A regenerated terylene tourmaline cloud wool and a preparation method thereof

Abstract

This invention relates to a recycled polyester tourmaline cloud-like fiber and its preparation method, belonging to the field of recycled polyester technology. The invention first prepares a self-made antistatic monomer by ring-opening alcoholysis of polyethylene glycol and succinic anhydride followed by methacrylic acid end-capping. This monomer is then subjected to transesterification and polycondensation with recycled PET and ethylene glycol to obtain intrinsically antistatic recycled PET chips. Nano-tourmaline powder is modified with a silane coupling agent containing double bonds, and melt-spun with the above chips. The resulting recycled polyester tourmaline cloud-like fiber is then cured by UV coagulation in a coagulation bath. The antistatic monomer is chemically bonded within the fiber, forming a conductive water film within the fiber to achieve long-lasting antistatic properties. Simultaneously, it reduces electrostatic adsorption, ensuring the continuous release of negative ions from the tourmaline, thus endowing the material with excellent antibacterial properties. The synergistic effect of the flexible PEG segments and the photocrosslinking chemical network significantly improves the material's mechanical properties. The recycled polyester tourmaline cloud-like fiber prepared by this invention exhibits antistatic, antibacterial, and good mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of recycled polyester technology, specifically to a recycled polyester tourmaline cloud wool and its preparation method. Background Technology

[0002] Recycled polyester materials are increasingly used in textiles, environmental protection, and other fields due to their advantages in resource recycling. However, their inherent insulation properties make them prone to static electricity accumulation, and their antibacterial properties are lacking, limiting their application in high-end scenarios. Existing antistatic modifications mostly use additive antistatic agents, which have problems such as easy migration, short-lived antistatic effects, and reduced mechanical properties of the material.

[0003] Tourmaline, as a natural negative ion generator, is often used to impart antibacterial properties to materials. However, the static electricity on the fiber surface easily attracts dust and microorganisms, obscuring the active sites of tourmaline and leading to a decrease in negative ion release efficiency. Furthermore, current technologies struggle to simultaneously achieve a synergistic improvement in the material's durable antistatic properties, antibacterial activity, and mechanical properties, failing to meet the demands of high-end functional textile materials. Therefore, developing a recycled polyester material that combines durable antistatic properties, highly efficient antibacterial activity, and excellent mechanical properties has become a hot research topic in the industry. Summary of the Invention

[0004] The purpose of this invention is to provide a recycled polyester tourmaline cloud wool and its preparation method, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a recycled polyester tourmaline cloud wool, comprising the following steps:

[0006] (1) Polyethylene glycol, succinic anhydride, catalyst A, polymerization inhibitor A and toluene are mixed in a mass ratio of 30~40:10~15:9~10:0.3:50. Under a nitrogen atmosphere, the mixture is heated in an oil bath to 60~70℃ and stirred for 5~7h. The mixture is then poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2~3. The mixture is extracted, the organic phases are combined, dried and filtered, and then vacuum rotary evaporated at 40℃ to obtain the intermediate. The intermediate, methacrylic acid, and p-methyl... Benzenesulfonic acid, polymerization inhibitor B, and toluene were mixed in a mass ratio of 40-50:9-10:1-2:0.3:100. The mixture was stirred and refluxed at 80-90°C for 4-6 hours under a nitrogen atmosphere. Then, it was rotary evaporated under vacuum at 50°C for 1 hour. The mixture was then added to a saturated sodium bicarbonate solution with a mass of 2 times that of the reaction solution. After stirring evenly, the mixture was allowed to stand and separate into layers. The mixture was repeatedly washed with water until the pH of the aqueous phase was 6.5-7.5. The mixture was then dried under vacuum at 80°C for 8 hours to obtain the self-made antistatic monomer.

[0007] (2) Mix recycled PET, ethylene glycol and catalyst B at a mass ratio of 50:4~6:0.1. Under a nitrogen atmosphere, heat to 200~220℃ and stir for 2~4h for transesterification reaction. Then add 0.1~0.2 times the mass of the recycled PET and the self-made antistatic monomer. Heat to 250~270℃ and stir for 3~5h. When cooled to 200℃, extrude into 25℃ water for cooling and molding. After pelleting, dry in a vacuum at 100℃ for 6h to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 3~5mm. Modify tourmaline powder with a double-bonded silane coupling agent to obtain modified tourmaline powder.

[0008] (3) Mix the self-made intrinsic antistatic recycled PET chips, modified tourmaline powder and photoinitiator at a mass ratio of 90~95:5~10:2, stir at high speed for 30 minutes at room temperature, melt spin, and then make recycled polyester tourmaline cloud wool through UV curing and finishing processes.

