中文摘要

本研究為將離子交換型黏土修飾於胺鹽界面活性劑及樹枝狀高分子及其於可濕性與氣體吸附上之應用。相較於線性胺鹽界面活性劑，含苯基之胺鹽界面活性劑呈現較為疏水性，此類疏水性改質後的黏土常來增進不飽和聚酯樹酯之機械強度，所有的有有機修飾黏土，僅需要混入重量百分率3%就能提高複合材料4倍拉伸強度、2.5倍拉伸模數及3倍彎曲模數。
由於全球暖化問題，減少溫室氣體產生，甚至開發新材料對於溫室氣體捕抓為目前最重要的議題，因此本研究設計一離子交換粘土修飾樹枝狀高分子探討二氧化碳之吸附效率，本研究發現最佳化之黏土混入樹枝狀高分子是在酸性環境下，樹枝狀高分子中的黏土含量會依照黏土種類不同而改變，合成鋰皂石(laponite) >水滑石(hydrotalcite) > 雲母(sericite)，此差異主要來自於黏土之表面積，而二氧化碳氣體吸附能力之順序為，合成鋰皂石(laponite) > 雲母(sericite) >水滑石(hydrotalcite)，對於氨氣吸附能力為，水滑石(hydrotalcite) > 雲母(sericite) 合成鋰皂石(laponite) >。此結果差異主要來於樹枝狀表面官能基，本研究選用表面結構具胺基之樹枝狀高分子增加了二氧化碳吸附力，且增加樹枝狀高分子含量也有助於二氧化碳之吸附，另一方面，為了增加二氧化碳吸復能力亦可藉由導入四甲基哌啶之氧化活性基於奈米纖維素薄膜。此外，已吸附氣體之脫附可藉由通入氮氣來達成，不論氨氣或二氧化碳皆可成功脫附自奈米纖維素薄膜，且經由氣體動力學分析此氣體吸附於此複合材料是依Langmuir單層吸附方式，

The ion-exchange clays have been modified by ion exchange Quaternary Ammonium Surfactant (QAS) and poly(amido amine) dendrimers (PAMAM) moieties to enhance wettability and gas adsorption properties, respectively. Cation-exchange clay such as montmorillonite have been modified by QASs modifier with different alkyl chain lengths and a benzyl substitute group for enhancement of hydrophobicity and wettability. The modified organo clays have been characterized by different analytical techniques. The loading of QASs was in the range of 0.60-0.75 mmol/g per clay, irrespective of the type of QAS used for the modification of the clays. Moreover, the presence of benzyl groups on the clay prevents water from penetrating into the interlayer spacing, which yields the hydrophobic surface. These behaviors can arise from the molecular arrangement of QAS on clay, but not be attributable to the amount of QASs, and the surface area, size, and zeta potential of particles. Such high hydrophobic clays have been dispersed in Unsaturated Polyester (UPE) resin for the enhancement of mechanical properties of nano composite. Among all the organo clays dispersed in UPE resin nano composite, 3% W/W montmorillonite clay modified by QASs having a chain length of C-18 with benzyl substitution enhanced tensile strength 4 times, tensile modulus 2.5 times, and flexural modulus 3 times compared to a polymer block without clay additives.

For gas adsorption properties of clays, ion-exchange clays have been modified by
ion-exchange dendrimers. During modification, loading of dendrimers have been obtained in the ordered of a BET surface area of clays, such as laponite> hydrotalcite> sericite, irrespective of the types of clays. Loading and distribution of the dendrimers are characterized by different analytical techniques. The capability of CO2 gas adsorption on pristine clays is the same order as the dendrimer loading. However, the capability of NH3 gas adsorption on pristine clays is in the order of hydrotalcite > sericite > laponite. This is due to difference in affinity of gas molecules with different clays. The CO2 gas adsorption with dendrimer loading increased on laponite and sericite organoclays but decreased on hydrotalcite organoclays. The same, but opposite behavior has been obtained with NH3 gas adsorption. Moreover, the gas adsorption amount remains higher at room temperature adsorption with compare to higher temperature. Moreover, gas adsorption on organoclays increases with increasing the loading of respective dendrimers. While gas molecules adsorbed on pristine clays are desorbed mostly, but some gas molecules on organoclays remain after desorption procedure. This indicates that CO2 molecules adsorb at the strong interaction with binding sites of dendrimer with NH2 terminated and NH3 molecules have strong interaction with COOH terminated dendrimers. Similar gas adsorptions have been performed on clay impregnated 2,2,6,6-tetramethylpiperidine- 1-oxyl radical (TEMPO) oxidized cellulose nanofiber (TOCNF) films. Loading and distribution of clays in TOCNF are characterized by different analytical techniques. The adsorption amount of gases is enhanced for clay-TOCNF films to compare with net clay materials. However, organo hydrotalcite clay increases both gas adsorptions with compare to laponite and sericite clay. This is due to the affinity of functionalized NH2 terminated PAMAM dendrimer towards COOH/COONa functionalized TOCNF increased and thus gas adsorption affinity decreased. Moreover, the time-course CO2 gas adsorption have been investigated on pristine clays and organoclays to find the binding sites of gas adsorption. Observed data of CO2 adsorption followed the Langmuir monolayer adsorption kinetics, when two adsorption sites of clays namely clay inter-layer and outer-layer of pristine clays and third adsorption sites of dendrimer moiety are taken in account for organoclays, respectively. However, third site is active with based on a terminal group of dendrimers. It can be mentioned that the amine-terminated dendrimer is a valuable solid adsorbent for CO2 gas; whereas carboxyl-terminated dendrimer is a valuable solid adsorbent for NH3 gas.

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