纳米胶囊化二元复合相变材料的制备及热性能
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摘要
以正十八烷(C18)和硬脂酸丁酯(BS)为复合芯材(PCMs),聚甲基丙烯酸甲酯(PMMA)为壁材,通过无皂乳液聚合法制备纳米胶囊化相变材料,探讨了乳化剂种类和用量、引发剂种类和用量、芯壁比对纳米胶囊的影响,并采用TEM、SEM、FTIR、XRD、DSC和TGA对纳米胶囊的形貌、化学结构和热性能进行了测试表征。结果表明:当烷基乙烯基磺酸盐(AVS)用量占油相总质量的3.0%,过硫酸铵(APS)用量占单体MMA质量的1.2%,芯材与壁材质量比(芯壁比)为2∶4时,制备的纳米胶囊单体转化率最高、粒径最小、球形形貌最规整。相变纳米胶囊的熔融焓和结晶焓分别为56.89和54.02 J/g,具有良好的储热能力和耐热性能,且整理于棉织物上有较好的调温效果。
Nanoencapsulated phase change materials were prepared through surfactant-free emulsion polymerization with n-octadecane(C18) and n-butyl stearate(BS) as binary cores and poly(methyl methacrylate)(PMMA) as shell. The effects of emulsifier type and dosage, initiator type and dosage and core/shell mass ratio on the nanocapsules were studied. The surface morphology, chemical structure and thermal properties of phase change nanocapsules were characterized by TEM, SEM, FTIR, XRD, DSC and TGA. The results indicate that the best preparation conditions of nanocapsules are alkyl vinyl sulfonate(AVS) dosage 3.0% of the total oil phase mass, ammonium persulfate(APS) dosage 1.2% of the mass of MMA and core/shell mass ratio 2∶4. Under these conditions, the monomer conversion of nanocapsules is the highest, particle size is the smallest and spherical morphology is the most regular. In addition, phase change nanocapsules have good latent heat storage capacity and heat resistance, and their melting enthalpy and crystallization enthalpy are 56.89 J/g and 54.02 J/g, respectively. The finished cotton fabrics with phase change nanocapsules have better thermoregulation effect.
Nanoencapsulated phase change materials were prepared through surfactant-free emulsion polymerization with n-octadecane(C18) and n-butyl stearate(BS) as binary cores and poly(methyl methacrylate)(PMMA) as shell. The effects of emulsifier type and dosage, initiator type and dosage and core/shell mass ratio on the nanocapsules were studied. The surface morphology, chemical structure and thermal properties of phase change nanocapsules were characterized by TEM, SEM, FTIR, XRD, DSC and TGA. The results indicate that the best preparation conditions of nanocapsules are alkyl vinyl sulfonate(AVS) dosage 3.0% of the total oil phase mass, ammonium persulfate(APS) dosage 1.2% of the mass of MMA and core/shell mass ratio 2∶4. Under these conditions, the monomer conversion of nanocapsules is the highest, particle size is the smallest and spherical morphology is the most regular. In addition, phase change nanocapsules have good latent heat storage capacity and heat resistance, and their melting enthalpy and crystallization enthalpy are 56.89 J/g and 54.02 J/g, respectively. The finished cotton fabrics with phase change nanocapsules have better thermoregulation effect.
引文
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[23]Zhao J,Yang Y,Li Y,et al.Microencapsulated phase change materials with TiO2-doped PMMA shell for thermal energy storage and UV-shielding[J].Solar Energy Materials and Solar Cells,2017,168:62-68.
[24]Xu Q,Liu H,Wang X,et al.Smart design and construction of nanoflake-like MnO2/SiO2 hierarchical microcapsules containing phase change material for in-situ thermal management of supercapacitors[J].Energy Conversion and Management,2018,164:311-328.
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[28]Su W,Darkwa J,Kokogiannakis G.Development of microencapsulated phase change material for solar thermal energy storage[J].Applied Thermal Engineering,2017,112:1205-1212.
[2]Wang T,Wang S,Luo R,et al.Microencapsulation of phase change materials with binary cores and calcium carbonate shell for thermal energy storage[J].Applied Energy,2016,171:113-119.
[3]Mou Siyang(牟思阳),Guo Jing(郭静),Qi Shanwei(齐善威),et al.Synthesis and characterization of poly(acrylonitrile-co-itaconate)-graft-poly(ethylene glycol)copolymers as novel solid-solid phase change materials for thermal energy storage[J].Chemical Research in Chinese Universities(高等学校化学学报),2015,36(12):2557-2562.
[4]Jiang F,Wang X,Wu D.Design and synthesis of magnetic microcapsules based on n-eicosane core and Fe3O4/SiO2 hybrid shell for dual-functional phase change materials[J].Applied Energy,2014,134:456-468.
[5]Li J,Liu H,Wang X,et al.Development of thermoregulatory enzyme carriers based on microencapsulated n-docosane phase change material for biocatalytic enhancement of amylases[J].ACSSustainable Chemistry&Engineering,2017,5(9):8396-8406.
[6]Xin Cheng(辛成),Lu Shaofeng(陆少锋),Shen Tianwei(申天伟),et al.Preparation and properties of network polyurethane shell microencapsulated phase change materials via an interfacial polymerization[J].Fine Chemicals(精细化工),2018,35(7):1121-1125.
