Antistatic high-flame-retardant polyester fabric for vehicles and preparation method thereof

Abstract

The invention discloses an antistatic high-flame-retardant polyester fabric for a vehicle and a preparation method of the antistatic high-flame-retardant polyester fabric, and relates to the technical field of polyester fibers. The method comprises the following steps: firstly, preparing a modified graphene-carbon nanotube composite conductive filler and a polyether ester block copolymer antistatic agent; then blending and extruding the two with PET slices, an aluminum diethylphosphinate flame retardant, an ionic liquid and hyperbranched polyester to prepare functional master batches; meanwhile, a flame-retardant monomer BHEPP and PET are copolymerized to prepare the reaction type flame-retardant slice. Mixing the two slices, performing melt spinning to obtain functional fibers, and finally blending and weaving the functional fibers and flame-retardant viscose fibers, and finishing to obtain the fabric. Through multi-component cooperation and structural design, a stable conductive network is effectively constructed and maintained while it is ensured that the fabric has the permanent flame retardant property, and therefore the antistatic and high-flame-retardant performance is integrated, and the antistatic and high-flame-retardant fabric is especially suitable for the fields of automobile interiors and the like.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber technology, specifically to an antistatic, highly flame-retardant automotive polyester fabric and its preparation method. Background Technology

[0002] Polyester fiber, due to its high mechanical strength, good abrasion resistance, and controllable cost, has become the mainstream raw material for automotive interior fabrics (seats, headliners, carpets, etc.). However, the inherent hydrophobicity and flammability of polyester present two major challenges in automotive applications: First, its high surface resistivity makes it prone to static electricity buildup due to friction in dry environments, attracting dust and affecting cleanliness, and potentially causing electronic device malfunctions or ignition risks of flammable materials. Second, its flame retardant effect is poor; during combustion, it releases heat quickly, produces large amounts of smoke, and easily generates molten droplets, making it difficult to meet automotive flame retardant safety standards. Existing modification technologies have significant shortcomings: In terms of antistatic properties, small-molecule antistatic agents are prone to migration and precipitation, leading to performance degradation; single conductive fillers are unevenly dispersed, damaging both the fiber's mechanical properties and feel, and failing to form a stable conductive network. In terms of flame retardancy, halogenated flame retardants release toxic gases upon combustion, while halogen-free flame retardants require high addition amounts and are prone to loss; grafting reactive flame retardant monomers can reduce the spinnability of polyester, and a single solution cannot simultaneously achieve both flame retardant efficiency and durability. Furthermore, antistatic and flame-retardant modifications are often simply combined, resulting in poor compatibility and functional antagonism. They also fail to adequately adapt to the extreme temperatures and friction conditions of automotive applications, leading to insufficient functional durability. Additionally, some processes pose environmental risks or affect fabric dimensional stability, making it difficult to meet the comprehensive requirements of automotive interiors for safety, durability, and environmental friendliness. Therefore, developing polyester automotive fabrics that combine durable, high antistatic properties with high flame-retardant performance has become an urgent problem to be solved in this field. Summary of the Invention

[0003] The purpose of this invention is to provide an antistatic and highly flame-retardant automotive polyester fabric and its preparation method, thereby solving the technical problems mentioned in the background section. The automotive polyester fabric prepared by this invention possesses both excellent antistatic and flame-retardant properties.

[0004] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: (1) Graphene and carbon nanotubes are dispersed and surface modified with silane coupling agent to obtain modified composite conductive filler; (2) Dimethyl terephthalate, ethylene glycol and polyethylene glycol are mixed, zinc acetate is added as a catalyst to carry out transesterification reaction, then triphenyl phosphate and antimony acetate are added, the temperature is raised and vacuum is drawn to carry out polycondensation reaction to obtain polyether ester block copolymer. (3) PET chips, modified composite conductive filler, aluminum diethylphosphinate, polyether ester block copolymer, 1-butyl-3-methylimidazolium phosphate dimethyl salt and hydroxyl-terminated hyperbranched polyester are premixed, and then the mixture is melt-extruded to obtain functional masterbatch. (4) The PET chips are mixed with the flame retardant monomer BHEPP and the catalyst antimony acetate for transesterification reaction, and then vacuumed for final polycondensation reaction to obtain reactive flame retardant copolymer chips. (5) The reactive flame-retardant copolymer chips are mixed with functional masterbatch, and then melt-spun, stretched and heat-set to obtain antistatic high flame-retardant polyester fiber. (6) The antistatic high flame retardant fiber is blended with flame retardant viscose fiber, woven into fabric, and then refined and heat-set to obtain antistatic high flame retardant automotive polyester fabric.

