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研究生:黃美雯
研究生(外文):Mei-Wen Huang
論文名稱:氫鍵作用力對高分子摻合系統相容性的影響
論文名稱(外文):Hydrogen Bonding and Miscibility Study on Polymer Blends
指導教授:張豐志
指導教授(外文):Feng-Chih Chang
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:79
中文關鍵詞:氫鍵酚醛樹脂高分子摻合
外文關鍵詞:Hydrogen bondingPhenolic resinPolymer blend
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本論文探討酚醛樹脂(Phenolic)與聚乙酸乙烯酯(PVAc(poly vinyl acetate))混摻後的氫鍵作用力及相容性。在酚醛樹脂/聚乙酸乙烯酯摻合系統中,酚醛樹脂上的羥基與聚乙酸乙酯上的羰基會產生氫鍵而利於相容。微分掃描熱卡計(DSC)的結果顯示,酚醛樹脂/聚乙酸乙烯酯摻合的所有組成均只有一個玻璃轉移溫度(Tg),顯示此摻合系統為相容。此外,分別以紅外線光譜儀(FT-IR)及固態核磁共振儀(NMR)定量及定性的探討羥基與羰基之間的氫鍵作用力,結果為一致,均顯示隨著酚醛樹脂的加入,羥基與羰基之間產生的氫鍵明顯增加,表示酚醛樹脂上的羥基與聚乙酸乙酯上的羰基可產生強的分子間氫鍵作用力(inter-association)。此外,由質子自旋晶格遲緩時間(T1ρH)的實驗結果中,顯示Phenolic/PVAc摻合系統在2-3nm 以下為相容。更進一步藉由Painter-Coleman association model,可計算出分子間結合作用力平衡常數(inter-association equilibrium constant)及相對焓。

The miscibility and hydrogen bonding of phenolic resin/poly(vinyl acetate) (PVAc) blends were studied. The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state 13C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (Tg) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both 13C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T1ρH), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.

中文摘要……………………………………………………………..…Ⅰ
英文摘要………………………………………………………..……....Ⅱ
誌謝…………………………………………………………………..…Ⅲ
目錄……………………………………………………………………..Ⅴ
圖目錄…………………………………………………………….….…Ⅷ
表目錄…………………………………………………………….…….Ⅹ
研究目的……………………………………………………………….Ⅸ
第一章 緒論
1-1 前言………………………………………………………....…..1
1-2 文獻回顧……………………………………………….….……4
1-3 理論部份─高分子聚摻合物的熱力學性質……………….…12
1-3-1 Huggins-Flory Theory…………………………………….…..12
1-3-2 分子間的交互作用力…………………………………….….14
1-3-3 高分子中的氫鍵………………………………………….….15
1-4 固態核磁共振應用在高分子聚摻合物相容性的原理….……18
1-4-1 交錯極化………………………………………………….….19
1-4-2 魔角旋轉………………………………………………….….22
1-4-3 核磁共振遲緩行為……………………………………….….24
1-4-3-1 Rotation frame中自旋鎖定遲緩時間………………….…..25
1-5酚醛樹脂的自身結合氫鍵參數…………………………….…..26
第二章 實驗
2-1 藥品………………………………………………………….….29
2-2 高分子混摻……………………………………………….…….30
2-3 儀器………………………………………………………….….30
2-4 熱力學性質的運算………………………………………….….32
第三章 結果與討論
3-1 熱分析--微分掃描熱卡計
(Differential scanning Calorimetry, DSC)……………….…...34
3-2 紅外光光譜儀分析
(Fourier Transform Infrared Spectroscopy Analyses)…….….36
3-2-1酚醛樹脂/聚乙酸乙烯酯聚摻合物的紅外線光譜
(hydroxyl region)……………………………………………..36
3-2-2酚醛樹脂/聚乙酸乙烯酯聚摻合物的紅外線光譜
(carbonyl region)及聚摻合物的分子間氫鍵含量…………....37
3-2-3變溫紅外線光譜分析氫鍵含量………………………...…....38
3-3 固態核磁共振光譜儀分析(Solid-State NMR)……………...40
3-3-1 酚醛樹脂/聚乙酸乙烯酯聚摻合物13CCP/MAS核磁共振光譜
…………………………………………………………………40
3-3-2 固態NMR模擬聚摻合物的分子間氫鍵含量………………41
3-3-3 酚醛樹脂/聚乙酸乙烯酯聚摻合物的T1*弛緩時間………...42
3-4 Painter-Coleman Association Model 分析結果………………..44
3-5 模型化合物模擬分子間氫鍵結合平衡常數-KA之測定
(Estimation of the Inter-association Hydrogen Bonding Parameters, KA )…………… ……………………………………………….47
第四章 結論……………………………………………………………50
參考文獻…………………………………………………………………52
作者簡歷…………………………………………………………………79
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