Regenerated polyester medical stone heat storage cloud velvet and preparation method thereof

Abstract

The invention relates to regenerated polyester medical stone heat storage cloud velvet and a preparation method thereof, and belongs to the technical field of regenerated polyester. The preparation method comprises the following steps: performing mixed acid activation on medical stone, preparing rare earth doped nano medical stone by a hydrothermal method, and performing surface modification by an epoxy-terminated flexible long-chain silane coupling agent to obtain self-made modified nano medical stone; and carrying out melt spinning on the polyester fibers, regenerated polyester and an initiator, preparing hollow fibers through a hollow spinning assembly, and carrying out after-finishing to obtain the cloud velvet material. Mixed acid activation and rare earth doping synergistically improve the far infrared emissivity and photo-thermal conversion efficiency of medical stone, and hollow fiber heat insulation effect and light heat storage synergistically endow the material with excellent heat storage performance; silane modification and epoxy ring-opening bonding reinforce the interface bonding force, and the toughness and mechanical properties of the material are both considered. The regenerated terylene medical stone heat storage cloud velvet prepared by the invention has the effects of excellent heat storage performance and good mechanical property.

Description

Technical Field

[0001] This invention relates to the field of recycled polyester technology, specifically to a recycled polyester maifanite heat-retaining cloud fleece and its preparation method. Background Technology

[0002] Due to its environmentally friendly recycling characteristics, recycled polyester materials are increasingly widely used in the field of textile functional materials, possessing both resource recycling value and market prospects. Among them, heat-storing and heat-insulating recycled polyester materials have attracted much attention.

[0003] Existing heat-storing textile materials often improve their performance by adding heat-storing fillers, but these methods generally have shortcomings: traditional heat-storing fillers, such as maifanite, have low surface activity, are prone to agglomeration when added directly, and have weak interfacial bonding with the polyester matrix, easily leading to increased material brittleness and decreased mechanical properties. Meanwhile, single heat-storing components have limited far-infrared emissivity and photothermal conversion efficiency, and are difficult to form a synergistic heat-storing effect with the fiber structure, failing to achieve both excellent heat-storing performance and good mechanical toughness. Furthermore, existing modification processes struggle to balance filler dispersibility, interfacial compatibility, and functional stability, hindering the industrial application of heat-storing recycled polyester materials. Therefore, an optimized preparation technology is urgently needed to address these issues. Summary of the Invention

[0004] The purpose of this invention is to provide a recycled polyester maifanite heat-retaining cloud fleece 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 maifanite heat-retaining cloud fleece, comprising the following steps: (1) Mix the maifan stone powder after mixed acid activation treatment, rare earth ion compound A, rare earth ion compound B and deionized water at a mass ratio of 10~20:0.4~0.6:0.4~0.6:100, and ultrasonically disperse at 30kHz for 30min at room temperature. Rare earth doped nano maifan stone is prepared by hydrothermal method. Then, the surface is modified by epoxy-terminated flexible long-chain silane coupling agent to obtain self-made modified nano maifan stone. (2) Mix recycled PET, self-made modified nano maifan stone and initiator at a mass ratio of 100:3~5:0.2, put them into a high-speed mixer, mix at 50℃ for 10 min to obtain a uniformly mixed raw material, melt spin spinning, use a circular hollow spinneret, and cold draw through a drawing machine to obtain self-made hollow fiber; (3) The self-made hollow fiber is bundled into barrels by a reciprocating machine, and then rapidly stretched in an oil bath. After that, it enters a steam box for micro-stretching and is fully formed in three-dimensional curling inside. Then it enters a cutting machine for cutting and is placed in a three-layer drying oven for heat setting to produce recycled polyester maifan stone heat storage cloud wool.

[0006] Furthermore, the mixed acid in step (1) is prepared by mixing 37wt% hydrochloric acid and 90wt% sulfuric acid in a mass ratio of 2~3:3~4.

[0007] Furthermore, the maifanite powder in step (1) has a particle size of 200 nm.

[0008] Furthermore, the rare earth ion compound A mentioned in step (1) is cerium chloride.

[0009] Furthermore, the rare earth ion compound B mentioned in step (1) is lanthanum nitrate.

[0010] Furthermore, the rare earth-doped nano-maifanite in step (1) has a particle size of 300~500nm.

[0011] Furthermore, the epoxy-terminated flexible long-chain silane coupling agent in step (1) is 3-glycidyl etheroxypropyltriethoxysilane.

