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研究生： 郭姵君
Kuo, Pei-Chun
論文名稱： 聚草酸二丁酯與聚草酸二丁酯/聚乳酸摻合物結晶行為之探討
The study of crystallization behavior of PBOX and PBOX/PLLA blends.
指導教授： 羅介聰
Lo, Chieh-Tsung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 99
中文關鍵詞： PBOX 、PLLA 、混摻 、等溫結晶 、非等溫結晶
外文關鍵詞： PBOX, PLLA, blends, isothermal crystallization, nonisothermal crystallization
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    • 本研究第一部份，主要探討生物可分解性高分子聚草酸二丁酯(poly(butylenes oxalate)) (PBOX)的等溫和非等溫結晶行為。等溫結晶下， PBOX的晶層厚度(lc)，隨時間和溫度增加，其PBOX的結晶結構為Triclinic系統。以偏光顯微鏡觀察PBOX結晶的成長速率和形態，可知PBOX為球晶，且成長速率隨溫度增加而下降。根據Gibbs-Thomson理論，利用DSC分析得到PBOX的平衡熔點(Tmo)為 117.4 oC，再將其結果代入Lauritzen-Hoffman理論可得到成核參數Kg = 97264 K2、側表面自由能 =17.68 erg/cm2。在非等溫結晶下，以Avrami方程式分析結晶行為，其Avrami指數n約為3，為三維球面生長機制。
    第二部份，探討聚乳酸/聚草酸二丁酯(PLLA/PBOX)摻合物的等溫結晶行為。在本研究的等溫結晶條件下，PBOX為無定形高分子，PLLA則可結晶。在相同結晶溫度下，長週期(L)和lc 均隨PBOX的組成增加而下降。在偏光顯微鏡下觀察PLLA/PBOX的結晶形態和成長速率，得到不同混摻比例下的PLLA/PBOX結晶形態均為環帶球晶，且隨著溫度增加，環帶球晶變得較不明顯、不規則；在低溫下，隨PBOX組成增加，環帶球晶顯得清晰。經混摻的PLLA結晶速率則隨PBOX的組成增加，這是因為PBOX的Tg較低，使得流動性較好，利於球晶生長和排列。根據Lauritzen-Hoffman理論分析PLLA/PBOX結晶機制，成核參數(Kg)約為9×105 K2。而PLLA/PBOX的熱穩定性，則隨PBOX的組成增加，使得熱穩定性降低。

    In the first section, we investigated the isothermal and nonisothermal crystallization of the biodegradable polymer, poly(butylenes oxalate) (PBOX). During isothermal crystallization, the lamellar thickness (lc) of PBOX increased with an increase in both time and temperature. PBOX crystal structure follows Triclinic system. The crystal growth rate and morphology of PBOX was analyzed by polarized optical microscopy. It was observed that PBOX crystal morphology is spherulite and the spherulite growth rate decreased with increasing temperature. Based on Gibbs-Thomson theory, the equilibrium melting temperature of PBOX is 117.4 oC. The values was used to calculate the crystal parameters. By Lauritzen-Hoffman theory, the nucleation parameter, Kg, is 97264 K2 and the lateral surface free energy, σ, is 17.68 erg/cm2. During nonisothermal crystallization, the Avrami exponent analyzed by the modified Avrami equation is 3.0, indicating that the PBOX crystallization follows three dimensional spherulite growth mechanism.
    In the second section, isothermal crystallization of PLLA/PBOX blends was studied. In the temperature of our interest, PBOX is amorphous and PLLA is crystalline. The change in the long period (L) and lc with time and temperature obtained by small angle X-ray scattering showed that both L and lc decreased with an increase in the PBOX composition. Additionally, PLLA/PBOX exhibited banded spherulite, and the banded spherulite became irregular at high temperatures. At low temperatures, banded spherulites dominated with an increase in the content of PBOX. Meanwhile, the crystallization rate of PLLA increased with PBOX composition. This was attributed to the low Tg of PBOX that enhanced the mobility of polymer chains, facilitating the chain arrangement and spherulite growth. By using the Lauritzen-Hoffman theory, the nucleation parameter (Kg) is approximately 9×105 K2. Finally, the thermal stability of PLLA/PBOX reduces upon the addition of PBOX.

    摘要 I Abstract II 誌謝 III 總目錄 IV 表目錄 VII 圖目錄 VIII 第一章 緒論 1 1.1前言 1 1.2生物可降解高分子(Biodegradable polymer) 1 1.3聚草酸二丁酯(Polybutylene oxalate，PBOX) 4 1.4聚乳酸(Polylactide，PLA) 5 1.4.1聚乳酸簡介 5 1.4.2聚乳酸的結晶 7 1.5研究動機 9 第二章 文獻回顧 10 2.1高分子結晶型態 10 2.1.1球晶(Spherulite) 10 2.1.2環帶球晶 12 2.2影響高分子結晶條件 13 2.3高分子之結晶動力學(Crystallization kinetics) 15 2.3.1等溫結晶動力學(Isothermal crystallization kinetics) 15 2.3.2平衡熔點(Equilibrium melting temperature) 17 2.3.3 Lauritzen-Hoffman成核理論 19 2.4 非等溫結晶動力學(Nonisothermal crystallization kinetics) 22 2.5 結晶度(Crystallinity) 24 2.6 聚合物混摻(Polymer blends) 25 第三章 實驗 26 3.1 實驗材料 26 3.2 實驗儀器設備 26 3.3 PBOX結晶分析架構 27 3.4 PBOX/PLLA結晶分析架構 27 3.5 實驗方法 28 3.5.1基本性質檢測分析 28 3.5.2 PBOX等溫結晶與熔融行為 28 3.5.3 PBOX非等溫結晶行為 29 3.5.4 PBOX/PLLA混摻 29 3.6 分析儀器原理 31 3.6.1偏光顯微鏡 31 3.6.2微差掃描熱量分析儀(differential sanning calorimetry，DSC) 32 3.6.3熱重分析儀(thermogravimetry analyzer，TGA) 33 3.6.4 X光繞射儀(X-ray Diffractometer，XRD) 34 3.6.5小角度X光散射(small angle X-ray sacttering，SAXS) 35 第四章 結果與討論 38 4.1 PBOX結晶行為 38 4.1.1 PBOX等溫結晶 38 4.1.1.1 PBOX的結晶形態-SAXS分析 38 4.1.1.2 PBOX的結晶形態-XRD 分析 44 4.1.1.3 PBOX球晶成長速率 45 4.1.1.4 PBOX之平衡熔點(Tmo) 49 4.1.1.5 PBOX等溫結晶下的Lauritzen-Hoffman參數 52 4.1.2 PBOX非等溫結晶行為 54 4.1.2.1 Modified Avrami Equation 55 4.1.2.2 Ozawa equation 57 4.2 PLLA/PBOX blends 59 4.2.1 PLLA/PBOX blends 於等溫結晶下SAXS分析 59 4.2.2 PLLA/PBOX blends 於等溫結晶下球晶形態 74 4.2.3 PLLA/PBOX blends於等溫結晶下球晶成長速率 80 4.2.4 PLLA/PBOX於等溫結晶下的Lauritzen-Hoffman參數 84 4.2.5 PLLA/PBOX blends 等溫結晶熔融行為 87 4.2.6 PLLA/PBOX blends 熱分析 92 4.2.7 PLLA/PBOX之綜合討論 95 第五章 結論 96 參考文獻 97

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