Fluorescent polyester fiber material, preparation method and application in bags and suitcases

Abstract

The invention relates to the technical field of high-performance polyester fibers, and discloses a fluorescent polyester fiber material, a preparation method and application in bags and suitcases. The preparation method of the fluorescent polyester fiber material comprises the following steps: reacting ethylene glycol, terephthalic acid and a multifunctional modified monomer to obtain modified polyester; the preparation method comprises the following steps: reacting 1, 5-hexene-1-amine with p-mercaptophenol to obtain an intermediate product; reacting the intermediate product with 3, 4, 9, 10-perylenetetracarboxylic dianhydride to obtain a perylene bisimide derivative; reacting the perylene bisimide derivative with phosphonitrilic chloride trimer to obtain the fluorescent flame-retardant microspheres; mixing the modified polyester, polyester chips and fluorescent flame-retardant microspheres, and performing melt spinning to obtain modified polyester fibers; and blending and weaving the modified polyester fibers and spandex fibers to obtain the fluorescent polyester fiber material. The fluorescent polyester fiber material disclosed by the invention not only has a fluorescent effect, but also has the advantages of wear resistance, flame retardance and static electricity resistance, and can be used in luggage fabrics.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-performance polyester fibers, in particular to a fluorescent polyester fiber material, a preparation method and application in luggage. BACKGROUND

[0002] Luggage is an indispensable item in daily life and work, and the performance of its fabric is directly related to the durability, functionality and aesthetics of the product. Polyester fiber is one of the main materials for luggage fabric, as it has excellent wrinkle resistance, shape retention, strength and elastic recovery capacity, and also has characteristics such as wear resistance and no hair sticking. However, luggage often rubs against the outside world, so it is necessary to further improve its wear resistance.

[0003] In addition, in the design of luggage, the use of fluorescent materials to improve visual effects not only enhances the aesthetics and fashion of the luggage, but also serves as a warning effect to ensure safety in low-light environments. However, polyester is a hydrophobic fiber with weak affinity for water molecules, and fluorescent dyes are difficult to penetrate, resulting in unsatisfactory and short-lived fluorescent effects. Luggage, as a daily necessity, also needs to have additional functions such as flame retardance and anti-static to meet the needs of different use scenarios. SUMMARY

[0004] To solve the above technical problems, the present application provides a fluorescent polyester fiber material, comprising the following steps: Step one, preparing modified polyester: mixing ethylene glycol, terephthalic acid, multifunctional modified monomer and tetrabutyl titanate in a mass ratio of 100: (60-80): (20-40): 0.02, esterification and polycondensation to obtain modified polyester; Step two, preparing fluorescent flame-retardant microspheres: 5-hexene-1-amine reacts with p-mercaptophenol to obtain an intermediate product; the intermediate product reacts with 3,4,9,10-perylenetetracarboxylic dianhydride to obtain a perylene imide derivative; the perylene imide derivative reacts with hexachlorocyclotriphosphazene to obtain fluorescent flame-retardant microspheres; Step three, preparing fluorescent polyester fiber material: mixing modified polyester, polyester chips and fluorescent flame-retardant microspheres in a mass ratio of (3.5-5.5): 10: (0.2-0.7), melt spinning to obtain modified polyester fiber; blending the modified polyester fiber with spandex fiber, weaving to obtain the fluorescent polyester fiber material.

[0005] Preferably, in the step one, the preparation method of the multifunctional modified monomer comprises the following steps: mixing 5-hexenoic acid, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, N,N-dimethylformamide and 1,5-pentanediamine in a mass ratio of (14.8-27.4):(28.9-43.4):(16.9-25.3):(300-400):(5.1-10.2), stirring and reacting at 28-32℃ for 14-16h, purifying to obtain a diamide compound; mixing 3,4-diaminobenzoic acid, 3-hydroxyphenylphosphonic acid and 3mol / L hydrochloric acid aqueous solution in a usage ratio of (15.2-30.4)g:(21.4-42.8)g:(400-600)mL, stirring, refluxing and reacting at 95-105℃ for 7-9h, purifying to obtain a benzimidazole compound; adding the benzimidazole compound into ethanol, constant stirring at 65-75℃, then adding a diamide compound / ethanol mixture with a mass fraction of 10%, dropping completely within 1-2h, then constant stirring and reacting at 65-75℃ for 9-15h, purifying to obtain the multifunctional modified monomer; wherein the mass ratio of the benzimidazole compound, ethanol and the diamide compound / ethanol mixture is (6.6-13.2):(100-120):(29-58).

