Flame-retardant hydrophobic polyester fiber fabric, and preparation method and application thereof

Abstract

This invention discloses a flame-retardant and hydrophobic polyester fiber fabric, its preparation method, and its application, relating to the technical field of polyester fiber fabrics. The preparation method first involves dispersing ammonium polyphosphate and melamine cyanurate in ethanol, adding pre-hydrolyzed silicon oligomers and a catalyst, and modifying the powder with a silane coupling agent to obtain a core-shell structured flame retardant powder. This powder is then melt-blended and granulated with a PET carrier to obtain a flame-retardant masterbatch. The masterbatch is then combined with PET chips in a specific ratio for core-sheath composite spinning to obtain flame-retardant fibers, which are then woven into a fabric. Subsequently, the fabric undergoes air plasma surface etching activation, followed by impregnation in a finishing sol prepared from tetraethyl orthosilicate, perfluorohexyltriethoxysilane, and modified nano-zinc oxide. After rolling, pre-drying, and baking, a polyester fiber fabric with both excellent flame retardancy and hydrophobic properties is finally obtained.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber fabric technology, specifically to a flame-retardant and hydrophobic polyester fiber fabric, its preparation method, and its application. Background Technology

[0002] Automotive interior fabrics are a crucial component of the car's interior space, and their performance directly impacts the safety, comfort, and overall aesthetics and texture of the vehicle's interior. Polyester fabrics, with their high tensile strength, excellent abrasion resistance, good wrinkle resistance, easy washing and quick drying, and low production cost, are widely used in numerous interior components such as car seat fabrics, headliners, door panel linings, trunk mats, and car carpets, making them one of the most widely used textile fabrics in the automotive interior sector. With the rapid development of the automotive industry and the continuous upgrading of consumer demands for automotive quality, the market has placed more stringent requirements on the performance standards of polyester fabrics used in automotive interiors. From a safety perspective, the relatively enclosed space of a car interior means that, in the event of an open flame or high-temperature heat source, the flame-retardant properties of the polyester fabric directly determine the speed of fire spread, playing a crucial role in ensuring the escape time and safety of passengers. Therefore, flame retardancy has become a core safety performance requirement for polyester fabrics used in automotive interiors. From a usage perspective, automotive interior polyester fabrics are constantly exposed to complex and changing environments, making them highly susceptible to contamination from spilled beverages, water stains, dust, and other pollutants. Polyester fabrics with excellent hydrophobic properties can effectively reduce liquid absorption, decrease the probability of bacterial growth and odor generation, and significantly improve the fabric's ease of cleaning and lifespan. Summary of the Invention

[0003] The purpose of this invention is to provide a flame-retardant and hydrophobic polyester fiber fabric, its preparation method, and its applications, to solve the technical problems mentioned in the background section. The polyester fiber fabric prepared by this invention has excellent flame-retardant and hydrophobic properties.

[0004] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: S1. Ammonium polyphosphate and melamine cyanurate are dispersed in anhydrous ethanol. Pre-hydrolyzed silicon oligomer solution A, prepared from tetraethyl orthosilicate, ethanol, water and acetic acid, and catalytic solution B, composed of ammonia and ethanol, are added dropwise in sequence. The pH is adjusted to alkaline, and silane coupling agent KH-560 is added to react. The resulting product is centrifuged, dried and air-jet pulverized to obtain a core-shell structured coated flame retardant powder. S2. Mix the flame retardant powder and PET carrier chips, then melt-extrude and granulate to obtain flame retardant masterbatch; S3. The flame retardant masterbatch is dried and then spun with PET chips in a set ratio. After spinning, stretching, setting and winding, flame retardant fibers are obtained and woven into fabric. S4. Perform air plasma surface etching treatment on the fabric to obtain activated fabric; S5. Tetraethyl orthosilicate, perfluorohexyltriethoxysilane, ethanol, water and acetic acid are mixed and hydrolyzed to prepare acidic silicon-based solution A; nano zinc oxide and silane coupling agent KH-550 are added to ethanol and refluxed to obtain modified zinc oxide solution B; solution B is titrated into solution A under stirring and neutralized to weak acidity to obtain a finishing sol; S6. The activated fabric is immersed in the finishing sol, and then rolled, pre-dried and baked at high temperature to obtain flame-retardant and hydrophobic polyester fiber fabric.

