Anti-pilling polyester fiber and preparation method thereof

Abstract

The invention discloses an anti-pilling polyester fiber and a preparation method thereof, belongs to the technical field of polyester fiber processing, and is used for solving the technical problem that the anti-pilling performance of the polyester fiber needs to be further improved in the prior art. And performing post-treatment to obtain the polyester fiber. According to the preparation method, the modified filler, the auxiliary additive and the polyethylene glycol terephthalate are subjected to melt spinning to prepare the polyester filament yarn, the polyester filament yarn is soaked in the finishing liquid containing the intermediate I and the modified graphene, and the polyester fiber is obtained through soaking, ultraviolet irradiation and drying, so that the anti-pilling performance of the polyester fiber is improved, and the anti-pilling performance of the polyester fiber is improved. The antistatic performance and the mechanical strength are also improved.

Description

Technical Field

[0001] This invention relates to the field of polyester fiber processing technology, specifically to an anti-pilling polyester fiber and its preparation method. Background Technology

[0002] Polyester fiber (polyethylene terephthalate, PET) is widely used in clothing, home textiles, industrial fabrics and other fields due to its advantages such as high strength, good abrasion resistance and low cost.

[0003] However, in actual use, polyester fibers are prone to fuzzing and pilling due to friction, affecting the appearance and performance of the fabric. To improve its anti-pilling performance, two main methods are material modification and surface finishing. On the one hand, commonly used functional fillers include inorganic particles such as nano-silica, nano-zinc oxide, bentonite, and graphene, which enhance the surface strength of the fiber. On the other hand, modification methods include melt blending, solution dyeing, and surface coating, in order to improve its wear resistance and surface stability without significantly affecting the fiber's intrinsic properties.

[0004] In existing technologies, traditional inorganic fillers such as nano-SiO2 and TiO2 can improve the surface hardness of polyester yarns. However, these functional particles lack effective chemical bonding with the polymer matrix, resulting in poor interfacial affinity between the polyester substrate and easy agglomeration or peeling. This leads to poor wash resistance and easy detachment of the finishing layer. Functional layers formed by physical coating or blending modification usually have problems such as weak adhesion and insufficient flexibility. The crosslinking density in finishing systems that rely solely on adsorption or physical action is not high, and they cannot form an effective bond with the matrix. As a result, the reinforcing effect of polyester fibers is easily lost in repeated friction, and the stability and film-forming ability of the finishing solution are insufficient, further affecting the mechanical properties of the modified polyester fibers. Summary of the Invention

[0005] The purpose of this invention is to provide a polyester fiber with anti-pilling properties and its preparation method, in order to solve the technical problem that the anti-pilling performance of polyester fibers in the prior art needs to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: a method for preparing anti-pilling polyester fiber, comprising the following steps:

[0007] S1. Polyethylene terephthalate, modified filler and auxiliary additives are added to a twin-screw extruder and melt-spun to obtain polyester filament;

[0008] The reaction principle for preparing polyester filament is as follows:

[0009] During the reaction, in the molten state, the terminal hydroxyl groups of polyethylene terephthalate undergo an esterification reaction with the carboxyl groups in the modified filler, and polyester filaments are obtained through spinning.

[0010] S2. The polyester filament is immersed in the finishing solution, dipped and rubbed twice, and then treated to obtain polyester fiber.

[0011] The reaction principle for preparing polyester fibers is as follows:

[0012] During the reaction, under alkaline conditions, some of the thiol groups in the modified graphene undergo a substitution reaction with the bromine atoms in the polyester filament segments to form chemical bonds. After two dips and two nips, the polyester filaments have a large amount of finishing liquid adsorbed on their surface. Under ultraviolet light irradiation, the 2-hydroxy-2-methyl-1-phenylpropanone in the finishing liquid decomposes to generate free radicals, which initiate a thiol-alkene click reaction between the terminal olefin unsaturated double bonds of intermediate I and the remaining thiol groups in the modified graphene. In this process, the modified graphene acts as a crosslinking agent, forming chemical bonds with intermediate I and the polyester filaments respectively. After drying, polyester fibers are obtained.

[0013] Further, in step S1, the mass ratio of polyethylene terephthalate, modified filler, and auxiliary additives is 70-80:10-15:10-13. The auxiliary additives are composed of plasticizer, light stabilizer, and lubricant in a mass ratio of 5:1:2. The plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, and diisononyl phthalate. The light stabilizer is one or more of 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2-(2-hydroxy-5-methylphenyl)benzotriazole. The lubricant is one or more of oleic acid, fatty acid amide, and oleic acid amide.

