Wear-resistant and high-temperature-resistant polyester fiber and preparation method thereof

Abstract

The invention discloses a wear-resistant and high-temperature-resistant polyester fiber and a preparation method thereof, belongs to the technical field of polyester processing, and aims to solve the technical problem that wear resistance and high-temperature resistance of polyester fibers in the prior art need to be further improved. Carrying out melt extrusion and spinning to obtain a polyester fiber precursor; the preparation method comprises the following steps: modifying an epoxy group on a carboxylated carbon nanotube through a free radical polymerization reaction to obtain a modified filler, carrying out melt spinning on the modified filler, an auxiliary additive and modified PET to obtain a polyester fiber precursor, preparing a modified antibacterial agent through a coprecipitation method, further preparing an antibacterial solution, and carrying out melt spinning on the antibacterial solution to obtain the antibacterial polyester fiber. The polyester fiber precursor is soaked in the antibacterial liquid to obtain the polyester fiber, so that the wear resistance and the high temperature resistance of the polyester fiber are improved, and the antibacterial performance of the polyester fiber is also improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester processing, in particular to a wear-resistant and high-temperature-resistant polyester fiber and a preparation method thereof. BACKGROUND

[0002] Polyester fiber (polyethylene terephthalate fiber, PET) is widely used in clothing, industrial cloth, geotextile and high-performance composite materials due to its excellent mechanical properties, chemical corrosion resistance and forming processing performance.

[0003] With the increasing requirements of application fields on material performance, especially the use requirements in harsh environments such as high temperature and high wear, the wear resistance and thermal stability of traditional polyester fibers have gradually become important factors limiting their further expansion. In order to improve the wear resistance and high-temperature resistance, researchers have carried out various modification methods, such as blending reinforcement, nano filler filling, heat stretching orientation, surface coating treatment, etc. These methods have the advantages of mature technology, controllable cost and easy large-scale application, and have become an important means to improve the comprehensive performance of polyester.

[0004] In the prior art, although the above modification methods improve the wear resistance and heat resistance of polyester fibers to some extent, there are still many deficiencies: first, in the filler blending method, the nanoparticles are easy to agglomerate, leading to uneven dispersion, and then affecting the continuity and mechanical stability of the fiber, second, although the surface coating can improve the wear resistance in the short term, the adhesion between the surface coating and the substrate is limited, and it is easy to fall off in the friction or washing process, reducing the durability, in addition, the interface compatibility between the added reinforcing filler and the PET substrate is poor and the interface adhesion is weak.

[0005] In view of the technical defects in this regard, a solution is proposed. SUMMARY

[0006] The present application aims to provide a wear-resistant and high-temperature-resistant polyester fiber and a preparation method thereof, which solves the technical problem that the wear resistance and high-temperature resistance of the polyester fiber in the prior art need to be further improved.

[0007] The purpose of the present application can be achieved by the following technical scheme: a preparation method of a wear-resistant and high-temperature-resistant polyester fiber, comprising the following steps:

[0008] S1, terephthalic acid, ethylene glycol, 1,4-butene diol and a catalyst are placed in a reaction kettle protected by nitrogen atmosphere and stirred, heated to 250-260℃, and kept for 2-3h to obtain a prepolymer;

[0009] S2, the prepolymer is placed in a reaction kettle protected by a nitrogen atmosphere, stirred, vacuumed, trimethyl phosphate is added, and the temperature is raised to 280-290 DEG C, and the reaction is kept for 4-6 h, and the modified PET is obtained after treatment;

[0010] The preparation reaction formula of the modified PET is:

[0011]

[0012] The preparation reaction principle of the modified PET is:

[0013] In the reaction process, under the action of high temperature and catalyst, the esterification reaction of phthalic acid, ethylene glycol and 1,4-butene glycol occurs, water is released, part of the polycondensation is generated, linear prepolymer is generated, trimethyl phosphate is added as stabilizer, the temperature is continuously raised and vacuumized, the polycondensation reaction is promoted to the right, the molecular weight is improved, and the modified PET is obtained.

[0014] S3, the modified PET, modified filler and auxiliary additive are added into a double screw extruder, melt extruded, spun, and the polyester fiber precursor is obtained;

[0015] The preparation reaction principle of the polyester fiber is:

[0016] In the reaction process, under the action of high temperature, the ring opening reaction of the hydroxyl group of the modified PET and the epoxy functional group in the modified filler occurs, and the covalent bond is generated, and after melt spinning, the polyester fiber is obtained.

[0017] S4, the polyester fiber precursor is immersed in the antibacterial liquid, and the polyester fiber is obtained after treatment.

[0018] The preparation reaction principle of the polyester fiber is:

[0019] In the reaction process, under the irradiation of the ultraviolet lamp, the phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide is cracked into free radicals, the thiol-ene click reaction of the polyester fiber precursor and the olefin unsaturated double bond in the antibacterial liquid is initiated, and the polyester fiber is obtained.