[0005] In this invention, regarding flame retardancy, a dense silica shell is grown in situ on the surface of ammonium polyphosphate (APP), constructing an inorganic-organic hybrid capsule. This not only blocks the hydrolysis path of APP but also utilizes Si to enhance the stability of the char-forming skeleton at high temperatures. During the spinning stage, an asymmetric structure with micro-flame retardancy in the sheath and layer height filling is employed: a small amount of flame-retardant masterbatch is introduced into the sheath to block the wick effect of pure PET and to assume the mechanical skeleton function; the core layer serves as a reservoir for high-concentration flame retardants. During combustion, APP catalyzes the dehydration and carbonization of the matrix (condensed-phase flame retardancy), and melamine cyanurate releases non-flammable gases to dilute oxygen (gas-phase flame retardancy). Combined with the thermal insulation effect of the SiO2 shell, a highly efficient PN-Si synergistic flame-retardant system is formed, thus achieving excellent flame-retardant performance. Regarding hydrophobicity, high-energy air plasma is used to physically bombard the fiber surface, removing the weak boundary layer and etching micro-roughness, significantly increasing the density of physical anchor points and wetting tension on the fiber surface, providing a foundation for coating adhesion. Then, a robust inorganic network skeleton (derived from TEOS) is formed on the fiber surface by self-assembly using composite sol. Combined with long-chain fluorosilane molecules, the free energy of the solid surface is significantly reduced, creating a micro-nano binary rough structure similar to a lotus leaf. This makes it difficult for water droplets to spread out and causes them to roll off in a spherical shape, thus achieving good hydrophobic properties.

[0006] Preferably, in step S1, the mass ratio of ammonium polyphosphate to melamine cyanurate is 10:(4-6).

[0007] Preferably, in step S1, the mass ratio of tetraethyl orthosilicate to silane coupling agent KH-560 is 15:(2-4).

[0008] Preferably, in step S2, the mass ratio of PET carrier slices to flame retardant powder is 6:(3-4).

[0009] Preferably, in step S3, the mass ratio of the pump supply to the skin layer to the core layer is 4:(6-7).

[0010] Preferably, the mass ratio of PET chips to flame retardant masterbatch in the skin layer is 95:5; The mass ratio of PET chips to flame retardant masterbatch in the core layer is 50:50.

[0011] Preferably, in step S5, the mass ratio of tetraethyl orthosilicate to perfluorohexyltriethoxysilane is 1:(1-2).

[0012] Preferably, in step S5, the mass ratio of nano zinc oxide to silane coupling agent KH-550 is 3:(0.1~0.5).

[0013] The present invention found in experiments that under high-temperature setting and baking extreme hot pressing, even with microcapsule protection, the highly filled ammonium polyphosphate core will still decompose and release trace amounts of acidic oligomers, which will migrate to the fiber surface through free volume diffusion of the polymer matrix to form an acidic weak boundary layer. This will shield the active sites generated by plasma etching and interfere with the self-assembly of the composite sol on the fiber surface to form an inorganic network skeleton, thereby affecting the improvement of the hydrophobic properties of polyester fabric and the long-term stability of hydrophobicity. To address this technical problem, this invention simultaneously introduces nano-zinc oxide (ZnO) and γ-aminopropyltriethoxysilane (KH-550) into a micro-nano hydrophobic sol. The core mechanism lies in the targeted adsorption of nano-zinc oxide and its chemical reaction with phosphoric acid pollutants migrating to the interface, transforming them in situ into thermodynamically stable zinc phosphate micro-nano crystals. This achieves in-situ mineralization transformation from acidic pollutants to interface-enhancing phases. Simultaneously, the amino terminus of KH-550 is used to lock residual acidic groups through protonation. The synergistic effect of nano-zinc oxide and γ-aminopropyltriethoxysilane completely solves the problem of acid interference, endowing polyester fabrics with long-term stability of hydrophobic properties.

[0014] A flame-retardant and hydrophobic polyester fiber fabric is prepared by the method described above.

[0015] Application of a flame-retardant and hydrophobic polyester fiber fabric in automotive interiors Compared with the prior art, the beneficial effects of the present invention are: 1. By constructing a PN-Si synergistic flame retardant system and a core-sheath composite spinning structure, the fabric achieves long-lasting and efficient flame retardant performance under the dual flame retardant mechanisms of gas phase and condensed phase.

[0016] 2. By utilizing plasma etching and composite sol self-assembly, a micro-nano rough structure and a low surface energy coating are formed on the fiber surface, giving the fabric a hydrophobic effect similar to that of a lotus leaf.

[0017] 3. Through the synergistic effect of nano zinc oxide and silane coupling agent KH-550, the acidic substances generated by the migration of flame retardants are effectively neutralized and solidified, ensuring the long-term stability of hydrophobic properties. Attached Figure Description

[0018] Figure 1 This is a SEM image of the polyester fiber filament prepared in Example 1 of the present invention.

[0019] Figure 2 This is the XPS image of the polyester fiber fabric prepared in Example 1 of the present invention. Detailed Implementation

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1 A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: Step 1: First, prepare the pre-hydrolyzed silica oligomer solution A by weight: Dissolve 15 parts of tetraethyl orthosilicate (TEOS) in 16 parts of anhydrous ethanol, add 3 parts of deionized water and 0.5 parts of glacial acetic acid, and stir at 40°C for 2 hours. Simultaneously, prepare the catalytic solution B: Dissolve 5 parts of concentrated ammonia (25% concentration) in 40 parts of anhydrous ethanol and mix well. Add 440 parts of anhydrous ethanol to the main reactor, followed by 100 parts of ultrafine ammonium polyphosphate (APP) and 55 parts of ultrafine melamine cyanurate (MCA), and disperse using a high-shear disperser at 5000 rpm for 30 minutes. After dispersion, first add solution A to the reactor and stir for 10 minutes to wet the particles; then slowly add solution B dropwise, controlling the rate to allow the pH of the system to slowly rise to 9.0. Then add 3.5 parts of silane coupling agent KH-560, and heat to 60°C for 6 hours. The product was centrifuged, washed with ethanol, dried under vacuum at 120°C, and then depolymerized by an air jet mill to obtain a core-shell structured flame retardant powder.

