技术领域Technical Field
本发明属于纺织领域，具体涉及一种快速调控人体温度具有皮芯结构的相变调温纤维膜及其制备方法。The invention belongs to the field of textiles, and in particular relates to a phase-change temperature-regulating fiber membrane with a skin-core structure for rapidly regulating human body temperature and a preparation method thereof.
背景技术Background technique
近几年国内外的专家学者在智能调温纤维的制备及应用方面做了大量研究，调温纺织品具有根据环境温度变化，快速吸放热，保持人体舒适性的特点，对提高能量利用，改善生活质量和保护环境有重大意义。调温纺织品的未来开发方向在于：探究提供潜热高、导热快、人体相容性好、热和机械稳定性良好的相变材料(Research progress oftemperature regulating properties of PCM fabrics[J].International textilereview,2020,48(11): 47-54)。In recent years, experts and scholars at home and abroad have done a lot of research on the preparation and application of intelligent temperature regulating fibers. Temperature regulating textiles have the characteristics of rapid heat absorption and release according to changes in ambient temperature and maintaining human comfort, which is of great significance to improving energy utilization, improving quality of life and protecting the environment. The future development direction of temperature regulating textiles is to explore phase change materials with high latent heat, fast thermal conductivity, good human compatibility, and good thermal and mechanical stability (Research progress of temperature regulating properties of PCM fabrics[J].International textilereview,2020,48(11): 47-54).
有机相变材料是性能优异的热能储存材料，可以用于热量的储存以及对生产过程中废热的转化。但相变材料固液转变中存在的易泄露的问题限制了其发展。人们主要采用多孔基体吸附法、微/纳胶囊包覆法、溶胶-凝胶法、高分子复合共聚法和静电纺丝法等方法制备复合相变材料来解决其泄露问题。静电纺丝法具有选材广泛，制备方法多样的优点，可制备具有高比表面积和高孔隙率的微纳米纤维膜，在功能纺织品领域具有广阔的应用前景。近几年人们开始采用静电纺丝技术制备相变调温纤维。该法可将相变材料与聚合物溶液共混纺丝，或者对于与聚合物相容性较差的相变材料，还可采用同轴静电纺丝技术制备皮-芯结构纤维膜。Lu Yuan et.al.(Novel Smart Textile with Phase ChangeMaterials Encapsulated Core-Sheath Structure Fabricated by CoaxialElectrospinning.Chemical Engineering Journal,2018(555):501-506.)。Organic phase change materials are excellent thermal energy storage materials that can be used for heat storage and the conversion of waste heat in the production process. However, the problem of easy leakage in the solid-liquid transition of phase change materials limits its development. People mainly use porous matrix adsorption method, micro/nano capsule coating method, sol-gel method, polymer composite copolymerization method and electrospinning method to prepare composite phase change materials to solve their leakage problem. The electrospinning method has the advantages of wide selection of materials and diverse preparation methods. It can prepare micro-nano fiber membranes with high specific surface area and high porosity, and has broad application prospects in the field of functional textiles. In recent years, people have begun to use electrospinning technology to prepare phase change thermostatic fibers. This method can blend phase change materials with polymer solutions for spinning, or for phase change materials with poor compatibility with polymers, coaxial electrospinning technology can also be used to prepare skin-core structure fiber membranes. Lu Yuan et.al. (Novel Smart Textile with Phase ChangeMaterials Encapsulated Core-Sheath Structure Fabricated by CoaxialElectrospinning. Chemical Engineering Journal, 2018(555):501-506.).
现有技术中，公开号为CN108374238A的发明申请，提供了一种利用同轴静电纺丝技术制备的相变储热织物，公开了该织物由如下步骤制备而成：(1)将相变材料加入到第一溶剂中搅拌至完全溶解，得到核层溶液，所述的核层溶液中相变材料的质量浓度为30％～90％；(2)将高分子材料加入到第二溶剂中搅拌至完全溶解，得到壳层溶液，所述的壳层溶液中高分子材料的质量浓度为5％～30％；(3)将步骤(1)得到的核层溶液和步骤 (2)中得到的壳层溶液分别注入同轴静电纺丝装置的两个溶液通道，调节同轴静电纺丝参数进行静电纺丝，得到相变储热织物。通过调节核层溶液和壳层溶液的质量浓度和推送速度获得不同潜热值的相变储热纤维膜，同时通过溶液静电纺丝技术，将功能性粒子加入静电纺丝溶液中，实现相变储热织物的功能化，方法简单可靠。In the prior art, an invention application with publication number CN108374238A provides a phase change heat storage fabric prepared by coaxial electrospinning technology, and discloses that the fabric is prepared by the following steps: (1) adding a phase change material to a first solvent and stirring until completely dissolved to obtain a core layer solution, wherein the mass concentration of the phase change material in the core layer solution is 30% to 90%; (2) adding a polymer material to a second solvent and stirring until completely dissolved to obtain a shell layer solution, wherein the mass concentration of the polymer material in the shell layer solution is 5% to 30%; (3) injecting the core layer solution obtained in step (1) and the shell layer solution obtained in step (2) into two solution channels of a coaxial electrospinning device respectively, adjusting the coaxial electrospinning parameters for electrospinning, and obtaining a phase change heat storage fabric. Phase change heat storage fiber membranes with different latent heat values are obtained by adjusting the mass concentration and pushing speed of the core layer solution and the shell layer solution, and at the same time, functional particles are added to the electrospinning solution by solution electrospinning technology to realize the functionalization of the phase change heat storage fabric, and the method is simple and reliable.
