臺灣博碩士論文加值系統

相較於傳統的化學性聚合如自由基聚合、縮合聚合反應，近年來物理性聚合亦備受重視。本研究是設計一個簡單的合成路徑將聚丙二醇兩端導入多點式氫鍵的官能基，在多點式互補氫鍵的驅使下產生自組裝形成高分子的鏈段，並進行性質測定。同時，我們亦合成對照組，即導入不同超分子官能基，以便探討此超分子官能基對各項物理性質的影響。
本文藉由1H-NMR、FT-IR鑑定其結構，證實(cy)2PPO、(ur-cy)2PPO及(cy-amide)2PPO成功被合成出來。並搭配DOSY核磁共振光譜分析，在濃度為0.3g/ml時，(ur-cy)2PPO重覆單元約為2500，說明此多點式互補氫鍵可自組裝成高分子的鏈段，並進行一系列物理性質的鑑定。經由旋光度的測定發現(ur-cy)2PPO具有光學活性，證明了類螺旋結構。在應用端，由於1:32混摻鋰鹽比例可以成膜，故此超分子作用力改善材料的機械性質。

Compared to traditional chemical polymerization, such as radical polymerization, condensation polymerization, physical aggregation in recent years has also been taken seriously.
This study is to design a simple synthetic pathway to import multi-point hydrogen bond functional groups at both ends of the polypropylene glycol, and self-assembly was driven to form the polymer chain segment by multiple complementary hydrogen bonding.
We determine the product's physical properties. At the same time,
we also synthesized the control group, that is to import different supramolecular functional groups, in order to explore the impact of different supramolecular functional groups on the various physical properties .By 1H-NMR, the FT-IR, structures were identified and confirmed (cy) 2PPO, (ur-cy) 2PPO and (cy-amide) 2PPO have been successfully synthesized. With DOSY NMR spectroscopy, in the concentration 0.3g/ml, (ur-cy) 2PPO repeat unit is about 2500,
indicate that this multiple complementary hydrogen bonding
indeed drive self-assembled into the polymer chain segments.
Through optical rotation measurements ,we found (ur-cy)2PPO optically active, the evidence of a class of spiral structure.
On the application side, due to the low molecular weight PPO monomer(with ratio polymer/lithium salt=32:1) can film ,therefore supramolecular interactions successfully improve the mechanical properties of the material.

目錄
中文摘要 I
英文摘要 II
誌謝 III
目錄 IV
圖目錄ⅸ VII
表目錄 X
第一章 緒論 1
1-1 前言 1
1-2 鋰電池的發展 2
第二章 原理介紹與文獻回顧 4
2-1 超分子化學 4
2-1.1 超分子中非共價鍵作用力 6
2-1.2氫鍵的基本性質 8
2-2 分子識別 12
2-3 分子自組裝簡介 15
2-4 cytosine module 17
第三章 實驗內容 22
3-1 實驗藥品 22
3-2 儀器設備 24
3-3 樣品製備 25
3-3.1 (amide-cy)2PPO 單體合成 25
3-3.2 (amine-cy)2PPO單體合成 26
3-3.3 (ur-cy)2PPO 單體合成 27
3-3.4 高分子電解薄膜製備 29
3-3.5 拉伸測試薄膜製備 30
3-4 儀器原理 31
3-4.1 核磁共振光譜 31
3-4.2 微差掃描卡計 31
3-4.3 傅立葉轉換紅外光光譜儀 32
3-4.4 穿透式電子 顯微鏡 32
3-4.5 高解析度場發射掃描式電子顯微鏡 33
3-4.6 圓二色光譜 34
3-4.7 廣角X光繞射儀 36
3-4.8 光學顯微鏡 37
3-4.9 擴散度核磁共振光譜儀 39
第四章 結果與討論 40
4-1 結構鑑定 40
4-1.1 (cy-amine)2PPO結構鑑定 40
4-1.2(ur-cy)2PPO結構鑑定 42
4-1.3.amide-cy)2PPO結構鑑定 44
4-2 物理性質分析與比較 46
4-2.1DOSY核磁共振光譜分析 46
4-2.2溶劑中變濃度下黏度的測定與分析 47
4-2.3自組裝型態觀察(TEM) 49
4-2.4變濃度下核磁共振光譜分析 52
4-2.5變溫度下核磁共振光譜分析 54
4-2.6變溫FT-IR分析 56
4-2.7 熱性質分析(DSC) 59
4-2.8 WAXS分析 62
4-2.9旋光度測量(CD) 67
4-2.10材料型態觀察(SEM) 69
4-3螺旋結構之探討 70
4-3.1混摻鋰鹽之相轉移 70
4-3.2導電度測量與分析 77
4-3.3混摻鋰鹽之WAXS測定 80
第五章 結論 83
參考文獻 85

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