微胶囊相变材料制备与应用研究进展

doi:10.16085/j.issn.1000-6613.2020-2165

摘要/Abstract

摘要：

微胶囊相变材料（MCPCM）利用微胶囊技术将相变材料包覆实现功能化，避免其泄漏及团聚问题，拓展了其应用范围，因而具有很大的应用前景。本文从制备方法出发，首先介绍了MCPCM的芯材和壳材，详细阐述了喷雾干燥法、溶胶-凝胶法、复凝聚法、界面聚合法、原位聚合法、悬浮聚合法和微乳液聚合法的原理及方法。围绕上述方法，文中阐述了MCPCM的微观形貌，并分析了粒径分布、包覆率、芯壳比对MCPCM储热和热稳定性等性能的影响。同时，概括了MCPCM在建筑节能、蓄热调温纺织、军事航空、能源利用等领域中的应用。最后，对微胶囊相变材料的研究方向进行了展望。

关键词: 微胶囊相变材料, 制备方法, 性能表征, 温度调控

Abstract:

Microcapsule phase change material (MCPCM) can achieve the encapsulation of the phase change materials and avoid leakage and agglomeration. It has broadened the application fields of phase change materials and has a great prospect. The core and shell materials of MCPCM were firstly introduced. Then, the principles of spray drying, sol gel, complex coacervation, interfacial polymerization, in-situ polymerization, suspension polymerization and microemulsion polymerization methods were elaborated. The microscopic morphology characteristics of MCPCM were presented. Furthermore, the influences of particle size distribution, encapsulation ratio and core-shell ratio on the thermal stability and heat storage capacity of MCPCM were analyzed. Meanwhile, the application of MCPCM in the fields of building energy conservation, heat storage and temperature regulation textile, military aviation, energy utilization and other fields were summarized. Finally, the research direction of microcapsule phase change materials had been prospected.

Key words: microcapsule phase change material, preparation methods, properties characterization, temperature regulation

中图分类号:

TK02

公雪, 王程遥, 朱群志. 微胶囊相变材料制备与应用研究进展[J]. 化工进展, 2021, 40(10): 5554-5576.

GONG Xue, WANG Chengyao, ZHU Qunzhi. Research progress on preparation and application of microcapsule phase change materials[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5554-5576.

图/表 16

参考文献 159

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分类	常见化合物	特点
醇类^［24］	十二醇、十四醇、环己醇、叔丁醇等多元醇	无过冷和相分离现象、无毒、腐蚀性小、热效率高、热导率小、储热密度小、易挥发燃烧、易氧化老化
酯类^［25］	硬脂酸丁酯、硬脂酸辛酯	良好的热性能和可靠性，有利于低温传热应用；热导率小、储热密度小、易挥发燃烧、易氧化老化
烃类^［26］	聚乙烯蜡、液体石蜡、正十六烷、正十八烷	无过冷和相分离现象、稳定性好、腐蚀性极小、热导率小、储热密度小、易挥发燃烧、易氧化老化
脂肪酸类^［27］	月桂酸、癸酸、辛酸、十二烷酸	潜热值大、过冷度低、无毒、稳定性好、相容性好、热导率小、储热密度小、易挥发燃烧、易氧化老化
无机物^［28］	结晶水和盐、熔融盐、金属合金	潜热值大、储能密度高、相变体积变化小、廉价易得、过冷度大、易析出分离、有一定腐蚀性

分类	常见化合物	特点
醇类^［24］	十二醇、十四醇、环己醇、叔丁醇等多元醇	无过冷和相分离现象、无毒、腐蚀性小、热效率高、热导率小、储热密度小、易挥发燃烧、易氧化老化
酯类^［25］	硬脂酸丁酯、硬脂酸辛酯	良好的热性能和可靠性，有利于低温传热应用；热导率小、储热密度小、易挥发燃烧、易氧化老化
烃类^［26］	聚乙烯蜡、液体石蜡、正十六烷、正十八烷	无过冷和相分离现象、稳定性好、腐蚀性极小、热导率小、储热密度小、易挥发燃烧、易氧化老化
脂肪酸类^［27］	月桂酸、癸酸、辛酸、十二烷酸	潜热值大、过冷度低、无毒、稳定性好、相容性好、热导率小、储热密度小、易挥发燃烧、易氧化老化
无机物^［28］	结晶水和盐、熔融盐、金属合金	潜热值大、储能密度高、相变体积变化小、廉价易得、过冷度大、易析出分离、有一定腐蚀性