现有技术中，已可见使用静电纺丝法制备的相变调温材料中，第一，没有设计针对人体舒适温度的相变调温纤维膜，第二，现有纤维膜导热性不高，对温度变化的响应速度不快。因此，本申请基于现有技术中关于相变材料，尤其是静电纺丝相变调温纤维膜所存在的问题，如不适于人体温度调控，相变材料导热性低等不足，通过将PEG相变材料复配，制备能够将人体温度控制在33-38℃的相变调温纤维膜；通过在静电纺丝纤维壳层中加入纳米导热填料，增强纤维的热稳定性能及快速导热效果。同时该相变调温纤维膜具有皮芯结构，高孔隙率和良好机械稳定性。In the prior art, it can be seen that among the phase change thermostatic materials prepared by electrospinning, first, there is no phase change thermostatic fiber membrane designed for the comfortable temperature of the human body, and second, the existing fiber membrane has low thermal conductivity and slow response to temperature changes. Therefore, based on the problems existing in the prior art regarding phase change materials, especially electrospinning phase change thermostatic fiber membranes, such as being unsuitable for human body temperature regulation and low thermal conductivity of phase change materials, this application prepares a phase change thermostatic fiber membrane that can control the human body temperature at 33-38°C by compounding PEG phase change materials; by adding nano-thermal conductive fillers to the electrospinning fiber shell layer, the thermal stability and rapid thermal conductivity of the fiber are enhanced. At the same time, the phase change thermostatic fiber membrane has a skin-core structure, high porosity and good mechanical stability.
发明内容Summary of the invention
针对现有技术的不足，本发明申请旨在提供一种快速调控人体温度具有皮芯结构的相变调温纤维膜及其制备方法，所制备出的相变储能纤维膜与人体温度相适应的控温，并且相变纤维膜不容易溢出泄露。In view of the deficiencies in the prior art, the present invention application aims to provide a phase change temperature regulating fiber membrane with a skin-core structure for quickly regulating human body temperature and a preparation method thereof. The prepared phase change energy storage fiber membrane has a temperature control adapted to human body temperature, and the phase change fiber membrane is not prone to overflow and leakage.
进一步的，本公开的构思在于，对相变材料进行选择，并对相变储能纤维膜的组成、配比进行研究，调整相变储能纤维膜的相变温度和相变焓，使得该相变储能纤维膜更加适应于人体温度的调节。Furthermore, the concept of the present disclosure is to select phase change materials, study the composition and ratio of phase change energy storage fiber membranes, adjust the phase change temperature and phase change enthalpy of the phase change energy storage fiber membranes, so that the phase change energy storage fiber membranes are more suitable for regulating human body temperature.
进一步的，本公开的另一构思还在于，将相变材料作为芯层材料，通过对皮层的选择和工艺的调整，保证芯层材料不发生溢出和外泄，提高相变储能纤维膜的使用寿命和调温稳定性。Furthermore, another concept of the present disclosure is to use phase change material as the core layer material, and through the selection of the skin layer and the adjustment of the process, ensure that the core layer material does not overflow or leak, thereby improving the service life and temperature control stability of the phase change energy storage fiber membrane.
进一步的，本公开的另一构思还在于，对皮层高分子材料进行选择，并对导热性进行调节，使得该皮层与芯层材料之间热导性能优异，同时防止内芯材料的溢出。Furthermore, another concept of the present disclosure is to select the polymer material of the skin layer and adjust the thermal conductivity so that the thermal conductivity between the skin layer and the core layer material is excellent, while preventing the overflow of the inner core material.
进一步的，本公开的另一构思还在于，对纺丝工艺进行调节，使得纺丝工艺稳定，制备出的相变储能纤维膜的外观稳定，皮层稳定的包覆芯层材料。Furthermore, another concept of the present disclosure is to adjust the spinning process so that the spinning process is stable, the appearance of the prepared phase change energy storage fiber membrane is stable, and the skin layer is stable to cover the core layer material.