[0012] Furthermore, the recycled PET in step (2) has the following properties: intrinsic viscosity 0.65 dL / g and particle size 3 mm.

[0013] Furthermore, the initiator in step (2) is dicumyl peroxide.

[0014] Furthermore, the circular hollow spinneret assembly described in step (2) has 24 spinneret holes with a diameter of 0.3 mm and a hollowness of 30%.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: This invention further processes the hollow fibers obtained by melt spinning rare earth-doped self-made modified nano-maifanite with recycled polyester into cloud-like materials to achieve excellent heat storage performance and good mechanical properties.

[0016] This invention first activates the surface of maifan stone with mixed acid, then prepares rare earth-doped nano-maifan stone via a hydrothermal method. Next, it modifies the surface using a flexible long-chain silane coupling agent with epoxy ends to obtain self-made modified nano-maifan stone. This modified nano-maifan stone is then mixed with recycled polyester, an initiator, and other components for melt spinning, followed by hollow spinning to obtain self-made hollow fibers. Further finishing processes are used to produce recycled polyester maifan stone heat-retaining cloud-like fibers. The mixed acid activation significantly increases the surface area of ​​the maifan stone, enhancing the degree of freedom of lattice vibration and thus improving its intrinsic infrared radiation capability. Simultaneously, it synergizes with the further broadened absorption band of rare earth ions, significantly improving the far-infrared emissivity and photothermal conversion efficiency. Furthermore, the thermal insulation effect of the hollow fibers synergizes with the photothermal storage of the self-made modified nano-maifan stone, endowing the material with excellent heat storage performance. The chemical bonds formed by the flexible long-chain silane and epoxy ring-opening in the material avoid increasing brittleness while improving interfacial bonding and enhancing the mechanical properties of the material. Detailed Implementation

[0017] 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.

[0018] 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 maifanite heat-retaining cloud fleece produced in the following embodiments are as follows: Photothermal storage performance test: The photothermal storage performance of the materials prepared in Examples 1-5 and Comparative Examples 1-5 was tested according to GB / T 18319-2019 "Test Method for Photothermal Storage Performance of Textiles", with an irradiance of 150 W / m². 2 .

[0019] Far-infrared performance test: The far-infrared emissivity of the materials prepared in Examples 1-5 and Comparative Examples 1-5 was tested in accordance with the standard of GB / T 30127-2013 "Test and Evaluation of Far-infrared Performance of Textiles".

[0020] Mechanical property testing: The breaking strength of the fibers prepared in Examples 1-5 and Comparative Examples 1-5 was tested in accordance with GB / T 14344-2022 "Test Method for Tensile Properties of Chemical Fiber Filaments".

[0021] Example 1; (1) Maifan stone with a particle size of 200 nm, 37 wt% hydrochloric acid and 90 wt% sulfuric acid were slowly mixed in a mass ratio of 1:2:3, stirred and refluxed at 100 rpm at 60 °C for 1 h, cooled to room temperature, filtered and collected the filter residue, and washed repeatedly with deionized water until the pH of the filtrate was 6.5. The filtrate was then dried in an oven at 105 °C for 12 h to obtain activated maifan stone powder; (2) The activated maifan stone powder, cerium chloride, lanthanum nitrate and deionized water were mixed in a mass ratio of 10:0.4:0.4:100 and ultrasonically dispersed at 30 kHz for 30 min at room temperature. The mixture was placed in a hydrothermal reactor and the parameters were set as follows: temperature 180℃, pressure 1.5 MPa, constant temperature reaction for 12 h. After naturally cooling to room temperature, the product was taken out and washed three times each with deionized water and anhydrous ethanol. It was then dried at 80℃ and vacuum degree -0.09 MPa for 6 h. After drying, it was pulverized to a particle size of 300 nm using a nano-pulverizer to obtain rare earth doped nano maifan stone. (3) Rare earth-doped nano-maifan stone and ethanol aqueous solution were mixed at a mass ratio of 1:5. The volume ratio of ethanol to water in the ethanol aqueous solution was 5:1. The pH was adjusted to 4.0 with 1M acetic acid aqueous solution. After stirring at 300 rpm for 30 min at room temperature, 0.1 times the mass of rare earth-doped nano-maifan stone and 3-glycidyl etheroxypropyltriethoxysilane were slowly added dropwise at a rate of 2 mL / min. The temperature was raised to 70℃ and the mixture was stirred and refluxed at 300 rpm for 5 h. The mixture was filtered and the residue was washed three times with anhydrous ethanol. The mixture was then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano-maifan stone. (4) Recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite, and dicumyl peroxide were mixed at a mass ratio of 100:3:0.2 and placed in a high-speed mixer. The mixture was mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material was then melt-spun. The extrusion temperature segment parameters were set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the spinneret temperature was 2... At 60℃, screw speed 150rpm, melt pressure controlled at 3.0MPa, a circular hollow spinneret assembly was used: 24 spinneret holes, hole diameter 0.3mm, hollowness 30%, spinneret speed 800m / min, cooling air temperature 25℃, air speed 1.5m / s, cooling distance 50cm. After cold drawing in a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃, and a winding machine speed of 2800rpm and a winding temperature of 60℃, self-made hollow fibers were obtained. (5) The self-made hollow fiber is bundled into barrels by a reciprocating machine. When the total denier of composite production reaches 600 denier, it is quickly 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 by three-dimensional curling inside. Then it is put into a cutting machine. After cutting, it is put into a three-layer oven for heat setting. The heat setting temperature is 180℃ to make recycled polyester maifan stone heat storage cloud wool.