[0009] Furthermore, the molecular weight of the polyethylene glycol in step (1) is 400.

[0010] Furthermore, the catalyst A mentioned in step (1) is anhydrous pyridine.

[0011] Furthermore, the polymerization inhibitor A mentioned in step (1) is hydroquinone.

[0012] Furthermore, the polymerization inhibitor B mentioned in step (1) is 2,6-di-tert-butyl-p-cresol.

[0013] Furthermore, the catalyst B mentioned in step (2) is zinc acetate.

[0014] Furthermore, the self-made intrinsic antistatic recycled PET chips mentioned in step (2) have a particle size of 3~5mm.

[0015] Furthermore, the double-bonded silane coupling agent mentioned in step (2) is KH-570.

[0016] Furthermore, the tourmaline powder in step (2) has a particle size of 200 nm.

[0017] Furthermore, the photoinitiator in step (3) is: photoinitiator 1173.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] This invention involves mixing self-made intrinsically antistatic recycled PET chips with modified tourmaline, then melting and spinning the mixture to produce cloud-like material, thereby achieving antistatic, antibacterial, and good mechanical properties.

[0020] This invention first involves a ring-opening alcoholysis reaction of polyethylene glycol and succinic anhydride, followed by methacrylic acid end-capping to obtain a self-made antistatic monomer. This monomer is then exchanged with recycled PET and ethylene glycol via transesterification and polycondensation to obtain self-made intrinsically antistatic recycled PET chips. Next, nano-tourmaline powder is modified with a silane coupling agent containing double bonds, mixed with the self-made intrinsically antistatic recycled PET chips and other components, and melt-spun. The mixture is then UV-cured in a coagulation bath to further produce recycled polyester tourmaline cloud-like fibers. The self-made antistatic monomer is chemically bonded to the fiber interior, adsorbing moisture from the air to form a conductive water film on the fiber surface. This provides a pathway for the directional migration and rapid dissipation of static charges, significantly reducing the fiber's surface resistance and achieving long-lasting antistatic properties. Simultaneously, it reduces the electrostatic adsorption of dust and microorganisms on the fiber surface, helping to maintain the cleanliness of the tourmaline surface and enabling it to continuously and efficiently release negative ions. This alters the cell membrane potential of positively charged bacteria, mold, and other microorganisms in the environment, giving the material excellent antibacterial properties. The self-made antistatic monomer containing flexible PEG segments synergistically with the photocrosslinking chemical network imparts excellent mechanical properties to the material. Detailed Implementation

[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0022] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the recycled polyester tourmaline fleece produced in the following embodiments are as follows:

[0023] Antistatic performance test: The surface resistivity of the cloud fibers prepared in Examples 1-5 and Comparative Examples 1-4 was tested in accordance with the standard GB / T12703.4-2010.

[0024] Antibacterial performance test: The antibacterial properties of the cloud fleece prepared in Examples 1-5 and Comparative Examples 1-4 were tested according to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method". The bacteria used for testing were: Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538.

[0025] Mechanical property testing: The cloud fibers prepared in Examples 1-5 and Comparative Examples 1-4 were tested for mechanical properties according to GB / T14344-2022 "Test Method for Tensile Properties of Chemical Fiber Filaments". The specific test conditions were as follows: the pre-tension value was set to 5cN, the clamping length was set to 250mm, the tensile rate was set to 250mm / min, and each group of fiber samples was tested 10-20 times until stable data was obtained. The CV value was required to be kept within 15%.

[0026] Example 1; (1) Polyethylene glycol with a molecular weight of 400, succinic anhydride, anhydrous pyridine, hydroquinone and toluene were mixed in a mass ratio of 30:10:9:0.3:50. Under a nitrogen atmosphere, the mixture was heated in an oil bath to 60°C and stirred at 300 rpm for 5 h. The reactants were poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and then the dichloromethane was removed by rotary evaporation at 40°C and a vacuum of -0.09 MPa to obtain an intermediate. The intermediate, methacrylic acid and p-toluenesulfonic acid were then mixed. 2,6-Di-tert-butyl-p-cresol and toluene were mixed in a mass ratio of 40:9:1:0.3:100 and reacted under nitrogen atmosphere at 80°C and reflux at 500 rpm for 4 h. Then, the toluene solvent was removed by rotary evaporation at 50°C and vacuum of -0.09 MPa for 1 h. The mixture was then added to a saturated sodium bicarbonate solution with a mass of 2 times that of the reaction solution, stirred evenly, and allowed to stand for separation. The aqueous phase containing unreacted monomers and catalysts was removed. The mixture was washed with water 3 times until the pH of the aqueous phase was 6.5. The mixture was then dried at 80°C and vacuum of -0.095 MPa for 8 h to obtain the self-made antistatic monomer.