[7]Zhang Qiuxiang(张秋香),Chen Jianhua(陈建华),Lu Hongbin(陆洪彬),et al.Preparation and properties of paraffin microencapsulated phase-change materials with fine particle size[J].Chemical Research in Chinese Universities(高等学校化学学报),2014,35(10):2258-2264.
[8]Jian Zhe(菅哲),Zhang Guoqing(张国庆),Feng Xinxing(冯新星),et al.Study on the preparation and the properties of polyurethane foamed cotton filled with n-ocatadecane[J].Journal of Zhejiang Sci-Tech University(浙江理工大学学报),2018,39(1):51-56.
[9]Yu Qiangqiang(于强强).Preparation and characterization of paraffinmicrocapsule phase change material[D].Beijing:Beijing Institute of Clothing Technology(北京服装学院),2015.
[10]Wang Lixin(王立新),Su Junfeng(苏峻峰),Ren Li(任丽).Study of compactibility of thermal energy storage microcapsule with melamine formaldehyde resin as shell[J].Fine Chemicals(精细化工),2003,(12):705-708.
[11]Qiao Z,Mao J.Enhanced thermal properties with graphene oxide in the urea-formaldehyde microcapsules containing paraffin PCMs[J].Journal of Microencapsulation,2017,34(1):1-9.
[12]Chen K,Yu X,Tian C,et al.Preparation and characterization of form-stable paraffin/polyurethane composites as phase change materials for thermal energy storage[J].Energy Conversion&Management,2014,77(8):13-21.
[13]Qiu X Z,Tao Y,Xu X Q,et al.Synthesis and characterization of paraffin/TiO2-P(MMA-co-BA)phase change material microcapsules for thermal energy storage[J].Journal of Applied Polymer Science,2018,135(27):46447-46457.
[14]Sar?A,Alkan C,Karaipekli A,et al.Microencapsulated n-octacosane as phase change material for thermal energy storage[J].Solar Energy,2009,83(10):1757-1763.
[15]Alkan C,Sar?A,Karaipekli A.Preparation,thermal properties and thermal reliability of microencapsulated n-eicosane as novel phase change material for thermal energy storage[J].Energy Conversion and Management,2011,52(1):687-692.
[16]Ma Luliang(麻录亮),Zhao Zhenhe(赵振河),Li Mizhuan(李密转).Synthesis and application of new soap-free acrylate coatings dyeing adhesives MZ-19[J].Textile Dyeing and Finishing Journal,2010,32(9):8-10,14.
[17]Carreira A S,Teixeira R F A,Beir?o A,et al.Preparation of acrylic based microcapsules using different reaction conditions for thermo-regulating textiles production[J].European Polymer Journal,2017,93:33-43.
[18]He Lang(何浪).Study on controllable preparation and rheological behavior of waterborne acrylic resin emulsion with core-shell structure[D].Wuhan:Wuhan University(武汉大学),2015.
[19]Huang Ming(黄明),Luo Yan(罗艳),Zhong Yi(钟毅),et al.Preparation and characterization of n-dodecyl alcohol/polymethyl methacrylate phase change microencapsules used in thermo-regulating fibre[J].Textile Auxiliaries(印染助剂),2017,34(10):30-34.
[20]Zhang Zhigang(张志岗),Zhang Liping(张丽平).Preparation and characterization of microcapsules with binary phase change core[J].Journal of Beijing Institute of Clothing Technology(北京服装学院学报),2016,36(2):33-39.
[21]Ma Lili(马丽丽).Preparation and characterization of phase change energy storage nanocapsules[D].Guangzhou:South China University of Technology(华南理工大学),2011.
[22]Liu Huan(刘欢),Wei Zhong(魏忠).Study on emulsion polymerization of butyl methacrylate[J].Journal of Shihezi University(石河子大学学报),2013,31(3):382-386.
[23]Zhao J,Yang Y,Li Y,et al.Microencapsulated phase change materials with TiO2-doped PMMA shell for thermal energy storage and UV-shielding[J].Solar Energy Materials and Solar Cells,2017,168:62-68.
[24]Xu Q,Liu H,Wang X,et al.Smart design and construction of nanoflake-like MnO2/SiO2 hierarchical microcapsules containing phase change material for in-situ thermal management of supercapacitors[J].Energy Conversion and Management,2018,164:311-328.
[25]Wang H,Li Y,Zhao L,et al.A facile approach to synthesize microencapsulated phase change materials embedded with silver nanoparicle for both thermal energy storage and antimicrobial purpose[J].Energy,2018,158:1052-1059.
[26]Xu B,Zhou J,Ni Z,et al.Synthesis of novel microencapsulated phase change materials with copper and copper oxide for solar energy storage and photo-thermal conversion[J].Solar Energy Materials and Solar Cells,2018,179:87-94.
[27]Ma Y,Zong J,Li W,et al.Synthesis and characterization of thermal energy storage microencapsulated n-dodecanol with acrylic polymer shell[J].Energy,2015,87:86-94.
[28]Su W,Darkwa J,Kokogiannakis G.Development of microencapsulated phase change material for solar thermal energy storage[J].Applied Thermal Engineering,2017,112:1205-1212.