合成及鑑定含有茀及直立共軛環為單位之聚苯乙炔衍生物

Abstract

中文摘要 利用以Pd為催化劑的碳-碳偶合反應，合成一系列主鏈方向共軛 而且垂直主鏈方向也共軛的聚苯乙炔衍生物，並以茀及直立共軛三環 為單位。所合成出來的聚合物其重量平均分子量(Mw)為13000-32000，聚分散性(PDI)為1.92-2.64。聚合物的熱性質由熱重分析儀(TGA)及熱微差掃瞄分析儀(DSC)測得，所量測到的聚合物熱裂解(Td)溫度範圍為300-371℃而聚合物的玻璃轉換溫度(Tg)為63-74℃引入茀可以改善聚合物的熱穩定性。而聚合物的光學性質則由紫外光/可見光光譜儀(UV/Vis)和螢光分光光譜儀測得，聚合物在極稀釋的氯仿溶劑中所得到的最大吸收波長範圍為360-377nm，而聚合物在薄膜狀態所測得的吸收光譜與溶液態大致相同，而聚合物在UV激發下所放射出的光為藍綠色螢光(443-471nm);而在薄膜狀態下所放射的光 從藍綠，綠，黃綠皆有。可以發現對於小分子而言，聚合物皆往長波 長方向移動，這可能是由於主鏈上的π共軛拉長所致。聚合物的電化 學性質由循環伏安電化學(CV)所測得，與單聚合物相比較(PFE)可以發現PFE-BBBOC12、PFE-BBBOME、PFE-BBB、PFE-M-PBP傳輸電洞的能力皆大於PFE，而PFE-P-PBP則較有利於電子傳輸。

英文摘要 Synthesis and Characterization of Poly(aryleneethynylene)s Based on Fluorene and Vertical Conjugated Ring Units Student: Hsm-Yi Sheu Advisor :Dr. Hong-Cheu Lin Department of Material Science and Engineering National Chiao Tung University Abstract A series of cross conjugated poly(aryleneethynylene)s based on fluorine(PFE) and vertical phenylene units are synthesized by a palladium-catalyzed coupling reaction. PFE-Ar type polymers have weight average molecular weights (Mw) of 13000∼32000 with polydispersity indices (Mw/Mn) of 1.92-2.64. The thermal properties of the polymers were determined by TGA and GPC. The onset decomposition temperatures (Td) of all polymers are 300-371℃ and the glass transition temperatures (Tg) of these polymers are 63~74℃. By introducing fluorine units can improve the thermal stability of polymers. The optical properties of the polymers are determined by UV (uv-vis) and PL (photoluminescence). All polymers show the maximum absorption in the range of 300~377 nm in diluted chloroform. The absorption in the film are almost identical to those in solution. All polymers in chloroform emit blue-green fluorescence around 443~471 nm. The thin film show greenish-blue, green, and greenish-yellow around 468~535 nm. All polymers show red shift compared with model compound, suggesting that π-conjugation is expanded beyond the neighboring repeating units. The elecchemical properties of all polymers are determined by CV (cyclic voltage). Compared with homopolymer PFE, PFE-BBBOC12, PFE-BBBOME, PFE-BBB, PFE-M-PBP have better hole transporting ability, and PFE-P-PBP have better electron transporting ability than PFE.