[0027] (2) Recycled PET, ethylene glycol and zinc acetate were mixed in a mass ratio of 50:4:0.1. Under a nitrogen atmosphere, the mixture was heated to 200°C and stirred at 300 rpm for 2 hours for transesterification. Then, 0.1 times the mass of the recycled PET was added to the self-made antistatic monomer. The mixture was heated to 250°C and stirred for 3 hours. At the same time, the system pressure of the reaction device was controlled to be less than 80 Pa. After the polycondensation reaction was completed, the vacuum and heating were stopped. When the mixture was cooled to 200°C, the melt was extruded into 25°C water for cooling and molding. After pelleting, the pellets were dried at 100°C and vacuum degree -0.095 MPa for 6 hours to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 3 mm.

[0028] (3) Mix silane coupling agent KH-570, anhydrous ethanol and deionized water in a mass ratio of 3:350:150, adjust the pH to 4.0 with 1M acetic acid aqueous solution, and hydrolyze at room temperature at 500 rpm for 30 min to obtain modified solution; mix tourmaline powder with a particle size of 200 nm with modified solution in a mass ratio of 100:2, stir and reflux at 60℃ at 300 rpm for 5 h, filter and wash three times with anhydrous ethanol to remove unreacted silane coupling agent and impurities, and dry in a 110℃ drying oven for 5 h to obtain modified tourmaline powder;

[0029] (4) The self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 were mixed at a mass ratio of 90:5:2 and stirred at 1000 rpm for 30 min at room temperature for melt spinning. The parameters were set as follows: zone 1 temperature 265℃, zone 2 temperature 270℃, zone 3 temperature 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, and spinning speed 800 m / min. The mixture was then introduced into a deionized water coagulation bath at 25℃ and 1 m in length for cooling and solidification. Subsequently, it was stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. The UV curing machine is set with the following curing parameters: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, and curing time 30s. This allows a photocrosslinking network to form on the fiber surface. The fibers are then bundled in a reciprocating machine. When the total denier of the composite production reaches 600 denier, the fibers are rapidly stretched in an oil bath, followed by micro-stretching in a steam box at 120℃ for 2s. Inside, they undergo three-dimensional curling to fully form the fiber. After cutting, the fibers are placed in a three-layer oven for heat setting at 180℃, producing recycled polyester tourmaline cloud wool.

[0030] Example 2; (1) Polyethylene glycol with a molecular weight of 400, succinic anhydride, anhydrous pyridine, hydroquinone and toluene were mixed in a mass ratio of 32:11:9.2:0.3:50. Under a nitrogen atmosphere, the mixture was heated in an oil bath to 62°C and stirred at 300 rpm for 5.5 h. The reactants were poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2.2. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and then the dichloromethane was removed by rotary evaporation at 40°C and a vacuum of -0.09 MPa to obtain an intermediate. The intermediate, methacrylic acid and p-toluenesulfonic acid were then mixed. 2,6-Di-tert-butyl-p-cresol and toluene were mixed in a mass ratio of 42:9.2:1.2:0.3:100 and refluxed at 82°C and 500 rpm for 4.5 h under a nitrogen atmosphere. The toluene solvent was then removed by rotary evaporation at 50°C and -0.09 MPa for 1 h. The mixture was then added to a saturated sodium bicarbonate solution with a mass of twice the mass of the reaction solution, stirred until homogeneous, and allowed to stand for separation. The aqueous phase containing unreacted monomers and catalysts was removed. The mixture was washed with water three times until the pH of the aqueous phase was 6.8. The mixture was then dried at 80°C and -0.095 MPa for 8 h to obtain the self-made antistatic monomer.

[0031] (2) Recycled PET, ethylene glycol and zinc acetate were mixed in a mass ratio of 50:4.5:0.1. Under a nitrogen atmosphere, the mixture was heated to 205°C and stirred at 300 rpm for 2.5 h for transesterification. Then, 0.12 times the mass of the recycled PET was added to the self-made antistatic monomer. The mixture was heated to 255°C and stirred for 3.5 h. At the same time, the system pressure of the reaction device was controlled to be less than 80 Pa. After the polycondensation reaction was completed, the vacuum and heating were stopped. When the mixture was cooled to 200°C, the melt was extruded into 25°C water for cooling and molding. After pelleting, the pellets were dried at 100°C under a vacuum of -0.095 MPa for 6 h to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 3.5 mm.