[0014] Furthermore, the temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 270℃, 270℃, 285℃, 285℃, 290℃, 290℃, 300℃, and 300℃ respectively. The main engine speed of the twin-screw extruder is 80-120 rpm, and the pressure is 100-150 bar.

[0015] Further, the spinning operation steps include: extruding the molten product through a spinneret and transferring it to a side-blowing chamber, where it is air-cooled and solidified to obtain polyester filament. The spinneret has circular channels with a mesh count of 36-48 and an aperture of 0.1-0.3 mm. The spinning pressure is 80-120 bar. The atmosphere in the side-blowing chamber is air with a relative humidity of 30-40%, a temperature of 20-30°C, and a flow rate maintained at 5-10 m / s.

[0016] Further, in step S2, the two-dip and two-nip operation steps include: immersing the polyester filament in the finishing solution for 20-30 minutes at an immersion ratio of 1:25-30, using a roller mill to press out excess liquid from the fiber, with a nip rate of 50-70%, immersing the fiber again in the finishing solution at a temperature of 50-60℃ for 30-40 minutes, using a roller mill to press out excess liquid from the fiber, with a nip rate of 70-80%. The post-treatment steps include: after the two dips and two nips, placing the modified polyester fiber under 400-500W ultraviolet light at a distance of 15cm for 25-35 minutes, and then transferring it to an oven at a temperature of 60-70℃ for drying for 1-2 hours to obtain polyester fiber.

[0017] Furthermore, in step S1, the modified filler is prepared by the following steps:

[0018] A1. Place silica, γ-methacryloxypropyltrimethoxysilane and ethanol in a reaction vessel and stir. Add saturated ammonia water and stir at room temperature for 10-12 hours. After post-treatment, modified silica is obtained.

[0019] The reaction formula for the preparation of modified silica is:

[0020]

[0021] The reaction principle for the preparation of modified silica is as follows:

[0022] During the reaction, under the catalysis of saturated ammonia water, the silicon-oxygen bond of γ-methacryloxypropyltrimethoxysilane is hydrolyzed into silanol. The silanol further undergoes a condensation reaction with the hydroxyl groups on the surface of silica to obtain modified silica with olefin unsaturated double bonds.

[0023] A2. Place modified silica and xylene in a reaction vessel, stir at room temperature for 20-30 min, add 5-hexenoic acid, p-bromostyrene and azobisisobutyronitrile, heat to 65-75℃, keep the temperature for 8-10 h, and then process to obtain the modified filler.

[0024] The reaction formula for preparing the modified filler is:

[0025]

[0026] The reaction principle for preparing modified fillers is as follows:

[0027] During the reaction, under high temperature conditions, azobisisobutyronitrile decomposes into free radicals, which initiate free radical polymerization of modified silica, 5-hexenoic acid, and p-bromostyrene to obtain the modified filler.

[0028] Further, in step A1, the ratio of silica, γ-methacryloxypropyltrimethoxysilane, ethanol, and saturated ammonia is 3-6g:0.5-1g:80-100mL:10-12mL. The post-treatment step includes: after the reaction is complete, filtration is performed, the filter cake is washed 2-4 times with deionized water and ethanol, transferred to an oven at 50-60℃, and dried to constant weight to obtain modified silica. In step A2, the ratio of modified silica, xylene, 5-hexenoic acid, p-bromostyrene, and azobisisobutyronitrile is 1-2g:50-80mL:5-7g:1-2g:0.2-0.4g. The post-treatment step includes: after the reaction is complete, the reaction system is cooled to room temperature, filtration is performed, the filter cake is washed 2-4 times with xylene, transferred to an oven at 60-70℃, and dried to constant weight to obtain modified filler.

[0029] Furthermore, in step S2, the finishing solution is prepared by the following steps:

[0030] B1. Place polyethylene glycol in a nitrogen-protected reactor and stir. Heat the reactor to 65-75°C and slowly add isocyanate methacrylate and dibutyltin dilaurate. Heat the reactor to reflux and keep it at this temperature for 2-4 hours to obtain intermediate I.

[0031] The reaction formula for the preparation of intermediate I is as follows:

[0032]

[0033] The reaction principle for the preparation of intermediate I is as follows:

[0034] During the reaction, under the catalysis of dibutyltin dilaurate, the terminal hydroxyl groups of polyethylene glycol undergo a nucleophilic reaction with the isocyanate groups of isocyanate methacrylate to give an olefin-terminated product, thus obtaining intermediate I.

[0035] B2. Place the modified graphene, photoinitiator, potassium carbonate, 2-butanone and intermediate I in a reaction vessel and stir for 0.5-1 h to obtain the finishing solution.

