WO2020056883A1 - Method of preparing graphene microcapsule fiber - Google Patents

Method of preparing graphene microcapsule fiber Download PDF

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WO2020056883A1
WO2020056883A1 PCT/CN2018/114236 CN2018114236W WO2020056883A1 WO 2020056883 A1 WO2020056883 A1 WO 2020056883A1 CN 2018114236 W CN2018114236 W CN 2018114236W WO 2020056883 A1 WO2020056883 A1 WO 2020056883A1
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graphene
microcapsule
phase change
preparing
modified
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PCT/CN2018/114236
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French (fr)
Chinese (zh)
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纪国营
张莹
曲欣欣
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南通和清纺织科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear

Definitions

  • the invention belongs to the technical field of material microcapsules, and particularly relates to a method for preparing graphene microcapsule fibers.
  • Phase change energy storage materials because they can absorb or release a large amount of heat during the phase change, can play the role of temperature control and energy storage, can solve the contradiction between the imbalance of energy supply and demand in time and space, and improve energy Effective means of utilization.
  • the key to people's current comfort is the surface temperature of the skin. Regardless of the ambient or internal temperature, the sensory temperature produced by the air layer between clothing and skin is related. "32 ⁇ 1 ° C" is the standard for people wearing comfortable clothes. Therefore, how to apply phase change storage materials to textile clothing and use graphene to solve the problem of low thermal conductivity, so that this kind of fabric can be controlled to maintain human comfort, so that it becomes a standard value is a problem that needs to be solved at present.
  • the purpose of the present invention is to provide a method for preparing graphene microcapsule fibers, so as to solve the problems raised in the background art mentioned above.
  • a graphene microcapsule fiber the spherical microcapsule prepared by the method has a shell and a core structure, and an emulsifier connecting the shell and the core structure, wherein the shell structure consists of a microcapsule wall
  • the core material is composed of a microcapsule core material, the wall material is mainly graphene, the core material is phase change material, graphene is modified graphene, and the phase change material is paraffin, including the following steps:
  • step S3 adding the modified graphene solution obtained in step S1 in the process of preparing the microcapsule wall material to obtain a graphene modified wall material;
  • step S4 heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying capsule;
  • microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension, and the microcapsule suspension is flow-soaked with silk fibers to obtain a fiber material with graphene microcapsules.
  • the ultrasonic time for preparing the modified graphene solution in step S1 is 1.5-3 hours
  • the drying environment is vacuum drying
  • the drying temperature is 60 ° C.
  • the time for preparing the phase change material emulsion in step S2 is 0.5-1.5 hours.
  • the graphene-modified wall material is prepared by stirring the reactants at 70-85 ° C for 1 hour.
  • the temperature of the water bath heating in step S4 is constant temperature 70 degrees Celsius, the time is 2-4 hours, the ultrasonic dispersion time is 0.5-1 hours, the vacuum drying temperature is 60-80 ° C, and the time is 36 hours.
  • the size of the paraffin in the microcapsule is 2-30 microns.
  • the microcapsule suspension in step S5 needs to be first heated to 80 ° C., and kept soaked with silk fibers for two hours, then cooled down, and repeated 3-4 times, and the silk fibers are silk.
  • the preparation method of graphene microcapsule fiber adopts a combination design of graphene as a microcapsule wall material and paraffin wax as a microcapsule core material.
  • Graphene has a high thermal conductivity and solves paraffin wax.
  • heat loss occurs during the heat transfer process and paraffin cannot absorb heat in the microcapsule core, so that the paraffin in the microcapsule can absorb excess heat in the body.
  • the release function is controlled, so that the absorbed heat can be released when the heat is generated, so that it can be applied to clothing textiles to control the temperature of the human body surface to a comfortable feeling.
  • the invention provides a graphene microcapsule fiber.
  • the spherical microcapsule prepared by the method has a shell and a core structure and an emulsifier connecting the shell and the core structure.