进一步的，本公开的另一构思还在于，所述制备的相变储能纤维膜具有潜热高、热稳定性高、储热性能优异和热导率高等特点，纤维膜的性能稳定。Furthermore, another concept of the present disclosure is that the prepared phase change energy storage fiber membrane has the characteristics of high latent heat, high thermal stability, excellent heat storage performance and high thermal conductivity, and the performance of the fiber membrane is stable.
进一步的，本公开的另一构思还在于，将所述的相变储能纤维膜进行应用，包括但不限于纺织辅料。Furthermore, another concept of the present disclosure is to apply the phase change energy storage fiber membrane, including but not limited to textile accessories.
具体的，本公开提供了一种相变储能纤维膜，所述的相变储能纤维膜为皮芯结构，也可以成为剑鞘结构，所述的相变储能纤维膜具有潜热高、热稳定性高、储热性能优异和热导率高的特点。Specifically, the present disclosure provides a phase-change energy storage fiber membrane, which is a skin-core structure and can also be a scabbard structure. The phase-change energy storage fiber membrane has the characteristics of high latent heat, high thermal stability, excellent heat storage performance and high thermal conductivity.
进一步的，所述的相变储能纤维膜的芯层材料为聚乙二醇(PEG)。Furthermore, the core layer material of the phase change energy storage fiber membrane is polyethylene glycol (PEG).
进一步的，所述的聚乙二醇的分子量为600-2000；优选的为800-1800。进一步的，所述的芯层材料的聚乙二醇的为至少两种不同分子量的聚乙二醇的复配，优选的为两种不同分子量聚乙二醇复配。Furthermore, the molecular weight of the polyethylene glycol is 600-2000, preferably 800-1800. Furthermore, the polyethylene glycol of the core material is a compound of at least two polyethylene glycols with different molecular weights, preferably a compound of two polyethylene glycols with different molecular weights.
进一步的，所述聚乙二醇可以为PEG600、PEG800、PEG1000和PEG1500中的一种或多种。进一步的，所述的两种分子量的聚乙二醇的分子量比值为1-3；优选的分子量比值为1-2；更优选的分子量比值为1.1-1.7；更有选的分子量比值为1:1.5。Further, the polyethylene glycol can be one or more of PEG600, PEG800, PEG1000 and PEG1500. Further, the molecular weight ratio of the two molecular weights of polyethylene glycol is 1-3; the preferred molecular weight ratio is 1-2; the more preferred molecular weight ratio is 1.1-1.7; the more preferred molecular weight ratio is 1:1.5.
进一步的，两种分子量的聚乙二醇，其中，高分子量的聚乙二醇的用量小于低分子量的聚乙二醇用量。Furthermore, there are two kinds of polyethylene glycol with different molecular weights, wherein the amount of the high molecular weight polyethylene glycol is less than that of the low molecular weight polyethylene glycol.
进一步的，所述的高分子量聚乙二醇的用量与低分子量聚乙二醇的用量的质量比为 1:1-10；优选的1:3-8；优选的为1:6。Furthermore, the mass ratio of the high molecular weight polyethylene glycol to the low molecular weight polyethylene glycol is 1:1-10; preferably 1:3-8; preferably 1:6.
更具体的，所述的芯层相变材料为PEG1000和PEG1500以质量比6:1复配。More specifically, the core layer phase change material is a compound of PEG1000 and PEG1500 in a mass ratio of 6:1.
在一些实施例中，所述的相变储能材料的皮层为高分子材料。In some embodiments, the skin layer of the phase change energy storage material is a polymer material.
进一步的，所述的高分子材料为聚丙烯腈(PAN)。Furthermore, the polymer material is polyacrylonitrile (PAN).
进一步的，所述的聚丙烯腈中还包括导热材料，所述导热材料为纳米导热材料。Furthermore, the polyacrylonitrile also includes a thermally conductive material, and the thermally conductive material is a nano thermally conductive material.
进一步的，所述的皮层材料采用溶解的方法制备成纺丝原液。Furthermore, the cortical material is prepared into spinning solution by dissolving.
其中，所述皮层材料的溶解剂为DMF，进而溶解高分子材料。Wherein, the solvent of the cortical material is DMF, which further dissolves the polymer material.
进一步的，所述的聚丙烯腈(PAN)的溶解量为10-15wt％，优选10wt％。Furthermore, the dissolved amount of polyacrylonitrile (PAN) is 10-15wt%, preferably 10wt%.
