Full-dull antistatic polyester fiber and preparation method thereof

Abstract

The invention discloses a full-dull antistatic polyester fiber and a preparation method thereof, belongs to the technical field of fiber preparation, and aims to solve the technical problem that the dull performance and antistatic performance of the polyester fiber need to be further improved in the prior art. The antistatic polyethylene glycol terephthalate composite material specifically comprises the following components in parts by weight: 60-80 parts of polyethylene glycol terephthalate, 4-6 parts of silicon resin filler, 10-15 parts of a modified antistatic agent and 1-3 parts of an auxiliary additive. According to the invention, the polyester fiber is prepared by preparing the modified antistatic agent with high hydrophilicity and carrying out melt spinning on the modified antistatic agent, the organic-inorganic hybrid silicon resin filler and the polyester base material, so that not only are the antistatic performance and the matting performance of the polyester fiber improved, but also the hydrophilicity and the mechanical strength of the polyester fiber are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fiber preparation, in particular to a full-dull anti-static polyester fiber and a preparation method thereof. BACKGROUND

[0002] With the development of textiles towards high-end and functionalization, polyester fiber (PET) is widely used due to its high mechanical strength, good wear resistance, good washing resistance and low cost. However, ordinary polyester fiber has high gloss and obvious surface mirror reflection, which cannot meet the needs of softness, matte and full-dull in some high-requirement consumer products or industrial applications. At the same time, polyester fiber itself has strong electrical insulation, which is easy to accumulate static electricity, affecting the wearing comfort, adsorbing dust, causing static discharge and even sparks, which is not conducive to clothing, safety, protection, underwear and bedding.

[0003] In order to integrate the appearance and functional requirements, researchers have improved the dullness and anti-static properties through various modification methods in recent years. Commonly used dull materials include adding dulling agents, modifying the fiber structure, such as using rough or irregular cross-section or applying a dull coating on the fiber surface to scatter light and reduce mirror reflection. Commonly used materials or methods for anti-static properties include adding conductive fibers, mixing polar / charge carrier additives, and surface coating anti-static agents.

[0004] Although the above technical means have achieved certain results in the laboratory or some industrial applications, there are still many limitations and deficiencies in actual products. First, although the dulling agent such as silica nanoparticle filler can reduce gloss and increase haze, excessive use will weaken the mechanical properties of the fiber, such as reducing the breaking strength and elongation, and may also affect the spinning stability, increase the melt viscosity or damage the processing equipment. Second, the anti-static additives or conductive materials may not be compatible with the heat resistance, washability and wear resistance of the polyester matrix, and may be easily washed or thermally decomposed in a high-temperature melting or washing environment. On the other hand, the poor dispersibility of polar additives or conductive fillers often leads to uneven distribution inside or on the surface of the fiber, resulting in serious local static accumulation. Furthermore, in the pursuit of full-dull appearance and anti-static properties, the hand feeling, softness, gloss control precision, hydrophilicity / hygroscopicity and other properties of the fiber are often sacrificed.

[0005] The main reasons for these deficiencies are the compatibility problems between the dulling agent and the anti-static agent in the compounding, and the poor thermal stability of the polar / conductive additive and the polyester melt or polyester segment. Therefore, a solution is proposed. SUMMARY

[0006] The present application aims to provide a full-dull anti-static polyester fiber and a preparation method thereof, and aims to solve the technical problem that the dullness and anti-static performance of polyester fibers need to be further improved in the prior art.

[0007] The present application can achieve the purpose by the following technical scheme: a full-dull anti-static polyester fiber, comprising the following components in parts by weight: 60-80 parts of polyethylene terephthalate, 4-6 parts of a silicon resin filler, 10-15 parts of a modified anti-static agent, and 1-3 parts of an auxiliary additive.

[0008] Further, the modified silicon resin is prepared by the following steps: A1, the core-shell silica and n-butanol are placed in a reaction kettle, stirred at room temperature for 20-40 min to obtain a dispersion liquid; A2, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, phenyltrimethoxysilane, 2,4-dihydroxyacetophenone, deionized water and n-butanol are placed in a reaction kettle and stirred, the dispersion liquid is slowly added, the reaction kettle is heated to 40-50 DEG C, and the reaction is kept for 15-30 min, concentrated sulfuric acid is added, the reaction kettle is heated to 80-90 DEG C, and the reaction is kept for 4-6 h, and the silicon resin filler is obtained after post-treatment.

