201107031 六、發明說明 【發明所屬之技術領域】 本發明係關於一種天然微管包埋的相變化微膠囊及其 製備方法。 【先前技術】 —般而言，相變化材料（Phase change materials， φ PCM)，又稱爲潛熱儲能材料（Latent thermal energy storage，LTES)是指物質發生相變化時能夠吸收或放出熱 量而該物質本身溫度不變或變化不大的一類材料。相變化 材料作爲儲能載體，由於其具有貯熱密度高、設備體積 小 '熱效率高以及吸放熱爲恆溫過程等優點，可以有效提 高能源的利用率、緩解能源緊張的難題β目前，已被廣泛 運用於冰箱和空調的製冷和蓄冷、智慧建築物的自動恆 溫、太陽能應用中的能量儲存和交換技術、電力的“移峰 • 塡谷（peak load shifting)” 、廢熱和餘熱的回收利用以及 曰用品中。由於它使用簡便、不耗能，因而具有很大的應 用前景和廣闊市場。 從材料的相態變化過程，相變化材料主要分爲固-液 相變化、固-固相變化、固-氣相變化及液-氣相變化， 後兩者在相變化過程中伴隨有大量的氣體存在，使材料體 積變化較大，在實際應用中很少被選用。固-液相變化由 於體積變化小，潛熱較大，儲能好，相變化溫度範圍廣， 在實際應用中得到了廣泛的應用。但由於該材料在相變化 201107031 過程中有液相產生，因此必須用容器密封盛裝，以防止洩 漏污染環境，並且谷器對相變化材料而言必須是惰性的。 這一缺點極大地束縛了固-液相變化儲能材料的實際應 用。近年來，隨著技術的發展和應用場合的要求，人們試 圖對其進行形狀穩定處理使其轉變成形式上的“固—固” 相變化，但實際上仍發生固-液相變化，解決了相變化材 料的熔融問題，大大方便了實際應用。目前對相變化材料 進行形狀穩定的方法主要有定型化和微膠囊 (microcapsules)化兩種方法。 定型化相變化材料實質上是一類複合相變化儲能材 料，是指將相變化材料與載體物質相結合，形成一種外形 上可保持固體形狀、具有不流動性的相變化材料，其可代 替固一固相變化材料。這類相變化材料的主要組成有兩 種：其一是工作物質成分，即相變化材料，利用其相變化 來進行儲能、放能，工作物質包括各種相變化材料，但用 的較多的主要是固-液相變化材料。其二是載體物質，其 作用是保持相變化材料的不流動性和可加工性，因而要求 載體物質的熔化溫度高於相變化材料的相變化溫度，使工 作物質在相變化範圍內保持其固體的形狀和材料性能。從 近年定型複合相變化材料的合成發展狀況看，主要製備方 法可大致歸爲：共混法’接枝法，燒結法，原位插層法和 溶膠-凝膠法。但由於定型化相變化材料的物理作用相對 較小’材料經多次使用時易發生固—液相變化材料在載體 上的脫附’洩漏滲出以及兩相分離等現象^ 201107031 微膠囊化相變化材料是利用微膠囊技術將固_液相變 化材料微粒表面包覆一層性能穩定的高分子膜或無機材料 而構成具有核一殼（core-shell)結構的複合相變化材料。微 膠囊化相變化材料在相變過程中，內核發生固-液相變 化，而其外層的高分子膜保持爲固態，因此該類相變化材 料在宏觀上表現爲固態顆粒。相變化微膠囊的化學製備方 法主要有原位聚合法、介面聚合法、反應相分離法、介面 φ 沈積反應以及複凝聚法等類’不同的製備方法所得到的外 殻性能有所差別。隨著聚合物科學的發展，微膠囊化技術 逐漸成熟，因此’相變化儲能微膠囊材料由於其特殊的性 能和用途受到了廣泛的關注和硏究。相變化微膠囊的吸 熱、放熱的儲熱原理相當於一種“熱電池”，微容器的包 、 埋（encapsulation)使相變化材料轉變成無數微小的工作單 元，因此，大大擴展了相變化材料的應用領域和場合。摻 混了相變化微膠囊的製品會在其周圍建立起所採用相變.化 鲁 物質熔點範圍的微氣候環境’從而可滿足對溫度之舒適度 的要求’例如’可應用於保暖衣料。微膠囊化相變化材料 可以很好地解決固-液相變化過程中極易熔融流動、滲透 遷移、相分離、腐蝕等嚴重問題，經殼層材料包埋保護 後’相變化材料與外界環境相分離而得以穩定，同時，聚 合物殼層材料或經改質的殼層材料大大增加了相變化材料 與基體材料的相容性’從而大大增加了相變化材料的實用 性。然而，微膠囊的囊壁的強度不足、相變化材料滲漏以 及耐熱性尙待提高，特別是成本較高，皆是目前業界急需 201107031 解決之問題。 【發明內容】 有鑑於此，本發明的目的是提供一種利用切短的天然 微管包埋相變化材料的相變化微膠囊及其製備方法》 本發明所提供的相變化微膠囊，係包含相變化材料、 切短的微管和聚合物；其中所述切短的微管是將中空管狀 天然纖維切成長度爲0.1mm-5cm的纖維段；所述中空管 狀天然纖維的直徑爲0.1 -1 000μπι，相變化材料包埋在所 述切短的微管中，切短的微管以所述聚合物包埋。 所述天然纖維其例如但不限於選自：木棉纖維、乳草 纖維、絲瓜纖維、竹纖維、天竹纖維、亞麻纖維、羊毛、 羽絨、及其混合物所組成之群組。 所述相變化材料可爲下述1)和2)中的至少一者： 1)爲固一液相變化材料，2)爲固-固相變化材料； 所述固一液相變化材料可爲下述a)和b)中的至少 —者：a)爲無機相變化材料，b)爲有機相變化材料； 其中，所述無機相變化材料可爲結晶水合鹽和/或熔 融鹽。所述結晶水合鹽可爲鹼金屬或鹼土金屬的鹵化物、 硫酸鹽、磷酸鹽、硝酸鹽、醋酸鹽或碳酸鹽中的任一者或 其任意組合，其例如但不限於Na2S〇W〇H20、 Na2HP04.12H20、CaCl2.6H20、SnC1.6H20 等；所述熔融 鹽可爲K2W04和/或k2m〇o4等。 所述有機相變化材料其例如但不限於選自：高級脂肪 -8- 201107031 烴、高級脂肪酸、高級脂肪酸酯、高級脂肪酸的鹽、高級 脂肪醇、芳香烴、芳香酮、芳香醯胺、氟氯烷、多羰基碳 酸、結晶高分子、及其混合物所構成之群組。 筒級脂肪烴通常是含6個以上碳原子的脂肪烴，較佳 爲6〜36個碳原子。高級脂肪酸通常指含C6〜C26的一元 羧酸。 所述高級脂肪烴爲下述十六種物質中的任一者或其任 參 意組合：正二十八烷、正二十七烷、正二十六烷、正二十 五烷、正二十四烷、正二十三烷、正二十二烷、正二十一 烷、正二十烷、正十九烷、正十八烷、正十七烷、正十六 烷、正十五烷、正十四烷和正十三烷；所述結晶高分子爲 密度高於0.94 g/cm3的高密度聚乙烯、聚乙二烯或結晶聚 氯乙烯。 所述固-固相變材料其例如但不限於選自：無機鹽、 多元醇、高分子交聯樹脂及其混合物所組成之群組。 # 其中’所述無機鹽可爲Li2S04和/或KHF2 ;所述多 元醇可爲下述六種物質中的任一者或其任意組合：季戊四 醇（PE) 、2,2-二羥甲基丙醇（？〇)、新戊二醇（^〇)、2-氨基-2-甲基- I,3-丙二醇、三羥甲基乙烷和三羥甲基氨基 甲烷；所述高分子交聯樹脂爲交聯聚烯烴、交聯聚縮醛、 交聯聚烯烴和交聯聚縮醛的共聚物或交聯聚烯烴和交聯聚 縮醛的共混物。 所述聚合物可爲下述十種聚合物中的任一者或其任意 共聚物或其任意共混物：脲醒樹脂、三聚氰胺一甲醒樹 -9- 201107031 脂'三聚氰胺脲醛樹脂、聚胺基甲酸酯、聚甲基丙烯酸甲 酯、聚甲基丙烯酸乙酯、酚醛樹脂、環氧樹脂、聚丙烯腈 或醋酸纖維素。 本發明所提供的製備切短微管包埋的相變化材料的微 膠囊的方法，包括以下步驟： 1 )芯材相變化材料的液化 將相變化材料加熱到熔點以上或用溶劑溶解得到液態 的相變材料： 2) 以液態相變化材料塡充切短的天然微管 將切短的天然微管分散於步驟1)的液態相變化材料 中’浸泡，經過毛細吸收使所述天然微管內充滿液態的相 變化材料； 3) 微膠囊化相變化材料的包埋 用聚合物包埋步驟2)中塡充了相變化材料的微管， 得到了所述的相變化材料的微膠囊。 所述方法還包括將所得的相變化材料的微膠囊表面所 吸附的相變化材料洗掉的步驟。 所述溶劑其例如但不限於選自：去離子水、Ν,Ν’-二 甲基甲醯胺、Ν，Ν’·二甲基乙醯胺、四氫呋喃、二氯甲 烷、三氯甲烷、環己烷、甲醇、乙醇、丙酮及其混合物所 組成之群組。 本發明與現有的微膠囊化相變化材料包埋技術相比具 有如下之有益效果： 1、本發明採用的包埋管是廉價易得的天然微管。例 -10- 201107031 如’木棉纖維是一種具有比表面積大且中空度大的的天然 纖維’其中空度高達80〜90%，是現有的人造纖維難以達 到的’因此應用於製造相變化儲能材料比人造纖維更具有 優勢：且木棉纖維熱穩定性好，在25(TC下基本上是不會 發生熱降解。