201131857 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種高分子電解質，其於低濕 子傳導性優異且因爲水所導致的膨潤少，並關於 高分子電解質所構成之高分子電解質膜，及使用 電解質膜之膜-電極接合體及固體高分子型燃料彳 【先前技術】 近年來，燃料電池技術就能源、環境問題的 策略而言，其爲未來的氫能時代的中心能源變換 柱之一。尤其，固體高分子型燃料電池（PEFC ； Electrolyte Fuel Cell)，從小型輕質化等觀點，探 用的驅動電源或行動設備用電源，更進一步探討 電及熱的家庭定置用的電源設備等。又，使用氫 者，從輸出、經濟性等觀點，期待開創廣泛的用ί 固體高分子型燃料電池，一般而言構成如下 質子傳導性的高分子電解質膜的兩側，配置觸媒 媒層含有載置鉛金屬之金屬觸媒的碳粉末與由高 質構成之離子傳導性黏結劑。於各觸媒層的外側 燃料氣體及氧化劑氣體分別通氣的爲多孔性材料 散層。就氣體擴散層而言，使用碳紙、碳布等。 氣體擴散層成一體化者稱爲氣體擴散電極，又， 體擴散電極分別以使觸媒層與高分子電解質膜互 方式接合於高分子電解質膜而成的構造體，稱爲 度下的離 一種由該 該闻分子 電池。 根本解決 系統的支 Polymer 討電動車 同時利用 作爲燃料 途。 。在具有 層，該觸 分子電解 ，配置將 的氣體擴 觸媒層與 將一對氣 相相對的 膜-電極 -4- 201131857 接合體（MEA; Membrane Electrode Assembly)。該膜—電極 接合體的兩側，配置有具有導電性與氣密性的分離件。對 於電極面供給燃料氣體或氧化劑氣體（例如空氣）的氣體流 路，形成在膜-電極接合體與分離件的接觸部分或分離件 內。對於其中之一的電極（燃料極）供給燃料氣體，對於另 一電極（氧極）供給含有氧的氧化劑氣體（空氣等）並發電。亦 即，於燃料極，燃料經離子化而產生質子與電子，質子透 過高分子電解質膜，電子藉由將兩電極連接而藉此在形成 的外部電路移動，分別到達氧極，並與氧化劑氣體反應而 生成水。如此，可將燃料的化學能直接變換爲電能並取出。 該等的固體高分子型燃料電池，如於上述一般的用途 中，並非連續運轉，通常係進行重複起動、運轉、停止的 間歇運轉。運轉時，高分子電解質膜會處於濕潤下，但是， 停止時會發生膜的濕度降低。因此，爲了於起動時迅速發 揮性能’希望有即使在低濕度下也具有高質子傳導性的高 分子電解質膜。 一般而言’固體高分子型燃料電池用的高分子電解質 膜’由於化學性安定的理由，係使用全氟碳磺酸系高分子 納菲薄膜（Nafi〇n、杜邦公司的註冊商標。以下同）。但是， 納菲薄膜雖於低濕度下的離子傳導性優異，但是長期使用 時或廢棄時就分解物而言可能會發生對於環境產生不好影 響的氟系化合物。且，有燃料透過性高、昂貴等缺點，因 此對於代替材料有所需求。 201131857 而’近年來就替代納菲薄膜等全氟碳磺酸系高分子的 材料而言，有人提出烴系材料。具體而言，有在聚醚楓（PEs) 或聚醚醚酮（PEEK)爲代表的工程塑膠系聚合物中導入磺酸 基等離子傳導性基而成的材料。 例如，專利文獻1提出PES的磺酸化物。如此的材料 由於不含氟’因此即便材料發生劣化，也完全不會發生氟 系化合物。又’雖然離子傳導性基導入或製膜等製造技術 方面存有課題’但是原料高分子本身比起全氟碳磺酸系高 分子在價格方面仍爲有利。 但是，使用此等工程塑膠系聚合物的高分子電解質， 由於離子傳導性基在分子內均勻分散，因此，離子傳導性 基的密度—低，難以達成高離子傳導性。 爲了形成高離子傳導性基密度的離子通道，有人提出 具有已導入離子傳導性基之聚合物嵌段及未導入離子傳導 性基之聚合物嵌段的變性PES的磺酸化物（參照專利文獻 2)’但是由於係縮合系聚合物，在合成時會發生重複單元 的交換反應’嵌段構造毀壞，造成無法獲得相分離構造， 無法形成足夠的離子通道。 另一方面，專利文獻3記載的高分子電解質膜，係由 具有芳香族乙烯基系聚合物嵌段與脂肪族乙烯基系聚合物 嵌段的嵌段聚合物構成，該等由於不會發生如上述重複單 元的交換反應，因此可維持嵌段構造。因此，能利用嵌段 聚合物特有的相分離構造而形成離子通道。 -6 - 201131857 [先前技術文獻] [專利文獻] [專利文獻1] 日本特開平10— 045913號公報 [專利文獻2] 日本特開平1 3 — 2 5 05 67號公報 [專利文獻3] 日本特開2〇〇6— 210326號公報 【發明內容】 [發明欲解決之課題] 但是’由具有芳香族乙烯基系聚合物嵌段與脂肪族乙 烯基系聚合物嵌段的嵌段聚合物構成的高分子電解質膜， 於低濕度狀態的性能不足，即使提高離子交換容量在性能 上仍有極限。因此，實際上爲在低濕度狀態無法確保足夠 的離子傳導性。 又，該高分子電解質膜使用於固體高分子型燃料電池 時’希望具有固體高分子型燃料電池於發電中因爲與高分 子電解質膜接觸的水所致之膨潤少的特性。高分子電解質 膜若因爲膨潤而變形，則於膜一電極接合體中，容易發生 高分子電解質膜從電極剝離等情形。又，前述固體高分子 型燃料電池的間歇運轉中，會發生高分子電解質膜的顯著 形狀變化，甚至發生破壞等對於長期耐久性可能有不好 的影響。 [解決課題之方式] 本案發明人等’爲了解決上述課題努力探討，結果發 現：提供由至少以芳香族乙烯基系聚合物嵌段（A)與脂肪族 201131857 乙烯基系聚合物嵌段（B)作爲構成成分的嵌段共聚物 成，且前述芳香族乙烯基系聚合物嵌段（A)中每一重複單元 的離子傳導性基含量爲1.5至3.0個，且前述脂肪族乙烯基 系聚合物嵌段（B)不具離子傳導性基的高分子電解質，可解 決上述課題，乃完成本發明。 亦即，申請專利範圍第1項記載之發明，係關於一種 高分子電解質，其特徵在於：由至少以芳香族乙烯基系聚 合物嵌段（A)與脂肪族乙烯基系聚合物嵌段（B)作爲構成成 分的嵌段共聚物所構成，且該芳香族乙烯基系聚合物嵌段 (A)中之每一重複單元的離子傳導性基含量爲1.5至3.0 個’且該脂肪族乙烯基系聚合物嵌段（B)係不具有離子傳導 性基。 又’申請專利範圍第2項記載之發明，係關於如申請 專利範圍第1項之高分子電解質，其中該芳香族乙烯基系 聚合物嵌段（A)佔該高分子電解質的5至50重量％。 又’申請專利範圍第3項之發明’係關於如申請專利 範圍第1項之高分子電解質’其中該芳香族乙烯基系聚合 物嵌段（A)每lg的離子傳導性基含量爲4 8meq/g以上。 又’申請專利範圍第4項記載之發明，係關於如申請 專利範圍第1項之高分子電解質’其中該脂肪族乙烯基系 聚合物嵌段（B)係以選自由碳數爲2至8之烯單元碳數爲 5至8之環烯單元、碳數爲7至1〇之乙烯基環烷單元、碳 數爲7至10之乙烯基環烯單元、碳數爲4至8之共軛二烯 -8- 201131857 單元及碳數爲5至8之共軛環烷二烯單元所構成的群組中 至少一種重複單元作爲主成分的橡膠狀聚合物嵌段。 又，如申請專利範圍第5項記載之發明，係關於如申 請專利範圍第1項之高分子電解質，其中該離子傳導性基 爲質子傳導性基。 又，如申請專利範圍第6項之發明，係關於如申請專 利範圍第1項之高分子電解質，其中含有20至60重量％ 的芳香族乙烯基系聚合物嵌段（C)作爲構成成分，該芳香族 乙烯基系聚合物嵌段（C)主要以不具有離子傳導性基之芳 香族乙烯基系化合物單元作爲重複單元。 又，申請專利範圍第7項記載之發明，係關於如申請 專利範圍第6項之高分子電解質，其中該芳香族乙烯基系 化合物單元係在芳香環上具有1至3個碳數爲1至8之烴 基的經取代之芳香族乙烯基系化合物單元，該芳香族乙烯 基系化合物單元係爲該芳香族乙烯基系聚合物嵌段（C)之 主要重複單元。 又，申請專利範圍第8項記載之發明，係關於一種高 分子電解質膜，其係由如申請專利範圍第1項之高分子電 解質所構成者。 又，申請專利範圍第9項記載之發明，係關於一種膜-電極接合體，其係如申請專利範圍第8項之高分子電解質 膜與電極層的多層結構。 -9- 201131857 又’申請專利範圍第1 〇項記載之發明，係關於一種固 體高分子型燃料電池，其係包含如申請專利範圍第9項之 膜-電極接合體。 [發明之效果] 本發明之高分子電解質嵌段共聚物，具有芳香族乙烯 基系聚合物嵌段（Α)與脂肪族乙烯基系聚合物嵌段（Β)發生 微相分離，芳香族乙烯基系聚合物嵌段（Α)彼此與脂肪族乙 烯基系聚合物嵌段（Β)彼此分別集合的性質，由於芳香族乙 烯基系聚合物嵌段（Α)具有離子傳導性基，因此芳香族乙烯 基系聚合物嵌段（Α)彼此的集合會形成離子通道，而成爲質 子等離子的通路。 又，在此，「微相分離」係指微觀上的相分離，更詳言 之’意指形成的微域大小在可見光的波長（3800至7800埃） 以下的相分離。 前述芳香族乙烯基系聚合物嵌段（Α)中，每一重複單元 的離子傳導性基含量爲1.5至3.0個，且前述脂肪族乙烯基 系聚合物嵌段（Β)不具有離子傳導性基，藉此該離子通道以 高密度存在離子傳導性基。 其結果，由本發明之高分子電解質構成的高分子電解 質膜，相分離顯著發生，離子傳導性提高，尤其於低濕度 狀態具有高離子傳導性，藉由將含有該高分子電解質膜而 形成的膜一電極接合體使用在固體高分子型燃料電池’於 低濕度狀態也能得到高輸出特性，且因爲水所致的膨潤也 少，與電極的接合性亦優異。 -10- 201131857 【實施方式】 以下就本發明詳細説明。 構成本發明之高分子電解質的嵌段共聚物’係以芳香 族乙矯基系聚合物嵌段（A)作爲構成成分。該方香族乙燦基 系聚合物嵌段（A)係以芳香族乙烯基系化合物單元作爲主 要的重複單元，且每一重複單元的離子傳導性基含量爲15 至3.0個’但可視高分子電解質要求的性能等而適當選擇。 由離子傳導性的觀點，以1ι7個以上較佳，由磺酸基導入 的容易度的觀點，以1 . 5個至2.0個較佳。 在此，爲芳香族乙烯基系聚合物嵌段（A)之重複單元的 芳香族乙烯基系化合物單元，係指可利用芳香族乙烯基系 化合物的聚合而形成的構造。該芳香族乙烯基系化合物， 係指一化合物具有至少1個芳香環及至少1個含有加成聚 合性碳雙鍵的官能基，該含有加成聚合性碳雙鍵的官能基 直接鍵結在至少1個芳香環上的碳原子。 例如苯環等芳香環上的氫取代爲乙烯基、1-烷基乙烯 基（例如異丙烯基）、1一芳基乙烯基等取代基後的化合物。 具體而言，例如苯乙烯、α—甲基苯乙烯 '二苯基乙烯。 又，可形成芳香族乙烯基系聚合物嵌段（Α)的重複單元 即芳香族乙烯基系化合物單元的芳香族乙烯基系化合物， 以形成芳香環的碳原子爲1 〇以上者較佳。例如，具有多個 苯環等碳數10以下的芳香環的化合物、具有該碳數10以 下之芳香環縮合後的縮合環的化合物。 -11- 201131857 具有多個苯環的芳香族乙烯基系化合物的例子，例如 乙烯基聯苯、乙烯基聯三苯、苯氧基苯'乙烯、二苯基乙烯。 又，前述縮合環例如：萘環、菲環、蒽環、芘環、筷環、 弗環。該等芳香族乙烯基系化合物的具體例，例如乙烯基 萘、乙烯基菲、乙烯基蒽、乙烯基芘、乙烯基筷、乙烯基 蒹。 其中從重複單元的分子量小、構造緊密，對於離子通 道的高密度化有利之觀點’乙烯基萘、乙烯基聯苯、乙烯 基聯三苯較佳，由離子傳導性基的導入容易性的觀點，乙 烯基聯苯又更佳。 芳香族乙烯基系化合物單元的平均分子量爲400以下 較佳，3 00以下更佳、200以下又更佳。該平均分子量，於 重複單元的芳香族乙烯基化合物單元爲具有離子傳導性基 時’係假定芳香族乙烯基系聚合物嵌段全部的離子傳導性 基取代爲氫的聚合物嵌段（亦即，不具有對應的離子傳導性 基的聚合物嵌段）而計算。重複單元的平均分子量若過大， 則離子通道的密度有時會下降爲不佳。 將芳香族乙烯基系化合物聚合成芳香族乙烯基系聚合 物嵌段（A)時’可將2種以上芳香族乙烯基系化合物組合使 用。使該等2種以上共聚合時的形態，無規共聚合、嵌段 共聚合、接枝共聚合、錐形（tapered)共聚合均可。 -12- 201131857 又，在無損發明效果的範圍內，芳香族乙烯基系聚合 物嵌段（A)也可含有1種或多數其他單體單元。可構成該其 他單體單元的單體’例如：碳數4至8之共軛二烯（1,3 — 丁 二稀、1，3 —戊二烯、異戊二烯、l，3 —己二烯、2,4 一己二 烯、2,3_ 二甲基一1,3 — 丁 二烯、2 —乙基一1，3_ 丁 二烯、 1，3—庚二烯、1，4—庚二烯'3,5—庚二烯等）'碳數2至8 之烯（乙烯、丙烯、1— 丁烯、2_ 丁烯、異丁烯、1_戊烯、 2 —戊稀、1_己稀、2 —己稀、1一庚嫌、2 —庚嫌、1 一辛 烯、2 —辛烯等）、（甲基）丙烯酸酯（（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸丁酯等）、乙烯基酯（乙酸乙 烯酯、丙酸乙烯酯、丁酸乙烯酯、三甲基乙酸乙烯酯等）、 乙烯基醚（甲基乙烯基醚 '異丁基乙烯基醚等）等。與上述 其他單體的共聚合形態，無規共聚合爲理想。 芳香族乙烯基系聚合物嵌段（A)佔前述高分子電解質 的5至50重量％，於使高分子電解質膜兼顧離子傳導性與 耐水性方面爲較佳。從離子傳導度的觀點，佔35至50重 量％更佳’從耐水性的觀點，佔5至25重量％更佳，爲了 兼顧離子傳導度與耐水性，佔2 0至4 0重量％更佳。 芳香族乙烯基系聚合物嵌段（A)，藉由以芳香族乙烯基 系化合物單元作爲主要的重複單元，對於發生與脂肪族乙 烯基系聚合物嵌段（B)的微相分離方面爲有利，其結果可提 高離子傳導性。該芳香族乙烯基系化合物單元爲主要的重 複單元’係指佔芳香族乙烯基系聚合物嵌段（A)的超過80 201131857 重量％，爲了賦予充分的離子傳導性’佔90重量％以上更 佳，佔9 5重量％以上又更佳。若低於8 0重量％，則芳香族 乙烯基系聚合物嵌段（A)當中每一重複單元的離子傳導性 基含量減少，離子傳導性基的密度也降低，故有時會得不 到本發明的效果。在此，該重量比例係假定芳香族乙嫌基 系聚合物嵌段的全部離子傳導性基取代爲氫的聚合物嵌段 (亦即不具有對應的離子傳導性基的聚合物嵌段）而計算。 如此，本發明所指芳香族乙烯基系聚合物嵌段（A)，不 僅指同種單體連續而構成主鏈者，只要是以芳香族乙稀基 系化合物單元作爲主要重複單元，且能形成均勻相者即包 含在內。又，相的觀察可利用穿透型電子顯微鏡（TEM)進 行。亦即，將由高分子電解質製作的高分子電解質膜以環 氧樹脂包埋後，使用冰凍超薄切片機（cry〇-ultramicrotome；> 製作厚度約90nm的超薄切片，將該超薄切片以乙酸鉛染 色，藉此可觀察芳香族乙烯基系聚合物嵌段（A)。 每一個芳香族乙烯基系聚合物嵌段（A)的分子量，可視 高分子電解質的性狀、要求的性能、其他聚合物成分等而 適當選擇。分子量大時，獲得的高分子電解質膜會傾向於 力學特性提高，但是若過大，則嵌段共聚物的成形、製膜 變得困難，分子量小時，不易形成微相分離構造，甚至不 易形成離子通道’因此’會有離子傳導性、力學特性降低 的傾向，因此視必要性能適當選擇分子量係爲重要。 -14- 201131857 每一個芳香族乙烯基系聚合物嵌段（A)的分子量，若就 將離子傳導性基取代爲氫之構造（亦即不具有對應的離子 傳導.性基的嵌段共聚物）進行計算，就標準聚苯乙烯換算的 數量平均分子量而言，通常從1，000至1，〇〇〇,〇〇〇之間選 擇，從2,000至250,000的範圍選擇較佳，從3,〇〇〇至 100,000之間選擇尤佳，從4,000至50,000之間選擇更佳， 從5,000至25,000之間選擇特佳。又，從製膜時的溶液製 備的容易度及製膜性的觀點，從5,000至1〇,〇〇〇之間選擇 較佳。 又，在不損及本發明效果的範圍內，也可將芳香族乙 烯基系聚合物嵌段（A)以習知方法交聯。藉由導入交聯，芳 香族乙烯基系聚合物嵌段（A)形成的離子通道相不易膨 潤，乾燥時與濕潤時的力學特性（拉伸特性等）的變化等有 變得更小的傾向。 芳香族乙烯基系聚合物嵌段（A)每lg的離子傳導性基 的莫耳數（A嵌段IEC)，爲了展現本發明的效果，以 4.8meq/g以上較佳’ 5.1meq/g以上更佳，5.6meq/g以上又 更佳。 芳香族乙烯基系聚合物嵌段（A)具有的離子傳導性 基，不特別限定，可使用具有離子傳導性的官能基，以與 陰離子及/或與陽離子的親和性高者，尤其官能基的一部分 容易解離成離子者爲適當，例如磺酸基、膦酸基、羧酸基、 4級銨鹽、吡啶之4級鹽等。尤其，質子傳導性基或該質 -15- 201131857 子傳導性基之質子交換爲其他離子而成的鹽的質子傳導性 優異’例如擴酸基、膦酸基、羧酸基及該等的鹽。由離子 傳導性、導入容易性、價格等觀點，宜使用磺酸基及膦酸 基及該等之鹽。藉由適當選擇離子傳導性基的種類或濃 度’可調整離子交換容量。 芳香族乙稀基系聚合物嵌段（A)中，關於離子傳導性基 的位置無特別限制’但從離子傳導性基導入的容易性的觀 點’較佳爲導入到芳香族乙烯基系化合物單元的芳香環上。 又’構成本發明之高分子電解質的嵌段共聚物，係以 脂肪族乙稀基系聚合物嵌段（B)作爲構成成分。該脂肪族乙 稀基系聚合物嵌段（B)，係以脂肪族乙烯基系化合物單元作 爲主要的重複單元，且不具有離子傳導性基。 在此’脂肪族乙烯基系聚合物嵌段（B)的主要重複單 元’即脂肪族乙烯基系化合物單元，係指能利用脂肪族乙 嫌基系化合物的聚合而形成的構造。該脂肪族乙烯基系化 合物’係指一化合物含有至少1個含加成聚合性碳雙鍵的 官能基’該含加1成聚合性碳雙鍵的官能基直接鍵結在至少 一個未構成芳香環的碳原子。 前述脂肪族乙烯基系化合物單元，例如：碳數2至8之 烯單元、碳數5至8之環烯單元、碳數7至10之乙烯基環 烷單元、碳數7至1〇之乙烯基環烯單元、碳數4至8之共 軛二烯單元及碳數5至8之共軛環烷二烯單元。從該等群 組選擇的重複單元可單獨使用或將2種以上組合使用。使 -16- 201131857 2種以上聚合（共聚合）時的形態，爲無規共聚合、嵌段共聚 合、接枝共聚合、錐形共聚合均可。又，供聚合之單體具 有多個碳-碳雙鍵時，可將其中任一者用在聚合，爲共麵 二烯時，有多種可聚合的位置（例如利用1，3 —二烯的丨2 一鍵結、3，4 —鍵結、1，4 —鍵結進行聚合），但不特別限定， 其比例（例如1，2 -鍵結與1，4 —鍵結的比例）也無特別限制。 構成如此的單體單元的單體當中，碳數2至8的燦， 例如：乙烯、丙烯、1_ 丁烯、2 — 丁烯、異丁烯、1_戊燦、 2 —戊烯、1一己烯、2-己烯、1—庚烯' 2_庚烯、1〜辛 烯、2_辛烯等；碳數5至8的環烯，例如環戊烯、環己燦、 環庚烯及環辛烯等；碳數7至10的乙烯基環烷，例如：乙；)¾ 基環戊烷、乙烯基環己烷 '乙烯基環庚烷、乙烯基環辛院 等；碳數7至10的乙烯基環烯，例如：乙烯基環戊烯、乙稀 基環己烯、乙烯基環庚烯、乙烯基環辛烯等；碳數4至8的 共軛二烯，例如：1，3— 丁二烯、1，3 —戊二烯、異戊二烯、 1，3—己二儲、2，4 一己二烧、2,3 —二甲基一丨，3 — 丁二稀、 2_乙基一 1，3 -丁二烯、1，3 —庚二烯、2,4_庚二烯等；碳 數5至8的共軛環烷二烯，例如：環戊二烯、I，3—環己二烯 等。