An anti-mildew differentiated polyester fiber, a method for preparing the same, and an application thereof in a polyester fiber sound absorption panel

Abstract

This invention discloses an anti-mildew differentiated polyester fiber, its preparation method, and its application in polyester fiber sound-absorbing panels, relating to the fields of polymer materials and functional fibers. The anti-mildew differentiated polyester fiber is made from raw materials comprising the following parts by weight: 80-95 parts polyester chips, 1-5 parts inorganic antibacterial agent, 0.5-3 parts composite photothermal catalyst, 3-10 parts functional filler, 0.2-1.5 parts UV stabilizer, 0.5-4 parts polyester anchoring anti-mildew synergist, and 0.1-1 parts additives. This synergistic design of the anti-mildew differentiated polyester fiber of this invention enables it to comprehensively and effectively solve the industry problems of easy mold growth and single, unsustainable anti-mildew measures in humid and quiet application environments while maintaining good spinnability and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of polymer materials and functional fiber technology, specifically to an anti-mildew differentiated polyester fiber, its preparation method, and its application in polyester fiber sound-absorbing panels. Background Technology

[0002] In the polyester fiber industry, polyethylene terephthalate (PET) fiber is widely used in textiles, apparel, home textiles, and industrial textiles due to its excellent mechanical properties, chemical resistance, and ease of processing. With the continuous expansion of application scenarios, especially when used as reinforcement or filler material for decorative panels in humid and poorly ventilated indoor environments, higher demands are placed on the functionality of the fiber. Traditional polyester fibers themselves lack antibacterial and antifungal capabilities, and under suitable temperature and humidity conditions, they easily become carriers for mold and bacteria growth. This not only causes the material to yellow and become brittle, affecting its service life and aesthetics, but may also release spores and odors, harming indoor air quality and human health.

[0003] Currently, the mainstream technologies for imparting anti-mildew properties to polyester fibers mainly involve blending with inorganic or organic antibacterial agents. However, these methods have significant limitations. Inorganic antibacterial agents tend to agglomerate in the polyester matrix, exhibiting poor dispersibility, which affects spinning processes and fiber mechanical properties. Furthermore, their antibacterial effect largely depends on the slow release of metal ions, leading to a decline in effectiveness over long-term use. Conventional small-molecule organic antibacterial agents, on the other hand, suffer from poor heat resistance, poor compatibility with polyester, and a tendency to migrate and precipitate, resulting in short-lasting anti-mildew properties and potential environmental and safety risks.

[0004] On the other hand, in the field of interior decoration, the demand for sound-absorbing materials is increasing, often employing porous, lightweight fiber materials to absorb sound waves. However, these porous structures are more prone to absorbing moisture from the environment. Without active moisture-proof and anti-mold mechanisms, they can actually exacerbate mold growth, creating a functional contradiction. Currently, there is a lack of a comprehensive solution that organically combines long-lasting anti-mold and active moisture-proof properties with good spinnability, fiber mechanical properties, and sound-absorbing characteristics.

[0005] Therefore, developing a functional, differentiated fiber with long-lasting and stable anti-mildew properties, capable of adapting to complex and humid environments, and compatible with existing polyester spinning processes, suitable for high-end soundproof decorative panels, has significant market value and is technically necessary. Summary of the Invention