[0032] (3) Mix silane coupling agent KH-570, anhydrous ethanol and deionized water at a mass ratio of 3:350:150, adjust the pH to 4.0 with 1M acetic acid aqueous solution, and hydrolyze at room temperature at 500 rpm for 30 min to obtain modified solution; mix tourmaline powder with a particle size of 200 nm with modified solution at a mass ratio of 100:2.5, and reflux at 62℃ at 300 rpm for 5.5 h, filter and wash three times with anhydrous ethanol to remove unreacted silane coupling agent and impurities, and dry in a 110℃ drying oven for 5 h to obtain modified tourmaline powder;

[0033] (4) Self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 were mixed at a mass ratio of 91:6:2 and stirred at 1000 rpm for 30 min at room temperature for melt spinning. The parameters were set as follows: zone 1 temperature 265℃, zone 2 temperature 270℃, zone 3 temperature 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, and spinning speed 800 m / min. The mixture was then introduced into a deionized water coagulation bath at 25℃ and 1 m in length for cooling and solidification. Subsequently, it was stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. The UV curing machine is set with the following curing parameters: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, and curing time 30s. This allows a photocrosslinking network to form on the fiber surface. The fibers are then bundled in a reciprocating machine. When the total denier of the composite production reaches 600 denier, the fibers are rapidly stretched in an oil bath, followed by micro-stretching in a steam box at 120℃ for 2s. Inside, they undergo three-dimensional curling to fully form the fiber. After cutting, the fibers are placed in a three-layer oven for heat setting at 180℃, producing recycled polyester tourmaline cloud wool.

[0034] Example 3; (1) Polyethylene glycol with a molecular weight of 400, succinic anhydride, anhydrous pyridine, hydroquinone and toluene were mixed in a mass ratio of 35:13:9.5:0.3:50. Under a nitrogen atmosphere, the mixture was heated in an oil bath to 65°C and stirred at 300 rpm for 6 hours. The reactants were poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2.5. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and then the dichloromethane was removed by rotary evaporation at 40°C and a vacuum of -0.09 MPa to obtain an intermediate. The intermediate, methacrylic acid and p-toluenesulfonic acid were then mixed. 2,6-Di-tert-butyl-p-cresol and toluene were mixed in a mass ratio of 45:9.5:1.5:0.3:100 and reacted under nitrogen atmosphere at 85°C and reflux at 500 rpm for 5 h. Then, the toluene solvent was removed by rotary evaporation at 50°C and vacuum of -0.09 MPa for 1 h. The mixture was then added to a saturated sodium bicarbonate solution with a mass of 2 times that of the reaction solution, stirred evenly, and allowed to stand for separation. The aqueous phase containing unreacted monomers and catalysts was removed. The mixture was washed with water 3 times until the pH of the aqueous phase was 7.0. The mixture was then dried at 80°C and vacuum of -0.095 MPa for 8 h to obtain the self-made antistatic monomer.

[0035] (2) Recycled PET, ethylene glycol and zinc acetate were mixed in a mass ratio of 50:5:0.1. Under a nitrogen atmosphere, the mixture was heated to 210°C and stirred at 300 rpm for 3 hours for transesterification. Then, 0.15 times the mass of the recycled PET was added to the self-made antistatic monomer. The mixture was heated to 260°C and stirred for 4 hours. At the same time, the system pressure of the reaction device was controlled to be less than 80 Pa. After the polycondensation reaction was completed, the vacuum and heating were stopped. When the mixture was cooled to 200°C, the melt was extruded into 25°C water for cooling and molding. After pelleting, the pellets were dried at 100°C and vacuum degree -0.095 MPa for 6 hours to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 4 mm.

[0036] (3) Mix silane coupling agent KH-570, anhydrous ethanol and deionized water at a mass ratio of 3:350:150, adjust the pH to 4.0 with 1M acetic acid aqueous solution, and hydrolyze at 500 rpm for 30 min at room temperature to obtain modified solution; mix tourmaline powder with a particle size of 200 nm with modified solution at a mass ratio of 100:3, stir and reflux at 300 rpm for 6 h at 65 °C, filter and wash three times with anhydrous ethanol to remove unreacted silane coupling agent and impurities, and dry in a 110 °C drying oven for 5 h to obtain modified tourmaline powder;

[0037] (4) Self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 were mixed at a mass ratio of 93:8:2 and stirred at 1000 rpm for 30 min at room temperature for melt spinning. The parameters were set as follows: zone 1 temperature 265℃, zone 2 temperature 270℃, zone 3 temperature 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, and spinning speed 800 m / min. The mixture was then introduced into a deionized water coagulation bath at 25℃ and 1 m in length for cooling and solidification. Subsequently, it was stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. The UV curing machine is set with the following curing parameters: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, and curing time 30s. This allows a photocrosslinking network to form on the fiber surface. The fibers are then bundled in a reciprocating machine. When the total denier of the composite production reaches 600 denier, the fibers are rapidly stretched in an oil bath, followed by micro-stretching in a steam box at 120℃ for 2s. Inside, they undergo three-dimensional curling to fully form the fiber. After cutting, the fibers are placed in a three-layer oven for heat setting at 180℃, producing recycled polyester tourmaline cloud wool.

