Light-accumulating antibacterial polyester fiber and preparation method and application thereof

Abstract

The application discloses a kind of light heat storage antibacterial polyester fibers and its preparation method and application, belong to composite fiber technical field. Contain 90-96 parts of PET chip, 2-4 parts of modified bixie, 1-2 parts of modified tea saponin-montmorillonite and 0.1-0.2 parts of glycerol monostearate by weight parts;When preparing, titanium ester coupling agent NDZ-101 is used to modify bixie, reduce metal ion aggregation, epoxy chloropropane is used to mediate tea saponin and montmorillonite covalent grafting, fix antibacterial component, improve washability, combine supercritical CO2 assisted dispersion melt blending, through spinning, stretching and setting to get finished product;It aims at solving the problems of existing fiber metal ion migration, poor antibacterial washability and functional powder aggregation.Proved by test, light heat storage performance is excellent, antibacterial long-acting, mechanical property meets the standard, applicable to outdoor warm clothing, medical protective fabric and other fields, and high performance and industrialization adaptability are considered.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite fibers, and particularly relates to a light heat-storing antibacterial polyester fiber as well as a preparation method and application thereof. BACKGROUND

[0002] The mainstream technical route of the light heat-storing antibacterial polyester fiber mainly includes metal-based inorganic particle compounding, bio-based and plant extraction compounding, and aerogel nano-porous structure technologies. The metal-based technology (such as nano-zirconium dioxide and silver-loaded apatite) has high light-heat conversion efficiency and significant antibacterial effect, but has problems such as inorganic particle agglomeration affecting spinnability, metal ion migration and dissolution affecting fiber color, etc. For example, the patent application CN113293544A reduces nano agglomeration through dispersion needle puncture and pulsating stirring system, although the uniformity of the antibacterial agent is improved by 30%, but nano-zirconium dioxide and silver-loaded apatite particles still need more than 5% dispersant auxiliary.

[0003] The bio-based technology uses plant extracts, which is environmentally friendly and safe, but the heat resistance of the active ingredients is poor, and the challenges of efficacy stability and durability are faced. For example, the patent application CN119593094A loads rhizoma polygonati extract on cellulose aerogel to realize the synergy of antibacterial and cooling, but the retention rate of the active ingredient is only 68% after spinning at 280℃; the patent application CN115961376A adopts hydrophilic modification to coat thyme extract, and the antibacterial rate decreases from 97% to 81% after 20 times of washing, which highlights the double challenges of heat resistance and washing resistance of natural ingredients.

[0004] The aerogel technology realizes light warmth by virtue of excellent heat insulation and temperature locking performance, but the nano-porous structure is difficult to maintain during processing, the dispersion process is complex and the cost is high. The patent application CN116949592A maintains 80% to 90% porosity through light reversible crosslinking, but needs ultraviolet irradiation curing equipment, which greatly increases the modification cost. In summary, the existing technology has made certain progress in the field of light heat-storing antibacterial polyester fiber, but there is still room for improvement in functional durability, processing cost and environmental friendliness. SUMMARY

[0005] One of the purposes of the present application is to provide a light heat-storing antibacterial polyester fiber to improve the high light-heat conversion efficiency, antibacterial performance and mechanical properties of the fiber, while avoiding the risk of metal ion migration and improving environmental friendliness.

[0006] The second purpose of the present application is to provide a preparation method of the light heat-storing antibacterial polyester fiber for preparing the light heat-storing antibacterial polyester fiber.

[0007] The third purpose of the present application is to provide an application of the light heat-storing antibacterial polyester fiber in the field of warm-keeping and antibacterial textiles.

[0008] The object of the present application can be achieved by the following technical solutions:

[0009] The light-accumulating antibacterial polyester fiber comprises 90-96 parts of PET chips, 2-4 parts of modified bixite, 1-2 parts of modified tea saponin-montmorillonite, and 0.1-0.2 parts of glycerol monostearate.

[0010] Further, the modified bixite is prepared by the following steps:

[0011] Step 1: Take bixite powder, add isopropyl alcohol solution, ultrasonic dispersion, and form a suspension;

[0012] Step 2: Add titanium ester coupling agent NDZ-101 dropwise, heat and stir; centrifugal separation, vacuum drying, and obtain modified bixite.

[0013] Further, the particle size of the bixite powder is between 60-80nm.

[0014] Further, the weight ratio of the bixite powder, isopropyl alcohol and titanium ester coupling agent is (2.5-3.5):(40-45):(0.1-0.2).

[0015] Further, the ultrasonic dispersion time is 40-50min, the power is 350-400W, and the frequency is 28-30kHz.

[0016] Further, the heating and stirring is stirring reaction at 70-75℃ for 120-150min; the centrifugal separation is centrifugal separation at 9000-10000rpm for 15-20min.

[0017] Further, the modified tea saponin-montmorillonite is prepared by the following steps:

[0018] Step 1: Take sodium-based montmorillonite, add deionized water, stir uniformly, and prepare a montmorillonite suspension;

[0019] Step 2: Add tea saponin and epichlorohydrin, adjust the pH to 8.8-9.0, heat and react; filter the product, vacuum dry, and crush to 100-150nm to obtain modified tea saponin-montmorillonite.

[0020] Further, the particle size of the sodium-based montmorillonite is between 100-150nm.