同時，木棉纖維的化學穩定性較好，只在高 濃度的強酸中才可溶解。 2、利用切短的具有比表面積大之微孔結構的天然微 • 管作爲支撐材料，經過微孔的毛細作用力，將液態的有機 相變化儲熱材料或無機相變化儲熱材料（高於相變溫度條 件下）吸入到微孔內’形成有機相變化儲熱材料、無機相 變化儲熱材料、或有機和無機所組成之複合相變化儲熱材 料。當上述相變化儲熱材料在微孔內發生固一液相變化 時’由於毛細管力的作用’液態的相變化儲熱材料很難從 微孔中溢出。 3'雖然毛細力作用在一定程度上解決了固一液相變 • 化材料的流動性問題，但其仍爲一個“開放”的包裹體 系’所以可進一步用聚合物對微膠囊化的已吸附了相變化 材料的微管封壁、封端。 4、 由於微管的中空度大使其儲能密度大，封閉結構 使能量傳輸穩定，極細的微米級管狀結構使傳熱迅速，熱 及化學穩定性有利於長期使用，特殊的親油疏水的浸潤性 能在加工過程中可被利用。 5、 微膠囊化的相變化材料形態在實際技術過程中能 更好地分散在基體材料中。與基體材料混合後，微米級的 -11 - 201107031 膠囊化相變化材料尺寸可以保持製品的外觀不受影響。 【實施方式】 實施例1、製備以天然木棉纖維管包埋石蠟並用脲醛 樹脂包埋的相變化微膠囊 (1 )芯材相變化材料的液化 將有機相變化材料石蠟加熱到熔點60 °c以上獲得液 態的石蠟相變化材料； (2 )以液態相變化材料塡充切短的天然微管 將lg長度爲1〇-50μιη的天然木棉纖維（切短的微 管）分散於l〇mL步驟（1)的液態相變化材料中，浸泡 使毛細吸收達到平衡，使木棉纖維管內充滿液態的相變化 材料； (3 )微膠囊化相變化材料的包埋 直接在步驟（2)塡充了相變化材料的天然木棉纖維 的熔體中滴加2g尿素甲醛預聚物（將lg尿素加到2ml的 3 6%甲醛水溶液中並攪拌到完全溶解，且受熱至60 °C，並 保溫1 5分鐘而得到的），提高熔體溫度到97〜98 °C，反 應1小時。在木棉纖維周圍生成脲賤樹脂聚合物進而產生 相分離而沉積’使微膠囊化的相變化材料被脲醛樹脂包 埋； (4 )微膠囊化相變化材料的純化 將步驟（3)中以脈醒樹脂包埋的吸滿了相變化材料 的微管撈出，再放入熱水中洗去管間吸附的相變化材料後 -12- 201107031 晾乾，即形成微膠囊化相變化材料。 相變化材料在迴圈升降溫下的DSC曲線如圖1所 示’掃描電子顯微鏡照片如圖2所示。 由圖1可知相變化微膠囊在迴圈升降溫下具有很好的 可迴圈相變化儲能效果。 由圖2可知裝塡了石蠟的膠囊化木棉纖維微管經過脲 醛樹脂包埋後形成了膠囊化相變化材料。 實施例2、製備以天然乳草纖維包埋季戊四醇並用醋 酸纖維素包埋的相變化微膠囊 (1 )芯材相變化材料的液化 將有機相變化材料季戊四醇（PE)溶解於少量乙醇中獲 得液態的季戊四醇（PE)溶液相變化材料； (2 )以液態相變化材料塡充切短的天然微管 將lg長度爲〇.5-10μιη的天然乳草纖維分散於10mL φ 步驟（1 )的液態相變化材料中，浸泡使毛細吸收達到平 衡，使乳草纖維管內充滿液態的相變化材料； (3)微膠囊化相變化材料的包埋 將步驟（2 )得到的含有乙醇溶劑的相變化材料微膠 囊中的乙醇揮發掉，使相變化材料季戊四醇（PE)溶液濃縮 固化後浸漬於5mL濃度爲5重量％的醋酸纖維素的二氯甲 烷溶液中，利用介面沉積反應使微膠囊化的相變化材料被 醋酸纖維素包埋； (4 )微膠囊化相變化材料的純化 -13- 201107031 將步驟（3)中以醋酸纖維素包埋的塡充了相變化材 料的乳草纖維，撈起後晾乾，即形成微膠囊化相變化材 料。 此方法製備的相變化微膠囊在迴圈升降溫下具有很好 的可迴圈相變化儲能效果，並且裝塡了季戊四醇（PE)的膠 囊化乳草纖維微管經過醋酸纖維素包埋後形成分散性較好 的膠囊化相變化材料。 實施例3、製備以天然竹纖維包埋CaCl24H20並用 醋酸纖維素包埋的相變化微膠囊 (1 )芯材相變化材料的液化 將lg無機相變化材料CaCl2«6H20溶解於10mL去離 子水中獲得液態的CaCl2«6H20溶液相變化材料； (2) 以液態相變化材料塡充切短的天然微管 將lg長度爲500- 1 000μπι的天然竹纖維分散於10mL 步驟（1 )的液態相變化材料中，浸泡使毛細吸收達到平 衡，使竹纖維管內充滿液態的相變化材料； (3) 微膠囊化相變化材料的包埋 將步驟（2)得到的含有去離子水的相變化材料微膠 囊中的去離子水揮發掉，使相變化材料CaCl2.6H20溶液 濃縮固化後浸漬於10mL濃度爲5重量％的醋酸纖維素的 二氯甲烷溶液中，利用介面沉積反應使微膠囊化的相變化 材料被醋酸纖維素包埋； (4 )微膠囊化相變化材料的純化 -14- 201107031 將步驟（3)中以醋酸纖維素包埋的塡充了相變化材 料的竹纖維，撈起後晾乾，即形成微膠囊化相變化材料。 此方法製備的相變化微膠囊在迴圈升降溫下具有很好 的可迴圈相變化儲能效果，並且裝塡了無機相變化材料 CaCl24H20的膠囊化竹纖維微管經過醋酸纖維素包埋後 形成分散性較好的膠囊化相變化材料。 φ 實施例 4、製備以天然亞麻纖維包埋季戊四醇和201107031 VI. Description of the Invention [Technical Field] The present invention relates to a phase change microcapsule embedded in a natural microtube and a preparation method thereof. [Prior Art] In general, phase change materials (φ PCM), also known as latent thermal energy storage (LTES), refers to the ability to absorb or release heat when a phase changes. A class of materials whose temperature does not change or does not change much. As a energy storage carrier, phase change material has the advantages of high heat storage density, small equipment volume, high thermal efficiency and constant temperature of heat absorption and release. It can effectively improve the utilization rate of energy and alleviate the problem of energy shortage. Refrigeration and cold storage for refrigerators and air conditioners, automatic constant temperature for smart buildings, energy storage and exchange technology for solar applications, "peak load shifting" for electricity, recycling of waste heat and waste heat, and 曰In the supplies. Because of its ease of use and non-energy consumption, it has great application prospects and a broad market. From the phase change process of materials, phase change materials are mainly divided into solid-liquid phase change, solid-solid phase change, solid-gas phase change and liquid-gas phase change, and the latter two are accompanied by a large number