第一部分
本研究成功合成主鏈含有疏水基結構之聚苯醚共聚物(SPAEs)，並將磺酸基導入在側鏈上，首先經由親核性取代聚合反應合成含CF3之Poly(arylene ether)s (PAEs)，以Chlorosulfonic acid為磺酸化試劑，直接將聚合物磺酸化，即可得到磺酸基位於側鏈上的SPAEs。
所合成的側鏈型SPAEs，均可塗佈成具有韌性的薄膜，且具有好的熱安定性與機械性質。其質子傳導度會隨著溫度增加而增加，本研究所合成側鏈型SPAEs，大部分它們的質子傳導度比Nafion 117高，在80 ℃，SPAE2系列(IEC=1.90 mequiv./g)有最高的質子傳導度為
200 mS/cm。與主鏈型聚合物相比較，側鏈型SPAEs系列具有相對低吸濕率、膨潤度與相對高質子傳導度的特性，由TEM結果顯示側鏈型SPAEs親水相顆粒直徑約為0.12-0.35 μm且均勻分布，所以較容易形成連續的離子通道，質子傳導度也較高。其甲醇滲透率在0.98~7.05×10-7 cm2/sec之間，都低於Nafion 117(16×10-7 cm2/sec)。因此這些含側鏈型磺酸基的SPAEs具有高質子傳導度、低甲醇滲透率和合理的穩定性，是很有潛力成為直接甲醇燃料電池的質子交換膜材料。

第二部分
本研究成功合成出側鏈含雜環之PBI聚合物，這些聚合物具有好的溶解度，其固有黏度範圍在0.9~2.83 dL/g之間，均可塗佈成具有韌性之薄膜，且有好的熱安定性，於氮氣下開始裂解溫度為488~532℃、高的玻璃轉換溫度(Tg超過350 ℃以上)，它的抗張強度大於78 MPa，但是當摻雜磷酸後，它們的機械強度會下降。在質子導電度方面，導電度隨溫度與磷酸摻雜程度增加而增加，其中PBI-2-10在200 ℃無水的環境下，飽和磷酸摻雜程度為361 wt%，質子導電度為68.9 mS/cm 比m-PBI(58.8 mS/cm)的質子傳導度高，而且這些薄膜於高溫時( >100℃)時質子傳導度都比Nafion 117質子傳導度高。
因此這些側鏈含雜環之PBI薄膜具有高磷酸摻雜量、高質子傳導度和好的熱安定性，是很有潛力成為中溫型燃料電池中質子交換膜材料。

Part I
A series of side-chain-type sulfonated trifluoromethyl-based poly(arylene ether)s (SPAEs) were prepared by polycondensation via a nucleophilic substitution reaction followed by post-sulfonation.
Tough and flexible films of the SPAEs with good thermal and mechanical stability were obtained by solvent cast process in N,N-dimethylacetamide (DMAc) solution. Proton conductivities of the coplymers increased gradually with increase in temperature. Most of SPAEs exhibited higher proton conductivity than Nafion 117. The highest proton conductivity of 200 mS/cm was obtained for SPAE2 coplymers (IEC=1.90 mequiv/g) at 80 ℃. The side-chain-type SPAEs film showed high proton conductivity and good dimensional stability, and their water uptake and swelling ratio were lower than those of the main-chain-type SPAEs with similar ion exchange capacity (IEC) value. Transmission electron microscopy (TEM) was used to examine the microstructures of the membranes and the side-chain-type results revealed that significant hydrophilic/hydrophobic microphase separation with spherical, uniform-size (0.12-0.35 μm) and well-dispersed hydrophilic domains was afforded. In addition, the membranes exhibited low methanol permeability in the range of 0.98~7.05×10-7 cm2/sec, which are much lower than that of Nafion 117 (16×10-7 cm2/sec).
Thus, these side-chain-type SPAEs could be the promising materials as alternative to Nafion membrane for direct methanol fuel cells applications because of them with high proton conductivity, low methanol permeability, and reasonable long-term stability.

Part Ⅱ
A series of new polybenzimidazoles (PBIs) with pendant heterocyclic ring have been synthesized. The resulting polymers showed good solubility in aprotic solvents. They had inherent viscosities in the range of 0.9~2.83 dLg-1, and they could form tough and flexible films. They exhibited high stability with initial decomposition temperature ranging from 488 to 532 ℃, and their glass transition temperature exceeded 350℃. These films exhibited good mechanical properties with tensile stress ranging from 78 to 198 MPa. The proton conductivity of phosphoric acid doped PBI is dependent on doping level and temperatures. The proton conductivity of PBI-2-10 is approximately 68.9 mS/cm at 200℃ under anhydrous conditions at a 361 wt% phosphoric acid doped, compared with 58.8 mS/cm of m-PBI membrane. The PBI membranes showed higher proton conductivity than Nafion 117 membrane at high temperature (>100℃).
Thus, these polybenzimidazoles (PBIs) with pendant heterocyclic ring membranes could be the promising materials alternative to Nafion membrane for medium-temperature fuel cells applications because of they had high phosphoric acid doped, good stability, and higher proton conductivity.

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