臺灣博碩士論文加值系統

本研究以原子轉移自由基聚合反應(atom transfer radical polymerization, ATRP)聚合聚甲基丙烯酸-2-二甲胺乙酯(poly(2-dimethylamino)ethyl methacrylate, PDMAEMA)，再以醯化反應接枝到幾丁聚醣(chitosan, CS)上，除調查具溫度及pH敏感性之PDMAEMA及CS-g-PDMAEMA對CO2之應答行為外，也調查藉由bubbling CO2，CS-g-PDMAEMA水溶液是否具有CO2-switchable乳化劑之功能，以及是否可由bubbling N2而可逆回復不具乳化劑功能之狀態。實驗中以質子核磁共振光譜儀(1H-NMR)、凝膠滲透層析儀(GPC)、熱重分析儀(TGA)、示差掃瞄熱卡分析儀(DSC)、粒徑分析、冷場發射掃描式電子顯微鏡(SEM)及Zeta potential鑑定分析PDMAEMA、CS、CS-g-PDMAEMA等樣品之組成、分子量及水溶液相關性質。以紫外光-可見光光譜儀(UV-Vis)與數位攝影等方法測定PDMAEMA、CS-g-PDMAEMA水溶液樣品之較低臨界溶解溫度(LCST)隨pH值改變之情形，樣品對bubbling CO2及N2之應答行為。實驗結果顯示我們成功聚合出CS-g-PDMAEMA。PDMAEMA及CS-g-PDMAEMA水溶液樣品之LCST會隨pH值下降而上升，下降至某特定pH值時LCST會消失，且CS-g-PDMAEMA水溶液樣品之溶解度會提升。觀察bubbling CO2 與N2對CS-g-PDMAEM水溶液相之變化，發現CS-g-PDMAEMA bubbling CO2後因PDMAEMA三級胺受碳酸水解離H+而質子化，增強PDMAEMA之親水性，LCST因而消失，再bubbling N2去除CO2會使PDMAEMA之質子化三級胺還原成三級胺，LCST因而會回復。將CS-g-PDMAEMA加入正丁醇/去離子水兩相溶液中，bubbling CO2能使兩相溶液完全乳化成為一相，再bubbling N2可使均一相溶液可逆回復成兩相溶液，證明CS-g-PDMAEMA水溶液具有CO2-switchable乳化劑之功能，而且具有可逆性。

In this study, poly(2-dimethylamino)ethyl methacrylate (PDMAEMA) was prepared by atom transfer radical polymerization followed by grafting to chitosan (CS). The temperature- and pH-sensitive PDMAEMA and CS-g-PDMAEMA were investigated into their CO2 responsiveness and reversible CO2-switchable behavior as an emulsifier via simple CO2 and N2 bubblings. Proton NMR, GPC, TGA, DSC, particle size analysis, SEM and Zeta potential were used for characterizations of compositions, molecular weights, and aqueous related properties of PDMAEMA and CS-g-PDMAEMA. The phase separation, or the lower critical solution temperatures (LCST), of PDMAEMA and CS-g-PDMAEMA aqueous solutions were characterized by solution turbidity as a function of temperature, pH, and CO2/N2 bubbling using a UV-vis spectrometer and digital camera. Experimental results confirmed that PDMAEMA and CS-g-PDMAEMA were obtained and found that the LCSTs of PDMAEMA and CS-g-PDMAEMA were increased with decreasing pH until LCST disappeared at a certain pH. LCST of CS-g-PDMAEMA aqueous solution was found to disappear by bubbling CO2 and appear by bubbling N2 at a certain elevated temperature. This could be attributed to the protonation of the tertiary amines in PDMAEMA during the CO2 bubbling resulting in hydrophilic PDMAEMA and disappearance of LCST and the deprotonation during the N2 bubbling resulting in hydrophobic PDMAEMA and appearance of LCST. The CS-g-PDMAEMA in the two-phase solution of n-butanol/ deionized water of 1/1 volume ratio enabled the formation of a completely emulsified single phase by bubbling CO2 and then reverting to the two-phase solution by bubbling N2. It could conclude that CS-g-PDMAEMA used as an emulsifier was CO2-switchable and reversible.