[0006] Preferably, in the step one, the esterification condition is: esterification at 180-240℃ for 2.5-3.5h, and the polycondensation condition is: melt polycondensation at 255-265℃ for 1.5-2.5h; in the above process, under the action of EDC (N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride) and NHS (N-hydroxysuccinimide), the amide reaction of 5-hexenoic acid and 1,5-pentanediamine occurs to obtain a diamide compound with two amide groups and a carbon-carbon double bond; the reaction of 3,4-diaminobenzoic acid and 3-hydroxyphenylphosphonic acid under heating conditions obtains a benzimidazole compound; then the benzimidazole compound and the diamide compound are combined through addition reaction to obtain the multifunctional modified monomer; finally, the multifunctional modified monomer is used to replace part of terephthalic acid, and the multifunctional modified monomer is introduced into the polyester structure; the hydrophilic and flexible diamide structure in the multifunctional modified monomer improves the antistatic property and flexibility of the polyester; the hydrogen bond donor (N-H) in the benzimidazole structure in the multifunctional modified monomer can form strong hydrogen bonds with the ester group, the amide group and the internal -C=N in the polyester chain, so that a strong physical crosslinking network is formed in the polyester, the strength of the polyester is improved, and the wear resistance of the polyester is improved; in addition, the multifunctional modified monomer contains rich flame-retardant nitrogen and phosphorus elements, which can play an excellent synergistic flame-retardant effect; therefore, the modified polyester has good mechanical properties, wear resistance, excellent flame-retardant properties and antistatic properties.

[0007] Preferably, in the step two, the preparation method of the intermediate product, specifically includes: 5-hexene-1-amine is added into ethanol, ultrasonic, heated to 60-70℃, then p-mercaptophenol, azobisisobutyronitrile / ethanol mixed solution is added, stirred for 3-5h, purified to obtain the intermediate product; wherein, the mass ratio of 5-hexene-1-amine, ethanol, p-mercaptophenol, azobisisobutyronitrile / ethanol mixed solution is (7.4-13.8):(200-300):(6.4-12.6):(30-44); preferably, in the step two, the preparation method of the perylene imide derivative, specifically includes: the intermediate product, 3,4,9,10-perylenetetracarboxylic dianhydride, zinc acetate, N,N-dimethylacetamide are mixed in a mass ratio of (4.5-9):(3.9-7.8):(0.04-0.06):(120-150), heated to 105-115℃ for 10-14h in a nitrogen atmosphere, purified to obtain the perylene imide derivative; preferably, in the step two, the preparation method of the fluorescent flame-retardant microspheres, specifically includes: the perylene imide derivative is added into nitrile, ultrasonic, then triethylamine is added, then 1% hexachlorocyclotriphosphazene / acetonitrile mixed solution is added dropwise within 30-60min, the mixed system is ultrasonic reacted at 38-42℃ for 50-70min, purified to obtain the fluorescent flame-retardant microspheres; wherein, the mass ratio of the perylene imide derivative, acetonitrile, triethylamine, hexachlorocyclotriphosphazene / acetonitrile mixed solution is (2.7-5.4):(60-90):(1-1.5):(39.7-71.5); in the above process, 5-hexene-1-amine and p-mercaptophenol are combined through click reaction between carbon-carbon double bond and thiol group under the catalysis of azobisisobutyronitrile to obtain the intermediate product containing phenolic hydroxyl, amino, alkyl short chain; the anhydride of 3,4,9,10-perylenetetracarboxylic dianhydride reacts with the amino of the intermediate product to generate the perylene imide derivative; then, the phenolic hydroxyl in the perylene imide derivative reacts with the halogen chlorine in hexachlorocyclotriphosphazene to form the fluorescent flame-retardant microspheres; the perylene imide derivative is known for its strong fluorescence and excellent photothermal, weather and chemical stability, the benzene ring and alkyl short chain introduced by the intermediate product in the perylene imide derivative help to increase steric hindrance, preventing the perylene imide derivative from gathering and affecting the fluorescence effect; the presence of nitrogen, phosphorus elements and aromatic ring in hexachlorocyclotriphosphazene endows it with excellent flame-retardant effect; the perylene imide derivative and hexachlorocyclotriphosphazene are polymerized to obtain the microspheres with fluorescence and flame-retardant properties; in addition, the presence of hydroxyl in the fluorescent flame-retardant microspheres makes it combine with the polyester matrix through hydrogen bond to improve the dispersibility of the fluorescent flame-retardant microspheres, further, the fluorescent flame-retardant microspheres also play the effect of reinforcing and toughening in the polyester matrix, thereby improving the wear resistance of the polyester material.