[0006] The purpose of this invention is to address the problems of the non-durable and easily migrated anti-mold function of polyester fibers in the prior art, as well as the passive and single anti-mold measures in humid and quiet application environments. The invention provides a differentiated anti-mold polyester fiber that has both long-lasting anchoring anti-mold and photothermal assisted moisture-proof and drying functions, is easy to process, and is suitable for sound-absorbing decorative panels, as well as its preparation method and its application in polyester fiber sound-absorbing panels.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a mildew-resistant differentiated polyester fiber, made from raw materials comprising the following parts by weight: 80-95 parts polyester chips, 1-5 parts inorganic antibacterial agent, 0.5-3 parts composite photothermal catalyst, 3-10 parts functional filler, 0.2-1.5 parts UV stabilizer, 0.5-4 parts polyester anchoring mildew synergist, and 0.1-1 parts additives; The preparation method of the polyester anchoring antifungal synergist is as follows: A1: Salicylic acid and dihydroxyethyl terephthalate were added to a reaction vessel at a molar ratio of 1:1.1-1.3. Tetrabutyl titanate was added as a catalyst at a mass of 0.05% of the total reactants. The mixture was heated to 180℃-195℃ under nitrogen protection for esterification reaction for 2-3 hours. The dewatering was collected and monitored. The reaction ended when no water was dewatered, and a polyester anchored antifungal primary polymer containing hydroxyethyl end groups was obtained. A2: The polyester anchored antifungal primordium is completely dissolved in anhydrous ethanol at a mass concentration of 20%, and acidified halloysite nanotubes are added, wherein the mass ratio of the primordium to the acidified halloysite nanotubes is 1:3. The mixture is placed in a vacuum reactor and maintained at room temperature and an absolute vacuum of -0.08MPa to -0.095MPa for 45-60 minutes. Then, the anhydrous ethanol is removed by rotary evaporation at 55-65℃ to obtain halloysite powder with the antifungal primordium loaded in the inner cavity. A3: Mix the halloysite powder with low molecular weight polyethylene wax at a mass ratio of 1:1-1.2, heat to 115℃-125℃ to completely melt the polyethylene wax, and use a high shear dispersion emulsifier to physically mix for 15-20 minutes under high-speed shear force of 12000-15000 rpm, so that the polyethylene wax uniformly and physically coats the outer surface of the halloysite nanotubes and seals the tube openings. After cooling, a wax-sealed hard block is obtained. A4: Immerse the wax-sealed hard block in liquid nitrogen at -196°C for 15-20 minutes to induce a physical embrittlement phase transition, then transfer it to an ultra-micro airflow pulverizer for cryogenic pulverization. Control the D50 particle size of the resulting powder to be 0.8-1.2 micrometers to obtain the polyester anchoring antifungal synergist.

[0008] Furthermore, the polyester chips are polyethylene terephthalate chips with an intrinsic viscosity of 0.60-0.68 dL / g.

[0009] Furthermore, the composite photothermal catalyst is a core-shell structure material formed by supporting noble metal nanoparticles on a semiconductor oxide support; Furthermore, the preparation method of the composite photothermal catalyst includes the following steps: B1: Nanoscale semiconductor oxide carriers are prepared by sol-gel or hydrothermal methods; B2: Disperse the carrier material in deionized water to form a uniform suspension; B3: Add a noble metal precursor salt solution to the suspension, and use stirring and sonication to make the precursor ions uniformly adsorbed on the surface of the carrier. B4: Under heating conditions of 60-120℃, the adsorbed noble metal ions are reduced to zero-valent metal atoms, the atoms aggregate to form nanoparticles, and anchor on the surface of the carrier to form a composite structure. B5: After filtration, washing, and drying, it is calcined in an inert atmosphere at 300-500℃ for 2-5 hours to obtain the composite photothermal catalyst.

[0010] Furthermore, the noble metal precursor salt solution is at least one of palladium chloride, palladium nitrate, palladium acetate, chloroplatinic acid, or potassium chloroplatinate; the concentration of the aqueous solution of the noble metal precursor salt is 0.01-0.5 mol / L. Furthermore, when the noble metal is palladium, the precursor salt solution is an aqueous solution of palladium chloride or palladium acetate with a concentration of 0.05-0.2 mol / L; when the noble metal is platinum, the precursor salt solution is an aqueous solution of chloroplatinic acid or potassium chloroplatinate with a concentration of 0.02-0.1 mol / L.

[0011] Furthermore, the semiconductor oxide carrier is titanium dioxide or zinc oxide.

[0012] Furthermore, the inorganic antibacterial agent is at least one of silver-loaded zirconium phosphate, silver-loaded glass powder, or nano zinc oxide.

[0013] Furthermore, the functional filler is at least one of porous silica, hollow glass microspheres, and expanded perlite powder, with a particle size D50 of 1-10 μm.

[0014] Furthermore, the UV absorber is at least one of benzotriazole UV absorbers, hindered amine light stabilizers, or nano-titanium dioxide; The benzotriazole UV absorber is selected from at least one of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole or 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole; At least one of the hindered amine light stabilizers bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol) ester, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or a compound of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and n-butyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0015] Furthermore, the preparation method of the acidified halloysite nanotubes is as follows: halloysite nanotubes are dispersed in a dilute hydrochloric acid solution with a concentration of 1-3 mol / L at a solid-liquid mass ratio of 1:10-1:20, and the mixture is stirred at a constant temperature of 60℃-80℃ for 2-4 hours; after the reaction is completed, the mixture is centrifuged and washed repeatedly with deionized water until the filtrate is neutral; then the obtained solid is placed in a vacuum drying oven at 80℃-100℃ and dried for 12-24 hours to obtain the acidified halloysite nanotubes.

