Thermal management fabric and preparation method thereof
By combining Fe-MIL-101-NH2-loaded phase change material and bifunctional agglomerate (N-isopropylacrylamide) on a textile substrate, the problem of poor bonding between phase change composite materials and textiles is solved, achieving stability and efficient temperature regulation of thermal management fabrics.
Patent Information
- Application Number
- CN202511174716.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-21
- Publication Date
- 2025-11-18
AI Technical Summary
In the existing technology, the post-treatment method of phase change composite materials has poor bonding with textiles, which makes the phase change composite materials easy to fall off, thus limiting the practical application of phase change composite material heat storage and temperature regulation textiles.
A phase change material loaded with Fe-MIL-101-NH2 is combined with a bifunctional polymer (N-isopropylacrylamide). The phase change composite material is fixed on a textile substrate by pad-drying. The bonding strength is enhanced by the adsorption of Fe-MIL-101-NH2 through its pores and the reaction of the amino and catechol groups of the bifunctional polymer (N-isopropylacrylamide) with the textile substrate and waterborne polyurethane.
It achieves the stability of phase change composite materials on textile substrates, improves the thermal management and washability of fabrics, and can effectively regulate temperature when the ambient temperature changes.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of fabrics, and particularly relates to a thermal management fabric and a preparation method thereof. BACKGROUND
[0002] In the current era of rapid technological development, people's demand for comfortable and intelligent life is increasingly urgent. As an indispensable necessity of life, the development of textiles in terms of functionality and intelligence has attracted much attention. Under the current background, textiles that can adjust temperature in hot / cold environments (thermal management fabrics) have received widespread attention.
[0003] Traditional clothing has obvious limitations in temperature regulation, and its warmth-keeping effect mainly depends on increasing the air content in the fabric, using the principle of heat insulation to reduce heat loss. This temperature regulation method is relatively passive, and the warmth-keeping performance is significantly affected by the thickness and density of the fabric, making it difficult to meet the higher demand for thermal comfort of contemporary people. Intelligent temperature-regulating clothing has the ability to regulate temperature in both directions, which can significantly improve the thermal comfort of the human body during wearing. One of the methods to prepare intelligent temperature-regulating textiles is to effectively combine textile materials with phase change composites, which can endow textiles with the ability to store and release heat. Phase change composites control the absorption and release of heat from the environment through phase changes (such as transitions between solid and liquid states) within the phase change temperature range, thereby achieving bidirectional temperature regulation of the fabric.
[0004] Generally, the application of phase change composites in textiles mainly includes spinning method and finishing method. The spinning method uses phase change composites as a component of the spinning solution, which has strict requirements for the particle size, acid and alkali resistance, and heat resistance of phase change microcapsules, and has many operation procedures and high requirements for equipment. The finishing method uses phase change composites as a finishing liquid component, which is processed on the surface of textiles through immersion, padding or coating. It is a common method for preparing phase change composite heat storage and temperature regulating textiles at present, but it has the problem of weak combination between phase change composites and textile substrates, which easily leads to shedding and limits the practical application of phase change composite heat storage and temperature regulating textiles. Therefore, improving the combination of phase change composites and textiles by the finishing method is a technical problem to be solved at present. SUMMARY
[0005] One of the purposes of the present application is to provide a thermal management fabric to solve the problem of poor combination of phase change composites and textiles by the finishing method in the prior art.
[0006] The second purpose of the present application is to provide a preparation method of a thermal management fabric for preparing the above-mentioned thermal management fabric.
[0007] The object of the present application can be achieved by the following technical solutions: A heat management fabric obtained by padding and drying a textile substrate and a temperature regulating finishing liquid, the temperature regulating finishing liquid comprising the following raw materials by weight: 100 parts of water-based polyurethane, 5-15 parts of phase change composite material, 3-5 parts of bifunctional poly(N-isopropyl acrylamide), 300-500 parts of deionized water.
[0008] Further, the phase change composite material is Fe-MIL-101-NH2 loaded phase change material.