  • the shell structure is composed of microcapsule wall materials and the core structure is composed of microcapsules.
  • the core material is composed of graphene, the core material is a phase change material, the graphene is a modified graphene, and the phase change material is a paraffin, including the following steps:
  • step S3 adding the modified graphene solution obtained in step S1 during the preparation of the microcapsule wall material to obtain a graphene modified wall material, and the reactants are stirred at 70-85 ° C during the preparation of the graphene modified wall material Prepared by reacting for 1 hour;
  • step S4 heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying Capsules are heated at a constant temperature of 70 degrees Celsius in a water bath, for a period of 2-4 hours, for an ultrasonic dispersion time of 0.5-1 hour, and for a vacuum drying temperature of 60-80 ° C, for a period of 36 hours;
  • microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension with a mass concentration of 25%, and the microcapsule suspension is soaked in silk fibers to obtain graphene microcapsules.
  • the microcapsule suspension needs to be heated up to 80 ° C, and kept soaked with silk fiber for two hours, then cooled down, and repeated 3-4 times, and the silk fiber is silk.
  • the invention provides a graphene microcapsule fiber.
  • the spherical microcapsule prepared by the method has a shell and a core structure and an emulsifier connecting the shell and the core structure.
  • the shell structure is composed of microcapsule wall materials and the core structure is composed of microcapsules
  • the core material is composed of graphene, the core material is a phase change material, the graphene is a modified graphene, and the phase change material is a paraffin, including the following steps:
  • step S3 adding the modified graphene solution obtained in step S1 during the preparation of the microcapsule wall material to obtain a graphene modified wall material, and the reactants are stirred at 70-85 ° C during the preparation of the graphene modified wall material Prepared by reacting for 1 hour;
  • step S4 heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying Capsules are heated at a constant temperature of 70 degrees Celsius in a water bath, for a period of 2-4 hours, for an ultrasonic dispersion time of 0.5-1 hour, and for a vacuum drying temperature of 60-80 ° C, for a period of 36 hours;
  • microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension with a mass concentration of 25%.
  • the microcapsule suspension is soaked in silk fibers to obtain graphene microcapsules.
  • the microcapsule suspension needs to be heated up to 80 ° C, and kept soaked with silk fiber for two hours, then cooled down, and repeated 3-4 times, and the silk fiber is silk.
  • Example 1 and 2 after the silk fibers were dehydrated and dried, the graphene microcapsules were subjected to flow soaking in the silk fibers, so that the graphene microcapsules were repeatedly heated and cooled in the flow soaking.
  • the flowing microcapsule solution is adhered to the surface of the silk fiber by the principle of adhesion and adhesion method, and the silk fiber with the microcapsule is formed.
  • the size of the paraffin in the microcapsule is 2-30 microns.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A method of preparing graphene microcapsule fiber. The spherical microcapsule prepared by the method has a shell, a core structure, and an emulsifier linking the shell and the core structure. The shell structure is composed of a microcapsule wall material, and the core structure is composed of a microcapsule core material. The microcapsule wall material is mainly graphene, the core material is a phase change material, the graphene is modified graphene, and the phase change material is paraffin. A certain amount of graphene is dissolved in water, followed by the addition of an ethanol solution of a silane coupling agent at a pH value of 3-5, stirring, filtering, washing, and drying to obtain the modified graphene. The method of preparing a graphene microcapsule fiber utilizes the characteristics of graphene and paraffin to increase the thermal conductivity coefficient of the microcapsule wall material, such that the paraffin in the microcapsule core material can achieve functions of absorbing heat and controlling heat release, ensuring that body temperature can be controlled to a comfortable perceived temperature.

Description

一种石墨烯微胶囊纤维的制备方法Preparation method of graphene microcapsule fiber 技术领域Technical field
本发明属于材料微胶囊技术领域，具体涉及一种石墨烯微胶囊纤维的制备方法。The invention belongs to the technical field of material microcapsules, and particularly relates to a method for preparing graphene microcapsule fibers.