該等單體可以單獨使用，也可併用2種以上。 用於形成脂肪族乙烯基系聚合物嵌段（B)的單體’於如 乙烯基環烯或共軛二烯或共軛環烷二烯的情形爲具有多個 碳一碳雙鍵時，聚合後的重複單元雖具有碳一碳雙鍵，但 也可將使該等飽和後之構造作爲重複單元。該等係使上述 -1 7- 201131857 單體聚合時，可藉由將殘留的碳一碳雙鍵氫化而獲得。從 使用本發明之高分子電解質膜的膜一電極接合體，其發電 性能、耐熱劣化性的提升等觀點，該碳-碳雙鍵的3 0莫耳 %以上經氫化的構造較佳，50莫耳％以上經氫化的構造更 佳’ 80莫耳％以上經氫化的構造又更佳。碳_碳雙鍵的存 在率（或氫化率），可利用一般使用的方法例如：碘價測定 法、1H — NMR測定等計算。 脂肪族乙烯基系聚合物嵌段（B)，由對於獲得的嵌段共 聚物賦與彈力性，甚至是膜-電極接合體或固體高分子型 燃料電池製作時賦予良好成形性的觀點，較佳爲爲由碳數 2至8之烯單元、碳數5至8之環烯單元、碳數7至10之 乙烯基環烯單元、碳數4至8之共軛二烯單元及碳數5至 8之共軛環烷二烯單元構成之群組中選擇的至少一種重複 單元構成的聚合物嵌段，更佳爲由碳數3至6之烯單元、 碳數4至6之共軛二烯單元選擇之至少1種重複單元構成 的聚合物嵌段，又更佳爲由碳數4至5之烯單元、碳數4 至5之共軛二烯單元選擇之至少1種重複單元構成之聚合 物嵌段。 上述中，作爲烯單元的較佳者’例如：異丁烯單元、使 1，3 - 丁二烯單元的雙鍵飽和後的構造單元（1— 丁烯單 元、2-丁烯單元）、使異戊二烯單元的雙鍵飽和後的構造 單元（2 —甲基一1 一丁烯單元、3 —甲基一 1~ 丁烯單元、2 -甲基一 2 - 丁烯單元），尤其從柔軟性高低的觀點，最佳 -18- 201131857 爲使u— 丁二烯單元的雙鍵飽和後之構造單元（1_ 丁烯 單元、2 - 丁烯單元）、使異戊二烯單元的雙鍵飽和後的構 造單兀（2 —甲基一 1 一丁烯單元、3_甲基—丨一丁烯單元、 2_甲基_2- 丁烯單元）。就共軛二烯單元而言，最佳者爲 1，3 — 丁二烯單元、異戊二烯單元。 脂肪族乙烯基系聚合物嵌段（B)，以脂肪族乙烯基系化 合物單元爲主要的重複單元，亦即，脂肪族乙烯基系化合 物單兀超過50重量％ ’超過70重量％者較佳，超過90重 量％者更佳。 脂肪族乙烯基系聚合物嵌段（B)，除了上述重複單元以 外’在不損及對於嵌段共聚物賦予彈力性的脂肪族乙烯基 系聚合物嵌段（B)的目的的範圍內，也可含有其他重複單元 例如苯乙烯單元、乙烯基萘單元等芳香族乙烯基系化合物 單元、氯化乙烯基單元等含鹵素之乙烯基化合物單元、具 有碳數1至12的側鏈的丙烯酸酯單元、及具有碳數1至 12的側鏈的甲基丙烯酸酯單元等。於該情形，上述單體與 其他單體的共聚合形態’宜爲無規共聚合。該其他單體的 使用量，爲少於脂肪族乙烯基系聚合物嵌段（B)的50重量 %，少於3 0重量％更佳，少於1 0重量％又更佳。 脂肪族乙烯基系聚合物嵌段（B)製成橡膠狀聚合物嵌 段時，嵌段共聚物全體帶有彈力性且柔軟，製作膜-電極 接合體或固體高分子型燃料電池時的成形性（組裝性、接合 性、緊固性等）等改善。在此所指橡膠狀聚合物嵌段，係指 -19- 201131857 玻璃轉移點或軟化點爲3 0 °C以下，較佳爲2 0 °C以下，更佳 爲l〇°C以下的聚合物嵌段。 聚合物嵌段（B)製成橡膠狀聚合物嵌段時，以由碳數2 至8之烯單元、碳數5至8之環烯單元、碳數7至10之乙 烯基環烷單元、碳數7至10之乙烯基環烯單元、碳數4至 8之共軛二烯單元及碳數5至8之共軛環烷二烯單元構成 之群組選擇的至少1種重複單元作爲主成分較佳，以由碳 數2至5之烯單元、碳數4.至5之共軛二烯單元構成之群 組選擇的至少1種重複單元作爲主成分更佳。 脂肪族乙烯基系聚合物嵌段（B)每一個的分子量，可視 高分子電解質的性狀、要求性能、其他聚合物成分等適當 選擇。就標準聚苯乙烯換算的數量平均分子量而言，通常 從1,000至1，〇〇〇,〇〇〇之間選擇，從5,〇〇〇至500,000之範 圍選擇較佳，從10,000至200,000之間選擇更佳。又，脂 肪族乙嫌基系聚合物嵌段（B)製成橡膠狀聚合物嵌段時，從 兼顧成形性及柔軟性的觀點’從1 5，〇 〇 〇至丨2 〇，〇 〇 〇之間選 擇尤佳。 脂肪族乙稀基系聚合物嵌段（B)不具離子傳導性基。在 此’不具離子傳導性基’係指實質上不具離子傳導性的程 度，於提局與芳香族乙烯基系聚合物嵌段（A)的微相分離性 的方面，例如每一重複單元的離子傳導性基含量爲個 以下較佳，0.01個以下更佳，完全沒有最佳。但，製造上， 母一重複單元含有約0.001至〇 〇5個的離子傳導性基，有 時會較有利。 -20- 201131857 脂肪族乙烯基系聚合物嵌段（B)爲疏水性時可使其與 芳香族乙烯基系聚合物嵌段（A)的相分離良好地發生故爲 較佳。例如實質上不具羥基、胺基等親水性基較佳，實質 上不具酯基等極性基亦爲較佳。 以芳香族乙烯基系聚合物嵌段（A)與脂肪族乙烯基系 聚合物嵌段（B)作爲構成成分的嵌段共聚物的嵌段構造不 特別限定，但是有多個芳香族乙烯基系聚合物嵌段（A)爲理 想，至少一個脂肪族乙烯基系聚合物嵌段（B )的兩端不是嵌 段共聚物的末端爲理想。例子例如：A _ B _ A型三嵌段共聚 物、A—B— A型三嵌段共聚物與A—B型二嵌段共聚物的 混合物、A— B— A—B型四嵌段共聚物、Α_Β— Λ—Β— A 型五嵌段共聚物、B— A — B — A— B型五嵌段共聚物、（A -B)nX型共聚物（X表示偶合成分）、（B—A)nX型共聚物（X 表示偶合成分）等。該等嵌段共聚物’可分別單獨使用’也 可組合2種以上使用。在此’嵌段共聚物具有多個芳香族 乙烯基系聚合物嵌段（A)及/或脂肪族乙烯基系聚合物嵌段 (B)時，該等嵌段可相同也可不同。 構成本發明之高分子電解質的嵌段共聚物中’構成該 嵌段共聚物的芳香族乙烯基系聚合物嵌段（A)與脂肪族乙 烯基系聚合物嵌段（B)的重量比’可視獲得的嵌段共聚物的 要求性能適當選擇，但是，從離子傳導度的觀點，95:5至 5 5:45較佳，從耐水性的觀點’ 45:5 5至5:95較佳’爲了兼 顧離子傳導度與耐水性，以60:40至40:60較佳。該重量 -2 1- 201131857 比爲95:5至5:95時，由於微相分離使芳香族乙烯基系聚 合物嵌段（A)形成之離子通道爲圓柱狀或連續相爲有利’實 用上可展現足夠的離子傳導性，又，爲疏水性的脂肪族乙 烯基系聚合物嵌段（B)的比例爲適當，可顯現優異的耐水 性。又，在此，上述重量比係假定嵌段共聚物的全部離子 傳導性基取代爲氫後的聚合物嵌段而計算。 本發明使用的嵌段共聚物，也包含一部分爲接枝鍵結 者。一部分包含接枝鍵結的嵌段共聚物，例如構成的聚合 物嵌段的一部分以接枝鍵結於嵌段共聚物的主要構造（例 如主鏈）者等。 本發明使用的嵌段共聚物的數量平均分子量無特限 制，但是，不考慮離子傳導性基的數量平均分子量，就標 準聚苯乙烯換算的數量平均分子量而言，通常以10,〇〇〇至 1，000,000 較佳，15,000 至 700,000 更佳，20,000 至 500,000 又更佳。 構成本發明之高分子電解質的嵌段共聚物，於芳香族 乙烯基系聚合物嵌段（A)必需具有離子傳導性基。本發明 中，提及離子傳導性時的離子，可列舉質子等。離子傳導 性基，只要是使用該高分子電解質製作之膜-電極接合體 可展現足夠的離子傳導度的基即可，不特別限定，其中又 以- S03M或一P〇3HM(式中，Μ表示氫原子、銨離子或鹼 金屬離子）表示的磺酸基、膦酸基或此等的鹽爲理想。又’ 離子傳導性基，可使用羧基或其鹽。藉由使芳香族乙烯基 -22- 201131857 系聚合物嵌段（A)具有離子傳導性基，對於提高高分子電解 質的耐自由基性特別有效。 離子傳導性基的導入量，可視獲得的嵌段共聚物要求 的性能等適當選擇’但是爲了展現作爲固體高分子型燃料 電池用高分子電解質膜使用的足夠離子傳導性，通常使嵌 段共聚物之離子交換容量（全體IEC)爲〇.4 0m eq/g以上之量 較佳’爲0_50meq/g以上之量更佳，爲0.60meq/g以上之量 又更佳。關於嵌段共聚物的離子交換容量的上限，若離子 交換容量過大’則親水性增高、耐水性有不足的傾向，因 此以4.5meq/g以下較佳，4.0meq/g以下更佳，3.5meq/g以 下又更佳。 本發明使用的嵌段共聚物，也可含有主要以不具離子 傳導性基之芳香族乙烯基系化合物單元作爲重複單元的芳 香族乙烯基系聚合物嵌段（C)。 藉由使芳香族乙烯基系聚合物嵌段（C)佔前述高分子 電解質的20至60重量％，作爲膜使用時的機械強度優異 且較佳。更佳爲佔23至50重量％，又更佳爲佔25至40 重量％。 主要以不具有離子傳導性基的芳香族乙嫌基系化合物 單元作爲重複單元的芳香族乙烯基系聚合物嵌段（C)’係指 以芳香族乙烯基系化合物單元作爲主要重複單元的聚合物 嵌段。該聚合物嵌段，使高分子電解質的成形體（例如高分 子電解質膜）的形狀安定性優異。因此，脂肪族乙烯基系聚 -23- 201131857 合物嵌段（B)爲橡膠狀聚合物嵌段時尤其有用。芳香族乙烯 基系聚合物嵌段（C)’與芳香族乙烯基系聚合物嵌段（A)、 脂肪族乙烯基系聚合物嵌段（B)均相分離並形成拘束相較 佳。亦即，由於不具有離子傳導性的芳香族乙烯基系聚合 物嵌段（C)形成獨立的相，故能成爲形狀安定性更爲優異 者。 芳香族乙烯基系聚合物嵌段（C)，主要以不具離子傳導 性基的芳香族乙烯基系化合物單元作爲重複單元。在此， 主要以不具離子傳導性基的芳香族乙烯基系化合物單元作 爲重複單元，係指芳香族乙烯基系聚合物嵌段（C)實質上不 具離子傳導性的程度，例如芳香族乙烯基系聚合物嵌段（C) 的每一重複單元的離子傳導性基含量爲0.1個以下，更佳 爲0.01個以下，最佳爲完全沒有。或，相對於芳香族乙烯 基系聚合物嵌段（A)具有的離子傳導性基爲1/10以下較 佳’ 1/20更佳，1/100以下更佳。其結果，芳香族乙烯基 系聚合物嵌段（C)實質上變爲不具離子傳導性，與形成離子 通道的芳香族乙烯基系聚合物嵌段（A)的相分離可良好地 展現’因此能有效率地進行離子傳導。 藉由芳香族乙烯基系聚合物嵌段（C)爲疏水性，與芳香 g I稀基系聚合物嵌段（A)的相分離可良好地發生，故爲較 佳。例如實質上不具羥基、胺基等親水性基較佳，實質上 不具酯基等極性基亦爲較佳。 -24- 201131857 在此，芳香族乙烯基系聚合物嵌段（C)的主要重複單元 即芳香族乙儲基系化合物單元，係能利用芳香族乙嫌基系 化合物的聚合形成的構造。該芳香族乙烯基系化合物，係 指一化合物具有至少1個芳香環以及至少1個含有加成聚 合性碳雙鍵的官能基，該含有加成聚合性碳雙鍵的官能基 直接鍵結在至少一個芳香環上之碳原子。 上述芳香族乙烯基系化合物具有的芳香環，以碳環式 芳香環較佳，例如苯環、萘環、蒽環、芘環等。該等芳香 族乙烯基系化合物，芳香族乙烯基系化合物單元以在芳香 環上具有1至3個碳數1至8之烴基的取代芳香族乙烯基 系化合物單元爲理想。例如，將芳香環上的氫取代爲乙烯 基、1_烷基乙烯基（例如異丙烯基）、1 一芳基乙烯基等取 代基而成的化合物。例如，苯乙烯、2 —甲基苯乙烯、3-甲基苯乙烯、4 —甲基苯乙烯、4_乙基苯乙烯、4_正丙基 苯乙烯、4_異丙基苯乙烯、4 —正丁基苯乙烯、4 -異丁基 苯乙烯、4_第三丁基苯乙烯、4_正辛基苯乙烯、2，4 一二 甲基苯乙烯、2，5 —二甲基苯乙烯、3,5—二甲基苯乙烯、 2，4,6_三甲基苯乙烯、2 —甲氧基苯乙烯、3_甲氧基苯乙 烯、4 —甲氧基苯乙烯、乙烯基萘、乙烯基蒽、將鍵結於α 一碳原子的氫原子取代爲碳數1至4之烷基（甲基、乙基、 正丙基、異丙基、正丁基、異丁基、第二丁基、或第三丁 基）、碳數1至4之鹵化烷基（氯甲基、2 —氯乙基、3-氯 乙基等）或苯基而成的芳香族乙烯基系化合物（具體而言，α -25- 201131857 —甲基苯乙烯、α，4_二甲基苯乙烯、α —甲基—4 —乙基苯 乙烯、a—甲基—4 —第三丁基苯乙烯、α 一甲基—4 一異丙 基苯乙烯、1，1—二苯基乙烯等）。 該等可使用1種或將2種以上組合使用，但其中又以 4_第三丁基苯乙烯、4—異丙基苯乙烯、α—甲基_4 一第 三丁基苯乙烯、α_甲基-4 —異丙基苯乙烯較佳。使該等 的2種以上共聚合時’共聚合形態爲無規共聚合、嵌段共 聚合、接枝共聚合、錐形共聚合均可*。 芳香族乙烯基系聚合物嵌段（C)，在無損於本發明效果 之範圍內，也可含有1種或多種其他單體單元。該其他單 體’例如：碳數4至8之共軛二烯（1，3- 丁二烯、ι，3—戊二 烯、異戊二烯、1，3—己二烯、2,4 —己二烯、2,3 —二甲基 —1，3 — 丁 二烯、2_ 乙基—1,3 — 丁 二烯、1，3_ 庚二烯、1，4 —庚二烯、3，5—庚二烯等）、碳數2至8之烯（乙烯、丙烯、 1— 丁烯'2 — 丁烯、異丁烯、1 一戊烯、2 —戊烯、1—己烯、 2 —己烯、1—庚烯、2 —庚烯、1一辛烯、2 -辛烯等）、（甲 基）丙烯酸酯（（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲 基）丙烯酸丁酯等）、乙烯基酯（乙酸乙烯酯 '丙酸乙烯酯、 丁酸乙烯酯、三甲基乙酸乙烯酯等）、乙烯基醚（甲基乙烯 基醚、異丁基乙烯基醚等）等。與上述其他單體的共聚合形 態，以無規共聚合爲理想。 芳香族乙烯基系聚合物嵌段（C)，宜於嵌段共聚物的60 重量％以下的範圍使用，更佳爲於5 0重量％以下的範圍使 用，又更佳爲於40重量％以下的範圍使用。 -26- 201131857 芳香族乙烯基系聚合物嵌段（C)與芳香族乙烯基系聚 合物嵌段（A)的比例’不特別限定，但是就導入離子傳導性 基前之單體單元的比率而言，以85:15至0:100之範圍較 佳’於兼顧來自於芳香族乙烯基系聚合物嵌段（C)之機械強 度及高離子傳導性方面，以65:35至20:80的範圍較佳， 55:45至35:65的範圍更佳，45:55至35:65的範圍又更佳。 芳香族乙烯基系聚合物嵌段（C)，也可由以下列通式（a) 表示之芳香族乙烯基系化合物單元作爲主要重複單元的聚 合物嵌段構成。以通式（a)之R1表示的碳數1至4的烷基， 可爲直鏈狀也可爲分支狀，例如：甲基、乙基、丙基、異丙 基、丁基、第二丁基、異丁基、第三丁基等。以通式（a)之 R2至R4表示之碳數1至8之烷基，可爲直鏈狀也可爲分支 狀，例如：甲基、乙基、丙基、異丙基、丁基、第二丁基、 異丁基、第三丁基、戊基、異戊基、新戊基、第三戊基' 己基、1—甲基戊基、庚基、辛基等。以通式（a)表示之芳 香族乙嫌基系化合物單兀的較佳具體例，例如：4 -甲基苯 乙烯單元、4 —第三丁基苯乙烯單元、α，4 一二甲基苯乙烯 單元、α—甲基一 4 -第三丁基苯乙烯單元等，此等可使用 1·種或將2種以上組合使用。使該等2種以上聚合（共聚合） 時的形態’爲無規共聚合、嵌段共聚合、接枝共聚合、錐 形共聚合均可。 -27- 201131857201131857 VI. Description of the Invention: [Technical Field] The present invention relates to a polymer electrolyte which is excellent in low-humidity conductivity and has little swelling due to water, and a polymer electrolyte composed of a polymer electrolyte Membrane, and membrane-electrode assembly and polymer electrolyte fuel using electrolyte membrane [Prior Art] In recent years, fuel cell technology has become a central energy transformation in the future hydrogen energy era in terms of energy and environmental issues. One of the columns. In particular, a polymer-based fuel cell (PEFC; Electrolyte Fuel Cell) is a power source for driving power supplies or mobile devices, which is used for small and light weight applications, and further discusses power supply devices for household appliances for electric and thermal applications. In addition, from the viewpoints of output, economy, etc., it is expected to create a wide range of solid polymer fuel cells. Generally, both sides of the polymer electrolyte membrane having the following proton conductivity are disposed, and the catalyst medium layer is disposed. A carbon powder of a metal catalyst on which lead metal is placed and an ion conductive binder composed of a high quality. Outside the respective catalyst layers, the fuel gas and the oxidant gas are respectively ventilated by a