[0020] Further, in step S1, the weight ratio of the terephthalic acid, ethylene glycol, 1,4-butene glycol and catalyst is 6-8:2-4:1-2:0.5-1, and the catalyst is antimony trioxide; in step S2, the weight ratio of the prepolymer and trimethyl phosphate is 8-10:0.2-0.4, and the treatment step includes: after the reaction is completed, the reaction system is cooled to room temperature, the reaction liquid is transferred to a rotary evaporator with a temperature of 80-100 DEG C, and the pressure is distilled to no liquid is obtained, and the modified PET is obtained;

[0021] Further, in step S3, the weight ratio of the modified PET, the modified filler and the auxiliary additive is 60-80:10-15:5-10, the auxiliary additive is composed of the antioxidant, the lubricant, the antistatic agent and the ultraviolet absorber in a mass ratio of 1:2:1:3, the antioxidant is one or more of tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, N,N'-diphenyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine, the lubricant is one or more of oleic acid amide, paraffin wax and polyethylene wax, the antistatic agent is one or more of amide phosphate, tritolyl phosphate and alkylphenol polyoxyethylene ether, and the ultraviolet absorber is one or more of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and 2-hydroxy-4-methoxybenzophenone;

[0022] Further, the eight temperature zones of the twin-screw extruder from the feeding port to the discharging port are 280℃, 280℃, 285℃, 285℃, 295℃, 295℃, 300℃ and 300℃ in sequence, the main motor speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150bar;

[0023] Further, the operation steps of the spinning include: transferring the melt to the side-blowing chamber after extruding through the spinneret, and obtaining the polyester fiber precursor after air cooling and solidification, wherein the spinneret has circular holes, the number of meshes is 36-48, the hole diameter is 0.1-0.3mm, and the spinning pressure is 80-120bar at the same time; the atmosphere in the side-blowing chamber is air, the relative humidity is 30-40%, the temperature is 20-30℃, and the flow rate is maintained at 5-10m / s at the same time;

[0024] Further, in step S4, the impregnation ratio is 1:30-35, and the impregnation operation includes the following steps: impregnating the polyester fiber precursor in the antibacterial liquid, impregnating for 10-15min, taking out, and irradiating under the ultraviolet lamp for 1-3min, wherein the wavelength of the ultraviolet lamp is 395-400nm, the light irradiation distance is 10-15cm, and the power is 100-500mW / cm²; the post-processing step includes: after the reaction is completed, placing the fiber in an oven with a temperature of 40-50℃, and drying to constant weight to obtain the polyester fiber.

[0025] Further, in step S3, the modified filler is prepared by the following steps:

[0026] A1, stirring styrene, ethyl acetate, azobisisobutyronitrile and glycidyl methacrylate in a reaction kettle, heating the reaction kettle to 65-75℃, adding maleic anhydride, and keeping the temperature for 1-2h to obtain intermediate I after post-processing;

[0027] The reaction principle for preparing the intermediate I is as follows:

[0028]

[0029] The reaction principle for preparing the intermediate I is as follows:

[0030] In the reaction process, under the action of high temperature and initiator, the maleic anhydride, styrene and glycidyl methacrylate undergo free radical polymerization to obtain the intermediate I.

[0031] A2, the carboxylated carbon nanotubes are added into a ball mill for ball milling to obtain activated carbon nanotubes;

[0032] A3, the activated carbon nanotubes and acetone are placed in a reaction kettle, stirred for 20-30 min, the intermediate I is added, heated to 45-55℃, and incubated for 4-6 h, and then treated to obtain the modified filler.

[0033] The reaction principle for preparing the modified filler is as follows:

[0034] In the reaction process, the activated carbon nanotubes are uniformly dispersed in the acetone, after the addition of the intermediate I, the maleic anhydride in the intermediate I undergoes ring-opening reaction with the carboxyl groups and hydroxyl groups on the surface of the activated carbon nanotubes to form a covalent bond grafted structure, and the epoxy-modified modified filler is obtained.

[0035] Further, in step A1, the amount ratio of the styrene, ethyl acetate, azobisisobutyronitrile, glycidyl methacrylate and maleic anhydride is 4-6 g:80-100 mL:0.5-1 g:2-4 g:1-2 g, and the post-treatment step includes: after the reaction is completed, the reaction system is cooled to room temperature, the reaction liquid is added into 200-300 mL of petroleum ether to precipitate the sediment, the filter cake is washed with petroleum ether for 2-3 times, and then transferred to an oven with a temperature of 30-40℃ for drying until the weight is constant to obtain the intermediate I; in step A2, the operation steps of the ball milling include: the activated carbon nanotubes are added into a planetary ball mill, 5-10 mm of stainless steel grinding balls are added, the ball-to-material ratio is 10:1, the rotation speed is set to 400-500 rpm, the ball milling is performed for 1-2 h, and then the activated carbon nanotubes are obtained by passing through a 300-400 mesh sieve; in step A3, the amount ratio of the activated carbon nanotubes, acetone and intermediate I is 1-2 g:50-100 mL:5-7 g, and the post-treatment step includes: after the reaction is completed, the reaction system is cooled to room temperature, the filter cake is washed with deionized water and ethanol for 2-3 times, and then transferred to an oven with a temperature of 50-60℃ for drying until the weight is constant to obtain the modified filler.

[0036] The preparation method of the activated carbon nanotube is as follows: the carboxylated carbon nanotube is added into a planetary ball mill, 5-10 mm stainless steel grinding balls are added, the ball-to-material ratio is 10:1, the rotation speed is set to 400-500 rpm, the ball milling is performed for 1-2 h, and then the activated carbon nanotube is obtained by screening through a 300-400 mesh sieve.