进一步的，所述的纳米导热材料加入到溶解剂中，纳米导热材料的溶解量为1-10wt％，优选为3-9wt％、优选5wt％。Furthermore, the nano thermal conductive material is added into the solvent, and the dissolved amount of the nano thermal conductive material is 1-10wt%, preferably 3-9wt%, preferably 5wt%.
进一步的，所述的纳米导热材料为纳米氧化铝(Al2O3)，纳米氮化硼(BN)，纳米二氧化硅中的一种或多种；Furthermore, the nano thermal conductive material is one or more of nano alumina (Al2 O3 ), nano boron nitride (BN), and nano silicon dioxide;
优选的，纳米导热材料为纳米氧化铝。Preferably, the nano thermal conductive material is nano alumina.
在一些实施例中，所述的相变储能纤维膜的调温温度范围为33-50℃，优选为 33-46℃。In some embodiments, the temperature range of the phase change energy storage fiber membrane is 33-50°C, preferably 33-46°C.
进一步的，所述的相变储能纤维膜的潜热为80-180J·g-1。Furthermore, the latent heat of the phase-change energy storage fiber membrane is 80-180 J·g-1 .
进一步的，所述的相变储能纤维膜中纤维的直径小于1um，优选的小于500nm。Furthermore, the diameter of the fiber in the phase change energy storage fiber membrane is less than 1 um, preferably less than 500 nm.
在一些实施例中，所述的相变储能纤维膜通过同轴静电纺丝制备得到；In some embodiments, the phase change energy storage fiber membrane is prepared by coaxial electrospinning;
其中，所述的同轴静电纺丝时，静电纺丝电压为10-20kV，优选16kV。Wherein, during the coaxial electrospinning, the electrospinning voltage is 10-20 kV, preferably 16 kV.
进一步的，纺丝温度为25-60℃，优选45℃。Further, the spinning temperature is 25-60°C, preferably 45°C.
进一步的，纺丝湿度为30-60％，优选30％。Furthermore, the spinning humidity is 30-60%, preferably 30%.
进一步的，针头与收集装置的距离为10-20cm，优选10cm。Furthermore, the distance between the needle and the collecting device is 10-20 cm, preferably 10 cm.
进一步的，滚筒收集装置的转速为50-150rpm，优选100rpm。Furthermore, the rotation speed of the drum collecting device is 50-150 rpm, preferably 100 rpm.
进一步的，所述的皮层纺丝液的推进速度大于芯层的推进速度。Furthermore, the propulsion speed of the skin layer spinning solution is greater than the propulsion speed of the core layer.
进一步的，所述皮层溶液推进速度为芯层推进速度的4倍以上，优选的5倍以上，更有选的6倍以上，且小于20倍，优选的小于16倍，优选的小于14倍，优选的小于 10倍，优选的小于8倍。Furthermore, the advancement speed of the cortex solution is more than 4 times that of the core layer, preferably more than 5 times, more preferably more than 6 times, and less than 20 times, preferably less than 16 times, preferably less than 14 times, preferably less than 10 times, and preferably less than 8 times.
具体的，所述皮层溶液推进速度为芯层推进速度为4-20倍，优选的4-14倍，更有选的4-8倍。Specifically, the advancement speed of the skin layer solution is 4-20 times, preferably 4-14 times, and more preferably 4-8 times, that of the core layer solution.
进一步的，皮层溶液推进速度为0.08-1.5mm/min，优选0.08mm/min。Furthermore, the advancement speed of the cortical solution is 0.08-1.5 mm/min, preferably 0.08 mm/min.
进一步的，芯层溶液推进速度0.005-0.02mm/min，优选0.015mm/min。Furthermore, the core layer solution advancing speed is 0.005-0.02 mm/min, preferably 0.015 mm/min.
在一些实施例中，本公开还提供了一种相变储能纤维膜的制备方法，具体包括如下步骤：In some embodiments, the present disclosure further provides a method for preparing a phase change energy storage fiber membrane, which specifically comprises the following steps:
(1)将纳米导热材料分散于有机溶剂中，超声1-2h；后加入聚丙烯腈(PAN)，搅拌溶解，使其混合成均匀的溶液，得到皮层溶液；(1) dispersing the nano thermal conductive material in an organic solvent and ultrasonicating for 1-2 hours; then adding polyacrylonitrile (PAN), stirring and dissolving, and mixing the mixture into a uniform solution to obtain a cortex solution;
(2)在一定温度下，将聚乙二醇(PEG)以复配形式按一定比例高温互溶，得到芯层溶液；(2) at a certain temperature, dissolving polyethylene glycol (PEG) in a composite form at a certain proportion at high temperature to obtain a core layer solution;
(3)将所述的皮层溶液和所述芯层溶液进行同轴静电纺丝，获得静电纺丝纤维；(3) coaxially electrospinning the skin layer solution and the core layer solution to obtain electrospun fibers;
(4)将所述静电纺丝纤维进行真空干燥，最终得到纳米导热材料/PAN@复合相变纤维膜。(4) vacuum drying the electrospun fibers to obtain a nano thermal conductive material/PAN@ composite phase change fiber membrane.