[0022] Example 2; (1) Maifan stone with a particle size of 200 nm, 37 wt% hydrochloric acid and 90 wt% sulfuric acid were slowly mixed in a mass ratio of 1.2:2.2:3.2 and stirred and refluxed at 100 rpm at 62 °C for 1.2 h. After cooling to room temperature, the filter residue was collected by filtration and washed repeatedly with deionized water until the pH of the filtrate was 6.6. The filtrate was then dried in an oven at 105 °C for 12 h to obtain activated maifan stone powder; (2) The activated maifan stone powder, cerium chloride, lanthanum nitrate and deionized water were mixed in a mass ratio of 12:0.45:0.45:100 and ultrasonically dispersed at 30 kHz for 30 min at room temperature. The mixture was placed in a hydrothermal reactor and the parameters were set as follows: temperature 180℃, pressure 1.5 MPa, constant temperature reaction for 14 h. After naturally cooling to room temperature, the product was taken out and washed three times each with deionized water and anhydrous ethanol. It was then dried at 80℃ and vacuum degree -0.09 MPa for 6 h. After drying, it was pulverized to a particle size of 350 nm using a nano-pulverizer to obtain rare earth doped nano maifan stone. (3) Rare earth-doped nano-maifan stone and ethanol aqueous solution were mixed at a mass ratio of 1.2:5, and the volume ratio of ethanol to water in the ethanol aqueous solution was 5:1. The pH was adjusted to 4.2 with 1M acetic acid aqueous solution. After stirring at 300 rpm for 30 min at room temperature, 0.12 times the mass of rare earth-doped nano-maifan stone and 3-glycidyl etheroxypropyltriethoxysilane were slowly added dropwise at a rate of 2 mL / min. The temperature was raised to 72℃ and the mixture was stirred and refluxed at 300 rpm for 5.5 h. The mixture was filtered and the residue was washed three times with anhydrous ethanol. The mixture was then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano-maifan stone. (4) Recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite and diisopropylbenzene peroxide are mixed at a mass ratio of 100:3.5:0.2 and placed in a high-speed mixer. The mixture is mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material is then melt-spun. The extrusion temperature segment parameters are set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the spinneret temperature is set as follows. At 260℃, screw speed 150rpm, melt pressure controlled at 3.0MPa, a circular hollow spinneret assembly was used: 24 spinneret holes, hole diameter 0.3mm, hollowness 30%, spinneret speed 800m / min, cooling air temperature 25℃, air speed 1.5m / s, cooling distance 50cm. After cold drawing in a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃, and a winding machine speed of 2800rpm and a winding temperature of 60℃, self-made hollow fibers were obtained. (5) The self-made hollow fiber is bundled into barrels by a reciprocating machine. When the total denier of composite production reaches 600 denier, it is quickly 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 by three-dimensional curling inside. Then it is put into a cutting machine. After cutting, it is put into a three-layer oven for heat setting. The heat setting temperature is 180℃ to make recycled polyester maifan stone heat storage cloud wool.