[0036] Further, in step B1, the weight ratio of polyethylene glycol, isocyanate methacrylate, and dibutyltin dilaurate is 3-4:0.5-1.5:0.1-0.3; in step B2, the ratio of modified graphene, photoinitiator, potassium carbonate, 2-butanone, and intermediate I is 2-4g:0.1-0.2g:1-2g:250-300mL:2-4g, and the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0037] Furthermore, the modified graphene is prepared by the following steps:

[0038] C1. Graphene oxide, γ-mercaptopropyltriethoxysilane, deionized water and ethanol are placed in a reaction vessel and stirred. The reaction vessel is heated to 45-55℃, acetic acid solution is added, and the reaction is kept at this temperature for 2-4 hours. The modified graphene precursor is obtained after post-treatment.

[0039] The preparation reaction principle of modified graphene precursor is as follows:

[0040] During the reaction, under the catalysis of acetic acid solution, the siloxane bonds of γ-mercaptopropyltriethoxysilane are hydrolyzed into silanols. The silanols then undergo a condensation reaction with the hydroxyl groups on the surface of graphene oxide to obtain a modified graphene precursor modified with an olefin silane coupling agent.

[0041] C2. Place the modified graphene precursor and ethanol in a reaction vessel under a nitrogen atmosphere, stir for 15-30 min, add hydrazine hydrate, react at room temperature for 4-6 h, and then perform post-treatment to obtain modified graphene.

[0042] The preparation reaction principle of modified graphene is as follows:

[0043] During the reaction, hydrazine hydrate is a strong reducing agent that can reduce the oxygen-containing functional groups on the surface of the modified graphene precursor to a carbon framework structure. During the reduction process, the sp³ carbon in the modified graphene precursor is gradually restored to sp² layers. Maintaining a nitrogen atmosphere can prevent the thiol groups in the modified graphene precursor from being oxidized to disulfide bonds by the air, ultimately yielding thiol-modified graphene.

[0044] Further, in step C1, the ratio of graphene oxide, γ-mercaptopropyltriethoxysilane, deionized water, ethanol, and acetic acid solution is 2-4 g: 1-2 g: 10-15 mL: 50-100 mL: 5-8 mL, and the acetic acid solution is a 30-50 wt% aqueous acetic acid solution. The post-treatment step includes: after the reaction is complete, the reaction system is cooled to room temperature, filtered, the filter cake is washed 2-4 times with deionized water and ethanol, and transferred to a temperature of 50-60°C. In an oven at 0°C, the modified graphene precursor is dried to constant weight to obtain the modified graphene precursor. In step C2, the ratio of the modified graphene precursor, ethanol, and hydrazine hydrate is 1-2g:50-80mL:10-12mL, and the concentration of the hydrazine hydrate is 80-85wt%. The post-processing steps include: after the reaction is completed, the mixture is filtered, the filter cake is washed 2-4 times with deionized water and ethanol, transferred to an oven at 50-60°C, and dried to constant weight to obtain the modified graphene.

[0045] The present invention also proposes a type of anti-pilling polyester fiber, which is prepared by the above-mentioned method for preparing an anti-pilling polyester fiber.

[0046] The present invention has the following beneficial effects:

[0047] 1. This invention involves preparing modified silica with olefin-modified unsaturated double bonds, and further preparing a modified filler by free radical polymerization with 5-hexenoic acid and p-bromostyrene. The modified filler is then melt-spun with auxiliary additives and polyethylene terephthalate to prepare polyester filaments. The nano-silica of the modified filler has high hardness, which can enhance the mechanical strength and abrasion resistance of polyester fibers, inhibit fiber breakage and fuzz formation caused by friction, and the organic polymer layer coated on the surface of the modified filler contains carboxyl groups, which can form chemical bonds with polyethylene terephthalate during the melting process, improve the interfacial bonding force between the matrix, avoid pores caused by uneven filler distribution, and improve the anti-pilling performance of polyester fibers.

[0048] 2. This invention modifies graphene precursors by modifying the surface of graphene oxide with mercaptosilane coupling agents. Through a reduction reaction, the oxygen-containing functional groups on the graphene oxide surface are reduced to a carbon skeleton structure. The modified graphene possesses a high-strength, high-modulus sheet structure, forming a flexible yet robust protective film on the surface of polyester fibers. This effectively inhibits fiber breakage and fuzzing caused by interlacing friction. After reduction treatment, the sp³ carbon in the modified graphene precursor gradually recovers to sp² sheets, improving the conductivity of the modified graphene. This makes the polyester fibers less prone to static electricity during use, improving the wearing comfort of polyester textiles. Furthermore, the modified graphene provides a hard yet non-brittle surface structure for the polyester fibers, significantly enhancing their abrasion resistance and further improving their anti-pilling properties.