[0009] Further, the phase change temperature of the phase change material is 25-40℃, and the phase change material is at least one of n-octadecane, n-nonadecane, n-eicosane, tetradecanol and paraffin.
[0010] Further, the bifunctional poly(N-isopropyl acrylamide) is poly(N-isopropyl acrylamide) carrying amino and o-diphenol groups.
[0011] Further, the phase change composite material preparation steps are as follows: Fe-MIL-101-NH2 is added to anhydrous ethanol, stirred uniformly, then the phase change material is added, stirred at 60-65℃ for 4-6h, after stirring is completed, the temperature is lowered to 15-20℃, filtered, and the filter cake is the phase change composite material.
[0012] Metal organic framework (MOFs) has high specific surface area and porosity, unique topological structure, adjustable structure and pore size, and can be modified, etc., and is a good carrier material, therefore, the present application utilizes the capillary force of the channel in the Fe-MIL-101-NH2 skeleton to make the phase change material firmly adsorbed in the channel, so as to achieve the purpose of preventing the phase change material from leaking.
[0013] Further, in the above preparation steps, the amount ratio of Fe-MIL-101-NH2, anhydrous ethanol and phase change material is 0.5g:100mL:0.5-1.5g.
[0014] Further, the bifunctional poly(N-isopropyl acrylamide) preparation steps are as follows: N-isopropyl acrylamide, azobisisobutyronitrile and methanol are added to a flask equipped with a reflux condenser, stirred uniformly, then cysteamine hydrochloride and 4-mercapto benzene-1,2-diol are added, vacuum is extracted, nitrogen protection is carried out, stirring is carried out at 55-65℃ for 12h, after the reaction is completed, sodium hydroxide methanol solution is added to neutralize HCl in the reaction system, stirring is carried out for 30min, vacuum filtration is carried out, the filter cake is dissolved in tetrahydrofuran and precipitated with diethyl ether, the precipitated product is vacuum dried to obtain the bifunctional poly(N-isopropyl acrylamide).
[0015] With azobisisobutyronitrile as initiator, mercaptoacetic acid and 4-mercapto benzene-1,2-diol as chain transfer agent, a double functional group poly(N-isopropyl acrylamide) is obtained by free radical polymerization, which not only has the temperature-sensitive characteristics of poly(N-isopropyl acrylamide) itself, but also carries amino and o-diphenol groups.
[0016] Further, in the above preparation step, the amount ratio of N-isopropyl acrylamide, azobisisobutyronitrile, methanol, cysteamine hydrochloride and 4-mercapto benzene-1,2-diol is 10g:0.25-0.30g:100-150mL:0.1-0.3g:0.1-0.3g.
[0017] Further, the CAS number of the 4-mercapto benzene-1,2-diol is 27320-22-5, which is purchased from Zhengzhou Alpha Chemical Co., Ltd.
[0018] Further, the textile substrate is any one of cotton fabric, silk fabric, polyester fabric, polyester-cotton fabric, modal fabric, Tencel fabric, polypropylene non-woven fabric and polyester non-woven fabric.
[0019] Further, the aqueous polyurethane is a single-component aqueous polyurethane, and the solid content is 30-50%.
[0020] A preparation method of a thermal management fabric, comprising the following steps: S1, preparing a temperature regulating finishing liquid: mixing phase change composite material, double functional group poly(N-isopropyl acrylamide) and deionized water uniformly, then adding aqueous polyurethane and continuing to stir uniformly to obtain the temperature regulating finishing liquid; S2, adding the textile substrate into the temperature regulating finishing liquid, treating the textile substrate by adopting the double-dip-double-pad mode, and the pick-up rate is 65%, after the padding is completed, pre-drying at 80℃ for 5-10min, and drying at 100-110℃ for 15-25min to obtain the thermal management fabric.
[0021] The beneficial effects of the present application are: 1. The present application provides a thermal management fabric, which is obtained by dip-padding and drying of a textile substrate and a temperature regulating finishing liquid, wherein the temperature regulating finishing liquid has good film forming effect, and can finish the phase change composite material and the temperature-sensitive polymer on the textile substrate, and improve the heat storage and temperature regulating performance and washing resistance of the textile substrate.