[0005] In the technical solution of this invention, the antistatic principle of polyester fabric is as follows: First, the graphene-multi-walled carbon nanotube composite conductive filler modified with silane coupling agent overcomes the compatibility problem with the PET matrix under the high shear force of the twin-screw extruder, effectively preventing filler agglomeration. It is uniformly dispersed in the carrier resin and constructs a continuous micro-conductive network, providing a stable channel for charge conduction using the percolation effect. At the same time, the polyether ester block copolymer antistatic agent added to the formula has good compatibility with the PET matrix. Its hydrophilic segments can adsorb trace amounts of moisture in the environment, further reducing charge transmission resistance and forming a synergistic effect with the conductive network. Ultimately, the fiber has a long-lasting and stable antistatic ability, and the charge can be quickly conducted and dissipated through the conductive network, avoiding static electricity accumulation. The principle behind flame retardancy in polyester fabric is as follows: On the one hand, the reactive flame retardant monomer BHEPP, under high-temperature catalytic conditions, undergoes a transesterification reaction to form covalent bonds with the PET macromolecular backbone. A high-vacuum final polycondensation reaction forces the removal of the byproduct ethylene glycol, shifting the reaction equilibrium towards a higher degree of polymerization. This achieves intrinsic grafting of the flame retardant component (preventing migration and loss during use) and restores the molecular weight reduction caused by monomer addition, ensuring the resin's spinnability. On the other hand, the highly thermally stable aluminum diethylphosphinate (ADP) flame retardant added to the functional masterbatch remains chemically stable at 300℃, preventing the hydrolytic failure of traditional flame retardants at high spinning temperatures. It forms a synergistic flame retardant system with the phosphate groups on the backbone: In the condensed phase, the phosphate groups promote the formation of a dense char layer during fiber combustion, blocking oxygen and heat transfer; ADP further inhibits the combustion reaction through decomposition and endothermic absorption. In the gas phase, the decomposition products of both can capture combustion free radicals, terminating the chain reaction. This dual effect significantly enhances the flame retardant performance of the fiber, ensuring it is not easily combustible at high temperatures and has no obvious dripping.

[0006] In experimental research, this invention discovered that aluminum diethylphosphonate (ADP), an insulating flame retardant added in large quantities to achieve excellent flame retardancy, physically coats the surface of conductive fillers such as graphene and carbon nanotubes, forming an insulating shielding layer. This severely disrupts the tunnel current pathways between fillers, leading to a deterioration in the surface resistivity of the fabric and a significant decrease in its antistatic properties. To further address this technical problem, this invention introduces 1-butyl-3-methylimidazolium phosphate dimethyl ester salt and hydroxyl-terminated hyperbranched polyester (HBP) simultaneously during the preparation of the functional masterbatch. Due to its polarity and high thermal stability, 1-butyl-3-methylimidazolium phosphate salt can be tightly adsorbed onto the surface of the conductive filler through cation-π interactions, constructing dynamic "ionic conductive bridges" between the insulating ADP particles. This enables electron trans-insulator conduction, forming an "electron-ion" hybrid conductive mechanism. Simultaneously, the hyperbranched polyester, utilizing its highly branched three-dimensional spherical structure and abundant terminal hydroxyl groups, selectively adsorbs onto the surface of the ADP particles, forming a nanoscale flexible insulating film. This film, through steric hindrance, prevents the ADP from encapsulating the conductive filler, forcing the conductive network to bypass the ADP particles and reassemble into a continuous, meandering three-dimensional pathway, thus ensuring the microscopic continuity of the conductive pathway. This synergistic mechanism fundamentally reconciles the contradiction between high flame retardancy and high conductivity, further improving the antistatic properties of polyester fabrics.

[0007] Preferably, in step (1), the mass ratio of graphene to carbon nanotubes is 1:(1-2).

[0008] Preferably, in step (1), the silane coupling agent is γ-aminopropyltriethoxysilane; the amount of γ-aminopropyltriethoxysilane added is 2 to 5 wt% of the total amount of graphene and carbon nanotubes.

[0009] Preferably, in step (2), the molar ratio of dimethyl terephthalate, ethylene glycol and polyethylene glycol is 1:2.1:(0.05~0.1).

[0010] Preferably, in step (3), the mass ratio of PET chips to modified composite conductive filler is 60:(4-6).

[0011] Preferably, in step (3), the mass ratio of PET chips to polyether ester block copolymer is 60:(8-12).

[0012] Preferably, in step (3), the mass ratio of 1-butyl-3-methylimidazolium dimethyl phosphate salt to hydroxyl-terminated hyperbranched polyester is 2:(1-2).

[0013] Preferably, in step (4), the amount of flame retardant monomer BHEPP added is 8 to 10 wt% of the PET slice weight.

[0014] Preferably, in step (5), the mass ratio of reactive flame-retardant copolymer chips to functional masterbatch is 8:(1-2).

[0015] An antistatic, highly flame-retardant automotive polyester fabric is prepared by the method described above.

[0016] Compared with the prior art, the beneficial effects of the present invention are: 1. By constructing a synergistic conductive mechanism between a modified conductive network and a polyether ester antistatic agent, and combining a synergistic flame retardant system of reactive graft flame retardant and highly efficient additive flame retardant, polyester fabrics possess both excellent and durable antistatic capabilities and a high level of flame retardant safety.