[0037] In step S4, the preparation method of the antibacterial solution comprises:

[0038] B1, β-cyclodextrin, deionized water and ethanol are stirred in a reaction kettle, the reaction kettle is heated to 55-65℃, and the reaction is kept for 15-30 min, tea polyphenols are slowly added, and the reaction is carried out in the dark for 1-2 h, the temperature is lowered to 0-5℃, and the reaction is carried out in the dark for 10-12 h, and then the modified antibacterial agent is obtained by post-treatment;

[0039] The preparation reaction principle of the modified antibacterial agent is as follows:

[0040] During the reaction, β-cyclodextrin is a cyclic polysaccharide molecule with a hydrophilic shell and a hydrophobic inner cavity, and has a molecular inclusion ability. Tea polyphenols are natural antibacterial components, and contain a large number of phenolic hydroxyl groups and phenyl groups in the molecule. The tea polyphenol benzene ring enters the hydrophobic inner cavity of the β-cyclodextrin, and the outer hydroxyl groups of the β-cyclodextrin and the phenolic hydroxyl groups of the tea polyphenol form a clathrate through hydrogen bonding. The light reaction is to avoid the oxidation and decomposition of tea polyphenols, and low temperature can promote the self-assembly and precipitation of the clathrate to form crystals to obtain the modified antibacterial agent.

[0041] B2, the modified antibacterial agent, γ-mercaptopropyl triethoxysilane, ethanol and deionized water are stirred in a reaction kettle, saturated ammonia water is added, the reaction kettle is heated to 45-55℃, and the reaction is kept for 1-2 h, and then the antibacterial solution is obtained by post-treatment.

[0042] The preparation reaction principle of the antibacterial solution is as follows:

[0043] During the reaction, the silicon-oxygen bond of γ-mercaptopropyl triethoxysilane can be hydrolyzed into silanol under the conditions of deionized water and heating, and the silanol further condenses with the hydroxyl groups in the modified antibacterial agent to obtain the antibacterial solution by post-treatment.

[0044] Further, in step B1, the use amount ratio of the beta-cyclodextrin, deionized water, ethanol and tea polyphenol is 2-4g:20-30mL:15-20mL:2-4g, and the post-processing step comprises: after the reaction is completed, the reaction system is cooled to room temperature, suction filtration is performed, the filter cake is washed with anhydrous ethanol for 2-3 times, and then the filter cake is transferred to an oven with a temperature of 35-45 DEG C for drying until the weight is constant, to obtain the modified antibacterial agent; in step B2, the use amount ratio of the modified antibacterial agent, gamma-mercapto propyl triethoxysilane, ethanol, deionized water and saturated ammonia water is 2-4g:0.5-1g:50-80mL:5-10mL:1-2mL, and the post-processing step comprises: after the reaction is completed, the reaction is cooled to room temperature, suction filtration is performed, the filter cake is washed with deionized water and ethanol for 2-3 times, and then the filter cake is transferred to an oven with a temperature of 50-60 DEG C for drying until the weight is constant, and then the product is taken out and added into 150-200mL of an ethanol water solution with a volume ratio of 2:1, and ultrasonic treatment is performed until the product is dissolved, to obtain the antibacterial liquid.

[0045] The application further provides the polyester fiber with wear resistance and high temperature resistance, which is prepared by the method.

[0046] The application has the following beneficial effects:

[0047] 1、The application is prepared by free radical polymerization to obtain the intermediate I, and then the intermediate I is grafted to the activated carbon nanotube by covalent bond through anhydride ring-opening reaction to obtain the modified filler, and the carboxylated carbon nanotube is subjected to ball milling to break the bundle-like agglomerates of the carbon nanotube, so that the carbon nanotube is peeled off into a single or small bundle with a finer dispersion, the exposed area of the outer surface is increased, the carboxyl or defect site originally buried in the inside is exposed, more reactive sites are provided for the anhydride ring-opening, the intermediate I is further grafted by covalent bond through the anhydride ring-opening, the modified filler can be more uniformly and stably dispersed in the modified PET matrix, the agglomeration phenomenon is avoided, the mechanical property of the polyester fiber is improved, the carbon nanotube has excellent mechanical strength, thermal stability and thermal conductivity, can form a skeleton support in the polymer matrix, disperse external force impact, reduce surface wear and scratch, and improve the wear resistance of the polyester fiber, the excellent thermal stability and high thermal conductivity of the carbon nanotube help to hinder the thermal motion of the polyester chain segment, improve the heat distortion temperature and thermal stability of the material, reduce the risk of deformation at high temperature, and improve the high temperature resistance of the polyester fiber.

[0048] 2、The application is prepared by preparing a modified filler modified with an epoxy group, through melt extrusion, with modified PET and auxiliary additives to prepare a polyester fiber precursor, in the melting process, the epoxy group in the modified filler and the hydroxyl group in the modified PET undergo ring-opening reaction to form covalent bonding, which improves the interfacial bonding force of the modified filler and the modified PET, further improves the wear resistance and mechanical properties of the polyester fiber, and the modified filler not only plays a reinforcing role in the PET matrix, but also shows good nucleation effect, in the polyester crystallization process, the abundant functional groups on the surface of the carbon nanotube in the modified filler can act as a heterogeneous nucleation center to induce the ordered arrangement of the modified PET molecular chain, thereby accelerating the crystallization rate and improving the crystallinity, the uniform dispersibility of the carbon nanotube makes the crystallization process more uniform and stable, which helps to form a crystal structure with small size and uniform distribution. The fine and dense crystal structure can effectively absorb and disperse external stress, hinder the initiation and expansion of cracks in the stress process, and significantly improve the impact resistance and toughness of the material.

