Preparation method of intelligent temperature control textile based on phase change microcapsules

Abstract

The invention relates to the technical field of non-woven materials and engineering, in particular to a preparation method of an intelligent temperature control textile based on phase-change microcapsules, which comprises the following steps: adding a polyurethane prepolymer and a composite phase-change material into a three-neck flask, heating to 80-100 DEG C to enable each component to be in a molten state, and stirring to obtain a mixture; putting the mixture into a high-speed shearing emulsifying machine, slowly increasing the rotating speed to 8000-9000r / min, slowly adding a certain amount of deionized water containing 1-2g / L of defoaming agent DM8317 within 30-40min, stirring for 60-120min to obtain a uniform emulsion, reducing the rotating speed to 400-450r / min, adding 1-2g of initiator potassium persulfate, heating to 50-70 DEG C, reacting for 3-4h, and cooling to room temperature to obtain the high-speed emulsion. The graphene A is co-modified by methoxytrimethylsilane and silane containing an epoxy group, a hydrophilic group is closed, bonding between the graphene A and polyurethane is improved, migration and dissolution are prevented, the optimization ratio is 1: 6: 1.5, and the graphene A is soft, wear-resistant and high in strength due to compounding of isocyanate; epoxy resin is added, so that bonding is improved, and hand feeling and moisture permeability are guaranteed. Graphene is added into the core material and the wall material, so that the temperature adjusting speed is increased.

Description

Technical Field

[0001] This invention relates to the field of nonwoven materials and engineering technology, and in particular to a method for preparing intelligent temperature-controlled textiles based on phase change microcapsules. Background Technology

[0002] Traditional textiles mostly reduce the severe impact of temperature changes on human physical and mental health by changing the fabric structure or fiber type, but they cannot simultaneously achieve both comfort and functionality. Phase change intelligent temperature control textiles can absorb or release a large amount of heat during the phase change process, maintaining a relatively constant temperature within the microclimate of the human body and clothing for a certain period of time. This can effectively prevent heat stress and meet the human body's comfort needs under extreme environmental conditions.

[0003] Currently, the main methods for preparing phase change intelligent temperature-controlled textiles include hollow fiber impregnation and filling, spinning, and finishing. Hollow fiber impregnation refers to the method of preparing temperature-regulating fibers by adsorbing and storing phase change materials inside the pores of hollow fibers. However, after multiple phase change processes, the phase change material easily migrates out of the fibers, severely limiting its performance. Spinning involves suspending phase change microcapsules in a spinning solution and forming fibers through spinning (such as electrospinning, wet spinning, and melt spinning), or mixing encapsulated phase change materials with other types of fibers before spinning into textiles. While textiles prepared by this method have good washability, they also suffer from drawbacks such as complex manufacturing processes, high costs, and poor uniformity. Post-treatment methods refer to the temporary or permanent attachment of phase change materials to fabrics in the form of finishing solutions through impregnation, padding, coating, etc. This method has advantages such as simple operation, relatively low cost, and wide applicability to fibers. However, the adhesives used in this method reduce the softness, flexibility, breathability, and moisture permeability of the fabric, ultimately affecting wearing comfort. To solve the adhesive problem, CN116024821A discloses a finishing method for textiles with phase change microcapsules. The shell material of the phase change microcapsules prepared by this method is a diacetone acrylamide-adipate dihydrazide type self-crosslinking resin. During the drying process, the active ketone carbonyl groups in the shell material react with the active α-H in the adipate dihydrazide under weakly acidic conditions, gradually completing the crosslinking reaction. The microcapsule particles self-crosslink to form a thin film, which is ultimately stably adsorbed onto the surface or pores of the textile. While the microcapsules prepared by this method form a thin film through self-crosslinking, the effect on improving the bonding force between the microcapsules and fibers is not significant, thus limiting the improvement in the durability of the effect.

[0004] Currently, phase change materials (PCMs) mainly include organic, inorganic, and composite PCMs. Among them, organic PCMs, with their diverse types, non-toxicity, and lack of supercooling requirement, are the most studied PCMs. Paraffin wax lacks functional groups and freely moving electrons, thus exhibiting high chemical stability. During PCM, it does not cause chemical reactions or damage to other materials. This chemical inertness, combined with paraffin wax's high heat storage density, allows it to store a large amount of thermal energy in a relatively small volume, making it a key focus in PCM research. It is well known that thermal conductivity is a major factor in enhancing heat transfer rates and plays a crucial role in melting and solidification. However, the irregular crystal structure of paraffin wax results in slow heat transfer during energy storage and release, leading to a significant decrease in the thermal performance of the heat storage system. To address the low thermal conductivity of paraffin wax PCMs, researchers have improved its thermal properties by combining it with other materials and incorporating metal nanoparticles. Studies have shown that graphene is the best material for improving the thermal conductivity of paraffin wax. However, the surface of unmodified graphene contains a large number of hydrophilic groups such as carboxyl, hydroxyl and epoxy groups, which makes its uniform dispersion in hydrophobic paraffin wax poor. How to improve the uniform dispersion of graphene in paraffin wax has become an urgent problem to be solved.

[0005] Furthermore, the thermal conductivity of the microcapsule wall material is also a crucial factor affecting its temperature control effect. To address the issue of poor wall material thermal conductivity, Qu Bingxian et al. (Research and Simulation of Thermal Transfer Characteristics of Graphene-Modified Phase Change Polyurethane Foaming Material, Packaging Materials, 2021, 42(11), 87-95) coated the surface of phase change microcapsules with a layer of graphene / sodium alginate composite material, increasing the thermal conductivity from 0.116 W·m⁻¹·K⁻¹ for uncoated microcapsules to 0.255 W·m⁻¹·K⁻¹. However, because this method involves coating the surface of commercially available phase change microcapsules with a thermally conductive material, rather than directly adding a thermally conductive material to the wall material encapsulating the phase change material, the improvement effect on the thermal conductivity of the phase change microcapsules is limited.

[0006] To address the aforementioned problems, this invention provides a phase change microcapsule that can form valence bonds with fibers and has good heat transfer efficiency, and a durable intelligent temperature-controlled textile is prepared by post-treatment. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing intelligent temperature-controlled textiles based on phase change microcapsules, which solves the problems of slow temperature regulation rate, poor washability, and the significant impact of phase change microcapsule finishing on the hand feel and moisture permeability of existing temperature-controlled textiles.