[0017] 2. Addressing the core challenge of high-content insulating flame retardants damaging the conductive network, a novel approach is adopted: ionic liquids and hyperbranched polyester are combined to form a synergistic system of interfacial conductive bridging and spatial isolation. This solution simultaneously repairs charge conduction paths and reconstructs the conductive network topology at the microscopic level, fundamentally overcoming the conductivity barrier effect of insulating fillers and further improving the antistatic properties of polyester fabrics. Attached Figure Description

[0018] Figure 1 This is a SEM image of the antistatic and highly flame-retardant polyester fiber prepared in Example 1 of the present invention.

[0019] Figure 2 XPS spectrum of the antistatic and highly flame-retardant polyester fabric prepared in Example 1 of this 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 an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: Step 1: Graphene powder and multi-walled carbon nanotubes were mixed at a mass ratio of 1:1.8 and added to anhydrous ethanol / deionized water mixed solvent at a mass ratio of 1 g / 50 mL. The mixture was ultrasonically dispersed at 600 W for 45 min to obtain a uniform suspension. γ-aminopropyltriethoxysilane (4% of the total mass of the filler) was added dropwise to the system. The pH was adjusted to 4.5-5.0 with glacial acetic acid. The mixture was heated to 75 °C and stirred for 5 h. After the reaction was completed, the mixture was centrifuged, washed, and vacuum dried at 80 °C for 24 h to obtain the modified composite conductive filler.

[0022] Step 2: Dimethyl terephthalate (DMT), ethylene glycol (EG), and polyethylene glycol (PEG) with a molecular weight of 2000 were added to a reactor in a molar ratio of 1:2.1:0.09. Zinc acetate (0.08% of the total amount) was added, and the transesterification reaction was carried out at 200°C. After the methanol distillation amount exceeded 95%, 0.1% triphenyl phosphate and 0.05% antimony acetate were added. The temperature was raised to 255°C and the pressure was reduced to below 100 Pa for 4 hours to carry out a polycondensation reaction to obtain a polyether ester block copolymer.

[0023] Step 3: Weigh 60 parts by weight of PET chips, 5.5 parts by weight of modified composite conductive filler, 20 parts by weight of aluminum diethylphosphinate (ADP), 11 parts by weight of polyether ester block copolymer, 2 parts by weight of 1-butyl-3-methylimidazolium phosphate dimethyl salt, and 1.8 parts by weight of hydroxyl-terminated hyperbranched polyester (HBP) and put them into a high-speed mixer. Premix at 80°C for 30 minutes. Feed them into a twin-screw extruder with the temperature of each zone set to 240°C, 260°C, 275°C, 280°C, and 275°C, and the screw speed at 250 rpm. After melt extrusion, water cooling pelletizing, and crystallization at 120°C, functional masterbatch is obtained.

[0024] Step 4: Add PET chips, flame-retardant monomer BHEPP (11% by mass of PET), and antimony acetate catalyst (0.05% by mass of PET) to the reactor. First, vacuum dry at 170℃ for 2 hours; then raise the temperature to 265℃ for transesterification reaction for 1.5 hours; turn on the high vacuum system (pressure <50Pa) to carry out the final polycondensation reaction, and monitor the motor torque to ensure that the intrinsic viscosity IV reaches 0.65-0.68 dL / g. Finally, discharge with high-pressure nitrogen and pelletize to obtain reactive flame-retardant copolymer chips.

[0025] Step 5: Mix reactive flame-retardant copolymer chips and functional masterbatch at a mass ratio of 8:1.8, and dry in 165℃ dry air circulation for 8 hours until the moisture content is ≤35ppm. Feed the mixture into a screw spinning machine, setting the screw zone and die head temperatures to 270℃, 280℃, 285℃, 285℃, and 282℃ respectively. The melt is filtered through a 50μm metal sand assembly and extruded through a 0.25mm orifice spinneret. After being cooled by side blowing at 22℃, the filaments undergo two stages of hot drawing (stage one: 90℃ / 3.0 times, stage two: 135℃ / 1.6 times), and finally heat-set and wound at 170℃ to obtain antistatic high flame-retardant polyester fiber.

[0026] Step 6: Comb and blend antistatic high flame retardant polyester fiber and flame retardant viscose fiber (FR-Viscose) at a mass ratio of 70:30. Use ring spinning to produce a functional blended yarn with a linear density of 14.5 tex (40 count) and a twist of 380 twists / 10cm. Then, weave it into a plain weave fabric on an air-jet loom (with a warp density of 420 ends / 10cm, a weft density of 320 ends / 10cm, and a weight controlled at 220g / m²). 2 The greige fabric is fed into a scouring machine and treated in a scouring liquor with a liquor ratio of 1:20. The scouring liquor consists of 2.0 g / L nonionic scouring agent JFC (polyoxyethylene ether) and 1.5 g / L chelating dispersant (a compound of polymaleic anhydride PMA and sodium hexametaphosphate in a mass ratio of 1:1). The fabric is immersed at a constant temperature of 70°C for 35 min. After treatment, it is washed twice with hot water at 60°C and thoroughly washed with cold water until the pH is neutral. Finally, the fabric is fed into a tenter frame and heat-set at 180°C for 45 s to obtain an antistatic, high flame-retardant automotive polyester fabric.

