本文經親核性逐步聚合反應直接合成出一系列可定量控制懸吊磺酸根基團之均聚合物及共聚合物。此新穎共聚合物是利用α-甲基-4, 4’-二苯乙烯(HMS) 、4,4’-二氯二苯碸(DCDPS) 和3,3’-磺酸基-4,4’二氯二苯碸(SDCDPS) 所合成，經由控制HMS、DCDPS和SDCDPS的莫耳比，可以得到由10 mol％到70 mol％有系統性磺酸化程度的共聚物。目的是為了得到具有熱、水解和氧化高穩定性，高分子量且具優良薄膜性質並可傳導質子的共聚物，以期可以使用於燃料電池中的質子交換薄膜。

　　磺酸化共聚物是先合成為鈉塩形式再經由轉換形成酸的形式，並以酸形式的共聚物薄膜於燃料電池的質子交換薄膜操作範圍進行研究。預期水及甲醇水溶液的平衡吸收會和雙苯酚單體的結構以及磺酸化的程度有關，並隨磺酸根基團的增加而增加，同時磺酸化程度亦和熱穩定性、Tg、質子傳導度有著相關聯性。

　　在完全水合的狀態下，磺酸化共聚物的質子傳導度也和雙苯酚單體的結構以及磺酸化程度有關，因此為了要使共聚物薄膜有較佳值必須謹慎考慮聚合物結構和磺酸化的方法，本實驗所合成磺酸化共聚物導電度可以提升至0.1 S/cm以上，並和市售聚全氟性磺酸化高分子
Nafion比較大致相同。

　A designed series of directly copolymerized homo- and disulfonated copolymers containing controlled degrees of pendant sulfonic acid groups have been synthesized via nucleophilic step polymerization. Novel sulfonated poly (arylene ether sulfone) copolymers using α-methylstilbene (HMS), with dichlorodiphenyl sulfone (DCDPS) and 3,3’-disodiumsulfonyl-4,4’-dichlorodiphenylsulfone (SDCDPS) were investigated. Molar ratios of DCDPS and SDCDPS were systematically varied to produce copolymers of controlled compositions, which contained up to 70 mol% of disulfonic acid moiety. The goal is to identify thermally, hydrolytically, and oxidatively stable high molecular weight,
film-forming, ductile ion conducting copolymers, which had properties desirable for proton exchange membranes (PEM) in fuel cells.

　The sulfonated copolymers were prepared in the sodium-salt form and converted to the acid moiety and subsequently investigated as proton exchange membranes for fuel cells. Hydrophilicity increased with the level of disulfonation, as expected. Moreover, water sorption increased with increasing mole percent incorporation of SDCDPS. The copolymers’ water uptake depended on both bisphenol structure and degree of disulfonation. Furthermore, the acidification procedures were shown to influence the Tg, water uptake, and conductivity of the copolymers.

　Proton conductivities for the sulfonated copolymers, under fully hydrated conditions, were a function of bisphenol structure and degree of sulfonation. A careful balance of copolymer composition and acidification method was necessary to afford films which can be both ductile and proton conductive. The copolymers of optimum design yielded conductivities of 0.1 S/cm or higher, which were comparable to those of commercial polyperfluorosulfonic acid films (Nafion™ ).

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