[0023] Example 3; (1) Maifan stone with a particle size of 200 nm, 37 wt% hydrochloric acid and 90 wt% sulfuric acid were slowly mixed in a mass ratio of 1.5:2.5:3.5, stirred and refluxed at 100 rpm at 65 °C for 1.5 h, cooled to room temperature, filtered and collected the filter residue, washed repeatedly with deionized water until the pH of the filtrate was 6.7, and dried in an oven at 105 °C for 12 h to obtain activated maifan stone powder; (2) The activated maifan stone powder, cerium chloride, lanthanum nitrate and deionized water were mixed in a mass ratio of 15:0.5:0.5:100 and ultrasonically dispersed at 30 kHz for 30 min at room temperature. The mixture was placed in a hydrothermal reactor and the parameters were set as follows: temperature 180℃, pressure 1.5 MPa, constant temperature reaction for 16 h. After naturally cooling to room temperature, the product was taken out and washed three times each with deionized water and anhydrous ethanol. It was then dried at 80℃ and vacuum degree -0.09 MPa for 6 h. After drying, it was pulverized to a particle size of 400 nm using a nano-pulverizer to obtain rare earth doped nano maifan stone. (3) Rare earth-doped nano-maifan stone and ethanol aqueous solution were mixed at a mass ratio of 1.5:5, and the volume ratio of ethanol to water in the ethanol aqueous solution was 5:1. The pH was adjusted to 4.5 with 1M acetic acid aqueous solution. After stirring at 300 rpm for 30 min at room temperature, 0.15 times the mass of rare earth-doped nano-maifan stone and 3-glycidyl etheroxypropyltriethoxysilane were slowly added dropwise at a rate of 2 mL / min. The temperature was raised to 75℃ and the mixture was stirred and refluxed at 300 rpm for 6 h. The mixture was filtered and the residue was washed three times with anhydrous ethanol. The mixture was then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano-maifan stone. (4) Recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite, and dicumyl peroxide were mixed at a mass ratio of 100:4:0.2 and placed in a high-speed mixer. The mixture was mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material was then melt-spun. The extrusion temperature segment parameters were set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the spinneret temperature was 2... At 60℃, screw speed 150rpm, melt pressure controlled at 3.0MPa, a circular hollow spinneret assembly was used: 24 spinneret holes, hole diameter 0.3mm, hollowness 30%, spinneret speed 800m / min, cooling air temperature 25℃, air speed 1.5m / s, cooling distance 50cm. After cold drawing in a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃, and a winding machine speed of 2800rpm and a winding temperature of 60℃, self-made hollow fibers were obtained. (5) The self-made hollow fiber is bundled into barrels by a reciprocating machine. When the total denier of composite production reaches 600 denier, it is quickly 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 by three-dimensional curling inside. Then it is put into a cutting machine. After cutting, it is put into a three-layer oven for heat setting. The heat setting temperature is 180℃ to make recycled polyester maifan stone heat storage cloud wool.

[0024] Example 4; (1) Maifan stone with a particle size of 200 nm, 37 wt% hydrochloric acid and 90 wt% sulfuric acid were slowly mixed in a mass ratio of 1.8:2.8:3.8 and stirred and refluxed at 100 rpm at 68 °C for 1.8 h. After cooling to room temperature, the filter residue was collected by filtration and washed repeatedly with deionized water until the pH of the filtrate was 6.9. The filtrate was then dried in an oven at 105 °C for 12 h to obtain activated maifan stone powder; (2) The activated maifan stone powder, cerium chloride, lanthanum nitrate and deionized water were mixed in a mass ratio of 18:0.55:0.55:100 and ultrasonically dispersed at 30 kHz for 30 min at room temperature. The mixture was placed in a hydrothermal reactor and the parameters were set as follows: temperature 180℃, pressure 1.5 MPa, constant temperature reaction for 18 h. After naturally cooling to room temperature, the product was taken out and washed three times each with deionized water and anhydrous ethanol. It was then dried at 80℃ and vacuum degree -0.09 MPa for 6 h. After drying, it was pulverized to a particle size of 450 nm using a nano-pulverizer to obtain rare earth doped nano maifan stone. (3) Rare earth-doped nano-maifan stone and ethanol aqueous solution were mixed at a mass ratio of 1.8:5, and the volume ratio of ethanol to water in the ethanol aqueous solution was 5:1. The pH was adjusted to 4.8 with 1M acetic acid aqueous solution. After stirring at 300 rpm for 30 min at room temperature, 0.18 times the mass of rare earth-doped nano-maifan stone and 3-glycidyl etheroxypropyltriethoxysilane were slowly added dropwise at a rate of 2 mL / min. The temperature was raised to 78℃ and the mixture was stirred and refluxed at 300 rpm for 6.5 h. The mixture was filtered and the residue was washed three times with anhydrous ethanol. The mixture was then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano-maifan stone. (4) Recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite and dicumyl peroxide are mixed at a mass ratio of 100:4.5:0.2 and placed in a high-speed mixer. The mixture is mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material is then melt-spun. The extrusion temperature segment parameters are set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the spinneret temperature is set as follows. At 260℃, screw speed 150rpm, melt pressure controlled at 3.0MPa, a circular hollow spinneret assembly was used: 24 spinneret holes, hole diameter 0.3mm, hollowness 30%, spinneret speed 800m / min, cooling air temperature 25℃, air speed 1.5m / s, cooling distance 50cm. After cold drawing in a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃, and a winding machine speed of 2800rpm and a winding temperature of 60℃, self-made hollow fibers were obtained. (5) The self-made hollow fiber is bundled into barrels by a reciprocating machine. When the total denier of composite production reaches 600 denier, it is quickly 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 by three-dimensional curling inside. Then it is put into a cutting machine. After cutting, it is put into a three-layer oven for heat setting. The heat setting temperature is 180℃ to make recycled polyester maifan stone heat storage cloud wool.