[0021] Further, the weight ratio of the sodium-based montmorillonite, deionized water, tea saponin and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35).

[0022] Further, the heating reaction is heating to 65-70℃ for 5-6h of stirring reaction.

[0023] Further, the vacuum drying is drying for 4-6h under vacuum at 75-80℃.

[0024] Further, the viscosity of the PET chip is 0.6-0.7dL / g, and the melting point is 255-260℃.

[0025] A preparation method of light heat storage antibacterial polyester fiber, comprising the following steps:

[0026] S1, PET chip, modified bixie, modified tea saponin-montmorillonite and glycerol monostearate are added into the hopper of the double screw extruder; supercritical CO2 is introduced into the screw segment, and melt blending is carried out; the polyester composite melt is obtained by filtering through a 25μm filter screen;

[0027] S2, the polyester composite melt is spun to obtain a primary fiber; after cooling, the primary fiber is stretched, set and wound to obtain the light heat storage antibacterial polyester fiber.

[0028] Further, the temperature of the supercritical CO2 is 38-39℃, the pressure is 12.8-13MPa, and the flow rate is 6.5-6.8L / kgPET.

[0029] Further, the melt blending parameters are: zone 1 235-240℃, zone 2 245-250℃, zone 3 260-265℃, zone 4 255-260℃, screw rotation speed 280-300rpm, and melt residence time 2.5-3min.

[0030] Further, the spinning temperature is 260-262℃, the spinneret aperture is 0.22mm, and the number of holes is 48.

[0031] Further, the stretching multiple is 3.2-3.3 times, and the temperature is 88-90℃; the setting condition is 110-115℃ for 25-28s; and the winding rate is 3500-3600m / min.

[0032] The application of the light heat storage antibacterial polyester fiber in the field of warm-keeping antibacterial textiles, the light heat storage antibacterial polyester fiber is knitted into a gray cloth, which is washed at 40-45℃ for 15-20min, pre-shrunk at 100-105℃ for 20-25s, and set at 120-125℃ for 35-40s to obtain the light heat storage antibacterial knitted fabric.

[0033] The beneficial effects of the application are:

[0034] (1) The 90-96 parts of PET chips by weight in the application guarantee the core mechanical properties of the fiber matrix; 2-4 parts of modified bixite realize high-efficiency light heat storage performance; 1-2 parts of modified tea saponin-montmorillonite realize long-acting antibacterial and auxiliary dispersion functions; and 0.1-0.2 parts of glycerol monostearate play the role of auxiliary lubrication, thereby improving the high light-heat conversion efficiency, antibacterial performance and mechanical properties of the fiber, and avoiding the risk of metal ion migration and improving the environmental friendliness.

[0035] (2) The modified bixite provided by the application is rich in metal ions such as Fe 3+ and Ti 4+ in bixite, and the pyrophosphoric acid group in NDZ-101 can form stable coordination bonds with Fe 3+ and Ti 4+ on the surface of bixite, which can significantly reduce the agglomeration of bixite powder caused by the electrostatic attraction of metal ions; the long-chain alkyl group at the other end of the NDZ-101 molecule can form van der Waals force with the ester group of the PET molecular chain, which can effectively reduce the interfacial tension and avoid the “interfacial slip” phenomenon during melt flow, thereby reducing the spinning breakage rate.

[0036] (3) The modified tea saponin-montmorillonite provided by the application grafts tea saponin (a natural glycoside antibacterial agent) to the interlayer of sodium-based montmorillonite through epichlorohydrin, the layered structure of the montmorillonite can fix the tea saponin, solving the problem of easy water washing loss of the bio-based antibacterial agent, and the lamella can block the agglomeration of bixite particles, realizing the dual functions of antibacterial and dispersion.

[0037] (4) The bixite modified by NDZ-101 has a weak positive charge on the surface, which can form electrostatic attraction with the modified tea saponin-montmorillonite, so that the lamella of the montmorillonite is uniformly adsorbed on the surface of the bixite, improving the dispersibility of the components and reducing the agglomeration; in combination with the electrostatic synergy of the supercritical CO2 assisted dispersion and the modified tea saponin-montmorillonite, the dispersion uniformity of the functional particles in the PET is improved, and a large amount of dispersant does not need to be additionally added, which takes into account the dispersing effect and economy. DETAILED DESCRIPTION

[0038] In order to make the above-mentioned purposes, features and advantages of the application more obvious and easy to understand, the specific embodiments of the application are described in detail below.

[0039] In some embodiments, a light-heat storage antibacterial polyester fiber includes 90-96 parts of PET chips, 2-4 parts of modified bixite, 1-2 parts of modified tea saponin-montmorillonite and 0.1-0.2 parts of glycerol monostearate by weight.

