Antibacterial heat-storing temperature-regulating textile material and preparation method and application thereof

Abstract

The present application belongs to the technical field of textile, and relates to a functional textile material, in particular to an antibacterial heat storage temperature regulating textile material and a preparation method thereof. The material is prepared by soaking a fiber base material containing hydroxyl groups on the surface in a certain concentration of quaternary ammonium double-shell phase change microcapsule aqueous solution for a period of time, and then being dried and compacted after grafting reaction. The preparation method is simple and easy for industrialized production. The quaternary ammonium double-shell phase change microcapsule takes composite phase change material, silane coupling agent, catalyst, silicon source material, dopamine monomer and organic silicon quaternary ammonium salt solution as main raw materials. The material has antibacterial property, with a bacterial antibacterial rate of greater than or equal to 95% and a fungus antibacterial rate of greater than or equal to 93%, and still has 5A antibacterial property after 100 cycles of washing; the material has heat storage and temperature regulating property; and the material can be used as raw material in the fields of clothing, household textiles, socks, medical and health products and the like.

Description

Technical Field

[0001] This invention belongs to the field of textile technology and relates to a functional textile material, particularly an antibacterial, heat-retaining, and temperature-regulating textile material and its preparation method, as well as its application as a raw material in the fields of clothing, home textiles, socks, and medical and health products. Background Technology

[0002] Currently, most temperature-regulating textiles on the market are made by blending phase change microcapsules with fibers. While phase change microcapsule technology can effectively prevent leakage of phase change materials, it also has drawbacks such as the thin shell of single-shell phase change microcapsules, making it difficult to control the thickness and resulting in low core material coverage. Moreover, the encapsulation and structural changes of the shell affect its heat transfer and thermal response capabilities. The thermal and mechanical properties of phase change microcapsules are also difficult to guarantee due to factors such as the properties of the core and shell materials themselves and existing microcapsule encapsulation technology. Furthermore, phase change microcapsules with a single heat storage function can no longer meet practical needs, necessitating the development of multifunctional phase change microcapsules.

[0003] Currently, while antibacterial technology in textiles is widely used, its limited finishing functions, short antibacterial cycle, and poor washability remain major factors hindering its large-scale application. Multifunctional microencapsulation technology, addressing these issues, has become an important development trend in the textile industry. Encapsulating antibacterial substances in phase change microcapsules is one method to achieve antibacterial and temperature-regulating multifunctional textiles; however, this method significantly reduces the antibacterial rate of the microcapsules, failing to achieve long-lasting antibacterial effects under repeated washing conditions. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to provide an antibacterial, heat-storing, and temperature-regulating textile material, which has antibacterial properties, with an antibacterial rate of ≥95% against bacteria and an antibacterial rate of ≥93% against fungi, and still has 5A-level antibacterial properties after 100 cycles of washing; and has heat-storing and temperature-regulating properties.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention provides an antibacterial, heat-storing, and temperature-regulating textile material, characterized by being prepared by immersing a fiber substrate containing hydroxyl groups on its surface in a quaternized double-shell phase change microcapsule aqueous solution of a certain concentration for a period of time, causing a grafting reaction, followed by drying and compaction. The quaternized double-shell phase change microcapsules are prepared by adding composite phase change materials, silane coupling agents, catalysts, silicon source materials, dopamine monomer (DA), and organosilicon quaternary ammonium salt solution as main raw materials to a solvent in a specific ratio, followed by reaction.

[0007] Furthermore, the amount of each component added in the quaternized double-shell phase change microcapsule includes the following parts by weight: 8-12 parts of composite phase change material, 1-2 parts of silane coupling agent, 1-2 parts of catalyst, 3-5 parts of silicon source material, 4-5 parts of dopamine monomer (DA), and 4-6 parts of organosilicon quaternary ammonium salt solution; wherein the composite phase change material is prepared by mixing any two polyethylene glycols with a molecular weight range of 600-1200 as the main raw materials in a weight ratio of 2:1-3.

[0008] Furthermore, the fiber substrate includes any one of cotton yarn, cotton cloth, polyester fiber, nylon fiber, and wool.

[0009] This invention also provides a method for preparing antibacterial, heat-storing, and temperature-regulating textile materials, characterized by mainly including the following steps:

[0010] S1, Preparation of composite phase change materials: Polyethylene glycol of different molecular weights is placed in a reaction vessel at different mass ratios and stirred evenly at a certain temperature to prepare composite phase change materials.

[0011] S2, Preparation of double-shell phase change microcapsules: First, silane coupling agent and the composite phase change material prepared in S1 are added to a reaction vessel in proportion and stirred and mixed evenly in a certain solvent. Then, catalyst and silicon source material are added in sequence to prepare single-shell SiO2-PEG phase change microcapsules. Then, the single-shell SiO2-PEG phase change microcapsules, dopamine monomer (DA), and Tris-HCl buffer are added to the reaction vessel in proportion. The mixture is mechanically stirred at room temperature to allow the dopamine monomer to self-assemble and oxidize on the surface of the single-shell SiO2-PEG phase change microcapsules. After post-treatment, double-shell PDA-SiO2-PEG phase change microcapsules are obtained.

[0012] S3, Preparation of Quaternized Ammonium Double-Shell Phase Change Microcapsules: A certain concentration of organosilicon quaternary ammonium salt solution was added to the reaction vessel. Under magnetic stirring, 3M NaOH was slowly added dropwise until pH=10. The double-shell PDA-SiO2-PEG phase change microcapsules prepared in S2 were then added to the reaction vessel. After the reaction was completed, the product was filtered, washed with deionized water and alcohol, and dried in a vacuum drying oven to obtain quaternized ammonium double-shell phase change microcapsules.

