臺灣博碩士論文加值系統

本文提出在不使用有機溶劑並以MMA單體搭配BPO為起始劑，EGDMA為架橋劑，PVA為穩定劑，製備出以PMMA為殼層材料、正十八烷為芯材的相變材料微膠囊。
文中藉由探討MMA單體之PMMA預聚物程度、PVA濃度以及核殼進料比例對合成正十八烷微膠囊、微膠囊粒徑分佈、表面型態、核包覆含量、熱穩定性及耐用性的影響。
實驗結果顯示，以MMA單體聚合30分所獲得之PMMA預聚物進行正十八烷包覆為最適化製程條件。此外，調控PVA濃度為0.01%以上方可合成出微膠囊，且隨著PVA濃度由0.01%增加至0.1%，所製備出之正十八烷微膠囊的核包覆量也由54%增加至84%；然數目平均粒徑卻由4.36μm下降至1.75μm。隨著殼層進料比由1:1增加至1:1.5及1:2，所製備出微膠囊之數目平均粒徑也由1.75μm增加至4.23μm及4.38μm；然正十八烷微膠囊的包覆量卻由84%下降至69%及59%。SEM顯示，所製備出微膠囊皆為球型，表面觀察出凹陷情形。由TGA及FTIR交叉分析顯示，所製備出微膠囊在溫度範圍為150℃-230℃、230℃-450℃下，有兩種不同的熱重損失速率，分別代表正十八烷完全氣化及PMMA殻層的分解階段。此外，以0.1%PVA所製備出之微膠囊測試100次DSC凍熔循環的再現性，顯示微膠囊維持良好的包覆效果及耐用性。

The core/shell microcapsules with n-octadecane and poly methyl methacrylate (PMMA) were successfully synthesized by interfacial polymerization without organic solvent using methyl methacrylate (MMA), benzoyl peroxide (BPO), ethylene glycol dimethylacrylate (EGDMA) and poly vinyl alcohol (PVA).
The characterization of microcapsules such as formation, morphology, particle size distribution, encapsulated n-octadecane percentage, thermal stability and thermal reliability were investigated by changing degree of PMMA pre-polymer, PVA concentration and core/shell mass ratio.
The experimental results showed that the optimal reaction time of PMMA pre-polymer was 30 minutes. In addition, when the PVA concentration was above 0.01%, the microcapsules could be fabricated successfully. Analysis of particle size distribution (PSD) and differential scanning calorimetry (DSC) indicated that encapsulated n-octadecane percentage of microcapsules increased with increasing PVA concentrations, but the number mean particle size decreased; the number mean particle size and thermal stability increased with increasing the shell mass ratio, but encapsulated n-octadecane percentage of microcapsules decreased. Analysis of scanning electron microscope (SEM) indicated that morphology of microcapsules were spherical, compact and concave. Analysis of thermal gravimetric analysis (TGA) and fourier transform infrared (FTIR) spectroscopy indicated that n-octadecane of the microcapsules degraded around 150℃ to 230℃ and PMMA shells of the microcapsules degraded around 230℃ to 450℃. In addition, the microcapsules on PVA concentration of 0.1% showed good thermal reliability by accelerated thermal cycling tests.

第一章 前言 1
1-1相變材料 1
1-2微粒包覆技術 9
1-3相變材料微膠囊 14
1-4 研究動機 17
第二章 研究背景與文獻回顧 19
2-1 國內合成PMMA微膠囊之製備方法 19
2-2國外合成PMMA微膠囊之製備方法 21
第三章 實驗步驟 30
3-1 微膠囊之製備 30
3-1-1 實驗藥品 30
3-1-2 實驗器材 31
3-1-3 實驗方法 32
3-2 微膠囊之測試及分析 35
3-2-1 顯微觀測 35
3-2-2 化學結構鑑定 35
3-2-3 熱重損失分析 36
3-2-4低溫微差掃描熱分析 36
第四章 結果討論 40
4-1相變材料十八烷之性質分析 40
4-1-1相變材料之熱重損失 40
4-1-2 相變材料之低溫微差掃描熱分析 41
4-2合成PMMA相變材料微膠囊 42
4-2-1 PMMA預聚程度的影響 42
4-2-2 PVA濃度的影響 45
4-3相變微膠囊之性質分析 49
4-3-1 微膠囊之顯微觀察與粒徑分布 49
4-3-2相變微膠囊的粒徑分佈與核含量 53
4-3-3微膠囊之熱穩定性及耐用性 58
第五章 結論 63
5-1結論 63
5-2未來工作 64
參考文獻 65

1.Hale D. V., Hoover M. J., O’Neill M. J., “Phase Change Material Handbook”, NASACR-61363 (1971).