[0040] When the content of PET chip is less than 90 parts, the continuous phase of PET is destroyed when the content of functional components is too high, and the fiber is easy to break, which cannot meet the mechanical requirements of textile weaving and use; when the content of PET chip is higher than 96 parts, the content of functional components is insufficient, and the light storage efficiency and antibacterial rate decrease. When the content of modified bixie is less than 2 parts, the concentration of metal ions is insufficient, the light energy absorption efficiency is low, and the heat storage effect is weak; when the content of modified bixie is higher than 4 parts, bixie is easy to agglomerate, which leads to uneven melt viscosity during spinning, increased breakage rate, and rough fiber hand feeling. When the content of modified tea saponin-montmorillonite is less than 1 part, the content of tea saponin is insufficient, the antibacterial rate is too low, and the montmorillonite layer is too few, which increases the risk of bixie agglomeration; when the content of modified tea saponin-montmorillonite is higher than 2 parts, the montmorillonite layer is too much and easy to stack, which leads to increased fiber rigidity, poor hand feeling, and easy precipitation of tea saponin. When the content of glycerol monostearate is less than 0.1 part, the lubricating effect is insufficient; when the content of glycerol monostearate is higher than 0.2 part, the excess lubricant is easy to migrate to the surface of the fiber, which leads to decreased fiber cohesion, easy yarn breakage during weaving, and affected skin-friendliness of the fabric.

[0041] In some embodiments, the modified bixie is prepared by the following steps:

[0042] Step 1: Take bixie powder, add isopropyl alcohol solution, ultrasonic dispersion, and form a suspension;

[0043] Step 2: Add titanium ester coupling agent NDZ-101 dropwise, heat and stir; centrifugal separation, vacuum drying, and obtain modified bixie.

[0044] In some embodiments, the particle size of the bixie powder is between 60-80 nm. Using 60-80 nm bixie powder can balance the specific surface area and dispersity, and ensure the light storage efficiency.

[0045] In some embodiments, the weight ratio of bixie powder, isopropyl alcohol, and titanium ester coupling agent is (2.5-3.5):(40-45):(0.1-0.2). This ratio can achieve uniform modification of bixie and cost balance.

[0046] In some embodiments, the ultrasonic dispersion time is 40-50 min, the power is 350-400 W, and the frequency is 28-30 kHz, which can achieve uniform suspension of bixie.

[0047] In some embodiments, the heating and stirring is stirring at 70-75℃ for 120-150 min; the centrifugal separation is centrifugal separation at 9000-10000 rpm for 15-20 min.

[0048] In some embodiments, the modified tea saponin-montmorillonite is prepared by the following steps:

[0049] Step 1: Take sodium-based montmorillonite, add deionized water, and stir uniformly to prepare a montmorillonite suspension;

[0050] Step 2, add tea saponin, epichlorohydrin, adjust pH to 8.8-9.0, heat reaction; collect the product by filtration, vacuum drying, crushing to 100-150 nm, to obtain modified tea saponin-montmorillonite.

[0051] In some embodiments, the particle size of the sodium-based montmorillonite is between 100-150 nm. Montmorillonite of 100-150 nm can balance the dispersion of the sheet layer and the grafting efficiency of the antibacterial agent.

[0052] In some embodiments, the weight ratio of the sodium-based montmorillonite, deionized water, tea saponin and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35). This ratio can guarantee the grafting efficiency and functional stability.

[0053] In some embodiments, the heating reaction is heating to 65-70℃ and stirring for 5-6h. Suitable experimental conditions can guarantee sufficient grafting and stability of the antibacterial agent.

[0054] In some embodiments, the vacuum drying is drying at 75-80℃ under vacuum for 4-6h. This can avoid the easy production of bubbles during subsequent spinning, guaranteeing the spinning quality.

[0055] In some embodiments, the viscosity of the PET chip is 0.6-0.7dL / g, and the melting point is 255-260℃. When the viscosity is <0.6dL / g, the PET molecular weight is low and the fiber tensile strength is insufficient; when the viscosity is >0.7dL / g, the melt viscosity is high and spinning is difficult. When the melting point is not within 255-260℃, the melting blending temperature does not match, which can easily lead to PET degradation or insufficient melting, affecting the fiber performance.

[0056] A preparation method of a light-heat-storage antibacterial polyester fiber, comprising the following steps:

[0057] S1, adding PET chip, modified tourmaline, modified tea saponin-montmorillonite and glycerol monostearate into the hopper of a twin-screw extruder; introducing supercritical CO2 into the screw segment, melt blending; filtering through a 25μm filter screen to obtain a polyester composite melt;

[0058] S2, spinning the polyester composite melt to obtain a nascent fiber; after cooling, the nascent fiber is stretched, set, and wound to obtain a light-heat-storage antibacterial polyester fiber.

[0059] Supercritical CO2 is used for auxiliary dispersion, which can reduce the melt viscosity and promote the uniform distribution of functional particles.

[0060] In some embodiments, the temperature of the supercritical CO2 is 38-39℃, the pressure is 12.8-13MPa, and the flow rate is 6.5-6.8L / kg PET.

[0061] In some embodiments, the melt blending parameters are a zone 235-240℃, a zone 245-250℃, a zone 260-265℃, a zone 255-260℃, a screw rotation speed 280-300rpm, and a melt residence time 2.5-3min. When the temperature is lower than the range, the PE is not fully melted and the mixture is not uniform; when the temperature is higher than the range, the PET is degraded, the fiber is yellow and the mechanical properties are decreased.

[0062] In some embodiments, the spinning temperature is 260-262℃, the spinneret aperture is 0.22mm, and the number of holes is 48. By limiting the number of holes, the spinning efficiency and fiber uniformity can be balanced to meet the weaving needs of textiles.