[0009] The preparation reaction principle of the silicon resin filler is: During the reaction, the core-shell silica is dispersed in n-butanol to form a stable dispersion liquid by stirring, and further, when 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, phenyltrimethoxysilane, 2,4-dihydroxyacetophenone, deionized water and n-butanol are mixed together and slowly added to the dispersion liquid containing silica, the system is subjected to a first-stage pre-hydrolysis and condensation reaction at 40-50 DEG C, mainly including hydrolysis reaction of silane and polycondensation reaction between hydroxyl groups, after adding concentrated sulfuric acid, the pH of the system drops sharply, and the system enters strong acid catalysis condition, the hydrolysis and condensation reaction speed is accelerated, and finally the silicon resin filler coated with core-shell silica is obtained.

[0010] Further, in step A1, the amount ratio of the core-shell silica and n-butanol is 2-4 g:50-100 mL; in step A2, the amount ratio of the 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, phenyltrimethoxysilane, 2,4-dihydroxyacetophenone, deionized water, n-butanol, dispersion liquid and concentrated sulfuric acid is 8-10 g:7-9 g:0.2-0.4 g:60-80 mL:1-2 mL:20-40 mL:1-2 mL, the concentration of the concentrated sulfuric acid is 50-70 wt%, and the post-treatment step comprises: after the reaction is completed, the reaction solution is cooled to room temperature, and then is left to stand for 4-6 h, is filtered, the filter cake is washed with deionized water and ethanol for 2-4 times, is transferred to an oven with a temperature of 50-60 °C, is dried to a constant weight, is ground, is passed through a 500-mesh sieve, and then the silicon resin filler is obtained.

[0011] Further, the core-shell silica is prepared by the following steps: B1, cyclohexane, polyoxyethylene tert-octyl phenyl ether, n-hexanol and deionized water are stirred in a reaction kettle, tetraethyl orthosilicate is added, and the reaction is carried out at room temperature for 1-2 h, an ammonia solution is added, and the reaction is stirred at room temperature for 4-6 h, and then the core-shell silica precursor is obtained by post-treatment; The preparation reaction principle of the core-shell silica precursor is as follows: During the reaction, in the reverse microemulsion system constructed by taking cyclohexane as the oil phase, polyoxyethylene tert-octyl phenyl ether as the nonionic surfactant and n-hexanol as the co-surfactant, the tiny water droplets are stably wrapped in the organic phase to form an oil-in-water microreactor, when tetraethyl orthosilicate is added, it is gradually hydrolyzed in the water droplets and occurs condensation reaction under the catalysis of ammonia water to generate spherical silica nanoparticles, and the core-shell silica precursor is obtained.

[0012] B2, the core-shell silica precursor and deionized water are placed in a reaction kettle, the reaction kettle is heated to 55-65 °C, and then is stirred and kept at the temperature for 15-30 min, an aqueous tin chloride solution is slowly added dropwise, an aqueous sodium hydroxide solution is added until the pH of the system is 9-10, and then the reaction is kept at the temperature for 0.5-1 h, and the core-shell silica is obtained by post-treatment.

[0013] The preparation reaction principle of the core-shell silica is as follows: During the reaction, the pretreated silica particles are re-dispersed in deionized water and heated to 55-65 DEG C for a certain time to ensure uniform dispersion of the particles and sufficient activity of the surface hydroxyl groups. Then, the aqueous solution of tin tetrachloride pentahydrate is slowly added dropwise, and the tin ions in the system are partially hydrolyzed in the aqueous solution. After approaching the surface of the silica, the tin ions are electrostatically attracted by the surface hydroxyl groups. Then, a certain amount of aqueous sodium hydroxide solution is added dropwise to control the pH of the system at a weak alkaline condition of 9-10. Under the alkaline hydrolysis reaction, tin hydroxide precipitates are further generated, and are deposited on the surface of the silica particles. After a constant temperature reaction and aging process for 0.5-1 h, the tin hydroxide precipitates are dehydrated to convert into tin oxide, forming a continuous and uniform shell layer on the surface of the silica, and obtaining the core-shell silica.

[0014] Further, in step B1, the amount ratio of the cyclohexane, polyoxyethylene tert-octyl phenyl ether, n-hexanol, deionized water, tetraethyl orthosilicate and aqueous ammonia solution is 300-400 mL: 100-120 g: 80-100 mL: 15-20 mL: 1-2 g: 5-7 mL, the concentration of the aqueous ammonia solution is 50-70 wt%, and the post-treatment step comprises: after the reaction is completed, the reaction solution is cooled to room temperature, 150-200 mL of ethanol is added to precipitate the precipitate, the filter cake is washed with deionized water and ethanol for 2-4 times, and then is transferred to an oven with a temperature of 50-60 DEG C for drying until the weight is constant, to obtain the core-shell silica precursor; in step B2, the amount ratio of the core-shell silica precursor, deionized water and tin tetrachloride pentahydrate solution is 2-4 g: 40-80 mL: 100-150 mL, the concentration of the aqueous tin tetrachloride pentahydrate solution is 0.3-0.5 mol / L, the concentration of the aqueous sodium hydroxide solution is 1.5-2 mol / L, and the post-treatment step comprises: after the reaction is completed, the reaction solution is cooled to room temperature, is filtered, the filter cake is washed with deionized water and ethanol for 2-4 times, and then is transferred to an oven with a temperature of 50-60 DEG C for drying until the weight is constant, to obtain the core-shell silica.