目錄 i
表目錄 iv
圖目錄 v
第一章 前言 1
1-1刺激應答型高分子 1
1-2幾丁聚醣之簡介 2
1-2-1 幾丁聚醣之性質應用 3
1-3 聚甲基丙烯酸-2 -二甲胺乙酯之簡介 4
1-4 較低臨界溶解溫度(LCST)之簡介 5
1-4-1 較低臨界溶解溫度(LCST)之測定 6
第二章 文獻回顧 7
2-1 利用傳統自由基接枝共聚物 7
2-2 原子轉移自由基聚合(ATRP)之簡介 8
2-2-1 原子轉移自由基聚合之原理 8
2-2-2 原子轉移自由基聚合優缺點 9
2-2-3 利用ATRP接枝共聚物 13
2-2-4 利用ATRP及Click chemistry 聚合接枝共聚物 17
2-3 高分子與二氧化碳交互作用 18
2-4 高分子之乳化行為 22
2-5 研究動機 26
第三章 實驗步驟與方法 27
3-1 實驗藥品 27
3-2實驗設備 29
3-3實驗步驟 32
3-3-1 以ATRP聚合PDMAEMA 32
3-3-2 PDMAEMA之純化 32
3-3-3 醯化反應接枝CS-g-PDMAEMA及純化 33
3-3-5 以1H-NMR鑑定分析CS、PDMAEMA、CS-g-PDMAEMA之組成 35
3-3-6 以GPC測定PDMAEMA及CS-g-PDMAEMA之分子量 35
3-3-7 以TGA量測CS、PDMAEMA及CS-g-PDMAEMA之熱裂解溫度 35
3-3-8 以DSC量測CS、PDMAEMA及CS-g-PDMAEMA之Tg點 36
3-3-9 以粒徑分析儀量測PDMAEMA及CS-g-PDMAEMA水溶液之粒徑 36
3-3-10 以溶液黏度法測量PDMAEMA水溶液及CS-g-PDMAEMA水溶液之黏度 36
3-3-11 以SEM觀察PDMAEMA及CS-g-PDMAEMA之表面形貌 37
3-3-12 以Zeta potential量測PDMAEMA及CS-g-PDMAEMA水溶液之界面電位 37
3-3-13 以UV-Vis光譜儀測量PDMAEMA及CS-g-PDMAEMA水溶液之相轉變(LCST) 37
3-3-14 以數位攝影觀察PDMAEMA及CS-g-PDMAEMA水溶液相轉變(LCST)之現象 37
3-3-15 以數位攝影觀察PDMAEMA及CS-g-PDMAEMA對CO2之應答行為 38
3-3-16 以數位攝影觀察PDMAEMA及CS-g-PDMAEMA之乳化行為 38
第四章 結果與討論 39
4-1 材料之鑑定分析 39
4-1-1質子核磁共振儀(1H-NMR)鑑定材料結構 39
4-1-2 以GPC測量PDMAEMA及CS-g-PDMAEMA之分子量 41
4-1-3以TGA測量CS、PDMAEMA及CS-g-PDMAEMA之熱裂解溫度 41
4-1-4 以DSC測量CS、PDMAEMA及CS-g-PDMAEMA之玻璃轉換溫度(Tg) 42
4-1-5 觀察PDMAEMA水溶液及CS-g-PDMAEMA水溶液之相轉變(LCST)行為 43
4-1-6 PDMAEMA及CS-g-PDMAEMA之粒徑分析 46
4-1-8 以溶液黏度法測量PDMAEMA水溶液及CS-g-PDMAEMA水溶液之黏度 51
4-1-9 以SEM觀察PDMAEMA及CS-g-PDMAEMA之表面形貌 52
4-1-10 PDMAEMA水溶液及CS-g-PDMAEMA水溶液之Zeta potential 53
4-2 PDMAEMA及CS-g-PDMAEMA之pH值應答行為分析 54
4-2-1 以UV-Vis測量PDMAEMA及CS-g-PDMAEMA之LCST 54
4-2-2 比較PDMAEMA及CS-g-PDMAEMA之LCST 57
4-2-3 PDMAEMA及CS-g-PDMAEMA水溶液之相轉變(LCST) 60
4-3 PDMAEMA及CS-g-PDMAEMA對CO2之應答行為分析 63
4-3-1 以Zeta potential測量PDMAEMA及CS-g-PDMAEMA bubbling CO2及N2之界面電位 63
4-3-2 以數位攝影觀察PDMAEMA及CS-g-PDMAEMA水溶液bubbling CO2及N2之相轉變(LCST)變化 64
4-4 PDMAEMA及CS-g-PDMAEMA之乳化行為分析 67
4-4-1 以數位攝影觀察PDMAEMA及CS-g-PDMAEMA之乳化行為 67
第五章 結論 70
第六章 參考文獻 73

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