[0022] 2. In the present application, the phase change composite material is Fe-MIL-101-NH2 loaded phase change material, which undergoes liquid-solid reversible change with the change of external environment temperature, that is, when the environment temperature rises, the phase change material absorbs and stores heat, and changes from solid to liquid, when the environment temperature decreases, the phase change material releases the stored heat, and changes from liquid to solid, so as to realize the temperature self-regulation of the textile.
[0023] 3. In the present application, the phase change composite material uses Fe-MIL-101-NH2 as a porous carrier, which not only has the effect of preventing leakage, but also carries amino groups that can react with waterborne polyurethane to fix the phase change composite material on the surface of the textile substrate; the catechol groups contained in the double functional group poly(N-isopropyl acrylamide) can not only coordinate with the iron ions in Fe-MIL-101-NH2 to firmly anchor the phase change composite material, but also form hydrogen bonds with the oxygen-containing groups on the surface of the textile substrate to strengthen the interfacial adhesion, and at the same time, the amino groups of the double functional group poly(N-isopropyl acrylamide) can also react with waterborne polyurethane to build a covalent network, and the synergistic effect of these multiple actions enhances the stability of the phase change composite material on the textile substrate.
[0024] 4. In the present application, the double functional group poly(N-isopropyl acrylamide) has a temperature-sensitive property, with a low critical solution temperature close to the body temperature of a human body. When the environmental temperature is lower than the critical solution temperature, the double functional group poly(N-isopropyl acrylamide) forms a polymer gel layer, which reduces the voids between fibers and is beneficial to reducing heat loss. When the environmental temperature is higher than the critical solution temperature, the molecular chains of the double functional group poly(N-isopropyl acrylamide) shrink to form small pores, which is beneficial to enhancing the heat dissipation effect. Therefore, the introduction of the double functional group poly(N-isopropyl acrylamide) is beneficial to enhancing the thermal management performance of the phase change textile. DETAILED DESCRIPTION
[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.
[0026] The waterborne polyurethane in the present application is waterborne polyurethane RL8302 produced by Guangzhou Ruilin New Material Co., Ltd., with a solid content of 30%. The 4-mercapto benzene-1,2-diol has a CAS number of 27320-22-5 and is purchased from Zhengzhou Alpha Chemical Co., Ltd. The textile substrate is pure cotton fabric, with a plain weave and a yarn density of 14.8 tex for both warp and weft, a warp and weft density of 216 and 138 respectively per 10 cm, a thickness of 0.24 mm, and a surface density of 115 g / m 2 The remaining raw materials are purchased from the market.
[0027] The following will be specifically described in combination with the embodiments.
[0028] Preparation Example 1
[0029] A phase change composite material, the preparation steps are as follows: 0.5g Fe-MIL-101-NH2 was added into 100mL anhydrous ethanol, after stirring evenly, 0.5g n-octadecane was added, stirring at 60℃ for 4h, after stirring, cooling to 15℃, filtering, the filter cake was the phase change composite material.
[0030] Preparation Example 2
[0031] A phase change composite material, the preparation steps were as follows: 0.5g Fe-MIL-101-NH2 was added into 100mL anhydrous ethanol, after stirring evenly, 1.0g n-octadecane was added, stirring at 62℃ for 5h, after stirring, cooling to 18℃, filtering, the filter cake was the phase change composite material.
[0032] Preparation Example 3
[0033] A phase change composite material, the preparation steps were as follows: 0.5g Fe-MIL-101-NH2 was added into 100mL anhydrous ethanol, after stirring evenly, 1.5g n-octadecane was added, stirring at 65℃ for 6h, after stirring, cooling to 20℃, filtering, the filter cake was the phase change composite material.