porous material. As the gas diffusion layer, carbon paper, carbon cloth, or the like is used. The gas diffusion layer is referred to as a gas diffusion electrode, and the body diffusion electrode is a structure in which a catalyst layer and a polymer electrolyte membrane are bonded to each other in a polymer electrolyte membrane. From the smell of the molecular battery. The fundamental solution of the system is to discuss the electric vehicle and use it as a fuel. . In the layer, the contact molecule is electrolyzed, and the gas diffusion medium layer is disposed opposite to the membrane-electrode -4- 201131857 conjugate (MEA; Membrane Electrode Assembly). Separate members having electrical conductivity and airtightness are disposed on both sides of the membrane-electrode assembly. A gas flow path for supplying a fuel gas or an oxidant gas (e.g., air) to the electrode face is formed in a contact portion or a separator of the membrane-electrode assembly and the separator. The fuel gas is supplied to one of the electrodes (fuel electrode), and the oxidant gas (air or the like) containing oxygen is supplied to the other electrode (oxygen electrode) to generate electricity. That is, at the fuel electrode, the fuel is ionized to generate protons and electrons, and the protons are transmitted through the polymer electrolyte membrane, and the electrons are moved by the external circuit formed by connecting the two electrodes to reach the oxygen electrode and the oxidant gas respectively. The reaction produces water. In this way, the chemical energy of the fuel can be directly converted into electrical energy and taken out. These solid polymer fuel cells are not continuously operated as in the above general use, and are usually intermittently operated by repeated starting, running, and stopping. During operation, the polymer electrolyte membrane is wet, but the humidity of the membrane decreases when it stops. Therefore, in order to rapidly perform performance at the time of starting, it is desirable to have a high molecular electrolyte membrane having high proton conductivity even under low humidity. In general, the polymer electrolyte membrane for a polymer electrolyte fuel cell uses a perfluorocarbonsulfonic acid-based polymer nanofilm (a registered trademark of Nafi〇n and DuPont) for chemical stability. ). However, although the phenanthrene film is excellent in ion conductivity at low humidity, a fluorine-based compound which adversely affects the environment may occur in the case of decomposition of the product for a long period of time or at the time of disposal. Moreover, there are disadvantages such as high fuel permeability and high cost, and therefore there is a demand for alternative materials. 201131857 In recent years, a hydrocarbon-based material has been proposed as a material for replacing a perfluorocarbonsulfonic acid-based polymer such as a Nafite film. Specifically, a material obtained by introducing a sulfonic acid ion conductive group into an engineering plastic polymer typified by polyether maple (PEs) or polyetheretherketone (PEEK). For example, Patent Document 1 proposes a sulfonate of PES. Since such a material does not contain fluorine, even if the material is deteriorated, the fluorine-based compound does not occur at all. Further, although there are problems in the production technology such as ion-conducting group introduction or film formation, the raw material polymer itself is advantageous in terms of price compared to the perfluorocarbonsulfonic acid-based polymer. However, in the polymer electrolyte using these engineering plastic polymers, since the ion conductive groups are uniformly dispersed in the molecules, the density of the ion conductive groups is low, and it is difficult to achieve high ion conductivity. In order to form an ion channel having a high ion conductive base density, a sulfonated compound having a polymer block into which an ion conductive group has been introduced and a polymer block in which an ion conductive group is not introduced has been proposed (refer to Patent Document 2) However, due to the condensation of the polymer, the exchange reaction of the repeating unit occurs during the synthesis. The block structure is destroyed, and the phase separation structure cannot be obtained, and sufficient ion channels cannot be formed. On the other hand, the polymer electrolyte membrane described in Patent Document 3 is composed of a block polymer having an aromatic vinyl polymer block and an aliphatic vinyl polymer block, and the like does not occur. The exchange reaction of the above repeating unit can maintain the block structure. Therefore, an ion channel can be formed by utilizing a phase separation structure peculiar to the block polymer. -6 - 201131857 [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 10-045913 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei. JP-A-6-210326 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] However, it is composed of a block polymer having an aromatic vinyl polymer block and an aliphatic vinyl polymer block. The polymer electrolyte membrane has insufficient performance in a low humidity state, and there is still a limit in performance even if the ion exchange capacity is increased. Therefore, it is actually impossible to ensure sufficient ion conductivity in a low humidity state. When the polymer electrolyte membrane is used in a polymer electrolyte fuel cell, it is desirable to have a property that the polymer electrolyte fuel cell has less swelling due to water in contact with the polymer electrolyte membrane during power generation. When the polymer electrolyte membrane is deformed by swelling, the polymer electrolyte membrane is likely to be peeled off from the electrode in the membrane-electrode assembly. Further, in the intermittent operation of the polymer electrolyte fuel cell, a significant shape change of the polymer electrolyte membrane occurs, and even damage may occur, which may adversely affect long-term durability. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have found that at least an aromatic vinyl polymer block (A) and an aliphatic 201131857 vinyl polymer block (B) are provided. The block copolymer as a constituent component is formed, and the ion conductive group content of each repeating unit in the aromatic vinyl polymer block (A) is 1. 5 to 3. The present invention can be solved by solving the above problems by solving a polymer electrolyte having 0 or less of the aliphatic vinyl polymer block (B) having no ion conductive group. In other words, the invention described in claim 1 relates to a polymer electrolyte characterized by comprising at least an aromatic vinyl polymer block (A) and an aliphatic vinyl polymer block ( B) The block copolymer is composed of a constituent component, and the ion conductive group content of each repeating unit in the aromatic vinyl polymer block (A) is 1. 5 to 3. 