[0025] Example 5; (1) Maifan stone with a particle size of 200 nm, 37 wt% hydrochloric acid and 90 wt% sulfuric acid were slowly mixed in a mass ratio of 2:3:4, stirred and refluxed at 100 rpm at 70 °C for 2 h, cooled to room temperature, filtered and collected the filter residue, washed repeatedly with deionized water until the pH of the filtrate was 7.0, and dried in an oven at 105 °C for 12 h to obtain activated maifan stone powder; (2) The activated maifan stone powder, cerium chloride, lanthanum nitrate and deionized water were mixed in a mass ratio of 20:0.6:0.6:100 and ultrasonically dispersed at 30 kHz for 30 min at room temperature. The mixture was placed in a hydrothermal reactor and the parameters were set as follows: temperature 180℃, pressure 1.5 MPa, constant temperature reaction for 20 h. After natural cooling to room temperature, the product was taken out and washed three times each with deionized water and anhydrous ethanol. It was dried at 80℃ and vacuum degree -0.09 MPa for 6 h. After drying, it was pulverized to a particle size of 500 nm using a nano-pulverizer to obtain rare earth doped nano maifan stone. (3) Rare earth-doped nano-maifan stone and ethanol aqueous solution were mixed at a mass ratio of 2:5. The volume ratio of ethanol to water in the ethanol aqueous solution was 5:1. The pH was adjusted to 5.0 with 1M acetic acid aqueous solution. After stirring at 300 rpm for 30 min at room temperature, 0.2 times the mass of rare earth-doped nano-maifan stone and 3-glycidyl etheroxypropyltriethoxysilane were slowly added dropwise at a rate of 2 mL / min. The temperature was raised to 80℃ and the mixture was stirred and refluxed at 300 rpm for 7 h. The mixture was filtered and the residue was washed three times with anhydrous ethanol. The mixture was then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano-maifan stone. (4) Recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite, and dicumyl peroxide were mixed at a mass ratio of 100:5:0.2 and placed in a high-speed mixer. The mixture was mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material was then melt-spun. The extrusion temperature segment parameters were set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the spinneret temperature was 2... At 60℃, screw speed 150rpm, melt pressure controlled at 3.0MPa, a circular hollow spinneret assembly was used: 24 spinneret holes, hole diameter 0.3mm, hollowness 30%, spinneret speed 800m / min, cooling air temperature 25℃, air speed 1.5m / s, cooling distance 50cm. After cold drawing in a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃, and a winding machine speed of 2800rpm and a winding temperature of 60℃, self-made hollow fibers were obtained. (5) The self-made hollow fiber is bundled into barrels by a reciprocating machine. When the total denier of composite production reaches 600 denier, it is quickly 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 by three-dimensional curling inside. Then it is put into a cutting machine. After cutting, it is put into a three-layer oven for heat setting. The heat setting temperature is 180℃ to make recycled polyester maifan stone heat storage cloud wool.