[0022] Step 2: Select medium-viscosity PET carrier chips with an intrinsic viscosity (IV) of 0.64 dL / g and mix them with coated flame retardant powder at a mass ratio of 6:3.8. Place the mixture in a double-cone rotary vacuum dryer, pre-crystallize at 165℃ for 2 hours, then cool to 135℃ and deep dry under a vacuum of <100Pa for 10 hours, controlling the measured moisture content to below 25ppm. Add the dried material to the main feed port of a twin-screw extruder. Set the temperatures of each zone of the extruder as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 255℃, and Die Head 250℃. Set the screw speed to 280r / min. After the melt is extruded through the die, it is cooled in a 30℃ circulating water cooling tank, dried by air knife, and cut into φ3mm×3mm cylindrical granules by a pelletizer. Immediately vacuum-seal the granules in aluminum foil bags to obtain flame retardant masterbatch.

[0023] Step 3: Place the flame retardant masterbatch in a dehumidifying dryer and dry at 115℃ for 15 hours (dew point -80℃); simultaneously, dry the spinning-grade high-viscosity PET chips (IV=0.68dL / g) at 165℃ for 6 hours. A core-sheath composite spinning assembly is used, with the pump supply mass ratio of the sheath to the core layer set at 4:6.7. A melt consisting of 95% high-viscosity PET chips and 5% flame retardant masterbatch is introduced into the sheath channel; a melt consisting of 50% high-viscosity PET chips and 50% flame retardant masterbatch is introduced into the core channel. The spinning box temperature is controlled at 274℃, and the melt is extruded through a 20μm metal sand filter assembly and a 72-hole spinneret. After being cooled, cured, and oiled by side-blowing air (air temperature 25℃, air speed 0.5m / s), the nascent fibers enter the hot roller stretching system: the first roller temperature is 85℃ (stretch ratio 3.2 times), the second roller temperature is 130℃ (stretch ratio 1.1 times), and heat-setting is carried out in a 190℃ hot box. Finally, they are wound into a bobbin at a speed of 3000m / min. After warping and sizing, the resulting filaments are woven on a water-jet loom into a twill fabric with a warp and weft density of 130×110.

[0024] Step 4: Place the woven and refined fabric in an atmospheric pressure plasma treatment machine. Use clean compressed air as the gas source, set the discharge power to 200W, and the processing speed to 8m / min to perform surface etching and hydroxylation modification on the fabric.

[0025] Step 5: Prepare acidic silica-based solution A by weight: Add 640 parts anhydrous ethanol, 64 parts deionized water, 30 parts tetraethyl orthosilicate (TEOS), and 50 parts perfluorohexyltriethoxysilane to a stirred tank. After stirring evenly, add 1.2 parts glacial acetic acid and hydrolyze under sealed stirring at 40°C for 4 hours. Prepare modified zinc oxide solution B: Add 320 parts anhydrous ethanol, 9 parts nano zinc oxide (ZnO), and 1.2 parts silane coupling agent KH-550 to another container. Heat the mixture to 60°C and reflux for 30 minutes, then ultrasonically disperse for 10 minutes. Mixing preparation: Under vigorous mechanical stirring, slowly pour all of solution B into solution A, allowing the pH of the system to naturally stabilize in the range of 5.0–5.5, obtaining a translucent bluish-green finishing sol.

[0026] Step 6: Introduce the activated fabric from Step 4 into a two-roller press and immerse it in the fresh sol prepared in Step 5 (to be used within 30 minutes of sol preparation). Adjust the roll pressure to 0.3 MPa to control the fabric roll-off rate at 70%. Send the rolled fabric flat into a hot air tenter frame. Set the first temperature zone to 100℃ and dry for 3 minutes to slowly evaporate ethanol and moisture; set the second and third temperature zones to 180℃ and bake for 90 seconds for cross-linking and curing. After equilibration in a constant temperature and humidity chamber for 24 hours, the finished fabric is rolled up to obtain the finished flame-retardant and hydrophobic polyester fiber fabric.

[0027] Example 2 A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: Step 1: First, prepare the pre-hydrolyzed silica oligomer solution A by weight: Dissolve 15 parts of tetraethyl orthosilicate (TEOS) in 16 parts of anhydrous ethanol, add 3 parts of deionized water and 0.5 parts of glacial acetic acid, and stir at a constant temperature of 40℃ for 2 hours. Simultaneously, prepare the catalytic solution B: Dissolve 5 parts of concentrated ammonia (25% concentration) in 40 parts of anhydrous ethanol and mix well. Add 440 parts of anhydrous ethanol to the main reactor, followed by 100 parts of ultrafine ammonium polyphosphate (APP) and 45 parts of ultrafine melamine cyanurate (MCA), and disperse using a high-shear disperser at 5000 rpm for 30 minutes. After dispersion, first add solution A to the reactor and stir for 10 minutes to wet the particles; then slowly add solution B dropwise, controlling the rate to allow the pH of the system to slowly rise to 9.0. Then add 2.5 parts of silane coupling agent KH-560, and heat to 60℃ for 6 hours. The product was centrifuged, washed with ethanol, dried under vacuum at 120°C, and then depolymerized by an air jet mill to obtain a core-shell structured flame retardant powder.