of phase changes. The presence of gas causes a large change in the volume of the material and is rarely used in practical applications. The solid-liquid phase change is widely used in practical applications due to small volume change, large latent heat, good energy storage, and wide temperature range of phase change. However, since the material has a liquid phase during the phase change 201107031, it must be sealed with a container to prevent leakage from polluting the environment, and the grain must be inert to the phase change material. This shortcoming greatly limits the practical application of solid-liquid phase change energy storage materials. In recent years, with the development of technology and the requirements of applications, people have tried to shape it to transform it into a formal "solid-solid" phase change, but in fact, solid-liquid phase changes still occur, and solved. The melting problem of phase change materials greatly facilitates practical applications. At present, the methods for shape stabilization of phase change materials mainly include stereotyping and microcapsules. The stereotyped phase change material is essentially a kind of composite phase change energy storage material, which refers to the phase change material combined with the carrier material to form a phase change material which can maintain a solid shape and has no fluidity in shape, which can replace solid A solid phase change material. There are two main components of such phase change materials: one is the working material component, that is, the phase change material, and the phase change is used for energy storage and energy release. The working materials include various phase change materials, but more are used. Mainly solid-liquid phase change materials. The second is a carrier material, which functions to maintain the fluidity and processability of the phase change material. Therefore, the melting temperature of the carrier material is required to be higher than the phase change temperature of the phase change material, so that the working material maintains its solid within the phase change range. Shape and material properties. From the recent development of the synthesis of phase-change composite phase change materials, the main preparation methods can be roughly classified into: blending method, grafting method, sintering method, in-situ intercalation method and sol-gel method. However, due to the relatively small physical effect of the materialized phase change material, the material is prone to desorption of the solid-liquid phase change material on the carrier when it is used multiple times, and leakage and two-phase separation. 201107031 Microencapsulation phase change The material is a composite phase change material having a core-shell structure by using a microcapsule technology to coat a surface of a solid-liquid phase change material particle with a stable polymer film or an inorganic material. In the phase change process of the microencapsulated phase change material, the core undergoes a solid-liquid phase change, and the polymer film of the outer layer remains solid, so the phase change material is macroscopically solid particles. The chemical preparation methods of the phase change microcapsules mainly include the in-situ polymerization method, the interface polymerization method, the reaction phase separation method, the interface φ deposition reaction, and the complex coacervation method. With the development of polymer science, microencapsulation technology has gradually