臺灣博碩士論文加值系統

合成主鏈型熱致液晶高分子(LCP)，並且用FTIR鑑定其結構。利用DSC及POM分析LCP的液晶相範圍及液晶相態。由DSC顯示LCP的液晶相範圍為加溫過程在202℃~246℃，降溫過程在232℃~191℃之間。用POM在液晶相範圍內觀察液晶相態，為層列型的液晶相態。將合成得到的LCP以不同比例和聚丙烯(PP)混摻，得到PP/LCP混摻物。利用TGA及Hot-disk分析PP/LCP 混摻物的物性。由TGA結果顯示，隨著LCP含量的增加，PP/LCP 混摻物的5%熱重損失溫度及600℃下焦炭殘餘率都有增加的趨勢。Hot-disk結果顯示，PP的熱傳導係數隨LCP添加量增加而增加，從0.22(W/mK)上升至0.82(W/mK)。利用modified Avrami equation探討PP/LCP混摻物的非等溫結晶動力學。以SEM及POM觀察PP/LCP混摻物的相形態。POM顯示LCP的添加有助於PP晶體的成長，並有不同尺寸的PP晶體產生。

The manin chain thermotropic liquid crystalline polymer (LCP) was synthesized and its chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR). The liquid crystal mesophase range and liquid crystal phase were characterized by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The DSC result showed that the liquid crystal mesophase range of LCP is at 202℃~246℃ on heating process and at 232℃~191℃ on cooling process. The Smectic phase was observed during liquid crystal mesophase range by POM. Blends of LCP with different ratios polypropylene (PP) to obtain PP/LCP blends. The physical properties of PP, LCP and PP/LCP blends were characterized by thermal gravimetric analysis (TGA) and Hot-disk. The TGA result showed that temperature of 5% weight loss and chair yield at 600℃ tended to increase with increasing LCP content. The Hot-disk result showed that PP thermal conductivity increasing with increasing LCP content from 0.22 (W/mK) to 0.82 (W/mK). The nonisothermal crystallization kinetics behavior of PP/LCP blends were studies by modified Avrami equation. The morphology of PP/LCP blends were characterized by field emission scanning electrical microscope (SEM) and POM. Under POM, we found that added LCP contribute to the PP crystal formation and let PP crystal have different size.

摘要 I
Abstract II
致謝 III
總目錄 IV
Scheme VII
表目錄 VIII
圖目錄 IX
第一章 緒論 1
1-1前言 1
1-2 導熱高分子複合材發展及現況 2
1-3研究目的 5
第二章 文獻回顧 6
2-1液晶簡介 6
2-1-1 液晶由來 8
2-1-2液晶分類 10
2-1-3 液晶分子的構造 18
2-1-4液晶高分子 19
2-2-1 液晶高分子複合材 34
2-2-2 導熱高分子複合材 38
第三章 實驗 40
3-1 實驗流程圖 40
3-2 材料與樣品 41
3-3 實驗裝置圖 42
3-4 儀器設備 44
3-5 實驗步驟 45
3-5-1 LCP的合成 45
3-5-2 LCP/PP混摻物的製備 46
3-5-3 PP/LCP混摻物試片製備 47
3-6結構鑑定與物性測試 47
第四章 結果與討論 50
4-1 LCP合成鑑定 50
4-2 液晶型態探討 52
4-2-1 DSC分析液晶相範圍： 52
4-2-2 POM觀察液晶相態： 54
4-3 LCP/PP混摻物之物性探討 57
4-3-1 TGA分析熱穩定性： 57
4-3-2 Hot-Disk分析熱傳導係數： 59
4-4結晶行為探討 62
4-4-1 XRD分析晶形態： 62
4-4-2 DSC分析結晶行為： 68
4-4-3非等溫結晶動力學： 72
4-5 PP/LCP混摻相形態探討 77
4-5-1 SEM觀察相形態： 77
4-5-2 POM觀察結晶行為： 79
第五章 結論 82
參考文獻 84
自傳簡歷 88

【1】薛敬和，2007，“高分子化學實驗法”，高立圖書有限公司。
【2】馬振基，1995，“高分子複合材料”，中正書局。
【3】郭玉國、張葉利、趙文元，2000，“液晶高分子材料的研究現狀及開發前景”，青島大學學報，卷15，頁42。
【4】李侃社、王琪，2002，“導熱高分子材料研究進展”，功能材料，卷33，頁631。
【5】林振隆，2010，“高導熱材料於電子元件封裝技術之應用”，工業材料雜誌，卷283，頁65。
【6】馬傳國、容敏智、章明秋，2002，“導熱高分子複合材料的研究與應用”，材料工程，卷7，頁40。
【7】廖春雄，2013，“高導熱塑膠之發展及應用”，工業材料，卷316，頁60。
【8】P. G. De Gennes, and J. Prost, 1993, “The Physics of Liquid Crystals-Second Edition”, International Series of Monographs on Physics, vol. 83 pp. 83-94.
