfide and self-healing waterborne polyurethane emulsion;

[0078] The mass ratio of modified hybrid molybdenum disulfide to self-healing waterborne polyurethane emulsion in the protective impregnation liquid is 5%;

[0079] The preparation of the self-repairing waterborne polyurethane emulsion includes the following steps:

[0080] 1) Mix 9.9 g of guanidine carbonate, 7.2 g of 2-acetyl-γ-butyrolactone, 60 mL of ethanol, and 15 mL of triethylamine, and incubate at 75-80° C. for 10-12 h. Filter, wash, and dry to obtain 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol;

[0081] 2) Under a nitrogen atmosphere, 7g of polytetrahydrofuran was kept at 110°C for 1-2h, 6.8g of isophorone diisocyanate, 1.5g of 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol, 3.5mL of N,N-dimethylacetamide, and 35mg of dibutyltin dilaurate were added, and the temperature was raised to 90-95°C and kept for 1-2h. The temperature was lowered to 45°C and 0.8g of bis(2-hydroxyethyl) disulfide was added and kept for 2h. After cooling to 40°C, 0.6g of trimethylolmethylamine methylsilicate cage ester was added and kept warm for 2h. 0.25g of perfluoropolyether alcohol was added and kept warm for 2h. The temperature was lowered to 25°C and 1mL of methanol was added. The mixture was rotary evaporated and emulsified with deionized water at a speed of 2500rpm to obtain a self-healing waterborne polyurethane emulsion with a mass fraction of 50%;

[0082] S4: The polyester composite fabric is double-dipped and double-rolled in a protective finishing liquid, and then pre-baked and baked to obtain a fire-retardant polyester fabric; the working conditions of the double-dip and double-rolling are: the dipping time is 20 minutes, and the rolling rate is 80%; the working conditions of the pre-baking are: keeping warm at 80°C for 3 minutes, and the working conditions of the baking are: keeping warm at 120°C for 10 minutes.

[0083] Comparative Example 1: Example 3 was used as the control group, except that tris(hydroxymethyl)methylammonium methylsilicate caged ester was not prepared and the other processes were normal.

[0084] Comparative Example 2: Taking Example 3 as the control group, molybdenum disulfide (M104968: Aladdin reagent) was used to replace the modified hybrid molybdenum disulfide, and the other processes were normal.

[0085] Comparative Example 3: Taking Example 3 as the control group, carbon nanotubes were used to replace the modified hybrid molybdenum disulfide, and the other processes were normal.

[0086] Comparative Example 4: Example 3 was used as a control group, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol was not prepared, and other processes were normal.

[0087] Comparative Example 5: Example 3 was used as the control group, except that perfluoropolyether alcohol was not added and the other processes were normal.

[0088] In the embodiment and the comparative example, the thickness of the polyester composite fabric is 1 mm, and the thickness of the protective finishing liquid formed on the polyester composite fabric is 100 μm.

[0089] Source of raw materials:

[0090] Polyester fiber (0.89 dtex × 38 mm): Yizheng Southeast Chemical Fiber Raw Materials Co., Ltd.; Perfluoropolyether alcohol 90317-77-4: Henan Weitixi Chemical Technology Co., Ltd.; Polyvinyl alcohol P139545, sodium alginate S100128, carbon nanotubes C313046, hexadecyltrimethylammonium bromide H108983, ammonium molybdate tetrahydrate A116375, thiourea T112512, perylenetetracarboxylic anhydride P121510, dimethyl sulfoxide D103272, imidazole I108707, tris(hydroxymethyl)aminomethane hydrochloride T4 31526, triethylamine T103285, dioxane D116157, methyltrichlorosilane M104828, guanidine carbonate G104710, 2-acetyl-γ-butyrolactone A108065, polytetrahydrofuran P118599, isophorone diisocyanate I109582, N,N-dimethylacetamide D108096, dibutyltin dilaurate D100274, bis(2-hydroxyethyl) disulfide B598951: Aladdin reagent; isopropyl alcohol, chloroform, acetone, anhydrous ethanol, methanol, analytical grade: Sinopharm reagents.

