本研究成功地合成出三種含有高非線性光學性質發色團4-N,N-bis(2- hydroxyethylene)amino-4’-nitro azobenzene (Disperse Red 19, DR-19)的側鏈型聚胺基甲酸酯(DR-PUn’s)並探討性質，高分子中的二異氰酸酯結構分別為4,4’-methylenebis(phenyl isocyanate)、tolylene-2,4-diisocyanate以及3,3’-dimethoxy-4,4’- biphenylene diisocyanate。另一方面，則以三官能基發色團單體(TDR-19)的合成為目標來進行架橋交聯。

DR-PUn’s可溶於極性非質子溶劑如THF、DMF及環己酮等，藉由旋轉塗佈可得到高光學品質薄膜，然後以電暈極化的方法將薄膜極化。DR-PUn’s玻璃轉移溫度(Tg)的高低由微差掃描熱卡儀(DSC)量測之結果為DR-PU2 > DR-PU1 > DR-PU3依序分別為142.3℃、138.5℃以及136.7℃，其DSC曲線中均沒有熔點而為不定形之狀態。由極化前後吸收光譜的測量可得到DR-PU1、DR-PU2及DR-PU3的序列參數值分別為0.210、0.262以及0.178，三個DR-PUn’s非線性光學性質的長時間熱穩定性會隨著聚胺基甲酸酯的Tg而增加，極化後的DR-PUn薄膜於90℃下非線性光學性質的時間熱穩定性均很優良。為了進一步研究熱交鏈系統所以合成TDR-19，本研究在TDR-19部份的合成經驗與性質探討等可作為相關研究之延續和參考。

In this study, three types of polyurethanes with a highly NLO active chromophore, 4-N,N-bis(2-hydroxy ethylene)amino-4’-nitroazobenzene (Disperse Red 19, DR-19), in the polymer side chain were successfully synthesized (DR-PUn’s) and characterized. The diisocyanate components of the polymers are 4,4’-methylenebis(phenyl isocyanate), tolylene-2,4-diisocyaate and 3,3’-dimethoxy-4,4’- biphenylene diisocyanate. Moreover, a trifunctionalized disperse red-type chromophore (TDR-19) was synthesized for crosslinking.

The DR-PUn’s are readily soluble in polar aprotic organic solvents, like tetrahydrofuran, N,N-dimethyl formamide, cyclohexanone, etc. Good optical quality, poled films were prepared by spin coating, followed by thermal corona poling. The glass transition temperatures (Tg) of DR-PUn’s determined by differential scanning calorimetry (DSC) decrease in the order: DR-PU2 > DR-PU1 > DR-PU3, corresponding to 142.3℃, 138.5℃ and 136.7℃, respectively. They showed no melting points in the DSC curves, suggesting an amorphous phase. The order parameters of DR-PU1, DR-PU2 and DR-PU3 were obtained to be 0.210, 0.262 and 0.178 respectively from absorption measurements before and after poling. The temporal stability of NLO properties for the three DR-PUn’s increases with Tg of the polyurethanes. The poled DR-PUn films exhibited good thermal stability of NLO properties at 90℃. The synthesis of TDR-19 is for the further study of thermally cross-linked systems. The synthesis experiences and property investigations of TDR-19 can be the extension of relative works.

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