[0028] Step 2: Select medium-viscosity PET carrier chips with an intrinsic viscosity (IV) of 0.64 dL / g and mix them with coated flame retardant powder at a mass ratio of 6:3.3. Place the mixture in a double-cone rotary vacuum dryer, pre-crystallize at 165℃ for 2 hours, then cool to 135℃ and deep dry under a vacuum of <100Pa for 10 hours, controlling the measured moisture content to below 25ppm. Add the dried material to the main feed port of a twin-screw extruder. Set the temperatures of each zone of the extruder as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 255℃, and Die Head 250℃. Set the screw speed to 280r / min. After the melt is extruded through the die, it is cooled in a 30℃ circulating water cooling tank, dried by air knife, and cut into φ3mm×3mm cylindrical granules by a pelletizer. Immediately vacuum-seal the granules in aluminum foil bags to obtain flame retardant masterbatch.

[0029] Step 3: Place the flame retardant masterbatch in a dehumidifying dryer and dry it at 115℃ for 15 hours (dew point -80℃); simultaneously, dry the spinning-grade high-viscosity PET chips (IV=0.68dL / g) at 165℃ for 6 hours. A core-sheath composite spinning assembly is used, with the pump supply mass ratio of the sheath to the core layer set at 4:6.2. A melt consisting of 95% high-viscosity PET chips and 5% flame retardant masterbatch is introduced into the sheath channel; a melt consisting of 50% high-viscosity PET chips and 50% flame retardant masterbatch is introduced into the core channel. The spinning box temperature is controlled at 274℃, and the melt is extruded through a 20μm metal sand filter assembly and a 72-hole spinneret. After being cooled, cured, and oiled by side-blowing air (air temperature 25℃, air speed 0.5m / s), the nascent fibers enter the hot roller stretching system: the first roller temperature is 85℃ (stretch ratio 3.2 times), the second roller temperature is 130℃ (stretch ratio 1.1 times), and heat-setting is carried out in a 190℃ hot box. Finally, they are wound into a bobbin at a speed of 3000m / min. After warping and sizing, the resulting filaments are woven on a water-jet loom into a twill fabric with a warp and weft density of 130×110.

[0030] Step 4: Place the woven and refined fabric in an atmospheric pressure plasma treatment machine. Use clean compressed air as the gas source, set the discharge power to 200W, and the processing speed to 8m / min to perform surface etching and hydroxylation modification on the fabric.

[0031] Step 5: Prepare acidic silica-based solution A by weight: Add 640 parts anhydrous ethanol, 64 parts deionized water, 30 parts tetraethyl orthosilicate (TEOS), and 40 parts perfluorohexyltriethoxysilane to a stirred tank. After stirring evenly, add 1.2 parts glacial acetic acid and hydrolyze under sealed stirring at 40°C for 4 hours. Prepare modified zinc oxide solution B: Add 320 parts anhydrous ethanol, 9 parts nano zinc oxide (ZnO), and 0.6 parts silane coupling agent KH-550 to another container. Heat the mixture to 60°C and reflux for 30 minutes, then ultrasonically disperse for 10 minutes. Mixing preparation: Under vigorous mechanical stirring, slowly pour all of solution B into solution A, allowing the pH of the system to naturally stabilize in the range of 5.0–5.5, obtaining a translucent bluish-green finishing sol.

[0032] Step 6: Introduce the activated fabric from Step 4 into a two-roller press and immerse it in the fresh sol prepared in Step 5 (to be used within 30 minutes of sol preparation). Adjust the roll pressure to 0.3 MPa to control the fabric roll-off rate at 70%. Send the rolled fabric flat into a hot air tenter frame. Set the first temperature zone to 100℃ and dry for 3 minutes to slowly evaporate ethanol and moisture; set the second and third temperature zones to 180℃ and bake for 90 seconds for cross-linking and curing. After equilibration in a constant temperature and humidity chamber for 24 hours, the finished fabric is rolled up to obtain the finished flame-retardant and hydrophobic polyester fiber fabric.

