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標題: 利用開環加成反應製備二次非線性光學超樹枝狀高分子
作者: 楊志強
Yang, Chih-Chiang
關鍵字: 非線性光學;電光係數;樹枝狀高分子
出版社: 化學工程學系
In order to develop new three-dimensional polymer for nonlinear optics, a hyperbranched polymeric structure was selected as a novel NLO material design. Hyperbranched polymers are synthesized from the difunctional compound (A2 type monomer) and the trifunctional monomers (B3 type monomers).
First, the difunctional chromophore 4-(4’-nitrophenyl-diazenyl) phenyl-1,3-diamine (NDPD) has been synthesized, which is then reacted with 4-isocyanato-4’-(3,3-dimethyl-2,4-dioxo-azetidino) diphenyl -methane (MIA) to form NDPDMIA (A2 type monomer). The A2 type monomer exhibit high selective reactivity, whose bis-azetidine -2,4-diones can react with aliphatic primary amines at mild temperatures rapidly. Therefore, hyperbranched polymers can be synthesized via ring-opening addition reaction based on NDPDMIA (A2 type monomer) and tris(3-aminoethyl)-amine (B3 type monomer). Moreover, the bis-azetidine-2,4-diones of A2 monomer are capable of performing ring-opening addition reaction toward aromatic primary amines of tris(3-aminophenyl)phenyl phosphine oxide (TAPPO) at high temperatures by using 1,8-Diazabicyclo(5.4.0.)undec-7-ene as a catalyst.
To further clarity the chemical structure of hyperbranched polymers, a series of model compounds were synthesized and analyzed by 13C-NMR. The degree of branching of hyperbranched polymers was estimated to be 0.74 by 13C-NMR spectroscopic technique. The inherent viscosity of hyperbranched polymers in DMSO ranged from 0.15~0.22 dLg-1. All of the obtained polymers were soluble in DMF、DMAc and DMSO. Using in situ contact poling, r33 coefficients of 6.4~17.5pm/V and their temporal stability at 60℃ were obtained. Optical loss measurement was also achieved by a prism coupling setup. Based on the above, this series of hyperbranched polymers are of potential for photonic applications.

摘 要
本研究合成出二次非線性光學超樹枝狀高分子(hyperbranched polymers)。利用A2 + B3之形式,進行hyperbranched polymers聚合反應,得到具有機可溶性之hyperbranched polymers。實驗先合成發光團基NDPD,再利用其雙NH2官能基與自行合成的MIA氰酸鹽官能基反應,形成具有兩個azetidine-2,4-diones官能基之單體(A2)。所製得之單體(A2)具有高反應選擇性,與脂肪族的一級胺在室溫即可進行開環加成反應,且其開環加成反應快速、產率極高、無副產物之生成。研究合成兩系列hyperbranched polymers,利用單體(A2)與具三個脂肪族一級胺之單體(B3) (tris(2-aminoethyl)amine)進行快速開環加成反應製備出一系列hyperbranched polymers。另外,利用1,8-Diazabicyclo -(5.4.0.)undec-7-ene當觸媒,於較高溫度下可與三個芳香族一級胺之單體(B3) TAPPO 進行開環反應製備。
實驗中利用13C-NMR計算hyperbranched polymers出的DB值為0.74;並以DMSO為溶劑,求得本質黏度0.22~0.15dLg-1;合成出之高分子皆可溶於DMF、DMAc、DMSO等溶劑中;在光電檢測部分,以即時接觸式極化(in-situ contact poling)裝置施與電場極化並同時監測電光係數,電光係數值約6.4~17.5pm/V之間。研究同時對於材料在60℃下100小時之長時間熱穩定偵測,結果顯示在60℃下經過100小時之熱處理仍有不錯的電光係數,其中以HB32在熱穩定性較佳,仍維持在70%。由於具三維立體結構的hyperbranched polymers有良好的光學透明性、成膜性佳和易加工等特性,未來這種不同於傳統線性高分子的新型材料,會在二次非線性領域中扮演更重要的角色。
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