[0049] 3、The application is prepared by a co-precipitation method, using β-cyclodextrin as a complexing material and tea polyphenol as a natural antibacterial substance, and through physical and hydrogen bonding to prepare a modified antibacterial agent, and then modifying the surface of the modified antibacterial agent with mercapto silane coupling agent and mixing it with a solvent to obtain an antibacterial agent, and then dipping the polyester fiber precursor in the antibacterial solution and further irradiating it under ultraviolet light to form a thiol-ene click reaction with the effective substances in the antibacterial solution, and then drying to obtain a polyester fiber, tea polyphenol as a natural antibacterial agent has the functions of broad-spectrum antibacterial and inhibiting microbial growth, and through β-cyclodextrin complexation, the structure is stabilized and the activity is released slowly, and through thiol-ene click to form a covalent bond, the antibacterial component is stably grafted on the surface of the fiber, thereby improving the antibacterial performance of the polyester fiber. DETAILED DESCRIPTION

[0050] The technical solutions of the application will be described below in conjunction with the embodiments, obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the application.

[0051] The carboxylated carbon nanotube used in the application has a diameter of 10-50nm, a length of 5-20um and a multi-walled type, the tea polyphenol used in the application has a molecular weight of 281.36 and a polyphenol content of ≥98% according to the national standard.

[0052] Embodiment 1

[0053] The embodiment provides a preparation method of a modified filler for wear-resistant and high-temperature-resistant polyester fiber, comprising the following steps:

[0054] Step I, preparation of intermediate I

[0055] Take: styrene 40 g, ethyl acetate 800 mL, azobisisobutyronitrile 5 g and glycidyl methacrylate 20 g in the reaction kettle stirring, the reaction kettle to 65 ℃, add maleic anhydride 10 g, keep the reaction for 1 h, after the reaction is completed, the reaction system is reduced to room temperature, the reaction liquid is added into 2000 mL petroleum ether to precipitate the precipitate, suction filtration, filter cake is washed with petroleum ether 2 times, transfer to the oven at a temperature of 30 ℃, dry to constant weight, to obtain intermediate I.

[0056] Step II, preparation of activated carbon nanotube

[0057] The carboxylated carbon nanotube is added to the planetary ball mill, 5 mm stainless steel balls are added, the ball to material ratio is 10:1, the rotation speed is set to 400 rpm, and the ball milling is carried out for 1 h, and then the activated carbon nanotube is obtained by passing through a 300 mesh sieve.

[0058] Step III, preparation of modified filler

[0059] Take: activated carbon nanotube 10 g and acetone 500 mL in the reaction kettle stirring, 20 min, add intermediate I 50 g, heating to 45 ℃, keep the reaction for 4 h, after the reaction is completed, the reaction system is reduced to room temperature, suction filtration, filter cake is washed with deionized water and ethanol 2 times, transfer to the oven at a temperature of 50 ℃, dry to constant weight, to obtain modified filler.

[0060] Example 2

[0061] The present embodiment provides a preparation method of a modified filler for wear-resistant and high-temperature-resistant polyester fiber, comprising the following steps:

[0062] Step I, preparation of intermediate I

[0063] Take: styrene 50 g, ethyl acetate 900 mL, azobisisobutyronitrile 7 g and glycidyl methacrylate 30 g in the reaction kettle stirring, the reaction kettle to 70 ℃, add maleic anhydride 15 g, keep the reaction for 1.5 h, after the reaction is completed, the reaction system is reduced to room temperature, the reaction liquid is added into 2500 mL petroleum ether to precipitate the precipitate, suction filtration, filter cake is washed with petroleum ether 2 times, transfer to the oven at a temperature of 35 ℃, dry to constant weight, to obtain intermediate I.

[0064] Step II, preparation of activated carbon nanotube

[0065] The carboxylated carbon nanotube is added to the planetary ball mill, 7 mm stainless steel balls are added, the ball to material ratio is 10:1, the rotation speed is set to 450 rpm, and the ball milling is carried out for 1.5 h, and then the activated carbon nanotube is obtained by passing through a 300 mesh sieve.

[0066] Step III, preparation of modified filler

[0067] Weigh: activated carbon nanotubes 15 g and acetone 750 mL are placed in a reaction kettle, stirred for 25 min, 60 g of intermediate I is added, the temperature is raised to 50 DEG C, and the reaction is kept for 5 h. After the reaction is completed, the reaction system is cooled to room temperature, filtered, the filter cake is washed with deionized water and ethanol for 3 times, and then transferred to an oven with a temperature of 55 DEG C for drying until the weight is constant to obtain the modified filler.

[0068] Example 3

[0069] The embodiment provides a preparation method of a modified filler for wear-resistant and high-temperature-resistant polyester fibers, which comprises the following steps:

[0070] Step I, preparation of intermediate I

[0071] Weigh: styrene 60 g, ethyl acetate 1000 mL, azobisisobutyronitrile 10 g and glycidyl methacrylate 40 g are placed in a reaction kettle and stirred, the reaction kettle is heated to 75 DEG C, 20 g of maleic anhydride is added, and the reaction is kept for 2 h. After the reaction is completed, the reaction system is cooled to room temperature, the reaction liquid is added into 3000 mL of petroleum ether to precipitate the sediment, filtered, the filter cake is washed with petroleum ether for 3 times, and then transferred to an oven with a temperature of 40 DEG C for drying until the weight is constant to obtain the intermediate I.