[0034] Comparative Example 1
[0035] A phase change composite material, compared with Preparation Example 1, the difference was that Fe-MIL-101-NH2 in Preparation Example 1 was replaced by mesoporous silica of the same mass, and the mesoporous silica was JK-04-003 purchased from Nanjing Jikeli Biological Technology Co., Ltd.
[0036] Preparation Example 4
[0037] A bifunctional poly(N-isopropylacrylamide), the preparation steps were as follows: 10g N-isopropylacrylamide, 0.25g azobisisobutyronitrile and 100mL methanol were added into a flask equipped with a reflux condenser, after stirring evenly, 0.1g cysteamine hydrochloride and 0.1g 4-mercaptobenzene-1,2-diol were added, vacuumizing and protecting by nitrogen, stirring at 55℃ for 12h, after reaction, sodium hydroxide methanol solution was added to neutralize HCl in the reaction system, stirring for 30min, vacuum filtration, the filter cake was dissolved in tetrahydrofuran and precipitated with diethyl ether, the precipitated product was vacuum dried to obtain the bifunctional poly(N-isopropylacrylamide).
[0038] Preparation Example 5
[0039] A bifunctional poly(N-isopropylacrylamide), the preparation steps were as follows: A double functional poly(N-isopropylacrylamide) was prepared by the following steps:
[0040] Preparation Example 6
[0041] A double functional poly(N-isopropylacrylamide) was prepared by the following steps: A double functional poly(N-isopropylacrylamide) was prepared by the following steps:
[0042] Comparative Example 2
[0043] A double functional poly(N-isopropylacrylamide) was prepared by the following steps:
[0044] Comparative Example 3
[0045] A double functional poly(N-isopropylacrylamide) was prepared by the following steps:
[0046] Comparative Example 4
[0047] A double functional poly(N-isopropylacrylamide) was prepared by the following steps:
[0048] Example 1
[0049] A method for preparing a thermal management fabric, comprising the following steps: S1, preparing a temperature regulating finishing liquid: mixing the phase change composite material, the bifunctional poly(N-isopropylacrylamide) and deionized water uniformly, then adding the water-based polyurethane, and continuing to stir uniformly to obtain the temperature regulating finishing liquid; S2, adding the textile substrate into the temperature regulating finishing liquid, treating the textile substrate by adopting the double-dip double-pad method, the pad percentage is 65%, after the padding is completed, pre-drying at 80°C for 5min, drying at 100°C for 15min, to obtain the thermal management fabric.
[0050] The temperature regulating finishing liquid includes the following raw materials by weight: 100 parts of the water-based polyurethane, 5 parts of the phase change composite material of Preparation Example 1, 3 parts of the bifunctional poly(N-isopropylacrylamide) of Preparation Example 4, and 300 parts of deionized water.
[0051] Example 2
[0052] A preparation method of a thermal management fabric includes the following steps: S1, preparing a temperature regulating finishing liquid: mixing the phase change composite material, the bifunctional poly(N-isopropylacrylamide) and deionized water uniformly, then adding the water-based polyurethane, and continuing to stir uniformly to obtain the temperature regulating finishing liquid; S2, adding the textile substrate into the temperature regulating finishing liquid, treating the textile substrate by adopting the double-dip double-pad method, the pad percentage is 65%, after the padding is completed, pre-drying at 80°C for 8min, drying at 105°C for 15-25min, to obtain the thermal management fabric.
[0053] The temperature regulating finishing liquid includes the following raw materials by weight: 100 parts of the water-based polyurethane, 10 parts of the phase change composite material of Preparation Example 1, 4 parts of the bifunctional poly(N-isopropylacrylamide) of Preparation Example 4, and 400 parts of deionized water.
[0054] Example 3
[0055] A preparation method of a thermal management fabric includes the following steps: S1, preparing a temperature regulating finishing liquid: mixing the phase change composite material, the bifunctional poly(N-isopropylacrylamide) and deionized water uniformly, then adding the water-based polyurethane, and continuing to stir uniformly to obtain the temperature regulating finishing liquid; S2, adding the textile substrate into the temperature regulating finishing liquid, treating the textile substrate by adopting the double-dip double-pad method, the pad percentage is 65%, after the padding is completed, pre-drying at 80°C for 10min, drying at 105°C for 25min, to obtain the thermal management fabric.