背景技术Background technique
全球经济的快速增长使得人类对能源的需求日益加大，化石能源的枯竭不可避免。因此，减少对化石燃料的依赖，提高能源利用率，开发环境友好型材料是当前人类面临的重要课题。相变储能材料因其在相变的过程中能够吸收或释放大量的热，可以起到控温和储能的作用，能够解决能量供求在时间和空间上分配不平衡的矛盾，是提高能源利用率的有效手段。The rapid growth of the global economy has caused an increasing demand for energy, and the depletion of fossil energy is inevitable. Therefore, reducing the dependence on fossil fuels, improving energy efficiency, and developing environmentally friendly materials are important issues facing humanity. Phase change energy storage materials, because they can absorb or release a large amount of heat during the phase change, can play the role of temperature control and energy storage, can solve the contradiction between the imbalance of energy supply and demand in time and space, and improve energy Effective means of utilization.
目前人们感觉舒适的关键是皮肤的表面温度。无论环境温度或体内温度如何，衣服与皮肤之间的空气层产生的感觉温度都是相关的。“32±1℃”是人们穿着舒适的衣服温度的标准。因此如何将相变储存材料应用到纺织衣物上，并利用石墨烯解决热导率低的问题，使通过这种织物可以控制保持人体舒适，从而使其成为标准值是当前需要解决的难题。The key to people's current comfort is the surface temperature of the skin. Regardless of the ambient or internal temperature, the sensory temperature produced by the air layer between clothing and skin is related. "32 ± 1 ° C" is the standard for people wearing comfortable clothes. Therefore, how to apply phase change storage materials to textile clothing and use graphene to solve the problem of low thermal conductivity, so that this kind of fabric can be controlled to maintain human comfort, so that it becomes a standard value is a problem that needs to be solved at present.
发明内容Summary of the Invention
本发明的目的在于提供一种石墨烯微胶囊纤维的制备方法，以解决上述背景技术中提出的问题。The purpose of the present invention is to provide a method for preparing graphene microcapsule fibers, so as to solve the problems raised in the background art mentioned above.
为实现上述目的，本发明提供如下技术方案：一种石墨烯微胶囊纤维，该方法制得球形的微胶囊具有外壳和内核结构以及连接外壳和内核结构的乳化剂，其中外壳结构由微胶囊壁材组成，内核结构由微胶囊芯材组成，壁材主要为石墨烯，芯材为相变材料，石墨烯为改性石墨烯，相变材料为石蜡，包括以下步骤：In order to achieve the above object, the present invention provides the following technical solution: a graphene microcapsule fiber, the spherical microcapsule prepared by the method has a shell and a core structure, and an emulsifier connecting the shell and the core structure, wherein the shell structure consists of a microcapsule wall The core material is composed of a microcapsule core material, the wall material is mainly graphene, the core material is phase change material, graphene is modified graphene, and the phase change material is paraffin, including the following steps:
S1：将一定含量的石墨烯溶于水中，加入pH值为3-5的硅烷偶联剂的乙醇容溶液，搅拌、抽滤、洗涤、干燥后得到改性石墨烯，并重新加入离子水， 搅拌、超声得到改性石墨烯溶液；S1: Dissolve a certain amount of graphene in water, add an ethanol-containing solution of a silane coupling agent with a pH value of 3-5, stir, suction filter, wash, and dry to obtain modified graphene, and add ion water again. Stirring and ultrasonic to obtain modified graphene solution;
S2：将乳化剂加入离子水中，搅拌并调节pH，加入相变材料，同时加热温度至相变材料开始融化，超声得到相变材料乳化液；S2: Add emulsifier to ionic water, stir and adjust pH, add phase change material, and heat the temperature until the phase change material begins to melt, and obtain the phase change material emulsion by ultrasound;
S3：在微胶囊壁材制备的过程中将步骤S1中得到的改性石墨烯溶液加入，得到石墨烯改性壁材；S3: adding the modified graphene solution obtained in step S1 in the process of preparing the microcapsule wall material to obtain a graphene modified wall material;
S4：将步骤S2得到的相变乳化液进行水浴加热，并将步骤S3得到的石墨烯改性壁材加入相变乳化液中，并经过超声分散、冷却、洗涤、干燥得到改性石墨烯微胶囊；S4: heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying capsule;
S5：将上述得到的微胶囊采用蒸馏水清理过滤后干燥，并加入水中，形成微胶囊悬浮液，并将微胶囊悬浮液对丝纤维进行流动浸泡，得到带有石墨烯微胶囊的纤维材料。S5: The microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension, and the microcapsule suspension is flow-soaked with silk fibers to obtain a fiber material with graphene microcapsules.