[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 3 is that step (1) is omitted, and step (2) is changed to: mixing maifanite with a particle size of 200 nm, cerium chloride, lanthanum nitrate and deionized water in a mass ratio of 15:0.5:0.5:100, ultrasonically dispersing at 30 kHz for 30 min at room temperature, placing in a hydrothermal reactor, setting the parameters as follows: temperature of 180 °C, pressure of 1.5 MPa, constant temperature reaction for 16 h, and naturally cooling to room temperature, taking out the product, washing it three times each with deionized water and anhydrous ethanol, drying it at 80 °C and vacuum degree of -0.09 MPa for 6 h, and then pulverizing it to a particle size of 400 nm using a nano-pulverizer to obtain rare earth doped nano-maifanite, and the remaining steps are the same as in Example 3.

[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that step (2) is omitted, and step (3) is changed to: the activated maifan stone powder and the ethanol aqueous solution are mixed at a mass ratio of 1:5, the volume ratio of ethanol to water in the ethanol aqueous solution is 5:1, the pH is adjusted to 4.0 with 1M acetic acid aqueous solution, stirred at 300 rpm for 30 min at room temperature, and then 0.1 times the mass of the activated maifan stone powder of 3-glycidyl etheroxypropyltriethoxysilane is slowly added dropwise at a rate of 2 mL / min. The temperature is raised to 70℃, and the reaction is stirred and refluxed at 300 rpm for 5 h. The residue is filtered and washed three times with anhydrous ethanol, and then dried at 80℃ and vacuum degree -0.09 MPa for 12 h to obtain the self-made modified nano maifan stone. The remaining steps are the same as in Example 3.

[0028] Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that step (3) is omitted, and step (4) is changed to: recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, rare earth-doped nano-maifanite and diisopropylbenzene peroxide are mixed at a mass ratio of 100:4:0.2, placed in a high-speed mixer, and mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material is then melt-spun, and the extrusion temperature segment parameters are set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C. The spinneret temperature was 260℃, the screw speed was 150rpm, the melt pressure was controlled at 3.0MPa, and a circular hollow spinneret assembly was used: 24 spinneret holes with a diameter of 0.3mm, a hollowness of 30%, a spinneret speed of 800m / min, a cooling air temperature of 25℃, a wind speed of 1.5m / s, and a cooling distance of 50cm. The spinneret was cold-drawn by a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃. The winding machine speed was 2800rpm and the winding temperature was 60℃ to obtain the self-made hollow fiber. The remaining steps were the same as in Example 3.

[0029] Comparative Example 4 The difference between Comparative Example 4 and Example 3 is that steps (1), (2), and (3) are omitted, and step (4) is changed to: recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm and dicumyl peroxide are mixed at a mass ratio of 100:0.2, placed in a high-speed mixer, and mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material is then melt-spun, and the extrusion temperature segment parameters are set as follows: Zone 1 240°C, Zone 2 250°C, Zone 3 255°C, Zone 4 260°C, and the die head is sprayed with... The filament temperature was 260℃, the screw speed was 150rpm, the melt pressure was controlled at 3.0MPa, and a circular hollow spinneret was used: 24 spinneret holes with a diameter of 0.3mm, a hollowness of 30%, a spinneret speed of 800m / min, a cooling air temperature of 25℃, a wind speed of 1.5m / s, and a cooling distance of 50cm. The fibers were cold-drawn by a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃. The winding machine speed was 2800rpm and the winding temperature was 60℃ to obtain the self-made hollow fiber. The remaining steps were the same as in Example 3.

[0030] Comparative Example 5 The difference between Comparative Example 5 and Example 3 lies in step (4). Step (4) is changed to: recycled PET with an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm, self-made modified nano-maifanite, and diisopropylbenzene peroxide are mixed at a mass ratio of 100:4:0.2, placed in a high-speed mixer, and mixed at 50°C and 1500 rpm for 10 min to obtain a uniformly mixed raw material. The mixed raw material is then melt-spun, and the extrusion temperature is set to segmented parameters: Zone 1 240°C, Zone 2 250°C, and Zone 3 250°C. The temperature of the spinneret was 255℃ in Zone 2 and 260℃ in Zone 4. The spinneret temperature was 260℃, the screw speed was 150 rpm, the melt pressure was controlled at 3.0 MPa, the spinneret orifice diameter was 0.3 mm, the spinneret speed was 800 m / min, the cooling air temperature was 25℃, the air speed was 1.5 m / s, the cooling distance was 50 cm, and the fiber was cold drawn by a drawing machine with a draw ratio of 3.5 times and a drawing temperature of 25℃. The winding machine speed was 2800 rpm and the winding temperature was 60℃ to obtain the self-made fiber. The remaining steps were the same as in Example 3.