进一步的，所述步骤(1)中，纳米导热材料为纳米氧化铝(Al2O3)，纳米氮化硼(BN)，二氧化硅中的一种或多种；优选Al2O3。Furthermore, in step (1), the nano thermal conductive material is one or more of nano alumina (Al2 O3 ), nano boron nitride (BN), and silicon dioxide; preferably Al2 O3 .
所述的纳米导热材料的用量为1-10wt％，优选5wt％。The amount of the nano thermal conductive material is 1-10wt%, preferably 5wt%.
进一步的，所述步骤(1)中，有机溶剂为DMF。Furthermore, in step (1), the organic solvent is DMF.
进一步的，所述步骤(1)中，PAN含量为10-15wt％，优选10wt％。Furthermore, in the step (1), the PAN content is 10-15 wt%, preferably 10 wt%.
所述步骤(2)中，芯层溶液为分子量为600-2000的PEG中的一种或几种。In the step (2), the core layer solution is one or more PEGs with a molecular weight of 600-2000.
优选PEG1000和PEG1500以质量比6:1复配。Preferably, PEG1000 and PEG1500 are compounded in a mass ratio of 6:1.
进一步的，所述步骤(3)中，静电纺丝的工艺参数为：静电纺丝电压为10-20kV，优选16kV；温度为25-60℃，优选45℃；湿度为30-60％，优选30％；针头与收集装置的距离为10-20cm，优选10cm；滚筒收集装置的转速为50-150rpm，优选100rpm；皮层溶液推进速度为0.08-1.5mm/min，优选0.08mm/min；芯层溶液推进速度0.005-0.02 mm/min，优选0.015mm/min。Furthermore, in the step (3), the process parameters of electrospinning are: electrospinning voltage is 10-20 kV, preferably 16 kV; temperature is 25-60°C, preferably 45°C; humidity is 30-60%, preferably 30%; the distance between the needle and the collecting device is 10-20 cm, preferably 10 cm; the rotation speed of the roller collecting device is 50-150 rpm, preferably 100 rpm; the cortex solution advancing speed is 0.08-1.5 mm/min, preferably 0.08 mm/min; the core layer solution advancing speed is 0.005-0.02 mm/min, preferably 0.015 mm/min.
所述步骤(4)中，真空干燥温度为50-100℃，优选70℃；压强0.01-0.05MPa，时间8-24h。In the step (4), the vacuum drying temperature is 50-100°C, preferably 70°C; the pressure is 0.01-0.05MPa, and the time is 8-24h.
本发明的有益效果：Beneficial effects of the present invention:
(1)制备的相变材料的纤维均一性好，有较高的比表面积，能实现热量的快速传递且对相变材料有较好的密封性，经多次循环吸热放热后不会有相变材料的泄露。(1) The prepared phase change material has good fiber uniformity and a high specific surface area, can achieve rapid heat transfer and has good sealing properties for the phase change material. After multiple cycles of heat absorption and heat release, there will be no leakage of the phase change material.
(2)在芯层材料的选择上，PEG1000与PEG1500在质量分数比为6:1时，复合材料的相变温度为36.4℃，与人体温度适宜，且有171J·g-1的潜热，是制备智能调温纺织品的优良复合材料。(2) In the selection of core layer materials, when the mass fraction ratio of PEG1000 to PEG1500 is 6:1, the phase transition temperature of the composite material is 36.4℃, which is suitable for human body temperature, and has a latent heat of 171J·g-1 , making it an excellent composite material for the preparation of intelligent temperature-regulating textiles.
(3)PAN@PEG纤维膜与Al2O3/PAN@PAEG相比，改性后的纤维膜热稳定性得到了提高，具有85.54J·g-1的潜热，且调温范围也扩大到36-46℃，纤维的直径增加到 500nm左右。(3) Compared with Al2O3/PAN@PAEG, the thermal stability of the modified PAN@PEG fiber membrane is improved, with a latent heat of 85.54 J·g-1 , and the temperature adjustment range is also expanded to 36-46℃, and the fiber diameter is increased to about 500 nm.