[0008] The technical solution adopted by this invention to solve its technical problem is: a method for preparing intelligent temperature-controlled textiles based on phase change microcapsules, characterized by comprising the following steps: (1) Preparation of aqueous phase change microcapsule emulsion Polyurethane prepolymer and composite phase change material were added to a three-necked flask and heated to 80-100 °C to bring all components to a molten state. The mixture was then placed in a high-speed shear emulsifier, and the rotation speed was slowly increased to 8000-9000 r / min. A certain amount of deionized water containing 1-2 g / L of defoamer DM8317 was slowly added over 30-40 min. The mixture was stirred for 60-120 min to obtain a homogeneous emulsion. The rotation speed was then reduced to 400-450 r / min, and 1-2 g of potassium persulfate initiator was added. The mixture was heated to 50-70 °C and reacted for 3-4 h. After cooling to room temperature, acetone was removed by rotary evaporation to obtain an aqueous phase change microcapsule emulsion.

[0009] The polyurethane prepolymer is made by the following steps: Polydiol was placed in a three-necked flask and heated to a molten state in a constant-temperature drying oven at 115-125°C. The temperature was then lowered to 50-60°C, and isocyanate was added. The temperature was raised to 60-70°C and reacted for 60-70 minutes. Then, 0.6-1 mL of dibutyltin dilaurate was added, and the temperature was raised to 70-80°C under reflux. The reaction was continued for 60-90 minutes. Modified graphene A, dimethylolpropionic acid, hydroxyethyl acrylate, epoxy resin, and 20-30 g of acetone were added. The temperature was raised to 80-90°C and reacted at a constant temperature for 60-90 minutes. The temperature was then lowered to 30-35°C to obtain the polyurethane prepolymer.

[0010] In the method for preparing the polyurethane prepolymer, the epoxy resin is one or more of EP-12, EP-13, EP-16 and EP-20; in the method for preparing the polyurethane prepolymer, the preferred mass ratio of diisocyanate, polydiol, modified graphene, dimethylolpropionic acid, hydroxyethyl acrylate and epoxy resin is 25:30:3:10:8:5.

[0011] The method for preparing modified graphene A includes the following steps: ultrasonically dispersing 5-10g of graphene in 500-550mL of deionized water, adding 50-80g of methoxytrimethylsilane, adjusting the stirrer speed to 300-400r / min, reacting at 30-40℃ for 60-120min, raising the temperature to 40-60℃, reacting for 30-60min, then adding 10-20g of 3-glycidyloxypropyltrimethoxysilane, continuing the reaction for 30-60min, thoroughly washing with deionized water, and drying.

[0012] The composite phase change material is made by the following steps. Place 100-110g of paraffin wax into a round-bottom flask, heat it to 80-100℃ to make it melt, add 0.3-0.5g of modified graphene B, and mix evenly while stirring at 500-550r / min.

[0013] The method for preparing modified graphene B includes the following steps: ultrasonically dispersing 5-10g of graphene in 500-550mL of deionized water, adding 80-120g of methoxytrimethylsilane, adjusting the stirring speed to 300-400r / min, reacting at 30-40℃ for 60-120min, raising the temperature to 40-60℃ and reacting for 60-90min, thoroughly washing with deionized water, and drying.

[0014] (2) Preparation of intelligent temperature-controlled textiles using phase change microcapsules The aqueous phase change microcapsule emulsion prepared in step (1) is applied to textiles using a two-dip and two-pick method, with a pick-up rate of 60-65%. The emulsion is pre-dried at 80-90℃ for 2-5 minutes and then baked at 140-160℃ for 3-5 minutes. The concentration of the aqueous phase change microcapsule emulsion is 60-100 g / L.

[0015] Preferably, in the preparation method of the phase change microcapsules, the mass percentage of polyurethane prepolymer to composite phase change material is 1:1.

[0016] Preferably, in the preparation method of the phase change microcapsules, the solid content of the aqueous phase change microcapsule emulsion is preferably 25%.

[0017] Preferably, the polydiol is any one of polycaprolactone diol (PCL), polyether diol (PPG), and polytetrahydrofuran diol (PTMEG).

[0018] Preferably, the diisocyanate is one or a mixture of several of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, and the preferred molar ratio of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate is 3:6:1.

[0019] Preferably, in the method for preparing modified graphene A, the mass ratio of graphene, methoxytrimethylsilane, and 3-glycidyloxypropyltrimethoxysilane is 1:6:1.5. Preferably, the textile is made of one or more of the following: natural cellulose fiber, regenerated fiber, polyamide fiber, and polyester fiber; the textile is one of the following: woven textile, knitted textile, and nonwoven textile.

[0020] Preferably, the high-speed shear emulsifier includes a base support, with rollers on all four sides of the bottom of the base support for overall movement of the equipment. A lifting support is vertically arranged on one side of the base support. Multiple guide rods are provided between the top and bottom of the inner wall of the lifting support and are correspondingly arranged. A motor mounting plate is provided at one end of the top of each guide rod, and a sliding guide sleeve is provided at the connection point. A shear emulsification mechanism is connected to one end of the motor mounting plate. The shear emulsification mechanism includes a drive motor. An output shaft is connected to one bottom end of the drive motor. Multiple positioning rods are provided at equal intervals around the output shaft. A stirring head is provided at the bottom of the output shaft and the positioning rods. An emulsification container is provided at the bottom of the stirring head, and multiple support legs are provided at the bottom of the emulsification container. A lifting drive assembly for driving the vertical lifting movement of the shear emulsification mechanism is provided on one side of the base support, and protective baffle assemblies are provided on both sides of the emulsification container. The combination of rollers and lifting supports enables convenient transfer and positioning of the equipment between different workstations, while ensuring structural stability and operational accessibility during emulsification operations. The structure of guide rods and sliding guide sleeves ensures smooth operation and accurate positioning during the lifting process, reducing eccentric loads and vibrations, which helps maintain the stability of shearing emulsification quality. The vertical lifting action driven by hydraulic cylinders facilitates quick switching of container height and processing posture, improving work efficiency and reducing manual handling and alignment intensity. The coordinated design of the stirring head and positioning rod enhances the structural strength and load distribution of the shearing mechanism, improving the emulsification stability and reliability of high-viscosity or multiphase systems. The protective baffle assembly effectively suppresses splashing, reduces cleaning difficulty and safety risks. The observation window enables process visualization. LED light groups provide uniform illumination of the working surface, improving the visibility of the operating environment and facilitating process judgment and quality control.