[0056] The temperature regulating finishing liquid includes the following raw materials by weight: 100 parts of waterborne polyurethane, 15 parts of the phase change composite material of Preparation Example 1, 5 parts of the difunctional poly(N-isopropylacrylamide) of Preparation Example 4, 500 parts of deionized water.
[0057] Example 4
[0058] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the phase change composite material in Preparation Example 1 is replaced by the product of equal mass of Preparation Example 2, and the difunctional poly(N-isopropylacrylamide) is replaced by the product of equal mass of Preparation Example 5.
[0059] Example 5
[0060] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the phase change composite material in Preparation Example 1 is replaced by the product of equal mass of Preparation Example 3, and the difunctional poly(N-isopropylacrylamide) is replaced by the product of equal mass of Preparation Example 6.
[0061] Comparative Example 1
[0062] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the phase change composite material in Preparation Example 1 is replaced by the product of equal mass of Comparative Example 1.
[0063] Comparative Example 2
[0064] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the difunctional poly(N-isopropylacrylamide) in Preparation Example 1 is replaced by the product of equal mass of Comparative Example 2.
[0065] Comparative Example 3
[0066] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the difunctional poly(N-isopropylacrylamide) in Preparation Example 1 is replaced by the product of equal mass of Comparative Example 3.
[0067] Comparative Example 4
[0068] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the difunctional poly(N-isopropylacrylamide) in Preparation Example 1 is replaced by the product of equal mass of Comparative Example 4.
[0069] Comparative Example 5
[0070] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the difunctional poly(N-isopropylacrylamide) in Example 1 is removed.
[0071] Comparative Example 6
[0072] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the phase change composite material in Preparation Example 1 is replaced by the product obtained in Comparative Example 1, and the bifunctional group (N-isopropyl acrylamide) is replaced by the product obtained in Comparative Example 4.
[0073] Comparative Example 7
[0074] A method for preparing a thermal management fabric, compared with Example 1, the difference is that the phase change composite material in Preparation Example 1 is replaced by the product obtained in Comparative Example 1, and the bifunctional group (N-isopropyl acrylamide) is removed.
[0075] The thermal management fabrics obtained in Examples 1-5 and Comparative Examples 1-7 are subjected to performance tests, and the test process is as follows: Each group of thermal management fabrics is transferred from room temperature (25°C) to a high-temperature environment (45°C), and the time for the temperature of the thermal management fabric to reach 40°C is recorded. Each group of thermal management fabrics at 40°C is transferred to a low-temperature environment (10°C), and the time for the temperature of the thermal management fabric to reach 20°C is recorded, thereby reflecting the management performance of the fabric. Each group of thermal management fabrics is weighed and recorded as m0, and then soaked in deionized water at 45°C for washing. After soaking for 2 min, it is taken out and wrung dry for 1 washing, and the same is repeated for 20 washings. Finally, it is dried at 40°C to a constant weight, weighed, and recorded as m1. The mass change rate before and after washing is calculated, and the mass change rate (%) = (m1-m0) / m0x100%. The results are shown in Table 1: Table 1
[0076] As can be seen from the data recorded in Table 1, the fabric in Examples 1-5 has a time of ≥30.5s from 25°C to 40°C, a time of ≥39.5s from 40°C to 20°C, and a mass change rate of ≤0.4%. Compared with Comparative Examples 1-7, it has better temperature adjustment performance and washing resistance.
[0077] It should be noted that in this document, relational terms such as first and second and the like can only be used to distinguish one entity or action from another entity or action, without necessarily requiring or implying that there is any such actual relationship or order between these entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof are intended to cover non-exclusive inclusions, so that a process, method, article, or apparatus that includes a list of elements does not only include those elements, but also includes other elements not explicitly listed, or other elements inherent to such a process, method, article, or apparatus.