[0016] Furthermore, the additives include one or more of antioxidant 1010, lubricant ethylene bis-stearamide, and coupling agent KH-550.

[0017] A method for preparing the anti-mildew differentiated polyester fiber includes the following steps: S1. Pre-processing: The polyester chips are vacuum dried at 100-120℃ for 4-6 hours; the inorganic antibacterial agent, composite photothermal catalyst, functional filler, UV stabilizer and additives are mixed evenly in a high-speed mixer to obtain functional masterbatch premix. S2. Blending and Melting: The dried polyester chips, functional masterbatch premix and polyester anchoring antifungal synergist are added to a twin-screw extruder, melt-blended, extruded, cooled and pelletized at 260-280℃ to obtain functional polyester masterbatch; S3. Spinning: The functional polyester masterbatch is dried in a vacuum drum and then fed into a screw extruder to melt at 265-285°C. After passing through a metering pump and a spinning assembly, it is spun into nascent fibers. S4. Post-processing: The nascent fibers are subjected to ring blowing cooling, oiling, stretching, heat setting and winding to obtain the mildew-resistant differentiated polyester fiber.

[0018] Furthermore, the application of a mildew-resistant differentiated polyester fiber in the preparation of a silent decorative material with photothermal drying effect and mildew resistance.

[0019] Furthermore, a polyester anchoring anti-mold synergist in anti-mold differentiated polyester fibers can also be used in high-performance nylon, polyester, acrylic, vinylon, polypropylene, and spandex.

[0020] Furthermore, the application of a mildew-resistant differentiated polyester fiber in the preparation of polyester fiber sound-absorbing panels.

[0021] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention employs an inner cavity loading-wax sealing structure design for a polyester-anchored antifungal synergist. This design anchors a polyester-anchored antifungal precursor containing hydroxyethyl end groups within the inner cavity of an acidified halloysite nanotube. A low-molecular-weight polyethylene wax is then uniformly and physically coated onto the outer surface of the halloysite nanotube, sealing the opening and forming a physical protective layer. This structure effectively solves the problems of poor compatibility, easy migration and precipitation, and poor heat resistance of conventional small-molecule organic antibacterial agents with polyester, leading to short-lasting antifungal function. It also overcomes the long-term efficacy degradation caused by the slow release of metal ions, which is a limitation of inorganic antibacterial agents. The polyester-anchored antifungal synergist and the inorganic antibacterial agent form a synergistic dual antifungal mechanism. After 50 standard washes, the antifungal level remains at level 0, demonstrating long-lasting and stable antifungal function while avoiding environmental and safety risks.

[0022] 2. This invention introduces a composite photothermal catalyst formed by loading noble metal nanoparticles onto a semiconductor oxide support. This catalyst endows the anti-mold differentiated polyester fiber with a significant photothermal heating effect under simulated sunlight, providing a heat source for active moisture-proofing and drying. This effectively suppresses the problem of mold growth exacerbated by the porous structure of the material adsorbing moisture in humid and quiet environments. Simultaneously, the functional filler, while maintaining sound absorption and noise reduction properties, works synergistically with the composite photothermal catalyst to achieve an organic combination of active moisture-proofing and drying with quiet operation. This overcomes the technical bottleneck of existing technologies that lack the integrated functionality of long-lasting anti-mold, active moisture-proofing, and quiet operation.

[0023] 3. The wax-sealing process of the polyester anchoring antifungal synergist after cryogenic pulverization with liquid nitrogen in this invention effectively prevents the aggregation of inorganic nanomaterials and the formation of interface defects in the polyester matrix, significantly improving the dispersibility of functional fillers, inorganic antibacterial agents, and composite photothermal catalysts in polyester chips. This not only avoids the problem of traditional inorganic antibacterial agents easily agglomerating and affecting the spinning process, leading to the deterioration of fiber mechanical properties, but also ensures that the antifungal differentiated polyester fibers maintain good spinnability and excellent mechanical properties during melt spinning, meeting the requirements of high-end silent decorative panels for fiber strength and processing adaptability. Attached Figure Description

[0024] Figure 1 This is a comparison chart of the maximum photothermal temperature rise ΔTmax (°C) between the examples and the comparative examples.