[0031] Example of effect Table 1 below presents the performance analysis results of the recycled polyester maifanite heat-retaining cloud fleece produced using Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention.

[0032] Table 1

[0033] A comparison of the experimental data on the photothermal heat storage temperature rise in the examples and comparative examples reveals that the present invention first activates the surface of maifan stone with mixed acid, prepares rare earth-doped nano-maifan stone via a hydrothermal method, then modifies the surface using a flexible long-chain silane coupling agent with epoxy ends to obtain self-made modified nano-maifan stone, mixes it with recycled polyester, initiator, and other components for melt spinning, and obtains self-made hollow fiber through a hollow spinneret. Further finishing processes are then used to produce recycled polyester maifan stone heat-storing cloud-like fabric. Rare earth-doped maifan stone enhances the photothermal conversion efficiency, and the thermal insulation effect of the hollow fiber synergistically complements the photothermal heat storage of the self-made modified nano-maifan stone. This invention endows the material with excellent heat storage performance. A comparison of the experimental data on far-infrared emissivity between the examples and comparative examples reveals that the mixed acid activation in this invention significantly increases the surface area of ​​the maifanite, enhancing the degree of freedom of lattice vibration and thus improving its intrinsic infrared radiation capability. Simultaneously, in synergy with the further broadened absorption band of rare earth ions, it significantly improves the far-infrared emissivity of the material. A comparison of the experimental data on fracture strength between the examples and comparative examples reveals that the chemical bonds formed by the flexible long-chain silane and epoxy ring-opening in the material of this invention avoid increasing brittleness while improving interfacial bonding strength and enhancing the mechanical properties of the material.

[0034] 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 type of recycled polyester maifanite heat-retaining cloud fleece, characterized in that, Includes the following steps: (1) Mix the maifan stone powder after mixed acid activation treatment, rare earth ion compound A, rare earth ion compound B and deionized water at a mass ratio of 10~20:0.4~0.6:0.4~0.6:100, and ultrasonically disperse at 30kHz for 30min at room temperature. Rare earth doped nano maifan stone is prepared by hydrothermal method. Then, the surface is modified by epoxy-terminated flexible long-chain silane coupling agent to obtain self-made modified nano maifan stone. (2) Mix recycled PET, self-made modified nano maifan stone and initiator at a mass ratio of 100:3~5:0.2, put them into a high-speed mixer, mix at 50℃ for 10 min to obtain a uniformly mixed raw material, melt spin spinning, use a circular hollow spinneret, and cold draw through a drawing machine to obtain self-made hollow fiber; (3) The self-made hollow fiber is bundled into barrels by a reciprocating machine, and then rapidly stretched in an oil bath. After that, it enters a steam box for micro-stretching and is fully formed in three-dimensional curling inside. Then it enters a cutting machine for cutting and is placed in a three-layer drying oven for heat setting to produce recycled polyester maifan stone heat storage cloud wool.

2. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The mixed acid mentioned in step (1) is prepared by mixing 37wt% hydrochloric acid and 90wt% sulfuric acid in a mass ratio of 2~3:3~4.

3. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The maifanite powder mentioned in step (1) has a particle size of 200 nm.

4. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The rare earth ion compound A mentioned in step (1) is cerium chloride.

5. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The rare earth ion compound B mentioned in step (1) is lanthanum nitrate.

6. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The rare earth-doped nano-maifanite in step (1) has a particle size of 300~500nm.

7. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The epoxy-terminated flexible long-chain silane coupling agent in step (1) is 3-glycidyl etheroxypropyltriethoxysilane.

8. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The recycled PET mentioned in step (2) has an intrinsic viscosity of 0.65 dL / g and a particle size of 3 mm.

9. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The initiator in step (2) is dicumyl peroxide.

10. The recycled polyester maifanite heat-retaining cloud fleece according to claim 1, characterized in that, The circular hollow spinneret assembly in step (2) has 24 spinneret holes with a diameter of 0.3 mm and a hollowness of 30%.

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