[0063] In some embodiments, the draw ratio is 3.2-3.3, the temperature is 88-90℃, the setting condition is 110-115℃ for 25-28s, and the winding speed is 3500-3600m / min. If the draw ratio is too low, the fiber has low crystallinity and insufficient strength; if the ratio is too high, the fiber is prone to breakage. If the temperature is too low, the fiber is difficult to stretch and stress concentration occurs; if the temperature is too high, the fiber has high thermal shrinkage and is difficult to set.

[0064] In some embodiments, the application of a light-accumulating heat-resistant antibacterial polyester fiber in the field of warm-keeping antibacterial textiles involves weaving the light-accumulating heat-resistant antibacterial polyester fiber into a gray cloth, washing the gray cloth in water at 40-45℃ for 15-20min, pre-shrinking the gray cloth at 100-105℃ for 20-25s, and setting the gray cloth at 120-125℃ for 35-40s to obtain a light-accumulating heat-resistant antibacterial knitted fabric. By limiting the weaving parameters, the cleanliness, dimensional stability, and functional retention of the fabric are ensured.

[0065] The specific embodiments of the present application are described in detail below, but it should be understood that the scope of protection of the present application is not limited by the specific embodiments.

[0066] Embodiment 1:

[0067] The present embodiment provides a light-accumulating heat-resistant antibacterial polyester fiber, a preparation method thereof, and an application thereof, which comprises the following steps:

[0068] S1. Take 3.0 parts by weight of natural orange bixie powder, add 40 parts by weight of isopropyl alcohol solution, and ultrasonically disperse for 40min (power 350W, frequency 28kHz) to form a suspension;

[0069] Drop 0.15 parts by weight of titanium coupling agent NDZ-101, and stir at 70℃ for 120min (rotation speed 350rpm); centrifugal separation (rotation speed 9000rpm, 18min), and vacuum drying at 80℃ for 4h to obtain modified bixie;

[0070] S2, 1.2 parts by weight of sodium-based montmorillonite was added to 80 parts by weight of deionized water, stirred for 30 min (speed 250 rpm) to prepare a montmorillonite suspension;

[0071] 0.8 parts by weight of tea saponin and 0.3 parts by weight of epichlorohydrin were added, the pH was adjusted to 9.0, and the reaction was carried out at 65°C for 5 h; the product was collected by filtration and dried at 75°C under vacuum for 4 h, and then ground to 100-150 nm to obtain modified tea saponin-montmorillonite;

[0072] S3, 94 parts by weight of PET chips, 3.0 parts by weight of modified bixite, 1.5 parts by weight of modified tea saponin-montmorillonite, and 0.15 parts by weight of glycerol monostearate were added to the hopper of a twin-screw extruder; supercritical CO2 was introduced into the screw section (temperature 38°C, pressure 13 MPa, flow rate 6.5 L / kgPET), and the melt blending parameters were: zone 1 235°C, zone 2 250°C, zone 3 260°C, zone 4 255°C, screw speed 280 rpm, and melt residence time 2.8 min; the polyester composite melt without agglomeration was obtained by filtering through a 25 μm filter screen;

[0073] S4, the melt was transported to a spinning box, the spinning temperature was 260°C, the spinneret aperture was 0.22 mm, the number of holes was 48, the cooling air temperature was 23°C, the air speed was 0.7 m / s, the nascent fiber was drawn (3.3 times, temperature 88°C), set (115°C, 25 s), and wound (3600 m / min) to obtain light heat-accumulating antibacterial polyester fiber;

[0074] The light heat-accumulating antibacterial polyester fiber was woven into a gray fabric on a circular weft knitting machine, washed in water at 45°C for 15 min, pre-shrunk at 105°C for 20 s, and set at 125°C for 35 s to obtain a light heat-accumulating antibacterial knitted fabric.

[0075] Example 2:

[0076] The difference between this example and Example 1 is that the proportions of the components of the light heat-accumulating antibacterial polyester fiber were adjusted, and the specific implementation steps of S3 are as follows:

[0077] S3, 96 parts by weight of PET chips, 2 parts by weight of modified bixite, 1 part by weight of modified tea saponin-montmorillonite, and 0.1 parts by weight of glycerol monostearate were added to the hopper of a twin-screw extruder; supercritical CO2 was introduced into the screw section (temperature 39°C, pressure 13 MPa, flow rate 6.6 L / kgPET), and the melt blending parameters were: zone 1 235°C, zone 2 250°C, zone 3 265°C, zone 4 258°C, screw speed 280 rpm, and melt residence time 2.8 min; the polyester composite melt without agglomeration was obtained by filtering through a 25 μm filter screen;

[0078] The remaining raw materials and preparation process were the same as in Example 1.

[0079] Example 3:

[0080] The difference between this embodiment and Embodiment 1 is that the proportions of each component of the light-heat-storing antibacterial polyester fiber are adjusted. The specific implementation steps of S3 are as follows:

[0081] S3. Add 90 parts by weight of PET chips, 4 parts by weight of modified tourmaline, 2 parts by weight of modified tea saponin-montmorillonite, and 0.2 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.7L / kgPET) into the screw section; melt blending parameters: zone 1 238℃, zone 2 248℃, zone 3 262℃, zone 4 255℃, screw speed 290rpm, melt residence time 3min; filter through a 25μm filter screen to obtain a non-agglomerated polyester composite melt;

[0082] The remaining raw materials and preparation process are the same as in Example 1.