[0025] Figure 2 This is a comparison chart of the fracture strength (cN / dtex) of the examples and the comparative examples. Detailed Implementation

[0026] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Preparation Example 1: Preparation of polyester-anchored antifungal synergist: Preparation of acidified halloysite nanotubes: Natural halloysite nanotubes (diameter: 50-300 nm, length: 1-10 μm) were dispersed in a 2 mol / L dilute hydrochloric acid solution at a solid-liquid mass ratio of 1:15 and stirred at 70 °C for 3 hours. After the reaction, the mixture was centrifuged at 8000 r / min for 10 minutes and washed repeatedly with deionized water until the filtrate was neutral (pH=7). The resulting solid was then dried in a vacuum drying oven at 90 °C for 18 hours to obtain acidified halloysite nanotubes, which were then sealed for later use.

[0028] The natural halloysite nanotubes were sourced from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0029] A1. Preparation of polyester anchored antifungal prepolymer: Salicylic acid and dihydroxyethyl terephthalate (molar ratio 1:1.2) were added to a reactor equipped with a mechanical stirrer, a nitrogen inlet pipe and a water separator. Tetrabutyl titanate, accounting for 0.05% of the total mass of the reactants, was added as a catalyst. Under nitrogen protection, the temperature was raised to 185°C for esterification reaction for 2.5 hours. During the reaction, the released water was continuously collected and monitored. The reaction ended when no water was released, and polyester anchored antifungal prepolymer containing hydroxyethyl end groups was obtained.

[0030] Note: Step A1 does not require the addition of solvent; it is a solvent-free bulk reaction. When the reactor temperature reaches 185°C, the solid raw materials have already exceeded their melting points, melting and mixing into a low-viscosity homogeneous melt. Mechanical stirring ensures thorough mixing and mass transfer of the reaction system, eliminating the need for external liquid solvents.

[0031] A2. Inner cavity loading: The above-mentioned polyester anchored anti-mildew primordium was completely dissolved in anhydrous ethanol at a mass concentration of 20%, and acidified halloysite nanotubes were added, wherein the mass ratio of the primordium to the acidified halloysite nanotubes was 1:3. The mixture was placed in a vacuum reactor and maintained at room temperature and an absolute vacuum of -0.09 MPa for 50 minutes to allow the primordium to fully enter the inner cavity of the halloysite nanotubes under negative pressure. Subsequently, the anhydrous ethanol was removed by rotary evaporation at 60°C to obtain halloysite powder with inner cavity loaded anti-mildew primordium.

[0032] A3. Wax sealing: Mix the above halloysite powder with low molecular weight polyethylene wax at a mass ratio of 1:1.1, heat to 120°C to completely melt the polyethylene wax, and use a high-shear dispersion emulsifier to physically mix for 18 minutes under high-speed shear force of 13000 rpm, so that the polyethylene wax uniformly and physically coats the outer surface of the halloysite nanotubes and seals the tube openings. After naturally cooling to room temperature, a wax-sealed hard block is obtained.

[0033] A4. Cryogenic pulverization: The wax-sealed hard block is immersed in liquid nitrogen at -196°C for 18 minutes to induce a physical embrittlement phase transition. It is then transferred to an ultra-micro airflow pulverizer for cryogenic pulverization. The airflow pressure is controlled at 0.8 MPa and the classifier speed is 8000 r / min. The resulting powder is measured to have a D50 particle size of 1.0 μm by a laser particle size analyzer, thus obtaining the polyester anchoring antifungal synergist.

[0034] Comparative preparation example 1: The preparation of the polyester anchoring antifungal synergist was carried out in accordance with the preparation method of Preparation Example 1, except that step A3 was omitted. The types and proportions of the remaining raw materials and the preparation steps were consistent with those of Preparation Example 1.

[0035] Example 1: Preparation of a mildew-resistant differentiated polyester fiber: 1. Raw material components by weight: Polyester chips: 90 portions, selected from polyethylene terephthalate chips, purchased from: Sinopec Yizheng Chemical Fiber Co., Ltd.; Inorganic antibacterial agent: 3 parts, selected from silver-loaded zirconium phosphate, purchased from Guangzhou Yuanda New Materials Co., Ltd.; Composite photothermal catalyst: 2 parts, selected from platinum / titanium dioxide core-shell structured nanomaterials; Functional filler: 6 parts, selected from porous silica, purchased from Suzhou Nanomicro Life Technology Co., Ltd., with a particle size of 5μm and model SPBNU-500; UV absorber: 0.8 parts, selected from benzotriazole UV absorbers, specifically 2-(2'-hydroxy-5'-methylphenyl)benzotriazole; Polyester anchoring antifungal synergist: 2 parts, selected from the polyester anchoring antifungal synergist prepared in Synthesis Example 1; Additive: 0.5 parts, selected from antioxidant 1010.