[0021] Preferably, the lifting drive assembly includes a fixed base associated with a base bracket. A hydraulic cylinder is mounted on the top of the fixed base, with a piston rod connected to one end of the hydraulic cylinder. The piston rod is connected to the bottom of a motor mounting plate. The lifting structure, with the hydraulic cylinder at its core, possesses excellent driving force and controllability, enabling smooth and precise lifting and lowering of the shearing emulsification mechanism, adapting to various working conditions and container specifications. The lifting process, through the direct connection between the piston rod and the motor mounting plate, shortens and simplifies the force transmission path, reducing gaps and loosening risks from intermediate links, and improving system stability and reliability. It facilitates rapid and controllable height adjustment, shortens process changeover time, and improves equipment operating efficiency and ease of operation.

[0022] Preferably, the protective baffle assembly includes a splash guard, which is bent towards the emulsification container to form a bent section. An observation window is located at the center of the outer wall of the splash guard, and an LED light group is located at the center of the inner wall of the bent section. The number of LED light groups is 20-30, arranged in an equally spaced array. The structural design of the bent section effectively reduces splash trajectory, decreases secondary splashing and cleaning frequency, and improves the hygiene and safety of the working environment. The observation window enables online visualization of the emulsification process, allowing operators to promptly grasp the dispersion and emulsification status, improving process controllability and quality consistency. The LED light group provides uniform supplementary lighting, eliminating shadows and uneven brightness on the working surface, improving detail visibility, assisting in judging emulsification quality, and reducing the risk of misoperation.

[0023] The advantages of this invention are: In the preparation of modified graphene A, this invention uses methoxytrimethylsilane and 3-glycidoxypropyltrimethoxysilane to modify graphene simultaneously. This not only improves the uniform dispersion of graphene in polyurethane by blocking hydrophilic groups (such as hydroxyl and carboxyl groups), but also allows the epoxy groups in 3-glycidoxypropyltrimethoxysilane to react chemically with the isocyanate groups in the polyurethane prepolymer preparation process. This prevents the migration of graphene in the phase change microcapsule wall material during drying and its dissolution during washing, which would affect the compactness of the wall material.

[0024] Furthermore, in the composite modification of methoxytrimethylsilane and 3-glycidoxypropyltrimethoxysilane, if the proportion of methoxytrimethylsilane is too low, the modified graphene A is difficult to disperse uniformly due to the low blocking rate of its hydrophilic groups, and its surface epoxy group content is too high, which easily causes explosive polymerization during the preparation of polyurethane prepolymer. If the proportion of methoxytrimethylsilane is too high, the hydrophilic groups in the modified graphene A are fully blocked, which can improve its uniform dispersion in polyurethane, but its surface epoxy group content is too low, preventing effective chemical bonding with polyurethane. Graphene is prone to migration during drying and dissolution during washing. Therefore, to balance the blocking rate of graphene's hydrophilic groups and its bonding ability with polyurethane prepolymer, the preferred mass ratio of graphene, methoxytrimethylsilane, and 3-glycidoxypropyltrimethoxysilane is 1:6:1.5.

[0025] In the preparation of polyurethane prepolymer, a compound of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and triphenylmethane triisocyanate is used as the isocyanate. The principle is mainly that: hexamethylene diisocyanate molecules have a chain structure, which can give polyurethane good flexibility; 4,4'-dicyclohexylmethane diisocyanate can appropriately improve its abrasion resistance in fabric use without affecting the flexibility of polyurethane; and a small amount of triphenylmethane triisocyanate can give polyurethane higher strength through a three-dimensional network structure.

[0026] Adding epoxy resin during the preparation of polyurethane prepolymer can significantly improve the bonding strength of phase change microcapsule wall material on the fiber surface, avoid the use of adhesives, and reduce the impact of finishing on the hand feel and moisture permeability of textiles.

[0027] In the preparation of phase change microcapsules, graphene with excellent thermal conductivity was added to both the core phase change material and the wall material, which improved the temperature regulation rate of the finished fabric.

[0028] The high-speed shear emulsifier achieves convenient transport and stable positioning through rollers and a lifting support. Guide rods and sliding guide sleeves ensure smooth and precise lifting, reducing vibration to maintain stable emulsification quality. The hydraulically driven lifting assembly provides strong and controllable driving force, allowing for smooth adjustment of the shear emulsification mechanism height, adapting to various working conditions and container sizes. The piston rod's direct connection to the motor mounting plate simplifies force transmission, reduces loosening, improves reliability, and shortens process changeover time. The stirring head and positioning rod work together to enhance structural strength and load distribution, improving the emulsification stability of high-viscosity / multiphase systems. The protective baffle's bends reduce splashing and cleaning frequency; the observation window provides process visualization; and the LED lights provide uniform illumination, eliminating shadows, improving visibility, reducing the risk of misoperation, and comprehensively optimizing equipment efficiency. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 This is a schematic diagram of the structure of the present invention.

[0031] Figure 2 This is a top view of the structure of the present invention.

[0032] Figure 3 This is a schematic diagram of the internal structure of the present invention.

[0033] Figure 4 For the present invention Figure 3Enlarged view of I in the middle.

[0034] Figure 5 For the present invention Figure 3 Enlarged view of section II.

[0035] In the diagram: 1. Support leg; 2. Roller; 3. Base bracket; 4. Emulsifying container; 5. Bending section; 6. Anti-splash baffle; 7. Lifting bracket; 8. Observation window; 9. Output shaft; 10. Positioning rod; 11. Drive motor; 12. Motor mounting plate; 13. Piston rod; 14. Hydraulic cylinder; 15. Fixed base; 16. Guide rod; 17. Sliding guide sleeve; 18. LED light assembly. Detailed Implementation

[0036] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1 Please see Figures 1-5 As shown, a method for preparing a smart temperature-controlled textile based on phase change microcapsules is characterized by comprising the following steps: (1) Preparation of aqueous phase change microcapsule emulsion Polyurethane prepolymer and composite phase change material were added to a three-necked flask and heated to 80 °C to bring all components to a molten state. The mixture was then placed in a high-speed shear emulsifier, and the rotation speed was slowly increased to 8000 r / min. A certain amount of deionized water containing 1 g / L of defoamer DM8317 was slowly added over 40 min. After stirring for 120 min to obtain a homogeneous emulsion, the rotation speed was reduced to 400 r / min, 1.5 g of potassium persulfate initiator was added, and the mixture was heated to 60 °C and reacted for 4 h. After cooling to room temperature, acetone was removed by rotary evaporation to obtain an aqueous phase change microcapsule emulsion.