2.Sharma A., Tyagi V. V., Chen C.R., Buddhi D., “Review on thermal energy storage with phase change materials and applications”, Renewable and Sustainable Energy Review 13 (2009) 318-345.
3.Zalba B., Marin J. M., Cabeza L. F., Mehling H., “Review on thermal energy storage with phase change: materials, heat transfer analysis and applications”, Applied Thermal Engineering 23 (2003) 251-283.
4.Dubey R., Shami T. C., Bhasker Rao K. U. , “Microencapsulation technology and applications”, Defence Science Journal 59 (2009) 82-95.
5.王宗櫚、謝達華、何國賢 “聚合物合成與鑑定法”，台灣復文興業股份有限公司 (1984) 119-145.
6.Kürklü A., “Energy Storage Applications in Greenhouses by Means of Phase Change Materials: a Review,” Renewable Energy 13 (1998) 89-103.
7.曹虹霞，“相變材料微膠囊的製備與應用”，天津工業大學學報 (2011) 12-15.
8.陳麗如，“建築外殼結構之潛熱熱控技術”，工業材料雜誌 (2008) 127-133.
9.Ho C. J., Huang J. B., Tsai P. S., Yang Y. M., “Water-based suspensions of Al2O3 nanoparticles and MEPCM particles on convection effectiveness in a circular tube”, International Journal of Thermal Sciences 50 (2011) 736-748.
10.Ho C. J., Huang J. B., Tsai P. S., Yang Y. M., “On laminar convective cooling performance of hybrid water-based suspensions of Al2O3 nanoparticles and MEPCM particles in a circular tube” , International Journal of Heat and Mass Transfer 54 (2011) 2397-2407.
11.Ho C. J., Huang J. B., Tsai P. S., Yang Y. M., “Preparation and properties of hybrid water-based suspension of Al2O3 nanoparticles and MEPCM particles as functional forced convection fluid”, International Communications in Heat and Mass Transfer 37 (2010) 490-494.
12.Outlast, http://www.outlast.com/index.php?id=70&L=0
13.張智中，“以溶膠凝膠法製備有機無機混成相轉移材料微膠囊”，國立中央大學化學工程研究所碩士論文 (2006).
14.Li W., Song G., Tang G., Chu X., Ma S., Liu C., “Morphology, structure and thermal stability of microencapsulated phase change material with copolymer shell”, Energy 36 (2011) 785-791.
15.Ma S. D., Zhong L. S., Wang P. G., Xu C. X., Li X. Y., “A fast way to fabricate poly methyl methacrylate for graded-index polymer optical fibers”, Polymer- plastics Technolology & Engineering 45 (2006) 373–378.
16.Ma S. D., Song G. L., Zhong L. S., Tang G. Y., “Study on bulk polymerization of methyl methacrylate initiated by low intensity ultrasonic irradiation”, Journal of Applied Polymer Science 116 (2010) 3127–3133.
17.楊雯欣，“懸浮聚合法製備相轉移材料微膠囊”，國立中央大學化學工程研究所碩士論文 (2007).
18.林岩錫, “包埋有相變化材料微膠囊之製造方法”，中華民國專利I239866，(2004).
19.Park B. J., Lee J. Y., “Microcapsules containing electrophoretic suspension of TiO2 modified with poly(methyl methacrylate)”, Current Applied Physics 6 (2006) 632-635.
