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標題: Organic modification and intercalation of synthetic fluorine mica with poly(oxyalkylene)-amines
作者: 陳育民
Chen, Yu-Min
關鍵字: intercalation;插層;synthetic fluorine mica;montmorillonite;poly(oxyalkylene)-amines;nanocomposite;合成雲母;蒙脫土;聚醚胺;奈米複合材料
出版社: 化學工程學系
This thesis, we discuss the intercalation of synthetic mica with poly(oxyalkylene)-amines and their self-assembling mechanism. Furthermore, the different intercalation profiles are compared with MMT.
(1) Intercalation of synthetic mica by different polar poly(oxyalkylene)-amines renders the organo-mica of varied properties. The incorporated organics change hydrophilic silicates into hydrophobic hybrids. In XRD pattern, POP-D4000/Mica and POP-T5000/Mica have high basal spacing (d =68.2 and 83.7 Å, respectively). The observation indicates the highly enlarged spacing by utilizing high molecular weight of poly(oxypropylene) amines.
(2) Layered aluminosilicates, including synthetic fluorine mica and natural montmorillonite (MMT), were intercalated with poly(oxypropylene)-polyamine quaternary salts with a 230 to 5000 g/mol molecular weight range. The X-ray basal spacing of these silicates had been expanded from 13.5 Å to 83.7 Å for the synthetic mica and to 92.0 Å for MMT. The relative silicate dimensions (300~1000 nm for synthetic mica and 80~100 nm for MMT) were ascertained by direct TEM observations in the case of the co-intercalated synthetic mica and MMT mixtures with 2000 g/mol quaternary ammonium salts. The tailored organic incorporation of synthetic mica and MMT clays could alter these hydrophilic clays, making them amphiphilic and enable the lowering of toluene/water interfacial tension until 2.0 mN/m at the critical concentration of 0.1 wt %.
(3) Unique formation of lengthy rods was prepared from a self-assembling process of the polyetheramine-intercalated mica clay. The incorporation of POP polymer strands (2000 g/mol Mw) consequently rendered the organoclay amphiphilic and dispersible in toluene. When examined under Scanning Electron Microscopy, the morphology of a rod-like microstructure with average dimension of 10~30 μm in length and 0.2~0.8 μm in width. The formation of lengthy rod crystalline was attributed to a self-aligning mechanism involving the platelet face-to-face stacking.

(1) 一系列聚醚胺插層雲母,經由不同極性鏈段的聚醚胺改質會有不同性質的結果。聚丙烯醚胺,隨著分子量的增加而層間距提升,性質從親水性轉變成親油性。經 XRD 分析,POP-T5000/Mica 將層間距撐開至 83.7 Å 之高層間距,是目前文獻報導中所僅見的。
(2) 與蒙脫土比較,經 POP-D2000 共插層,以 TEM 直接辨別雲母與蒙脫土的片狀大小為 300 ~ 1000 nm (synthetic mica) 及 80 ~ 100 nm (MMT)。插層後的雲母,層間距與有機含量均較低於蒙脫土,可能與片狀大小及電荷密度有關。此外,經高分子量聚丙烯醚胺 (Mw 2000 g/mol) 改質後的有機黏土具有雙性特質,可以將甲苯/水的界面張力降低至 2 mN/m (黏土之濃度為0.1 wt%)。
(3) 以 POP-D2000 插層雲母之雙性特性,導致其自我排列的現象。自我排列的柱狀結構形態經 SEM 的分析,長度約 10 ~30 μm,寬度約 0.2 ~ 0.8μm。以 AFM 觀察,更可發現其特殊微細結構的排列,可分辨出層狀黏土排列方向及柱狀複合形態。
(4) 自我排列之機制可以用片狀黏土, face to face 的離子交互作用及 edge to edge 的聚丙烯醚鏈段 hydrophobic 作用力之兩種化學鍵的互補力量說明之。
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