matured. Therefore, the phase change energy storage microcapsule material has received extensive attention and research due to its special properties and uses. The heat absorption and exothermic heat storage principle of phase change microcapsules is equivalent to a "thermal battery". The encapsulation and encapsulation of the micro-container transforms the phase change material into numerous tiny working units, thus greatly expanding the phase change material. Application areas and occasions. An article incorporating phase-change microcapsules establishes a microclimate environment around which the phase change of the substance is used, thereby satisfying the requirement for temperature comfort. For example, it can be applied to warm clothing. The microencapsulated phase change material can solve the serious problems of melt flow, osmotic migration, phase separation and corrosion in the solid-liquid phase change process. After the shell material is embedded and protected, the phase change material and the external environment are phased. Separation and stabilization, at the same time, the polymer shell material or the modified shell material greatly increases the compatibility of the phase change material with the matrix material', thereby greatly increasing the practicability of the phase change material. However, the insufficient strength of the capsule wall of the microcapsule, the leakage of the phase change material, and the heat resistance need to be improved, especially the high cost, are the problems that the industry urgently needs to solve 201107031. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a phase change microcapsule using a chopped natural microtube embedding phase change material and a preparation method thereof. The phase change microcapsule provided by the present invention comprises a phase. a material, a shortened microtube, and a polymer; wherein the chopped microtube is a fiber segment cut into a length of 0.1 mm to 5 cm; the hollow tubular natural fiber has a diameter of 0.1 -1 000 μπι, a phase change material is embedded in the chopped microtubule, and the chopped microtubule is embedded in the polymer. The natural fibers are, for example but not limited to, selected from the group consisting of kapok fibers, milk grass fibers, loofah fibers, bamboo fibers, diatom fibers, flax fibers, wool, down, and mixtures thereof. The phase change material may be at least one of the following 1) and 2): 1) a solid-liquid phase change material, 2) a solid-solid phase change material; At least one of the following a) and b): a) is an inorganic phase change material, and b) is an organic phase change material; wherein the inorganic phase change material may be a crystalline hydrated salt and/or a molten salt. The crystalline hydrated salt may be any of an alkali metal or alkaline earth metal halide, sulfate, phosphate, nitrate, acetate or carbonate, or any combination thereof, such as, but not limited to, Na2S〇W〇H20 And Na2HP04.12H20, CaCl2.6H20, SnC1.6H20, etc.; the molten salt may be K2W04 and/or k2m〇o4 or the like. The organic phase change material is, for example but not limited to, selected from the group consisting of: higher fat-8-201107031 hydrocarbon, higher fatty acid, higher fatty acid ester, higher fatty acid salt, higher fatty alcohol, aromatic hydrocarbon, aromatic ketone, aromatic decylamine, fluorine A group consisting of chloroalkane, polycarbonyl carbonic acid, crystalline polymer, and mixtures thereof. The hydrocarbon grade hydrocarbon is usually an aliphatic hydrocarbon