[0072] Step II, preparation of activated carbon nanotubes

[0073] The carboxylated carbon nanotubes are added into a planetary ball mill, 10 mm stainless steel balls are added, the ball-to-material ratio is 10:1, the rotation speed is set to 500 rpm, ball milling is performed for 2 h, and then the activated carbon nanotubes are obtained by passing through a 400-mesh sieve.

[0074] Step III, preparation of the modified filler

[0075] Weigh: activated carbon nanotubes 20 g and acetone 1000 mL are placed in a reaction kettle, stirred for 30 min, 70 g of intermediate I is added, the temperature is raised to 55 DEG C, and the reaction is kept for 6 h. After the reaction is completed, the reaction system is cooled to room temperature, filtered, the filter cake is washed with deionized water and ethanol for 3 times, and then transferred to an oven with a temperature of 60 DEG C for drying until the weight is constant to obtain the modified filler.

[0076] Example 4

[0077] The embodiment provides a preparation method of a modified liquid for a modified filler for wear-resistant and high-temperature-resistant polyester fibers, which comprises the following steps:

[0078] Step 1, preparation of a modified antibacterial agent

[0079] Take: β-cyclodextrin 20g, deionized water 200mL and ethanol 150mL in the reaction kettle stirring, the reaction kettle to 55℃, keep the reaction for 15min, slowly add tea polyphenols 20g, avoid light reaction 1h, cooling to 0℃, avoid light reaction 10h, after the reaction, the reaction system is reduced to room temperature, filter, filter cake with anhydrous ethanol washing 2 times, transfer to the temperature is 35℃ oven, drying to constant weight, get modified antibacterial agent.

[0080] Step 2, preparation of antibacterial liquid

[0081] Take: modified antibacterial agent 20g, γ-mercapto propyl triethoxysilane 5g, ethanol 500mL and deionized water 50mL in the reaction kettle stirring, add saturated ammonia 10mL, the reaction kettle to 45℃, keep the reaction for 1h, after the reaction, the reaction is reduced to room temperature, filter, filter cake with deionized water and ethanol washing 2 times, transfer to the temperature is 50℃ oven, drying to constant weight, take out the product added in 1500mL volume ratio of 2:1 ethanol aqueous solution, ultrasonic to product dissolution, get antibacterial liquid.

[0082] Example 5

[0083] The present embodiment provides a kind of modified filler for wear-resistant, high-temperature-resistant polyester fiber modified liquid preparation method, including the following steps:

[0084] Step 1, preparation of modified antibacterial agent

[0085] Take: β-cyclodextrin 30g, deionized water 250mL and ethanol 170mL in the reaction kettle stirring, the reaction kettle to 60℃, keep the reaction for 20min, slowly add tea polyphenols 30g, avoid light reaction 1.5h, cooling to 3℃, avoid light reaction 11h, after the reaction, the reaction system is reduced to room temperature, filter, filter cake with anhydrous ethanol washing 3 times, transfer to the temperature is 40℃ oven, drying to constant weight, get modified antibacterial agent.

[0086] Step 2, preparation of antibacterial liquid

[0087] Take: modified antibacterial agent 30g, γ-mercapto propyl triethoxysilane 7g, ethanol 650mL and deionized water 80mL in the reaction kettle stirring, add saturated ammonia 15mL, the reaction kettle to 50℃, keep the reaction for 1.5h, after the reaction, the reaction is reduced to room temperature, filter, filter cake with deionized water and ethanol washing 3 times, transfer to the temperature is 55℃ oven, drying to constant weight, take out the product added in 1750mL volume ratio of 2:1 ethanol aqueous solution, ultrasonic to product dissolution, get antibacterial liquid.

[0088] Example 6

[0089] The embodiment provides a preparation method of a modified liquid of a modified filler for wear-resistant and high-temperature-resistant polyester fibers, and comprises the following steps.

[0090] Step 1, preparing a modified antibacterial agent

[0091] Taking 40g of beta-cyclodextrin, 300mL of deionized water and 200mL of ethanol, stirring in a reaction kettle, heating the reaction kettle to 65 DEG C, and keeping the reaction for 30 minutes; slowly adding 40g of tea polyphenol, avoiding light reaction for 2 hours, cooling to 5 DEG C, avoiding light reaction for 12 hours; after the reaction is completed, the reaction system is cooled to room temperature, and the filter cake is washed with anhydrous ethanol for 3 times; the filter cake is transferred to an oven with a temperature of 45 DEG C, and dried to constant weight to obtain the modified antibacterial agent.

[0092] Step 2, preparing an antibacterial liquid

[0093] Taking 40g of the modified antibacterial agent, 10g of gamma-mercapto propyl triethoxysilane, 800mL of ethanol and 100mL of deionized water, stirring in a reaction kettle, adding 20mL of saturated ammonia water, heating the reaction kettle to 55 DEG C, and keeping the reaction for 2 hours; after the reaction is completed, the reaction is cooled to room temperature, and the filter cake is washed with deionized water and ethanol for 3 times; the filter cake is transferred to an oven with a temperature of 60 DEG C, and dried to constant weight; the product is taken out and added into 2000mL of an ethanol water solution with a volume ratio of 2:1, ultrasonic treatment is performed until the product is dissolved, and an antibacterial liquid is obtained.

[0094] Example 7

[0095] The embodiment provides a preparation method of a modified PET for a modified filler for wear-resistant and high-temperature-resistant polyester fibers, and comprises the following steps.