[0038] The polyurethane prepolymer is made by the following steps: Polydiol was placed in a three-necked flask and heated to a molten state in a constant-temperature drying oven at 115°C. The temperature was then lowered to 50°C, and isocyanate was added. The temperature was raised to 60°C and reacted for 70 min. Then, 0.6 mL of dibutyltin dilaurate was added, and the temperature was raised to 70°C under reflux. The reaction was continued for 90 min. Modified graphene A, dimethylolpropionic acid, hydroxyethyl acrylate, epoxy resin, and 20 g of acetone were added. The temperature was raised to 80°C and reacted at a constant temperature for 75 min. The temperature was then lowered to 30°C to obtain the polyurethane prepolymer.

[0039] In the method for preparing the polyurethane prepolymer, the epoxy resin is one or more of EP-12, EP-13, EP-16 and EP-20, preferably EP-12; in the method for preparing the polyurethane prepolymer, the mass ratio of diisocyanate, polydiol, modified graphene, dimethylolpropionic acid, hydroxyethyl acrylate and epoxy resin is preferably 25:30:3:10:8:5.

[0040] The method for preparing modified graphene A includes the following steps: 6g of graphene is ultrasonically dispersed in 550 mL of deionized water, 60g of methoxytrimethylsilane is added, the stirring speed is adjusted to 300r / min, the reaction is carried out at 30℃ for 120min, the temperature is raised to 60℃, the reaction is carried out for 30min, then 15g of 3-glycidyloxypropyltrimethoxysilane is added, the reaction is continued for 45min, the graphene is thoroughly washed with deionized water, and then dried.

[0041] The composite phase change material is made by the following steps. Place 100g of paraffin wax into a round-bottom flask, heat it to 90℃ to make it melt, add 0.4g of modified graphene B, and mix evenly while stirring at 500r / min.

[0042] The method for preparing modified graphene B includes the following steps: 6g of graphene is ultrasonically dispersed in 500mL of deionized water, 100g of methoxytrimethylsilane is added, the stirring speed is adjusted to 300r / min, the reaction is carried out at 30℃ for 90min, the temperature is raised to 60℃ and the reaction is carried out for 60min, the graphene is thoroughly washed with deionized water and dried.

[0043] (2) Preparation of intelligent temperature-controlled textiles using phase change microcapsules The aqueous phase change microcapsule emulsion prepared in step (1) was applied to textiles using a two-dip and two-ply method with a pick-up rate of 60%. The emulsion was pre-dried at 80°C for 5 minutes and then baked at 150°C for 4 minutes. The concentration of the aqueous phase change microcapsule emulsion was 100 g / L.

[0044] Comparative Example 1 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that in step (1), no modified graphene A is added during the preparation of the polyurethane prepolymer, and the amount of isocyanate is reduced according to the amount of isocyanate groups consumed by the modified graphene A.

[0045] Comparative Example 2 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that unmodified graphene is added during the preparation of polyurethane prepolymer in step (1).

[0046] Comparative Example 3 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that modified graphene B is added during the preparation of polyurethane prepolymer in step (1).

[0047] Comparative Example 4 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that the isocyanate used in the preparation of the polyurethane prepolymer in step (1) is hexamethylene diisocyanate.

[0048] Comparative Example 5 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. For details, please refer to Example 1. The difference is that in step (1), the isocyanate used in the preparation of the polyurethane prepolymer is 4,4'-dicyclohexylmethane diisocyanate.

[0049] Comparative Example 6 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that in step (1), the isocyanate in the preparation of the polyurethane prepolymer is a compound of hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and the molar ratio of hexamethylene diisocyanate to 4,4'-dicyclohexylmethane diisocyanate is 3:6.

[0050] Comparative Example 7 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that epoxy resin EP-12 is not added during the preparation of polyurethane prepolymer in step (1), and the amount of isocyanate is reduced according to the amount of isocyanate groups consumed by epoxy resin EP-12.

[0051] Comparative Example 8 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that unmodified graphene is added during the preparation of the composite phase change material in step (1).

[0052] Comparative Example 9 This comparative example provides a smart temperature-controlled textile based on phase change microcapsules and its preparation method. See Example 1 for details. The difference is that in step (2), adhesive DM-5129 is added during the preparation of the smart temperature-controlled textile based on phase change microcapsules, and the amount of adhesive is 10g / L.

[0053] 1. The effect of graphene on the thermal conductivity of polyurethane prepolymer films Preparation method of polyurethane prepolymer film: The polyurethane prepolymers prepared in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 were coated onto a polytetrafluoroethylene plate by spin coating and dried at room temperature to obtain polyurethane prepolymer film.

[0054] Performance testing: Thermal conductivity test of polyurethane prepolymer film: The thermal constant analyzer (TPS2500S, Hot Disk) with isotropic standard module and 7577 sensor was used to measure the thermal conductivity of each sample 10 times, and the average value and standard deviation of the 10 data were calculated; The polyurethane prepolymer film was washed with water in accordance with the standard of GB / T 3921-2008 Textiles - Tests for Color Fastness to Soap Washing.

[0055] The thermal conductivity test results of the polyurethane prepolymer films prepared in Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are shown in Table 1.

[0056] Table 1. Effect of graphene on the thermal conductivity of polyurethane prepolymer films As can be seen from the data in Table 1, the thermal conductivity of the polyurethane prepolymer film without graphene is only 0.033 W·m. -1 ·K -1 The thermal conductivity of all samples with added graphene exceeded 1 W·m. -1 ·K -1 The thermal conductivity of Example 1 is slightly higher than that of Comparative Examples 2 and 3. Table 2 also shows that the standard deviation of Comparative Example 3 is similar to that of Example 1, while the standard deviation of Comparative Example 2 is significantly higher than that of Example 1. This is because the surface of unmodified graphene contains a large number of hydrophilic groups such as hydroxyl and carboxyl groups, which are difficult to disperse uniformly in the hydrophobic polyurethane prepolymer. Therefore, the thermal conductivity of Comparative Example 2 is lower, while its standard deviation is larger. Most of the hydrophilic groups in modified graphene B have been blocked by methoxytrimethylsilane, allowing for uniform dispersion in the polyurethane prepolymer. Therefore, the average thermal conductivity and standard deviation of Comparative Example 3 are similar to those of Example 1.