[0049] 3. This invention involves preparing an olefin-terminated intermediate I from polyethylene glycol and isocyanate methacrylate, then combining it with modified graphene to form a finishing solution. This solution is used to impregnate polyester filaments, followed by ultraviolet irradiation and drying to obtain polyester fibers. During impregnation and ultraviolet irradiation, the thiol groups in the modified graphene undergo a substitution reaction with the bromine atoms in the polyester filament segments, and a thiol-olefin click reaction occurs with intermediate I. This forms an interpenetrating three-dimensional network coating on the surface of the polyester filaments, inhibiting micro-damage to the polyester fiber surface. Together with the modified graphene, it enhances the abrasion resistance of the polyester fibers, prevents fuzz formation, and improves the anti-pilling properties of the polyester fibers. Furthermore, intermediate I, with polyethylene glycol as the main chain, has a flexible and hydrophilic molecular chain, exhibiting good flowability and film-forming properties. After ultraviolet curing, it forms a soft yet dense cross-linked layer, preventing fiber surface cracks or powdering caused by excessive hardness or brittleness. This improves the smooth adhesion between the finishing layer and the fiber, enhancing the mechanical properties of the polyester fibers. Detailed Implementation

[0050] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only 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.

[0051] The graphene oxide used in this invention has a fixed carbon content of 99.9%, an oversize particle size of 4 μm, and an undersize particle size of 0.335 nm-4 μm.

[0052] The polyethylene glycol used in this invention has a molecular weight of 1000, a pH of 5-7, and a freezing point of 38-41℃.

[0053] The polyethylene terephthalate used in this invention has a density of 1.4 g / cm³ and a melting point of 255-260 °C.

[0054] Example 1

[0055] This embodiment provides a method for preparing a finishing solution for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0056] Step I: Preparation of modified graphene precursor

[0057] Weigh out 20g of graphene oxide, 10g of γ-mercaptopropyltriethoxysilane, 100mL of deionized water and 500mL of ethanol and place them in a reaction vessel and stir. Heat the reaction vessel to 45℃, add 50mL of 30wt% acetic acid aqueous solution, and keep the reaction at this temperature for 2h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake twice with deionized water and ethanol, transfer it to an oven at 50℃ and dry it to constant weight to obtain the modified graphene precursor.

[0058] Step II: Preparation of modified graphene

[0059] Weigh 10g of modified graphene precursor and 500mL of ethanol and place them in a reaction vessel under nitrogen atmosphere protection. Stir for 15min, add 100mL of 80wt% hydrazine hydrate, and react at room temperature for 4h. After the reaction is complete, filter, wash the filter cake twice with deionized water and ethanol, transfer it to an oven at 50℃ and dry it to constant weight to obtain modified graphene.

[0060] Step III: Preparation of Intermediate I

[0061] Weigh out 30g of polyethylene glycol and place it in a nitrogen-protected reactor and stir. Heat the reactor to 65-75℃, slowly add 5g of isocyanate methacrylate and 1g of dibutyltin dilaurate, heat the reactor to reflux, and keep it at this temperature for 2 hours to obtain intermediate I.

[0062] Step IV: Preparation of finishing solution

[0063] Weigh out 20g of modified graphene, 1g of 2-hydroxy-2-methyl-1-phenylpropanone, 10g of potassium carbonate, 2500mL of 2-butanone, and 20g of intermediate I and place them in a reaction vessel. Stir for 0.5h to obtain the finishing solution.

[0064] Example 2

[0065] This embodiment provides a method for preparing a finishing solution for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0066] Step I: Preparation of modified graphene precursor

[0067] Weigh out 30g of graphene oxide, 15g of γ-mercaptopropyltriethoxysilane, 125mL of deionized water and 700mL of ethanol and place them in a reaction vessel and stir. Heat the reaction vessel to 50℃, add 65mL of 40wt% acetic acid aqueous solution, and keep the reaction at this temperature for 3h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake three times with deionized water and ethanol, transfer it to an oven at 55℃ and dry it to constant weight to obtain the modified graphene precursor.

[0068] Step II: Preparation of modified graphene

[0069] Weigh 15g of modified graphene precursor and 700mL of ethanol and place them in a reaction vessel under nitrogen atmosphere protection. Stir for 20min, add 110mL of 82wt% hydrated hydrazine, and react at room temperature for 5h. After the reaction is complete, filter the mixture and wash the filter cake three times with deionized water and ethanol. Transfer the cake to an oven at 55℃ and dry it to constant weight to obtain modified graphene.