[0038] Example 4; (1) Polyethylene glycol with a molecular weight of 400, succinic anhydride, anhydrous pyridine, hydroquinone and toluene were mixed in a mass ratio of 38:14:9.8:0.3:50. Under a nitrogen atmosphere, the mixture was heated in an oil bath to 68°C and stirred at 300 rpm for 6.5 h. The reactants were poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2.8. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and then the dichloromethane was removed by rotary evaporation at 40°C and a vacuum of -0.09 MPa to obtain an intermediate. The intermediate, methacrylic acid and p-toluenesulfonic acid were then mixed. 2,6-Di-tert-butyl-p-cresol and toluene were mixed in a mass ratio of 48:9.8:1.8:0.3:100 and refluxed at 88°C and 500 rpm for 5.5 h under a nitrogen atmosphere. The toluene solvent was then removed by rotary evaporation at 50°C and -0.09 MPa for 1 h. The mixture was then added to a saturated sodium bicarbonate solution with a mass of twice the mass of the reaction solution, stirred until homogeneous, and allowed to stand for separation. The aqueous phase containing unreacted monomers and catalyst was removed. The mixture was washed with water three times until the pH of the aqueous phase was 7.2. The mixture was then dried at 80°C and -0.095 MPa for 8 h to obtain the self-made antistatic monomer.

[0039] (2) Recycled PET, ethylene glycol and zinc acetate were mixed in a mass ratio of 50:5.5:0.1. Under a nitrogen atmosphere, the mixture was heated to 215°C and stirred at 300 rpm for 3.5 h for transesterification. Then, 0.18 times the mass of the recycled PET was added to the self-made antistatic monomer. The mixture was heated to 265°C and stirred for 4.5 h. At the same time, the system pressure of the reaction device was controlled to be less than 80 Pa. After the polycondensation reaction was completed, the vacuum and heating were stopped. When the mixture was cooled to 200°C, the melt was extruded into 25°C water for cooling and molding. After pelleting, the pellets were dried at 100°C and vacuum degree -0.095 MPa for 6 h to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 4.5 mm.

[0040] (3) Mix silane coupling agent KH-570, anhydrous ethanol and deionized water at a mass ratio of 3:350:150, adjust the pH to 4.0 with 1M acetic acid aqueous solution, and hydrolyze at 500 rpm for 30 min at room temperature to obtain modified solution; mix tourmaline powder with a particle size of 200 nm with modified solution at a mass ratio of 100:3.5, and reflux at 68℃ and 300 rpm for 6.5 h, filter and wash three times with anhydrous ethanol to remove unreacted silane coupling agent and impurities, and dry in a 110℃ drying oven for 5 h to obtain modified tourmaline powder;

[0041] (4) Self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 were mixed at a mass ratio of 94:9:2 and stirred at 1000 rpm for 30 min at room temperature for melt spinning. The parameters were set as follows: zone 1 temperature 265℃, zone 2 temperature 270℃, zone 3 temperature 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, and spinning speed 800 m / min. The mixture was then introduced into a deionized water coagulation bath at 25℃ and 1 m in length for cooling and solidification. Subsequently, it was stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. The UV curing machine is set with the following curing parameters: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, and curing time 30s. This allows a photocrosslinking network to form on the fiber surface. The fibers are then bundled in a reciprocating machine. When the total denier of the composite production reaches 600 denier, the fibers are rapidly stretched in an oil bath, followed by micro-stretching in a steam box at 120℃ for 2s. Inside, they undergo three-dimensional curling to fully form the fiber. After cutting, the fibers are placed in a three-layer oven for heat setting at 180℃, producing recycled polyester tourmaline cloud wool.

[0042] Example 5; (1) Polyethylene glycol with a molecular weight of 400, succinic anhydride, anhydrous pyridine, hydroquinone and toluene were mixed in a mass ratio of 40:15:10:0.3:50. Under a nitrogen atmosphere, the mixture was heated in an oil bath to 70°C and stirred at 300 rpm for 7 h. The reactants were poured into excess ice water and acidified to pH 3 with 1M dilute hydrochloric acid. The aqueous phase was extracted three times with dichloromethane. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and then the dichloromethane was removed by rotary evaporation at 40°C and a vacuum of -0.09 MPa to obtain an intermediate. The intermediate, methacrylic acid and p-toluenesulfonic acid were then mixed. 2,6-Di-tert-butyl-p-cresol and toluene were mixed in a mass ratio of 50:10:2:0.3:100 and reacted under nitrogen atmosphere at 90°C and reflux at 500 rpm for 6 h. Then, the toluene solvent was removed by rotary evaporation at 50°C and vacuum of -0.09 MPa for 1 h. The mixture was then added to a saturated sodium bicarbonate solution with a mass of 2 times that of the reaction solution, stirred evenly, and allowed to stand for separation. The aqueous phase containing unreacted monomers and catalysts was removed. The mixture was washed with water 3 times until the pH of the aqueous phase was 7.5. The mixture was then dried at 80°C and vacuum of -0.095 MPa for 8 h to obtain the self-made antistatic monomer.