[0057] Furthermore, the data in Table 2 show that after five water washes, the thermal conductivity and standard deviation of Example 1 showed no significant change, while the thermal conductivity and standard deviation of Comparative Example 3 both decreased significantly. This is because the polyurethane prepolymer film has a certain degree of hygroscopicity, and during the water washing process, it swells due to moisture absorption, reducing the adhesion between the polyurethane and the modified graphene B, which can cause the modified graphene B to dissolve from the polyurethane prepolymer film. However, the epoxy groups contained in the modified graphene A form valence bonds with the isocyanate groups, so even if the polyurethane prepolymer film swells due to moisture absorption, the modified graphene A will not dissolve.

[0058] 2. Wash resistance of textiles in terms of energy storage properties Performance Testing: Washability Test of Phase Change Microcapsule Modified Cotton Fabrics: Washing was conducted according to the standards specified in GB / T 3921-2008 Textiles - Tests for Color Fastness to Soap Washing. Energy Storage Performance Test of Phase Change Microcapsule Modified Cotton Fabrics: Differential scanning calorimetry was used to analyze the energy storage performance of the phase change microcapsule modified cotton fabrics under a nitrogen atmosphere. The nitrogen flow rate was 50 mL / min, the test temperature was 10 ~ 80 ℃, and the heating rate was 10 ℃ / min.

[0059] The test results of the water resistance of the textiles prepared in Example 1, Comparative Example 4, Comparative Example 5, Comparative Example 6 and Comparative Example 7 are shown in Table 2.

[0060] Table 2 Wash resistance of textiles for energy storage properties As shown in Table 2, before washing, the energy storage performance of the textiles prepared in Comparative Examples 4, 5, 6, and 7 was similar to that of the textile prepared in Example 1. However, after five washes, the enthalpy change of Example 1 decreased slightly, while the enthalpy change of the comparative examples decreased significantly, with Comparative Example 5 showing the most significant change. This is because, although hexamethylene diisocyanate can impart good flexibility to polyurethane wall materials, it lacks hardness and can be damaged by mechanical force during washing; 4,4'-dicyclohexylmethane diisocyanate can impart good hardness to polyurethane wall materials, but its flexibility is poor and it will crack during washing; triphenylmethane triisocyanate can impart higher strength to polyurethane through a three-dimensional network structure; and epoxy resin can impart adhesive strength between the polyurethane wall material and the fiber matrix.

[0061] 3. The effect of graphene modification on the energy storage and thermal conductivity of paraffin wax Performance testing: Thermal conductivity of paraffin wax: Paraffin wax was placed in a mold with a length of 20 mm, a width of 15 mm, and a thickness of 2 mm, and pressed under a pressure of 25 MPa for 15 min to obtain a block sample. The thermal constant was measured by a thermal constant analyzer (TPS 2500S, Hot Disk) with an isotropic standard module and a 7577 sensor. Each sample was tested 10 times, and the mean and standard deviation of the 10 data were calculated. Energy storage performance of paraffin wax: Differential scanning calorimetry was used to analyze the energy storage performance of paraffin wax and modified paraffin wax under a N2 atmosphere. The nitrogen flow rate was 50 mL / min, the test temperature was 10 ~ 80 ℃, and the heating rate was 10 ℃ / min.

[0062] The standard methods for the thermal storage performance, thermal conductivity, and maximum thermal coefficient of the composite phase change material and paraffin in Example 1 and Comparative Example 8 are shown in Table 3.

[0063] Table 3. Effects of graphene modification on the energy storage and thermal conductivity of paraffin. As shown in Table 3, graphene significantly improves the thermal conductivity of paraffin wax while having little impact on energy storage performance. Table 3 also indicates that the enthalpy change of Comparative Example 8 is slightly greater than that of Example 1, while its thermal conductivity and standard deviation are significantly lower than those of Example 1. This is because Comparative Example 8 uses unmodified graphene, which has a certain degree of hydrophilicity and poor uniform dispersion in hydrophobic paraffin wax, resulting in significant differences in values ​​across multiple sampling tests.

[0064] 4. The effect of adhesives on the properties of phase change microcapsule-finished textiles Performance testing: The hand feel of the textiles was tested using the touch method; the air permeability of the textiles was tested according to the standard GB / T 5453-2025 "Textiles - Determination of Air Permeability of Fabrics"; the air permeability of the textiles was tested according to the standard GB / T12704.1-2009 "Textiles - Test Method for Moisture Permeability of Fabrics - Part 1: Moisture Absorption Method"; the energy storage performance of the phase change microcapsule modified cotton fabric was analyzed using a differential scanning calorimeter under a N2 atmosphere, with a nitrogen flow rate of 50 mL / min, a test temperature of 10 ~ 80 ℃, and a heating rate of 10 ℃ / min; the wash fastness test of the phase change microcapsule modified cotton fabric was conducted according to the standard GB / T3921-2008 "Textiles - Test for Color Fastness - Color Fastness to Soap Washing".

[0065] The test results of hand feel and moisture permeability of the unfinished textiles, the textiles prepared in Example 1, and the textiles prepared in Comparative Example 9 are shown in Table 4.

[0066] Table 4. Effects of adhesives on the properties of phase change microcapsule-finished textiles As shown in Table 4, the textile prepared in Example 1 has a soft hand feel, and its air permeability and moisture permeability are slightly lower than those of the unfinished textile. In contrast, the textile prepared in Comparative Example 9 has a slightly stiffer hand feel, and its air permeability and moisture permeability are significantly lower than those of the unfinished textile. Furthermore, the addition of the adhesive did not significantly improve the washability of the textile. This is because the phase change microcapsules prepared in Example 1 have good adhesion to the fibers, while the adhesive added in Comparative Example 9 increases the stiffness of the textile and has a certain sealing effect on the pores.

[0067] In this embodiment, the preferred mass ratio of polyurethane prepolymer to composite phase change material in the preparation method of the phase change microcapsules is 1:1.

[0068] In this embodiment, the solid content of the aqueous phase change microcapsule emulsion is preferably 25% in the preparation method of the phase change microcapsule.

[0069] In this embodiment, the polydiol is any one of polycaprolactone diol (PCL), polyether diol (PPG), and polytetrahydrofuran diol (PTMEG), with polycaprolactone diol (PCL) being preferred.

[0070] In this embodiment, the diisocyanate is one or a mixture of several of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, preferably a mixture of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, and the preferred molar ratio of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate is 3:6:1.