[0036] 2. The preparation method of the composite photothermal catalyst is as follows: S201. Preparation of Semiconductor Oxide Support: Nanoscale titanium dioxide support was prepared using the sol-gel method. 20 mL of tetrabutyl titanate was dissolved in 80 mL of anhydrous ethanol to prepare solution A; 10 mL of deionized water, 0.5 mL of concentrated hydrochloric acid (37% by mass), and 40 mL of anhydrous ethanol were mixed to prepare solution B. At room temperature (25℃), solution B was slowly added dropwise to solution A at a rate of 2 mL / min, while continuously stirring at 500 r / min. After the addition was complete, stirring continued for 2 hours to form a uniform milky white sol. The sol was transferred to a hydrothermal reactor and hydrothermally reacted at 180℃ for 12 hours. After the reaction was completed, the mixture was cooled to room temperature. The precipitate was washed three times by centrifugation with deionized water (centrifugation speed 8000 r / min, 10 minutes each time), and then washed once with anhydrous ethanol. Subsequently, it was dried in a vacuum drying oven at 80℃ for 12 hours to obtain anatase nano titanium dioxide powder with a particle size distribution of 20-50 nm, which was denoted as the carrier material. S202. Carrier dispersion: Take 5g of the nano titanium dioxide carrier prepared above, disperse it in 200mL of deionized water, and ultrasonically disperse it for 30 minutes (ultrasonic power 200W, frequency 40kHz) to form a uniform suspension. S203. Noble Metal Loading: A chloroplatinic acid aqueous solution with a concentration of 0.05 mol / L was added to the above suspension in a volume of 20 mL, resulting in a theoretical platinum loading of 4 wt% (based on the percentage of platinum element mass to the carrier mass). After addition, the mixture was stirred at 300 r / min for 2 hours, and ultrasonic-assisted dispersion was used (ultrasonication for 10 minutes every 30 minutes of stirring, with an ultrasonic power of 150 W) to ensure uniform adsorption of platinum precursor ions onto the titanium dioxide carrier surface. S204. Reduction treatment: The above suspension of adsorbed platinum ions was transferred to a three-necked flask, protected by nitrogen gas, heated to 80°C, and kept at this temperature with continuous stirring (stirring speed 300 r / min) for 2 hours to reduce the adsorbed platinum ions to zero-valent platinum metal atoms. The atoms aggregated to form platinum nanoparticles with a particle size of 3-8 nm, and anchored on the surface of the titanium dioxide support to form a Pt / TiO2 composite structure. S205. Calcination treatment: The reduced product was cooled to room temperature and filtered (using a mixed cellulose ester microporous membrane with a pore size of 0.22 μm). It was washed with deionized water until the filtrate was neutral (pH=7), then washed once with anhydrous ethanol, and subsequently dried in a vacuum drying oven at 80℃ for 6 hours. The dried powder was transferred to a tube furnace and calcined at 400℃ at a heating rate of 5℃ / min under a nitrogen atmosphere (inert atmosphere) for 3 hours. After naturally cooling to room temperature, it was ground and sieved (200 mesh) to obtain the composite photothermal catalyst (Pt / TiO2).