优选的，步骤S1中制备改性石墨烯溶液的超声时间为1.5-3小时，干燥环境为真空干燥，干燥温度为60℃。Preferably, the ultrasonic time for preparing the modified graphene solution in step S1 is 1.5-3 hours, the drying environment is vacuum drying, and the drying temperature is 60 ° C.
优选的，步骤S2中制备相变材料乳化液的时间为0.5-1.5小时。Preferably, the time for preparing the phase change material emulsion in step S2 is 0.5-1.5 hours.
优选的，步骤S3制备石墨烯改性壁材时通过反应物在70-85℃下搅拌反应1小时制得。Preferably, in step S3, the graphene-modified wall material is prepared by stirring the reactants at 70-85 ° C for 1 hour.
优选的，步骤S4中水浴加热的温度为恒温70摄氏度，时间为2-4小时，超声分散的时间为0.5-1小时，真空干燥的温度为60-80℃，时间为36小时。Preferably, the temperature of the water bath heating in step S4 is constant temperature 70 degrees Celsius, the time is 2-4 hours, the ultrasonic dispersion time is 0.5-1 hours, the vacuum drying temperature is 60-80 ° C, and the time is 36 hours.
优选的，所述石蜡在微胶囊中的大小为2-30微米。Preferably, the size of the paraffin in the microcapsule is 2-30 microns.
优选的，步骤S5中微胶囊悬浮液需先升温至80℃，并与丝纤维保温浸泡两小时后，再降温，重复3-4次，且丝纤维为蚕丝。Preferably, the microcapsule suspension in step S5 needs to be first heated to 80 ° C., and kept soaked with silk fibers for two hours, then cooled down, and repeated 3-4 times, and the silk fibers are silk.
本发明的技术效果和优点：该石墨烯微胶囊纤维的制备方法，采用石墨烯为微胶囊壁材和石蜡作为微胶囊芯材的组合设计，由石墨烯具有较高的导热系数，解决了石蜡作为芯材在传输热量过程中发生热量的损耗和石蜡在微胶囊内核中无法进行热量的吸收问题，从而使微胶囊中的石蜡能够对体内多 余的热量进行吸收，同时根据微胶囊所具有的的控制释放功能，使吸收的热量能够在发热时进行释放，从而应用到衣服纺织上，使将人体表面的温度控制到舒适的感觉。Technical effects and advantages of the present invention: The preparation method of graphene microcapsule fiber adopts a combination design of graphene as a microcapsule wall material and paraffin wax as a microcapsule core material. Graphene has a high thermal conductivity and solves paraffin wax. As a core material, heat loss occurs during the heat transfer process and paraffin cannot absorb heat in the microcapsule core, so that the paraffin in the microcapsule can absorb excess heat in the body. The release function is controlled, so that the absorbed heat can be released when the heat is generated, so that it can be applied to clothing textiles to control the temperature of the human body surface to a comfortable feeling.
