臺灣博碩士論文加值系統

本研究利用傳統Suzuki polymerization與Suzuki polymerization in miniemulsion聚合法合成線性(LCF)與超分枝狀共軛聚芴高分子(HCF)，並分別導入苯環與吲哚基團作為末端基分子，探討不同聚合方法與不同構形高分子之熱、光、電化學以及高分子形態學性質，並觀察其能量轉移之機制。
本實驗利用傳統Suzuki polymerization所合成的線性共軛聚芴高分子LCF-B和LCF-I的重量平均分子量分別為4225與1436 g/mol，而PDI值為1.33與1.19。本實驗所合成所有高分子之熱裂解溫度(Td)介於214~373 oC之間，而玻璃轉移溫度(Tg)介於107~144 oC之間；觀察UV-vis圖譜可發現高分子在THF溶液態之最大吸收波長都接近350 nm，而PL放射圖譜可發現末端基為indole之高分子其波長較寬廣；觀察CV能階圖譜可發現高分子之能階非常接近，而藉由密度泛涵理論所計算之值可發現超分枝的能階差(Eg)有稍微高於線性分子；觀察DLS、TEM與SEM圖譜可發現微乳化高分子在溶液態皆呈圓球狀且顆粒很細小(粒徑介於62~168 nm之間)，而在固體狀態有微乳化之高分子呈現較明顯的微胞或孔洞形狀(粒徑介於2.5~26.75 nm之間)。
本研究所合成微乳化聚合技術製備的線性和超分枝狀共軛聚芴高分子，後續將利用氣體吸/脫附實驗分析其孔洞大小與比表面積之範圍以及作為化學感測器的可能性。

This study describes the synthesis of linear (LCF) and hyperbranched conjugated polyfluorenes (HCF) containing various end-capping agents (phenyl and indole groups) in the main chain, through conventional Suzuki and Suzuki coupling polymerization in miniemulsion. The optical, photophysical, and electrochemical properties, and polymeric morphologies of conjugated polymers were characterized using UV-vis, PL, CV, SEM, TEM, and DLS methods. The corresponding intramolecular charge and energy transfers were also investigated. The weight-average molecular weights (Mws) of LCF-B and LCF-I, using conventional Suzuki coupling polymerization, were 4225 and 1436 g/mol, with the corresponding polydispersity indices of 1.33 and 1.19, respectively. These synthesized polymers exhibited the decomposition temperatures (Tds) in the range of 214 and 373 oC. The glass transition temperatures (Tgs) were in the range of 107 and 144 oC. In THF, these polymers showed strong absorption that peaked at approximately 350 nm, resulting from π-π* electronic transitions within the polymer backbone. The fluorescence spectra of indole-based polymers showed broad peaks in the range of 375-500 nm. The estimated HOMO and LUMO energy levels of polymers were similar, as confirmed by CV. The energy bandgaps (Egs) of HCFs were larger than those of LCFs, using density functional theory (DFT) calculations. The spherical particles of polymers, using Suzuki coupling polymerization in miniemulsion, with average diameter in the range of 62.5~168.2 nm and 2.5~ 26.75 nm can be confirmed clearly by SEM, TEM images and dynamic laser scattering (DLS) measurements, respectively. In order to compare the role of structure and dimensionality on the specific surface area and porosity, nitrogen sorption experiments for LCFs and HCFs, using Suzuki coupling polymerization in miniemulsion, will also conducted. The chemosensory applications will also be studied.

摘要 II
Abstract III
致謝 V
目錄 VI
圖目錄 X
流程圖目錄 XV
表目錄 XV
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 1
第二章 原理與文獻回顧 5
2-1 有機共軛高分子 5
2-1-1 共軛高分子的介紹 5
2-1-2 共軛高分子的應用 7
2-1-3 能帶理論 8
2-2 乳化聚合 10
2-2-1 乳化聚合的介紹 10
2-2-2 乳化聚合的原理 10
2-2-3 微乳化聚合的介紹 14
2-3 超分枝高分子 14
2-3-1 超分枝/樹枝狀高分子介紹 14
2-3-2 超分枝/樹枝狀高分子應用 16
2-4 螢光原理 17
2-4-1 螢光能量轉移 19
2-4-2 影響螢光現象之因素 21
2-5 螢光化學感測器 24
2-5-1 螢光化學感測器的基本架構和原理 24
2-5-2 常見之分子辨識基團 25
2-5-3 螢光感測器的訊號變化與傳遞機制 28
2-5-4 共軛高分子在螢光感測器的應用 32
2-5-5 螢光化學感測器的可逆性 34
2-5-6 螢光萃熄常數 37
2-5-7 以Donor-acceptor型分子作為螢光感測器之發展 39
第三章 實驗內容 42
3-1 實驗儀器與裝置 42
3-2 儀器鑑定 43
3-3 物性測量儀器 45
3-4 實驗藥品與材料 50
3-5 合成步驟 51
3-5-1 單體合成 51
3-5-2 高分子合成 53
3-5-3 溶劑與高分子之純化 58
3-6 合成反應機制 59
3-7 高分子熱學性質探討 60
3-8 高分子光學性質探討 60
3-8-1 溶液態與薄膜態之光學性質 60
3-8-2 螢光感測現象的量測 61
3-8-3 量子效率測量 62
3-8-4 最低檢測濃度測量 63
3-9 高分子電化學性質探討 64
3-10 高斯軟體模擬探討 65
3-11 高分子型態學性質探討 66
第四章 結果與討論 67
4-1 化學結構鑑定 68
4-1-1 單體結構鑑定 68
4-1-2 高分子結構鑑定 71
4-2 高分子分子量量測 71
4-3 高分子熱學性質探討 73
4-3-1 熱重分析微差式掃描分析 73
4-3-2 熱卡度計分析 73
4-4 高分子光學性質探討 74
4-4-1 高分子在溶液態及薄膜態之光學性質 74
4-4-2 相對量子效率 76
4-5 高分子電化學性質探討 76
4-6 高斯軟體模擬探討 78
4-7 高分子型態學性質探討 79
4-7-1 掃描式電子顯微鏡分析 79
4-7-2 高解析穿透式電子顯微鏡分析 80
4-7-3 奈米粒徑分析儀分析 80
第五章 結論 98
第六章 未來工作 100
參考文獻 101
自述 106

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