[0078] While embodiments of the application have been shown and described, it is to be understood that the embodiments described are merely exemplary of the principles and application of the present application. Numerous modifications and adaptions can be effected without departing from the spirit and scope of the present application, which is not limited to the exact construction and arrangement described. It is intended, therefore, to cover all modifications and adaptions that fall within the scope of the claims and their equivalents.
Claims
1. A thermal management fabric, characterized in that, It is obtained by pad-drying a textile substrate and a temperature-regulating finishing solution, wherein the temperature-regulating finishing solution comprises the following raw materials in parts by weight: 100 parts waterborne polyurethane, 5-15 parts phase change composite material, 3-5 parts bifunctional polymer (N-isopropylacrylamide), 300-500 parts deionized water; The phase change composite material is a Fe-MIL-101-NH2 supported phase change material; The bifunctional polymer (N-isopropylacrylamide) is a poly(N-isopropylacrylamide) carrying amino and catechol groups.
2. The thermal management fabric according to claim 1, characterized in that, The phase change temperature of the phase change material is 25-40℃.
3. A thermal management fabric according to claim 1 or 2, characterized in that, The phase change material is at least one of n-octadecane, n-nonadecane, n-eicosane, tetradecyl alcohol, and paraffin.
4. The thermal management fabric according to claim 1, characterized in that, The preparation steps of the phase change composite material are as follows: Add Fe-MIL-101-NH2 to anhydrous ethanol, stir until homogeneous, then add phase change material, stir at 60-65℃ for 4-6 hours, after stirring is complete, cool to 15-20℃, filter, and the filter cake is the phase change composite material.
5. A thermal management fabric according to claim 4, characterized in that, The ratio of Fe-MIL-101-NH2, anhydrous ethanol, and phase change material is 0.5g:100mL:0.5-1.5g.
6. A thermal management fabric according to claim 1, characterized in that, The preparation steps of the bifunctional polymer (N-isopropylacrylamide) are as follows: N-Isopropylacrylamide, azobisisobutyronitrile, and methanol were added to a flask equipped with a reflux condenser and stirred until homogeneous. Cysteine hydrochloride and 4-mercaptobenzene-1,2-diol were then added. The mixture was evacuated under nitrogen protection and stirred at 55-65°C for 12 hours. After the reaction was completed, sodium hydroxide methanol solution was added and stirred for 30 minutes. The mixture was then filtered under reduced pressure. The filter cake was dissolved in tetrahydrofuran and precipitated with diethyl ether. The precipitate was dried under vacuum to obtain the bifunctional agglomerate (N-isopropylacrylamide).
7. A thermal management fabric according to claim 6, characterized in that, The ratio of N-isopropylacrylamide, azobisisobutyronitrile, methanol, cysteine hydrochloride, and 4-mercaptobenzene-1,2-diol is 10g:0.25-0.30g:100-150mL:0.1-0.3g:0.1-0.3g.
8. A thermal management fabric according to claim 1, characterized in that, The textile substrate is any one of cotton fabric, silk fabric, polyester fabric, cotton-polyester fabric, modal fabric, Tencel fabric, polypropylene nonwoven fabric, and polyester nonwoven fabric.
9. A thermal management fabric according to claim 1, characterized in that, The waterborne polyurethane is a single-component waterborne polyurethane with a solid content of 30-50%.
10. A method for preparing a thermal management fabric, characterized in that, The preparation of the thermal management fabric according to any one of claims 1-9 includes the following steps: S1. Preparation of temperature-controlled finishing solution: Mix phase change composite material, bifunctional polymer (N-isopropylacrylamide) and deionized water evenly, then add waterborne polyurethane and continue stirring evenly to obtain temperature-controlled finishing solution. S2. Add the textile substrate to the temperature-regulating finishing solution and treat the textile substrate by two dips and two pads with a padding rate of 65%. After dips and pads are completed, pre-dry at 80°C for 5-10 minutes and dry at 100-110°C for 15-25 minutes to obtain the thermal management fabric.