[0027] Example 2 A method for preparing an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: Step 1: Graphene powder and multi-walled carbon nanotubes were mixed at a mass ratio of 1:1.2 and added to anhydrous ethanol / deionized water mixed solvent at a mass ratio of 1 g / 50 mL. The mixture was ultrasonically dispersed at 600 W for 45 min to obtain a uniform suspension. γ-aminopropyltriethoxysilane (3% of the total mass of the above filler) was added dropwise to the system. The pH was adjusted to 4.5-5.0 with glacial acetic acid. The mixture was heated to 75 °C and stirred for 5 h. After the reaction was completed, the mixture was centrifuged, washed, and vacuum dried at 80 °C for 24 h to obtain the modified composite conductive filler.

[0028] Step 2: Dimethyl terephthalate (DMT), ethylene glycol (EG), and polyethylene glycol (PEG) with a molecular weight of 2000 were added to a reactor in a molar ratio of 1:2.1:0.06. Zinc acetate (0.08% of the total amount) was added, and the transesterification reaction was carried out at 200°C. After the methanol distillation amount exceeded 95%, 0.1% triphenyl phosphate and 0.05% antimony acetate were added. The temperature was raised to 255°C and the pressure was reduced to below 100 Pa for polycondensation reaction for 4 hours to obtain a polyether ester block copolymer.

[0029] Step 3: Weigh 60 parts by weight of PET chips, 4.5 parts by weight of modified composite conductive filler, 20 parts by weight of aluminum diethylphosphinate (ADP), 9 parts by weight of polyether ester block copolymer, 2 parts by weight of 1-butyl-3-methylimidazolium phosphate dimethyl salt, and 1.2 parts by weight of hydroxyl-terminated hyperbranched polyester (HBP) and put them into a high-speed mixer. Premix at 80°C for 30 minutes. Feed the mixture into a twin-screw extruder with the temperatures of each zone set to 240°C, 260°C, 275°C, 280°C, and 275°C, and the screw speed at 250 rpm. After melt extrusion, water cooling pelletizing, and crystallization at 120°C, functional masterbatch is obtained.

[0030] Step 4: Add PET chips, flame-retardant monomer BHEPP (9% by mass of PET), and antimony acetate catalyst (0.05% by mass of PET) to the reactor. First, vacuum dry at 170℃ for 2 hours; then raise the temperature to 265℃ for transesterification reaction for 1.5 hours; turn on the high vacuum system (pressure < 50 Pa) to carry out the final polycondensation reaction, and monitor the motor torque to ensure that the intrinsic viscosity IV reaches 0.65-0.68 dL / g. Finally, discharge with high-pressure nitrogen and granulate to obtain reactive flame-retardant copolymer chips.

[0031] Step 5: Mix reactive flame-retardant copolymer chips and functional masterbatch at a mass ratio of 8:1.2, and dry in 165℃ dry air circulation for 8 hours until the moisture content is ≤35ppm. Feed the mixture into a screw spinning machine, setting the screw zone and die head temperatures to 270℃, 280℃, 285℃, 285℃, and 282℃ respectively. The melt is filtered through a 50μm metal sand assembly and extruded through a 0.25mm orifice spinneret. After being cooled by side blowing at 22℃, the filaments undergo two stages of hot drawing (stage one: 90℃ / 3.0 times, stage two: 135℃ / 1.6 times), and finally heat-set and wound at 170℃ to obtain antistatic high flame-retardant polyester fiber.

[0032] Step 6: Comb and blend antistatic high flame retardant polyester fiber and flame retardant viscose fiber (FR-Viscose) at a mass ratio of 70:30. Use ring spinning to produce a functional blended yarn with a linear density of 14.5 tex (40 count) and a twist of 380 twists / 10cm. Then, weave it into a plain weave fabric on an air-jet loom (with a warp density of 420 ends / 10cm, a weft density of 320 ends / 10cm, and a weight controlled at 220g / m²). 2The greige fabric is fed into a scouring machine and treated in a scouring liquor with a liquor ratio of 1:20. The scouring liquor consists of 2.0 g / L nonionic scouring agent JFC (polyoxyethylene ether) and 1.5 g / L chelating dispersant (a compound of polymaleic anhydride PMA and sodium hexametaphosphate in a mass ratio of 1:1). The fabric is immersed at a constant temperature of 70°C for 35 min. After treatment, it is washed twice with hot water at 60°C and thoroughly washed with cold water until the pH is neutral. Finally, the fabric is fed into a tenter frame and heat-set at 180°C for 45 s to obtain an antistatic, high flame-retardant automotive polyester fabric.