具体实施方式detailed description
下面将结合本发明的内容，对本发明中的技术方案进行清楚、完整地描述，显然，所描述的内容仅仅是本发明一部分内容，而不是全部的内容。基于本发明中的内容，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他内容，都属于本发明保护的范围。The technical solution in the present invention will be clearly and completely described in combination with the content of the present invention. Obviously, the described content is only a part of the present invention, but not the entire content. Based on the content of the present invention, all other content obtained by a person of ordinary skill in the art without making creative work shall fall within the protection scope of the present invention.
实施例1Example 1
本发明提供了一种石墨烯微胶囊纤维，该方法制得球形的微胶囊具有外壳和内核结构以及连接外壳和内核结构的乳化剂，其中外壳结构由微胶囊壁材组成，内核结构由微胶囊芯材组成，壁材主要为石墨烯，芯材为相变材料，石墨烯为改性石墨烯，相变材料为石蜡，包括以下步骤：The invention provides a graphene microcapsule fiber. The spherical microcapsule prepared by the method has a shell and a core structure and an emulsifier connecting the shell and the core structure. The shell structure is composed of microcapsule wall materials and the core structure is composed of microcapsules. The core material is composed of graphene, the core material is a phase change material, the graphene is a modified graphene, and the phase change material is a paraffin, including the following steps:
S1：将40g的石墨烯溶于水中，加入pH值为3-5的硅烷偶联剂的乙醇容溶液，搅拌、抽滤、洗涤、干燥后得到改性石墨烯，并重新加入离子水，搅拌、超声得到改性石墨烯溶液，制备改性石墨烯溶液的超声时间为1.5-3小时，干燥环境为真空干燥，干燥温度为60℃；S1: Dissolve 40g of graphene in water, add an ethanol-containing solution of a silane coupling agent with a pH value of 3-5, stir, suction filter, wash, and dry to obtain modified graphene, and then add ion water and stir 2. The modified graphene solution is obtained by ultrasound. The ultrasonic time for preparing the modified graphene solution is 1.5-3 hours, the drying environment is vacuum drying, and the drying temperature is 60 ° C;
S2：将乳化剂为烷基酚聚氧乙烯醚加入离子水中，搅拌并调节pH，加入120g相变材料，同时加热温度至相变材料开始融化，超声得到相变材料乳化液，制备相变材料乳化液的时间为0.5-1.5小时；S2: Add alkylphenol polyoxyethylene ether emulsifier to ionic water, stir and adjust the pH, add 120g phase change material, and heat the temperature until the phase change material begins to melt, ultrasonically obtain the phase change material emulsion, and prepare the phase change material The time of the emulsion is 0.5-1.5 hours;
S3：在微胶囊壁材制备的过程中将步骤S1中得到的改性石墨烯溶液加入，得到石墨烯改性壁材，制备石墨烯改性壁材时通过反应物在70-85℃下搅拌反应1小时制得；S3: adding the modified graphene solution obtained in step S1 during the preparation of the microcapsule wall material to obtain a graphene modified wall material, and the reactants are stirred at 70-85 ° C during the preparation of the graphene modified wall material Prepared by reacting for 1 hour;
S4：将步骤S2得到的相变乳化液进行水浴加热，并将步骤S3得到的石墨烯改性壁材加入相变乳化液中，并经过超声分散、冷却、洗涤、干燥得到 改性石墨烯微胶囊，水浴加热的温度为恒温70摄氏度，时间为2-4小时，超声分散的时间为0.5-1小时，真空干燥的温度为60-80℃，时间为36小时；S4: heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying Capsules are heated at a constant temperature of 70 degrees Celsius in a water bath, for a period of 2-4 hours, for an ultrasonic dispersion time of 0.5-1 hour, and for a vacuum drying temperature of 60-80 ° C, for a period of 36 hours;
S5：将上述得到的微胶囊采用蒸馏水清理过滤后干燥，并加入水中，形成质量浓度为25％微胶囊悬浮液，并将微胶囊悬浮液对丝纤维进行流动浸泡，得到带有石墨烯微胶囊的纤维材料，微胶囊悬浮液需先升温至80℃，并与丝纤维保温浸泡两小时后，再降温，重复3-4次，且丝纤维为蚕丝。S5: The microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension with a mass concentration of 25%, and the microcapsule suspension is soaked in silk fibers to obtain graphene microcapsules. For the fiber material, the microcapsule suspension needs to be heated up to 80 ° C, and kept soaked with silk fiber for two hours, then cooled down, and repeated 3-4 times, and the silk fiber is silk.