(4)在经Al2O3改性后，5％Al2O3改性后的纤维膜，形貌完好、直径较大，热稳定性好，调温范围大，储热性能优异，热导率高，适宜制备调温纺织品纤维膜。(4) After modification withAl2O3 , the fiber membrane modified with 5%Al2O3 has intact morphology, large diameter, good thermal stability, large temperature regulation range, excellent heat storage performance, and high thermal conductivity, which is suitable for the preparation of temperature regulating textile fiber membranes.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
以下将结合附图和优选实施例来对本公开进行进一步详细描述，但是本领域技术人员将领会的是，这些附图仅是出于解释优选实施例的目的而绘制的，并且因此不应当作为对本公开范围的限制。The present disclosure will be further described in detail below in conjunction with the accompanying drawings and preferred embodiments, but those skilled in the art will appreciate that these drawings are only drawn for the purpose of explaining the preferred embodiments and therefore should not be taken as limiting the scope of the present disclosure.
图1：为实施例1中PEG1000和PEG1500质量比6:1复配所得DSC图。Figure 1: DSC graph obtained by compounding PEG1000 and PEG1500 in a mass ratio of 6:1 in Example 1.
图2：为实施例1中相变储热材料SEM图。Figure 2: SEM image of the phase change heat storage material in Example 1.
图3：实施例2-4与实施例2-3、实施例1和实施例2-5样品的热成像图。附图图中所示 SP1为9％Al2O3/PAN@PEG、SP2为7％Al2O3/PAN@PEG、SP3为5％Al2O3/PAN@PEG、 SP4为PAN@PEG。Figure 3: Thermal imaging of samples of Example 2-4, Example 2-3, Example 1 and Example 2-5. As shown in the figure, SP1 is 9% Al2 O3 /PAN@PEG, SP2 is 7% Al2 O3 /PAN@PEG, SP3 is 5% Al2O3/PAN@PEG, and SP4 is PAN@PEG.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
聚乙二醇作为相变材料，具有过冷程度小、且不存在相分离现象，同事具有良好的潜热和热传导性能，因此作为相变储能材料得到广泛的关注。但是，不同分子量的聚乙二醇的相变温度随着温度的变化存在较大的差异，相变温度可以从室温到65℃的范围，并且潜热大。如何选择符合要求聚乙二醇作为的相变材料，能够及时的相应需要的温变范围是一个非常困难，并且难以预期所选择的相变材料是否能够复合要求。As a phase change material, polyethylene glycol has a small degree of supercooling and no phase separation phenomenon. At the same time, it has good latent heat and thermal conductivity. Therefore, it has received widespread attention as a phase change energy storage material. However, the phase change temperature of polyethylene glycol with different molecular weights varies greatly with the change of temperature. The phase change temperature can range from room temperature to 65°C, and the latent heat is large. How to choose polyethylene glycol that meets the requirements as a phase change material and can respond to the required temperature change range in time is very difficult, and it is difficult to predict whether the selected phase change material can meet the requirements.
本公开旨在以聚乙二醇作为相变材料，并制备响应与人体温度变化的相变材料，人体皮肤温度恒定在33℃左右，深度血液温度在38℃左右，且温度变化范围小，因此对相变材料的要求近乎苛刻。本公开即基于这种特征，欲开发一种相变储能材料，该材料能在能够在33℃以上发生相变，释放储能，进而调节温度。另外，释放储能后所调节的最高温度必须限定，最高的温度必须是人体能够承受的，如不超过50℃，优选的不超过48℃。The present disclosure aims to use polyethylene glycol as a phase change material and prepare a phase change material that responds to changes in human body temperature. The human skin temperature is constant at around 33°C, the deep blood temperature is around 38°C, and the temperature change range is small, so the requirements for phase change materials are almost harsh. Based on this feature, the present disclosure intends to develop a phase change energy storage material that can undergo a phase change above 33°C, release stored energy, and then adjust the temperature. In addition, the maximum temperature adjusted after releasing the stored energy must be limited, and the maximum temperature must be what the human body can withstand, such as not exceeding 50°C, and preferably not exceeding 48°C.
相变储能材料的另一个指标在于材料对温度的影响速度，对于相应速度又与相变材料的皮层有关，如果皮层的导热性能过低，则相应的时间会延迟，甚至无法相应。因此，本公开选择聚丙烯腈作为相变材料的皮层，聚丙烯腈，聚丙烯腈材料具有较好的导热性能，能够满足作为相变材料的皮层。为了进一步的提高皮层的导热性能，提高相变储能材料对温度的相应敏感性，本公开的方案在皮层中还加入了导热的无机材料，这些材料在一定的程度上显著的提高了相变储能材料对温度变化的相应敏感性。Another indicator of phase change energy storage materials is the speed at which the material affects temperature. The corresponding speed is related to the cortex of the phase change material. If the thermal conductivity of the cortex is too low, the corresponding time will be delayed or even unable to respond. Therefore, the present disclosure selects polyacrylonitrile as the cortex of the phase change material. Polyacrylonitrile and polyacrylonitrile materials have good thermal conductivity and can meet the requirements of the cortex of the phase change material. In order to further improve the thermal conductivity of the cortex and improve the corresponding sensitivity of the phase change energy storage material to temperature, the scheme of the present disclosure also adds thermally conductive inorganic materials to the cortex. These materials significantly improve the corresponding sensitivity of the phase change energy storage material to temperature changes to a certain extent.