[0033] Example 3 A method for preparing an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: Step 1: Graphene powder and multi-walled carbon nanotubes were mixed at a mass ratio of 1:1.5 and added to anhydrous ethanol / deionized water mixed solvent at a mass ratio of 1 g / 50 mL. The mixture was ultrasonically dispersed at 600 W for 45 min to obtain a uniform suspension. γ-aminopropyltriethoxysilane (3.5% of the total mass of the above filler) was added dropwise to the system. The pH was adjusted to 4.5-5.0 with glacial acetic acid. The mixture was heated to 75 °C and stirred for 5 h. After the reaction was completed, the mixture was centrifuged, washed, and vacuum dried at 80 °C for 24 h to obtain the modified composite conductive filler.

[0034] Step 2: Dimethyl terephthalate (DMT), ethylene glycol (EG), and polyethylene glycol (PEG) with a molecular weight of 2000 were added to a reactor in a molar ratio of 1:2.1:0.08. Zinc acetate (0.08% of the total amount) was added, and the transesterification reaction was carried out at 200°C. After the methanol distillation amount exceeded 95%, 0.1% triphenyl phosphate and 0.05% antimony acetate were added. The temperature was raised to 255°C and the pressure was reduced to below 100 Pa for 4 hours to carry out a polycondensation reaction to obtain a polyether ester block copolymer.

[0035] Step 3: Weigh 60 parts by weight of PET chips, 5 parts by weight of modified composite conductive filler, 20 parts by weight of aluminum diethylphosphinate (ADP), 10 parts by weight of polyether ester block copolymer, 2 parts by weight of 1-butyl-3-methylimidazolium phosphate dimethyl salt, and 1.5 parts by weight of hydroxyl-terminated hyperbranched polyester (HBP) and put them into a high-speed mixer. Premix at 80°C for 30 minutes. Feed the mixture into a twin-screw extruder with the temperatures of each zone set to 240°C, 260°C, 275°C, 280°C, and 275°C, and the screw speed at 250 rpm. After melt extrusion, water cooling pelletizing, and crystallization at 120°C, functional masterbatch is obtained.

[0036] Step 4: Add PET chips, flame-retardant monomer BHEPP (10% by mass of PET), and antimony acetate catalyst (0.05% by mass of PET) to the reactor. First, vacuum dry at 170℃ for 2 hours; then raise the temperature to 265℃ for transesterification reaction for 1.5 hours; turn on the high vacuum system (pressure < 50 Pa) to carry out the final polycondensation reaction, and monitor the motor torque to ensure that the intrinsic viscosity IV reaches 0.65-0.68 dL / g. Finally, discharge with high-pressure nitrogen and granulate to obtain reactive flame-retardant copolymer chips.

[0037] Step 5: Mix reactive flame-retardant copolymer chips and functional masterbatch at a mass ratio of 8:1.5, and dry in 165℃ dry air circulation for 8 hours until the moisture content is ≤35ppm. Feed the mixture into a screw spinning machine, setting the screw zone and die head temperatures to 270℃, 280℃, 285℃, 285℃, and 282℃ respectively. The melt is filtered through a 50μm metal sand assembly and extruded through a 0.25mm orifice spinneret. After being cooled by side blowing at 22℃, the filaments undergo two stages of hot drawing (stage one: 90℃ / 3.0 times, stage two: 135℃ / 1.6 times), and finally heat-set and wound at 170℃ to obtain antistatic high flame-retardant polyester fiber.

[0038] Step 6: Comb and blend antistatic high flame retardant polyester fiber and flame retardant viscose fiber (FR-Viscose) at a mass ratio of 70:30. Use ring spinning to produce a functional blended yarn with a linear density of 14.5 tex (40 count) and a twist of 380 twists / 10cm. Then, weave it into a plain weave fabric on an air-jet loom (with a warp density of 420 ends / 10cm, a weft density of 320 ends / 10cm, and a weight controlled at 220g / m²). 2 The greige fabric is fed into a scouring machine and treated in a scouring liquor with a liquor ratio of 1:20. The scouring liquor consists of 2.0 g / L nonionic scouring agent JFC (polyoxyethylene ether) and 1.5 g / L chelating dispersant (a compound of polymaleic anhydride PMA and sodium hexametaphosphate in a mass ratio of 1:1). The fabric is immersed at a constant temperature of 70°C for 35 min. After treatment, it is washed twice with hot water at 60°C and thoroughly washed with cold water until the pH is neutral. Finally, the fabric is fed into a tenter frame and heat-set at 180°C for 45 s to obtain an antistatic, high flame-retardant automotive polyester fabric.