[0070] Step III: Preparation of Intermediate I

[0071] Weigh out 35g of polyethylene glycol and place it in a nitrogen-protected reactor and stir. Heat the reactor to 70°C and slowly add 10g of isocyanate methacrylate and 2g of dibutyltin dilaurate. Heat the reactor to reflux and keep it at that temperature for 3 hours to obtain intermediate I.

[0072] Step IV: Preparation of finishing solution

[0073] Weigh out 30g of modified graphene, 1.5g of 2-hydroxy-2-methyl-1-phenylpropanone, 15g of potassium carbonate, 2700mL of 2-butanone, and 30g of intermediate I and place them in a reaction vessel. Stir for 1 hour to obtain the finishing solution.

[0074] Example 3

[0075] This embodiment provides a method for preparing a finishing solution for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0076] Step I: Preparation of modified graphene precursor

[0077] Weigh out 40g of graphene oxide, 20g of γ-mercaptopropyltriethoxysilane, 150mL of deionized water and 1000mL of ethanol and place them in a reaction vessel and stir. Heat the reaction vessel to 55℃, add 80mL of 50wt% acetic acid aqueous solution, and keep the reaction at this temperature for 4h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake 4 times with deionized water and ethanol, transfer it to an oven at 60℃ and dry it to constant weight to obtain the modified graphene precursor.

[0078] Step II: Preparation of modified graphene

[0079] Weigh 20g of modified graphene precursor and 800mL of ethanol and place them in a reaction vessel under nitrogen atmosphere protection. Stir for 30min, add 120mL of 85wt% hydrated hydrazine, and react at room temperature for 6h. After the reaction is complete, filter, wash the filter cake 4 times with deionized water and ethanol, transfer it to an oven at 60℃ and dry it to constant weight to obtain modified graphene.

[0080] Step III: Preparation of Intermediate I

[0081] Weigh out 40g of polyethylene glycol and place it in a nitrogen-protected reactor and stir. Heat the reactor to 75°C and slowly add 15g of isocyanate methacrylate and 3g of dibutyltin dilaurate. Heat the reactor to reflux and keep it at that temperature for 4 hours to obtain intermediate I.

[0082] Step IV: Preparation of finishing solution

[0083] Weigh out 40g of modified graphene, 2g of 2-hydroxy-2-methyl-1-phenylpropanone, 20g of potassium carbonate, 3000mL of 2-butanone, and 40g of intermediate I and place them in a reaction vessel. Stir for 1 hour to obtain the finishing solution.

[0084] Example 4

[0085] This embodiment provides a method for preparing a modified filler for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0086] Step ①: Preparation of modified silica

[0087] Weigh out 30g of silica, 5g of γ-methacryloxypropyltrimethoxysilane and 800mL of ethanol and place them in a reaction vessel and stir. Add 100mL of saturated ammonia water and stir at room temperature for 10h. After the reaction is complete, filter the mixture and wash the filter cake twice with deionized water and ethanol. Transfer the cake to an oven at 50℃ and dry it to constant weight to obtain modified silica.

[0088] Step 2: Preparation of modified filler

[0089] Weigh 10g of modified silica and 500mL of xylene and place them in a reaction vessel. Stir at room temperature for 20min. Add 50g of 5-hexenoic acid, 10g of p-bromostyrene and 2g of azobisisobutyronitrile. Heat to 65℃ and keep the temperature for 8h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake twice with xylene, transfer it to an oven at 60℃ and dry it to constant weight to obtain the modified filler.

[0090] Example 5

[0091] This embodiment provides a method for preparing a modified filler for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0092] Step ①: Preparation of modified silica

[0093] Weigh out 45g of silica, 7g of γ-methacryloxypropyltrimethoxysilane and 900mL of ethanol and place them in a reaction vessel and stir. Add 110mL of saturated ammonia water and stir at room temperature for 11h. After the reaction is complete, filter the mixture and wash the filter cake three times with deionized water and ethanol. Transfer the cake to an oven at 55℃ and dry it to constant weight to obtain modified silica.

[0094] Step 2: Preparation of modified filler

[0095] Weigh 15g of modified silica and 700mL of xylene and place them in a reaction vessel. Stir at room temperature for 25min. Add 60g of 5-hexenoic acid, 15g of p-bromostyrene and 3g of azobisisobutyronitrile. Heat to 70℃ and keep the temperature for 9h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake three times with xylene, transfer it to an oven at 65℃ and dry it to constant weight to obtain the modified filler.