[0043] (2) Recycled PET, ethylene glycol and zinc acetate were mixed in a mass ratio of 50:6:0.1. Under a nitrogen atmosphere, the mixture was heated to 220°C and stirred at 300 rpm for 4 hours for transesterification. Then, 0.2 times the mass of the recycled PET was added to the self-made antistatic monomer. The mixture was heated to 270°C and stirred for 5 hours. At the same time, the system pressure of the reaction device was controlled to be less than 80 Pa. After the polycondensation reaction was completed, the vacuum and heating were stopped. When the mixture was cooled to 200°C, the melt was extruded into 25°C water for cooling and molding. After pelleting, the pellets were dried at 100°C and vacuum degree -0.095 MPa for 6 hours to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 5 mm.

[0044] (3) Mix silane coupling agent KH-570, anhydrous ethanol and deionized water at a mass ratio of 3:350:150, adjust the pH to 4.0 with 1M acetic acid aqueous solution, and hydrolyze at 500 rpm for 30 min at room temperature to obtain modified solution; mix tourmaline powder with a particle size of 200 nm with modified solution at a mass ratio of 100:4, stir and reflux at 70℃ at 300 rpm for 7 h, filter and wash three times with anhydrous ethanol to remove unreacted silane coupling agent and impurities, and dry in a 110℃ drying oven for 5 h to obtain modified tourmaline powder;

[0045] (4) The self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 were mixed at a mass ratio of 95:10:2 and stirred at 1000 rpm for 30 min at room temperature. Melt spinning was then performed with the following parameters: zone 1 temperature 265℃, zone 2 temperature 270℃, zone 3 temperature 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, and spinning speed 800 m / min. The mixture was then introduced into a deionized water coagulation bath at 25℃ and 1 m in length for cooling and solidification. Subsequently, it was stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. The fibers are cured in a UV curing machine with the following parameters set: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, and curing time 30s. This allows a photocrosslinking network to form on the fiber surface. The fibers are then bundled in a reciprocating machine. When the total denier of the composite production reaches 600 denier, the fibers are rapidly stretched in an oil bath and then micro-stretched in a steam box at 120℃ for 2s. This process allows for three-dimensional curling and full shaping. The fibers are then cut and placed in a three-layer oven for heat setting at 180℃, producing recycled polyester tourmaline cloud wool.

[0046] Comparative Example 1

[0047] The difference between Comparative Example 1 and Example 3 is that steps (1) and (2) are omitted, and step (4) is changed to: recycled PET, modified tourmaline powder and photoinitiator 1173 are mixed at a mass ratio of 93:8:2, stirred at 1000 rpm for 30 min at room temperature, and melt-spun. The parameters are set as follows: temperature of zone 1 of the barrel 265℃, zone 2 270℃, zone 3 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, spinning speed 800 m / min, introduced into a deionized water coagulation bath with a temperature of 25℃ and a bath length of 1 m for cooling and solidification, and then stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. Then, using a UV curing machine, the curing parameters are set as follows: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, curing time 30s, to form a photocrosslinking network on the fiber surface. Then, the fiber is bundled into sections by a reciprocating machine. When the total denier of the composite production reaches 600 denier, it is rapidly stretched in an oil bath, and then micro-stretched in a steam box at a temperature of 120℃ for 2s. It is fully formed in three-dimensional curling inside the steam box, and then cut in a cutting machine. After cutting, it is placed in a three-layer oven for heat setting at a temperature of 180℃ to produce recycled polyester tourmaline cloud wool. The remaining steps are the same as in Example 3.