having 6 or more carbon atoms, preferably 6 to 36 carbon atoms. Higher fatty acids generally refer to monocarboxylic acids containing C6 to C26. The higher aliphatic hydrocarbon is any one of the following sixteen substances or a combination thereof: n-octacosane, n-heptadecane, n-hexadecane, n-pentadecane, and n. Tetradecane, n-docosane, n-docosane, n-docosane, n-icosane, n-nonadecane, n-octadecane, n-heptadecane, n-hexadecane, n. Alkane, n-tetradecane and n-tridecane; the crystalline polymer is a high density polyethylene, a polydiene or a crystalline polyvinyl chloride having a density higher than 0.94 g/cm3. The solid-solid phase change material is, for example but not limited to, selected from the group consisting of inorganic salts, polyols, polymer crosslinked resins, and mixtures thereof. #中的 The inorganic salt may be Li2S04 and/or KHF2; the polyol may be any one of the following six substances or any combination thereof: pentaerythritol (PE), 2,2-dimethylolpropane Alcohol (?〇), neopentyl glycol (^〇), 2-amino-2-methyl-I,3-propanediol, trimethylolethane and trishydroxymethylaminomethane; the polymer cross-linking The resin is a crosslinked polyolefin, a crosslinked polyacetal, a copolymer of a crosslinked polyolefin and a crosslinked polyacetal or a blend of a crosslinked polyolefin and a crosslinked polyacetal. The polymer may be any one of the following ten polymers or any copolymer thereof or any blend thereof: urea waking resin, melamine-a waking tree-9-201107031 lipid 'melamine urea-formaldehyde resin, polyamine Carbamate, polymethyl methacrylate, polyethyl methacrylate, phenolic resin, epoxy resin, polyacrylonitrile or cellulose acetate. The method for preparing microcapsules for cutting short microtubule-embedded phase change materials provided by the invention comprises the following steps: 1) liquefaction of the core phase change material, heating the phase change material to above the melting point or dissolving in a solvent to obtain a liquid state Phase change material: 2) Dissolving the short natural microtubule with a liquid phase change material, dispersing the chopped natural microtubule in the liquid phase change material of step 1), soaking, and absorbing the capillary into the natural microtubule The liquid phase change material is filled; 3) The encapsulation polymer encapsulation step 2) of the microencapsulated phase change material is filled with the microtube of the phase change material, and the microcapsule of the phase change material is obtained. The method also includes the step of washing away the phase change material adsorbed on the surface of the microcapsule of the resulting phase change material. The solvent is, for example but not limited to, selected from the group consisting of deionized water, hydrazine, Ν'-dimethylformamide, hydrazine, Ν'. dimethyl acetamide, tetrahydrofuran, dichloromethane, chloroform, and ring. A group consisting of hexane, methanol, ethanol, acetone, and mixtures thereof. Compared with the existing microencapsulated phase change material embedding technology, the present invention has the following beneficial effects: 1. The embedding tube used in the present invention is a natural micro tube which is cheap and easy to obtain. Example-10-201107031 For example, 'Kapok fiber is a kind of natural fiber with large specific surface area and large hollowness', and its emptyness is as high as 80~90%, which is difficult to achieve by existing man-made fibers'. Therefore, it is applied to the manufacture of phase change energy storage. The