0' and the aliphatic vinyl polymer block (B) does not have an ion conductive group. The invention according to claim 2, wherein the aromatic vinyl polymer block (A) accounts for 5 to 50% by weight of the polymer electrolyte. %. Further, the invention of claim 3 is related to the polymer electrolyte of the first aspect of the patent application, wherein the aromatic vinyl polymer block (A) has an ion conductive group content of 4 8 meq per lg. /g or more. The invention described in the fourth aspect of the invention is the polymer electrolyte of the first aspect of the patent application, wherein the aliphatic vinyl polymer block (B) is selected from the group consisting of carbon numbers of 2 to 8. a cycloolefin unit having 5 to 8 carbon atoms, a vinylcycloalkane unit having 7 to 1 carbon atoms, a vinylcycloolefin unit having 7 to 10 carbon atoms, and a conjugate having a carbon number of 4 to 8. A rubbery polymer block having a diene-8-201131857 unit and at least one repeating unit of a group consisting of 5 to 8 conjugated cycloalkanedene units as a main component. The invention described in claim 5 is the polymer electrolyte according to the first aspect of the invention, wherein the ion conductive group is a proton conductive group. Further, the invention of claim 6 is the polymer electrolyte according to the first aspect of the invention, which contains 20 to 60% by weight of the aromatic vinyl polymer block (C) as a constituent component. The aromatic vinyl-based polymer block (C) mainly contains an aromatic vinyl-based compound unit having no ion-conductive group as a repeating unit. Further, the invention of claim 7 is the polymer electrolyte according to claim 6, wherein the aromatic vinyl compound unit has 1 to 3 carbon atoms in the aromatic ring of 1 to A substituted aromatic vinyl compound unit of a hydrocarbon group of 8, wherein the aromatic vinyl compound unit is a main repeating unit of the aromatic vinyl polymer block (C). Further, the invention described in claim 8 relates to a polymer electrolyte membrane comprising the polymer electrolyte of the first aspect of the patent application. Further, the invention of claim 9 relates to a membrane-electrode assembly which is a multilayer structure of a polymer electrolyte membrane and an electrode layer of claim 8 of the patent application. The invention described in the first aspect of the invention relates to a solid polymer fuel cell comprising the membrane-electrode assembly according to claim 9 of the patent application. [Effects of the Invention] The polymer electrolyte block copolymer of the present invention has an aromatic vinyl polymer block (Α) and an aliphatic vinyl polymer block (Β) which is microphase-separated, and aromatic vinyl The base polymer block (Α) and the aliphatic vinyl polymer block (Β) are separately collected from each other, and the aromatic vinyl polymer block (Α) has an ion conductive group, so the fragrance The collection of the group of vinyl-based polymer blocks (Α) forms an ion channel and becomes a pathway for proton plasma. Here, "microphase separation" means microscopic phase separation, and more specifically, means phase separation of the formed microdomain size at a wavelength of visible light (3800 to 7800 angstroms) or less. In the above aromatic vinyl polymer block (Α), the ion conductive group content of each repeating unit is 1. 5 to 3. There are 0, and the above aliphatic vinyl polymer block (Β) does not have an ion conductive group, whereby the ion channel has an ion conductive group at a high density. As a result, the polymer electrolyte membrane composed of the polymer electrolyte of the present invention has a remarkable phase separation, and has improved ion conductivity, particularly high ion conductivity in a low-humidity state, and a film formed by containing the polymer electrolyte membrane. When the one electrode assembly is used in a polymer electrolyte fuel cell, high output characteristics can be obtained in a low humidity state, and swelling due to water is also small, and the adhesion to the electrode is also excellent. -10- 201131857 [Embodiment] Hereinafter, the present invention will be described in detail. The block copolymer ′ constituting the polymer electrolyte of the present invention has an aromatic ethane-based polymer block (A) as a constituent component. The aromatic succinyl polymer block (A) is an aromatic vinyl compound unit as a main repeating unit, and the ion conductive group content of each repeating unit is 15 to 3. 0' is selected as appropriate depending on the performance required for the polymer electrolyte. From the viewpoint of ion conductivity, it is preferably 1 to 7 or more, and from the viewpoint of easiness of introduction of a sulfonic acid group, 1 is used. 5 to 2. 0 is preferred. Here, the aromatic vinyl-based compound unit which is a repeating unit of the aromatic vinyl-based polymer block (A) means a structure which can be formed by polymerization of an aromatic vinyl-based compound. The aromatic vinyl compound means a compound having at least one aromatic ring and at least one functional group containing an addition polymerizable carbon double bond, and the functional group containing an addition polymerizable carbon double bond is directly bonded to At least one carbon atom on the aromatic ring. For example, a hydrogen atom on an aromatic ring such as a benzene ring is substituted with a substituent such as a vinyl group, a 1-alkylvinyl group (e.g., isopropenyl group) or a monoarylvinyl group. Specifically, for example, styrene or α-methylstyrene 'diphenylethylene. Further, an aromatic vinyl compound which is an aromatic vinyl compound unit which is a repeating unit of an aromatic vinyl polymer block can be formed, and it is preferred that the carbon atom forming the aromatic ring is 1 Å or more. For example, a compound having a plurality of aromatic rings having a carbon number of 10 or less such as a benzene ring or a compound having a condensed ring obtained by condensing an aromatic ring having 10 or less carbon atoms. -11- 201131857 Examples of the aromatic vinyl compound having a plurality of benzene rings are, for example, vinylbiphenyl, vinylbitriphenyl, phenoxybenzene'ethylene, and diphenylethylene. Further, the condensed ring is, for example, a naphthalene ring, a phenanthrene ring, an anthracene ring, an anthracene ring, a chopstick ring or an anthracene ring Specific examples of such aromatic vinyl compounds include vinyl naphthalene, vinyl phenanthrene, vinyl anthracene, vinyl anthracene, vinyl chopsticks, and vinyl anthracene. Among them, the repeating unit has a small molecular weight and a compact structure, and is advantageous for the high density of ion channels. 'Vinyl naphthalene, vinyl biphenyl, vinyl triphenyl is preferable, and the ease of introduction of an ion conductive group is preferable. , vinyl biphenyl is even better. The average molecular weight of the aromatic vinyl compound unit is preferably 400 or less, more preferably 300 or less, and still more preferably 200 or less. The average molecular weight is a polymer block in which all of the ion-conductive groups of the aromatic vinyl-based polymer block are substituted with hydrogen when the aromatic vinyl compound unit of the repeating unit is an ion-conductive group (ie, Calculated without a polymer block having a corresponding ion-conducting group. If the average molecular weight of the repeating unit is too large, the density of the ion channel sometimes falls to a poor level. When the aromatic vinyl compound is polymerized into the aromatic vinyl polymer block (A), two or more kinds of aromatic vinyl compounds can be used in combination. The form of the two or more types of copolymerization may be random copolymerization, block copolymerization, graft copolymerization, or tapered copolymerization. -12- 201131857 Further, the aromatic vinyl polymer block (A) may contain one type or a plurality of other monomer units insofar as the effect of the invention is not impaired. a monomer which can constitute the other monomer unit, for example, a conjugated diene having a carbon number of 4 to 8 (1,3-butadiene, 1,3-pentadiene, isoprene, 1,3) Diene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 1,4-g Diene '3,5-heptadiene, etc.) 