[0039] Example 4 A method for preparing an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: Step 1: Mix graphene powder and multi-walled carbon nanotubes at a mass ratio of 1:2, and add them to anhydrous ethanol / deionized water mixed solvent at a mass ratio of 1g / 50mL. Disperse the mixture by ultrasonication at 600W for 45min to obtain a uniform suspension. Add 5% of the total mass of the above filler to the system with γ-aminopropyltriethoxysilane, adjust the pH to 4.5-5.0 with glacial acetic acid, heat to 75℃ and stir for 5h. After the reaction is completed, centrifuge, wash and vacuum dry at 80℃ for 24h to obtain the modified composite conductive filler.

[0040] Step 2: Dimethyl terephthalate (DMT), ethylene glycol (EG), and polyethylene glycol (PEG) with a molecular weight of 2000 were added to a reactor in a molar ratio of 1:2.1:0.1. Zinc acetate (0.08% of the total amount) was added, and the transesterification reaction was carried out at 200°C. After the methanol distillation amount exceeded 95%, 0.1% triphenyl phosphate and 0.05% antimony acetate were added. The temperature was raised to 255°C and the pressure was reduced to below 100 Pa for polycondensation reaction for 4 hours to obtain a polyether ester block copolymer.

[0041] Step 3: Weigh 60 parts by weight of PET chips, 6 parts by weight of modified composite conductive filler, 20 parts by weight of aluminum diethylphosphinate (ADP), 12 parts by weight of polyether ester block copolymer, 2 parts by weight of 1-butyl-3-methylimidazolium phosphate dimethyl salt, and 2 parts by weight of hydroxyl-terminated hyperbranched polyester (HBP) and put them into a high-speed mixer. Premix at 80°C for 30 minutes. Feed the mixture into a twin-screw extruder, set the temperature of each zone to 240°C, 260°C, 275°C, 280°C, and 275°C, and the screw speed to 250 rpm. After melt extrusion, water cooling pelletizing, and crystallization at 120°C, functional masterbatch is obtained.

[0042] Step 4: Add PET chips, flame-retardant monomer BHEPP (12% by mass of PET), and antimony acetate catalyst (0.05% by mass of PET) to the reactor. First, vacuum dry at 170℃ for 2 hours; then raise the temperature to 265℃ for transesterification reaction for 1.5 hours; turn on the high vacuum system (pressure <50Pa) to carry out the final polycondensation reaction, and monitor the motor torque to ensure that the intrinsic viscosity IV reaches 0.65-0.68 dL / g. Finally, discharge with high-pressure nitrogen and granulate to obtain reactive flame-retardant copolymer chips.

[0043] Step 5: Mix reactive flame-retardant copolymer chips and functional masterbatch at a mass ratio of 8:2, and dry in 165℃ dry air circulation for 8 hours until the moisture content is ≤35ppm. Feed the mixture into a screw spinning machine, setting the screw zone and die head temperatures to 270℃, 280℃, 285℃, 285℃, and 282℃ respectively. The melt is filtered through a 50μm metal sand assembly and extruded through a 0.25mm orifice spinneret. After being cooled by side blowing at 22℃, the filaments undergo two stages of hot drawing (stage one: 90℃ / 3.0 times, stage two: 135℃ / 1.6 times), and finally heat-set and wound at 170℃ to obtain antistatic high flame-retardant polyester fiber.

[0044] Step 6: Comb and blend antistatic high flame retardant polyester fiber and flame retardant viscose fiber (FR-Viscose) at a mass ratio of 70:30. Use ring spinning to produce a functional blended yarn with a linear density of 14.5 tex (40 count) and a twist of 380 twists / 10cm. Then, weave it into a plain weave fabric on an air-jet loom (with a warp density of 420 ends / 10cm, a weft density of 320 ends / 10cm, and a weight controlled at 220g / m²). 2 The greige fabric is fed into a scouring machine and treated in a scouring liquor with a liquor ratio of 1:20. The scouring liquor consists of 2.0 g / L nonionic scouring agent JFC (polyoxyethylene ether) and 1.5 g / L chelating dispersant (a compound of polymaleic anhydride PMA and sodium hexametaphosphate in a mass ratio of 1:1). The fabric is immersed at a constant temperature of 70°C for 35 min. After treatment, it is washed twice with hot water at 60°C and thoroughly washed with cold water until the pH is neutral. Finally, the fabric is fed into a tenter frame and heat-set at 180°C for 45 s to obtain an antistatic, high flame-retardant automotive polyester fabric.

[0045] Example 5 A method for preparing an antistatic, highly flame-retardant automotive polyester fabric includes the following steps: Step 1: Mix graphene powder and multi-walled carbon nanotubes at a mass ratio of 1:1, and add them to anhydrous ethanol / deionized water mixed solvent at a mass ratio of 1g / 50mL. Disperse the mixture by ultrasonication at 600W for 45min to obtain a uniform suspension. Add 2% of the total mass of the above filler to the system with γ-aminopropyltriethoxysilane, adjust the pH to 4.5-5.0 with glacial acetic acid, heat to 75℃ and stir for 5h. After the reaction is completed, centrifuge, wash and vacuum dry at 80℃ for 24h to obtain the modified composite conductive filler.