[0033] Example 3 A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: Step 1: First, prepare the pre-hydrolyzed silica oligomer solution A by weight: Dissolve 15 parts of tetraethyl orthosilicate (TEOS) in 16 parts of anhydrous ethanol, add 3 parts of deionized water and 0.5 parts of glacial acetic acid, and stir at 40°C for 2 hours. Simultaneously, prepare the catalytic solution B: Dissolve 5 parts of concentrated ammonia (25% concentration) in 40 parts of anhydrous ethanol and mix well. Add 440 parts of anhydrous ethanol to the main reactor, followed by 100 parts of ultrafine ammonium polyphosphate (APP) and 50 parts of ultrafine melamine cyanurate (MCA), and disperse using a high-shear disperser at 5000 rpm for 30 minutes. After dispersion, first add solution A to the reactor and stir for 10 minutes to wet the particles; then slowly add solution B dropwise, controlling the rate to allow the pH of the system to slowly rise to 9.0. Then add 3 parts of silane coupling agent KH-560, and heat to 60°C for 6 hours. The product was centrifuged, washed with ethanol, dried under vacuum at 120°C, and then depolymerized by an air jet mill to obtain a core-shell structured flame retardant powder.

[0034] Step 2: Select medium-viscosity PET carrier chips with an intrinsic viscosity (IV) of 0.64 dL / g and mix them with coated flame retardant powder at a mass ratio of 6:3.5. Place the mixture in a double-cone rotary vacuum dryer, pre-crystallize at 165℃ for 2 hours, then cool to 135℃ and deep dry under a vacuum of <100Pa for 10 hours, controlling the measured moisture content to below 25ppm. Add the dried material to the main feed port of a twin-screw extruder. Set the temperatures of each zone of the extruder as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 255℃, and Die Head 250℃. Set the screw speed to 280r / min. After the melt is extruded through the die, it is cooled in a 30℃ circulating water cooling tank, dried by air knife, and cut into φ3mm×3mm cylindrical particles by a pelletizer. Immediately vacuum-seal the particles in aluminum foil bags to obtain flame retardant masterbatch.

[0035] Step 3: Place the flame retardant masterbatch in a dehumidifying dryer and dry at 115℃ for 15 hours (dew point -80℃); simultaneously, dry the spinning-grade high-viscosity PET chips (IV=0.68dL / g) at 165℃ for 6 hours. A core-sheath composite spinning assembly is used, with the pump supply mass ratio of the sheath to the core layer set at 4:6.5. A melt consisting of 95% high-viscosity PET chips and 5% flame retardant masterbatch is introduced into the sheath channel; a melt consisting of 50% high-viscosity PET chips and 50% flame retardant masterbatch is introduced into the core channel. The spinning box temperature is controlled at 274℃, and the melt is extruded through a 20μm metal sand filter assembly and a 72-hole spinneret. After being cooled, cured, and oiled by side-blowing air (air temperature 25℃, air speed 0.5m / s), the nascent fibers enter the hot roller stretching system: the first roller temperature is 85℃ (stretch ratio 3.2 times), the second roller temperature is 130℃ (stretch ratio 1.1 times), and heat-setting is carried out in a 190℃ hot box. Finally, they are wound into a bobbin at a speed of 3000m / min. After warping and sizing, the resulting filaments are woven on a water-jet loom into a twill fabric with a warp and weft density of 130×110.

[0036] Step 4: Place the woven and refined fabric in an atmospheric pressure plasma treatment machine. Use clean compressed air as the gas source, set the discharge power to 200W, and the processing speed to 8m / min to perform surface etching and hydroxylation modification on the fabric.

[0037] Step 5: Prepare acidic silica-based solution A by weight: Add 640 parts anhydrous ethanol, 64 parts deionized water, 30 parts tetraethyl orthosilicate (TEOS), and 45 parts perfluorohexyltriethoxysilane to a stirred tank. After stirring evenly, add 1.2 parts glacial acetic acid and hydrolyze under sealed stirring at 40°C for 4 hours. Prepare modified zinc oxide solution B: Add 320 parts anhydrous ethanol, 9 parts nano zinc oxide (ZnO), and 1.0 part silane coupling agent KH-550 to another container. Heat the mixture to 60°C and reflux for 30 minutes, then ultrasonically disperse for 10 minutes. Mixing preparation: Under vigorous mechanical stirring, slowly pour all of solution B into solution A, allowing the pH of the system to naturally stabilize in the range of 5.0–5.5, obtaining a translucent bluish-green finishing sol.

[0038] Step 6: Introduce the activated fabric from Step 4 into a two-roller press and immerse it in the fresh sol prepared in Step 5 (to be used within 30 minutes of sol preparation). Adjust the roll pressure to 0.3 MPa to control the fabric roll-off rate at 70%. Send the rolled fabric flat into a hot air tenter frame. Set the first temperature zone to 100℃ and dry for 3 minutes to slowly evaporate ethanol and moisture; set the second and third temperature zones to 180℃ and bake for 90 seconds for cross-linking and curing. After equilibration in a constant temperature and humidity chamber for 24 hours, the finished fabric is rolled up to obtain the finished flame-retardant and hydrophobic polyester fiber fabric.

