本研究利用縮聚合反應來合成直鏈型硬桿式高分子hPBI與利用2-羥基對苯二甲酸與5-羥基間苯二甲酸以不同比例(50:1，25:1和15:1)進行共聚合反應來形成鉸鏈型硬桿式高分子a-hPBI，兩者分別並接上硫化丙烷鋰離子懸垂基，以形成俱有水溶性的hPBI-PS(Li+)和a-hPBI-PS(Li+)。
直鏈型聚電解質hPBI-PS(Li+)摻雜不同濃度的鋰鹽並澆鑄成膜，其在室溫下平行膜面的直流導電度(σ∥)可達4.02×10-3 S/cm。硬桿式聚電解質hPBI-PS(Li+)其分子量較小造成分子長寬比大幅下降，分子排列較不規則，亂度高，形成較多鋰離子導電通道，鋰鹽陰離子的大小對導電度的影響反而不顯著。經由電子顯微鏡觀察發現並無明顯的層狀薄膜截面結構，證明澆鑄的hPBI-PS(Li+)薄膜有近似於三維等向性的結構及導電性。

Polycondensation reaction was carried out for synthesizing rigid-rod polymer hPBI. Various molar ratios (50:1, 25:1, and 15:1) of 2-hydroterephthalic acid and 5-hydroisophthalic acid were also introduced in the synthesis for articulated rigid-rod polymer a-hPBI. The polymers were further derivatized with 1,3-propanesulton for pendants of lithium ionomer to become water soluble polyelectrolytes hPBI-PS(Li+) and a-hPBI-PS(Li+), respectively.
Lithium salt doped cast film of the rigid-rod polyelectrolyte hPBI-PS(Li+) showed a room-temperature DC conductivity parallel to film surface as high as 4.02×10-3 S/cm. Molecular weight of the rigid-rod polyelectrolyte was low indicating a small molecular aspect ratio. In cast film, the molecules were randomly distributed and highly isotropic facilitated Li cations mobility for a high film conductivity. The conductivity was also insensitive to the anion of lithium salt. No apparent layered structure was revealed by scanning electron microscope suggesting that the cast films had near three-dimensionally isotropic structure and conductivity.

目錄
目錄 I
流程目錄 V
表目錄 VI
圖目錄 VIII
壹、前言 1
貳、文獻回顧 4
2-1 固態聚電解質簡介 4
2-2 硬桿式高分子簡介 8
2-3 導電機制 10
參、研究動機 14
3-1 高分子主鏈的改質 16
3-2 高分子側鏈的改質 17
肆、實 驗 …..20
4-1 單體之合成 20
4-1-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride(簡稱TABTHC)的合成反應 20
4-1-2 羥基對苯二甲酸(2-Hydroxyterephthalic acid) (簡稱MHT)的合成反應 23
4-2 硬桿式高分子合成反應介質 24
4-2-1 聚磷酸的製備 25
4-3 硬桿式聚合物 25
4-3-1 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6- diyl(2-(2- hydroxyl)-p-phenylene)](簡稱hPBI)的合 成反應 26
4-3-2 Poly[1,7-dipropsulfobenzo[1,2-d:4,5-d’]diimidazo- 2,6-diyl(2-[(2-propylsulfo)oxy]-p-phenylene)](簡稱hPBI-PS(Li+))的合成反應 27
4-3-3 利用5-羥基間苯二甲酸合成之鉸鏈型硬桿式聚電 解質的合成反應 30
4-3-4 鉸鏈型硬桿式聚電解質(簡稱ah-PBI-PS(Li+))的合 成反應 31
4-4 甲基磺酸(Methanesulfonic Acid，MSA)的純化 34
4-5 化學分析 35
4-5-1 傅立葉轉換紅外線(Fourier Transform Infrared， FTIR)光譜 35
4-5-2 核磁共振(Nuclear Magnetic Resonance，NMR) 35
4-5-3 元素分析儀(Elemental Analyzer，EA) 36
4-6 聚合物分子量的量測 37
4-7 鋰鹽摻雜和澆鑄成膜 40
4-8 導電度的量測 41
4-9 掃描式電子顯微鏡(Scanning Electron Microscopy，SEM) ..43
伍、實驗結果與討論 45
5-1 單體之合成分析 45
5-1-1 1,2,4,5-Tetraaminobenzene tetrahydrochloride (簡稱TABTHC)的合成反應 45
5-1-2 2-Hydroxyterephthalic acid之化學分析 53
5-2 聚電解質之合成與分析 55
5-2-1 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo-2,6- diyl(2-(2-hydroxyl)-p-phenylene)](簡稱hPBI)之 化學分析 55
5-2-2 Poly[1,7-dihydrobenzo[1,2-d:4,5-d’]diimidazo- 2,6- diyl(2-(2-hydroxyl)-p-phenylene)-co-1,7- dihydrobenzo[1,2-d:4,5-d’]-diimidazo-2,6-diyl (2-(3-hydroxy)-m-phenylene)] (簡稱a-hPBI)之 化學分析 57
5-2-3 Poly[1,7-dipropsulfobenzo[1,2-d:4,5-d’]diimidazo- 2,6-diyl(2-[(2-propylsulfo)oxy]-p-phenylene)](簡稱hPBI-PS)之化學分析 60
5-2-4 Poly[1,7-dipropylsulfobenzo[1,2-d:4,5-d’]diimidazo- 2,6-diyl[(2-(2-sulfpropoxy)-2(3-sulfopropoxy)-m- phenylene](簡稱a-hPBI-PS)之化學分析 62
5-2-5 hPBI之極限黏度的量測 64
5-3 形態微結構檢視 65
5-4 導電度的量測 66
5-4-1 硬桿式聚電解質 68
5-4-2 定電壓導電度的衰退率……………………………..78

陸、結論 82
柒、參考文獻 84

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