單官能基之聚醚胺鹽插層蒙脫土之機制探討
及其原油吸附應用

本論文以單官能基之聚醚胺(Poly(oxypropylene)-monoamine)為插層劑，進而探討在末端官能基對於天然蒙脫土之層間距變化影響，並與實驗室早期以發表之雙官能基之聚醚胺(Poly(oxypropylene)-diamine)插層蒙脫土進行比較。此外，也將其應用於有機物質或原油吸附上，皆具良好之應用特性。利用親油性單官能基之聚醚胺POP-M2000對天然蒙脫土進行改質後發現，在相同分子量以及相似的主鍊結構下，單官能基之聚醚胺鹽插層蒙托土之層間距可高達74 Å，而雙官能基之聚醚胺鹽插層蒙脫土則僅達到52 Å。其主要原因為雙官能基之聚醚胺鹽之酸化與未酸化官能基，彼此之間具有氫鍵之作用力存在，導致經由雙官能基插層之蒙脫土層間距較低，且無法再經由添加物提高其層間距。反觀單官能基之聚醚胺鹽在層間可產生一強烈之親油相，與親水性之蒙脫土表面具有一定之排斥力，且無雙官能基之氫鍵影響，因此層間距較高；且若再經由親油性物質的添加，其層間距可再提升約10 Å。此外，經改質後的蒙脫土可自我排列於甲苯與水界面並形成薄膜，利用掃描式電子顯微鏡(TEM)與穿透式電子顯微鏡(SEM)可觀察到次序性的排列結構。利用有機黏土應用於原油吸附上已發展有一段時間，但皆未深入探討不同改質黏土及其環境溫度對於有機黏土吸附原油之影響。在本研究結果中發現，具有50 wt% 親油性插層劑之含量，可擁有最大之吸附能力，且其吸附過程主要有兩階段所造成。而有機黏土之聚集程度、插層劑主鏈性質以及環境溫度皆為影響吸附結果之主要原因。此外，為了有效回收吸附後之有機黏土，藉由添加些許磁性有機混合物，則可以在保有其最大吸附力下，仍具有一良好之磁性並可加速回收過程及速度。

關鍵字

聚醚胺鹽；插層；層狀黏土；蒙脫土；原油吸附

並列摘要

Poly(oxypropylene)-segmented monoamine salts (POP-monoamine) of different molecular weights including 600, 1000, and 2000 g/mol were first time used for ionic exchange reaction with sodium montmorillonite (Na+-MMT) to probe the clay intercalation mechanism. The expansion of the clay layered spacing was more substantial for achieving 74 Å XRD d spacing than the analogous di-amine salts of POP-2000 Mw blocks (52 Å). Hydrophobic effect may create a separated phase in the silicate plate interlayer by the influence of amine end groups. As a result, monoamine is different from diamine and expanding the MMT spacing more than 10 Å than the diamine. The modified clay could self-assemble at the toluene/water interface to form film, exhibiting an aligned an ordered structure as revealed by TEM and SEM. The POP-intercalated MMT (or POP-MMT) is considered to be organic-inorganic amphiphiles possessing organic solvent dispersing affinity as well as a unique property of lower critical aggregation temperature (LCAT) in water. The poly(oxypropylene) segment is exhibiting its hydrophobic phase aggregation in accordance with the amine functionalities through different noncovalent bonding interactions. The potential application for adsorbing crude oil spills is demonstrated. The maximum adsorption capacities of crude oil occurred at the POP/MMT weight ratio of 50 wt % and responded to the environmental temperature or a “lower critical aggregation temperature (LCAT)” property. The adsorption of crude oil occurred in two stages. The first order adsorption is the formation of POP/MMT interaction with crude oil through the MMT layer spacing by an increasing d spacing. The second order adsorption is a micelle-like aggregation of POP/MMT/oil units into a large oil lump. Further addition of 10 wt % magnetic Fe3O4 nanoparticles enabled the adsorbed oil lumps to be removable under a magnetic field.

並列關鍵字

Poly(oxypropylene)amine ； Intercalation ； Layered Silicate ； Amphiphilic ； Montmorillonite

參考文獻

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單官能基之聚醚胺鹽插層蒙脫土之機制探討及其原油吸附應用

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