[0008] Preferably, in the step three, the mass ratio of the modified polyester, polyester chip and fluorescent flame-retardant microspheres is (3.5-5.5):10:(0.2-0.7); the melt spinning condition is that the spinning temperature is 230-250 DEG C and the spinning speed is 3500-4000 m / min.

[0009] Preferably, in the step three, the mass ratio of the modified polyester fiber and spandex fiber is 8:(1.5-2.5); the areal density of the fluorescent polyester fiber material is 170-190 g / m 2 The preparation method of the fluorescent polyester fiber material is adopted to prepare the fluorescent polyester fiber material.

[0010] The application of the fluorescent polyester fiber material in luggage.

[0011] Compared with the prior art, the present application has the following beneficial effects: 1. The present application prepares a multifunctional modified monomer by reacting a diamide compound with a benzimidazole-based compound, and the multifunctional modified monomer is used to replace part of terephthalic acid to copolymerize with ethylene glycol, so that a modified polyester with excellent wear resistance, flame retardance and antistatic property is obtained. 2. The present application polymerizes a perylene imide derivative with hexachlorotriphosphazene to obtain a fluorescent flame-retardant microsphere with good fluorescent property and excellent flame retardance; the fluorescent flame-retardant microsphere is blended with polyester chips to be spun, the fluorescent flame-retardant microsphere is combined with the polyester matrix through hydrogen bond, the dispersibility of the fluorescent flame-retardant microsphere is improved, and the migration of the fluorescent flame-retardant microsphere is avoided; compared with the polyester fiber dyed with a fluorescent dye, the fluorescent polyester fiber of the present application has more ideal and durable fluorescent effect; in addition, the fluorescent flame-retardant microsphere of the present application can play the roles of reinforcement and toughening in the polyester matrix, so that the wear resistance of the polyester is improved; therefore, the modified polyester fiber obtained by blending the fluorescent flame-retardant microsphere, the modified polyester and the polyester chips to be spun has not only the fluorescent effect, but also improved wear resistance, flame retardance and antistatic property compared with the conventional polyester fiber. 3. The fluorescent polyester fiber material obtained by blending the modified polyester fiber of the present application with spandex fiber has the advantages of the modified polyester fiber and spandex fiber; when the fluorescent polyester fiber material is used in luggage, the luggage not only has fashion and beauty, but also has excellent comprehensive performance, so that the service life of the luggage is prolonged. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 is a synthesis schematic diagram of the diamide compound of the present application; Figure 2 is a synthesis schematic diagram of the benzimidazole-based compound of the present application; Figure 3 is a synthesis schematic diagram of the multifunctional modified monomer of the present application; Figure 4is a synthetic diagram of an intermediate product of the present application; Figure 5 is a synthetic diagram of a perylene imide derivative of the present application; Figure 6 is a test comparison chart of the abrasion resistance (abrasion times) of fluorescent polyester fiber materials prepared in Examples 1-3 and Comparative Example 1-2 of the present application; Figure 7 is a test comparison chart of the limiting oxygen index of fluorescent polyester fiber materials prepared in Examples 1-3 and Comparative Example 1-2 of the present application. DETAILED DESCRIPTION