[0096] Example 6

[0097] This embodiment provides a method for preparing a modified filler for polyester fibers that resists pilling and fuzzing, comprising the following steps:

[0098] Step ①: Preparation of modified silica

[0099] Weigh out 60g of silica, 10g of γ-methacryloxypropyltrimethoxysilane and 1000mL of ethanol and place them in a reaction vessel and stir. Add 120mL of saturated ammonia water and stir at room temperature for 12h. After the reaction is complete, filter the mixture and wash the filter cake four times with deionized water and ethanol. Transfer the cake to an oven at 60℃ and dry it to constant weight to obtain modified silica.

[0100] Step 2: Preparation of modified filler

[0101] Weigh 20g of modified silica and 800mL of xylene and place them in a reaction vessel. Stir at room temperature for 30min. Add 70g of 5-hexenoic acid, 20g of p-bromostyrene and 4g of azobisisobutyronitrile. Heat to 75℃ and keep the temperature for 10h. After the reaction is complete, wait for the reaction system to cool to room temperature, filter, wash the filter cake 4 times with xylene, transfer it to an oven at 70℃ and dry to constant weight to obtain the modified filler.

[0102] Example 7

[0103] This embodiment provides a method for preparing anti-pilling polyester fibers, including the following steps:

[0104] Step (1): Preparation of polyester filament

[0105] Dioctyl phthalate, 2-hydroxy-4-methoxybenzophenone and fatty acid amide were mixed evenly in a mass ratio of 5:1:2 to obtain an auxiliary additive for later use.

[0106] Polyethylene terephthalate, the modified filler prepared in Example 4, and auxiliary additives were added to a twin-screw extruder at a mass ratio of 70:10:10 and melted. The molten product was extruded through a spinneret and transferred to a side-blowing chamber. After air cooling and curing, polyester filament was obtained.

[0107] The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 270℃, 270℃, 285℃, 285℃, 290℃, 290℃, 300℃, and 300℃ respectively. The main motor speed of the twin-screw extruder is 80 rpm, and the pressure is 100 bar.

[0108] The spinneret has circular channels with a mesh count of 36 and an aperture of 0.1 mm. The spinneret pressure is 80 bar. The side-blowing chamber is filled with air with a relative humidity of 30% and a temperature of 20°C. The flow rate is maintained at 5 m / s.

[0109] Step 2: Preparation of polyester fibers

[0110] The polyester filament was immersed in the finishing solution for 0.5 min at a ratio of 1:25. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 50%. The fiber was then immersed again in the finishing solution prepared in Example 1 at a temperature of 50°C for 1 min. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 70%. After two immersions and two nips, the modified polyester fiber was placed under 400W ultraviolet light at a distance of 15 cm for 25 min. Then it was transferred to an oven at a temperature of 60°C and dried for 1 h to obtain polyester fiber.

[0111] Example 8

[0112] This embodiment provides a method for preparing anti-pilling polyester fibers, including the following steps:

[0113] Step (1): Preparation of polyester filament

[0114] Dioctyl phthalate, 2-hydroxy-4-methoxybenzophenone and fatty acid amide were mixed evenly in a mass ratio of 5:1:2 to obtain an auxiliary additive for later use.

[0115] Polyethylene terephthalate, the modified filler prepared in Example 5, and auxiliary additives were added to a twin-screw extruder at a mass ratio of 75:12:11 and melted. The molten product was extruded through a spinneret and transferred to a side-blowing chamber. After air cooling and curing, polyester filament was obtained.

[0116] The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 270℃, 270℃, 285℃, 285℃, 290℃, 290℃, 300℃, and 300℃ respectively. The main motor speed of the twin-screw extruder is 100 rpm, and the pressure is 125 bar.

[0117] The spinneret has circular channels with a mesh count of 48 and an aperture of 0.2 mm. The spinneret pressure is 100 bar. The side-blowing chamber is filled with air with a relative humidity of 35% and a temperature of 25°C. The flow rate is maintained at 8 m / s.

[0118] Step 2: Preparation of polyester fibers

[0119] The polyester filament was immersed in the finishing solution for 1 minute at a ratio of 1:27. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 60%. The fiber was then immersed again in the finishing solution prepared in Example 2 at a temperature of 55°C for 2 minutes. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 75%. After two dips and two nips, the modified polyester fiber was placed under 450W ultraviolet light at a distance of 15cm for 30 minutes. Then it was transferred to an oven at a temperature of 65°C and dried for 1.5 hours to obtain polyester fiber.