[0048] Comparative Example 2

[0049] The difference between Comparative Example 2 and Example 3 is that step (3) is omitted, and step (4) is changed to: mixing self-made intrinsic antistatic recycled PET chips and photoinitiator 1173 at a mass ratio of 93:2, stirring at 1000 rpm for 30 min at room temperature, and performing melt spinning. The parameters are set as follows: temperature of zone 1 of the barrel 265℃, zone 2 270℃, zone 3 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, spinning speed 800 m / min, and then cooling and solidifying in a deionized water coagulation bath with a temperature of 25℃ and a bath length of 1 m. Subsequently, it is stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 1000 m / min. Then, using a UV curing machine, the curing parameters are set as follows: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, curing time 30s, to form a photocrosslinking network on the fiber surface. Then, the fiber is bundled into sections by a reciprocating machine. When the total denier of the composite production reaches 600 denier, it is rapidly stretched in an oil bath, and then micro-stretched in a steam box at a temperature of 120℃ for 2s. It is fully formed in three-dimensional curling inside the steam box, and then cut in a cutting machine. After cutting, it is placed in a three-layer oven for heat setting at a temperature of 180℃ to produce recycled polyester tourmaline cloud wool. The remaining steps are the same as in Example 3.

[0050] Comparative Example 3

[0051] The difference between Comparative Example 3 and Example 3 is that step (3) is omitted, and step (4) is changed to: self-made intrinsic antistatic recycled PET chips, tourmaline powder with a particle size of 200nm and photoinitiator 1173 are mixed at a mass ratio of 93:8:2, stirred at 1000rpm for 30min at room temperature, and melt-spun. The parameters are set as follows: temperature of zone 1 of the barrel 265℃, zone 2 270℃, zone 3 275℃, spinneret temperature 275℃, screw speed 80rpm, spinneret orifice diameter 0.2mm, spinning speed 800m / min, introduced into a deionized water coagulation bath with a temperature of 25℃ and a bath length of 1m for cooling and solidification, and then stretched by a traction machine with a stretching ratio of 2.5 times and a traction speed of 10. The fiber speed is 00 m / min, and then it is passed through a UV curing machine with the following curing parameters: UV lamp power 80W, wavelength 365nm, curing distance 10cm, fiber running speed 0.5m / min, curing time 30s, so that a photocrosslinking network is formed on the fiber surface. Then it is passed through a reciprocating machine for binning and bundling. When the technology reaches a total denier of 600 denier for composite production, it is rapidly stretched in an oil bath tank, and then put into a steam box for micro-stretching. The steam box temperature is 120℃ and the micro-stretching time is 2s. It is fully formed in three-dimensional curling inside, and then it is put into a cutting machine. After cutting, it is placed in a three-layer oven for heat setting. The heat setting temperature is 180℃ to produce recycled polyester tourmaline cloud wool. The remaining steps are the same as in Example 3.

[0052] Comparative Example 4

[0053] The difference between Comparative Example 4 and Example 3 lies in step (4). Step (4) is changed to: mixing self-made intrinsic antistatic recycled PET chips, modified tourmaline powder, and photoinitiator 1173 at a mass ratio of 93:8:2, stirring at 1000 rpm for 30 min at room temperature, and then performing melt spinning. The parameters are set as follows: temperature of zone 1 of the barrel 265℃, zone 2 270℃, zone 3 275℃, spinneret temperature 275℃, screw speed 80 rpm, spinneret orifice diameter 0.2 mm, spinning speed 800 m / min, and a bath length of 1 m for the removal process. The material is cooled and solidified in a coagulation bath, then stretched by a traction machine at a stretching ratio of 2.5 times and a traction speed of 1000 m / min. It is then bundled into sections by a reciprocating machine. When the total denier of the composite production reaches 600 denier, it is rapidly stretched in an oil bath, and then micro-stretched in a steam box at a temperature of 120°C for 2 seconds. It is fully formed in three-dimensional curling inside the steam box, and then cut by a cutting machine. After cutting, it is placed in a three-layer oven for heat setting at a temperature of 180°C to produce recycled polyester tourmaline cloud wool. The remaining steps are the same as in Example 3.

[0054] Example of effect

[0055] Table 1 below shows the performance analysis results of the recycled polyester tourmaline cloud wool produced using Examples 1 to 5 and Comparative Examples 1 to 4 of the present invention.

[0056] Table 1

[0057]