[0039] Example 4 A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: Step 1: First, prepare the pre-hydrolyzed silica oligomer solution A by weight: Dissolve 15 parts of tetraethyl orthosilicate (TEOS) in 16 parts of anhydrous ethanol, add 3 parts of deionized water and 0.5 parts of glacial acetic acid, and stir at a constant temperature of 40℃ for 2 hours. Simultaneously, prepare the catalytic solution B: Dissolve 5 parts of concentrated ammonia (25% concentration) in 40 parts of anhydrous ethanol and mix well. Add 440 parts of anhydrous ethanol to the main reactor, followed by 100 parts of ultrafine ammonium polyphosphate (APP) and 60 parts of ultrafine melamine cyanurate (MCA), and disperse using a high-shear disperser at 5000 rpm for 30 minutes. After dispersion, first add solution A to the reactor and stir for 10 minutes to wet the particles; then slowly add solution B dropwise, controlling the rate to allow the pH of the system to slowly rise to 9.0. Then add 4 parts of silane coupling agent KH-560, and heat to 60℃ for a constant temperature reaction for 6 hours. The product was centrifuged, washed with ethanol, dried under vacuum at 120°C, and then depolymerized by an air jet mill to obtain a core-shell structured flame retardant powder.

[0040] Step 2: Select medium-viscosity PET carrier chips with an intrinsic viscosity (IV) of 0.64 dL / g and mix them with coated flame retardant powder at a mass ratio of 6:4. Place the mixture in a double-cone rotary vacuum dryer, pre-crystallize at 165℃ for 2 hours, then cool to 135℃ and deep dry under a vacuum of <100Pa for 10 hours, controlling the measured moisture content to below 25ppm. Add the dried material to the main feed port of a twin-screw extruder. Set the temperatures of each zone of the extruder as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 255℃, and Die Head 250℃. Set the screw speed to 280r / min. After the melt is extruded through the die, it is cooled in a 30℃ circulating water cooling tank, dried by air knife, and cut into φ3mm×3mm cylindrical granules by a pelletizer. Immediately vacuum-seal the granules in aluminum foil bags to obtain flame retardant masterbatch.

[0041] Step 3: Place the flame retardant masterbatch in a dehumidifying dryer and dry at 115℃ for 15 hours (dew point -80℃); simultaneously, dry the spinning-grade high-viscosity PET chips (IV=0.68dL / g) at 165℃ for 6 hours. A core-sheath composite spinning assembly is used, with the pump supply mass ratio of the sheath to the core layer set at 4:7. A melt consisting of 95% high-viscosity PET chips and 5% flame retardant masterbatch is introduced into the sheath channel; a melt consisting of 50% high-viscosity PET chips and 50% flame retardant masterbatch is introduced into the core channel. The spinning box temperature is controlled at 274℃, and the melt is extruded through a 20μm metal sand filter assembly and a 72-hole spinneret. After being cooled, cured, and oiled by side-blowing air (air temperature 25℃, air speed 0.5m / s), the nascent fibers enter the hot roller stretching system: the first roller temperature is 85℃ (stretch ratio 3.2 times), the second roller temperature is 130℃ (stretch ratio 1.1 times), and heat-setting is carried out in a 190℃ hot box. Finally, they are wound into a bobbin at a speed of 3000m / min. After warping and sizing, the resulting filaments are woven on a water-jet loom into a twill fabric with a warp and weft density of 130×110.

[0042] Step 4: Place the woven and refined fabric in an atmospheric pressure plasma treatment machine. Use clean compressed air as the gas source, set the discharge power to 200W, and the processing speed to 8m / min to perform surface etching and hydroxylation modification on the fabric.

[0043] Step 5: Prepare acidic silica-based solution A by weight: Add 640 parts anhydrous ethanol, 64 parts deionized water, 30 parts tetraethyl orthosilicate (TEOS), and 60 parts perfluorohexyltriethoxysilane to a stirred tank. After stirring evenly, add 1.2 parts glacial acetic acid and hydrolyze under sealed stirring at 40°C for 4 hours. Prepare modified zinc oxide solution B: Add 320 parts anhydrous ethanol, 9 parts nano zinc oxide (ZnO), and 1.5 parts silane coupling agent KH-550 to another container. Heat the mixture to 60°C and reflux for 30 minutes, then ultrasonically disperse for 10 minutes. Mixing preparation: Under vigorous mechanical stirring, slowly pour all of solution B into solution A, allowing the pH of the system to naturally stabilize in the range of 5.0–5.5, obtaining a translucent bluish-green finishing sol.

[0044] Step 6: Introduce the activated fabric from Step 4 into a two-roller press and immerse it in the fresh sol prepared in Step 5 (to be used within 30 minutes of sol preparation). Adjust the roll pressure to 0.3 MPa to control the fabric roll-off rate at 70%. Send the rolled fabric flat into a hot air tenter frame. Set the first temperature zone to 100℃ and dry for 3 minutes to slowly evaporate ethanol and moisture; set the second and third temperature zones to 180℃ and bake for 90 seconds for cross-linking and curing. After equilibration in a constant temperature and humidity chamber for 24 hours, the finished fabric is rolled up to obtain the finished flame-retardant and hydrophobic polyester fiber fabric.

