Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3451
標題: Orderly Stacking Arrays from Copper Ion/Poly-(oxyalkylene)amine Intercalated Montmorillonite
銅離子/聚醚胺鏈段插層蒙脫土之有序堆疊結構
作者: CHEN, SHIUE BIN
徐彬城
關鍵字: copper ion
銅離子
hybrid
intercalation
ICP
混成材料
插層
感應偶合電漿光譜儀
出版社: 化學工程學系
摘要: 本研究目的主要在於製備含金屬離子之有機/無機混成材料,金屬離子以二價銅離子為主,無機材料為具有天然層狀結構之蒙脫土(montmorillonite)。本研究特點在於有機/無機混成材料中加入銅離子,並探討其不同於一般高分子插層型複合材料的特性。 (1)以不同比例之聚丙烯醚(polyoxypropylene)鏈段(分子量約2000g/mol)與銅離子製備複合插層劑,插層進入黏土層間,由感應偶合電漿光譜儀 (ICP)分析得知此複合材料中銅元素的含量,經實驗證實黏土之層間距高度與插層劑之聚丙烯醚加入比例成正比關係,而由X-ray繞射證實黏土之層間距(d-spacing)可達55.0 Å以上(單一插層劑聚丙烯醚插層黏土可達58.0 Å以上),但銅離子會被聚丙烯醚鏈段吸附的量所限定,若銅離子之添加量過多(>2.2wt﹪),即銅離子莫爾數大於聚丙烯醚之莫爾數一倍以上,則會造成銅離子與聚丙烯醚競爭,聚丙烯醚無法順利進行插層反應,層間距無法達到53.0 Å以上。若以此複合插層劑改質黏土,其分散性質已不同於聚丙烯醚改質後之黏土可分散於有機溶劑中。於熱性質的分析方面,亦與一般有機黏土之裂解曲線不同,於100~300℃間有明顯的催化裂解現象。 (2)與複合插層劑改質黏土對照之二次插層反應(先後插層條件),以不同莫爾數之聚丙烯醚(分子量約2000g/mol)改質黏土,將此有機/無機混成材料分散於有機溶劑中(甲苯/乙醇),並加入銅離子水溶液,使其在乳化相中反應,反應中銅離子的添加量為1.3~6.2wt﹪,由X-ray繞射發現層間距下降(由58.0 Å下降至18.0 Å),由此得知銅離子取代有機/無機複合材料中的聚丙烯醚鏈段,並可從TGA有機值下降佐證其銅離子取代反應。另一個對照組實驗則是銅離子先插層進入黏土層間,則聚丙烯醚無法進行插層反應,層間距只有20.5 Å,由此可知銅離子與蒙脫土有較好的反應性及穩定性。 (3)此含有銅離子之有機/無機混成材料在加入還原劑還原金屬,銅離子瞬間的氧化還原,破壞此複合材料三種物質之間的平衡,此有機黏土之層間距從55.1Å下降為18.0 Å。 以高分子和金屬離子之複合插層劑插層進行黏土改質為最佳的插層方法,二次插層反應(先後插層條件)則會造成競爭、取代反應(以XRD、TGA和ICP分析得知);此系列之複合材料,以熱重分析儀(TGA)測定其熱性質,催化效應使解裂速度增快,因銅離子的添加導致最大裂解溫度可提前50℃以上。此複合材料在TEM下可觀察到奈米級之微結構(100~50 nm),為黏土之一級堆疊結構;利用溶劑與溫度探討對結晶性質的影響,在SEM觀察下,可見規則之有序堆疊具代表性柱狀結晶。
Organic/inorganic hybrid materials containing metal ions were prepared, in which metal ions part is duad copper ions and inorganic part is layered-silicate clay (Na+-montmorillonite or Na+-MMT). The particular of this research is the chemical and physical properties of the new nanocomposite were different from general oligomer intercalated composites. In part one, different ratios of copper ion and polyoxypropylene diamine (Mw=2000) were intercalated into MMT simultaneously. The quantity of copper ions in the hybrid could be obtained by using inductively coupled plasma (ICP), and the interlayer spacing of the hybrid clay confirmed by X-ray diffraction (XRD) was 55.0Å (The d-spacing of the single intercalating agent, POP-diamine, modified MMT is 58.0Å). But copper ions would limit by the adsorption of polyoxypropylene chains. If the additive of copper ions more than 2.2 wt﹪, in which the molar ratio of copper ions and polyoxypropylene diamines more than 1: 1, we would find the competition for copper ions and polyoxypropylene, and polyoxypropylene can not smoothly intercalate into silicate layers, and the basal-spacing of this modified clay can not reach 53.0 Å. Beside, the analysis of thermal property have different result of this modified clay and general organic clay, we find this modified clay have obvious appearance of catalytic cracking in 100~300℃. This modified clay cannot easily dispersible. In part two, a contrast experiment between second intercalated reaction and complex intercalating agent into clay. We use different molar weight polyoxypropylene (Mw=2000) modified clay, and make the organic clay disperse by co-solvent (toluene/ethanol), than add copper ion solution, let it react in emulsion solution (the additive of copper ions =1.3~6.2 wt﹪). We proved the basal-spacing of organic clay decrease from 58.8 Å to 18.0 Å. From this we know copper ions replace the polyoxypropylene chains in silicate layer. We also proof the copper ion replace reaction by organic value decreasing by TGA. In other contrast experiment, we use copper ions intercalated into clay layers first. Then we find the polyoxypropylene partially intercalated into silicate layers (The basal-spacing is 20.5 Å). From this we know copper ions have better reacting property with clay, and it have better stability in clay layers. In part three, adding the reducing agent to the organic/inorganic hybrid containing copper ion, the reaction is violent and the balance between MMT, oligomer and copper ion were broken. The basal-spacing of the hybrid was decreased from 55.1 Å to 18.0 Å. Using the complex intercalating agent, oligomer and metal ion, to modify MMT is the best intercalating method in our research. Second intercalating reaction would lead to the competition and replace reaction from the evidences of TGA, XRD and ICP. Using thermal gravimetric analysis (TGA) to analyze the thermal property of the nanocomposite, we found its thermal catalyzing effect cause to increase the cracking speed. Because of adding copper ions, the max cracking temperature advance more than 50℃. Under TEM, the dispersion of the hybrid in co-solvents (deionized water, ethanol and toluene) was observed. Under SEM, effects of the solvent and temperature to the crystallization were studied and the orderly stacking arrays (pillared crystals) from copper ion/poly (oxyalkylene) amine intercalated MMT were observed.
URI: http://hdl.handle.net/11455/3451
Appears in Collections:化學工程學系所

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