[0091] Performance testing:

[0092] Breaking strength: Cut into 30cm×5cm pieces, refer to GB / T3923.1-2013, and test the warp breaking strength; Hydrophobicity: Characterize the water contact angle, and test with a 4μL deionized water droplet; Limiting oxygen index: Refer to ASTMD2863-08, and test using a limiting oxygen index tester. Cut the test sample into 5×15cm pieces and wash the test sample 20 times with standard water before measurement. The standard water wash is 25℃ water washing for 20 minutes; Self-healing property: A scratch with a length of 100μm, a width of 20μm, and a depth of 100μm was made on the surface of the test sample. The sample was kept at 25℃ for 12 hours, and the scratch length was observed with an electron microscope. The self-healing rate was used to characterize the self-healing property. Self-healing rate = (1-l / l0)×100%, where l0 is the initial scratch length and l is the scratch length after holding; as shown in Table 1;

[0093] Table 1

[0094] Breaking strength (N) Water contact angle (°) Limiting oxygen index Self-repair rate (%) Example 1 600.7 155 42 99.8 Example 2 601.4 155 43 99.9 Example 3 602.9 156 44 100 Comparative Example 1 497.6 153 31 99.7 Comparative Example 2 472.3 149 28 96.5 Comparative Example 3 483.5 148 29 95.8 Comparative Example 4 / 150 37 89.4 Comparative Example 5 / 132 36 99.6

[0095] The fabrics prepared in Examples 1-3 of the present invention have a warp breaking strength of 600.7-602.9 N, a water contact angle of 155-156°, a limiting oxygen index of 42-44, and a self-repair rate of 99.8-100%. This indicates that the polyester fabrics prepared according to the present invention are fire-retardant polyester fabrics with a self-repairing superhydrophobic surface. / in the table indicates that this item was not tested.

[0096] Comparing Example 3 with Comparative Example 1, grafting tris(hydroxymethyl)methylammonium methyl silicate cage ester onto hybrid molybdenum disulfide is beneficial to improving the flame retardancy of the fabric.

[0097] Comparing Example 3 with Comparative Examples 2 and 3, adding modified hybrid molybdenum disulfide to the flame retardant fiber and protective finishing liquid can effectively improve the mechanical strength and flame retardancy of the fabric.

[0098] Example 3 is compared with Comparative Example 4 and Comparative Example 5. In the preparation of the self-repairing water-based polyurethane emulsion, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidine-4-ol containing multiple hydrogen bonds is selected from polytetrahydrofuran and isophorone diisocyanate to prepare a prepolymer, bis(2-hydroxyethyl) disulfide is introduced as a chain extender, trimethylolmethylamine methyl silicate cage ester and perfluoropolyether alcohol are introduced as end-capping agents to synthesize a fluorine-containing water-based self-repairing polyurethane containing multiple hydrogen bonds and dynamic disulfide bonds. The self-repairing water-based polyurethane emulsion is emulsified with deionized water to obtain a self-repairing water-based polyurethane emulsion, and then modified hybrid molybdenum disulfide is added as a toughening agent and flame retardant for the protective finishing liquid. The polyester composite fabric is then double-dipped and double-rolled in the protective finishing liquid, pre-baked, and baked to obtain a fire-retardant polyester fabric with a self-repairing superhydrophobic surface, thereby greatly improving the self-cleaning property of the fabric and achieving a long-lasting flame retardant effect.