[0015] Further, the preparation method of the modified antistatic agent is as follows: the eucommia ulmoides gum and toluene are stirred in a reaction kettle, the reaction kettle is heated to 75-85 DEG C, and is kept at the temperature for 15-30 min, the glycidyl methacrylate, polyethylene glycol diacrylate and dibenzoyl peroxide are added, and the reaction is kept for 4-6 h, and the modified antistatic agent is obtained after post-treatment.

[0016] The preparation reaction formula of the modified antistatic agent is as follows:

[0017] The preparation reaction principle of the modified antistatic agent is as follows: During the reaction, under high temperature conditions, the benzoyl peroxide decomposes to generate free radicals, which initiates the radical polymerization of the gutta-percha, glycidyl methacrylate and polyethylene glycol diacrylate to obtain the modified antistatic agent.

[0018] Further, the dosage ratio of the gutta-percha, toluene, glycidyl methacrylate, polyethylene glycol diacrylate and benzoyl peroxide is 4-6 g: 80-100 mL: 4-6 g: 2-4 g: 0.3-0.5 g, and the post-treatment step comprises: after the reaction is completed, the reaction system is cooled to room temperature, the reaction liquid is added to anhydrous ethanol for precipitation, suction filtration, the filter cake is washed with deionized water and acetone for 2-4 times, and then is transferred to an oven with a temperature of 50-60 DEG C for drying until the weight is constant to obtain the modified antistatic agent.

[0019] The application further provides a preparation method of the full-dull antistatic polyester fiber. S1, polyethylene terephthalate, silicone filler, modified antistatic agent and auxiliary additive are placed in a high-speed homogenizer, mixed uniformly to obtain a mixture; S2, the mixture is added to a twin-screw extruder for melt extrusion and spinning to obtain the polyester fiber.

[0020] The preparation reaction principle of the polyester fiber is as follows: During the reaction, under heating conditions, the epoxy groups in the modified antistatic agent and the hydroxyl and amino groups in the polyethylene terephthalate and the silicone filler undergo ring-opening reaction to form chemical bonds, thereby obtaining the polyester fiber.

[0021] Further, in step S2, the auxiliary additive is composed of a plasticizer, a flame retardant, an antioxidant and a lubricant in a mass ratio of 4:2:2:4, the plasticizer is one or more of diisononyl phthalate, dioctyl adipate and dibutyl sebacate, the flame retardant is one or more of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphate and magnesium hydroxide, the antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and dioctadecyl thiodipropionate, and the lubricant is one or more of oleic acid amide, paraffin and oleic acid. Further, the temperatures of the eight temperature zones of the twin-screw extruder from the feeding port to the discharging port are 190 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 250 DEG C and 250 DEG C in sequence, the main machine rotating speed of the twin-screw extruder is 120-160 rpm, and the pressure is 80-120 bar.

[0022] The application has the following beneficial effects: 1. The application is to graft polymerize the modified antistatic agent by grafting gum of eucommia ulmoides, glycidyl methacrylate and polyethylene glycol diacrylate under the initiation of dibenzoyl peroxide, the molecular structure of the antistatic agent introduces hydrophilic polyethylene glycol segment, eucommia ulmoides skeleton and active epoxy functional group, so that it not only has good polarity and flexibility, but also can occur ring opening reaction with carboxyl or hydroxyl group at the end of polyester molecular chain to form covalent bond connection, improve its dispersibility and durability in polyester matrix, and migrate to the surface of the fiber during fiber forming process, thereby improving the adsorption capacity of water molecules on the surface of the fiber, effectively reducing the surface resistance of the fiber, significantly improving the static accumulation problem of polyester fiber, at the same time, the epoxy group in the antistatic agent can also react with the hydroxyl or amino functional group on the surface of the silicone filler, to build the chemical bridging structure between the antistatic agent, filler and polyester, enhance the interfacial compatibility and stability of the whole fiber material system, so that the modified antistatic agent is not easy to precipitate or migrate, and can maintain the functional integrity in the process of high temperature melting extrusion and spinning, realizing long-term and stable antistatic modification of polyester fiber.