[0045] Example 5 A method for preparing a flame-retardant and hydrophobic polyester fiber fabric includes the following steps: Step 1: First, prepare the pre-hydrolyzed silica oligomer solution A by weight: Dissolve 15 parts of tetraethyl orthosilicate (TEOS) in 16 parts of anhydrous ethanol, add 3 parts of deionized water and 0.5 parts of glacial acetic acid, and stir at a constant temperature of 40℃ for 2 hours. Simultaneously, prepare the catalytic solution B: Dissolve 5 parts of concentrated ammonia (25% concentration) in 40 parts of anhydrous ethanol and mix well. Add 440 parts of anhydrous ethanol to the main reactor, followed by 100 parts of ultrafine ammonium polyphosphate (APP) and 40 parts of ultrafine melamine cyanurate (MCA), and disperse using a high-shear disperser at 5000 rpm for 30 minutes. After dispersion, first add solution A to the reactor and stir for 10 minutes to wet the particles; then slowly add solution B dropwise, controlling the rate to allow the pH of the system to slowly rise to 9.0. Then add 2 parts of silane coupling agent KH-560, and heat to 60℃ for a constant temperature reaction for 6 hours. The product was centrifuged, washed with ethanol, dried under vacuum at 120°C, and then depolymerized by an air jet mill to obtain a core-shell structured flame retardant powder.

[0046] Step 2: Select medium-viscosity PET carrier chips with an intrinsic viscosity (IV) of 0.64 dL / g and mix them with coated flame retardant powder at a mass ratio of 6:3. Place the mixture in a double-cone rotary vacuum dryer, pre-crystallize at 165℃ for 2 hours, then cool to 135℃ and deep dry under a vacuum of <100Pa for 10 hours, controlling the measured moisture content to below 25ppm. Add the dried material to the main feed port of a twin-screw extruder. Set the temperatures of each zone of the extruder as follows: Zone 1 245℃, Zone 2 250℃, Zone 3 255℃, Zone 4 255℃, and Die Head 250℃. Set the screw speed to 280r / min. After the melt is extruded through the die, it is cooled in a 30℃ circulating water cooling tank, dried by air knife, and cut into φ3mm×3mm cylindrical granules by a pelletizer. Immediately vacuum-seal the granules in aluminum foil bags to obtain flame retardant masterbatch.

[0047] Step 3: Place the flame retardant masterbatch in a dehumidifying dryer and dry at 115℃ for 15 hours (dew point -80℃); simultaneously, dry the spinning-grade high-viscosity PET chips (IV=0.68dL / g) at 165℃ for 6 hours. A core-sheath composite spinning assembly is used, with the pump supply mass ratio of the sheath to the core layer set at 4:6. A melt consisting of 95% high-viscosity PET chips and 5% flame retardant masterbatch is introduced into the sheath channel; a melt consisting of 50% high-viscosity PET chips and 50% flame retardant masterbatch is introduced into the core channel. The spinning box temperature is controlled at 274℃, and the melt is extruded through a 20μm metal sand filter assembly and a 72-hole spinneret. After being cooled, cured, and oiled by side-blowing air (air temperature 25℃, air speed 0.5m / s), the nascent fibers enter the hot roller stretching system: the first roller temperature is 85℃ (stretch ratio 3.2 times), the second roller temperature is 130℃ (stretch ratio 1.1 times), and heat-setting is carried out in a 190℃ hot box. Finally, they are wound into a bobbin at a speed of 3000m / min. After warping and sizing, the resulting filaments are woven on a water-jet loom into a twill fabric with a warp and weft density of 130×110.

[0048] Step 4: Place the woven and refined fabric in an atmospheric pressure plasma treatment machine. Use clean compressed air as the gas source, set the discharge power to 200W, and the processing speed to 8m / min to perform surface etching and hydroxylation modification on the fabric.

[0049] Step 5: Prepare acidic silica-based solution A by weight: Add 640 parts anhydrous ethanol, 64 parts deionized water, 30 parts tetraethyl orthosilicate (TEOS), and 30 parts perfluorohexyltriethoxysilane to a stirred tank. After stirring evenly, add 1.2 parts glacial acetic acid and hydrolyze under sealed stirring at 40°C for 4 hours. Prepare modified zinc oxide solution B: Add 320 parts anhydrous ethanol, 9 parts nano zinc oxide (ZnO), and 0.3 parts silane coupling agent KH-550 to another container. Heat the mixture to 60°C and reflux for 30 minutes, then ultrasonically disperse for 10 minutes. Mixing preparation: Under vigorous mechanical stirring, slowly pour all of solution B into solution A, allowing the pH of the system to naturally stabilize in the range of 5.0–5.5, obtaining a translucent bluish-green finishing sol.

[0050] Step 6: Introduce the activated fabric from Step 4 into a two-roller press and immerse it in the fresh sol prepared in Step 5 (to be used within 30 minutes of sol preparation). Adjust the roll pressure to 0.3 MPa to control the fabric roll-off rate at 70%. Send the rolled fabric flat into a hot air tenter frame. Set the first temperature zone to 100℃ and dry for 3 minutes to slowly evaporate ethanol and moisture; set the second and third temperature zones to 180℃ and bake for 90 seconds for cross-linking and curing. After equilibration in a constant temperature and humidity chamber for 24 hours, the finished fabric is rolled up to obtain the finished flame-retardant and hydrophobic polyester fiber fabric.