实施例2Example 2
本发明提供了一种石墨烯微胶囊纤维，该方法制得球形的微胶囊具有外壳和内核结构以及连接外壳和内核结构的乳化剂，其中外壳结构由微胶囊壁材组成，内核结构由微胶囊芯材组成，壁材主要为石墨烯，芯材为相变材料，石墨烯为改性石墨烯，相变材料为石蜡，包括以下步骤：The invention provides a graphene microcapsule fiber. The spherical microcapsule prepared by the method has a shell and a core structure and an emulsifier connecting the shell and the core structure. The shell structure is composed of microcapsule wall materials and the core structure is composed of microcapsules The core material is composed of graphene, the core material is a phase change material, the graphene is a modified graphene, and the phase change material is a paraffin, including the following steps:
S1：将60g的石墨烯溶于水中，加入pH值为3-5的硅烷偶联剂的乙醇容溶液，搅拌、抽滤、洗涤、干燥后得到改性石墨烯，并重新加入离子水，搅拌、超声得到改性石墨烯溶液，制备改性石墨烯溶液的超声时间为1.5-3小时，干燥环境为真空干燥，干燥温度为60℃；S1: Dissolve 60g of graphene in water, add an ethanol-containing solution of a silane coupling agent with a pH value of 3-5, stir, suction filter, wash, and dry to obtain modified graphene. Then add ionized water and stir 2. The modified graphene solution is obtained by ultrasound. The ultrasonic time for preparing the modified graphene solution is 1.5-3 hours, the drying environment is vacuum drying, and the drying temperature is 60 ° C;
S2：将乳化剂为烷基酚聚氧乙烯醚加入离子水中，搅拌并调节pH，加入240g相变材料，同时加热温度至相变材料开始融化，超声得到相变材料乳化液，制备相变材料乳化液的时间为0.5-1.5小时；S2: Add alkylphenol polyoxyethylene ether emulsifier to ionic water, stir and adjust the pH, add 240g of phase change material, and heat the phase change material to start melting at the same time, ultrasonically obtain phase change material emulsion, prepare phase change material The time of the emulsion is 0.5-1.5 hours;
S3：在微胶囊壁材制备的过程中将步骤S1中得到的改性石墨烯溶液加入，得到石墨烯改性壁材，制备石墨烯改性壁材时通过反应物在70-85℃下搅拌反应1小时制得；S3: adding the modified graphene solution obtained in step S1 during the preparation of the microcapsule wall material to obtain a graphene modified wall material, and the reactants are stirred at 70-85 ° C during the preparation of the graphene modified wall material Prepared by reacting for 1 hour;
S4：将步骤S2得到的相变乳化液进行水浴加热，并将步骤S3得到的石墨烯改性壁材加入相变乳化液中，并经过超声分散、冷却、洗涤、干燥得到改性石墨烯微胶囊，水浴加热的温度为恒温70摄氏度，时间为2-4小时，超声分散的时间为0.5-1小时，真空干燥的温度为60-80℃，时间为36小时；S4: heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying Capsules are heated at a constant temperature of 70 degrees Celsius in a water bath, for a period of 2-4 hours, for an ultrasonic dispersion time of 0.5-1 hour, and for a vacuum drying temperature of 60-80 ° C, for a period of 36 hours;
S5：将上述得到的微胶囊采用蒸馏水清理过滤后干燥，并加入水中，形成质量浓度为25％微胶囊悬浮液，并将微胶囊悬浮液对丝纤维进行流动浸泡，得到带有石墨烯微胶囊的纤维材料，微胶囊悬浮液需先升温至80℃，并与丝纤维保温浸泡两小时后，再降温，重复3-4次，且丝纤维为蚕丝。S5: The microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension with a mass concentration of 25%. The microcapsule suspension is soaked in silk fibers to obtain graphene microcapsules. For the fiber material, the microcapsule suspension needs to be heated up to 80 ° C, and kept soaked with silk fiber for two hours, then cooled down, and repeated 3-4 times, and the silk fiber is silk.