[0071] In this embodiment, the textile is a textile made of one or more of the following: natural cellulose fiber, regenerated fiber, polyamide fiber, and polyester fiber; the textile is a type of woven textile, knitted textile, or nonwoven textile.

[0072] In this embodiment, the high-speed shear emulsifier includes a base support 3. Rollers 2 are provided around the bottom of the base support 3 to enable overall movement of the equipment. A lifting support 7 is vertically mounted on one side of the base support 3. Multiple guide rods 16 are provided between the top and bottom of the inner wall of the lifting support 7, and are correspondingly arranged. A motor mounting plate 12 is provided at one end of the top of each guide rod 16, and a sliding guide sleeve 17 is provided at the connection point. A shear emulsification mechanism is connected to one end of the motor mounting plate 12. The shear emulsification mechanism includes a drive motor 11. The drive motor 11 is model Y2-132S-4 and is a commercially available product that can be directly purchased. An output shaft 9 is connected to one end of the bottom of the drive motor 11. Multiple positioning rods 10 are provided at equal intervals around the output shaft 9. A stirring head is provided at the bottom of the output shaft 9 and the positioning rods 10. An emulsification container 4 is provided at the bottom of the stirring head, and multiple support legs 1 are provided at the bottom of the emulsification container 4. A lifting drive assembly for driving the vertical lifting movement of the shear emulsification mechanism is provided on one side of the base support 3. Protective baffle assemblies are provided on both sides of the emulsification container 4. The combination of rollers 2 and lifting brackets 7 enables convenient transfer and positioning of the equipment between different workstations, while ensuring structural stability and operational accessibility during emulsification operations. The structure of guide rod 16 + sliding guide sleeve 17 ensures smooth operation and accurate positioning during the lifting process, reducing eccentric loads and vibrations, which helps maintain the stability of shearing emulsification quality. The vertical lifting action driven by hydraulic cylinder 14 facilitates quick switching of container height and processing posture, improving work efficiency and reducing manual handling and alignment intensity. The coordinated design of stirring head and positioning rod 10 enhances the structural strength and load distribution of the shearing mechanism, improving the emulsification stability and reliability of high viscosity or multiphase systems. The protective baffle assembly effectively suppresses splashing, reduces cleaning difficulty and safety risks. The observation window 8 enables process visualization. The LED light group 18 provides uniform illumination of the working surface, improving the visibility of the operating environment and facilitating process judgment and quality control.

[0073] In this embodiment, the lifting drive assembly includes a fixed base 15, which is associated with a base bracket 3. A hydraulic cylinder 14 is provided on the top of the fixed base 15, and a piston rod 13 is connected to one end of the hydraulic cylinder 14. The piston rod 13 is associated with the bottom of the motor mounting plate 12. The lifting structure with the hydraulic cylinder 14 as its core has good driving force and controllability, and can smoothly and accurately complete the lifting and lowering adjustment of the shearing emulsification mechanism, adapting to various working conditions and container specifications. The lifting process shortens and simplifies the force transmission path through the direct connection between the piston rod 13 and the motor mounting plate 12, reducing the gaps and loosening risks caused by intermediate links, and improving the stability and reliability of the system. It facilitates rapid and controllable height adjustment, shortens process changeover time, and improves equipment operating efficiency and ease of operation.

[0074] In this embodiment, the protective baffle assembly includes a splash guard 6, which is a detachable structure. The splash guard 6 is bent towards the emulsification container 4 to form a bent portion 5. An observation window 8 is provided at the center of the outer wall of the splash guard 6, and an LED light group 18 is provided at the center of the inner wall of the bent portion 5 of the splash guard 6. The number of LED light groups 18 is 20 to 30 and they are arranged in an equally spaced array. The structural design of the bent portion 5 effectively converges the splash trajectory, reduces secondary splashing and cleaning frequency, and improves the hygiene and safety of the working environment. The observation window 8 enables online visualization of the emulsification process, allowing operators to promptly grasp the dispersion and emulsification status, improving process controllability and quality consistency. The LED light group 18 provides uniform supplementary lighting, eliminates shadows and uneven brightness on the working surface, improves detail recognition, assists in judging emulsification quality, and reduces the risk of misoperation.

[0075] Example 2 Please see Figures 1-5 As shown, (1) Preparation of aqueous phase change microcapsule emulsion Polyurethane prepolymer and composite phase change material were added to a three-necked flask and heated to 80 °C to bring all components to a molten state. The mixture was then placed in a high-speed shear emulsifier, and the rotation speed was slowly increased to 9000 r / min. A certain amount of deionized water containing 1.5 g / L of defoamer DM8317 was slowly added over 30 min. After stirring for 60 min to obtain a homogeneous emulsion, the rotation speed was reduced to 400 r / min, 2 g of potassium persulfate initiator was added, and the mixture was heated to 70 °C and reacted for 3 h. After cooling to room temperature, acetone was removed by rotary evaporation to obtain an aqueous phase change microcapsule emulsion.

[0076] The polyurethane prepolymer is made by the following steps: Polydiol was placed in a three-necked flask and heated to a molten state in a constant-temperature drying oven at 115°C. The temperature was then lowered to 50°C, and isocyanate was added. The temperature was raised to 70°C and reacted for 60 min. Next, 0.8 mL of dibutyltin dilaurate was added, and the temperature was raised to 75°C under reflux. The reaction was continued for 60 min. Then, modified graphene A, dimethylolpropionic acid, hydroxyethyl acrylate, epoxy resin, and 20 g of acetone were added. The temperature was raised to 85°C and reacted at a constant temperature for 60 min. The temperature was then lowered to 30°C to obtain the polyurethane prepolymer.

[0077] In the method for preparing the polyurethane prepolymer, the epoxy resin is one or more of EP-12, EP-13, EP-16 and EP-20, preferably EP-12; in the method for preparing the polyurethane prepolymer, the mass ratio of diisocyanate, polydiol, modified graphene, dimethylolpropionic acid, hydroxyethyl acrylate and epoxy resin is preferably 25:30:3:10:8:5.

[0078] The method for preparing modified graphene A includes the following steps: 8g of graphene is ultrasonically dispersed in 550mL of deionized water, 70g of methoxytrimethylsilane is added, the stirring speed is adjusted to 400r / min, the reaction is carried out at 35℃ for 90min, the temperature is raised to 50℃, the reaction is carried out for 45min, then 10g of 3-glycidyloxypropyltrimethoxysilane is added, the reaction is continued for 60min, the graphene is thoroughly washed with deionized water, and then dried.