[0037] 3. Preparation steps: S1. Pre-processing: The polyester chips are placed in a vacuum drying oven and vacuum dried at 110°C for 5 hours to remove moisture from the polyester chips and prevent hydrolysis during melt spinning; then the inorganic antibacterial agent, composite photothermal catalyst, functional filler, UV stabilizer and antioxidant 1010 are added to a high-speed mixer and mixed at 800 r / min for 15 minutes. After uniform mixing, functional masterbatch premix is ​​obtained. S2. Blending and Melting: The dried polyester chips, functional masterbatch premix, and polyester anchoring antifungal synergist 1 prepared in Synthesis Example 1 were added to a co-rotating twin-screw extruder according to the specified ratio. The temperature settings of each section of the twin-screw extruder were controlled as follows: Zone 1 265℃, Zone 2 270℃, Zone 3 275℃, Zone 4 275℃, Zone 5 270℃, and Die Head 270℃. The screw speed was 150 r / min. The mixture was melt-blended at 270℃. The melt was extruded into strips through the die head, cooled by a water cooling tank (water temperature 20±2℃), and pelletized by a pelletizer (particle size 3 mm, length 4 mm) to obtain functional polyester masterbatch. S3. Spinning: The functional polyester masterbatch is placed in a vacuum drum dryer and vacuum dried at 110°C (vacuum degree ≤ -0.09MPa) for 6 hours to reduce the moisture content of the masterbatch to below 20ppm. After drying, it is fed into a screw extruder. The temperature settings of each section of the screw extruder are as follows: Zone 1 270°C, Zone 2 275°C, Zone 3 280°C, Zone 4 280°C, and Metering pump zone 280°C. The masterbatch is fully melted at 280°C and accurately metered by the metering pump (pump supply 2.5mL / r). The melt is filtered through the spinning assembly (the assembly is equipped with a metal sand filter layer with a filtration accuracy of 30μm) and then spun out by the spinneret (48 spinneret holes, 0.25mm in diameter) to form nascent fibers. S4. Post-treatment: The nascent fibers are cooled and shaped by a ring blower at a temperature of 25°C, a wind speed of 0.5 m / s, and a relative humidity of 65%. Then, they are oiled using an oiler specifically for polyester fiber spinning (such as NF-770 from Takemoto Oils Co., Ltd., Japan), with an oiling rate controlled at 1.2 wt%. Next, the fibers undergo three stages of drawing, with a total draw ratio of 3.5 (first stage draw ratio 1.1, temperature 70°C; second stage draw ratio 1.3, temperature 80°C; third stage draw ratio 2.5, temperature 90°C). Following this, they are heat-set at 130°C (heat-setting time 2 seconds), and then wound on a winding machine (winding speed 3000 m / min) to obtain the aforementioned anti-mildew differentiated polyester fiber with a specification of 167 dtex / 48f.

[0038] Example 2: The preparation of a mildew-resistant differentiated polyester fiber is carried out according to the preparation method of Example 1, except that "inorganic antibacterial agent: 3 parts, selected from silver-loaded zirconium phosphate" is replaced with "inorganic antibacterial agent: 3 parts, selected from silver-loaded glass powder", and the other raw material types, ratios and preparation steps are consistent with those of Example 1.

[0039] Example 3: The preparation of a mildew-resistant differentiated polyester fiber is carried out according to the preparation method of Example 1, except that "functional filler: 6 parts, selected from porous silica" is replaced with "functional filler: 6 parts, selected from hollow glass microspheres", and the other raw material types, ratios and preparation steps are consistent with those of Example 1.

[0040] Comparative Example 1: The preparation of a mildew-resistant differentiated polyester fiber is carried out by referring to the preparation method of Example 1, except that the polyester anchoring mildew synergist is replaced with an equal amount of salicylic acid, and the other raw material types, ratios and preparation steps are consistent with those of Example 1.

[0041] Comparative Example 2: The preparation of a mildew-resistant differentiated polyester fiber is carried out according to the preparation method of Example 1, without adding the composite photothermal catalyst, and the other raw material types, ratios and preparation steps are consistent with those of Example 1.

[0042] Comparative Example 3: The preparation of a mildew-resistant differentiated polyester fiber is carried out by referring to the preparation method of Example 1, except that the polyester anchoring mildew synergist is replaced with the polyester anchoring mildew synergist prepared in Comparative Preparation Example 1, and the other raw material types, ratios and preparation steps are consistent with those of Example 1.

[0043] Performance testing: Anti-mildew performance test: The test was conducted according to GB / T24346-2009 standard using the plate culture method. Specifically, the anti-mildew differentiated polyester fibers prepared in Examples 1-5 and Comparative Examples 1-5 were woven into 10cm×10cm standard non-woven fabric sheets and placed in sterile petri dishes. Aspergillus niger and Aspergillus flavus were selected as test strains, and the spore suspension concentration was adjusted to 1×10⁻⁶. 6 After spraying spores / mL evenly onto the surface of the sample and the blank control (ordinary PET nonwoven fabric), the inoculated sample was then placed in an incubator at 28±1℃ and 90% relative humidity for 28 consecutive days. During this period, the growth of mold on the sample surface was observed and recorded every 7 days. Finally, the anti-mold level was rated according to the percentage of mold growth area: Level 0 (no growth), Level 1 (growth area ≤10%), Level 2 (10%<growth area ≤30%), Level 3 (30%<growth area ≤60%), and Level 4 (growth area >60%). The anti-mold level data after 28 days of incubation are recorded in Table 1.