[0023] 2. The application is to obtain core-shell silica precursor by hydrolysis and condensation of tetraethyl orthosilicate under alkaline catalysis, and further modify the tin oxide shell structure on the outside by chemical precipitation method to obtain core-shell silica. Firstly, the nanometer particle size and shell structure of the core-shell silica provide good dispersibility, which can be uniformly distributed in the polyester matrix during the melt spinning process, forming a micro-enhanced network to effectively improve the mechanical strength of the fiber. Secondly, the tin element contained in the shell layer of the core-shell silica gives it certain electrical conductivity and ion migration ability, which has a synergistic effect on improving the static accumulation problem of polyester fiber. In addition, the inorganic core structure of the core-shell silica has good light scattering ability, which can significantly reduce the gloss of the fiber surface, increase the haze, improve the extinction performance of the fiber, and give it a soft and matte visual effect. As a precursor of silicone filler, the surface functional groups of the core-shell silica provide reaction sites for subsequent organic modification, enhance the interfacial compatibility of the filler and the polyester matrix, and help to improve the stability of the fiber structure.

[0024] 3、 The present application is a kind of organic-inorganic hybrid silica resin filler obtained by modifying various organosilane coupling agents and functional small molecules on the surface of core-shell silica.The silica resin filler not only has the dimensional stability and optical performance of inorganic silica, but also improves the compatibility and reactivity with the polyester matrix through the introduction of organic functional groups. The silica resin filler has nanoscale particle size and uniform dispersion characteristics, can fully disperse in the molten polyester system, form a stable three-dimensional filler network structure, improve the mechanical strength of polyester fiber, the inorganic phase part of the filler provides skeleton support, enhances the structural integrity of polyester fiber, the organic segment provided by the silane coupling agent improves the interfacial compatibility of polyester molecules, reduces the interface delamination phenomenon, and improves the overall stability of the composite. Secondly, the silica resin filler contains a large number of hydroxyl groups in its structure, which can chemically react with the polyester molecular chain and the epoxy groups in the modified antistatic agent to form a certain crosslinked structure during high temperature melting, thereby inhibiting the migration of functional components and improving the antistatic durability and dispersion stability of polyester fiber. In addition, the inorganic components in the silica resin filler have good light scattering ability, which can significantly reduce the gloss of polyester fiber, improve its haze and extinction, and make the fiber surface present a soft and matte texture, thereby improving the visual quality of polyester fiber in high-end applications such as clothing fabrics. DETAILED DESCRIPTION

[0025] The technical solutions of the present application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0026] The polyethylene terephthalate used in the present application is purchased from Dongguan Leirui Plastic Co., Ltd., model NRSC2697, brand nairui, molecular weight 30-50K; The eucommia ulmoides gum used in the present application is purchased from Guangdong Fangxin Biological Technology Co., Ltd., brand Penglei, grade superior product.

[0027] Example 1 The present embodiment provides a preparation method of core-shell silica for modified silica resin for full-matte antistatic polyester fiber, comprising the following steps: Step I, preparation of core-shell silica precursor Take: cyclohexane 3000 mL, polyoxyethylene tertiary octyl phenyl ether 1000 g, n-hexanol 800 mL and deionized water 150 mL in the reaction kettle stirring, adding tetraethyl orthosilicate 10 g, room temperature reaction 1 h, add ammonia solution 50 mL, room temperature stirring 4 h, after the reaction is completed, the reaction liquid is reduced to room temperature, add 1500 mL ethanol precipitate, suction filtration, filter cake with deionized water and ethanol washing 2 times, transfer to the temperature is 50 ℃ oven, drying to constant weight, get core-shell silica precursor.

[0028] Step II, preparation of core-shell silica Take: core-shell silica precursor 20 g and deionized water 400 mL in the reaction kettle, the reaction kettle to 55 ℃, keep warm stirring 15 min, slowly add 0.3 mol / L tin tetrachloride aqueous solution 1000 mL, add 1.5 mol / L sodium hydroxide solution to the system pH = 9, keep warm reaction 0.5 h, after the reaction is completed, the reaction liquid is reduced to room temperature, suction filtration, filter cake with deionized water and ethanol washing 2 times, transfer to the temperature is 50 ℃ oven, drying to constant weight, get core-shell silica.

[0029] Example 2 The present embodiment provides a kind of preparation method of modified silicon resin used for full extinction antistatic polyester fiber, including the following steps: Step I, preparation of core-shell silica precursor Take: cyclohexane 3500 mL, polyoxyethylene tertiary octyl phenyl ether 1100 g, n-hexanol 900 mL and deionized water 175 mL in the reaction kettle stirring, adding tetraethyl orthosilicate 15 g, room temperature reaction 1.5 h, add ammonia solution 60 mL, room temperature stirring 5 h, after the reaction is completed, the reaction liquid is reduced to room temperature, add 1750 mL ethanol precipitate, suction filtration, filter cake with deionized water and ethanol washing 3 times, transfer to the temperature is 55 ℃ oven, drying to constant weight, get core-shell silica precursor.