【9】S. Malkondu, and A. Kocak, 2013, “Novel liquid crystal trimers with a wide mesophase range”, Journal of Molecular Liquids, vol. 188, pp. 167-171.
【10】T. J. Sluckin, D. A. Dunmur, H. Stegemeyer, 2004, “Crystals That Flow: Classic Papers from the History of Liquid Crystals”, Taylor & Francis Inc.
【11】F. Reinitzer, 1989, “Contributions to the knowledge of cholesterol”, Liquid Crystals, vol. 5, pp.7-14.
【12】G. Friedel, 1912, “Leçons de Cristallographie”, Bull. Amer. Math. Soc, vol. 18, pp. 364-375.
【13】松本正一、角田市良合著，劉瑞祥譯，1996“液晶之基礎與應用”國立編譯館出版。
【14】P. J. Colling, M. Hird著，楊怡寬、郭蘭生、鄭殷立編譯，2001，“液晶化學及物理入門(Introduction to Liquid Crystals Chemistry and Physicals)”，偉明圖書有限公司。
【15】B.Bahadur, 1990, “Liquid Crystal, Applications and Uses”, World Scientific, vol. 1, pp. 1-521.
【16】X. J. Wang, and Q. F. Zhou, 2004, “Liquid Crystalline Polymers”, World Scientific, Singapore.
【17】D. Demus, J. Goodby, G. W. Gray, and H. W. Spiess, V. Vill, 1998, ”Handbook of Liquid crystals”, Wiley-VCH,Vol. 2a, 2b.
【18】Q.Y. Li, J. S. Hu, B. L. Zang, and B. Y. Zhang, 2004, “Textuees of Side-Chain Cholesteric Liquid Crystalline Elastomers”, International Symposium on Polymer Chemistry.
【19】肖桂真，2011，“液晶高分子材料的現狀及研究進展”，紡織學院。
【20】H. Finkelmann, and G. Rehage, 1984, “Liquid crystal side chain polymers”,Adv. Polym. Sci., vol.60/61, pp. 99-121.
【21】V. P. Shibaev, and N. A. Plate, 1984, “Thermotropic liquid-crystalline polymers with mesogenic side groups”, Adv. Polym. Sci., vol. 60, pp. 173-184.
【22】桓內宏，1999，“環氧樹脂應用實務”，復漢出版社。
【23】M. M. Sonpatki, K. Ravindranatht, and S. Ponrathnam, 1995, “Random thermotropic elastomers: effect of hard/soft-segment lengths on the properties of liquid-crystalline copoly(ether ester)s”, Polymer, vol. 36, pp. 3127-3141.
【24】A. Jannesari1, et. al., 2004, “Synthesis of Main Chain Liquid Crystalline Polyesters Based on Mesogenic Monomers with Controlled Transition Temperatures”, Iranian Polymer Journal, vol. 13, pp. 121-139.
【25】P. Kannan, and S. Senthil, “Novel Thermotropic Liquid Crystalline Polyphosphonates”, 2004, Polymer, vol. 45, pp. 3609-3621.
【26】P. Kannan, P. Sudhakara, and A. Ravikrishnan, “Liquid Crystalline and Photoactive poly[4,4’-stilbeneoxy]alkylbiphenylphosphates”, 2004, Polymer, vol. 45, pp. 3609-3633.
【27】M. Bagheri, and Reza Zahedi Rad, 2008, “Synthesis and Characterization of Thermotropic Liquid Crystalline Ppolyesters with Biphenyl Unit in the Main Chain”, Reactive & Functional Polymers, vol. 68, pp. 613-626.
【28】M. Talukdar, and P. G. Raju Achary, 2010, “Synthesis and Characterization of Some Controlled Structure Thermotropic Liquid Crystalline Polyesters”, IJRRAS, vol. 3, pp. 2-14.