'Alkene having 2 to 8 carbons (ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1_hexene) , 2 — diarrhea, 1 genus, 2 — gh, 1 octene, 2 — octene, etc., (meth) acrylate (methyl (meth) acrylate, ethyl (meth) acrylate , (butyl) (meth) acrylate, etc., vinyl ester (vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, etc.), vinyl ether (methyl vinyl ether 'isobutyl Vinyl ether, etc.). The copolymerization form with the above other monomers is preferably a random copolymerization. The aromatic vinyl polymer block (A) accounts for 5 to 50% by weight of the polymer electrolyte, and is preferable in that the polymer electrolyte membrane has both ion conductivity and water resistance. From the viewpoint of ion conductivity, it is preferably from 35 to 50% by weight. From the viewpoint of water resistance, it is preferably from 5 to 25% by weight, and more preferably from 20 to 40% by weight in order to achieve both ion conductivity and water resistance. . The aromatic vinyl polymer block (A) is obtained by using an aromatic vinyl compound unit as a main repeating unit and microphase separation from the aliphatic vinyl polymer block (B). Advantageously, the result is improved ion conductivity. The aromatic vinyl-based compound unit is a main repeating unit, which means that the aromatic vinyl-based polymer block (A) accounts for more than 80, 2011,31,857% by weight, and in order to impart sufficient ion conductivity, it accounts for 90% by weight or more. Good, accounting for more than 95% by weight. When the amount is less than 80% by weight, the content of the ion conductive group per repeating unit in the aromatic vinyl polymer block (A) is decreased, and the density of the ion conductive group is also lowered, so that it may not be obtained. The effect of the present invention. Here, the weight ratio is a polymer block in which all of the ion conductive groups of the aromatic B-based polymer block are substituted with hydrogen (that is, a polymer block having no corresponding ion conductive group). Calculation. Thus, the aromatic vinyl polymer block (A) referred to in the present invention means not only the same monomer but also a main chain, as long as the aromatic vinyl compound unit is the main repeating unit and can be formed. The homogeneous phase is included. Further, the observation of the phase can be carried out using a transmission electron microscope (TEM). In other words, the polymer electrolyte membrane made of the polymer electrolyte is embedded in an epoxy resin, and then an ultrathin section having a thickness of about 90 nm is produced using a cryo-microtome (> Lead acid dyeing, whereby the aromatic vinyl polymer block (A) can be observed. The molecular weight of each aromatic vinyl polymer block (A) can be regarded as the properties of the polymer electrolyte, the required properties, and the like. When the molecular weight is large, the obtained polymer electrolyte membrane tends to have improved mechanical properties. However, if it is too large, formation and film formation of the block copolymer become difficult, and the molecular weight is small, and it is difficult to form a microphase. Separation structure, even if it is difficult to form an ion channel, "There is a tendency for ion conductivity and mechanical properties to decrease. Therefore, it is important to appropriately select a molecular weight system depending on the necessary properties. -14- 201131857 Each aromatic vinyl polymer block ( The molecular weight of A), if the ion-conducting group is replaced by hydrogen (ie, does not have corresponding ion conduction. The base-based block copolymer) is calculated, and in terms of the number average molecular weight in terms of standard polystyrene, it is usually selected from 1,000 to 1, 〇〇〇, 〇〇〇, and from 2,000 to 250,000. Preferably, the choice between 3, 〇〇〇 and 100,000 is preferred, the choice between 4,000 and 50,000 is better, and the choice between 5,000 and 25,000 is preferred. Further, from the viewpoint of easiness of preparation of the solution at the time of film formation and film forming properties, it is preferably selected from 5,000 to 1 Torr. Further, the aromatic vinyl polymer block (A) may be crosslinked by a known method within the range not impairing the effects of the present invention. When the cross-linking is introduced, the ion channel phase formed by the aromatic vinyl-based polymer block (A) is less likely to swell, and the change in mechanical properties (tensile properties, etc.) during drying and drying tends to be smaller. . 4. The number of moles of the ion conductive group per lg of the aromatic vinyl polymer block (A) (A block IEC), in order to exhibit the effects of the present invention, More than 8meq/g is better. More than 1meq/g, 5. More than 6meq/g is better. The ion-conductive group which the aromatic vinyl-based polymer block (A) has is not particularly limited, and a functional group having ion conductivity can be used, and the affinity with an anion and/or a cation is high, particularly a functional group. A part of the compound which is easily dissociated into an ion is suitable, for example, a sulfonic acid group, a phosphonic acid group, a carboxylic acid group, a quaternary ammonium salt, a pyridine 4-grade salt or the like. In particular, a proton conductive group or a salt in which a proton of the -15-201131857 sub-conductive group is exchanged for other ions is excellent in proton conductivity, such as an acid-expanding group, a phosphonic acid group, a carboxylic acid group, and the like. . From the viewpoints of ion conductivity, ease of introduction, price, and the like, a sulfonic acid group and a phosphonic acid group and salts thereof are preferably used. The ion exchange capacity can be adjusted by appropriately selecting the type or concentration of the ion conductive group. In the aromatic vinyl-based polymer block (A), the position of the ion-conductive group is not particularly limited, but from the viewpoint of easiness of introduction of the ion-conductive group, it is preferably introduced into an aromatic vinyl-based compound. The unit's aromatic ring. Further, the block copolymer constituting the polymer electrolyte of the present invention contains the aliphatic ethylenic polymer block (B) as a constituent component. The aliphatic ethylenic polymer block (B) has an aliphatic vinyl compound unit as a main repeating unit and does not have an ion conductive group. The main repeating unit of the aliphatic vinyl polymer block (B), i.e., the aliphatic vinyl compound unit, is a structure which can be formed by polymerization of an aliphatic ethylenic compound. The aliphatic vinyl compound ' refers to a compound containing at least one functional group containing an addition polymerizable carbon double bond. The functional group containing a polymerizable carbon double bond is directly bonded to at least one unconstituted aromatic group. The carbon atoms of the ring. The above aliphatic vinyl compound unit, for example, an ethylene unit having 2 to 8 carbon atoms, a cycloolefin unit having 5 to 8 carbon atoms, a vinylcycloalkane unit having 7 to 10 carbon atoms, and ethylene having 7 to 1 carbon atoms. a cyclene unit, a conjugated diene unit having 4 to 8 carbon atoms, and a conjugated cycloalkene unit having 5 to 8 carbon atoms. The repeating units selected from the groups may be used singly or in combination of two or more. In the case of two or more kinds of polymerization (copolymerization) of -16 to 201131857, it may be a random copolymerization, a block copolymerization, a graft copolymerization or a cone copolymerization. Further, when the monomer to be polymerized has a plurality of carbon-carbon double bonds, any of them may be used for polymerization, and when it is a coplanar diene, there are a plurality of polymerizable sites (for example, using 1,3 -diene)丨2 One-bond, 3,4-bond, 1,4-bonding, but not limited, the ratio (for example, the ratio of 1,2-bond to 1,4-bond) Special restrictions. Among the monomers constituting such a monomer unit, a carbon having 2 to 8 carbon atoms, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentancan, 2-pentene, 1-hexene, 2-hexene, 1-heptene '2-heptene, 1-octene, 2-octene, etc.; cycloolefin having 5 to 8 carbon atoms, such as