[0030] Step II, preparation of core-shell silica Take: core-shell silica precursor 30 g and deionized water 600 mL in the reaction kettle, the reaction kettle to 60 ℃, keep warm stirring 20 min, slowly add 0.4 mol / L tin tetrachloride aqueous solution 1250 mL, add 1.7 mol / L sodium hydroxide solution to the system pH = 9.5, keep warm reaction 0.5 h, after the reaction is completed, the reaction liquid is reduced to room temperature, suction filtration, filter cake with deionized water and ethanol washing 3 times, transfer to the temperature is 55 ℃ oven, drying to constant weight, get core-shell silica.

[0031] Example 3 The embodiment provides a preparation method of core-shell silicon dioxide for modified silicon resin used for full-dull antistatic polyester fibers, and comprises the following steps. Step I, preparing core-shell silicon dioxide precursor Take 4000mL of cyclohexane, 1200g of polyoxyethylene tert-octyl phenyl ether, 1000mL of n-hexanol and 200mL of deionized water in a reaction kettle and stir, add 20g of tetraethyl orthosilicate, react at room temperature for 2h, add 70mL of ammonia solution, stir at room temperature for 6h, after the reaction is completed, the reaction liquid is reduced to room temperature, 2000mL of ethanol is added to precipitate, suction filtration is performed, the filter cake is washed with deionized water and ethanol for 4 times, and then the filter cake is transferred to an oven with a temperature of 60 DEG C, and dried to constant weight, to obtain the core-shell silicon dioxide precursor.

[0032] Step II, preparing core-shell silicon dioxide Take 40g of the core-shell silicon dioxide precursor and 800mL of deionized water in a reaction kettle, heat the reaction kettle to 65 DEG C, and stir for 30min, slowly add 1500mL of 0.5mol / L tin tetrachloride pentahydrate aqueous solution, add 2mol / L sodium hydroxide aqueous solution to the system until the pH is 10, and heat for 1h, after the reaction is completed, the reaction liquid is reduced to room temperature, suction filtration is performed, the filter cake is washed with deionized water and ethanol for 4 times, and then the filter cake is transferred to an oven with a temperature of 60 DEG C, and dried to constant weight, to obtain the core-shell silicon dioxide.

[0033] Example 4 The embodiment provides a preparation method of full-dull antistatic polyester fibers, comprising the following steps. Step 1, preparing a dispersion liquid Take 20g of the core-shell silicon dioxide prepared in the example 1 and 500mL of n-butanol in a reaction kettle, stir at room temperature for 20min, and obtain the dispersion liquid.

[0034] Step 2, preparing a silicon resin filler Take 80g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 70g of phenyltrimethoxysilane, 2g of 2,4-dihydroxyacetophenone, 600mL of deionized water and 10mL of n-butanol in a reaction kettle and stir, slowly add 200mL of the dispersion liquid, heat the reaction kettle to 40 DEG C, heat for 15min, add 10mL of 50wt% concentrated sulfuric acid, heat the reaction kettle to 80 DEG C, heat for 4h, after the reaction is completed, the reaction liquid is reduced to room temperature, stand for 4h, suction filtration is performed, the filter cake is washed with deionized water and ethanol for 2 times, and then the filter cake is transferred to an oven with a temperature of 50 DEG C, and dried to constant weight, ground, and then passed through a 500-mesh sieve, to obtain the silicon resin filler.

[0035] Example 5 The embodiment provides a preparation method of full-dull antistatic polyester fibers, comprising the following steps: Step 1, preparation of dispersion Take: the core-shell silica prepared in Example 2 30 g and n-butanol 750 mL were placed in a reaction kettle, stirred at room temperature for 30 min, and a dispersion was obtained.

[0036] Step 2, preparation of silicone filler Take: 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane 90 g, phenyltrimethoxysilane 80 g, 2,4-dihydroxyacetophenone 3 g, deionized water 700 mL and n-butanol 15 mL were placed in a reaction kettle and stirred, then 300 mL of the dispersion was slowly added, the reaction kettle was heated to 45°C, and the reaction was kept for 20 min. 15 mL of 60 wt% concentrated sulfuric acid was added, the reaction kettle was heated to 85°C, and the reaction was kept for 5 h. After the reaction was completed, the reaction liquid was allowed to cool to room temperature, and was left to stand for 5 h. Filtration was performed, the filter cake was washed with deionized water and ethanol for 3 times, was transferred to an oven with a temperature of 55°C, was dried to a constant weight, was ground, and was passed through a 500 mesh sieve to obtain a silicone filler.