material has more advantages than man-made fiber: and the kapok fiber has good thermal stability, and basically does not undergo thermal degradation at 25 (TC). At the same time, the chemical stability of the kapok fiber is good, only in the high concentration of strong acid. Dissolving 2. Using a short natural micro-tube with a large specific surface area as a supporting material, the liquid organic phase changes the heat storage material or the inorganic phase change heat storage material through the capillary force of the micropores ( Above the phase transition temperature, inhaled into the micropores to form an organic phase change heat storage material, an inorganic phase change heat storage material, or a composite phase change heat storage material composed of organic and inorganic. When the above phase change heat storage material When a solid-liquid phase change occurs in the micropores, 'the action of the capillary force' liquid phase change heat storage material is difficult to overflow from the micropores. 3' Although the capillary force acts on To solve the problem of the fluidity of the solid-liquid phase change material, but it is still an “open” package system. Therefore, the microcapsules of the microcapsules to which the phase change material has been adsorbed can be further polymerized. Wall and end cap 4. Due to the large hollowness of the microtube, the energy storage density is large, the closed structure makes the energy transmission stable, and the extremely fine micron-sized tubular structure makes the heat transfer rapid, and the thermal and chemical stability is favorable for long-term use. The oleophilic hydrophobic infiltration properties can be utilized during processing. 5. The microencapsulated phase change material morphology can be better dispersed in the matrix material in the actual technical process. After mixing with the matrix material, the micron-scale -11 - 201107031 The size of the encapsulating phase change material can keep the appearance of the product unaffected. [Embodiment] Example 1. Preparation of phase change microcapsules (1) core phase embedded in paraffin wax with natural kapok fiber tube and embedded with urea resin Liquefaction of varying materials The organic phase change material paraffin is heated to a melting point of 60 ° C or more to obtain a liquid paraffin phase change material; (2) a liquid phase change material 塡Cut the natural microtubules to disperse the natural kapok fiber (short microtubule) with a length of 1〇-50μιη in the liquid phase change material of step (1), soak the capillary absorption to make the kapok The fiber tube is filled with a liquid phase change material; (3) The encapsulation of the microencapsulated phase change material is directly added to the melt of the natural kapok fiber filled with the phase change material in step (2) by adding 2 g of urea formaldehyde prepolymer. (Add lg urea to 2 ml of 3 6% formaldehyde aqueous solution and stir until completely dissolved, and heat to 60 ° C, and keep it for 15 minutes), increase the melt temperature to 97~98 °C, reaction 1 Hours. Formation of a urea resin polymer around the kapok fiber to produce phase separation and deposition 'the microencapsulated phase change material is embedded in the urea resin; (4) Purification of the microencapsulated phase change material in step (3) The microtubes filled with the phase change material embedded in the pulse awakening resin are taken out, and then the hot phase is used to wash away the phase change material adsorbed between the