[0051] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that tetraethyl orthosilicate is not added in step 1, that is, ammonium polyphosphate is not coated with silica.

[0052] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that tetraethyl orthosilicate and perfluorohexyltriethoxysilane are not added in step 5.

[0053] Comparative Example 3: The difference between Comparative Example 3 and Example 1 is that modified zinc oxide solution B is not prepared in step 5, that is, solution B is not poured into solution A.

[0054] Performance testing: 1. Limiting Oxygen Index Test: According to the national standard GB / T 5454-1997 "Test for Burning Performance of Textiles - Oxygen Index Method", the fabric was cut into 150mm×58mm samples and placed in an oxygen index tester. The mixing flow rate of oxygen and nitrogen was adjusted, and the minimum oxygen concentration required for the sample to sustain combustion was determined. Five samples were tested for each example and comparative example, and the average value was taken as the final result. The test results are shown in Table 1.

[0055] 2. Vertical Burning Performance Test: According to the national standard GB / T 5455-1997 "Textiles - Test for Burning Performance - Vertical Method", the fabric was cut into 300mm × 80mm samples and vertically fixed on the burning test apparatus. A flame at a specified height was used to ignite the sample 12mm from the bottom. After ignition for 12 seconds, the flame source was removed, and the afterflame time and damage length were recorded. The burning rating was determined according to the standard. The test results are shown in Table 1.

[0056] 3. Water Contact Angle Test: The hydrophobicity of the fabric surface was tested using a contact angle meter via the droplet method. At room temperature, a 5 μL droplet of deionized water was dropped onto the fabric surface using a micro-syringe. After the droplet stabilized for 30 seconds, the droplet morphology was captured by a CCD camera system, and the angle between the droplet and the fabric surface was calculated using software. Five points were randomly selected from different parts of the fabric for testing, and the average value was taken. A larger water contact angle indicates better hydrophobicity of the fabric surface. The test results are shown in Table 1.

[0057] 4. Hydrophobic stability test: According to the national standard GB / T 8629-2017 "Home washing and drying procedures for textile testing", the fabric sample was subjected to 50 standard home washing cycles. After washing, it was dried according to the standard procedure. Then, the water contact angle value after washing was measured according to the above-mentioned water contact angle test method to evaluate the durability of the fabric's hydrophobic properties. The test results are shown in Table 1.

[0058] Table 1: Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a flame-retardant and hydrophobic polyester fiber fabric, characterized in that, Includes the following steps: S1. Ammonium polyphosphate and melamine cyanurate are dispersed in anhydrous ethanol. Pre-hydrolyzed silicon oligomer solution A, prepared from tetraethyl orthosilicate, ethanol, water and acetic acid, and catalytic solution B, composed of ammonia and ethanol, are added dropwise in sequence. The pH is adjusted to alkaline, and silane coupling agent KH-560 is added to react. The resulting product is centrifuged, dried and air-jet pulverized to obtain a core-shell structured coated flame retardant powder. S2. Mix the flame retardant powder and medium-viscosity PET carrier chips, and then melt-extrude and granulate them to obtain flame retardant masterbatch; S3. The flame retardant masterbatch is dried and then spun with PET chips in a set ratio. After spinning, stretching, setting and winding, flame retardant fibers are obtained and woven into fabric. S4. Perform air plasma surface etching treatment on the fabric to obtain activated fabric; S5. Tetraethyl orthosilicate, perfluorohexyltriethoxysilane, ethanol, water and acetic acid are mixed and hydrolyzed to prepare acidic silicon-based solution A; nano zinc oxide and silane coupling agent KH-550 are added to ethanol and refluxed to obtain modified zinc oxide solution B. Solution B was titrated into solution A with stirring, and the solution was neutralized to a weakly acidic state to obtain a sol. S6. The activated fabric is immersed in the finishing sol, and then rolled, pre-dried and baked at high temperature to obtain flame-retardant and hydrophobic polyester fiber fabric.

2. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S1, the mass ratio of ammonium polyphosphate to melamine cyanurate is 10:(4-6).

3. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S1, the mass ratio of tetraethyl orthosilicate to silane coupling agent KH-560 is 15:(2-4).

4. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S2, the mass ratio of PET carrier slices to flame retardant powder is 6:(3-4).

5. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S3, the mass ratio of the pump supply to the skin layer to the core layer is 4:(6-7).

6. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 5, characterized in that, The mass ratio of PET chips to flame retardant masterbatch in the leather layer is 95:5; The mass ratio of PET chips to flame retardant masterbatch in the core layer is 50:

50.

7. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S5, the mass ratio of tetraethyl orthosilicate to perfluorohexyltriethoxysilane is 1:(1-2).

8. The method for preparing a flame-retardant and hydrophobic polyester fiber fabric according to claim 1, characterized in that, In step S5, the mass ratio of nano zinc oxide to silane coupling agent KH-550 is 3:(0.1~0.5).

9. A flame-retardant and hydrophobic polyester fiber fabric, characterized in that, It is prepared by the method described in any one of claims 1 to 8.

10. The application of the flame-retardant and hydrophobic polyester fiber fabric as described in claim 9 in automotive interiors.

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