[0013] S4, Preparation of antibacterial heat storage and temperature regulation textile material: The quaternized double-shell phase change microcapsules prepared in S3 are uniformly dispersed in deionized water to form a grafting reaction solution. The fiber substrate containing hydroxyl groups is immersed in the grafting reaction solution for a certain period of time, and then baked at a certain temperature to obtain the antibacterial heat storage and temperature regulation textile material.

[0014] Furthermore, the steps for preparing the double-shell phase change microcapsules described in S2 specifically include:

[0015] S21. A certain amount of the composite phase change material prepared in S1 is placed into a reaction vessel containing a certain amount of solvent, and a certain amount of silane coupling agent is added dropwise. The mixture is stirred evenly at room temperature to obtain a phase change material dispersion.

[0016] S22, a catalyst is added dropwise to the phase change material dispersion, heated and stirred, and impurities are removed by filtration to obtain a siloxane PEG prepolymer solution.

[0017] S23, a certain amount of silicon source material is added to the siloxane PEG prepolymer solution, stirred evenly and then sonicated. During the sonication process, a mixed solution of hydrochloric acid and ethanol with pH=1~2 is added dropwise to emulsify until the system turns milky white. The emulsion is placed in an oil bath and stirred at low speed. The product is filtered, washed with deionized water and alcohol in sequence, and dried in a vacuum drying oven to obtain single-shell SiO2-PEG phase change microcapsules.

[0018] S24, the single-shell SiO2-PEG phase change microcapsules, dopamine monomer (DA), and Tris-HCl buffer solution are added to the reaction vessel, and mechanical stirring is carried out at room temperature to allow the dopamine monomer to self-assemble and oxidize on the surface; the synthesized product is filtered, washed with deionized water, and dried to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0019] Further, the weight ratio of the composite phase change material, silane coupling agent, and solvent in S21 includes 10:1-2:80-100; the reaction solvent includes any one of toluene, acetonitrile, xylene, and acetone; the silane coupling agent includes any one of γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), γ-methacryloyloxypropyltrimethoxysilane (KH570), and 3-aminopropyltriethoxysilane (APS).

[0020] Further, the weight ratio of the composite phase change material to the catalyst in S22 is 10:1-2; the catalyst includes any one of boron trifluoride diethyl ether, potassium persulfate, ammonia, sodium hydroxide, and potassium hydroxide; the heating temperature is 60-100℃, the stirring reaction time is 3-5h, and the stirring rate is 200-250r / min.

[0021] Further, the weight ratio of the silicon source material to the composite phase change material in S23 is 3-5:10; the silicon source material includes any one of tetraethyl orthosilicate, tetramethoxysilane, tetrapropoxysilane, and tetra-n-butoxysilane, and has the following chemical structural formula, wherein R is any one of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3.

[0022]

[0023] Furthermore, in S23, the ultrasonic power is 250-300W, the ultrasonic time is 30-50min; the stirring rate is 80-120r / min, the stirring time is 12-16h, and the stirring temperature is 60-80℃; the vacuum drying temperature is 40-60℃, and the drying time is 22-26h.

[0024] Furthermore, in S24, the weight ratio of the single-shell SiO2-PEG phase change microcapsules, dopamine monomer (DA), and Tris-HCl buffer solution is 10:4-5:80-120; the stirring rate is 200-300 r / min, and the stirring time is 22-26 h; the drying temperature is 40-60℃, and the drying time is 16-24 h.

[0025] Further, the weight ratio of the organosilicon quaternary ammonium salt solution to the double-shell PDA-SiO2-PEG phase change microcapsules in S3 is 5:5-10; the mass concentration of the organosilicon quaternary ammonium salt solution is 0.05-0.1%, and the organosilicon quaternary ammonium salt includes any one of 3-(trimethoxysilylpropyl)dimethyloctadecyl ammonium chloride, 3-(triethoxysilylpropyl)dimethyloctadecyl ammonium chloride, and 3-(trihydroxysilylpropyl)dimethyloctadecyl ammonium chloride, wherein 3-(trimethoxysilylpropyl)dimethyloctadecyl ammonium chloride and 3-(triethoxysilylpropyl)dimethyloctadecyl ammonium chloride will automatically hydrolyze into 3-(trihydroxysilylpropyl)dimethyloctadecyl ammonium chloride when dissolved in water; the magnetic stirring speed is 200-300 r / min, the reaction temperature is 60-80℃, and the reaction time is 10-14 h; the drying temperature is 40-60℃, and the drying time is 16-24 h.

[0026] Furthermore, the phase change composite material described in S1 is prepared by mixing any two polyethylene glycols with a molecular weight range of 600-1200 as the main raw materials, preferably PEG600, PEG800, PEG1000 and PEG1200, in a weight ratio of 2:1-3, and stirring uniformly at 50℃±2℃ for 2h±0.5h.

[0027] Furthermore, the concentration of the aqueous solution of the quaternized double-shell phase change microcapsules in S4 is 50-110 g / L; the soaking time is 10-20 min, the baking temperature is 80-120℃, the baking time is 10-20 min, and the weight gain is 10%-30%.

[0028] This invention further provides the application of antibacterial, heat-retaining, and temperature-regulating textile materials as raw materials in the fields of clothing, home textiles, socks, and medical and health products.

[0029] The beneficial effects of this invention are:

[0030] 1. This invention provides an antibacterial, heat-retaining, and temperature-regulating textile material with high antibacterial rate and high latent heat performance. Even after 100 wash cycles, the textile retains high latent heat and 5A-level antibacterial properties, meeting green and environmentally friendly requirements. The phase transition temperature of this textile material is closest to the most comfortable temperature for the human body. When used as a raw material in clothing, home textiles, socks, and medical and hygiene products, it helps maintain a thermal equilibrium in the environment surrounding the human body, thus playing a role in heat storage and temperature regulation.