具体的，实施例1和实施例2中，丝纤维经脱水烘干处理后，使得石墨烯微胶囊在丝纤维内进行流动浸泡，使得石墨烯微胶囊在流动浸泡中经反复升温、降温处理，使流动微胶囊溶液通过附着粘连法的原理附着在丝纤维表面，形成带有微胶囊的丝纤维。Specifically, in Examples 1 and 2, after the silk fibers were dehydrated and dried, the graphene microcapsules were subjected to flow soaking in the silk fibers, so that the graphene microcapsules were repeatedly heated and cooled in the flow soaking. The flowing microcapsule solution is adhered to the surface of the silk fiber by the principle of adhesion and adhesion method, and the silk fiber with the microcapsule is formed.
具体的，所述石蜡在微胶囊中的大小为2-30微米。Specifically, the size of the paraffin in the microcapsule is 2-30 microns.
具体的，该石墨烯微胶囊纤维的制备方法，人们通过将制备的石墨烯微胶囊纤维使用在人体衣服的纺织物中，衣服与皮肤之间进行温度的传递，石墨烯微胶囊纤维中的石蜡它能够感知并吸收收体内多余的热量，并在发热时释放储存的热量，从而实现控制到舒适的感觉温度，以满足在炎热的太阳和最冷的地区也是如此。Specifically, for the method for preparing graphene microcapsule fibers, people use the prepared graphene microcapsule fibers in the textiles of human clothes, and transfer the temperature between the clothes and the skin. It can sense and absorb the excess heat in the body, and release the stored heat when it is hot, so as to achieve a comfortable temperature control to meet the hot sun and the coldest regions.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will remain the same for those skilled in the art. Modifications to the technical solutions described in the foregoing embodiments, or equivalent replacements of some of the technical features may be made. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in Within the scope of the present invention.

Claims (6)

  1. 一种石墨烯微胶囊纤维的制备方法，该方法制得球形的微胶囊具有外壳和内核结构以及连接外壳和内核结构的乳化剂，其中外壳结构由微胶囊壁材组成，内核结构由微胶囊芯材组成，壁材主要为石墨烯，芯材为相变材料，石墨烯为改性石墨烯，相变材料为石蜡，其特征在于：包括以下步骤：A method for preparing graphene microcapsule fibers. The spherical microcapsules have a shell and a core structure and an emulsifier connecting the shell and the core structure. The shell structure is composed of a microcapsule wall material and the core structure is composed of a microcapsule core. Material, wall material is mainly graphene, core material is phase change material, graphene is modified graphene, phase change material is paraffin, which is characterized by including the following steps:
    S1：将一定含量的石墨烯溶于水中，加入pH值为3-5的硅烷偶联剂的乙醇容溶液，搅拌、抽滤、洗涤、干燥后得到改性石墨烯，并重新加入离子水，搅拌、超声得到改性石墨烯溶液；S1: Dissolve a certain amount of graphene in water, add an ethanol-containing solution of a silane coupling agent with a pH value of 3-5, stir, suction filter, wash, and dry to obtain modified graphene, and add ion water again. Stirring and ultrasonic to obtain modified graphene solution;
    S2：将乳化剂加入离子水中，搅拌并调节pH，加入相变材料，同时加热温度至相变材料开始融化，超声得到相变材料乳化液；S2: Add emulsifier to ionic water, stir and adjust pH, add phase change material, and heat the temperature until the phase change material begins to melt, and obtain the phase change material emulsion by ultrasound;