cyclopentene, cyclohexene, cycloheptene and cyclooctene Alkene, etc.; a vinylcycloalkane having a carbon number of 7 to 10, for example: B;) 3⁄4-cyclopentane, vinylcyclohexane 'vinylcycloheptane, vinyl cycline, etc.; carbon number 7 to 10 Vinylcycloolefin, for example, vinylcyclopentene, ethylenecyclohexene, vinylcycloheptene, vinylcyclooctene, etc.; conjugated diene having 4 to 8 carbon atoms, for example, 1,3— Butadiene, 1,3-pentadiene, isoprene, 1,3 - hexanate, 2,4 hexane, 2,3 - dimethyl hydrazine, 3 - butyl bismuth, 2_ Ethyl-1,3-butadiene, 1,3-heptadiene, 2,4-heptadiene, etc.; a conjugated cycloalkene having a carbon number of 5 to 8, such as cyclopentadiene, I, 3-cyclohexadiene and the like. These monomers may be used singly or in combination of two or more. The monomer for forming the aliphatic vinyl-based polymer block (B) is, for example, a vinylcycloolefin or a conjugated diene or a conjugated cycloalkene, having a plurality of carbon-carbon double bonds. Although the repeating unit after the polymerization has a carbon-carbon double bond, the saturated structure may be used as a repeating unit. These are obtained by polymerizing the above -1 7 - 201131857 monomer by hydrogenating a residual carbon-carbon double bond. From the viewpoint of improving the power generation performance and heat deterioration resistance of the membrane-electrode assembly using the polymer electrolyte membrane of the present invention, it is preferable that the carbon-carbon double bond has a hydrogenation structure of 30% by mole or more. More than 80% of the hydrogenated structure is more than 80% of the hydrogenated structure. The rate of occurrence of the carbon-carbon double bond (or hydrogenation rate) can be calculated by a commonly used method such as an iodine value measurement method or a 1H-NMR measurement. The aliphatic vinyl polymer block (B) is imparted with elasticity to the obtained block copolymer, and even a film-electrode assembly or a polymer electrolyte fuel cell is provided with good formability. Preferably, it is an olefin unit having 2 to 8 carbon atoms, a cycloolefin unit having 5 to 8 carbon atoms, a vinyl cyclic olefin unit having 7 to 10 carbon atoms, a conjugated diene unit having 4 to 8 carbon atoms, and a carbon number of 5 a polymer block composed of at least one repeating unit selected from the group consisting of 8 conjugated cycloalkanedene units, more preferably an olefin unit having 3 to 6 carbon atoms and a conjugated carbon having 4 to 6 carbon atoms The polymer block composed of at least one repeating unit selected from the olefin unit is more preferably composed of at least one repeating unit selected from the group consisting of a olefin unit having 4 to 5 carbon atoms and a conjugated diene unit having 4 to 5 carbon atoms. Polymer block. In the above, as the preferred one of the olefin unit, for example, an isobutylene unit, a structural unit (1-butene unit, 2-butene unit) obtained by saturating a double bond of a 1,3-butadiene unit, and an isoprene a structural unit of a diene unit saturated with a double bond (2-methyl-1-butene unit, 3-methyl-1-butene unit, 2-methyl-2-butene unit), especially from softness High and low point of view, best -18- 201131857 After the structural unit (1_butene unit, 2-butene unit) which saturates the double bond of the u-butadiene unit, the double bond of the isoprene unit is saturated The structure is monoterpene (2-methyl-1-monobutene unit, 3-methyl-nonyl-butene unit, 2-methyl-2-butene unit). In the case of a conjugated diene unit, the most preferred one is a 1,3 -butadiene unit or an isoprene unit. The aliphatic vinyl polymer block (B) is mainly a repeating unit of an aliphatic vinyl compound unit, that is, an aliphatic vinyl compound is more than 50% by weight, and more preferably 70% by weight. More than 90% by weight is better. In addition to the above-mentioned repeating unit, the aliphatic vinyl polymer block (B) is within the range of the purpose of not impairing the aliphatic vinyl polymer block (B) which imparts elasticity to the block copolymer. Other repeating units such as an aromatic vinyl compound unit such as a styrene unit or a vinyl naphthalene unit, a halogen-containing vinyl compound unit such as a vinyl chloride unit, or an acrylate having a side chain of 1 to 12 carbon atoms may be contained. a unit, a methacrylate unit having a side chain having 1 to 12 carbon atoms, or the like. In this case, the copolymerization form of the above monomer with other monomers is preferably a random copolymerization. The other monomer is used in an amount of less than 50% by weight of the aliphatic vinyl-based polymer block (B), more preferably less than 30% by weight, still more preferably less than 10% by weight. When the aliphatic vinyl polymer block (B) is formed into a rubbery polymer block, the entire block copolymer is elastic and flexible, and is formed when a membrane-electrode assembly or a polymer electrolyte fuel cell is produced. Improvement (assembly, bonding, fastening, etc.) and the like. The rubbery polymer block as used herein refers to a polymer having a glass transition point or softening point of 30 ° C or less, preferably 20 ° C or less, more preferably 10 ° C or less. Block. When the polymer block (B) is formed into a rubbery polymer block, the olefin unit having 2 to 8 carbon atoms, the cycloolefin unit having 5 to 8 carbon atoms, and the vinylcycloalkane unit having 7 to 10 carbon atoms, At least one repeating unit selected from the group consisting of a vinylcycloolefin unit having 7 to 10 carbon atoms, a conjugated diene unit having 4 to 8 carbon atoms, and a conjugated cycloaldiene unit having 5 to 8 carbon atoms as a main group The composition is preferred, and the number of carbon atoms is from 4 to 5 carbon atoms. It is more preferable that at least one type of repeating unit selected from the group consisting of conjugated diene units of 5 is a main component. The molecular weight of each of the aliphatic vinyl polymer blocks (B) can be appropriately selected depending on the properties of the polymer electrolyte, the required properties, and other polymer components. In terms of the number average molecular weight in terms of standard polystyrene, it is usually selected from 1,000 to 1, 〇〇〇, 〇〇〇, and preferably from 5, 〇〇〇 to 500,000, and from 10,000 to 200,000. The choice is better. In addition, when the aliphatic polymer base block (B) is made into a rubber-like polymer block, from the viewpoint of both moldability and flexibility, 'from 15 to 丨2 〇, 〇〇〇 The choice between the two is especially good. The aliphatic ethylenic polymer block (B) does not have an ion conductive group. Here, 'there is no ion-conducting group' means a degree of substantially no ion conductivity, in terms of the microphase separation property of the aromatic vinyl-based polymer block (A), for example, each repeating unit The ion conductive group content is preferably one or less, 0. 