tubes, and then -12-201107031 is dried to form a microencapsulated phase change material. . The DSC curve of the phase change material at the temperature of the loop rise and fall is shown in Fig. 1. The scanning electron microscope photograph is shown in Fig. 2. It can be seen from Fig. 1 that the phase change microcapsules have a good energy recovery effect of the loopable phase change at the temperature of the loop. It can be seen from Fig. 2 that the encapsulated kapok fiber microtubes filled with paraffin are embedded in a urea resin to form an encapsulated phase change material. Example 2: Preparation of Phase Change Microcapsules Embedding Pentaerythritol with Natural Milk Fiber Fiber and Embedding with Cellulose Acetate (1) Liquefaction of Core Phase Change Material The organic phase change material pentaerythritol (PE) was dissolved in a small amount of ethanol to obtain a liquid state. Phase change material of pentaerythritol (PE) solution; (2) Dispersing the natural milkweed fiber of lg length 〇5-10μιη in 10mL φ liquid of step (1) with a liquid phase change material In the phase change material, the immersion is used to balance the capillary absorption, so that the milk fiber tube is filled with the liquid phase change material; (3) The embedding of the microencapsulated phase change material changes the phase of the ethanol solvent-containing phase obtained in the step (2) The ethanol in the material microcapsules is volatilized, and the phase change material pentaerythritol (PE) solution is concentrated and solidified, and then immersed in 5 mL of a 5% strength by weight cellulose acetate solution in dichloromethane, and the microencapsulated phase is formed by the interface deposition reaction. The change material is embedded in cellulose acetate; (4) Purification of microencapsulated phase change material-13-201107031 The cellulose acetate embedded in step (3) is filled with phase change material The milkweed fiber of the material is picked up and dried to form a microencapsulated phase change material. The phase change microcapsules prepared by the method have good reversible phase change energy storage effect under the temperature of the loop, and the encapsulated milk fiber microtubules loaded with pentaerythritol (PE) are embedded in cellulose acetate. An encapsulated phase change material having good dispersibility is formed. Example 3: Preparation of phase change microcapsules encapsulating CaCl24H20 with natural bamboo fiber and embedding with cellulose acetate (1) Liquefaction of core material phase change material The lg inorganic phase change material CaCl2 «6H20 was dissolved in 10 mL of deionized water to obtain a liquid state. CaCl2 «6H20 solution phase change material; (2) Dispersing the natural micro-tube with lg length of 500-1 000μπι in the liquid phase change material of step (1) with the liquid phase change material Soaking to achieve capillary balance, so that the bamboo fiber tube is filled with liquid phase change material; (3) Encapsulation of microencapsulated phase change material The phase change material microcapsule containing deionized water obtained in step (2) The deionized water is evaporated, and the phase change material CaCl2.6H20 solution is concentrated and solidified, and then immersed in 10 mL of a 5% by weight cellulose acetate solution in methylene chloride, and the microencapsulated phase change material is subjected to an interface deposition reaction. (7) Purification of microencapsulated phase change material-14- 201107031 After drying, it forms a microencapsulated phase change material. The phase change microcapsules prepared by the method have a good energy recovery effect of the loopable phase change at the temperature of the loop, and the encapsulated bamboo fiber microtubules with the inorganic phase change material CaCl24H20 are embedded in the cellulose acetate. An encapsulated phase change material having good dispersibility is formed. φ Example 4, preparation of natural flax fiber embedding pentaerythritol and