    S3：在微胶囊壁材制备的过程中将步骤S1中得到的改性石墨烯溶液加入，得到石墨烯改性壁材；S3: adding the modified graphene solution obtained in step S1 in the process of preparing the microcapsule wall material to obtain a graphene modified wall material;
    S4：将步骤S2得到的相变乳化液进行水浴加热，并将步骤S3得到的石墨烯改性壁材加入相变乳化液中，并经过超声分散、冷却、洗涤、干燥得到改性石墨烯微胶囊；S4: heating the phase change emulsion obtained in step S2 in a water bath, adding the graphene-modified wall material obtained in step S3 to the phase change emulsion, and obtaining the modified graphene microparticles by ultrasonic dispersion, cooling, washing, and drying capsule;
    S5：将上述得到的微胶囊采用蒸馏水清理过滤后干燥，并加入水中，形成微胶囊悬浮液，并将微胶囊悬浮液对丝纤维进行流动浸泡，得到带有石墨烯微胶囊的纤维材料。S5: The microcapsules obtained above are cleaned and filtered with distilled water, dried, and added to water to form a microcapsule suspension, and the microcapsule suspension is flow-soaked with silk fibers to obtain a fiber material with graphene microcapsules.
  2. 根据权利要求1所述的一种石墨烯微胶囊纤维的制备方法，其特征在于：步骤S1中制备改性石墨烯溶液的超声时间为1.5-3小时，干燥环境为真空干燥，干燥温度为60℃。The method for preparing graphene microcapsule fibers according to claim 1, wherein the ultrasonic time for preparing the modified graphene solution in step S1 is 1.5-3 hours, the drying environment is vacuum drying, and the drying temperature is 60 ℃.
  3. 根据权利要求1所述的一种石墨烯微胶囊纤维的制备方法，其特征在于：步骤S2中制备相变材料乳化液的时间为0.5-1.5小时。The method for preparing graphene microcapsule fiber according to claim 1, wherein the time for preparing the phase change material emulsion in step S2 is 0.5-1.5 hours.
  4. 根据权利要求1所述的一种石墨烯微胶囊纤维的制备方法，其特征在于：步骤S3制备石墨烯改性壁材时通过反应物在70-85℃下搅拌反应1小时制得。The method for preparing graphene microcapsule fibers according to claim 1, wherein, in step S3, the graphene modified wall material is prepared by stirring the reactants at 70-85 ° C for 1 hour.
  5. 根据权利要求1所述的一种石墨烯微胶囊纤维的制备方法，其特征在于：步骤S4中水浴加热的温度为恒温70摄氏度，时间为2-4小时，超声分散的时间为0.5-1小时，真空干燥的温度为60-80℃，时间为36小时。The method for preparing graphene microcapsule fiber according to claim 1, characterized in that: the temperature of the water bath heating in step S4 is constant temperature 70 degrees Celsius, the time is 2-4 hours, and the ultrasonic dispersion time is 0.5-1 hours The vacuum drying temperature is 60-80 ° C, and the time is 36 hours.
  6. 根据权利要求1所述的一种石墨烯微胶囊纤维的制备方法，其特征在于：步骤S5中微胶囊悬浮液需先升温至80℃，并与丝纤维保温浸泡两小时后，再降温，重复3-4次，且丝纤维为蚕丝。The method for preparing graphene microcapsule fiber according to claim 1, characterized in that: in step S5, the microcapsule suspension needs to be heated up to 80 ° C, and kept warm and soaked with silk fiber for two hours, then cooled down and repeated 3-4 times, and the silk fiber is silk.
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