臺灣博碩士論文加值系統

本研究藉由 RAFT (Reversible Addition-Fragmentation Chain Transfer polymerization)活性聚合技術將親水性N-異丙基丙烯醯胺(N-isopropylacrylamide, NIPAM)單體與具pH酸鹼值響應的丙烯酸acrylic acid (AA)或2-乙烯基吡啶 2-vinylpyridine (2-VP)單體進行一系列不同進料比例且同時具有溫度與pH酸鹼值雙重刺激響應的poly(NIPAM-co-AA)及poly(NIPAM-co-2VP)高分子合成，最後將擁有光異構化響應性質的偶氮苯(azobenzene)單體導入上述高分子中，形成多重刺激響應型的poly((NIPAM75-co-AA15)-b-Azo2)及poly((NIPAM81-co-2VP15)-b-Azo2)高分子。實驗結果發現將AA和NIPAM共聚後，由於NIPAM醯胺基團和AA的羧酸基團之間的強烈分子間氫鍵作用力會提高共聚高分子的玻璃轉移溫度(Tg)。隨著pH酸鹼值提高時，高分子溶液的最低臨界溶液溫度(the lower critical solution temperature, LCST)都有上升的情況。光學性質方面，藉由UV發現Azo單體、poly((NIPAM75-co-AA15)-b-Azo2)和poly((NIPAM81-co-2VP15)-b-Azo2)一階光異構化反應速率常數(kt)為0.011 min-1、0.128 min-1及0.069 min-1。照射紫外光，高分子螢光強度增強，歸因順式Azo分子聚集所造成。PL發光圖譜中金屬離子辨識方面，也發現poly((NIPAM75-co-AA15)-b-Azo2)和poly((NIPAM81-co-2VP15)-b-Azo2)各自對Ag+、Ru3+及Fe3+、Ru3+有螢光感測現象並算出poly((NIPAM-co-2VP)-b-Azo)的Ksv為3.75 × 103 M-1。本研究預期有助對光感應和化學感應聚合物材料有良好發展。

This article reports on studies regarding the synthesis of a series of poly(N-isopropylacrylamide-co-acrylic acid) (poly(NIPAM-co-AA)) and poly(N-isopropylacrylamide-co-2-vinylpyridine) (poly(NIPAM-co-2VP)) random block copolymers with various monomer feed ratios through reverse addition-fragmentation transfer (RAFT) polymerization. These block copolymers exhibited the dual stimuli-responsive properties (i.e., temperature and pH). The corresponding polymers were characterized using 1H NMR, LCST, DSC and TGA. We found that incorporation of the acrylic acid (AA) units into PNIPAM tended to enhance the glass transition temperature (Tg) because of the existence of the strong intermolecular hydrogen bonding between the amide groups of PNIPAM and the carboxyl groups of PAA, as observed using 1H NMR and FTIR analyses. poly((NIPAM75-co-AA15)-b-Azo2) and poly((NIPAM81-co-2VP15)-b-Azo2) showed larger photoisomerization rate constant (kt = 0.128 s-1 and 0.069 s-1) compared with azo monomer (kt = 0.032 s-1). After UV irradiation, the fluorescence intensity gradually increased, indicating that self-assembled cis-isomers of azobenzenes experience fluorescence enhancement upon UV irradiation. Photoluminescence titrations demonstrated that the poly((NIPAM75-co-AA15)-b-Azo2) and poly((NIPAM81-co-2VP15)-b-Azo2) were respectively showed high sensitivity toward Ag+/Ru3+ and Fe3+/Ru3+, respectively. The results of this study contribute to the literature regarding the development of photoresponsive and chemosensory polymer materials.

摘要 I
Abstract II
目錄 III
圖目錄 VI
流程圖目錄 XII
表目錄 XIII
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 3
第二章 文獻回顧與原理 5
2-1 聚合反應簡介 5
2-1-1 聚合反應分類 5
2-1-2 自由基聚合反應介紹 7
2-1-3 控制/活性自由基聚合反應簡介 8
2-1-3-1 氮氧調節自由基聚合 (nitroxide mediated radical polymerization, NMP) 10
2-1-3-2 原子轉移自由基聚合反應(atom transfer radical polymerization, ATRP) 11
2-1-3-3 可逆型加成-分裂鏈轉移聚合反應(reversible addition-fragmentation transfer polymerization, RAFT) 13
2-2分子自組裝和團聯狀高分子簡介 17
2-3光致變色系統簡介 23
2-3-1 光致變材料與變色機制 25
2-3-2 分子能階與光激發原理 27
2-3-3 偶氮苯與二苯乙烯衍生物之光異構化 29
2-4 溫度敏感型高分子 33
2-4-1 簡介 33
2-4-2 最低臨界溶解溫度 35
第三章 實驗內容 37
3-1 實驗儀器與裝置 37
3-2 儀器鑑定 38
3-3 物性測量儀器 41
3-4 表面型態鑑定儀器 48
3-5 實驗藥品與材料 50
3-6 合成步驟 51
3-6-1 溶劑與高分子的純化 51
3-6-2 NIPAM單體純化 52
3-6-3 高分子純化 52
3-6-4 單體的合成 53
3-6-5 高分子合成 55
3-7 高分子光學性質探討 59
3-8 螢光感測現象的量測 59
第四章 結果與討論 61
4-1結構鑑定 61
4-1-1單體結構鑑定 61
4-1-2 高分子結構之鑑定 62
4-2 高分子分子量的量測 71
4-2-1 高分子poly(NIPAM-co-AA) 71
4-2-2 高分子poly(NIPAM-co-2VP) 71
4-2-3 高分子poly((NIPAM-co-AA)-b-Azo) 72
4-2-4 高分子poly((NIPAM-co-2VP) -b-Azo) 72
4-3 高分子熱性質分析 74
4-3-1熱重分析 74
4-3-2 微差式掃描熱卡計分析 76
4-4 高分子溫度感應性質探討 81
4-4-1 高分子粒徑大小 88
4-5 光致變性化合物與高分子之光學性質探討 98
4-6 高分子光學性質探討 104
4-6-1 高分子螢光在UV光照射下的光學性質 104
4-6-2 高分子螢光在溶液態的陽離子感測效應 105
第五章 結論 109
未來工作 111
參考文獻 112

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