[0079] The composite phase change material is made by the following steps. Place 110g of paraffin wax into a round-bottom flask, heat it to 90℃ to make it melt, add 0.5g of modified graphene B, and mix evenly while stirring at 550r / min.

[0080] The method for preparing modified graphene B includes the following steps: ultrasonically dispersing 5g of graphene in 500mL of deionized water, adding 80g of methoxytrimethylsilane, adjusting the stirring speed to 300r / min, reacting at 40℃ for 60min, raising the temperature to 60℃ and reacting for 60min, thoroughly washing with deionized water, and drying.

[0081] (2) Preparation of intelligent temperature-controlled textiles using phase change microcapsules The aqueous phase change microcapsule emulsion prepared in step (1) was applied to textiles using a two-dip and two-ply method with a pick-up rate of 65%. The emulsion was pre-dried at 90°C for 3 minutes and then baked at 160°C for 3 minutes. The concentration of the aqueous phase change microcapsule emulsion was 80 g / L.

[0082] In this embodiment, the preferred mass ratio of polyurethane prepolymer to composite phase change material in the preparation method of the phase change microcapsules is 1:1.

[0083] In this embodiment, the solid content of the aqueous phase change microcapsule emulsion is preferably 25% in the preparation method of the phase change microcapsule.

[0084] In this embodiment, the polydiol is any one of polycaprolactone diol (PCL), polyether diol (PPG), and polytetrahydrofuran diol (PTMEG), with polycaprolactone diol (PCL) being preferred.

[0085] In this embodiment, the diisocyanate is one or a mixture of several of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, preferably a mixture of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, and the preferred molar ratio of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate is 3:6:1.

[0086] In this embodiment, the textile is a textile made of one or more of the following: natural cellulose fiber, regenerated fiber, polyamide fiber, and polyester fiber; the textile is a type of woven textile, knitted textile, or nonwoven textile.

[0087] The rest of the content is the same as in Example 1.

[0088] Example 3 Please see Figures 1-5 As shown, (1) Preparation of aqueous phase change microcapsule emulsion Polyurethane prepolymer and composite phase change material were added to a three-necked flask and heated to 100 °C to bring all components to a molten state. The mixture was then placed in a high-speed shear emulsifier, and the rotation speed was slowly increased to 9000 r / min. A certain amount of deionized water containing 1.5 g / L of defoamer DM8317 was slowly added over 30 min. After stirring for 60 min to obtain a homogeneous emulsion, the rotation speed was reduced to 450 r / min, 2 g of potassium persulfate initiator was added, and the mixture was heated to 65 °C and reacted for 3.5 h. After cooling to room temperature, acetone was removed by rotary evaporation to obtain an aqueous phase change microcapsule emulsion.

[0089] The polyurethane prepolymer is made by the following steps: Polydiol was placed in a three-necked flask and heated to a molten state in a constant-temperature drying oven at 115 °C. The temperature was then lowered to 55 °C, and isocyanate was added. The temperature was raised to 65 °C and reacted for 70 min. Then, 0.8 mL of dibutyltin dilaurate was added, and the temperature was raised to 70 °C under reflux. The reaction was continued for 90 min. Modified graphene A, dimethylolpropionic acid, hydroxyethyl acrylate, epoxy resin, and 25 g of acetone were added. The temperature was raised to 90 °C and reacted at a constant temperature for 60 min. The temperature was then lowered to 30 °C to obtain the polyurethane prepolymer.

[0090] In the method for preparing the polyurethane prepolymer, the epoxy resin is one or more of EP-12, EP-13, EP-16 and EP-20, preferably EP-12; in the method for preparing the polyurethane prepolymer, the mass ratio of diisocyanate, polydiol, modified graphene, dimethylolpropionic acid, hydroxyethyl acrylate and epoxy resin is preferably 25:30:3:10:8:5.

[0091] The method for preparing modified graphene A includes the following steps: 6g of graphene is ultrasonically dispersed in 500mL of deionized water, 55g of methoxytrimethylsilane is added, the stirring speed is adjusted to 350r / min, the reaction is carried out at 40℃ for 60min, the temperature is raised to 55℃, the reaction is carried out for 60min, then 20g of 3-glycidyloxypropyltrimethoxysilane is added, the reaction is continued for 60min, the graphene is thoroughly washed with deionized water, and then dried.

[0092] The composite phase change material is made by the following steps. Place 100g of paraffin wax into a round-bottom flask, heat it to 100℃ to make it melt, add 0.5g of modified graphene B, and mix evenly while stirring at 500r / min.

[0093] The method for preparing modified graphene B includes the following steps: 10g of graphene is ultrasonically dispersed in 500mL of deionized water, 120g of methoxytrimethylsilane is added, the stirring speed is adjusted to 350r / min, the reaction is carried out at 40℃ for 60min, the temperature is raised to 60℃ and the reaction is carried out for 60min, the graphene is thoroughly washed with deionized water and dried.

[0094] (2) Preparation of intelligent temperature-controlled textiles using phase change microcapsules The aqueous phase change microcapsule emulsion prepared in step (1) was applied to textiles using a two-dip and two-pinch method with a pick-up rate of 60%. The emulsion was pre-dried at 90°C for 3 minutes and then baked at 160°C for 3 minutes. The concentration of the aqueous phase change microcapsule emulsion was 100 g / L.

[0095] In this embodiment, the preferred mass ratio of polyurethane prepolymer to composite phase change material in the preparation method of the phase change microcapsules is 1:1.

[0096] In this embodiment, the solid content of the aqueous phase change microcapsule emulsion is preferably 25% in the preparation method of the phase change microcapsule.

[0097] In this embodiment, the polydiol is any one of polycaprolactone diol (PCL), polyether diol (PPG), and polytetrahydrofuran diol (PTMEG), with polycaprolactone diol (PCL) being preferred.

[0098] In this embodiment, the diisocyanate is one or a mixture of several of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, preferably a mixture of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, and the preferred molar ratio of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate is 3:6:1.

[0099] In this embodiment, the textile is a textile made of one or more of the following: natural cellulose fiber, regenerated fiber, polyamide fiber, and polyester fiber; the textile is a type of woven textile, knitted textile, or nonwoven textile.

[0100] The rest of the content is the same as in Example 1.