[0037] Example 6 The present example provides a preparation method of full-dull antistatic polyester fiber, comprising the following steps: Step 1, preparation of dispersion Take: the core-shell silica prepared in Example 3 40 g and n-butanol 1000 mL were placed in a reaction kettle, stirred at room temperature for 40 min, and a dispersion was obtained.

[0038] Step 2, preparation of silicone filler Take: 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane 100 g, phenyltrimethoxysilane 90 g, 2,4-dihydroxyacetophenone 4 g, deionized water 800 mL and n-butanol 20 mL were placed in a reaction kettle and stirred, then 400 mL of the dispersion was slowly added, the reaction kettle was heated to 50°C, and the reaction was kept for 30 min. 20 mL of 70 wt% concentrated sulfuric acid was added, the reaction kettle was heated to 90°C, and the reaction was kept for 6 h. After the reaction was completed, the reaction liquid was allowed to cool to room temperature, and was left to stand for 6 h. Filtration was performed, the filter cake was washed with deionized water and ethanol for 4 times, was transferred to an oven with a temperature of 60°C, was dried to a constant weight, was ground, and was passed through a 500 mesh sieve to obtain a silicone filler.

[0039] Example 7 The present example provides a preparation method of full-dull antistatic polyester fiber, comprising the following steps: Step 1, preparation of modified antistatic agent Take: 40 g of eucommia ulmoides gum and 800 mL of toluene in the reaction kettle, stir, the reaction kettle is heated to 75℃, keep stirring for 15 min, add glycidyl methacrylate 40 g, polyethylene glycol diacrylate 20 g and dibenzoyl peroxide 3 g, keep reaction for 4 h, after the reaction is completed, the reaction system is reduced to room temperature, the reaction liquid is added to anhydrous ethanol for precipitation, suction filtration, the filter cake is washed with deionized water and acetone for 2 times, and is transferred to an oven with a temperature of 50℃, dried to constant weight, to obtain the modified antistatic agent.

[0040] Step 2, preparation of the mixture The diisononyl phthalate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and oleic acid are mixed uniformly according to the mass ratio of 4:2:2:4 to obtain an auxiliary additive, which is ready for use. According to the weight part, 60 parts of polyethylene terephthalate, 4 parts of the silicon resin filler prepared in Example 4, 10 parts of the modified antistatic agent and 1 part of the auxiliary additive are placed in a high-speed homogenizer, mixed uniformly to obtain a mixture.

[0041] Step 6, preparation of polyester fibers The mixture is added to a double-screw extruder, melt-extruded, extruded through a nozzle plate with a pore size of 0.3 mm, drawn 3 times, and cooled in a ring-shaped air, to obtain polyester fibers. The eight temperature zones of the double-screw extruder from the feeding port to the discharging port are 190℃, 190℃, 200℃, 200℃, 220℃, 220℃, 250℃ and 250℃, respectively. The main machine speed of the double-screw extruder is 120 rpm, and the pressure is 80 bar.

[0042] Example 8 The present embodiment provides a preparation method of full-dull antistatic polyester fibers, comprising the following steps: Step 1, preparation of a modified antistatic agent Take: 50 g of eucommia ulmoides gum and 900 mL of toluene in the reaction kettle, stir, the reaction kettle is heated to 80℃, keep stirring for 20 min, add glycidyl methacrylate 50 g, polyethylene glycol diacrylate 30 g and dibenzoyl peroxide 4 g, keep reaction for 5 h, after the reaction is completed, the reaction system is reduced to room temperature, the reaction liquid is added to anhydrous ethanol for precipitation, suction filtration, the filter cake is washed with deionized water and acetone for 3 times, and is transferred to an oven with a temperature of 55℃, dried to constant weight, to obtain the modified antistatic agent.

[0043] Step 2, preparation of the mixture Mix diisononyl phthalate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and oleic acid in a mass ratio of 4:2:2:4 to obtain an auxiliary additive, which is ready for use; According to the weight parts, 70 parts of polyethylene terephthalate, 5 parts of the silicon resin filler prepared in Example 5, 12.5 parts of the modified antistatic agent and 2 parts of the auxiliary additive are placed in a high-speed homogenizer, mixed uniformly to obtain a mixture.