20.Taguchi Y., Yokoyama H., Kado H., Tanaka M., “Preparation of PCM Microcapsules by using oil absorbable polymer particles”, Colloids and Surfaces A: Physicochemical and Engineering Aspects 301 (2007) 41-47.
21.Zhang Y., Lin W., Yang R., Zhang Y., Zhang Q., “Preparation and Thermal Property of Phase Change Material Microcapsules by Phase Separation”, Materials Science Forum 561-565 (2007) 2293-2296.
22.Wang Y., Guo B. H., Wan X., Xu J., Wang X., Zhang Y. P., “Janus-like polymer particles prepared via internal phase separation from emulisified polymer /oil droplets”, Polymer 50 (2009) 3361-3369.
23.Streubel A., Siepmann J., Bodmeier R., “Multiple unit gastroretentive drug delivery systems: a new preparation method for low density microcapsules”, Journal of Microencapsulation 20 (2003) 329-347.
24.Lavergne F. M., Cot D., Ganachaud F., “Polymer Microcapsules with Foamed Membranes”, Lagmuir 23 (2007) 6744-6753.
25.Morello III A. P., Burrill R., Mathiowtz E., “Preparation and characterization of poly(methyl methacrylate)-iron III oxide microcapsules using a modified solvent evaporation method”, Journal of Microencapsulation 24 (2007) 476-491.
26.Nordstierna L., Abdalla A. A., Nordin M., Nyden M., “Comparison of release behavior from microcapsules and microspheres”, Progress in Organic Coatings 69 (2010) 49-51.
27.賴茂柏，“界面聚合法包覆石蠟製備微膠囊複合材料”，先進技術研究通報 (2010) 58-62.
28.Gao F., Su Z. G., Wang P., Ma G. H., “Double Emulsion Templated Microcapsules with Single Hollow Cavities and Thickness-Controllable Shells”, Lagmuir 25 (2009) 3832-3838.
29.Sanchez-Silva L., Tsavalas J., Sundberg D., Sanchez P., Rodriguez J. F., “Synthesis and Characterization of Paraffin Wax Microcapsules with Acrylic-Based Polymer Shells”, Industrial & Engineering Chemistry Research 49 (2010) 12204-12211.
30.Sari A., Alkan C., Karaipekli A., Uzun O., “Microencapsulated n-octacosane as phase change material for thermal energy storage”, Solar Energy 83 (2009) 1757-1763.
31.Alkan C., Sari A., Karaipekli A., Uzun O., “Preparation, characterization, and thermal properties of microencapsulated phase change material for thermal energy storage”, Solar Energy Materials & Solar Cells 93 (2009) 143-147.
32.Tan T., Wang S., Li X., Wang C., An Y., “Facile preparation and characterization of hollow poly(St-co-MMA-co-BA-co-MMA) core-double shell latex nanoparicles for electrophoretic displays”, Current Applied Physics 9 (2009) 989-992.
33.Sari A., Alkan C., Karaipekli A., “Preparation, characterization, and thermal properties of PMMA/n-heptadecane microcapsules as novel solid-liquid microPCM for thermal energy storage”, Applied Energy 87 (2010) 1529-1534.
34.An P., Ba X., Lu S., “Preparation and characterization of crosslinked poly(methyl methacrylate) heat sensitive color-developing nanocapsules”, Polymer Bulletin 64 (2010) 375-386.
35.Ma S., Song G., Li W., Fan P., Tang G., “UV irradiation-initiated MMA polymerization to prepare microcapsules containing phase change paraffin”, Solar Energy Materials & Solar Cells 94 (2010) 1643-1647.
36.Alkan C., Sari A., Karaipekli A., “Preparation, thermal properties and thermal reliability of microencapsulated n-eicosane as novel phase change for material energy storage”, Energy Conversion and Management 52 (2011) 687-692.
37.Alay S., Alkan C., Gode F., “Synthesis and characterization of poly (methyl methacrylate)/n-hexadecane microcapsules using different cross-linker and their application to some fabrics”, Thermochimica Acta 518 (2011) 1-8.
38.李曉，“MMA基混凝土修補材料的製備與性能”，南京工業大學學報 (2004) 58-62.