01 or less is better, and there is no best at all. However, in manufacturing, the parent-repeating unit contains about 0. Between 001 and 〇 〇 5 ion-conducting groups are sometimes advantageous. -20-201131857 When the aliphatic vinyl polymer block (B) is hydrophobic, phase separation from the aromatic vinyl polymer block (A) can be favorably formed. For example, a hydrophilic group such as a hydroxyl group or an amine group is not preferable, and a polar group such as an ester group is not particularly preferable. The block structure of the block copolymer having the aromatic vinyl polymer block (A) and the aliphatic vinyl polymer block (B) as a constituent component is not particularly limited, but has a plurality of aromatic vinyl groups. It is preferable that the polymer block (A) is at least one end of at least one of the aliphatic vinyl polymer blocks (B) is not the end of the block copolymer. Examples are: A _ B _ type A triblock copolymer, a mixture of A-B-A type triblock copolymer and A-B type diblock copolymer, A-B-A-B type tetrablock Copolymer, Α_Β-Λ-Β-type A pentablock copolymer, B-A-B-A-B type pentablock copolymer, (A-B) nX type copolymer (X represents the coupling component), B—A) nX type copolymer (X represents an even component) and the like. These block copolymers 'may be used singly or in combination of two or more kinds. When the block copolymer has a plurality of aromatic vinyl polymer blocks (A) and/or aliphatic vinyl polymer blocks (B), the blocks may be the same or different. In the block copolymer constituting the polymer electrolyte of the present invention, 'the weight ratio of the aromatic vinyl polymer block (A) constituting the block copolymer to the aliphatic vinyl polymer block (B)' The desired properties of the block copolymer which can be obtained are appropriately selected, but from the viewpoint of ion conductivity, 95:5 to 5:5:45 is preferable, and from the viewpoint of water resistance, '45:5 5 to 5:95 is preferable' In order to achieve both ion conductivity and water resistance, it is preferably 60:40 to 40:60. When the ratio of the weight - 2 1- 201131857 is 95:5 to 5:95, the ion channel formed by the aromatic vinyl polymer block (A) is cylindrical or continuous phase due to microphase separation. A sufficient ion conductivity can be exhibited, and the ratio of the hydrophobic aliphatic vinyl polymer block (B) which is hydrophobic is appropriate, and excellent water resistance can be exhibited. Here, the above weight ratio is calculated assuming that all the ion conductive groups of the block copolymer are substituted with the polymer block after hydrogen. The block copolymer used in the present invention also contains a part of a graft bond. A portion of the block copolymer comprising a graft linkage, such as a portion of the constituent polymer block, is graft-bonded to the main structure of the block copolymer (e.g., the main chain). The number average molecular weight of the block copolymer used in the present invention is not particularly limited, but the number average molecular weight of the ion conductive group is not considered, and in terms of the number average molecular weight in terms of standard polystyrene, it is usually 10, 1,000,000 is better, 15,000 to 700,000 is better, and 20,000 to 500,000 is better. The block copolymer constituting the polymer electrolyte of the present invention must have an ion conductive group in the aromatic vinyl polymer block (A). In the present invention, examples of the ion at the time of ion conductivity include protons and the like. The ion-conductive group is not particularly limited as long as it is a group which exhibits sufficient ion conductivity by using the membrane-electrode assembly produced using the polymer electrolyte, and further, -S03M or a P〇3HM (wherein, Μ A sulfonic acid group, a phosphonic acid group or a salt represented by a hydrogen atom, an ammonium ion or an alkali metal ion is preferred. Further, as the ion conductive group, a carboxyl group or a salt thereof can be used. By making the aromatic vinyl-22-201131857 polymer block (A) have an ion conductive group, it is particularly effective for improving the radical resistance of the polymer electrolyte. The amount of introduction of the ion-conductive group can be appropriately selected depending on the performance required for the obtained block copolymer, etc. However, in order to exhibit sufficient ion conductivity as a polymer electrolyte membrane for a polymer electrolyte fuel cell, a block copolymer is usually used. The ion exchange capacity (all IEC) is 〇. The amount of 40 m eq/g or more is preferably 'the amount of 0_50 meq/g or more is more preferably 0. The amount above 60meq/g is even better. Regarding the upper limit of the ion exchange capacity of the block copolymer, if the ion exchange capacity is too large, the hydrophilicity is increased and the water resistance tends to be insufficient, so that the ratio is 4. 5meq/g or less is better, 4. 0meq/g or less is better, 3. It is better below 5meq/g. The block copolymer used in the present invention may contain an aromatic vinyl-based polymer block (C) mainly having an aromatic vinyl-based compound unit having no ion-conductive group as a repeating unit. When the aromatic vinyl polymer block (C) accounts for 20 to 60% by weight of the polymer electrolyte, it is excellent in mechanical strength when used as a film, and is preferable. More preferably, it is 23 to 50% by weight, and more preferably 25 to 40% by weight. The aromatic vinyl-based polymer block (C)' mainly having an aromatic ethyl-based compound unit having no ion-conductive group as a repeating unit means polymerization having an aromatic vinyl-based compound unit as a main repeating unit Block. This polymer block is excellent in shape stability of a molded body of a polymer electrolyte (e.g., a polymer electrolyte membrane). Therefore, the aliphatic vinyl group poly-23-201131857 compound block (B) is particularly useful when it is a rubbery polymer block. The aromatic vinyl-based polymer block (C)' is preferably phase-separated from the aromatic vinyl-based polymer block (A) and the aliphatic vinyl-based polymer block (B) to form a restraint phase. In other words, since the aromatic vinyl-based polymer block (C) having no ion conductivity forms an independent phase, it is more excellent in shape stability. The aromatic vinyl polymer block (C) mainly contains an aromatic vinyl compound unit having no ion conductive group as a repeating unit. Here, the aromatic vinyl-based compound unit having no ion-conductive group as a repeating unit mainly means that the aromatic vinyl-based polymer block (C) has substantially no ionic conductivity, for example, an aromatic vinyl group. The ionic conductivity group content of each repeating unit of the polymer block (C) is 0. 1 or less, more preferably 0. 01 or less, the best is not at all. Or, the ion-conductive group of the aromatic vinyl-based polymer block (A) is preferably 1/10 or less, more preferably 1/20, more preferably 1/100 or less. As a result, the aromatic vinyl polymer block (C) is substantially free of ion conductivity, and the phase separation from the aromatic vinyl polymer block (A) forming the ion channel can be favorably exhibited. Ion conduction can be performed efficiently. The aromatic vinyl polymer block (C) is hydrophobic, and the phase separation from the aromatic g I dilute polymer block (A) can be favorably formed, which is preferable. For example, a hydrophilic group such as a hydroxyl group or an amine group is not preferable, and a polar group such as an ester group is not preferable. Here, the aromatic repeating unit compound unit which is a main repeating unit of the aromatic vinyl polymer block (C) is a structure which can be formed by polymerization of an aromatic ethyl compound. The aromatic vinyl compound means a compound having at least one aromatic ring and at least one functional group containing an addition polymerizable carbon double bond, and the functional group containing an addition polymerizable carbon double bond is directly bonded at At least one carbon atom on the aromatic ring. The aromatic ring of the aromatic vinyl compound is preferably a carbocyclic aromatic ring, for example, a benzene ring, a naphthalene ring, an anthracene ring or an anthracene ring. The aromatic vinyl compound and the aromatic vinyl compound unit are preferably a substituted aromatic vinyl compound unit having 1 to 3 hydrocarbon groups having 1 to 8 carbon atoms in the aromatic ring. For example, a compound obtained by substituting hydrogen at the aromatic ring with a substituent such as a vinyl group, a 1-alkylvinyl group (e.g., isopropenyl group) or a monoarylvinyl