[0031] 2. This invention provides a method for preparing antibacterial, heat-storing, and temperature-regulating textile materials, using quaternized double-shell phase change microcapsules as the main raw material. The quaternized double-shell phase change microcapsules possess a novel double-shell structure and are prepared through in-situ polymerization of dopamine in the inner shell of the phase change microcapsule. This method improves the core material coverage while enhancing phase change energy storage and heat conversion efficiency.

[0032] 3. This invention provides a method for preparing antibacterial, heat-storing, and temperature-regulating textile materials, using quaternized double-shell phase change microcapsules as the main raw material. Grafting organosilicon quaternary ammonium salt antibacterial agents onto the surface of the double-shell phase change microcapsules significantly improves their antibacterial rate. The organosilicon quaternary ammonium salt acts as a connecting bridge; its silanol groups can be chemically grafted to form stable and strong covalent bonds with the amino groups on the surface of polydopamine and the hydroxyl groups on the surface of the fiber substrate. This allows the phase change microcapsules to adhere firmly to the fiber substrate surface through chemical grafting, making them difficult to detach. Polydopamine, as a good light absorber and thermal conductor, can quickly achieve dynamic temperature regulation when the ambient temperature changes.

[0033] 4. This invention provides a method for preparing antibacterial, heat-storing, and temperature-regulating textile materials, using quaternized double-shell phase change microcapsules as the main raw material. The outer shell of the double-shell phase change microcapsule acts as a buffer layer, preventing damage to the microcapsule structure during impregnation and rolling of the fiber substrate, avoiding leakage of the phase change material, and improving thermal stability.

[0034] 5. This invention provides a method for preparing antibacterial, heat-storing, and temperature-regulating textile materials, using composite phase change materials as the main raw material. By employing multiple phase change materials in combination, the fabric achieves precise temperature control, overcoming the limitation of single phase change materials in meeting the requirements for precise temperature regulation. Attached Figure Description

[0035] To more clearly illustrate the technical solution of the present invention, 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.

[0036] Appendix Figure 1 Schematic diagram of the grafting principle of double-shell antibacterial temperature-regulating phase change microcapsules;

[0037] Appendix Figure 2 Simplified structural diagram of double-shell PDA-SiO2-PEG phase change microcapsules;

[0038] Appendix Figure 3 The DSC spectra of Example 1 and Comparative Examples 1-2 before washing are shown, with the left image showing the heating process and the right image showing the cooling process. Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. All mentioned embodiments are implemented based on the technical solutions of the present invention, and detailed implementation processes are given. However, it should be stated that the scope of protection of the present invention is not limited to the following embodiments. Example 1

[0040] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0041] I. Preparation of Composite Phase Change Materials

[0042] Five parts each of phase change materials PEG800 and PEG1000 were added to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0043] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0044] Ten parts of a composite phase change material PEG800:PEG1000 (1:1) were added to 100 parts of a toluene solution. One part of silane coupling agent KH-550 was added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, one part of boron trifluoride diethyl ether was added dropwise, and the mixture was magnetically stirred in an 80°C oil bath for 4 hours. The resulting solution was then filtered through filter paper to remove the white precipitate B(OH)3 formed after the hydrolysis of boron trifluoride, yielding a toluene solution of siloxane-terminated PEG. Three parts of tetraethyl orthosilicate were added to the toluene solution of the siloxane-terminated PEG, and the mixture was stirred until homogeneous and then sonicated for 40 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=1 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 60℃ oil bath and stirred at 100r / min. The product was filtered, washed three times with deionized water and alcohol, and then dried in a vacuum drying oven at 40℃ for 26h to obtain single-shell SiO2-PEG phase change microcapsules.

[0045] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0046] Five parts of single-shell SiO2-PEG phase change microcapsules, four parts of DA, and 100 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at 250 r / min for 22 h at room temperature. The synthesized product was filtered, washed three times with deionized water and alcohol, and dried in a vacuum drying oven at 40 °C for 26 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0047] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0048] Five portions of a 0.08% solution of 3-(trimethoxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the mixture was reacted at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0049] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0050] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 80 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in a 100℃ oven for 15 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 2

[0051] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0052] I. Preparation of Composite Phase Change Materials

[0053] Five parts each of phase change materials PEG600 and PEG1000 were added to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0054] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0055] Ten parts of a composite phase change material PEG600:PEG1000 (1:1) were added to 100 parts of an acetonitrile solution. Two parts of silane coupling agent KH-560 were added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, two parts of potassium persulfate were added dropwise, and the mixture was magnetically stirred in a 70°C oil bath for 4 hours to obtain a siloxane-terminated PEG acetonitrile solution. Five parts of tetramethoxysilane were added to the siloxane-terminated PEG acetonitrile solution, and the mixture was stirred until homogeneous and then sonicated for 30 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=1.2 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 65°C oil bath and stirred at 100 r / min. The product was filtered, washed three times with deionized water and alcohol, and dried in a vacuum drying oven at 45°C for 25 hours to obtain single-shell SiO2-PEG phase change microcapsules.