[0013] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0014] Example 1 The present embodiment discloses a preparation method of a fluorescent polyester fiber material, comprising the following steps: Step one, preparation of modified polyester: 14.8g 5-hexenoic acid, 28.9g N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 16.9g N-hydroxysuccinimide are added into 300g N,N-dimethylformamide, stirred for 20min, then 5.1g 1,5-pentanediamine is added, stirred at 28℃ for 16h, after the reaction is completed, the solvent is removed by rotary evaporation, the obtained solid product is washed with deionized water, and dried to obtain a diamide compound; 15.2g 3,4-diaminobenzoic acid and 21.4g 3-hydroxyphenyl phosphoropropionic acid are added into 400mL of 3mol / L hydrochloric acid aqueous solution, stirred, and refluxed at 95℃ for 9h, a small amount of insoluble impurities is removed by filtration to obtain a brown transparent filtrate, the pH of the filtrate is adjusted to 5.8 by 28% ammonia water to precipitate the product, which is filtered, washed, and dried to obtain a benzimidazole compound; 6.6g of the benzimidazole compound is added into 100g of ethanol, constant stirring is carried out at 65℃, then 29g of a 10% diamide compound / ethanol mixture is added, and the addition is completed within 1h, then constant stirring is carried out at 65℃ for 15h, after the reaction is completed, the solvent is removed by rotary evaporation to obtain a multifunctional modified monomer; ethylene glycol, terephthalic acid, the multifunctional modified monomer, and a catalyst tetrabutyl titanate are mixed in a mass ratio of 100:60:20:0.02, esterification is carried out at 180℃ for 3.5h, and then melt polycondensation is carried out at 255℃ for 2.5h to obtain a modified polyester; Step two, preparation of fluorescent flame-retardant microspheres: 7.4g 5-hexene-1-amine was added to 200g ethanol, ultrasonic treatment for 40min, heated to 60℃, then 6.4g p-mercaptophenol, 30g 0.5% mass fraction of azobisisobutyronitrile / ethanol mixed solution was added, stirring for 5h, after the reaction, filtration, washing, drying, to obtain the intermediate product; 4.5g intermediate product, 3.9g 3,4,9,10-perylenetetracarboxylic dianhydride, 0.04g zinc acetate, 120g N,N-dimethylacetamide was mixed, heated to 105℃ under nitrogen atmosphere for 14h, after the reaction, the solvent was removed by rotary evaporation, the obtained solid product was washed by deionized water, and dried to obtain perylene imide derivative; 2.7g perylene imide derivative was added to 60g acetonitrile, ultrasonic treatment for 40min, then 1g triethylamine was added, and then 71.5g 1% mass fraction of hexachlorocyclotriphosphazene / acetonitrile mixed solution was added dropwise within 30min, the mixed system was ultrasonically reacted at 38℃ for 70min, after the reaction, centrifugation, washing, drying, to obtain fluorescent flame-retardant microspheres; Step three, preparation of fluorescent polyester fiber material: the modified polyester, polyester chip and fluorescent flame-retardant microspheres were mixed in a mass ratio of 3.5:10:0.7, and melt spinning was carried out to obtain modified polyester fiber, wherein the melt spinning conditions were: spinning temperature was 230℃, and spinning speed was 3500m / min; the modified polyester fiber and spandex fiber were blended in a mass ratio of 8:1.5 to obtain blended yarn, and the blended yarn was woven into plain fabric to obtain fluorescent polyester fiber material with a surface density of 170g / m 2 .