[0083] Example 4:

[0084] The difference between this embodiment and Example 1 is that the weight ratio of tourmaline powder, isopropanol, and titanate coupling agent is adjusted. The specific implementation steps of S1 are as follows:

[0085] S1. Take 3.5 parts by weight of natural orange tourmaline powder, add 45 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension.

[0086] Add 0.1 parts by weight of titanate coupling agent NDZ-101, stir at 75°C for 150 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline;

[0087] The remaining raw materials and preparation process are the same as in Example 1.

[0088] Example 5:

[0089] The difference between this embodiment and Example 1 is that the weight ratio of tourmaline powder, isopropanol, and titanate coupling agent is adjusted. The specific implementation steps of S1 are as follows:

[0090] S1. Take 2.5 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 45 minutes (power 380W, frequency 30kHz) to form a suspension;

[0091] Add 0.2 parts by weight of titanate coupling agent NDZ-101, stir at 70°C for 120 min (350 rpm), centrifuge (10000 rpm, 15 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline;

[0092] The remaining raw materials and preparation process are the same as those in Example 1.

[0093] Example 6:

[0094] This example is different from Example 1 in that the weight ratio of sodium-based montmorillonite, deionized water, tea saponin and epichlorohydrin is adjusted, and the specific implementation steps of S2 are as follows:

[0095] S2, take 1.5 parts by weight of sodium-based montmorillonite, add 90 parts by weight of deionized water, stir for 30 min (speed 250 rpm), and prepare a montmorillonite suspension;

[0096] Add 0.7 parts by weight of tea saponin and 0.35 parts by weight of epichlorohydrin, adjust the pH to 8.8, and react at 65°C for 6h; collect the product by filtration, vacuum dry at 75°C for 4h, and crush to 100-150nm to obtain modified tea saponin-montmorillonite;

[0097] The remaining raw materials and preparation process are the same as those in Example 1.

[0098] Example 7:

[0099] This example is different from Example 1 in that the weight ratio of sodium-based montmorillonite, deionized water, tea saponin and epichlorohydrin is adjusted, and the specific implementation steps of S2 are as follows:

[0100] S2, take 1 part by weight of sodium-based montmorillonite, add 85 parts by weight of deionized water, stir for 30 min (speed 250 rpm), and prepare a montmorillonite suspension;

[0101] Add 1 part by weight of tea saponin and 0.35 parts by weight of epichlorohydrin, adjust the pH to 9.0, and react at 68°C for 5h; collect the product by filtration, vacuum dry at 80°C for 4h, and crush to 100-150nm to obtain modified tea saponin-montmorillonite;

[0102] The remaining raw materials and preparation process are the same as those in Example 1.

[0103] Comparative Example 1:

[0104] This comparative example is different from Example 1 in that the coupling agent of bixite is different (KH-550), and the specific implementation steps of S1 are as follows:

[0105] S1, take 3.0 parts by weight of natural orange bixite powder, add 40 parts by weight of isopropyl alcohol solution, ultrasonic dispersion for 40 min (power 350 W, frequency 28 kHz), and form a suspension;

[0106] Drop 0.15 parts by weight of KH-550, stir at 70°C for 120 min (rotation speed 350 rpm); centrifugal separation (rotation speed 9000 rpm, 18 min), vacuum drying at 80°C for 4 h, to obtain modified bixie;

[0107] The remaining raw materials and preparation process remain the same as in Example 1.

[0108] Comparative Example 2:

[0109] This comparative example is different from Example 1 in that the bixie is not modified with a coupling agent, and the specific implementation steps are as follows:

[0110] S1, take 1.2 parts by weight of sodium-based montmorillonite, add 80 parts by weight of deionized water, stir for 30 min (rotation speed 250 rpm), and prepare a montmorillonite suspension;

[0111] Add 0.8 parts by weight of tea saponin and 0.3 parts by weight of epichlorohydrin, adjust the pH to 9.0, and react at 65°C for 5 h; filter the product, vacuum dry at 75°C for 4 h, and crush to 100-150 nm to obtain modified tea saponin-montmorillonite;

[0112] S2, add 94 parts by weight of PET chips, 3.0 parts by weight of bixie, 1.5 parts by weight of modified tea saponin-montmorillonite, and 0.15 parts by weight of glycerol monostearate to the hopper of the twin-screw extruder; introduce supercritical CO2 (temperature 38°C, pressure 13 MPa, flow rate 6.5 L / kgPET) into the screw section; melt blending parameters: zone 1 235°C, zone 2 250°C, zone 3 260°C, zone 4 255°C, screw rotation speed 280 rpm, melt residence time 2.8 min; filter through a 25μm filter screen to obtain a polyester composite melt without agglomeration;

[0113] S3, convey the melt to a spinning box, the spinning temperature is 260°C, the spinneret hole diameter is 0.22mm, the number of holes is 48; the cooling air temperature is 23°C, the wind speed is 0.7m / s, the nascent fiber is stretched (3.3 times, temperature 88°C), set (115°C, 25s), and wound (3600m / min) to obtain light heat-accumulating antibacterial polyester fiber;

[0114] The light heat-accumulating antibacterial polyester fiber is knitted into a gray fabric on a circular weft knitting machine, washed in water at 45°C for 15 min, pre-shrunk at 105°C for 20s, and set at 125°C for 35s to obtain a light heat-accumulating antibacterial knitted fabric.

[0115] The remaining raw materials and preparation process remain the same as in Example 1.