相变储能材料中相变材料能够稳定保持且不泄露能决定了相变材料的使用耐久性和调温效果，本公开在选用的皮层为聚丙烯腈，该材料具有良好的耐磨性，因此能够稳定的将相变材料固定在皮层所限定的空间内。而在加入了纳米导热材料时，皮层体系属于两相材料，为了提高密封性能，选用的纳米导热材料的粒径必须严格控制，防止皮层发生破裂导致相变材料的泄露。The ability of the phase change material in the phase change energy storage material to be stably maintained and not leaking can determine the durability and temperature control effect of the phase change material. The skin layer selected in the present disclosure is polyacrylonitrile, which has good wear resistance, so the phase change material can be stably fixed in the space defined by the skin layer. When the nano thermal conductive material is added, the skin layer system belongs to a two-phase material. In order to improve the sealing performance, the particle size of the selected nano thermal conductive material must be strictly controlled to prevent the skin layer from rupturing and causing leakage of the phase change material.
更进一步的，相变储能材料的性能与纺丝工艺存在密切的关系，纺丝原液的粘度，尤其是皮层的粘度，芯层和皮层的推进速度，都与纺丝工艺存在一定关联，本公开对相变储能材料，对纺丝工艺进行了调整，确保了相变储能材料中纤维的表观形态稳定，且芯层的含量充足稳定，该相变储能材料对温度反应更加准确。在本公开中，所选用PEG 的分子量为600-2000，具体不同分子量PEG的来源为PEG600、PEG800、PEG1000和 PEG1500。Furthermore, the performance of the phase change energy storage material is closely related to the spinning process. The viscosity of the spinning solution, especially the viscosity of the cortex, and the propulsion speed of the core layer and the cortex are all related to the spinning process. The present disclosure adjusts the spinning process for the phase change energy storage material to ensure that the apparent morphology of the fiber in the phase change energy storage material is stable, and the content of the core layer is sufficient and stable, and the phase change energy storage material responds to temperature more accurately. In the present disclosure, the molecular weight of the selected PEG is 600-2000, and the specific sources of PEG with different molecular weights are PEG600, PEG800, PEG1000 and PEG1500.
具体的，本公开了一个实施例1，用以制备相变储能纤维膜，具体方案如下：Specifically, the present invention discloses an embodiment 1 for preparing a phase change energy storage fiber membrane, and the specific scheme is as follows:
将1g的Al2O3分散于17g的DMF中，超声2h；后加入2g的PAN，搅拌24h，使其混合成均匀的纺丝液，得到皮层溶液。该皮层溶液PAN的浓度为10％，Al2O3的浓度为5％。1g ofAl2O3 was dispersed in 17g of DMF and ultrasonicated for 2h; then 2g of PAN was added and stirred for 24h to mix into a uniform spinning solution to obtain a cortex solution. The concentration of PAN in the cortex solution was 10% and the concentration of Al2O3 was 5%.
将PEG1000和PEG1500以质量比6:1在高温下搅拌溶解互溶，获得同轴静电纺丝的芯层溶液。以铝箔纸为接收基底，进行同轴静电纺丝。调节芯层推进速度为0.015 mm/min，皮层推进速度为0.08mm/min，接收距离10cm，电压16kV，得到具有皮芯结构的相变储热纤维(5％Al2O3/PAN@PEG)。PEG1000 and PEG1500 were stirred and dissolved at a mass ratio of 6:1 at high temperature to obtain a core solution for coaxial electrospinning. Aluminum foil was used as a receiving substrate for coaxial electrospinning. The core layer propulsion speed was adjusted to 0.015 mm/min, the skin layer propulsion speed was 0.08 mm/min, the receiving distance was 10 cm, and the voltage was 16 kV to obtain a phase change heat storage fiber (5% Al2 O3 /PAN@PEG) with a skin-core structure.
将5％Al2O3/PAN@PEG复合相变纤维于真空干燥箱70℃真空干燥24h，获得对应的相变储能纤维膜。The 5% Al2 O3 /PAN@PEG composite phase change fiber was vacuum dried in a vacuum drying oven at 70°C for 24 h to obtain the corresponding phase change energy storage fiber membrane.