[0015] Example 2 The embodiment discloses a preparation method of a fluorescent polyester fiber material, comprising the following steps: Step one, preparation of modified polyester: 27.4g 5-hexenoic acid, 43.4g N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 25.3g N-hydroxysuccinimide were added into 400g N,N-dimethylformamide, stirred for 40min, then 10.2g 1,5-pentanediamine was added, stirred at 32℃ for 14h, after the reaction was completed, the solvent was removed by rotary evaporation, the obtained solid product was washed by deionized water and dried to obtain diamide compound; 15.2g 3,4-diaminobenzoic acid and 21.4g 3-hydroxyphenyl phosphoropropionic acid were added into 600mL 3mol / L hydrochloric acid aqueous solution, stirred and refluxed at 105℃ for 7h, a small amount of insoluble impurities was removed by filtration to obtain brown transparent filtrate, the pH of the filtrate was adjusted to 6.2 by 28% ammonia water to precipitate the product, which was filtered, washed and dried to obtain benzimidazole compound; 13.2g benzimidazole compound was added into 120g ethanol, stirred constantly at 75℃, then 58g 10% diamide compound / ethanol mixture was added, which was added dropwise within 2h, then reacted at 75℃ for 9h, after the reaction was completed, the solvent was removed by rotary evaporation to obtain multifunctional modified monomer; ethylene glycol, terephthalic acid, multifunctional modified monomer and catalyst tetrabutyl titanate were mixed in a mass ratio of 100:80:40:0.02, esterification was carried out at 240℃ for 2.5h, then melt polycondensation was carried out at 265℃ for 1.5h to obtain modified polyester; Step two, preparation of fluorescent flame-retardant microspheres: 7.4g 5-hexene-1-amine was added into 300g ethanol, ultrasonic treated for 40min, heated to 70℃, then 12.6g p-mercaptophenol, 44g 0.5% azobisisobutyronitrile / ethanol mixed solution were added, stirred and reacted for 3h, after the reaction was completed, it was filtered, washed and dried to obtain intermediate product; 9g intermediate product, 7.8g 3,4,9,10-perylenetetracarboxylic dianhydride, 0.06g zinc acetate, 150g N,N-dimethylacetamide were mixed, heated to 115℃ for 10h under nitrogen atmosphere, after the reaction was completed, the solvent was removed by rotary evaporation, the obtained solid product was washed by deionized water and dried to obtain perylene imide derivative; 5.4g perylene imide derivative was added into 60g acetonitrile, ultrasonic treated for 80min, then 1.5g triethylamine was added, then 71.5g 1% hexachlorotriphosphazene / acetonitrile mixed solution was added dropwise within 60min, the mixed system was ultrasonic reacted at 42℃ for 50min, after the reaction was completed, it was centrifuged, washed and dried to obtain fluorescent flame-retardant microspheres; Step three, preparing the fluorescent polyester fiber material: mixing the modified polyester, polyester chip and fluorescent flame-retardant microspheres in a mass ratio of 5.5:10:0.7, melt spinning to obtain the modified polyester fiber, wherein the melt spinning condition is that the spinning temperature is 250℃ and the spinning speed is 4000m / min; mixing the modified polyester fiber and spandex fiber in a mass ratio of 8:2.5 to obtain the blended yarn, weaving the blended yarn into the plain fabric to obtain the fluorescent polyester fiber material with a surface density of 190g / m 2 .

[0016] Example 3 The embodiment discloses a preparation method of a fluorescent polyester fiber material, comprising the following steps: Step one, preparing the modified polyester: adding 21.1g 5-hexenoic acid, 36.2g N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and 21.1g N-hydroxysuccinimide into 350g N,N-dimethylformamide, stirring for 30min, then adding 7.7g 1,5-pentanediamine, stirring at 30℃ for 15h, after the reaction is completed, removing the solvent by rotary evaporation, washing the obtained solid product with deionized water and drying to obtain a diamide compound; adding 22.8g 3,4-diaminobenzoic acid and 32.1g 3-hydroxyphenylphosphorylpropionic acid into 500mL 3mol / L hydrochloric acid aqueous solution, stirring and refluxing at 100℃ for 8h, removing a small amount of insoluble impurities by filtration to obtain a brown transparent filtrate, adjusting the pH of the filtrate to 6 by 28% ammonia water to precipitate the product, filtering, washing and drying to obtain a benzimidazole compound; adding 9.9g benzimidazole compound into 110g ethanol, stirring constantly at 70℃, then adding 43.5g 10% diamide compound / ethanol mixed solution, dropping at a constant rate within 1.5h, then stirring constantly at 70℃ for 12h, after the reaction is completed, removing the solvent by rotary evaporation to obtain a multifunctional modified monomer; mixing ethylene glycol, terephthalic acid, the multifunctional modified monomer and the catalyst tetrabutyl titanate in a mass ratio of 100:70:30:0.02, esterifying at 210℃ for 3h, then melt polycondensing at 260℃ for 2h to obtain the modified polyester; Step two, preparation of fluorescent flame-retardant microspheres: 10.6g 5-hexene-1-amine was added to 250g ethanol, ultrasonic treatment for 30min, heated to 65℃, then 9.5g p-mercaptophenol, 37g 0.5% mass fraction of azobisisobutyronitrile / ethanol mixed solution was added, stirring for 4h, after the reaction, filtration, washing, drying, to get intermediate product; 6.8g intermediate product, 5.9g 3,4,9,10-perylenetetracarboxylic dianhydride, 0.05g zinc acetate, 135g N,N-dimethylacetamide was mixed, heated to 110℃ under nitrogen atmosphere for 12h, after the reaction, the solvent was removed by rotary evaporation, the obtained solid product was washed by deionized water, and dried to obtain perylene imide derivative; 4.1g perylene imide derivative was added to 75g acetonitrile, ultrasonic treatment for 60min, then 1.3g triethylamine was added, and then 55.6g 1% mass fraction of hexachlorocyclotriphosphazene / acetonitrile mixed solution was added dropwise within 45min, the mixed system was ultrasonically reacted at 40℃ for 60min, after the reaction, centrifugation, washing, drying, to obtain fluorescent flame-retardant microspheres; Step three, preparation of fluorescent polyester fiber material: the modified polyester, polyester chip and fluorescent flame-retardant microspheres were mixed in a mass ratio of 4.5:10:0.5, and melt spinning was carried out to obtain modified polyester fiber, wherein the melt spinning conditions were: spinning temperature was 240℃, and spinning speed was 3800m / min; the modified polyester fiber and spandex fiber were blended in a mass ratio of 8:2 to obtain blended yarn, and the blended yarn was woven into plain fabric to obtain fluorescent polyester fiber material with a surface density of 180g / m 2 .