[0044] Step ⑶, preparation of polyester fiber The mixture is added to a double-screw extruder, melt-extruded, extruded through a nozzle plate with a pore size of 0.4 mm, drawn 3.5 times, and then cooled in a ring-shaped air cooling device to obtain polyester fibers. The eight temperature zones of the double-screw extruder from the feeding port to the discharging port are 190℃, 190℃, 200℃, 200℃, 220℃, 220℃, 250℃ and 250℃, respectively. The main machine speed of the double-screw extruder is 140 rpm, and the pressure is 100 bar.

[0045] Example 9 The present embodiment provides a preparation method of full-dull antistatic polyester fiber, comprising the following steps: Step ⑴, preparation of modified antistatic agent Take: 60g of eucommia ulmoides gum and 1000mL of toluene are placed in a reaction kettle and stirred, the reaction kettle is heated to 85℃, and stirred for 30min, then 60g of glycidyl methacrylate, 40g of polyethylene glycol diacrylate and 5g of dibenzoyl peroxide are added, and the reaction is kept for 6h. After the reaction is completed, the reaction system is cooled to room temperature, and the reaction liquid is added to anhydrous ethanol for precipitation. After filtration, the filter cake is washed with deionized water and acetone for 4 times, and then transferred to an oven with a temperature of 60℃ for drying until the weight is constant to obtain the modified antistatic agent.

[0046] Step ⑵, preparation of mixture Mix diisononyl phthalate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester and oleic acid in a mass ratio of 4:2:2:4 to obtain an auxiliary additive, which is ready for use; According to the weight parts, 80 parts of polyethylene terephthalate, 6 parts of the silicon resin filler prepared in Example 6, 15 parts of the modified antistatic agent and 3 parts of the auxiliary additive are placed in a high-speed homogenizer, mixed uniformly to obtain a mixture.

[0047] Step ⑶, preparation of polyester fiber The mixture is added into a twin-screw extruder, melt-extruded, extruded through a die plate with a hole diameter of 0.5 mm, drawn 4 times, and obtained after annular air cooling to obtain polyester fibers. The eight temperature zones of the twin-screw extruder from the feeding port to the discharging port are 190℃, 190℃, 200℃, 200℃, 220℃, 220℃, 250℃, and 250℃, respectively. The main motor speed of the twin-screw extruder is 160 rpm, and the pressure is 120 bar.

[0048] Comparative Example 1 The difference between this comparative example and Example 9 is that the core-shell silica precursor is used instead of the core-shell silica in the preparation of the dispersion in step ①.

[0049] Comparative Example 2 The difference between this comparative example and Example 9 is that the modified antistatic agent is not added in the preparation of the mixture in step ⑵.

[0050] Comparative Example 3 The difference between this comparative example and Example 9 is that the modified antistatic agent is not added in the preparation of the mixture in step ⑵.

[0051] Performance test: The breaking strength and elongation at break of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 are tested according to the standard GB / T 14337-2008 "Chemical fibers - Test method for tensile properties of staple fibers"; The volume resistivity of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 is tested according to the standard GB / T 12703.4-2010 "Textiles - Evaluation of the electrostatic properties - Part 4: Resistivity"; The glossiness of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 is tested according to the standard FZ / T 01097-2006 "Test method for fabric glossiness"; The haze of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 is tested according to the standard GB / T 2410-2008 "Determination of the transmission and haze of transparent plastics"; The water absorption of the polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 is tested according to the standard GB / T 21655.1-2023 "Textiles - Evaluation of the moisture management properties - Part 1: Single combination test method", and the specific data are shown in Table 1.

[0052] Table 1 - Performance test data table of each sample

[0053] Data analysis: Comparative analysis of the data in Table 1 can find that the breaking strength of the polyester fiber prepared by the application is 4.2 cN·dtex, the elongation at break is 31.2%, the volume resistivity is 3.5*10 9 Ω·m, the gloss is 34GU, the haze is 17%, and the water absorption is 11.2%, all of which are better than those of the comparative examples. Therefore, by grafting polybutylene succinate with glycidyl methacrylate and polyethylene glycol diacrylate under the initiation of dibenzoyl peroxide, a modified antistatic agent is obtained. By hydrolysis and condensation of tetraethyl orthosilicate under alkaline catalysis, a core-shell silica precursor is obtained. Further, by chemical precipitation method, a tin oxide shell structure is modified on the outside of the core-shell silica, to obtain a core-shell silica. By modifying a variety of organosilane coupling agents and functional small molecules on the surface of the core-shell silica, an organic-inorganic hybrid silicone resin filler is obtained, which not only improves the antistatic property and matting property of the polyester fiber, but also improves the hydrophilicity and mechanical strength of the polyester fiber.