[0056] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0057] Five parts of single-shell SiO2-PEG phase change microcapsules, five parts of DA, and 80 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at room temperature for 23 h at a stirring speed of 250 r / min. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 45 °C for 25 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0058] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0059] Five portions of a 0.1% solution of 3-(trimethoxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. 10 g of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the reaction was carried out at 60 °C for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40 °C for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0060] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0061] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 60 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in an 80℃ oven for 20 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 3

[0062] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0063] I. Preparation of Composite Phase Change Materials

[0064] Six parts of phase change material PEG800 and four parts of phase change material PEG1000 were added sequentially to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0065] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0066] Ten parts of a composite phase change material PEG800:PEG1000 (3:2) were added to 100 parts of xylene solution. One part of silane coupling agent KH-570 was added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, one part of ammonia water was added dropwise, and the mixture was magnetically stirred in a 60°C oil bath for 4 hours to obtain a xylene solution of siloxane-terminated PEG. Three parts of tetrapropoxysilane were added to the xylene solution of the siloxane-terminated PEG obtained above. After stirring evenly, the mixture was sonicated for 35 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=1.4 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 70°C oil bath and stirred at 100 r / min. The product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 50°C for 24 hours to obtain single-shell SiO2-PEG phase change microcapsules.

[0067] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0068] Five parts of single-shell SiO2-PEG phase change microcapsules, 4.2 parts of DA, and 90 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at room temperature for 24 h at a stirring speed of 250 r / min. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 50 °C for 24 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0069] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0070] Five portions of a 0.05% solution of 3-(triethoxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the reaction was carried out at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0071] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0072] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 70 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in a 90℃ oven for 18 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 4

[0073] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0074] I. Preparation of Composite Phase Change Materials

[0075] Four parts of phase change material PEG800 and six parts of phase change material PEG1000 were added sequentially to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0076] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0077] Ten parts of a composite phase change material PEG800:PEG1000 (2:3) were added to 100 parts of an acetone solution. One part of the silane coupling agent APS was added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, two parts of sodium hydroxide were added dropwise, and the mixture was magnetically stirred in a 90°C oil bath for 4 hours to obtain an acetone solution of siloxane-terminated PEG. Five parts of tetrabutoxysilane were added to the acetone solution of the siloxane-terminated PEG obtained above. After stirring evenly, the mixture was sonicated for 45 minutes. During the sonication process, a hydrochloric acid / ethanol / water solution with pH=1.6 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 75°C oil bath and stirred at 100 r / min. The product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 55°C for 23 hours to obtain single-shell SiO2-PEG phase change microcapsules.

[0078] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0079] Five parts of single-shell SiO2-PEG phase change microcapsules, 4.4 parts of DA, and 100 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at room temperature for 25 h at a stirring speed of 250 r / min. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 55 °C for 23 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0080] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0081] Five portions of 0.1% 3-(triethoxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the mixture was reacted at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0082] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0083] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 90 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in an oven at 110℃ for 13 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 5

[0084] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0085] I. Preparation of Composite Phase Change Materials

[0086] Five parts each of phase change materials PEG800 and PEG1200 were added to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0087] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0088] Ten parts of a composite phase change material PEG800:PEG1200 (1:1) were added to 100 parts of a toluene solution. 1.5 parts of silane coupling agent KH-550 were added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, 1 part of potassium hydroxide was added dropwise, and the mixture was magnetically stirred in a 100℃ oil bath for 4 hours. The resulting solution was then filtered through filter paper to remove the white precipitate B(OH)3 formed after the hydrolysis of boron trifluoride, yielding a toluene solution of siloxane-terminated PEG. Four parts of tetraethyl orthosilicate were added to the toluene solution of the siloxane-terminated PEG, and the mixture was stirred until homogeneous and then sonicated for 50 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=1.8 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in an 80℃ oil bath and stirred at 100r / min. The product was filtered, washed three times with deionized water and alcohol, and then dried in a vacuum drying oven at 60℃ for 22h to obtain single-shell SiO2-PEG phase change microcapsules.

[0089] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0090] Five parts of single-shell SiO2-PEG phase change microcapsules, 4.6 parts of DA, and 120 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at room temperature for 26 h at a stirring speed of 250 r / min. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 60 °C for 22 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0091] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0092] Five portions of a 0.05% solution of 3-(trihydroxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the mixture was reacted at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0093] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0094] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 100 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in an oven at 120 ℃ for 10 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 6

[0095] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0096] I. Preparation of Composite Phase Change Materials

[0097] Four parts each of phase change materials PEG800 and PEG1000 were added to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0098] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0099] Eight parts of a composite phase change material PEG800:PEG1000 (1:1) were added to 100 parts of a toluene solution. One part of silane coupling agent KH-550 was added dropwise, and the mixture was magnetically stirred at room temperature for 1 hour. Then, one part of boron trifluoride diethyl ether was added dropwise, and the mixture was magnetically stirred in an oil bath at 80°C for 4 hours. The resulting solution was then filtered through filter paper to remove the white precipitate B(OH)3 formed after the hydrolysis of boron trifluoride, thus obtaining a toluene solution of siloxane-terminated PEG. Three parts of tetraethyl orthosilicate were added to the toluene solution of the siloxane-terminated PEG obtained above, and the mixture was stirred evenly and then sonicated for 40 minutes. During the sonication process, a hydrochloric acid / ethanol / water solution with pH=1 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 60℃ oil bath and stirred at 100r / min. The product was filtered, washed three times with deionized water and alcohol, and then dried in a vacuum drying oven at 40℃ for 26h to obtain single-shell SiO2-PEG phase change microcapsules.

[0100] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0101] Five parts of single-shell SiO2-PEG phase change microcapsules, four parts of DA, and 100 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at 250 r / min for 22 h at room temperature. The synthesized product was filtered, washed three times with deionized water and alcohol, and dried in a vacuum drying oven at 40 °C for 26 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0102] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0103] Six portions of a 0.08% solution of 3-(trimethoxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the reaction was carried out at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0104] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0105] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 80 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in a 100℃ oven for 15 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions. Example 7

[0106] A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, comprising the following main steps:

[0107] I. Preparation of Composite Phase Change Materials

[0108] Six parts each of phase change materials PEG800 and PEG1000 were added to a reaction vessel and stirred uniformly at 50°C for 1 hour to prepare a composite phase change material.