[0120] Example 9

[0121] This embodiment provides a method for preparing anti-pilling polyester fibers, including the following steps:

[0122] Step (1): Preparation of polyester filament

[0123] Dioctyl phthalate, 2-hydroxy-4-methoxybenzophenone and fatty acid amide were mixed evenly in a mass ratio of 5:1:2 to obtain an auxiliary additive for later use.

[0124] Polyethylene terephthalate, the modified filler prepared in Example 6, and auxiliary additives were added to a twin-screw extruder at a mass ratio of 80:15:113 and melted. The molten product was extruded through a spinneret and transferred to a side-blowing chamber. After air cooling and curing, polyester filament was obtained.

[0125] The temperatures of the eight temperature zones of the twin-screw extruder from the feed inlet to the discharge outlet are 270℃, 270℃, 285℃, 285℃, 290℃, 290℃, 300℃, and 300℃ respectively. The main motor speed of the twin-screw extruder is 120 rpm, and the pressure is 150 bar.

[0126] The spinneret has circular channels with a mesh count of 48 and an aperture of 0.3 mm. The spinneret pressure is 120 bar. The side-blowing chamber is filled with air with a relative humidity of 40% and a temperature of 30°C. The flow rate is maintained at 10 m / s.

[0127] Step 2: Preparation of polyester fibers

[0128] The polyester filament was immersed in the finishing solution for 1 minute at a ratio of 1:30. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 70%. The fiber was then immersed again in the finishing solution prepared in Example 3 at a temperature of 60°C for 2 minutes. The excess liquid was squeezed out of the fiber using a roller mill, with a residual rate of 80%. After two immersions and two nips, the modified polyester fiber was placed under 500W ultraviolet light at a distance of 15cm for 35 minutes. Then it was transferred to an oven at a temperature of 70°C and dried for 2 hours to obtain polyester fiber.

[0129] Comparative Example 1

[0130] The difference between this comparative example and Example 9 is that, in step IV, when preparing the finishing solution, an equal amount of modified graphene precursor is used instead of modified graphene.

[0131] Comparative Example 2

[0132] The difference between this comparative example and Example 9 is that intermediate I is omitted in step IV when preparing the finishing solution.

[0133] Comparative Example 3

[0134] The difference between this comparative example and Example 9 is that, in step (1) when preparing polyester filament, modified silica is used in an equal amount to replace the modified filler.

[0135] Comparative Example 4

[0136] The difference between this comparative example and Example 9 is that polyester filament is used in place of polyester fiber in equal amounts.

[0137] Performance testing:

[0138] The breaking strength and elongation at break of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-4 were tested in accordance with the standard GB / T 14337-2008 "Test Method for Tensile Properties of Chemical Fibers (Short Fibers)".

[0139] The polyester fibers prepared in Examples 7-9 and Comparative Examples 1-4 were warped and sized, and then spun into polyester fabrics using an air-jet loom.

[0140] The visual anti-pilling grade of the polyester fabrics prepared in Examples 7-9 and Comparative Examples 1-4 was tested in accordance with the standard GB / T 4802.2-2008 "Textiles - Determination of pilling properties of fabrics - Part 2: Modified Martindale method".

[0141] The antistatic properties of the polyester fabrics prepared in Examples 7-9 and Comparative Examples 1-4 were tested in accordance with the standard GB / T 12703.1-2021 "Textiles - Test Methods for Electrostatic Properties - Part 1: Corona Charging Method". The specific data are shown in Table 1.

[0142] Table 1 - Performance Test Data for Each Sample

[0143] Project Group Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Fracture strength / MPa 8.5 8.9 8.7 7.8 6.5 5.2 5.4 Elongation at break / % 14.3 15.4 14.9 13.5 9.5 8.3 8.6 <![CDATA[Volume wear amount / mm 3 > 25.9 25.3 25.7 27.5 30.3 31.4 32.5 Anti-pilling grade / level 5 5 5 4 3 2 2 Antistatic properties / % Excellent Excellent Excellent Difference better Difference Difference

[0144] Data Analysis:

[0145] A comparative analysis of the data in Table 1 reveals that the polyester fiber prepared by this invention has a breaking strength of 8.9 MPa, a breaking elongation of 15.4%, and a volumetric abrasion loss of 25.3 mm. 3 The present invention achieves a pilling resistance grade of 5 and excellent antistatic properties, with all data superior to the comparative example. This invention prepares modified silica modified with olefin-unsaturated double bonds, and further prepares a modified filler by free radical polymerization with 5-hexenoic acid and p-bromostyrene. Polyester filaments are then prepared by melt spinning the modified filler, auxiliary additives, and polyethylene terephthalate. The polyester filaments are then impregnated in a finishing solution containing intermediate I and modified graphene, and polyester fibers are obtained through impregnation, ultraviolet irradiation, and drying. This process not only improves the pilling resistance of the polyester fibers but also enhances their antistatic properties and mechanical strength.