[0046] Step 2: Dimethyl terephthalate (DMT), ethylene glycol (EG), and polyethylene glycol (PEG) with a molecular weight of 2000 were added to a reactor in a molar ratio of 1:2.1:0.05. Zinc acetate (0.08% of the total amount) was added, and the transesterification reaction was carried out at 200°C. After the methanol distillation amount exceeded 95%, 0.1% triphenyl phosphate and 0.05% antimony acetate were added. The temperature was raised to 255°C and the pressure was reduced to below 100 Pa for a polycondensation reaction for 4 hours to obtain a polyether ester block copolymer.

[0047] Step 3: Weigh 60 parts by weight of PET chips, 4 parts by weight of modified composite conductive filler, 20 parts by weight of aluminum diethylphosphinate (ADP), 8 parts by weight of polyether ester block copolymer, 2 parts by weight of 1-butyl-3-methylimidazolium phosphate dimethyl salt, and 1 part by weight of hydroxyl-terminated hyperbranched polyester (HBP) and put them into a high-speed mixer. Premix at 80°C for 30 minutes. Feed the mixture into a twin-screw extruder with the temperatures of each zone set to 240°C, 260°C, 275°C, 280°C, and 275°C, and the screw speed at 250 rpm. After melt extrusion, water cooling pelletizing, and crystallization at 120°C, functional masterbatch is obtained.

[0048] Step 4: Add PET chips, flame-retardant monomer BHEPP (8% by mass of PET), and antimony acetate catalyst (0.05% by mass of PET) to the reactor. First, vacuum dry at 170℃ for 2 hours; then raise the temperature to 265℃ for transesterification reaction for 1.5 hours; turn on the high vacuum system (pressure < 50 Pa) to carry out the final polycondensation reaction, and monitor the motor torque to ensure that the intrinsic viscosity IV reaches 0.65-0.68 dL / g. Finally, discharge with high-pressure nitrogen and granulate to obtain reactive flame-retardant copolymer chips.

[0049] Step 5: Mix the reactive flame-retardant copolymer chips and functional masterbatch at a mass ratio of 8:1, and dry them in 165℃ dry air circulation for 8 hours until the moisture content is ≤35ppm. Feed the mixture into a screw spinning machine, setting the screw zone and die head temperatures to 270℃, 280℃, 285℃, 285℃, and 282℃ respectively. The melt is filtered through a 50μm metal sand assembly and extruded through a 0.25mm orifice spinneret. After being cooled by side blowing at 22℃, the filaments undergo two stages of hot drawing (stage one: 90℃ / 3.0 times, stage two: 135℃ / 1.6 times), and finally heat-set and wound at 170℃ to obtain antistatic, high flame-retardant polyester fiber.

[0050] Step 6: Comb and blend antistatic high flame retardant polyester fiber and flame retardant viscose fiber (FR-Viscose) at a mass ratio of 70:30. Use ring spinning to produce a functional blended yarn with a linear density of 14.5 tex (40 count) and a twist of 380 twists / 10cm. Then, weave it into a plain weave fabric on an air-jet loom (with a warp density of 420 ends / 10cm, a weft density of 320 ends / 10cm, and a weight controlled at 220g / m²).2 The greige fabric is fed into a scouring machine and treated in a scouring liquor with a liquor ratio of 1:20. The scouring liquor consists of 2.0 g / L nonionic scouring agent JFC (polyoxyethylene ether) and 1.5 g / L chelating dispersant (a compound of polymaleic anhydride PMA and sodium hexametaphosphate in a mass ratio of 1:1). The fabric is immersed at a constant temperature of 70°C for 35 min. After treatment, it is washed twice with hot water at 60°C and thoroughly washed with cold water until the pH is neutral. Finally, the fabric is fed into a tenter frame and heat-set at 180°C for 45 s to obtain an antistatic, high flame-retardant automotive polyester fabric.

[0051] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that step 1 is omitted and no modified composite conductive filler is added in step 3.

[0052] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that step 2 is omitted and polyether ester block copolymer is not added in step 3.

[0053] Comparative Example 3: The difference between Comparative Example 3 and Example 1 is that the flame-retardant monomer BHEPP is not added in step 4.

[0054] Comparative Example 4: The difference between Comparative Example 4 and Example 1 is that 1-butyl-3-methylimidazolium dimethyl phosphate salt and hydroxyl-terminated hyperbranched polyester HBP are not added in step 3.

[0055] Comparative Example 5: The difference between Comparative Example 5 and Example 1 is that 1-butyl-3-methylimidazolium dimethyl phosphate salt is not added in step 3.

[0056] Comparative Example 6: The difference between Comparative Example 6 and Example 1 is that hydroxyl-terminated hyperbranched polyester HBP is not added in step 3.