[0101] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

[0102] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0103] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for preparing intelligent temperature-controlled textiles based on phase change microcapsules, characterized in that, Includes the following steps: (1) Preparation of aqueous phase change microcapsule emulsion Polyurethane prepolymer and composite phase change material are added to a three-necked flask and heated to 80-100 °C to bring all components to a molten state. The mixture is then placed in a high-speed shear emulsifier and the rotation speed is slowly increased to 8000-9000 r / min. A certain amount of deionized water containing 1-2 g / L of defoamer DM8317 is slowly added over 30-40 min. The mixture is stirred for 60-120 min to obtain a homogeneous emulsion. The rotation speed is then reduced to 400-450 r / min, and 1-2 g of potassium persulfate initiator is added. The mixture is heated to 50-70 °C and reacted for 3-4 h. After cooling to room temperature, acetone is removed by rotary evaporation to obtain an aqueous phase change microcapsule emulsion. The polyurethane prepolymer is made by the following steps: Polydiol was placed in a three-necked flask and heated to a molten state in a constant temperature drying oven at 115-125°C. The temperature was then lowered to 50-60°C, and isocyanate was added. The temperature was raised to 60-70°C and reacted for 60-70 minutes. Then, 0.6-1 mL of dibutyltin dilaurate was added, and the temperature was raised to 70-80°C under reflux. The reaction was continued for 60-90 minutes. Modified graphene A, dimethylolpropionic acid, hydroxyethyl acrylate, epoxy resin, and 20-30 g of acetone were added. The temperature was raised to 80-90°C and reacted at a constant temperature for 60-90 minutes. The temperature was then lowered to 30-35°C to obtain the polyurethane prepolymer. In the method for preparing the polyurethane prepolymer, the epoxy resin is one or more of EP-12, EP-13, EP-16, and EP-20; in the method for preparing the polyurethane prepolymer, the mass ratio of diisocyanate, polydiol, modified graphene, dimethylolpropionic acid, hydroxyethyl acrylate, and epoxy resin is 25:30:3:10:8:

5. The method for preparing modified graphene A includes the following steps: ultrasonically dispersing 5-10g of graphene in 500-550mL of deionized water, adding 50-80g of methoxytrimethylsilane, adjusting the stirrer speed to 300-400r / min, reacting at 30-40℃ for 60-120min, raising the temperature to 40-60℃, reacting for 30-60min, then adding 10-20g of 3-glycidyloxypropyltrimethoxysilane, continuing the reaction for 30-60min, thoroughly washing with deionized water, and drying. The composite phase change material is made by the following steps. Place 100-110g of paraffin wax into a round-bottom flask, heat it to 80-100℃ to make it melt, add 0.3-0.5g of modified graphene B, and mix evenly while stirring at 500-550r / min. The method for preparing modified graphene B includes the following steps: ultrasonically dispersing 5-10g of graphene in 500-550mL of deionized water, adding 80-120g of methoxytrimethylsilane, adjusting the stirring speed to 300-400r / min, reacting at 30-40℃ for 60-120min, raising the temperature to 40-60℃ and reacting for 60-90min, thoroughly washing with deionized water, and drying. (2) Preparation of intelligent temperature-controlled textiles with phase change microcapsules The aqueous phase change microcapsule emulsion prepared in step (1) is applied to textiles using a two-dip and two-pick method, with a pick-up rate of 60-65%. The emulsion is pre-dried at 80-90℃ for 2-5 minutes and then baked at 140-160℃ for 3-5 minutes. The concentration of the aqueous phase change microcapsule emulsion is 60-100 g / L.

2. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: In the preparation method of the phase change microcapsules, the mass percentage of polyurethane prepolymer to composite phase change material is 1:

1.

3. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: In the preparation method of the phase change microcapsules, the solid content of the aqueous phase change microcapsule emulsion is 25%.

4. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: The polydiol is any one of polycaprolactone diol (PCL), polyether diol (PPG), or polytetrahydrofuran diol (PTMEG).

5. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: The diisocyanate is one or a mixture of several of hexamethylene diisocyanate, diphenylmethane diisocyanate, pentamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate, with a compound molar ratio of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and triphenylmethane triisocyanate of 3:6:

1.

6. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: In the method for preparing modified graphene A, the mass ratio of graphene, methoxytrimethylsilane and 3-glycidyloxypropyltrimethoxysilane is 1:6:1.

5.

7. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: The textiles are textiles made from one or more of the following: natural cellulose fibers, regenerated fibers, polyamide fibers, and polyester fibers.

8. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: The textiles mentioned are one of the following: woven textiles, knitted textiles, and nonwoven textiles.

9. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 1, characterized in that: The high-speed shear emulsifier includes a base support (3), with rollers (2) for overall movement of the equipment on all four sides of the bottom of the base support (3). A lifting support (7) is vertically arranged on one side of the base support (3). Multiple guide rods (16) are provided between the top and bottom of the inner wall of the lifting support (7) and are correspondingly arranged. A motor mounting plate (12) is provided at one end of the top of the guide rod (16) and a sliding guide sleeve (17) is provided at the connection. A shear emulsification mechanism is connected to one end of the motor mounting plate (12). The shear emulsification mechanism includes a drive motor (11). An output shaft (9) is connected to one end of the bottom of the drive motor (11). Multiple positioning rods (9) are provided at equal intervals around the output shaft (9). 10), the bottom of the output shaft (9) and the positioning rod (10) are provided with a stirring head, the bottom of the stirring head is provided with an emulsification container (4), the bottom of the emulsification container (4) is provided with multiple support legs (1); the base support (3) is provided with a lifting drive assembly for driving the vertical lifting and lowering movement of the shearing emulsification structure on one side, and the emulsification container (4) is provided with protective baffle assemblies on both sides; the lifting drive assembly includes a fixed base (15), the fixed base (15) is associated with the base support (3), the top of the fixed base (15) is provided with a hydraulic cylinder (14), one end of the hydraulic cylinder (14) is connected to a piston rod (13), and one end of the piston rod (13) is associated with the bottom of the motor mounting plate (12).

10. The method for preparing a smart temperature-controlled textile based on phase change microcapsules according to claim 9, characterized in that: The protective baffle assembly includes a splash guard (6), which is bent toward the emulsification container (4) to form a bent portion (5); the outer wall of the splash guard (6) is provided with an observation window (8), and the inner wall of the bent portion (5) of the splash guard (6) is provided with an LED light group (18), which consists of 20 to 30 LED light groups arranged in an equally spaced array.

Images