[0146] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing anti-pilling polyester fiber, characterized in that, Includes the following steps: S1. Polyethylene terephthalate, modified filler and auxiliary additives are added to a twin-screw extruder and melt-spun to obtain polyester filament; S2. The polyester filament is immersed in the finishing solution, dipped and rubbed twice, and then treated to obtain polyester fiber.

2. The method for preparing anti-pilling polyester fiber according to claim 1, characterized in that, In step S1, the mass ratio of polyethylene terephthalate, modified filler and auxiliary additives is 70-80:10-15:10-13.

3. The method for preparing anti-pilling polyester fiber according to claim 1, characterized in that, In step S1, the modified filler is prepared by the following steps: A1. Place silica, γ-methacryloxypropyltrimethoxysilane and ethanol in a reaction vessel and stir. Add saturated ammonia water and stir at room temperature for 10-12 hours. After post-treatment, modified silica is obtained. A2. Place modified silica and xylene in a reaction vessel, stir at room temperature for 20-30 min, add 5-hexenoic acid, p-bromostyrene and azobisisobutyronitrile, heat to 65-75℃, keep the temperature for 8-10 h, and then process to obtain the modified filler.

4. The method for preparing anti-pilling polyester fiber according to claim 3, characterized in that, In step A1, the ratio of silica, γ-methacryloxypropyltrimethoxysilane, ethanol, and saturated ammonia is 3-6g:0.5-1g:80-100mL:10-12mL; in step A2, the ratio of modified silica, xylene, 5-hexenoic acid, p-bromostyrene, and azobisisobutyronitrile is 1-2g:50-80mL:5-7g:1-2g:0.2-0.4g.

5. The method for preparing anti-pilling polyester fiber according to claim 1, characterized in that, In step S2, the finishing solution is prepared by the following steps: B1. Place polyethylene glycol in a nitrogen-protected reactor and stir. Heat the reactor to 65-75°C and slowly add isocyanate methacrylate and dibutyltin dilaurate. Heat the reactor to reflux and keep it at this temperature for 2-4 hours to obtain intermediate I. B2. Place the modified graphene, photoinitiator, potassium carbonate, 2-butanone and intermediate I in a reaction vessel and stir for 0.5-1 h to obtain the finishing solution.

6. The method for preparing anti-pilling polyester fiber according to claim 5, characterized in that, In step B1, the weight ratio of polyethylene glycol, isocyanate methacrylate, and dibutyltin dilaurate is 3-4: 0.5-1.5:0.1-0.3; In step B2, the ratio of the amount of modified graphene, photoinitiator, potassium carbonate, 2-butanone and intermediate I is 2-4g:0.1-0.2g:1-2g:250-300mL:2-4g, and the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

7. The method for preparing anti-pilling polyester fiber according to claim 5, characterized in that, The modified graphene was prepared by the following steps: C1. Graphene oxide, γ-mercaptopropyltriethoxysilane, deionized water and ethanol are placed in a reaction vessel and stirred. The reaction vessel is heated to 45-55℃, acetic acid solution is added, and the reaction is kept at this temperature for 2-4 hours. The modified graphene precursor is obtained after post-treatment. C2. Place the modified graphene precursor and ethanol in a reaction vessel under a nitrogen atmosphere, stir for 15-30 min, add hydrazine hydrate, react at room temperature for 4-6 h, and then perform post-treatment to obtain modified graphene.

8. The method for preparing anti-pilling polyester fiber according to claim 7, characterized in that, In step C1, the ratio of graphene oxide, γ-mercaptopropyltriethoxysilane, deionized water, ethanol, and acetic acid solution is 2-4 g: 1-2 g: 10-15 mL: 50-100 mL: 5-8 mL, and the acetic acid solution is a 30-50 wt% aqueous solution of acetic acid; in step C2, the ratio of modified graphene precursor, ethanol, and hydrated hydrazine is 1-2 g: 50-80 mL: 10-12 mL, and the concentration of hydrated hydrazine is 80-85 wt%.

9. A polyester fiber resistant to pilling and fuzzing, characterized in that, The anti-pilling polyester fiber is prepared by the method for preparing anti-pilling polyester fiber as described in any one of claims 1-8.

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