[0109] II. Preparation of Single-Shell SiO2-PEG Phase Change Microcapsules

[0110] Take 12 parts of the composite phase change material PEG800:PEG1000 (1:1) and add it to 100 parts of toluene solution. Add 1 part of silane coupling agent KH-550 dropwise and stir magnetically for 1 hour at room temperature. Then add 1 part of boron trifluoride diethyl ether dropwise and react magnetically in an oil bath at 80°C for 4 hours. Filter the resulting solution with filter paper to remove the white precipitate B(OH)3 formed after the hydrolysis of boron trifluoride, thus obtaining a toluene solution of siloxane-terminated PEG. Add 3 parts of tetraethyl orthosilicate to the toluene solution of siloxane-terminated PEG, stir evenly, and sonicate for 40 minutes. During sonication, add hydrochloric acid / ethanol / water solution (pH=1) dropwise. As hydrochloric acid is added, the system gradually turns milky white. The emulsion was placed in a 60℃ oil bath and stirred at 100r / min. The product was filtered, washed three times with deionized water and alcohol, and then dried in a vacuum drying oven at 40℃ for 26h to obtain single-shell SiO2-PEG phase change microcapsules.

[0111] III. Preparation of double-shell PDA-SiO2-PEG phase change microcapsules

[0112] Five parts of single-shell SiO2-PEG phase change microcapsules, four parts of DA, and 100 parts of Tris-HCl buffer were added to a reaction vessel and mechanically stirred at 250 r / min for 22 h at room temperature. The synthesized product was filtered, washed three times with deionized water and alcohol, and dried in a vacuum drying oven at 40 °C for 26 h to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

[0113] IV. Preparation of Quaternized Double-Shell Phase Change Microcapsules

[0114] Four portions of a 0.08% solution of 3-(trihydroxysilylpropyl)dimethyloctadecylammonium chloride were added to a reaction vessel and stirred on a magnetic stirrer at a speed of 250 r / min. 3M NaOH was slowly added dropwise until the pH reached 10. Ten portions of the double-shell PDA-SiO2-PEG phase change microcapsules were then added to the reaction vessel, and the mixture was reacted at 60℃ for 12 h. The synthesized product was filtered, washed three times repeatedly with deionized water and alcohol, and dried in a vacuum drying oven at 40℃ for 24 h to obtain quaternized double-shell phase change microcapsules with antibacterial effects.

[0115] V. Preparation of antibacterial, heat-storing, and temperature-regulating textile materials

[0116] The dried quaternized double-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 80 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in a 100℃ oven for 15 min to obtain a multifunctional textile material with antibacterial, heat storage and temperature regulation functions.

[0117] Comparative Example 1

[0118] A method for preparing a modified textile material, comprising the following main steps:

[0119] I. Preparation of single-shell phase change microcapsules

[0120] Ten parts of phase change material PEG800 were added to 90 parts of toluene solution, and 1.2 parts of silane coupling agent KH-550 were added dropwise. The mixture was magnetically stirred at room temperature for 1 hour, and then 2 parts of boron trifluoride diethyl ether were added dropwise. The mixture was then magnetically stirred in an oil bath at 80°C for 4 hours. The resulting solution was then filtered through filter paper to remove the white precipitate B(OH)3 formed after the hydrolysis of boron trifluoride, yielding a toluene solution of siloxane-terminated PEG. Four parts of tetraethyl orthosilicate were added to the toluene solution of the siloxane-terminated PEG, and the mixture was stirred until homogeneous and then sonicated for 40 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=2 was added dropwise, and the system gradually turned milky white with the addition of hydrochloric acid. The emulsion was placed in a 60°C oil bath and stirred at 100 r / min. The product was filtered, washed three times repeatedly with deionized water and alcohol, and then dried in a vacuum drying oven at 40°C for 24 hours to obtain single-shell phase change microcapsules.

[0121] II. Preparation of Modified Textile Materials

[0122] The dried single-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 80 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in an oven at 120°C for 15 min to obtain the modified textile material.

[0123] Comparative Example 2

[0124] A method for preparing a modified textile material, comprising the following main steps:

[0125] I. Preparation of single-shell phase change microcapsules

[0126] Ten parts of the phase change material PEG1000 were added to 90 parts of acetonitrile solution, and two parts of silane coupling agent KH-550 were added dropwise. The mixture was magnetically stirred at room temperature for 1 hour, and then 1.5 parts of boron trifluoride diethyl ether were added dropwise. The mixture was then magnetically stirred in an oil bath at 80°C for 4 hours. The resulting solution was then filtered through filter paper to remove the white precipitate particles of B(OH)3 generated after the hydrolysis of boron trifluoride, yielding a toluene solution of siloxane-terminated PEG. Four parts of tetramethoxysilane were added to the toluene solution of the siloxane-terminated PEG, and the mixture was stirred until homogeneous and then sonicated for 50 minutes. During sonication, a hydrochloric acid / ethanol / water solution with pH=1.5 was added dropwise. As hydrochloric acid was added, the system gradually turned milky white. The emulsion was placed in a 60°C oil bath and stirred at 100 r / min. The product was filtered, washed three times repeatedly with deionized water and alcohol, and then dried in a vacuum drying oven at 60°C for 24 hours to obtain single-shell phase change microcapsules.

[0127] II. Preparation of Modified Textile Materials

[0128] The dried single-shell phase change microcapsules were placed in deionized water to prepare a finishing solution of 80 g / L. The fiber substrate was soaked in the finishing solution for 15 min and then placed in an oven at 100°C for 20 min to obtain the modified textile material.