[0017] Comparative example 1 This comparative example discloses a preparation method of a fluorescent polyester fiber material, comprising the following steps: Step one, preparation of fluorescent flame-retardant microspheres: 10.6g 5-hexene-1-amine was added to 250g ethanol, ultrasonic treatment for 30min, heated to 65℃, then 9.5g p-mercaptophenol, 37g 0.5% mass fraction of azobisisobutyronitrile / ethanol mixed solution was added, stirring for 4h, after the reaction, filtration, washing, drying, to get the intermediate product; 6.8g intermediate product, 5.9g 3,4,9,10-perylenetetracarboxylic dianhydride, 0.05g zinc acetate, 135g N,N-dimethylacetamide was mixed, heated to 110℃ in nitrogen atmosphere for 12h, after the reaction, the solvent was removed by rotary evaporation, the obtained solid product was washed by deionized water, and dried to obtain perylene imide derivative; 4.1g perylene imide derivative was added to 75g acetonitrile, ultrasonic treatment for 60min, then 1.3g triethylamine was added, and then 55.6g 1% mass fraction of hexachlorocyclotriphosphazene / acetonitrile mixed solution was added dropwise within 45min, the mixed system was ultrasonically reacted at 40℃ for 60min, after the reaction, centrifugation, washing, drying, to obtain fluorescent flame-retardant microspheres; Step two, preparation of fluorescent polyester fiber material: polyester chips, fluorescent flame-retardant microspheres were mixed in a mass ratio of 14.5:0.5, melt spinning, to obtain modified polyester fiber, wherein the melt spinning conditions: spinning temperature is 240℃, spinning speed is 3800m / min; the modified polyester fiber, spandex fiber was blended in a mass ratio of 8:2 to obtain blended yarn, the blended yarn was woven into plain fabric to obtain fluorescent polyester fiber material with a surface density of 180g / m 2 .