[0116] Comparative Example 3:

[0117] This comparative example is different from Example 1 in that the modified tea saponin-montmorillonite is replaced by conventional chitosan, and the specific implementation steps are as follows:

[0118] S1, take 3.0 parts by weight of natural orange bixie powder, add 40 parts by weight of isopropyl alcohol solution, ultrasonic dispersion for 40 min (power 350 W, frequency 28 kHz), form a suspension;

[0119] Drop 0.15 parts by weight of titanium coupling agent NDZ-101, stir at 70℃ for 120 min (speed 350 rpm); centrifugal separation (speed 9000 rpm, 18 min), vacuum drying at 80℃ for 4h, to obtain modified bixie;

[0120] S2, add 94 parts by weight of PET chips, 3.0 parts by weight of modified bixie, 1.5 parts by weight of chitosan, 0.15 parts by weight of glycerol monostearate into the hopper of the twin-screw extruder; supercritical CO2 is introduced into the screw segment (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET), melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter screen to obtain a polyester composite melt without aggregation;

[0121] S3, the melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret hole diameter is 0.22mm, the number of holes is 48; the cooling wind is 23℃, the wind speed is 0.7m / s, the nascent fiber is stretched (3.3 times, temperature 88℃), set (115℃, 25s), and wound (3600m / min) to obtain light heat-accumulating antibacterial polyester fiber;

[0122] The light heat-accumulating antibacterial polyester fiber is woven into a gray fabric on a circular weft knitting machine, washed at 45℃ for 15min, pre-shrunk at 105℃ for 20s, and set at 125℃ for 35s to obtain a light heat-accumulating antibacterial knitted fabric.

[0123] The remaining raw materials and preparation process are the same as those of Example 1.

[0124] Comparative Example 4:

[0125] This comparative example is different from Example 1 in that no epichlorohydrin is added, and the specific implementation steps of S2 are as follows:

[0126] S2, take 1.5 parts by weight of sodium-based montmorillonite, add 80 parts by weight of deionized water, stir for 30 min (speed 250 rpm) to prepare a montmorillonite suspension;

[0127] Add 1 part by weight of tea saponin, adjust the pH to 9.0, and react at 65℃ for 5h; collect the product by filtration, vacuum dry at 75℃ for 4h, and crush to 100-150nm to obtain modified tea saponin-montmorillonite;

[0128] The remaining raw materials and preparation process are the same as those in Example 1.

[0129] Comparative Example 5:

[0130] This comparative example is different from Example 1 in that no modified tea saponin-montmorillonite is added, and the specific implementation steps are as follows:

[0131] S1, take 3.0 parts by weight of natural orange bixie powder, add 40 parts by weight of isopropyl alcohol solution, ultrasonic dispersion for 40 min (power 350 W, frequency 28 kHz), form a suspension;

[0132] Drop 0.15 parts by weight of titanium coupling agent NDZ-101, stir at 70°C for 120 min (speed 350 rpm); centrifugal separation (speed 9000 rpm, 18 min), vacuum drying at 80°C for 4h, to obtain modified bixie;

[0133] S2, add 95 parts by weight of PET chips, 3.5 parts by weight of modified bixie, and 0.2 parts by weight of glycerol monostearate to the hopper of the twin-screw extruder; supercritical CO2 is introduced into the screw segment (temperature 38°C, pressure 13MPa, flow rate 6.5L / kgPET), melt blending parameters: zone 1 235°C, zone 2 250°C, zone 3 260°C, zone 4 255°C, screw speed 280 rpm, melt residence time 2.8 min; filter through a 25μm filter screen to obtain a polyester composite melt without agglomeration;

[0134] S3, the melt is conveyed to a spinning box, the spinning temperature is 260°C, the spinneret hole diameter is 0.22mm, the number of holes is 48; the cooling air temperature is 23°C, the wind speed is 0.7m / s, the nascent fiber is stretched (3.3 times, temperature 88°C), set (115°C, 25s), and wound (3600m / min) to obtain light heat-accumulating antibacterial polyester fiber;

[0135] The light heat-accumulating antibacterial polyester fiber is knitted into a gray fabric on a circular weft knitting machine, washed at 45°C for 15 min, pre-shrunk at 105°C for 20s, and set at 125°C for 35s to obtain a light heat-accumulating antibacterial knitted fabric.

[0136] The remaining raw materials and preparation process are the same as those in Example 1.

[0137] Comparative Example 6:

[0138] This comparative example is different from Example 1 in that the bixie is not modified with a coupling agent, and the modified tea saponin-montmorillonite is replaced by conventional chitosan, and the specific implementation steps are as follows:

[0139] S1, take 1.2 parts by weight of sodium-based montmorillonite, add 80 parts by weight of deionized water, stir for 30 min (speed 250 rpm) to prepare a montmorillonite suspension;

[0140] 0.8 parts by weight of tea saponin, 0.3 parts by weight of epichlorohydrin were added, the pH was adjusted to 9.0, and reaction was carried out at 65°C for 5h; the product was collected by filtration and dried at 75°C under vacuum for 4h, and then ground to 100-150nm to obtain modified tea saponin-montmorillonite;

