林江珍臺灣大學:高分子科學與工程學研究所廖一驎Liao, Yi-LinYi-LinLiao2010-05-122018-06-292010-05-122018-06-292008U0001-2406200815132000http://ntur.lib.ntu.edu.tw//handle/246246/183112本論文以聚醚胺(poly(oxypropylene)-amine)與馬來酸酐(maleic anhydride)合成插層劑poly(oxypropylene)-bis-amidoacids (POAs)，對人工合成的陰離子型黏土水滑石(LDH)進行改質，探討其反應機制，並與實驗室早期已發表的陽離子型黏土(蒙脫土、雲母)比較。1)一系列POAs插層水滑石，經由不同極性鏈段的POAs改質會有不同的性質的結果。隨著POP-amidoacids分子量的增加而層間距提升，最高可將水滑石層間撐開至XRD 94 Å之高層間距。2)隨著POP2000-2MA-2Na量的增加，水滑石層間變化會有個臨界點，超出此臨界點層間距會瞬間增大，利用此機制可輕易控制分子在層間的型態改變。3)經由POP2000-2MA-Na改質後的有機黏土具有雙性性質，為一新穎的有機無機界面活性劑，在臨界微胞濃度下(CMC=0.01wt%)可使甲苯/水的界面張力降低至4.5 mN/m。4)以同一類型插層劑對此三種不同類型黏土做比較，有別於傳統離子交換改質的黏土，新的改質機制包含氫鍵力及螯合分別作用在不同類型的黏土上(水滑石，蒙脫土和雲母)。5)有機改質的水滑石複材具有酸鹼應答特性，其層狀結構可在較低pH的環境下分解並釋放出層間有機物，此黏土複材同時具有溫度敏感特性，可在低溫下分散(5~10 oC)，高溫下聚集(>20 oC)。結合上述特性，此有機水滑石可應用在藥物釋放等生醫工程上。This thesis concerns the organic modification for the Mg–Al layered double hydroxides (LDHs), more specifically, the intercalation profile of the clay with a series of poly(oxypropylene)-bis-amidoacids (POAs). number of important issues are included in the thesis. 1)The intercalation of LDH by the POP-amidoacids and the spatial enlargement of the gallery up to 94 Å d spacing.2)The critical intercalation of using the POP2000-2MA-2Na for expanding the LDH gallery. It provides a new way for manipulating nanomaterials and control of polymer conformations in the LDH confinement.3)The amphiphilic property of POP2000-2MA-Na/LDH hybrid and their ability of lowering the toluene/water interfacial intension to 4.5 mN/m at the critical micelle concentration (CMC) of 0.01 wt%.4)Newly discovered mechanisms that involving hydrogen-bonding and chelation. The different clays such as LDH, MMT and Mica are compared for the generality of the new mechanisms.5)A pH dependence of the organo-LDH hybrids that particularly occurrence of layered structure collapse at low pH environment. The implication is an application of organic encapsulation and control release that could be developed for such a clay hybrid. In addition, the hybrids also possess thermal-sensitivity, that allows a fine dispersion at low temperature (5~10 oC) and aggregation at higher temperature (>20 oC).口試委員會審定書 icknowledgement iibstract (English) iiibstract (Chinese) vhapter 1. Introduction 1hapter 2. Literature review 4-1. Layered silicate 4-2. Intercalation profile for organically modified layered silicate 6-3. Layered double hydroxides 12-3-1. Synthesis of organo-LDHs 13-3-2. Application of LDH complexes 15hapter 3. Experimental section 19-1. Materials 19-2. Experimental Process 21-2-1. Preparation of Mg2Al-NO3-LDH 21-2-2. Synthesis of Poly(oxyalkylene)-bis-amidoacids(POA) as intercalating agent 21-2-3. Intercalation of LDH by POA-xNa 23-2-4. Chelation of layered silicate by POA 23-3. Instrument 24hapter 4. Results and Discussion 25-1. Correlation between LDH basal spacing and intercalating agents 25-2. Critical conformation change of POP2000-2MA/LDH 28-3. Comparison between POP2000-2MA-Na/LDH and POE2000-2MA-Na/LDH in interfacial tensions 31-4. Correlation between LDH basal spacing and Basification Ratio of POP2000-2MA 33-5. Comparison of intercalation among LDH, MMT and Mica with the same intercalating agents 38-6. pH-sensitivity of POP2000-2MA/LDH, POP2000-2MA/MMT and POP2000-2MA/Mica 39-7. Thermal-sensitivity of POP2000-2MA/LDH in water 41hapter 5. Conclusion 44hapter 6. Reference 46application/pdf896049 bytesapplication/pdfen-US水滑石聚醚醯胺酸插層氫鍵酸鹼溫度敏感性Layered Double Hydroxides (LDH)poly(oxypropylene)-bis-amidoacidsintercalationhydrogen-bondingpH- and thermal-sensitivitythesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/183112/1/ntu-97-R95549001-1.pdf