本實驗利用活性自由基聚合和點擊化學合成出PS衍生物(PVB-DAP)與偶氮苯結合具有氫鍵作用力的基團(Azo-T)，並將具有互補氫鍵官能基的小分子、高分子進行混摻，藉由非共價鍵吸引力，探討彼此間多點式氫鍵(Diamidopyridine和Thymine)，達到勻相系統。由傅立葉轉換紅外光光譜儀(FT-IR)、氫核磁共振光譜(1H NMR)、碳核磁共振光譜( 13C NMR)進行結構鑑定，熱重分析儀(TGA) 、微差掃描熱卡計(DSC)等熱性質分析結果觀察材料之混摻均勻性以及形態學之探討；由於偶氮苯分子具有特殊光響應性，於365 nm UV光照射下產生結構上的變化，形成兩種不同的異構物(光異構化)。導入氫鍵後此偶氮分子同時具有光異構及熱敏感的雙重刺激響應能力，也可藉由氫鍵本身的非共價作用力來達到熱可逆性。另外材料本身熱性質及成膜性也可與具另一互補官能基之高分子PVB-DAP來得到強化。由靜態接觸角的實驗結果觀察到光異構化前後對於超分子薄膜表面親疏水性的改變並且由於修飾有多點氫鍵官能基也為材料帶來了表面性質的調控及可逆性；而鑑於以往的研究指出偶氮苯可應用於光學儲存與記憶，故利用光學儀器設計將超分子薄膜作讀取紀錄形成光柵並利用OM、 AFM觀察其表面起伏變化。綜合上述結果利用混摻方式，能製備同時具有光可調控與熱可調控之新穎材料，氫鍵作用力的導入也為分子設計提供新的思考方向，有助於材料各方面性質的提升。

In this study, we prepared PS-derivatives (PVB-DAP) through NMP polymerization and the post-functionalization of H-bonding moieties be proceeded via “click chemistry”. FT-IR, 1H NMR, 13C NMR confirmed the chemical structure of PVB-DAP and Azo-T. The supramolecular complexes through Hetero-complementary hydrogen bonding between Diamidopyridine and Thymine were investigated. We demonstrate thermal stability of small molecules which has hydrogen bonding by DSC and TGA, respectively. Due to the unique photoresponsive of azobenzene materials after exposed UV lamp (365 nm), so the conformation of azobenzene will be changed because the dipole moment of trans and cis is difference. Surface contact angle (CA) of supramolecular films decreased after UV and back to its original state after exposure to visible light. The reversibility was also observed through physical crosslinking network and dipole moment change. Previous studies indicate that azobenzene can be applied to optical storage and memory. We performed OM and AFM to investigate the surface relief gratings through hydrogen-bond supramolecular film. We prepared novel supramolecular materials that possess photo-tunable and thermal conformity through Hetero-Complementary hydrogen bonding.

國立中山大學研究生學位論文審定書 i
誌謝 ii
摘要 iv
Abstract v
目錄 vi
圖目錄 ix
表目錄 xii
第一章 緒論 1
1.1前言 1
1.2超分子化學(Supramolecular Chemistry ) 2
1.2.1分子識別(Molecular recognition) 3
1.2.2氫鍵(Hydrogen bond) 4
1.3偶氮苯介紹與文獻回顧 6
1.4混摻原理 9
1.5目的與研究動機 12
第二章 儀器與藥品 13
2.1溶媒及處理過程 13
2.2藥品 13
2.3實驗儀器 14
第三章 實驗合成 19
3.1 Azo-T合成 19
3.1.1 11-azidoundecanoic acid製備 19
3.1.2 Azo-N3 製備 19
3.1.3利用點擊化學製備Azo-T 19
3.2 PVB-DAP合成 20
3.2.1 PVBC製備 20
3.2.2 PVBN3製備 20
3.2.3 SA-DAP製備 20
3.2.4利用點擊化學製備PVB-DAP 21
3.3混摻的製備 21
第四章 結果與討論 24
4.1 Azo-T合成鑑定 24
4.2 PVB-DAP合成鑑定 25
4.3混摻物之樣品分析 32
4.3.1混摻之氫鍵作用力探討 32
4.3.2微分掃描熱卡計熱分析結果(DSC) 38
4.3.3熱重分析儀之分析結果(TGA) 39
4.3.4小角度X光散射分析(SAXS) 39
4.4光學性質探討 41
4.4.1液態光學性質探討 42
4.4.2固態光學性質探討 45
第五章 光學應用探討-光柵 47
5.1偶氮苯於光學儲存回顧與探討 47
5.2全像干涉紀錄讀取與分析 48
5.3超分子薄膜表面起伏光柵探討 53
第六章 結論 60
第七章 參考文獻 61
圖附錄 64

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