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研究生： 郭乃慈
Kuo, Nai-Tzu
論文名稱： 生物可分解聚乳酸與其他聚酯高分子作用下之相 行為、結晶型態及動力分析
Crystalline Morphology, Phase Behavior and Kinetic Analysis in Biodegradable Poly(L-lactic acid) Interacting with Other Polyesters
指導教授： 吳逸謨
Woo, Eamor M.
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： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 89
中文關鍵詞： 聚乳酸 、聚酯高分子 、混摻
外文關鍵詞： PLLA, polyester, blend
相關次數： 點閱：82  下載：2 
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    • 本研究利用微分掃描熱卡計(differential scanning calorimeter, DSC)、偏光顯微鏡(polarized optical light microscope, POM)來探討生物可分解高分子: 低分子量聚乳酸poly(L-lactic acid) (PLLA)各別與其他聚酯高分子: 聚己二酸二乙酯poly(ethylene adipate) (PEA), 聚己二酸二丙酯poly(trimethylene adipate) (PTA)和聚丁二酸二乙酯poly(ethylene succinate) (PESu)之兩成份摻合系統，觀察不同摻合系統之相行為、球晶型態、作用力及結晶動力。
    LMw-PLLA/PEA和LMw-PLLA/PTA兩摻合系統皆為相容系統，由平衡熔點下降來估算其作用力參數分別為-0.65及-0.57。LMw-PLLA與PESu形成的摻合系統，在溫度220~245℃存有非對稱上臨界溶液溫度(upper critical solution temperature, UCST)。此外，PLLA分子量的高低亦會影響PLLA與其他聚酯高分子摻合系統之相行為，相較於LMw-PLLA/PTA和LMw-PLLA/PEA的相容系統，高分子量聚乳酸(HMw-PLLA)與PTA的摻合系統，在溫度195~240 ℃存有非對稱上臨界溶液溫度，然而HMw-PLLA與PEA混摻後，為不相容系統。LMw-PLLA在結晶溫度為122~128 ℃呈現環狀消光環之球晶型態，在與LMw-PLLA/PEA(或PTA)混摻後，隨PEA、PTA含量增加，環狀消光環 (ring-banded spherulite)出現的溫度範圍往低溫位移且變得更加寬廣。深入探討LMw-PLLA與PEA或PTA混摻後的regime轉變行為，neat LMw-PLLA隨溫度增加(Tc=110~138 ℃)，從regime III轉變到regime II，與LMw-PLLA/PEA(或PTA)混摻後，隨著溫度增加(Tc=110~128 ℃)由regime II轉變到regime I，顯示不定形高分子加入讓regime行為改變往高溫機制位移。

    Miscibility, crystalline morphology and kinetic analysis in blends of low-molecular-weight poly(L-lactic acid) (LMw-PLLA)/poly(ethylene adipate) (PEA), LMw-PLLA/poly(trimethylene adipate) (PTA) and LMw-PLLA/poly(ethylene succinate) (PESu) were explored using differential scanning calorimeter (DSC) and polarized optical-light microscopy (POM).
    The blends of LMw-PLLA/PEA and LMw-PLLA/PTA are miscible in melt and amorphous glassy states with interaction parameters = -0.65 and -0.57, respectively. The LMw-PLLA/PESu blend is immiscible with an asymmetry-shaped upper critical solution temperature (UCST) at 220~245 ℃ depending on blend composition. In addition, molecular weight of PLLA shows influence on phase behavior of PLLA in blends with polyesters. In contrast to miscible LMw-PLLA/PTA and LMw-PLLA/PEA blends, high-molecular-weight poly(L-lactic acid) (HMw-PLLA)/PTA blend is immiscible with an asymmetry-shaped UCST at 195~240 ℃ depending on blend composition. LMw-PLLA exhibits ring-banded spherulites at Tc=122~128 ℃ and upon blending with PEA or PTA, the temperature range of the ring-banded spherulites in LMw-PLLA shifts to lower temperature and becomes wider. According to the secondary nucleation theory, LMw-PLLA shows regime transition behavior from regime III to regime II with increasing Tc from 110 ℃ to 138 ℃. However, in LMw-PLLA/PTA and LMw-PLLA/PEA blends, the regime transition changes from regime II to regime I with increasing Tc from 110 ℃ to 128 ℃.

    中文摘要 I 英文摘要 II 總目錄 III 表目錄 V 圖目錄 VI 第一章 簡介 1 第二章 原理 5 2.1高分子相容性 5 2.2玻璃相轉移行為 7 2.3摻合系統之相分離 10 2.4平衡熔點下降 13 2.5球晶成長理論 14 2.6結晶動力理論 16 第三章 實驗 20 3.1試藥 20 3.2試樣之製備 22 3.3儀器 22 第四章 結果與討論 23 4-1 LMw-PLLA/PEA兩成分混摻系統 23 4-1-1相型態之分析 23 4-1-2熱分析及冷結晶放熱和結晶熔融峰分析 23 4-1-3分子間作用力分析(平衡熔點分析) 23 4-1-4球晶型態觀察 24 4-1-5球晶成長速率分析及regime行為與球晶型態之關聯 25 4-1-6恆溫結晶動力分析 27 4-2 LMw-PLLA/PTA兩成分混摻系統 46 4-2-1相型態之分析 46 4-2-2熱分析及冷結晶放熱和結晶熔融峰分析 46 4-2-3分子間作用力分析(平衡熔點分析) 46 4-2-4球晶型態觀察 47 4-2-5球晶成長速率分析及regime行為與球晶型態之關聯 48 4-2-6恆溫結晶動力分析 48 4-3 LMw-PLLA/PESu兩成分混摻系統 64 4-3-1相型態之分析 64 4-3-2 UCST相轉移行為及再現性 64 4-3-3熱行為之分析及冷結晶放熱和結晶熔融峰分析 65 4-3-4球晶型態觀察 66 4-4 HMw-PLLA/PTA & HMw-PLLA/PEA兩成分混摻系統 75 4-4-1相型態之分析 75 4-4-2 UCST相轉移行為及再現性 75 4-4-3熱行為分析及分子間作用力分析 75 4-5 PLLA與polyester (PESu、PEA、PTA)兩成分摻合系統之相行為總結 76 第五章 結論 83 參考文獻 84

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