如图1所示为实施例1中PEG1000和PEG1500质量比6:1复配所得DSC图， PEG1000与PEG1500在质量分数比为6:1时，复合材料的相变温度为36.4℃，与人体温度适宜，且有171J·g-1的潜热，是制备智能调温纺织品的优良复合材料。As shown in Figure 1, this is the DSC graph obtained by compounding PEG1000 and PEG1500 in a mass ratio of 6:1 in Example 1. When the mass fraction ratio of PEG1000 to PEG1500 is 6:1, the phase transition temperature of the composite material is 36.4°C, which is suitable for human body temperature, and has a latent heat of 171 J·g-1, making it an excellent composite material for preparing intelligent temperature regulating textiles.
如图2所示为实施例1中相变储热材料SEM图。FIG. 2 is a SEM image of the phase change heat storage material in Example 1.
在另一实施例2中，制备相变储能纤维膜的步骤与实施例1相同，不同之处在于Al2O3溶液浓度分别为0wt％、1wt％、3wt％、7wt％、9wt％。In another embodiment 2, the steps of preparing the phase change energy storage fiber membrane are the same as those of embodiment 1, except that the concentrations of the Al2 O3 solution are 0wt%, 1wt%, 3wt%, 7wt% and 9wt% respectively.
如图3所示，实施例2-4与实施例2-3、实施例1和实施例2-5样品的热成像图。附图中所示SP1为9％Al2O3/PAN@PEG、SP2为7％Al2O3/PAN@PEG、SP3为5％ Al2O3/PAN@PEG、SP4为PAN@PEG。As shown in Figure 3, thermal imaging images of samples of Example2-4 , Example 2-3, Example 1 and Example 2-5. As shown in the figure, SP1 is 9%Al2O3 /PAN@PEG, SP2 is 7% Al2O3/PAN@PEG, SP3 is 5%Al2O3/ PAN@PEG, and SP4 is PAN@PEG.
经过Al2O3改性后的纤维膜Al2O3/PAN@PAEG，与PAN@PEG纤维膜相比，改性后的纤维膜热稳定性得到了提高，具有85.54J·g-1的潜热，且调温范围也扩大到33-46℃，纤维的直径增加到500nm左右。如图3所示，经过改性后的Al2O3/PAN@PAEG纤维膜在90s内还具有一个快速的相变效果产生。Compared with PAN@PEG fiber membrane, the thermal stability of the fiber membrane modified by Al2 O3 is improved, with a latent heat of 85.54J ·g-1 , and the temperature adjustment range is also expanded to 33-46 °C , and the fiber diameter is increased to about 500 nm. As shown in Figure 3, the modified Al2O3/PAN@PAEG fiber membrane also has a rapid phase change effect within 90 s.
其中，经实验验证，在经Al2O3改性后，5％Al2O3改性后的纤维膜，形貌完好、直径较大，热稳定性好，调温范围大，储热性能优异，热导率高，适宜制备调温纺织品纤维膜。Among them, it has been verified experimentally that after modification with Al2 O3 , the fiber membrane modified with 5% Al2 O3 has intact morphology, large diameter, good thermal stability, large temperature adjustment range, excellent heat storage performance, high thermal conductivity, and is suitable for the preparation of temperature regulating textile fiber membranes.
表1实施例1与是实施例2的对比表Table 1 is a comparison table of Example 1 and Example 2
在另一实施例3中，制备相变储能纤维膜的步骤与实施例1相同，不同之处在于芯层材料为PEG1000、PEG1500。In another embodiment 3, the steps of preparing the phase change energy storage fiber membrane are the same as those of embodiment 1, except that the core layer material is PEG1000 or PEG1500.
表2为实施例3的对比表Table 2 is a comparison table of Example 3
在一些实施例4中，制备相变储能纤维膜的步骤与实施例1相同，不同之处在于芯层和皮层的推进速度，其中芯层推进速度为0.005mm/min，皮层推进速度为0.08mm/min；芯层推进速度为0.02mm/min，皮层推进速度为1.5mm/min；In some embodiments 4, the steps for preparing the phase change energy storage fiber membrane are the same as those in embodiment 1, except that the advancing speeds of the core layer and the skin layer are 0.005 mm/min and 0.08 mm/min, respectively; the advancing speed of the core layer is 0.02 mm/min and 1.5 mm/min respectively;
表3实施例1与实施例4的对比表Table 3 Comparison table of Example 1 and Example 4
在另一些实施例5中，制备相变储能材料的步骤与实施例1相同，不同在于导热材料的粒径不同，设置氧化铝的粒径影响。In other embodiments 5, the steps of preparing the phase change energy storage material are the same as those in embodiment 1, except that the particle size of the thermal conductive material is different, and the particle size of aluminum oxide is set.
表4实施例1与实施例5的对比表Table 4 Comparison of Example 1 and Example 5
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