[0058] A comparison of the surface resistivity experimental data of the comparative examples and embodiments reveals that the present invention uses polyethylene glycol and succinic anhydride to undergo ring-opening alcoholysis, followed by methacrylic acid end-capping to obtain a self-made antistatic monomer. This monomer is then combined with recycled PET and ethylene glycol through transesterification and polycondensation processes to obtain self-made intrinsically antistatic recycled PET chips. Nano-tourmaline powder is modified with a silane coupling agent containing double bonds, mixed with the self-made intrinsically antistatic recycled PET chips and other components, and melt-spun. The mixture is then UV-cured in a coagulation bath to further produce recycled polyester tourmaline cloud wool. The self-made antistatic monomer is chemically bonded and fixed within the fiber, forming a conductive water film on the fiber surface by adsorbing moisture from the air, thus facilitating the fixation of static charge. This provides pathways for migration and rapid dissipation, thereby significantly reducing the surface resistance of the fiber and achieving long-lasting antistatic properties. A comparison of the antibacterial rate experimental data from the examples and comparative examples reveals that the intrinsically antistatic regenerated PET chips in this invention reduce the electrostatic adsorption of dust and microorganisms on the fiber surface, helping to maintain the cleanliness of the tourmaline surface and enabling it to continuously and efficiently release negative ions. This alters the cell membrane potential of positively charged bacteria, molds, and other microorganisms in the environment, giving the material excellent antibacterial properties. A comparison of the tensile strength experimental data from the examples and comparative examples reveals that the self-made antistatic monomer containing flexible PEG segments in this invention synergistically combines with the photocrosslinking chemical network to impart excellent mechanical properties to the material.

[0059] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A regenerated terylene tourmaline cloud wool, characterized in that, Includes the following steps: (1) Polyethylene glycol, succinic anhydride, catalyst A, polymerization inhibitor A and toluene are mixed in a mass ratio of 30~40:10~15:9~10:0.3:

50. Under a nitrogen atmosphere, the mixture is heated in an oil bath to 60~70℃ and stirred for 5~7h. The mixture is then poured into excess ice water and acidified with 1M dilute hydrochloric acid to pH 2~3. The mixture is extracted, the organic phases are combined, dried and filtered, and then vacuum rotary evaporated at 40℃ to obtain the intermediate. The intermediate, methacrylic acid, and p-methyl... Benzenesulfonic acid, polymerization inhibitor B, and toluene were mixed in a mass ratio of 40-50:9-10:1-2:0.3:

100. The mixture was stirred and refluxed at 80-90°C for 4-6 hours under a nitrogen atmosphere. Then, it was rotary evaporated under vacuum at 50°C for 1 hour. The mixture was then added to a saturated sodium bicarbonate solution with a mass of 2 times that of the reaction solution. After stirring evenly, the mixture was allowed to stand and separate into layers. The mixture was repeatedly washed with water until the pH of the aqueous phase was 6.5-7.

5. The mixture was then dried under vacuum at 80°C for 8 hours to obtain the self-made antistatic monomer. (2) Mix recycled PET, ethylene glycol and catalyst B at a mass ratio of 50:4~6:0.

1. Under a nitrogen atmosphere, heat to 200~220℃ and stir for 2~4h for transesterification reaction. Then add 0.1~0.2 times the mass of the recycled PET and the self-made antistatic monomer. Heat to 250~270℃ and stir for 3~5h. When cooled to 200℃, extrude into 25℃ water for cooling and molding. After pelleting, dry in a vacuum at 100℃ for 6h to obtain self-made intrinsic antistatic recycled PET chips with a particle size of 3~5mm. Modify tourmaline powder with a double-bonded silane coupling agent to obtain modified tourmaline powder. (3) Mix the self-made intrinsic antistatic recycled PET chips, modified tourmaline powder and photoinitiator at a mass ratio of 90~95:5~10:2, stir at high speed for 30 minutes at room temperature, melt spin, and then make recycled polyester tourmaline cloud wool through UV curing and finishing processes.

2. A regenerated terylene tourmaline cloud wool according to claim 1, characterized by, The molecular weight of the polyethylene glycol mentioned in step (1) is 400.

3. A regenerated terylene tourmaline cloud wool according to claim 1, characterized by, The catalyst A mentioned in step (1) is anhydrous pyridine.

4. A regenerated terylene tourmaline cloud wool according to claim 1, characterized by, The polymerization inhibitor A mentioned in step (1) is hydroquinone.

5. The recycled polyester tourmaline cloud wool according to claim 1, characterized in that, The polymerization inhibitor B mentioned in step (1) is 2,6-di-tert-butyl-p-cresol.

6. The recycled polyester tourmaline cloud wool according to claim 1, characterized in that, The catalyst B mentioned in step (2) is zinc acetate.

7. The recycled polyester tourmaline fleece according to claim 1, characterized in that, The self-made intrinsic antistatic recycled PET chips mentioned in step (2) have a particle size of 3~5mm.

8. The recycled polyester tourmaline cloud wool according to claim 1, characterized in that, The double-bonded silane coupling agent mentioned in step (2) is KH-570.

9. The recycled polyester tourmaline cloud wool according to claim 1, characterized in that, The tourmaline powder mentioned in step (2) has a particle size of 200 nm.

10. A recycled polyester tourmaline cloud wool according to claim 1, characterized in that, The photoinitiator in step (3) is photoinitiator 1173.

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