[0141] S2, 94 parts by weight of PET chips, 3.0 parts by weight of bixbite, 1.5 parts by weight of chitosan, and 0.15 parts by weight of glycerol monostearate were added to the hopper of the twin-screw extruder; supercritical CO2 (temperature 38°C, pressure 13MPa, flow rate 6.5L / kgPET) was introduced into the screw section, and the melt blending parameters were: zone 1 235°C, zone 2 250°C, zone 3 260°C, zone 4 255°C, screw rotation speed 280rpm, and melt residence time 2.8min; the polyester composite melt without aggregation was obtained by filtering through a 25μm filter screen;

[0142] S3, the melt was conveyed to a spinning box, the spinning temperature was 260°C, the spinneret aperture was 0.22mm, and the number of holes was 48; the cooling air temperature was 23°C, the air speed was 0.7m / s, the nascent fiber was stretched (3.3 times, temperature 88°C), set (115°C, 25s), and wound (3600m / min) to obtain the light heat-accumulating antibacterial polyester fiber;

[0143] The light heat-accumulating antibacterial polyester fiber was knitted into a gray fabric on a circular weft knitting machine, and the gray fabric was washed at 45°C for 15min, pre-shrunk at 105°C for 20s, and set at 125°C for 35s to obtain the light heat-accumulating antibacterial knitted fabric.

[0144] The remaining raw materials and preparation process were the same as those of Example 1.

[0145] Performance test

[0146] 1. Light heat-accumulating performance (400W / m 2 ): According to GB / T 18319-2019 “Textiles - Test method for light heat-accumulating performance”, the light heat-accumulating performance of the light heat-accumulating antibacterial polyester fiber obtained in each example and the comparative example of the present application was tested;

[0147] 2. Antibacterial performance: According to GB / T 20944.3-2008 “Textiles - Evaluation of antibacterial properties - Part 3: Shake flask method”, the antibacterial performance (Escherichia coli / Staphylococcus aureus) of the light heat-accumulating antibacterial polyester fiber obtained in each example and the comparative example of the present application was tested;

[0148] 3. Breaking strength: According to GB / T 14344-2022 “Chemical fibers - Test method for filament tensile properties”, the breaking strength of the light heat-accumulating antibacterial polyester fiber obtained in each example and the comparative example of the present application was tested;

[0149] 4. Wash resistance: The light-heat storage antibacterial polyester fibers obtained from each embodiment and comparative example of the present application were tested for wash resistance according to GB / T 8629-2017 "Textiles - Household laundry and drying procedures for test purposes";

[0150] The results are shown in Table 1:

[0151] Table 1

[0152]

[0153] As can be seen from Table 1, the light-heat storage performance of the embodiments is excellent, with an average temperature rise of 5.6-6.2°C. This is because the energy level transition of Fe 3+ / Fe 2+ , Ti 4+ in bixite can efficiently absorb light energy in the 400-1100 nm band, and the pyrophosphoric acid group of NDZ-101 forms a stable coordination bond with the metal ions on the surface of bixite, ensuring stable light-heat conversion performance. The antibacterial rate is higher than 90% after 50 washes, because the epoxy chloropropane end of the modified tea saponin-montmorillonite forms an ether bond with the hydroxyl group of tea saponin, and the other end forms a covalent bond with the Si-OH of montmorillonite, so that the loss rate of tea saponin is low during washing. The PET chip ensures the continuous phase structure of the matrix, and the lubricating effect of glycerol monostearate avoids the melt fracture caused by excessive functional components. And the lamellar support of modified tea saponin-montmorillonite can supplement part of the mechanical strength to meet the weaving demand of textiles. The average light-heat storage temperature of Example 1 is still 5.8°C after 50 washes, which is much higher than 4.1°C of Comparative Example 3. This is because the coordination bond structure of modified bixite and the interlayer fixation of modified tea saponin-montmorillonite together improve the wash resistance. The specific reason is that the modification of NDZ-101 makes the bixite firmly anchored in the PET matrix, which is not easy to fall off during washing; the layered barrier structure of montmorillonite protects tea saponin from water flow erosion.

[0154] The KH-550 used in Comparative Example 1 can only form hydrogen bonds with the surface hydroxyl groups of bixite and cannot form strong coordination bonds with metal ions like NDZ-101; meanwhile, the KH-550 lacks compatibility with long-chain alkyl groups and PET, thus leading to a sharp drop in light heat storage and mechanical properties; in Comparative Example 2, the unmodified bixite leads to a decrease in light energy absorption efficiency, and the average temperature rise is only 4.5℃; and the particle agglomeration leads to a decrease in fiber breaking strength to 3.1 cN / dtex. In Comparative Example 3, the modified tea saponin-montmorillonite is replaced by chitosan, and the conventional chitosan lacks an interlayer fixed structure and is easily dissolved and lost during washing, so that the antibacterial rate against E. coli decreases from 98.5% to 76.3% after 50 times of washing; meanwhile, the chitosan has poor interfacial compatibility with PET, and the light heat storage wash resistance retention rate decreases significantly. In Comparative Example 4, the tea saponin is only attached to the interlayer of the montmorillonite through physical adsorption due to the lack of covalent grafting of epoxy chloropropane, and the loss rate is high after 50 times of washing, thus leading to a decrease in the antibacterial rate; and without the action of epoxy chloropropane, the interlayer spacing of the montmorillonite cannot be expanded, the embedding effect of bixite decreases, and the light heat storage wash resistance retention rate decreases. In Comparative Example 5, the lack of modified tea saponin-montmorillonite leads to a lack of dispersibility and antibacterial function, because of the lack of physical barrier of the montmorillonite sheet, the agglomeration rate of bixite increases, and the average temperature rise of light heat storage decreases to 5.2℃; and the lack of antibacterial components leads to a lack of antibacterial performance of the fiber, and the dispersing auxiliary effect of the montmorillonite disappears. In Comparative Example 6, the unmodified bixite and the use of chitosan instead lead to the dual defects of high agglomeration rate of the unmodified bixite and low wash resistance of chitosan, so that the average temperature rise of light heat storage is only 4.3℃, the antibacterial rate decreases to 74.6% after 50 times of washing, and the fiber breaking strength decreases to 3.0 cN / dtex, which verifies the necessity of using the modified bixite and the modified tea saponin-montmorillonite system in the present application.