[0129] Implementation Results Example

[0130] 1. Differential scanning calorimetry (DSC) was used to test the phase transition temperature and enthalpy of the textile materials prepared in Examples 1-7 and Comparative Examples 1-2.

[0131] Accurately weigh 5-10 mg of sample; test temperature range: -20-100℃; test atmosphere: N2; heating and cooling rate: 10℃ / min. The textile materials prepared in Examples 1-7 and Comparative Examples 1-2 were tested using a differential scanning calorimeter. The test results are shown in Tables 1 and 2.

[0132] (1) Table 1 compares the thermal properties of the antibacterial heat storage and temperature-regulating textile materials prepared in Examples 1-7 with those of Comparative Examples 1-2 before washing.

[0133] Example Melting point Tm (°C) Enthalpy of fusion (J / g) Crystallization point Tc (°C) Enthalpy of crystallization (J / g) Example 1 31.61 189.7 27.11 193.9 Example 2 29.24 176.6 24.06 171.4 Example 3 27.55 151.3 22.18 163.7 Example 4 34.16 209.5 25.76 204.6 Example 5 35.49 220.2 26.37 214.9 Example 6 32.13 179.8 26.95 185.3 Example 7 32.89 185.7 27.23 190.5 Comparative Example 1 21.68 128.1 13.57 124.9 Comparative Example 2 52.09 156.3 33.96 149.8

[0134] Table 1 shows that different composite phase change materials were obtained by adjusting the ratio of PEG with different molecular weights, which allowed for control of the phase transition temperature range of textile materials. The phase transition temperatures of the modified textile materials prepared with single phase change materials in Comparative Examples 1-2 far exceeded the optimal human body temperature of 26-32℃. However, the textile materials prepared by adjusting the type and ratio of composite phase change materials not only achieved precise temperature control, but also, especially, the textile materials prepared under the condition of PEG800:PEG1000=(1:1), had phase transition temperatures within the optimal human body temperature range of 26-32℃. According to the enthalpy results, the addition of polydopamine to the double-shell phase change microcapsules effectively increased the enthalpy value of the textile materials. For example, in Example 1, the melting enthalpy and crystallization enthalpy were 189.7 J / g and 193.9 J / g, respectively, which were much higher than those in Comparative Examples 1-2, indicating that the textile materials prepared with the addition of polydopamine have good photothermal conversion efficiency and heat storage function.

[0135] (2) Table 2 compares the thermal properties of the antibacterial, heat-storing, and temperature-regulating textile materials prepared in Examples 1-7 after washing.

[0136] Example Melting point Tm (°C) Enthalpy of fusion (J / g) Crystallization point Tc (°C) Enthalpy of crystallization (J / g) Example 1 30.31 136.9 26.09 133.6 Example 2 28.69 124.7 25.44 134.9 Example 3 26.42 111.3 22.03 107.3 Example 4 33.78 153.1 25.71 149.1 Example 5 35.32 169.2 27.89 152.4 Example 6 31.97 128.32 28.46 124.35 Example 7 32.01 130.78 28.97 130.84

[0137] The results in Table 2 show that the DSC results of Examples 1-7 before and after washing indicate that the antibacterial heat storage and temperature regulation textile materials prepared by the method provided in this invention have almost no change in phase transition temperature after 100 cycles of washing. The enthalpy value is reduced but still has a large heat storage capacity. In particular, the melting enthalpy and crystallization enthalpy of Example 1 can still be as high as 136.9 J / g and 133.6 J / g, respectively. This indicates that the textile materials treated with double-shell phase change microcapsules have high washability and phase change energy storage.

[0138] 2. Antibacterial performance test: The textile materials prepared in the examples and comparative examples were washed 100 times according to the method in Appendix C of standard FZ / T73023-2006 Antibacterial Knitted Fabrics, and then dried for later use. Antibacterial performance was tested according to GB / T 20944.3-2008 Evaluation of Antibacterial Properties of Textiles Part 3: Shaking Method, using Escherichia coli 8099, Staphylococcus aureus ATCC 6538, and Candida albicans ATCC 10231.

[0139] Test procedure: Sterilize textile material samples before and after washing, place them in Erlenmeyer flasks, add PBS buffer and inoculate with bacterial solution, shake on a constant temperature shaker and dilute, transfer the liquid from the flasks to sterile Petri dishes, pour in nutrient agar or Sabouraud agar medium, let it solidify at room temperature, then invert the plates and incubate at 37℃±1℃ for 24h-48h (48h-72h for Candida albicans), record the number of colonies in each plate, and calculate the inhibition rate according to the formula in the standard.

[0140] (1) Table 3 shows the antibacterial rates of the examples and comparative examples before washing.

[0141] Example Antibacterial rate against Staphylococcus aureus (%) Antibacterial rate of Escherichia coli (%) Antibacterial rate of Candida albicans (%) Example 1 99.36 99.78 96.71 Example 2 97.25 98.94 94.98 Example 3 98.87 98.63 94.07 Example 4 97.99 96.82 95.87 Example 5 96.04 95.57 93.62 Example 6 99.83 99.06 96.69 Example 7 97.05 97.89 93.13 Comparative Example 1 0 0 0 Comparative Example 2 0 0 0

[0142] Table 3 shows that the preparation method provided by the present invention, which grafts organosilicon quaternary ammonium salt antibacterial agent onto the surface of double-shell phase change microcapsules, has a high antibacterial rate against both bacteria and fungi, and greatly improves the antibacterial performance of textile materials.

[0143] (2) Table 4 shows the antibacterial rate of the examples after washing.

