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研究生:林雅婷
研究生(外文):Ya-Ting Lin
論文名稱:幾丁聚醣與聚乙烯氧摻合薄膜物性之研究
論文名稱(外文):An Investigation on Physical Properties of Chitosan/Poly(ethylene oxide) Blends
指導教授:謝永堂謝永堂引用關係
指導教授(外文):Yeong-Tarng Shieh
學位類別:碩士
校院名稱:國立雲林科技大學
系所名稱:工業化學與災害防治研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2006
畢業學年度:94
語文別:中文
論文頁數:119
中文關鍵詞:幾丁聚醣平衡熔點聚乙烯氧
外文關鍵詞:Chitosanpoly(ethylene oxide)polymer-polymer interaction parametersCole-Cole plotsHoffman-Weeks plots
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本研究係利用溶液法製備幾丁聚醣(CS)與聚乙烯氧(PEO)的摻合薄膜,探討CS/PEO 摻合薄膜之分子間交互作用力、結晶行為及機械性質。為了了解CS及PEO之間的分子作用力是否存在,我們利用DSC 及2D FTIR 進行探討,首先藉由DSC量測CS/PEO 摻合薄膜之熔融熱及根據Nishi and Wang 方程式之計算僅得負值的交互作用參數(χ),兩者表示CS 及PEO 之間有分子作用力存在,因而抑制聚乙烯氧之結晶,然後輔以2D FTIR 觀察聚乙烯氧與幾丁聚醣之間的分子間作用力,可發現到聚乙烯氧次甲基上的氫與幾丁聚醣之第六個碳上的氫氧基、amideⅡ上的NH 基及amide Ι 上的C=O 基團產生氫鍵鍵結,且聚乙烯氧的氧與幾丁聚醣的胺基產生氫鍵鍵結。此外由IR 分析聚乙烯氧分子組型時,發現到由於CS 與PEO 之間有氫鍵鍵結作用力存在,而使幾丁聚醣的加入會造成聚乙烯氧在組型上的變化,漸漸由穩定的Helix 結構轉變成平面的Trans 結構。由負值之χ值推斷CS 與PEO 間,非結晶區是相容,但由Cole-Cole Plot 只觀察此CS/PEO 摻合薄膜屬於部份相容的摻合體。除此之外,利用Hoffman-Weeks plot 隨CS 含量增加而降低,由 Gibbs-Thomson equation 調查平衡熔點下降的原因,是由結晶形態的改變及稀釋作用所造成的。透過DMA 分析可得知,隨CS含量增加儲存模數隨之增加,表示聚乙烯氧加入會提高幾丁聚醣的機械強度。由tanδ所觀察到的Tg點,可發現CS/PEO 系統之摻合膜的Tg 皆比純PEO的Tg 來得低,此可能為水的存在形成塑化效應,造成聚乙烯氧的Tg降低;或由於結晶區域將非結晶區域排出的關係,使非結晶區域的分子沒有受到束縛,故降低聚乙烯氧之Tg。
Chitosan (CS) and poly(ethylene oxide) (PEO) blends were prepared by casting from water/acetic acid solutions and were investigated into intermolecular interactions, crystallization behavior, and dynamic mechanical properties using FTIR, 2D FTIR, DSC, and DMA. DSC data found that the polymer-polymer interaction parameters (χ) of the blends were negative as determined using the Nishi-Wang equation. 2D FTIR data revealed that two types of specific interactions (weak hydrogen bonding) were present in the blends, including those between the H of the methylene groups of PEO and the O of the C3-hydroxyl groups or the N of the amide Ⅱ groups of CS, and those between the O of PEO and the H of the amine groups on CS. FTIR data found that the conformation of PEO was transformed from helix to trans by the presence of CS. The negative χ values suggested that CS and PEO were compatible in amorphous region; however, the Cole-Cole plots indicated that CS and PEO were partially compatible. Hoffman-Weeks plots were used to determine the composition variations of the equilibrium melting temperatures of blends and found that decreased with increasing CS content. DMA was used to measure storage modulus and glass transition temperature (Tg) of the blends and found that the storage modulus increased with increasing CS content. The Tg of blends were lower than that of pure PEO due to the plasticization effects of the present water or the segregation of impurity from crystals during crystallization.
目錄 頁次
中文摘要 I
英文摘要 II
誌謝 III
目錄 IV
表目錄 VI
圖目錄 VIII
符號說明 XI
第一章 緒論 1
1.1 前言 1
1.2 文獻回顧 2
1.2.1 PEO/CS�浀X系統文獻回顧: 2
1.2.2 PEO之組型FTIR文獻回顧 4
1.2.3 2D FTIR文獻回顧 9
第二章 理論 12
2.1 �浀X體之相容性 12
2.1.1 聚�浀X之介紹 12
2.1.2 聚�浀X原理 14
2.1. 聚�浀X之親合性 14
2.1.4 研究摻合體相容的方法 16
2.1.5 玻璃轉移點(Tg)法 17
2.2 結晶性高分子摻合體之結晶行為與型態行為 19
2.2.1 Segregation 距離:δ參數 20
2.3 平衡熔點 22
2.3.1 線性Hoffman-Weeks equation 22
2.3.2 Flory-Huggins theory 23
2.3.3 Thompson-Gibbs equation 24
2.4 幾丁聚醣的性質 26
2.4.1 幾丁質/幾丁聚醣的來源與簡介 26
2.4.2 幾丁質/幾丁聚醣的結構 27
2.4.3 幾丁聚醣的製備 29
2.4.5 幾丁聚醣的應用 30
第三章 實驗方法 32
3.1 實驗藥品 32
3.2 實驗設備 33
3.3 實驗方法 34
3.3.1 試樣之製備 34
3.3.2 試樣之鑑定分析 34
第四章 結果與討論 36
4.1 PEO分子組型之研究 36
4.2 CS/PEO之交互作用力對結晶與熔融行為之影響 43
4.3 CS/PEO分子間作用力之研究 73
4.4 DMA分析 87
4.1-1 storage modulus 87
4.1.2 tanδ 88
4.1.3 loss modulus 89
4.5 Cole-Cole Plot分析 94
第五章 結論 97
第六章 參考文獻 98
自述 105
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