[0044] Photothermal heating performance test: The surface temperature change of the sample was monitored using an infrared thermal imager. During the test, the nonwoven fabric sample was placed under a standard light source simulating sunlight (light intensity 1000W / m²). 2 The light source was positioned 20 cm vertically above the sample, and the ambient temperature was kept constant at 25°C. The surface temperature at the center of the sample was recorded at 0 minutes and 30 minutes of illumination, and the maximum temperature rise (ΔT) within 30 minutes was calculated. max =T 30min -T 0min The test data is listed in Table 1.

[0045] Mechanical property testing: The test was conducted in accordance with GB / T14337-2008 standard. After the fibers of each component product were equilibrated under standard temperature and humidity conditions (20℃, 65%RH) for 24 hours, they were tested using an electronic single fiber tensile tester at a clamping distance of 20mm and a tensile speed of 20mm / min. Each sample was tested 30 times and the average value was taken. The breaking strength (cN / dtex) and breaking elongation (%) were recorded. The test data are listed in Table 1.

[0046] Washability test: The washing procedure in GB / T12490-2014 was slightly modified to evaluate the durability of the function. Specifically, the nonwoven fabric sample was placed in a washing solution containing standard detergent (liquor ratio 1:50) and mechanically stirred at 40°C for 45 minutes to simulate one washing cycle. After rinsing, dehydration and drying, the samples that had undergone 0 and 50 standard washes were tested again according to the aforementioned anti-mildew performance test method after 28 days of incubation to evaluate the long-lasting anti-mildew function. The anti-mildew level data after 50 washes are listed in Table 1.

[0047] Table 1 like Figures 1-2 As shown, the example group containing the complete formulation achieved a good synergistic balance in terms of anti-mildew durability, photothermal heating effect, and fiber mechanical properties, and maintained excellent anti-mildew function after washing. However, when the polyester anchoring anti-mildew synergist was directly replaced by a simple small molecule, although the photothermal performance was retained, the fiber mechanical strength was significantly deteriorated, and the anti-mildew function's wash-resistance durability was greatly reduced. If the composite photothermal catalyst was removed, the anti-mildew performance and mechanical properties were basically unaffected, but the active photothermal moisture-proof and drying effect was almost completely lost. If an unsealed halloysite loading system was used, the initial anti-mildew and photothermal performance could still be maintained, but the fiber mechanical properties and the anti-mildew durability after washing both showed a significant decrease, indicating that the wax-sealed hard shell structure plays a key role in ensuring interfacial compatibility and long-term functional release.

[0048] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A mildew-resistant differentiated polyester fiber, characterized in that, It is made from raw materials containing the following parts by weight: 80-95 parts polyester chips, 1-5 parts inorganic antibacterial agent, 0.5-3 parts composite photothermal catalyst, 3-10 parts functional filler, 0.2-1.5 parts UV stabilizer, 0.5-4 parts polyester anchoring antifungal synergist, and 0.1-1 parts additives; The preparation method of the polyester anchoring antifungal synergist is as follows: A1: Salicylic acid and dihydroxyethyl terephthalate were added to a reaction vessel at a molar ratio of 1:1.1-1.

3. Tetrabutyl titanate was added as a catalyst at a mass of 0.05% of the total reactants. The mixture was heated to 180℃-195℃ under nitrogen protection for esterification reaction for 2-3 hours. The dewatering was collected and monitored. The reaction ended when no water was dewatered, and a polyester anchored antifungal primary polymer containing hydroxyethyl end groups was obtained. A2: The polyester anchored antifungal primordium is completely dissolved in anhydrous ethanol at a mass concentration of 20%, and acidified halloysite nanotubes are added, wherein the mass ratio of the primordium to the acidified halloysite nanotubes is 1:

3. The mixture is placed in a vacuum reactor and maintained at room temperature and an absolute vacuum of -0.08MPa to -0.095MPa for 45-60 minutes. Then, the anhydrous ethanol is removed by rotary evaporation at 55-65℃ to obtain halloysite powder with the antifungal primordium loaded in the inner cavity. A3: Mix the halloysite powder with low molecular weight polyethylene wax at a mass ratio of 1:1-1.2, heat to 115℃-125℃ to completely melt the polyethylene wax, and use a high shear dispersion emulsifier to physically mix for 15-20 minutes under high-speed shear force of 12000-15000 rpm, so that the polyethylene wax uniformly and physically coats the outer surface of the halloysite nanotubes and seals the tube openings. After cooling, a wax-sealed hard block is obtained. A4: Immerse the wax-sealed hard block in liquid nitrogen at -196°C for 15-20 minutes to induce a physical embrittlement phase transition, then transfer it to an ultra-micro airflow pulverizer for cryogenic pulverization. Control the D50 particle size of the resulting powder to be 0.8-1.2 micrometers to obtain the polyester anchoring antifungal synergist.

2. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The polyester chips are polyethylene terephthalate chips with an intrinsic viscosity of 0.60-0.68 dL / g.

3. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The composite photothermal catalyst is a core-shell structured material formed by loading noble metal nanoparticles onto a semiconductor oxide support. The preparation method of the composite photothermal catalyst includes the following steps: B1: Nanoscale semiconductor oxide carriers are prepared by sol-gel or hydrothermal methods; B2: Disperse the carrier material in deionized water to form a uniform suspension; B3: Add a noble metal precursor salt solution to the suspension, and use stirring and sonication to make the precursor ions uniformly adsorbed on the surface of the carrier. B4: Under heating conditions of 60-120℃, the adsorbed noble metal ions are reduced to zero-valent metal atoms, the atoms aggregate to form nanoparticles, and anchor on the surface of the carrier to form a composite structure. B5: After filtration, washing, and drying, it is calcined in an inert atmosphere at 300-500℃ for 2-5 hours to obtain the composite photothermal catalyst.

4. The anti-mildew differentiated polyester fiber according to claim 3, characterized in that, The noble metal precursor salt solution is at least one of palladium chloride, palladium nitrate, palladium acetate, chloroplatinic acid, or potassium chloroplatinate; the concentration of the aqueous solution of the noble metal precursor salt is 0.01-0.5 mol / L. Furthermore, when the noble metal is palladium, the precursor salt solution is an aqueous solution of palladium chloride or palladium acetate with a concentration of 0.05-0.2 mol / L; when the noble metal is platinum, the precursor salt solution is an aqueous solution of chloroplatinic acid or potassium chloroplatinate with a concentration of 0.02-0.1 mol / L. The semiconductor oxide carrier is titanium dioxide or zinc oxide.

5. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The inorganic antibacterial agent is at least one of silver-loaded zirconium phosphate, silver-loaded glass powder, or nano zinc oxide. The functional filler is at least one of porous silica, hollow glass microspheres, and expanded perlite powder, with a particle size D50 of 1-10 μm.

6. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The UV absorber is at least one of benzotriazole UV absorbers, hindered amine light stabilizers, or nano-titanium dioxide. The benzotriazole UV absorber is selected from at least one of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole or 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole; At least one of the hindered amine light stabilizers bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol) ester, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or a compound of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and n-butyl-3,5-di-tert-butyl-4-hydroxybenzoate.

7. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The preparation method of the acidified halloysite nanotubes is as follows: Halloysite nanotubes are dispersed in a dilute hydrochloric acid solution with a concentration of 1-3 mol / L at a solid-liquid mass ratio of 1:10-1:20, and the mixture is stirred at a constant temperature of 60℃-80℃ for 2-4 hours; after the reaction is completed, the mixture is centrifuged and washed repeatedly with deionized water until the filtrate is neutral; then the obtained solid is placed in a vacuum drying oven at 80℃-100℃ and dried for 12-24 hours to obtain the acidified halloysite nanotubes.

8. The anti-mildew differentiated polyester fiber according to claim 1, characterized in that, The additive is one or more of antioxidant 1010, lubricant ethylene bis-stearamide, and coupling agent KH-550.

9. A method for preparing an anti-mildew differentiated polyester fiber according to any one of claims 1-8, characterized in that, Includes the following steps: S1. Pre-processing: The polyester chips are vacuum dried at 100-120℃ for 4-6 hours; the inorganic antibacterial agent, composite photothermal catalyst, functional filler, UV stabilizer and additives are mixed evenly in a high-speed mixer to obtain functional masterbatch premix. S2. Blending and Melting: The dried polyester chips, functional masterbatch premix and polyester anchoring antifungal synergist are added to a twin-screw extruder, melt-blended, extruded, cooled and pelletized at 260-280℃ to obtain functional polyester masterbatch; S3. Spinning: The functional polyester masterbatch is dried in a vacuum drum and then fed into a screw extruder to melt at 265-285°C. After passing through a metering pump and a spinning assembly, it is spun into nascent fibers. S4. Post-processing: The nascent fibers are subjected to ring blowing cooling, oiling, stretching, heat setting and winding to obtain the mildew-resistant differentiated polyester fiber.

10. The use of any one of the anti-mildew differentiated polyester fibers according to claims 1-8 in the preparation of polyester fiber sound-absorbing panels.

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