【29】林唯芳，1989，“有機無機攙合材料”，塑膠資訊，卷60，頁4。
【30】郭玉國，張亞利，趙文元，2000，“液晶高分子材料的研究現狀及開發前景”，青島大學學報，卷15，頁12。
【31】馬會茹，段華軍，唐紅，2008，“液晶高分子複合材料的新進展”，複合材料，卷10。
【32】梁伯德，顏德嶽，2006，“高分子液晶材料”，自然雜誌，卷12，頁25。
【33】N.G. Sahooa, C.K. Das, K.N. Pandey, and G.N. Mathur, 2002, “Structural Characterization of PBT–LCP Blends”, Materials Letters, vol. 56, pp. 194-200.
【34】N. G. Sahoo and C. K. Das, 2003, “Structure -Properties Relations of Polypropylene/Liquid Crystalline Polymer Blends”, Macromolecular Research, vol. 11, pp. 224-233.
【35】H. Shimizu, T. Kitano, and K. Nakayama, 2004, “Morphological Control of LCP/PET Blends Using a Melt Mixer Equipped with a Milling part”, Materials Letters, vol. 58, pp. 1277-1290.
【36】N. G. Sahoo, S. Gupta, C. K. Das, P. K. Patra, A. R. Tripathy, and W. Millns, 2007, “Studieson PET/Glass Filled LCP Blends”, POLYMER–PLASTICS TECHNOLOGY AND ENGINEERING, vol. 42, pp. 417-437.
【37】王文進、李鴻岩、姜其斌，2008，“高導熱絕緣複合材料的研究進展”，絕緣材料，卷41，頁30。
【38】肖善雄、張藝、孫世彧、劉四委、池振國、許家瑞，2010，“導熱高分子複合材料的研究進展”，材料科學，卷37。
【39】S. Yu, P. Hing, and X. Hu, 2002, “Thermal conductivity of polystyrene–aluminum nitride composite”, Composites Part A, vol. 33, pp. 289-293.
【40】L.C. Sima, S.R. Ramanana, H. Ismaila, K.N. Seetharamub, and T.J. Gohc, 2005, “Thermal Characterization of Al2O3 and ZnO Reinforced Silicone Rubber as Thermal Pads for Heat Dissipation Purposes”, Thermochimica Acta, vol. 430, pp. 155-172.
【41】Y. Liu, Y. F. Wang, T. G. Gerasimov, K. H. Heffner, and P. Harmon1, 2005, “Thermal Analysis of Novel Underfill Materials with Optimum Processing Characteristics”, Applied Polymer Science, vol. 98, pp. 1300-1311.
【42】W. Wanga, X. Yang, Y. Fang, J. Ding, and J. Yan, 2009, “Enhanced thermal conductivity and thermal performance of form-stable composite phase change materials by using β-Aluminum nitride”, Applied Energy, vol. 86, pp. 1196-1204.
【43】A. Turner Jones, Jean M. Aizlewood, and D. R. Beckett, “Die Makromolekulare Chemie”, vol. 75 pp1211-1231.
【44】H. M. Wang, Y. C. Zhang, L. R. Zhu, B. L. Zhang, Y. Y. Zhang, 2011, “Curing behavior and kinetics of epoxy resins cured with liquid crystalline curing agent”, Therm Anal Calorim, vol. 10, pp. 1163-1182.
【45】M. Avrami, 1939, “Kinetics of Phase Change. I. General Theory”, Journal of Chemical Physics, vol. 7, pp. 1103-1121.
【46】A. Jeziorny, 1978,“Parameters characterizing the Kinetics of thenon-isothermal Crystallization of Pol(ethyleneterephthalate)　determined by DSC”, Polymer, vol. 19, pp. 1124-1136.
【47】MC. Tobin, 1974, “Theory of phase transition of high-molecularweightamylase by dispersion of starch granules with urea”,Polymer Phys, vol. 12, pp. 399-412.
【48】P. Cebe, and S. D. Hong, 1986 “Crystallization Behaviour of Poly(ether-ether-ketone)”, Polymer, vol. 27, pp. 1183-1192.
【49】I. H. HILLIER, 1965, “Modified Avrami Equation for the Bulk Crystallization Kinetics of Spherulitic Polymers”, JOURNAL OF POLYMER SCIENCE, vol. 3, pp. 3067-3071.
【50】Y. Lee, RS. Porter, 1987, “Double-Melting Behavior of Poly(ether ether ketone”, Macromoleules, vol. 20, pp. 1336-1342.