[0096] Step 1, preparing a prepolymer

[0097] Taking 80g of terephthalic acid, 40g of ethylene glycol, 20g of 1,4-butenediol and 10g of antimony trioxide, stirring in a reaction kettle under the protection of a nitrogen atmosphere, heating to 260 DEG C, and keeping the reaction for 3 hours to obtain a prepolymer.

[0098] Step 2, preparing a modified PET

[0099] Taking 100g of the prepolymer, stirring in a reaction kettle under the protection of a nitrogen atmosphere, vacuumizing to a vacuum degree of 0.01kPa, adding 4g of trimethyl phosphate, heating to 290 DEG C, and keeping the reaction for 6 hours; after the reaction is completed, the reaction system is cooled to room temperature, and the reaction liquid is transferred to a rotary evaporator with a temperature of 100 DEG C; vacuum distillation is performed until no liquid is collected to obtain a modified PET.

[0100] Example 8

[0101] The embodiment provides a preparation method of modified PET for modified filler for wear-resistant and high-temperature-resistant polyester fiber, and comprises the following steps:

[0102] Step 1, preparing a prepolymer

[0103] Taking 70g of terephthalic acid, 30g of ethylene glycol, 15g of 1,4-butenediol and 7g of antimony trioxide, stirring in a reaction kettle protected by a nitrogen atmosphere, heating to 255 DEG C, and keeping the reaction for 2.5h to obtain a prepolymer.

[0104] Step 2, preparing modified PET

[0105] Taking 90g of the prepolymer, stirring in a reaction kettle protected by a nitrogen atmosphere, vacuumizing to a vacuum degree of 0.08kPa, adding 3g of trimethyl phosphate, heating to 285 DEG C, and keeping the reaction for 5h, after the reaction is completed, transferring the reaction liquid to a rotary evaporator with a temperature of 90 DEG C, and distilling under reduced pressure until no liquid is collected to obtain modified PET.

[0106] Example 9

[0107] The embodiment provides a preparation method of modified PET for modified filler for wear-resistant and high-temperature-resistant polyester fiber, and comprises the following steps:

[0108] Step 1, preparing a prepolymer

[0109] Taking 80g of terephthalic acid, 40g of ethylene glycol, 20g of 1,4-butenediol and 10g of antimony trioxide, stirring in a reaction kettle protected by a nitrogen atmosphere, heating to 260 DEG C, and keeping the reaction for 3h to obtain a prepolymer.

[0110] Step 2, preparing modified PET

[0111] Taking 100g of the prepolymer, stirring in a reaction kettle protected by a nitrogen atmosphere, vacuumizing to a vacuum degree of 0.13kPa, adding 4g of trimethyl phosphate, heating to 290 DEG C, and keeping the reaction for 6h, after the reaction is completed, transferring the reaction liquid to a rotary evaporator with a temperature of 100 DEG C, and distilling under reduced pressure until no liquid is collected to obtain modified PET.

[0112] Example 10

[0113] The embodiment provides a preparation method of modified filler for wear-resistant and high-temperature-resistant polyester fiber, and comprises the following steps:

[0114] Step A, preparing a polyester fiber precursor

[0115] N,N'-diphenyl-p-phenylenediamine, polyethylene wax, alkylphenol polyoxyethylene ether and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate were mixed uniformly in a mass ratio of 1:2:1:3 to obtain an auxiliary additive, which was prepared for later use;

[0116] The modified PET prepared in Example 7, the modified filler prepared in Example 1 and the auxiliary additive were added into a twin-screw extruder in a mass ratio of 60:10:5, and were melt-extruded. The melt was extruded through a spinneret and then transferred into a side-blowing chamber. After air cooling and solidification, a polyester fiber precursor was obtained.

[0117] The eight temperature zones of the twin-screw extruder from the feeding port to the discharging port were 280℃, 280℃, 285℃, 285℃, 295℃, 295℃, 300℃ and 300℃, respectively. The main motor speed of the twin-screw extruder was 80 rpm, and the pressure was 100 bar.

[0118] The spinneret had a circular hole with a mesh number of 36 and a hole diameter of 0.1 mm. The simultaneous spinning pressure was 80 bar. The atmosphere in the side-blowing chamber was air with a relative humidity of 30% and a temperature of 20℃. The flow rate was maintained at 10 m / s.

[0119] Step ⒝, preparation of a polyester fiber

[0120] The polyester fiber precursor was immersed in the antibacterial solution prepared in Example 4 for 10 min, taken out and irradiated under a UV lamp for 1 min. The wavelength of the UV lamp was 395 nm, the light distance was 10 cm, and the power was 100 mW / cm². After the reaction was completed, the fiber was placed in an oven at a temperature of 40℃ and dried to constant weight to obtain a polyester fiber.

[0121] Example 11

[0122] The present example provides a preparation method of a modified filler for wear-resistant and high-temperature-resistant polyester fiber, comprising the following steps:

[0123] Step ⒜, preparation of a polyester fiber precursor

[0124] N,N'-diphenyl-p-phenylenediamine, polyethylene wax, alkylphenol polyoxyethylene ether and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate were mixed uniformly in a mass ratio of 1:2:1:3 to obtain an auxiliary additive, which was prepared for later use;

[0125] The modified PET prepared in Example 8, the modified filler prepared in Example 2 and the auxiliary additive were added into a twin-screw extruder in a mass ratio of 70:12:8, and were melt-extruded. The melt was extruded through a spinneret and then transferred into a side-blowing chamber. After air cooling and solidification, a polyester fiber precursor was obtained.