[0018] Comparative example 2 The present comparative example discloses a preparation method of a fluorescent polyester fiber material, comprising the following steps: Step one, preparation of modified polyester: 21.1g 5-hexenoic acid, 36.2g N-(3- dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, 21.1g N-hydroxysuccinimide were added into 350g N,N-dimethylformamide, stirred for 30min, then 7.7g 1,5-pentanediamine was added, stirred at 30℃ for 15h, after the reaction was completed, the solvent was removed by rotary evaporation, and the obtained solid product was washed with deionized water and dried to obtain a diamide compound; 22.8g 3,4-diaminobenzoic acid and 32.1g 3-hydroxyphenyl phosphoroyl propionic acid were added into 500mL 3mol / L hydrochloric acid aqueous solution, stirred and refluxed at 100℃ for 8h, a small amount of insoluble impurities was removed by filtration to obtain a brown transparent filtrate, the pH of the filtrate was adjusted to 6 by 28% ammonia water to precipitate the product, which was filtered, washed and dried to obtain a benzimidazole compound; 9.9g benzimidazole compound was added into 110g ethanol, stirred constantly at 70℃, then 43.5g 10% diamide compound / ethanol mixture was added, and the addition was completed in 1.5h, then the reaction was constantly stirred at 70℃ for 12h, after the reaction was completed, the solvent was removed by rotary evaporation to obtain a multifunctional modified monomer; ethylene glycol, terephthalic acid, multifunctional modified monomer and catalyst tetrabutyl titanate were mixed in a mass ratio of 100:70:30:0.02, esterification was carried out at 210℃ for 3h, and then melt polycondensation was carried out at 260℃ for 2h to obtain the modified polyester; Step two, preparation of perylene imide derivative: 6.8g intermediate product, 5.9g 3,4,9,10-perylenetetracarboxylic dianhydride, 0.05g zinc acetate, 135g N,N-dimethylacetamide were mixed, heated to 110℃ for 12h under nitrogen atmosphere, after the reaction was completed, the solvent was removed by rotary evaporation, and the obtained solid product was washed with deionized water and dried to obtain the perylene imide derivative; Step three, preparation of fluorescent polyester fiber material: the modified polyester, polyester chip and perylene imide derivative were mixed in a mass ratio of 4.5:10:0.5, melt spinning was carried out to obtain the modified polyester fiber, wherein the melt spinning conditions were: spinning temperature was 240℃, and spinning speed was 3800m / min; the modified polyester fiber and spandex fiber were blended in a mass ratio of 8:2 to obtain blended yarn, the blended yarn was woven into plain fabric to obtain the fluorescent polyester fiber material with a surface density of 180g / m 2 .

[0019] Experimental example The fluorescent polyester fiber materials prepared in examples 1-3 and comparative examples 1-2 were tested for performance.

[0020] I. Flame retardant performance test: (1) Limiting oxygen index test: The oxygen index tester was used to test according to the international standard GB / T 5454-2018; (2) Vertical burning (UL-94) grade test: The CZF-5 type vertical burning instrument was used to test.

[0021] II. Abrasion resistance test: The abrasion tester was used to test according to the international standard GB / T21196.3-2007. The test fabric was cut into a circle with a diameter of 38±0.5mm, the standard 600 mesh sandpaper was used as the abrasive (the abrasive was replaced once more than 5000 times), the pressure was 9kPa, the breaking of two independent yarns of the fabric was the end point of abrasion resistance, and the number of abrasion was recorded.

[0022] The test results are shown in Table 1:

[0023] As can be seen from the test results in Table 1, the fluorescent polyester fiber material prepared by Examples 1-3 has good abrasion resistance and flame retardance. As can be seen from the comparison between Comparative Example 1 and Example 3, the introduction of diamide structure, benzimidazole structure and flame-retardant nitrogen and phosphorus elements in the modified polyester by the multifunctional modified monomer improves the abrasion resistance and flame retardance of the fluorescent polyester fiber material. As can be seen from the comparison between Comparative Example 2 and Example 3, the presence of nitrogen, phosphorus elements and aromatic rings in the fluorescent flame-retardant microspheres gives them excellent flame-retardant effect, and the uniform dispersion of the fluorescent flame-retardant microspheres in the polyester matrix and the reinforcing and toughening effect of the micro-nano particles improve the flame retardance and abrasion resistance of the polyester fiber, thereby giving the fluorescent polyester fiber material better abrasion resistance and flame retardance.

