2014-01-012024-05-16https://scholars.lib.ntu.edu.tw/handle/123456789/666719摘要：有機二次非線性光電材料須具備高的光電係數以及長時間熱穩定。實驗室曾經將含發色團基的樹枝狀高分子，當作介面活性劑與蒙脫土離子交換，再與高分子混摻後形成二次非線性奈米複合材料(Second-order Nonlinear Optical Materials)，蒙脫土的導入提升了材料的熱穩定性。而除了熱性質外，實驗結果還發現，未經電場極化，就能夠量測到介於4.1~5.7 pm/V的光電係數，這是因為蒙脫土玻璃間引力，搭配樹枝狀分子結構的立體障礙，使材料自組裝成同方向，於 ITO 玻璃上形成非中心對稱排列。 本研究利用含金剛烷 (Adamantane) 官能基側鏈寡聚物，取代合成繁複的樹枝狀高分子，在高分子結構中導入剛硬的金剛烷衍生物，將降低高分子間堆疊，提升透明度；全飽和的碳氫化合物鍵結，使材料的含水率降低，降低介電常數，提升材料的熱穩定性。 除此之外，雙環戊二烯 (Dyclopentadiene，DCPD) 為金剛烷的前驅物，共聚性良好，能夠提升材料的電氣與機械性質，增加材料的耐候與耐熱性，廣泛用於特用化學品。實驗利用環戊二烯的衍生物，跟環氧樹脂上的醇基反應生成帶有雙鍵的末端官能基，在&#21579;喃的存在下進行 Diels-Alder 交聯，固定二次非線性光學材料的非中心對稱，交聯後的系統在熱穩定上的提升是可以預期的結果。兩種 C5 化學結構的衍生物將透過不同方式，提升非極化系統的二次非線性光學材料性質。 <br> Abstract: In this work, dicyclopentadiene (DCPD) derivatives will be utilized to enhance second order nonlinear optical (NLO) properties for epoxy/MMT composites. First, NLO epoxy polymers are to be prepared for serving as the intercalating agents for montmorillonite (MMT) via an ion-exchange process. The presence of exfoliated morphology in the organoclay epoxy/MMT composites is essential for the realization of NLO properties, i.e. the Pockels effect will be observed for these nanocomposites without resorting to the poling process. Polymers with adamantanes as pendant groups or in the backbone show enormous changes in their physical and chemical properties. Moreover, the large steric size of the adamantane rings increases the rigidity of the polymer chains, which, in turn, gives more space between chromophores, i.e. bringing about site-isolation effect for the second order NLO polymers. Apart from that, Diels-Alder cycloadditions have been successfully adopted for controlling lattice hardening in the stable NLO polymers. These encouraging results have shown the potential and versatility of using these Diels-Alder reactions to create improved NLO properties for polymers. In this work, the MMT/epoxy polymers consisting of thermally reversible furan-norbornene Diels-Alder adducts are to be prepared to further stabilize the non-centrosymmetric orientation. Based on the above, self-alignment behavior, electro-optical (EO) coefficient and temporal stability of the MMT/epoxy nanocomposites are certainly to be improved by the incorporation of the C5 chemistry.二次非線性光電材料自組裝光電效應C5 化學nonlinear opticsself-assemblyPockels effectC5 chemistry