[0155] The above disclosure is only several specific embodiments of the present application, but the embodiments of the present application are not limited thereto, and any changes that can be thought of by those skilled in the art shall fall within the protection scope of the present application.

Claims

1. A light-retaining, heat-storing, antibacterial polyester fiber, characterized in that, 90-96 parts by weight of PET chips, 2-4 parts by weight of modified bixbite, 1-2 parts by weight of modified tea saponin-montmorillonite, and 0.1-0.2 parts by weight of glycerol monostearate; The modified bixbite is prepared by the following steps: Step 1: Take bixbite powder, add isopropanol solution, ultrasonic dispersion, and form a suspension; Step 2: Add titanium ester coupling agent NDZ-101 dropwise, heat and stir; centrifugal separation, vacuum drying, to obtain modified bixbite; The particle size of the bixbite powder is between 60-80 nm; the ultrasonic dispersion time is 40-50 min, the power is 350-400 W, and the frequency is 28-30 kHz; the heating and stirring is stirring at 70-75℃ for 120-150 min; the centrifugal separation is centrifugation at 9000-10000 rpm for 15-20 min; the vacuum drying is drying at 75-80℃ under vacuum for 4-6 h; The modified tea saponin-montmorillonite is prepared by the following steps: Step 1: Take sodium-based montmorillonite, add deionized water, stir evenly, and prepare a montmorillonite suspension; Step 2: Add tea saponin and epichlorohydrin, adjust the pH to 8.8-9.0, heat and react; filter the product, vacuum dry, and crush to 100-150 nm to obtain modified tea saponin-montmorillonite; The particle size of the sodium-based montmorillonite is between 100-150 nm; the heating reaction is heating to 65-70℃ for 5-6 h; the vacuum drying is drying at 75-80℃ under vacuum for 4-6 h.

2. The light-accumulating antibacterial polyester fiber according to claim 1, characterized by The weight ratio of the bixbite powder, isopropanol, and titanium ester coupling agent is (2.5-3.5):(40-45):(0.1-0.2).

3. The light-accumulating antibacterial polyester fiber according to claim 1, characterized by The weight ratio of the sodium-based montmorillonite, deionized water, tea saponin, and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35).

4. The light-accumulative antibacterial polyester fiber according to claim 1, characterized in that, The viscosity of the PET chips is 0.6-0.7 dL / g, and the melting point is 255-260℃.

5. A method for preparing a light-storing, heat-retaining, antibacterial polyester fiber, characterized in that, A method for preparing the light-heat-storage antibacterial polyester fiber of any one of claims 1-4, comprising the following steps: S1: Add PET chips, modified bixbite, modified tea saponin-montmorillonite, and glycerol monostearate into the hopper of a twin-screw extruder; introduce supercritical CO2 into the screw segment, melt blend; filter through a 25μm filter screen to obtain a polyester composite melt; S2: Spin the polyester composite melt to obtain a nascent fiber; after cooling, stretch, set, and wind the nascent fiber to obtain a light-heat-storage antibacterial polyester fiber.

6. The method for preparing a photothermal heat-storing antibacterial polyester fiber according to claim 5, characterized in that, The temperature of the supercritical CO2 is 38-39℃, the pressure is 12.8-13 MPa, and the flow rate is 6.5-6.8 L / kg PET; The melt blending parameters are zone 1: 235-240℃, zone 2: 245-250℃, zone 3: 260-265℃, zone 4: 255-260℃, screw rotation speed: 280-300 rpm, and melt residence time: 2.5-3 min.

7. The method for preparing a photothermal heat-storing antibacterial polyester fiber according to claim 5, characterized in that, The spinning temperature is 260-262℃, the spinneret hole diameter is 0.22 mm, and the number of holes is 48. The stretching multiple is 3.2-3.3 times, the temperature is 88-90 DEG C; the setting condition is 110-115 DEG C, 25-28s; the winding speed is 3500-3600 m / min.

8. The use of the light heat-accumulating antibacterial polyester fiber in the field of warm-keeping antibacterial textiles, characterized in that, The application of the light-accumulating heat antibacterial polyester fiber is prepared by the preparation method in any one of claims 5-7. The application step comprises: weaving the light-accumulating heat antibacterial polyester fiber into a gray cloth, washing in water at 40-45 DEG C for 15-20 min, pre-shrinking at 100-105 DEG C for 20-25 s, setting at 120-125 DEG C for 35-40 s, to obtain a light-accumulating heat antibacterial knitted fabric.

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