[0024] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A process for the production of a fluorescent polyester fibre material, characterised in that, It comprises the following steps: Step one, preparation of modified polyester: ethylene glycol, terephthalic acid, multifunctional modified monomer, tetrabutyl titanate are mixed in a mass ratio of 100: (60-80): (20-40): 0.02, esterification, polycondensation, to obtain modified polyester; Step two, preparation of fluorescent flame-retardant microspheres: 5-hexene-1-amine is reacted with p-mercaptophenol to obtain an intermediate product; the intermediate product is reacted with 3,4,9,10-perylenetetracarboxylic dianhydride to obtain a perylene imide derivative; the perylene imide derivative is reacted with hexachlorocyclotriphosphazene to obtain fluorescent flame-retardant microspheres; Step three, preparation of fluorescent polyester fiber material: modified polyester, polyester chip, fluorescent flame-retardant microspheres are mixed in a mass ratio of (3.5-5.5): 10: (0.2-0.7), melt spinning, to obtain modified polyester fiber; the modified polyester fiber and spandex fiber are blended and woven to obtain the fluorescent polyester fiber material. In step one, the preparation method of the multifunctional modified monomer comprises: 5-hexenoic acid, N-(3-dimethylaminopropyl)-N'-ethyl carbodiimide hydrochloride, N-hydroxysuccinimide, N,N-dimethylformamide, and 1,5-pentanediamine are mixed in a mass ratio of (14.8-27.4): (28.9-43.4): (16.9-25.3): (300-400): (5.1-10.2), stirred and reacted at 28-32℃ for 14-16h, purified to obtain a diamide compound; 3,4-diaminobenzoic acid, 3-hydroxyphenylphosphorylpropionic acid, and 3mol / L hydrochloric acid aqueous solution are mixed in a mass ratio of (15.2-30.4)g: (21.4-42.8)g: (400-600)mL, stirred, and refluxed at 95-105℃ for 7-9h, purified to obtain a benzimidazole compound; the benzimidazole compound is added into ethanol, stirred constantly at 65-75℃, then the diamide compound / ethanol mixture with a mass fraction of 10% is added dropwise in 1-2h, then stirred constantly at 65-75℃ for 9-15h, and purified to obtain the multifunctional modified monomer; wherein the mass ratio of the benzimidazole compound, ethanol, and the diamide compound / ethanol mixture is (6.6-13.2): (100-120): (29-58).

2. The method of making a fluorescent polyester fiber material according to claim 1, characterized in that, In step one, the esterification conditions are: esterification at 180-240℃ for 2.5-3.5h, and the polycondensation conditions are: melt polycondensation at 255-265℃ for 1.5-2.5h.

3. The method of making a fluorescent polyester fiber material according to claim 1, wherein, In step two, the preparation method of the intermediate product specifically comprises: 5-hexene-1-amine is added into ethanol, ultrasonicated, heated to 60-70℃, then p-mercaptophenol and azobisisobutyronitrile / ethanol mixed solution are added, stirred and reacted for 3-5h, and purified to obtain the intermediate product; wherein the mass ratio of 5-hexene-1-amine, ethanol, p-mercaptophenol, and azobisisobutyronitrile / ethanol mixed solution is (7.4-13.8): (200-300): (6.4-12.6): (30-44).

4. The method of making a fluorescent polyester fiber material according to claim 1, wherein, ​ 5. The method of making a fluorescent polyester fiber material according to claim 1, wherein, In step two, the preparation method of the perylene imide derivative specifically includes: mixing the intermediate product, 3,4,9,10-perylenetetracarboxylic dianhydride, zinc acetate, and N,N-dimethylacetamide in a mass ratio of (4.5-9):(3.9-7.8):(0.04-0.06):(120-150), heating to 105-115℃ for 10-14 h in a nitrogen atmosphere, and purifying to obtain the perylene imide derivative.

6. The method of making a fluorescent polyester fiber material according to claim 1, wherein, In step two, the preparation method of the fluorescent flame-retardant microspheres specifically includes: adding perylene imide derivative to a nitrile, sonicating, then adding triethylamine, and then adding a 1% (w / w) hexachlorocyclotriphosphazene / acetonitrile mixture dropwise over 30-60 min. The mixture is then sonicated at 38-42℃ for 50-70 min, purified, and fluorescent flame-retardant microspheres are obtained. The mass ratio of perylene imide derivative, acetonitrile, triethylamine, and hexachlorocyclotriphosphazene / acetonitrile mixture is (2.7-5.4):(60-90):(1-1.5):(39.7-71.5).

7. The method of making a fluorescent polyester fiber material according to claim 1, wherein, In step three, the melt spinning conditions are: spinning temperature of 230-250℃ and spinning speed of 3500-4000m / min.

8. The method of making a fluorescent polyester fiber material according to claim 1, wherein, The mass ratio of the modified polyester fiber and the spandex fiber in the third step is 8: (1.5-2.5); the areal density of the fluorescent polyester fiber material is 170-190 g / m 2 .

9. A fluorescent polyester fiber material prepared by the method for preparing fluorescent polyester fiber material as described in any one of claims 1-8.

10. The application of the fluorescent polyester fiber material according to claim 9 in bags and luggage.

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