[0099] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the present invention specification under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A process for preparing a fire-retardant polyester fabric, characterized by: The steps include: S1: Electrospinning solution was prepared using polyvinyl alcohol, modified hybrid molybdenum disulfide, sodium alginate, and deionized water, and flame-retardant fibers were obtained by electrospinning. S2: blending and weaving the flame retardant fiber with the polyester fiber to obtain a polyester composite fabric; S3: Preparation of protective finishing liquid using modified hybrid molybdenum disulfide and self-healing waterborne polyurethane emulsion; S4: double-dipping and double-rolling the polyester composite fabric in a protective finishing solution, and then pre-baking and baking to obtain a fire-retardant polyester fabric; The preparation of the self-repairing waterborne polyurethane emulsion includes the following steps: 1) Mix guanidine carbonate, 2-acetyl-γ-butyrolactone, ethanol, and triethylamine, and heat at 75-80°C for 10-12 hours. Filter, wash, and dry to obtain 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol. 2) Under a nitrogen atmosphere, polytetrahydrofuran is kept at 110°C for 1-2 hours, isophorone diisocyanate, 2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol, N,N-dimethylacetamide, and dibutyltin dilaurate are added, the temperature is raised to 90-95°C and kept for 1-2 hours, the temperature is lowered to 40-45°C, bis(2-hydroxyethyl) disulfide is added, and the temperature is kept for 1-2 hours. After the temperature is lowered to 35-40°C, trimethylolmethylamine methylsilicate caged ester is added and the temperature is kept for another 1-2 hours, perfluoropolyether alcohol is added and the temperature is kept for 1-2 hours, the temperature is lowered to 18-25°C, methanol is added, the temperature is rotary evaporated, and deionized water is added for emulsification to obtain a self-healing waterborne polyurethane emulsion with a mass fraction of 40-50%; The preparation of the modified hybrid molybdenum disulfide comprises the following steps: (1) Mix carbon nanotubes, hexadecyltrimethylammonium bromide, ammonium molybdate tetrahydrate, thiourea, and deionized water, ultrasonically disperse for 10-15 minutes, transfer to a hydrothermal autoclave, keep warm at 168-172°C for 9-10 hours, cool, centrifuge, wash, and dry to obtain hybrid molybdenum disulfide; (2) Hybrid molybdenum disulfide and isopropanol are mixed, and a mixture of perylene tetracarboxylic anhydride, chloroform, and deionized water is added, and ultrasonic treatment is performed for 15-20 minutes to obtain composite molybdenum disulfide; (3) Under nitrogen protection, tris(hydroxymethyl)methylammonium methyl silicate) caged ester and dimethyl sulfoxide are mixed, and a mixture of composite molybdenum disulfide, imidazole, and acetone is added. The mixture is heated to 115-120°C and kept warm for 5-6 hours, then cooled, anhydrous ethanol is added, centrifuged, washed, and dried to obtain modified hybrid molybdenum disulfide. The preparation of tris(hydroxymethyl)methylammonium methylsilicate caged ester comprises the following steps: under nitrogen protection, tris(hydroxymethyl)aminomethane hydrochloride, triethylamine and dioxane are mixed, methyltrichlorosilane is added, the mixture is heated at 35-40°C for 20-30 minutes, the temperature is raised to 68-72°C and the temperature is kept for 6-7 hours, the mixture is filtered while hot, deionized water is added, the pH value is adjusted to 7.9-8.1 with triethylamine, the mixture is filtered and washed to obtain tris(hydroxymethyl)methylammonium methylsilicate caged ester.

2. The process for preparing a fire-retardant polyester fabric according to claim 1, characterized in that: The working conditions of the electrospinning are: the propulsion speed of the electrospinning solution is 0.8 mL / h, the receiving distance is 15 cm, the voltage is 23 kV, and the temperature is 18-25°C.

3. The process for preparing a fire-retardant polyester fabric according to claim 1, characterized in that: The working conditions of double dipping and double rolling are: dipping time is 10-20 minutes, rolling rate is 75%-80%; the working conditions of pre-baking are: keeping warm at 75-80℃ for 3-5 minutes, and the working conditions of baking are: keeping warm at 110-120℃ for 10-12 minutes.

4. The process for preparing a fire-retardant polyester fabric according to claim 1, characterized in that: The mass ratio of polyvinyl alcohol, sodium alginate and modified hybrid molybdenum disulfide in the electrospinning solution is 4:2:

1.

5. The process for preparing a fire-retardant polyester fabric according to claim 1, characterized in that: The blending ratio of the flame retardant fiber to the polyester fiber in the polyester composite fabric is 50:

50.

6. The process for preparing a fire-retardant polyester fabric according to claim 1, characterized in that: The mass ratio of modified hybrid molybdenum disulfide to self-repairing waterborne polyurethane emulsion in the protective finishing liquid is 4-5%.

7. A fire-retardant polyester fabric, characterized by: The invention is prepared by the process according to any one of claims 1 to 6.