分类	壳材	特点
无机高分子材料	碳酸钙、石墨烯、硅酸盐、二氧化钛、二氧化硅、黏土、硫化物、铝、铜等	成膜性能非常差，具有功能性
有机高分子材料
天然高分子材料^［29］	动物蛋白：明胶、乳清蛋白、丝素蛋白植物蛋白：大豆蛋白、豌豆蛋白多糖：阿拉伯树胶、果胶、壳聚糖、琼脂、海藻酸钠、卡拉胶、羧甲基纤维素钠	良好的生物降解性、无毒，稳定、成膜性好
半合成高分子材料	甲酸乙酸纤维素、邻苯二甲酸丁酸纤维素、丁酸乙酸纤维素、甲基纤维素、羧甲基纤维素、羧甲基纤维素钠、乙基纤维素、羟丙基纤维素、琥珀酸乙酸纤维素等	毒性小，黏度大，成盐后溶解度增大易水解，不宜高温处理，需临时用现制
合成高分子材料^［30-31］	酚醛树脂、密胺树脂、脲醛树脂、聚氨酯、聚丁二烯、聚乙烯、环氧树酯、聚酰胺、聚苯乙烯、三聚氰胺-甲醛树脂、氨基树脂类、乙酸树脂类、聚脲、合成橡胶等	成膜性好，化学性能稳定，部分材料释放甲醛，不利于环境保护

分类	壳材	特点
无机高分子材料	碳酸钙、石墨烯、硅酸盐、二氧化钛、二氧化硅、黏土、硫化物、铝、铜等	成膜性能非常差，具有功能性
有机高分子材料
天然高分子材料^［29］	动物蛋白：明胶、乳清蛋白、丝素蛋白植物蛋白：大豆蛋白、豌豆蛋白多糖：阿拉伯树胶、果胶、壳聚糖、琼脂、海藻酸钠、卡拉胶、羧甲基纤维素钠	良好的生物降解性、无毒，稳定、成膜性好
半合成高分子材料	甲酸乙酸纤维素、邻苯二甲酸丁酸纤维素、丁酸乙酸纤维素、甲基纤维素、羧甲基纤维素、羧甲基纤维素钠、乙基纤维素、羟丙基纤维素、琥珀酸乙酸纤维素等	毒性小，黏度大，成盐后溶解度增大易水解，不宜高温处理，需临时用现制
合成高分子材料^［30-31］	酚醛树脂、密胺树脂、脲醛树脂、聚氨酯、聚丁二烯、聚乙烯、环氧树酯、聚酰胺、聚苯乙烯、三聚氰胺-甲醛树脂、氨基树脂类、乙酸树脂类、聚脲、合成橡胶等	成膜性好，化学性能稳定，部分材料释放甲醛，不利于环境保护

方法	芯材	壳材	芯材熔化潜热 /J·g^-1	微胶囊熔化潜热/J·g^-1	芯材凝固潜热/J·g^-1	微胶囊凝固潜热/J·g^-1	包覆率 /％	结论	参考文献
原位聚合法和化学镀法	1-十四醇（TD）	三聚氰胺、尿素和甲醛	209.8 209.8 209.8 209.8	116.7 98.5 126.6 119.4	207.5 207.5 207.5 207.5	116.4 93.9 120.9 111.0	55.6 46.9 60.3 56.9	相变微胶囊镀银后可有效抑制相变材料的过冷，并提高包覆效率	［112］
原位聚合法	石蜡	三聚氰胺、尿素和甲醛	70.1 70.1 70.1 70.1 70.1	35.6 28.8 23.7 32.2 29.4	73.6 73.6 73.6 73.6 73.6	45.5 33.6 29.6 39.5 39.0	56.4 43.4 37.1 49.9 47.6	加入氧化石墨烯后增强了MCPCM粒度均匀性、热稳定性和不渗透性。随着微胶囊含量的增加，石膏材料的力学性能下降	［113］
悬浮聚合法	正十二醇	丙烯酸树脂	216.0	93.31	207.8	78.16	43	MEPCM降低了PCM过冷度，提升了PCM对温度变化的响应速度，增大了储能	［114］
溶胶-凝胶法	石蜡	二氧化钛	130.3	90.37	127.8	94.66	69.36	MEPCM具有良好的热稳定性，包覆较好，可有效防止石蜡泄漏	［38］
溶胶-凝胶法	正十二醇	二氧化硅	210.13	103.4	209.3	99.64	49.21	乳化剂、溶液pH、芯壳比都会影响MCPCM的包覆率	［36］
化学沉淀法	正十二醇	二氧化硅	210.13	116.7	209.3	114.61	55.54	当芯壳比由2∶1增加到 5∶1时，微胶囊的相变焓先增大后减少，形成的壳材较薄，后处理中易泄漏	［36］