[0126] The temperature of eight temperature sections of the twin-screw extruder from the feeding port to the discharging port is 280℃, 280℃, 285℃, 285℃, 295℃, 295℃, 300℃, and 300℃ in turn, the main motor speed of the twin-screw extruder is 100 rpm, and the pressure is 125 bar;

[0127] The orifice of the spinneret is circular, the mesh number is 48, the hole diameter is 0.2 mm, the simultaneous spinning pressure is 100 bar, the atmosphere in the side-blowing chamber is air, the relative humidity is 35%, the temperature is 25℃, and the flow rate is maintained at 7 m / s at the same time.

[0128] Step ⒝, preparing the polyester fiber

[0129] The polyester fiber precursor is immersed in the antibacterial solution prepared in Example 5 for 12 min, taken out, and irradiated under a UV lamp for 2 min, the wavelength of the UV lamp is 395 nm, the light distance is 12 cm, and the power is 300 mW / cm², after the reaction is completed, the fiber is placed in an oven with a temperature of 45℃, and dried to constant weight, to obtain the polyester fiber.

[0130] Example 12

[0131] The present embodiment provides a preparation method of a modified filler for wear-resistant and high-temperature-resistant polyester fiber, comprising the following steps:

[0132] Step ⒜, preparing the polyester fiber precursor

[0133] The N,N'-diphenyl-p-phenylenediamine, polyethylene wax, alkylphenol polyoxyethylene ether and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate are uniformly mixed according to a mass ratio of 1:2:1:3 to obtain an auxiliary additive, which is ready for use;

[0134] The modified PET prepared in Example 9, the modified filler prepared in Example 3 and the auxiliary additive are added into a twin-screw extruder according to a mass ratio of 80:15:10, and melt-extruded, the melt is transferred to a side-blowing chamber after being extruded through a spinneret, and the polyester fiber precursor is obtained after air cooling and solidification.

[0135] The temperature of eight temperature sections of the twin-screw extruder from the feeding port to the discharging port is 280℃, 280℃, 285℃, 285℃, 295℃, 295℃, 300℃, and 300℃ in turn, the main motor speed of the twin-screw extruder is 120 rpm, and the pressure is 150 bar;

[0136] The orifice of the spinneret is circular, the mesh number is 48, the hole diameter is 0.3 mm, the simultaneous spinning pressure is 120 bar, the atmosphere in the side-blowing chamber is air, the relative humidity is 40%, the temperature is 30℃, and the flow rate is maintained at 10 m / s at the same time.

[0137] Step ⒝, preparing polyester fiber

[0138] The polyester fiber precursor was immersed in the antibacterial solution prepared in Example 6 for 15 min, taken out, and irradiated under a UV lamp for 3 min. The wavelength of the UV lamp was 400 nm, the light irradiation distance was 15 cm, and the power was 500 mW / cm2. After the reaction was completed, the fiber was placed in an oven at a temperature of 50°C and dried to constant weight to obtain the polyester fiber.

[0139] Comparative Example 1

[0140] The difference between this comparative example and Example 12 is that in Step ⒜, preparing the polyester fiber precursor, the modified filler was replaced with an equal amount of carboxylated carbon nanotubes.

[0141] Comparative Example 2

[0142] The difference between this comparative example and Example 12 is that in Step ⒜, preparing the polyester fiber precursor, the modified filler was not added.

[0143] Comparative Example 3

[0144] The difference between this comparative example and Example 12 is that the polyester fiber precursor was used instead of the polyester fiber.

[0145] Performance test:

[0146] The breaking strength of the polyester fibers prepared in Examples 10-12 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 14337-2008 “Chemical fibers - Test method for tensile properties of staple fibers”.

[0147] The volume abrasion amount of the polyester fibers prepared in Examples 10-12 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 9867-2008 “Determination of abrasion resistance of vulcanized or thermoplastic rubber (rotary drum abrasion machine method)”.

[0148] The antibacterial rate of the polyester fibers prepared in Examples 10-12 and Comparative Examples 1-3 against Staphylococcus aureus was tested in accordance with the standard GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles - Part 3: oscillation method”.

[0149] The polyester fibers prepared in Examples 10-12 and Comparative Examples 1-3 were subjected to heat aging test in accordance with the standard GB / T 13767-1992 “Textiles - Determination of heat resistance”. The breaking strength retention rate and the volume abrasion amount change rate of the polyester fibers after heat aging were calculated in accordance with the standards GB / T 14337-2008 and GB / T 9867-2008, respectively. The specific data are shown in Table 1.

[0150] Table 1 - Performance test data table of each sample

[0151] Item group Example 10 Example 11 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Breaking strength / MPa 7.1 7.6 7.4 4.6 3.5 5.1 Volume wear amount / mm 3 ]] 26.7 24.3 25.5 41.2 54.8 48 Antibacterial rate / % 92.6 94.3 93.7 91.5 89.9 43.5 Breaking strength retention rate / % 98.1 98.6 98.3 84.6 76.3 76.2 Volume abrasion amount change rate / % 102.73 101.5 101.9 129.6 138.2 128.0

[0152] Data analysis:

[0153] Comparative analysis of the data in Table 1 can find that the breaking strength of the polyester fiber prepared by the application is 7.6MPa, the volume abrasion amount is 24.3mm 3 , the antibacterial rate is 94.3%, at the same time, the breaking strength retention rate after heat aging is 98.6% and the volume abrasion amount change rate is 101.5%, all the data are better than the comparative example, then the application modifies the epoxy group on the carboxylated carbon nanotube through free radical polymerization reaction, obtains a modified filler, and melts and spins the modified filler, auxiliary additives and modified PET to obtain a polyester fiber precursor, the hydroxyl group in the modified PET forms a chemical bond with the epoxy group in the modified filler, and a modified antibacterial agent is prepared by coprecipitation method, and an antibacterial liquid is further prepared, the polyester fiber precursor is immersed in the antibacterial liquid under the irradiation of ultraviolet lamp, the olefin in the modified PET segment reacts with the mercapto group in the antibacterial liquid through mercapto-ene click reaction, and the polyester fiber is obtained, which not only improves the wear resistance and high temperature resistance of the polyester fiber, but also improves the antibacterial performance.