[0054] The preferred embodiments disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments. Obviously, many modifications and variations can be made according to the content of the specification. The specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the application, so that those skilled in the art can well understand and utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A fully-dull antistatic polyester fiber, characterized by, Comprise the following components by weight parts: 60-80 parts of polyethylene terephthalate, 4-6 parts of silicone resin filler, 10-15 parts of modified antistatic agent and 1-3 parts of auxiliary additive.

2. A fully-dull, anti-static polyester fiber according to claim 1, characterized in that, The modified silicone resin is prepared by the following steps: A1, the core-shell silica and n-butanol are placed in a reaction kettle, stirred at room temperature for 20-40 min to obtain a dispersion liquid; A2, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane, phenyl trimethoxysilane, 2, 4-dihydroxyacetophenone, deionized water and n-butanol are placed in a reaction kettle and stirred, the dispersion liquid is slowly added, the reaction kettle is heated to 40-50 DEG C, and the reaction is carried out for 15-30 min, concentrated sulfuric acid is added, the reaction kettle is heated to 80-90 DEG C, and the reaction is carried out for 4-6 h, and the post-treatment is carried out to obtain a silicone resin filler.

3. A fully-dull, anti-static polyester fiber according to claim 2, characterized in that, In step A1, the amount ratio of the core-shell silica and n-butanol is 2-4 g:50-100 mL; in step A2, the amount ratio of 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane, phenyl trimethoxysilane, 2, 4-dihydroxyacetophenone, deionized water, n-butanol, dispersion liquid and concentrated sulfuric acid is 8-10 g:7-9 g:0.2-0.4 g:60-80 mL:1-2 mL:20-40 mL:1-2 mL, and the concentration of the concentrated sulfuric acid is 50-70 wt%.

4. A fully-dull, anti-static polyester fiber according to claim 2, characterized by The core-shell silica is prepared by the following steps: B1, cyclohexane, polyoxyethylene tertiary octyl phenyl ether, n-hexanol and deionized water are placed in a reaction kettle and stirred, tetraethyl orthosilicate is added, and the reaction is carried out at room temperature for 1-2 h, ammonia solution is added, and the reaction is carried out at room temperature for 4-6 h, and the post-treatment is carried out to obtain a core-shell silica precursor; B2, the core-shell silica precursor and deionized water are placed in a reaction kettle, the reaction kettle is heated to 55-65 DEG C, and the reaction is carried out for 15-30 min, and the five water four tin chloride aqueous solution is slowly added dropwise, and the sodium hydroxide aqueous solution is added until the pH of the system is 9-10, and the reaction is carried out for 0.5-1 h, and the post-treatment is carried out to obtain a core-shell silica.

5. A fully-dull, anti-static polyester fiber according to claim 4, characterized in that, In step B1, the amount ratio of cyclohexane, polyoxyethylene tertiary octyl phenyl ether, n-hexanol, deionized water, tetraethyl orthosilicate and ammonia solution is 300-400 mL:100-120 g:80-100 mL:15-20 mL:1-2 g:5-7 mL, and the concentration of the ammonia solution is 50-70 wt%; in step B2, the amount ratio of the core-shell silica precursor, deionized water and five water four tin chloride solution is 2-4 g:40-80 mL:100-150 mL, the concentration of the five water four tin chloride aqueous solution is 0.3-0.5 mol / L, and the concentration of the sodium hydroxide aqueous solution is 1.5-2 mol / L.

6. A full-dull antistatic polyester fiber according to claim 1, characterized by The preparation method of the modified antistatic agent is that the eucommia ulmoides gum and toluene are placed in a reaction kettle and stirred, the reaction kettle is heated to 75-85 DEG C, and the reaction is carried out for 15-30 min, and glycidyl methacrylate, polyethylene glycol diacrylate and dibenzoyl peroxide are added, and the reaction is carried out for 4-6 h, and the post-treatment is carried out to obtain a modified antistatic agent.

7. A fully-dull, anti-static polyester fiber according to claim 6, characterized by The dosage ratio of the eucommia ulmoides gum, toluene, glycidyl methacrylate, polyethylene glycol diacrylate and dibenzoyl peroxide is 4-6g:80-100mL:4-6g:2-4g:0.3-0.5g.

8. A process for the preparation of fully-dull, antistatic polyester fibres as claimed in any one of claims 1 to 7, characterised in that, The method comprises the following steps: S1, polyethylene terephthalate, silicone filler, modified antistatic agent and auxiliary additive are placed in a high-speed homogenizer, mixed uniformly to obtain a mixture; S2, the mixture is added into a double screw extruder, melt extruded, and spun to obtain polyester fibers.

9. A process for the production of a full-dull antistatic polyester fiber according to claim 8, characterized by, In step S2, the auxiliary additive is composed of plasticizer, flame retardant, antioxidant and lubricant in a mass ratio of 4:2:2:4.

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