[0057] Performance testing: 1. Surface Resistivity Test: The test was conducted according to GB / T 12703.4-2010 "Evaluation of Electrostatic Properties of Textiles - Part 4: Resistivity". The fabric samples were pre-conditioned for 24 hours at a temperature of (20±2)℃ and a relative humidity of (35±5)%. The surface resistance of the fabric was measured using a high-resistivity meter, and the initial surface resistivity was recorded. Simultaneously, the fabric was subjected to 50 standard washes according to GB / T 8629 standard, and its surface resistivity was tested again to evaluate the durability of the antistatic properties. The test results are shown in Table 1.

[0058] 2. Limiting Oxygen Index (LOI) Test: The test was conducted according to GB / T 5454-1997 "Test for Burning Performance of Textiles - Oxygen Index Method". The sample was vertically fixed on a sample holder inside the combustion chamber. It was ignited from the top of the sample in an oxygen-nitrogen mixed gas stream, and its combustion equilibrium state was observed. The minimum oxygen concentration (expressed as a volume percentage) required to maintain combustion of the sample was determined. A higher LOI value indicates better flame retardant properties of the material. The test results are shown in Table 1.

[0059] 3. Vertical Burning Performance Test: The test was conducted according to GB / T 5455-2014 "Determination of Vertical Destruction Length, Afterflame and Afterglow Time of Burning Performance of Textiles". A sample of a certain size was placed vertically under a specified flame and ignited for 12 seconds. After the flame was removed, the afterflame time, afterglow time, and destruction length were recorded, and the presence of molten droplets was observed. Referring to the UL-94 standard rating, a V-0 rating requires an afterflame time ≤10 seconds and no burning material falling. The test results are shown in Table 1.

[0060] 4. Tests were conducted according to GB / T 3923.1-2013 "Textiles - Tensile Properties of Fabrics - Part 1: Determination of Breaking Strength and Elongation at Break". A tensile testing machine was used, with a tensile speed of 100 mm / min and a spacing of 200 mm. The sampling size was 50 mm × 200 mm. The maximum force (N) at fabric breakage was recorded and converted to breaking strength (cN / dtex) to evaluate the effect of the modification process on the fiber's mechanical properties. The test results are shown in Table 1.

[0061] 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 an antistatic, high flame-retardant automotive polyester fabric, characterized in that, Includes the following steps: (1) Graphene and carbon nanotubes are dispersed and surface modified with silane coupling agent to obtain modified composite conductive filler; (2) Dimethyl terephthalate, ethylene glycol and polyethylene glycol are mixed, zinc acetate is added as a catalyst to carry out transesterification reaction, then triphenyl phosphate and antimony acetate are added, the temperature is raised and vacuum is drawn to carry out polycondensation reaction to obtain polyether ester block copolymer. (3) PET chips, modified composite conductive filler, aluminum diethylphosphinate, polyether ester block copolymer, 1-butyl-3-methylimidazolium phosphate dimethyl salt and hydroxyl-terminated hyperbranched polyester are premixed, and then the mixture is melt-extruded to obtain functional masterbatch. (4) The PET chips are mixed with the flame retardant monomer BHEPP and the catalyst antimony acetate for transesterification reaction, and then vacuumed for final polycondensation reaction to obtain reactive flame retardant copolymer chips. (5) The reactive flame-retardant copolymer chips are mixed with functional masterbatch, and then melt-spun, stretched and heat-set to obtain antistatic high flame-retardant polyester fiber. (6) The antistatic high flame retardant fiber is blended with flame retardant viscose fiber, woven into fabric, and then refined and heat-set to obtain antistatic high flame retardant automotive polyester fabric.

2. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (1), the mass ratio of graphene to carbon nanotubes is 1:(1-2).

3. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (1), the silane coupling agent is γ-aminopropyltriethoxysilane; the amount of γ-aminopropyltriethoxysilane added is 2 to 5 wt% of the total amount of graphene and carbon nanotubes.

4. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (2), the molar ratio of dimethyl terephthalate, ethylene glycol and polyethylene glycol is 1:2.1:(0.05~0.1).

5. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (3), the mass ratio of PET chips to modified composite conductive filler is 60:(4-6).

6. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (3), the mass ratio of PET chips to polyether ester block copolymer is 60:(8-12).

7. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (3), the mass ratio of 1-butyl-3-methylimidazolium dimethyl phosphate salt to hydroxyl-terminated hyperbranched polyester is 2:(1-2).

8. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (4), the amount of flame retardant monomer BHEPP added is 8 to 10 wt% of the PET chip mass.

9. The method for preparing an antistatic, high flame-retardant automotive polyester fabric according to claim 1, characterized in that, In step (5), the mass ratio of reactive flame-retardant copolymer chips to functional masterbatch is 8:(1-2).

10. A type of antistatic, high flame-retardant automotive polyester fabric, characterized in that, It is prepared by the method described in any one of claims 1 to 9 above.

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