[0154] The preferred embodiments of the application 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 changes can be made according to the content of the specification. The specification selects and 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 by the claims and their entire scope and equivalents.

Claims

1. A method for preparing wear-resistant, high-temperature-resistant polyester fibers, characterized by, The method comprises the following steps: S1, terephthalic acid, ethylene glycol, 1, 4-butene diol and catalyst are placed in a reaction kettle protected by nitrogen atmosphere and stirred, and then heated to 250-260 DEG C, and kept for 2-3h to obtain a prepolymer; S2, the prepolymer is placed in a reaction kettle protected by nitrogen atmosphere and stirred, and then vacuumized, and then trimethyl phosphate is added, and then heated to 280-290 DEG C, and kept for 4-6h to obtain modified PET after treatment; S3, the modified PET, modified filler and auxiliary additive are added into a double screw extruder, and then melt extruded and spun to obtain a polyester fiber precursor; S4, the polyester fiber precursor is immersed in an antibacterial solution, and then treated to obtain a polyester fiber.

2. The method according to claim 1, wherein the method is characterized by, In step S1, the weight ratio of terephthalic acid, ethylene glycol, 1, 4-butene diol and catalyst is 6-8:2-4:1-2:0.5-1, and the catalyst is antimony trioxide; in step S2, the weight ratio of the prepolymer and trimethyl phosphate is 8-10:0.2-0.4; in step S3, the weight ratio of the modified PET, modified filler and auxiliary additive is 60-80:10-15:5-10, and the auxiliary additive is composed of antioxidants, lubricants, antistatic agents and ultraviolet absorbers with a mass ratio of 1:2:1:3; in step S4, the immersion ratio is 1:30-35.

3. The method according to claim 1, wherein the method is characterized by, In step S3, the modified filler is prepared by the following steps: A1, styrene, ethyl acetate, azobisisobutyronitrile and glycidyl methacrylate are placed in a reaction kettle and stirred, the reaction kettle is heated to 65-75 DEG C, maleic anhydride is added, and then kept for 1-2h to obtain an intermediate I after treatment; A2, the carboxylated carbon nanotube is added into a ball mill for ball milling to obtain an activated carbon nanotube; A2, the activated carbon nanotube and acetone are placed in a reaction kettle and stirred for 20-30min, the intermediate I is added, and then heated to 45-55 DEG C, and kept for 4-6h to obtain a modified filler after treatment.

4. The method according to claim 3, wherein the method is characterized by, In step A1, the amount ratio of styrene, ethyl acetate, azobisisobutyronitrile, glycidyl methacrylate and maleic anhydride is 4-6g:80-100mL:0.5-1g:2-4g:1-2g; in step A3, the amount ratio of the activated carbon nanotube, acetone and intermediate I is 1-2g:50-100mL:5-7g.

5. The method according to claim 3, wherein the method is characterized by, The preparation method of the activated carbon nanotube is as follows: the carboxylated carbon nanotube is added into a planetary ball mill, 5-10mm stainless steel grinding balls are added, the ball-to-material ratio is 10:1, the rotation speed is set to 400-500rpm, and the activated carbon nanotube is obtained by ball milling for 1-2h and then screening through a 300-400 mesh sieve.

6. The method of claim 1, wherein the polyester fiber is abrasion resistant and high temperature resistant. In step S4, the preparation method of the antibacterial solution comprises the following steps: B1, β-cyclodextrin, deionized water and ethanol are placed in a reaction kettle and stirred, the reaction kettle is heated to 55-65 DEG C, and kept for 15-30min, and then tea polyphenol is slowly added, and then reacted for 1-2h in the dark, and then cooled to 0-5 DEG C, and then reacted for 10-12h in the dark, and then treated to obtain a modified antibacterial agent; B2, the modified antibacterial agent, γ-mercapto propyl triethoxysilane, ethanol and deionized water were stirred in a reaction kettle, saturated ammonia was added, the reaction kettle was heated to 45-55℃, and the reaction was kept for 1-2h, and then the antibacterial liquid was obtained by post-treatment.

7. The method according to claim 6, wherein the method is characterized by, In step B1, the β-cyclodextrin, deionized water, ethanol and tea polyphenol were used in a ratio of 2-4g:20-30mL:15-20mL:2-4g; in step B2, the modified antibacterial agent, γ-mercapto propyl triethoxysilane, ethanol, deionized water and saturated ammonia were used in a ratio of 2-4g:0.5-1g:50-80mL:5-10mL:1-2mL.

8. A wear-resistant, high-temperature-resistant polyester fiber, characterized in that, The wear-resistant and high-temperature-resistant polyester fiber is prepared by the method of any one of claims 1-7.

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