[0144] Example Antibacterial rate against Staphylococcus aureus (%) Antibacterial rate of Escherichia coli (%) Antibacterial rate of Candida albicans (%) Example 1 96.97 88.65 78.17 Example 2 95.19 86.89 79.45 Example 3 90.58 82.64 72.95 Example 4 92.73 86.87 74.46 Example 5 90.82 83.44 70.37 Example 6 97.02 87.96 80.37 Example 7 94.38 87.23 75.65

[0145] Table 4 shows that the antibacterial, heat-storing, and temperature-regulating textile material still retains its 5A-level antibacterial properties after 100 cycles of washing. Organosilicon quaternary ammonium salts act as connecting bridges, and their silanol groups can be chemically grafted to form stable and strong covalent bonds with the amino groups on the surface of polydopamine and the hydroxyl groups on the surface of the fiber substrate. This allows the phase change microcapsules to adhere firmly to the surface of the fiber substrate through chemical grafting, making them difficult to detach.

[0146] The above results demonstrate that this invention selects two polyethylene glycols of different molecular weights and prepares a novel binary composite phase change material using a heating and eutectic method. Adding this material to textiles enables the fabric to possess a unique bidirectional temperature-regulating function, ensuring its phase change temperature falls within the required range for the application. This overcomes the limitation of single-molecular-weight polyethylene glycol, which cannot fully meet the temperature regulation requirements within the human-perceived comfortable temperature range of 26-32°C. This newly formed binary composite phase change material possesses the advantages of single-molecular-weight polyethylene glycol phase change materials while also addressing, to some extent, the limitations of single-molecular-weight polyethylene glycol phase change materials. This precise temperature regulation characteristic can be applied not only to textiles but also widely to fields such as construction, medicine, and energy.

[0147] Dopamine can spontaneously oxidize and polymerize on the shell of solid materials to form a buffer layer polydopamine (PDA). This not only provides chemical adsorption sites for subsequent modification and grafting, activating surface activity, but also provides a material with good photothermal absorption and high thermal conductivity. It has strong light absorption capabilities in ultraviolet, visible, and near-infrared light. The broad light absorption and excellent photothermal performance of the PDA layer can promote energy absorption and photothermal conversion efficiency, achieving a rapid dynamic temperature regulation effect.

[0148] Among the many types of antibacterial agents for textiles, organosilicon quaternary ammonium salts are a class of antibacterial agents with ideal comprehensive performance. This antibacterial agent does not require high-temperature baking when treating fabrics, and the treated fabrics not only possess excellent antibacterial properties but also good water absorption, softness, stain resistance, and are non-irritating and non-carcinogenic to human skin. This antibacterial agent can form covalent bonds not only with the amino groups on polydopamine but also with the hydroxyl groups on textiles through dehydration condensation, forming covalent bonds that can be firmly grafted onto the surface of textiles at certain temperatures.

[0149] In this invention, dopamine is oxidatively polymerized on the surface of SiO2 spheres, and the exposed amino groups on the sphere surface increase a large number of binding sites. Organosilicon quaternary ammonium salts act as connecting bridges, and their silanol groups can tightly bind with the amino groups on the surface of polydopamine and the hydroxyl groups of cotton fibers to form stable and strong covalent bonds. This allows the phase change microcapsules to attach to the surface of cotton fibers through chemical grafting, thereby playing an antibacterial and temperature-regulating role and not easily falling off.

[0150] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an antibacterial, heat-storing, and temperature-regulating textile material, characterized in that, The main steps include the following: S1, Preparation of composite phase change material: Polyethylene glycol of different molecular weights is placed into a reaction vessel in different mass ratios and stirred evenly at a certain temperature to prepare composite phase change material; S2, Preparation of double-shell phase change microcapsules: First, silane coupling agent and the composite phase change material prepared in S1 are added to a reaction vessel in proportion and stirred and mixed evenly in a certain solvent. Then, catalyst and silicon source material are added sequentially to prepare single-shell SiO2-PEG phase change microcapsules. Then, the single-shell SiO2-PEG phase change microcapsules, dopamine monomer, and Tris-HCl buffer are added to the reaction vessel in proportion. The mixture is mechanically stirred at room temperature to allow the dopamine monomer to self-assemble and oxidize on the surface of the single-shell SiO2-PEG phase change microcapsules. After post-treatment, double-shell PDA-SiO2-PEG phase change microcapsules are obtained. S3, Preparation of Quaternized Ammonium Double-Shell Phase Change Microcapsules: A certain concentration of organosilicon quaternary ammonium salt solution was added to the reaction vessel. Under magnetic stirring, 3M NaOH was slowly added dropwise until pH=10. The double-shell PDA-SiO2-PEG phase change microcapsules prepared in S2 were then added to the reaction vessel. After the reaction was completed, the product was filtered, washed with deionized water and alcohol, and dried in a vacuum drying oven to prepare quaternized ammonium double-shell phase change microcapsules. S4, Preparation of antibacterial heat storage and temperature regulation textile material: The quaternized double-shell phase change microcapsules prepared in S3 are uniformly dispersed in deionized water to form a grafting reaction solution. The fiber substrate containing hydroxyl groups is immersed in the grafting reaction solution for a certain time, and then baked at a certain temperature to obtain the antibacterial heat storage and temperature regulation textile material. The amount of each component added in the quaternized double-shell phase change microcapsule includes the following parts by weight: 8-12 parts of composite phase change material, 1-2 parts of silane coupling agent, 1-2 parts of catalyst, 3-5 parts of silicon source material, 4-5 parts of dopamine monomer, and 4-6 parts of organosilicon quaternary ammonium salt solution; wherein the composite phase change material is prepared by mixing any two polyethylene glycols with a molecular weight range of 600-1200 as the main raw materials in a weight ratio of 2:1-3.

2. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 1, characterized in that, The steps for preparing double-shell phase change microcapsules as described in S2 specifically include: S21, a certain amount of the composite phase change material prepared in S1 is placed into a reaction vessel containing a certain amount of solvent, a certain amount of silane coupling agent is added dropwise, and the mixture is stirred evenly at room temperature to obtain a phase change material dispersion. S22, a catalyst is added dropwise to the phase change material dispersion, heated and stirred, and impurities are removed by filtration to obtain a siloxane PEG prepolymer solution; S23, a certain amount of silicon source material is added to the siloxane PEG prepolymer solution, and after stirring evenly, it is ultrasonicated. During the ultrasonication process, a mixed solution of hydrochloric acid and ethanol with pH=1~2 is added dropwise to emulsify until the system turns milky white. The emulsion is placed in an oil bath and stirred at low speed. The product is filtered, washed with deionized water and alcohol in sequence, and placed in a vacuum drying oven to dry, thus obtaining single-shell SiO2-PEG phase change microcapsules. S24, the single-shell SiO2-PEG phase change microcapsules, dopamine monomer, and Tris-HCl buffer solution are added to the reaction vessel, and mechanical stirring is carried out at room temperature to allow the dopamine monomer to self-assemble and oxidize and polymerize on the surface; the synthesized product is filtered, washed with deionized water, and dried to obtain double-shell PDA-SiO2-PEG phase change microcapsules.

3. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 2, characterized in that, The weight ratio of the composite phase change material, silane coupling agent, and solvent in S21 includes 10:1-2:80-100; the solvent includes any one of toluene, acetonitrile, xylene, and acetone; the silane coupling agent includes any one of γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), γ-methacryloyloxypropyltrimethoxysilane (KH570), and 3-aminopropyltriethoxysilane (APS).

4. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 2, characterized in that, The weight ratio of the composite phase change material to the catalyst in S22 is 10:1-2; the catalyst includes any one of boron trifluoride ether, potassium persulfate, ammonia, sodium hydroxide, and potassium hydroxide; the heating temperature is 60-100℃, the stirring reaction time is 3-5h, and the stirring rate is 200-250r / min.

5. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 2, characterized in that, The silicon source material described in S23 includes the following chemical structural formula, wherein R is any one of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3. 。 6. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 2, characterized in that, The weight ratio of the silicon source material to the composite phase change material in S23 is 3-5:10; the silicon source material includes any one of tetraethyl orthosilicate, tetramethoxysilane, tetrapropoxysilane, and tetra-n-butoxysilane; the ultrasonic power is 250-300W, and the ultrasonic time is 30-50min; the stirring rate is 80-120r / min, the stirring time is 12-16h, and the stirring temperature is 60-80℃; the vacuum drying temperature is 40-60℃, and the drying time is 22-26h.

7. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 2, characterized in that, The weight ratio of the single-shell SiO2-PEG phase change microcapsules, dopamine monomer, and Tris-HCl buffer in S24 is 10:4-5:80-120; the stirring rate is 200-300 r / min, and the stirring time is 22-26 h; the drying temperature is 40-60℃, and the drying time is 16-24 h.

8. The method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to claim 1, characterized in that, The weight ratio of the organosilicon quaternary ammonium salt solution to the double-shell PDA-SiO2-PEG phase change microcapsules in S3 is 5:5-10; the mass concentration of the organosilicon quaternary ammonium salt solution is 0.05-0.1%, and the organosilicon quaternary ammonium salt includes any one of 3-(trimethoxysilylpropyl)dimethyloctadecyl ammonium chloride, 3-(triethoxysilylpropyl)dimethyloctadecyl ammonium chloride, and 3-(trihydroxysilylpropyl)dimethyloctadecyl ammonium chloride; the magnetic stirring speed is 200-300 r / min, the reaction temperature is 60-80℃, and the reaction time is 10-14 h; the drying temperature is 40-60℃, and the drying time is 16-24 h.

9. The method for preparing antibacterial, heat-storing, and temperature-regulating textile material according to any one of claims 1-8, characterized in that, The phase change composite material described in S1 is prepared by mixing any two polyethylene glycols with a molecular weight range of 600-1200 as the main raw materials, mixing them in a weight ratio of 2:1-3, and stirring uniformly at 50℃±2℃ for 2h±0.5h.

10. The method for preparing antibacterial, heat-storing, and temperature-regulating textile material according to claim 9, characterized in that, The concentration of the aqueous solution of the quaternized double-shell phase change microcapsules in S4 is 50-110 g / L; the soaking time is 10-20 min, the baking temperature is 80-120℃, the baking time is 10-20 min, and the weight gain is 10%-30%.

11. An antibacterial, heat-storing, and temperature-regulating textile material, characterized in that, It was prepared using the method for preparing antibacterial, heat-storing, and temperature-regulating textile materials according to any one of claims 1-10.

12. The antibacterial, heat-storing, and temperature-regulating textile material according to claim 11, characterized in that, It has antibacterial properties, with an antibacterial rate of ≥95% against bacteria and ≥93% against fungi. After 100 cycles of washing, it has 5A-level antibacterial properties; it also has heat storage and temperature regulation properties.

13. The antibacterial, heat-storing, and temperature-regulating textile material according to claim 12, characterized in that, The fiber substrate includes any one of cotton yarn, cotton cloth, polyester fiber, nylon fiber, and wool.

14. The application of an antibacterial, heat-storing, and temperature-regulating textile material according to any one of claims 11-13 as a raw material in the fields of clothing, home textiles, socks, and medical and health products.

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