Li2S04並用聚丙烯腈包埋的相變化微膠囊 (1 )芯材相變化材料的液化 將l〇g有機相變化材料季戊四醇（PE)和10g無機相變 化材料Li2S04溶解於10mL去離子水和酒精的等體積混合 溶液中獲得液態的有機/無機混合相變化材料； (2 )以液態相變化材料塡充切短的天然微管 將5g長度爲1 00-500μιη的天然亞麻纖維分散於l〇mL φ 步驟（1 )的液態相變化材料中，浸泡使毛細吸收達到平 衡，使亞麻纖維管內充滿液態的相變化材料； (3)微膠囊化相變化材料的包埋 將步驟（2 )得到的含有去離子水和酒精溶劑的相變 化材料微膠囊中的去離子水和酒精揮發掉，使相變化材料 季戊四醇（PE)和Li2S04的混合溶液濃縮固化後浸漬於 5mL濃度爲5重量％的聚丙烯腈的N，N’-二甲基甲醯胺溶 液中，利用介面沉積反應，使微膠囊化的相變化材料被聚 丙烯腈包埋； -15- 201107031 (4 )微膠囊化相變化材料的純化 將步驟（3)中被聚丙烯腈包埋的塡充了相變化材料 的亞麻纖維，撈起後浸入去離子水中使聚丙烯腈固化，然 後晾乾。 此方法製備的相變化微膠囊在迴圈升降溫下具有很好 的可迴圈相變化儲能效果，並且裝塡了相變化材料季戊四 醇（PE)和Li2S04的膠囊化天然亞麻纖維微管經過聚丙烯 腈包埋後形成分散性較好的膠囊化相變化材料。 【圖式簡單說明】 圖1爲實施例1製備的相變化微膠囊在迴圈升降溫下 的DSC曲線圖。 圖2爲實施例1製備的相變化微膠囊掃描電子顯微鏡 照片，其中a)切短的天然木棉纖維管；b)和c)裝塡了 石蠟的膠囊化木棉纖維微管：d)以脲醛樹脂進一步包埋 後的膠囊化石躐塡充木棉纖維管。 -16-Li2S04 phase-change microcapsules embedded in polyacrylonitrile (1) Liquefaction of core phase change material l〇g organic phase change material pentaerythritol (PE) and 10g inorganic phase change material Li2S04 dissolved in 10mL deionized water and alcohol A liquid organic/inorganic mixed phase change material is obtained in an equal volume of mixed solution; (2) 5 g of natural flax fiber having a length of 100-500 μm is dispersed in l〇mL φ by a liquid phase change material which is shortened by a natural microtubule. In the liquid phase change material of step (1), the immersion is used to balance the capillary absorption, so that the flax fiber tube is filled with the liquid phase change material; (3) the encapsulation of the microencapsulated phase change material is obtained by the step (2) Deionized water and alcohol solvent phase change material Deionized water and alcohol in the microcapsules volatilize, so that the phase change material mixed solution of pentaerythritol (PE) and Li2S04 is concentrated and solidified, and then immersed in 5mL of 5% by weight of polyacrylonitrile. In the N,N'-dimethylformamide solution, the microencapsulated phase change material is embedded in polyacrylonitrile by interfacial deposition reaction; -15- 201107031 (4) Microencapsulated phase change material Purification of the material The flax fiber embedded in the polyacrylonitrile in step (3) is filled with the phase change material, and then immersed in deionized water to solidify the polyacrylonitrile, and then dried. The phase change microcapsules prepared by the method have good reversible phase change energy storage effect under the temperature of the loop temperature, and the encapsulated natural flax fiber microtubules with phase change materials pentaerythritol (PE) and Li2S04 are assembled. After encapsulation of acrylonitrile, a capsule phase change material with better dispersibility is formed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a DSC chart of phase change microcapsules prepared in Example 1 under reflux temperature. 2 is a scanning electron micrograph of a phase change microcapsule prepared in Example 1, wherein a) a chopped natural kapok fiber tube; b) and c) a paraffin-embellized encapsulated kapok fiber microtube: d) a urea resin The further encapsulated fossils are filled with kapok fiber tubes. -16-