group. For example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-isopropylstyrene, 4 —n-butyl styrene, 4-isobutyl styrene, 4 —t-butyl styrene, 4—n-octyl styrene, 2,4-dimethyl styrene, 2,5-dimethylbenzene Ethylene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2-methoxystyrene, 3-methoxy styrene, 4-methoxystyrene, vinyl Naphthalene, vinyl anthracene, substituted with a hydrogen atom bonded to an α-carbon atom to an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, An aromatic vinyl group derived from a second butyl group or a tert-butyl group, a halogenated alkyl group having 1 to 4 carbon atoms (chloromethyl group, 2-chloroethyl group, 3-chloroethyl group, etc.) or a phenyl group Compound (specifically, α -25- 201131857 - methyl styrene, α, 4 - dimethyl styrene, α - methyl - 4 - ethyl styrene, a - methyl - 4 - tert-butyl Styrene, α-methyl-4-isopropylstyrene, 1,1-diphenyl Ethylene, etc.). These may be used alone or in combination of two or more, but among them, 4_t-butylstyrene, 4-isopropylstyrene, α-methyl-4-tetrabutylstyrene, α Preferably, _methyl-4-isopropylstyrene. When the two or more kinds of these copolymerizations are carried out, the 'copolymerization form' can be random copolymerization, block copolymerization, graft copolymerization, or cone copolymerization. The aromatic vinyl polymer block (C) may contain one or more other monomer units within the range not impairing the effects of the present invention. The other monomer 'for example: a conjugated diene having 4 to 8 carbon atoms (1,3-butadiene, iota, 3-pentadiene, isoprene, 1,3-hexadiene, 2, 4) —hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-heptadiene, 1,4-heptadiene, 3, 5-heptadiene, etc., alkene having 2 to 8 carbons (ethylene, propylene, 1-butene '2 - butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2 - Alkene, 1-heptene, 2-heptene, 1-octene, 2-octene, etc., (meth) acrylate (methyl (meth) acrylate, ethyl (meth) acrylate, (methyl) ) butyl acrylate, etc., vinyl ester (vinyl acetate 'vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, etc.), vinyl ether (methyl vinyl ether, isobutyl vinyl ether) and many more. The copolymerization state with the above other monomers is preferably a random copolymerization. The aromatic vinyl polymer block (C) is preferably used in the range of 60% by weight or less of the block copolymer, more preferably 50% by weight or less, and still more preferably 40% by weight or less. The scope of use. -26-201131857 The ratio of the aromatic vinyl polymer block (C) to the aromatic vinyl polymer block (A) is not particularly limited, but the ratio of the monomer unit before introduction of the ion conductive group is not limited. In the range of 85:15 to 0:100, it is preferable to take into consideration the mechanical strength and high ion conductivity from the aromatic vinyl polymer block (C), from 65:35 to 20:80. The range is better, with a better range from 55:45 to 35:65 and a better range from 45:55 to 35:65. The aromatic vinyl polymer block (C) may be composed of a polymer block having an aromatic vinyl compound unit represented by the following formula (a) as a main repeating unit. The alkyl group having 1 to 4 carbon atoms represented by R1 of the formula (a) may be linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, and second. Butyl, isobutyl, tert-butyl and the like. The alkyl group having 1 to 8 carbon atoms represented by R2 to R4 of the formula (a) may be linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, Second butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-amyl 'hexyl, 1-methylpentyl, heptyl, octyl and the like. Preferred examples of the aromatic aryl group-based compound represented by the formula (a) include, for example, a 4-methylstyrene unit, a 4-tert-butylstyrene unit, and an α,4-dimethyl group. The styrene unit, the α-methyl-4-tetrabutylstyrene unit, and the like may be used in combination of two or more kinds. The form ' when the two or more types of polymerization (copolymerization) are used may be random copolymerization, block copolymerization, graft copolymerization, or pyramidal copolymerization. -27- 201131857
(式中，R1爲氫原子或碳數1至4之院基，R2至R4各 自獨立地表示氫原子或碳數1至8之烷基，但至少其中之 一表示碳數1至8之烷基） 本發明之高分子電解質之製造方法之一，例如製造不 具有離子傳導性基之嵌段共聚物後，導入離子傳導性基之 方法。例如，導入磺酸基作爲離子傳導性基時，聚苯乙烯 之磺酸化反應會優先發生在芳香環的對位，因此，當芳香 族乙烯基系聚合物嵌段的主要重複單元爲上述4 -甲基苯 乙烯單元、4 一第三丁基苯乙烯單元、α，4_二甲基苯乙烯 單元、α_甲基-4 一第三丁基苯乙烯單元等4位（對位）經 取代的苯乙烯構造時’不易發生對於對應的芳香族乙烯基 系聚合物嵌段的磺酸化反應（磺酸化反應速度降低或完全 不進行反應）。因此，不易對於芳香族乙烯基系聚合物嵌段 導入磺酸基’對於使該芳香族乙烯基系聚合物嵌段成爲不 具有離子傳導性基之芳香族乙烯基化合物單元方面爲有 利。尤其’當4位以大體積的取代基取代的構造的情形， -28- 201131857 更爲有利，該取代基例如：異丙基、第二丁基、第三丁基’ 又以4 —第二丁基苯乙烯單元更有利。如此，以不易發生 離子傳導性基導入的芳香族乙烯基系化合物（例如取代芳 香族乙燒基系化合物）的聚合獲得芳香族乙烯基系聚合物 嵌段（C)，使用比起用於至少構成芳香族乙烯基系聚合物嵌 段（A)之芳香族乙烯基系化合物（例如無取代芳香族乙烯基 系化合物）的離子傳導性基導入反應的反應性足夠低的單 體’於利用製造不具有離子傳導性基之嵌段共聚物製造 後’導入離子傳導性基之方法，製造本發明之高分子電解 質方面爲有利。 對於嵌段共聚物導入離子傳導性基之方法，於製造本 發明之高分子電解質時，於離子傳導性基導入前之嵌段共 聚物中，相當於芳香族乙烯基系聚合物嵌段（C)之芳香族乙 烯基系聚合物嵌段，比起相當於芳香族乙烯基系聚合物嵌 段（A)之芳香族乙烯基系聚合物嵌段，非常難以導入離子傳 導性基，因此，芳香族乙烯基系聚合物嵌段（A)之離子傳導 性基導入率，於各種情形均比起芳香族乙烯基系聚合物嵌 段（C)顯著較高。芳香族乙烯基系聚合物嵌段（A)之離子傳 導性基，佔嵌段共聚物的總離子傳導性基的至少8 5 %以上 較佳，佔90%以上更佳，佔95%以上又更佳。 就發揮拘束相之機能的觀點，上述芳香族乙烯基系化 合物單元，爲芳香族乙烯基系聚合物嵌段（C)的主要重複單 元，且超過50重量％。又，佔70重量％以上更佳’佔90 重量。/。以上又更佳。 -29- 201131857 芳香族乙烯基系聚合物嵌段（C)之分子量，可視高分子 電解質之性狀、要求性能、其他聚合物成分等適當選擇。 分子量大時，高分子電解質的力學特性有提高的傾向，但 是若過大，則嵌段共聚物的成形、製膜會變得困難，分子 量過小時，力學特性有降低的傾向，因應必要性能分子量 適當選擇係爲重要。就標準聚苯乙烯換算之數量平均分子 量而言，通常從8 00至5 00,000之間選擇較佳，從2,000 至150,000之間選擇更佳，從3,000至50,000之間選擇又 更佳。 本發明使用之嵌段共聚物，係由芳香族乙烯基系聚合 物嵌段（C)、芳香族乙烯基系聚合物嵌段（A)及脂肪族乙烯 基系聚合物嵌段（B)構成時，該嵌段共聚物之構造不特別限 定，但是就例子而言，例如A — B ~ C - A四嵌段共聚物、B —A—B—C四嵌段共聚物、A— B—C—B四嵌段共聚物、C —B—C—A四嵌段共聚物、A_B—A—C四嵌段共聚物、A ~C— B—C— A五嵌段共聚物、C— A—B—A—C五嵌段共 聚物、A—C—B— C—A五嵌段共聚物、C— B— A— B— C 五嵌段共聚物' A—B — C— A - B五嵌段共聚物、A— B— C ~A_C五嵌段共聚物、A— B_C— B— C五嵌段共聚物、A —B_A— B—C五嵌段共聚物、A—B— A— C—B五嵌段共 聚物、B—A— B— A—C五嵌段共聚物、B—A— B— C—A 五嵌段共聚物、B— A— B— C— B五嵌段共聚物、C— A—C -B- C五嵌段共聚物等。從拘束性的觀點，具有多個C嵌 -30- 201131857 段較佳，尤其兩端具有C嵌段較佳。又，使本發明之高分 子電解質乳化使用時，從容易製備乳化液之觀點，於兩端 具有A嵌段較佳。又，從對於有機溶劑之溶解性、分散性 之觀點，以C — A — C — B _ C五嵌段共聚物爲理想。 本發明使用之嵌段共聚物，也包含一部分含有接枝鍵 結者。一部分含有接枝鍵結的嵌段共聚物，例如構成之聚 合物嵌段的一部分接枝鍵結於嵌段共聚物的主要部分（例 如主鏈）者等。 關於本發明可使用之高分子電解質中的嵌段共聚物之 製造方法，不特別限定，可使用習知的方法，較佳爲製造 不具有離子傳導性基之嵌段共聚物後，使離子傳導性基鍵 結的方法。以下就該不具有離子傳導性基之嵌段共聚物 中，將相當於芳香族乙烯基系聚合物嵌段（A)之不具有離子 傳導性基的聚合物嵌段作爲芳香族乙烯基系聚合物嵌段 (A)’進行說明。 依照構成芳香族乙烯基系聚合物嵌段（A)’或脂肪族乙 烯基系聚合物嵌段（B)之單體的種類、分子量等，芳香族乙 烯基系聚合物嵌段（A)’或脂肪族乙烯基系聚合物嵌段（B) 之製造方法可從自由基聚合法、陰離子聚合法、陽離子聚 合法、配位聚合法等適當選擇，但是從工業上的容易度來 看，選擇自由基聚合法、陰離子聚合法、陽離子聚合法較 佳。尤其，從分子量控制、分子量分布控制、聚合物構造 控制、芳香族乙烯基系聚合物嵌段（A)’與脂肪族乙烯基系 201131857 聚合物嵌段（B)之鍵結容易度等看來，使用所謂的活性 法較佳，具體而言，活性自由基聚合法、活性陰離子 法、活性陽離子聚合法較佳。 就製造方法之具體例而言，敘述由以4 -乙稀基 等芳香族乙烯基系化合物作爲主要重複單元之芳香族 基系聚合物嵌段（A)’及共軛二烯構成之脂肪族乙烯基 合物嵌段（B)爲成分的嵌段共聚物的製造方法。 於該情形，從工業上的容易度、分子量、分子量分 芳香族乙烯基系聚合物嵌段（A)’與脂肪族乙烯基系聚 嵌段（B)之鍵結容易度等來看，以活性陰離子聚合法進 造較佳，例如以下的具體合成例。 (1) 於甲苯溶劑中使用陰離子聚合起始劑，於1〇至 之溫度條件下，將4 -乙烯基聯苯等芳香族乙烯基系 物進行聚合，之後，使共軛二烯、4 -乙烯基聯苯等芳 乙烯基系化合物逐次聚合，獲得A’—B - A’型嵌段共 之方法。 (2) 於甲苯溶劑中使用陰離子聚合起始劑，於1 〇至 之溫度條件下，將4 一乙烯基聯苯等芳香族乙烯基系 物進行聚合，之後使共軛二烯聚合後，添加苯甲酸苯 偶合劑，獲得A’-B — A’型嵌段共聚物之方法。 就製造方法之具體例而言’敘述由以4 一第三丁 乙烯等芳香族乙烯基系化合物作爲主要重複單元之芳 乙烯基系聚合物嵌段（C)、4 一乙烯基聯苯等芳香族乙 聚合 聚合 聯苯 乙烯 系聚 布、 合物 行製 4 0°C 化合 香族 聚物 4 0°C 化合 酯等 基苯 香族 稀基 -32- 201131857 系化合物作爲主要重複單元之芳香族乙烯基系聚合物 (A)’及共軛二烯構成之聚合物嵌段（B)作爲構成成分 段共聚物之製造方法。於該情形，從工業上的容易度 子量 '分子量分布、聚合物嵌段（C)、（B)及（A)，之鍵結 度等來看’活性陰離子聚合法較佳，例如如下的具體 例，可採用/應用之。 (3) 於甲苯溶劑中使用陰離子聚合起始劑，於1 〇至 之溫度條件下’將4 -第三丁基苯乙烯等芳香族乙嫌 化合物進行聚合，之後使共軛二烯、4 -乙烯基聯苯等 族乙嫌基系化合物逐次聚合，獲得C- B-A’型嵌段丑 之方法。 (4) 於甲苯溶劑中使用陰離子聚合起始劑，於至 之溫度條件下’將4一第三丁基苯乙稀等芳香族乙稀 化合物進行聚合’之後使4-乙烯基聯苯等芳香族乙 系化α物、共範一儲逐次聚合後’添加苯甲酸苯醋等 劑，獲得C — A’_B — A’— C型嵌段共聚物之方法。 (5) 於甲苯溶劑中使用陰離子聚合起始劑，於1〇至 之溫度條件下，將4一第三丁基苯乙烯等芳香族乙烯 化合物進行聚合’之後使4-乙烯基聯苯等芳香族乙 系化合物、共軛二烯、4 -乙烯基聯苯等芳香族乙烯基 合物、4-第三丁基苯乙烯等芳香族乙烯基系化合物逐 合，獲得C — A’— B — A’— C型嵌段共聚物之方法。 嵌段 之嵌 、分 容易 合成 4 0°C 基系 芳香 聚物 4 0°C 基系 烯基 偶合 4 0°C 基系 烯基 系化 次聚 -33- 201131857 以該方式製造的嵌段共聚物’供予構成脂肪族乙烯基 系聚合物嵌段（B)之碳數4至8的共軛二烯單元的雙鍵的氫 化反應。該氫化反應的方法，例如將以陰離子聚合等獲得 之嵌段共聚物的溶液放入耐壓容器，使用Ni/Al系等 Ziegler系氫化觸媒，於氫氣氣體環境下進行氫化反應之方 法。 其次，敘述使離子傳導性基鍵結於獲得之嵌段共聚物 的方法。 首先，敘述將磺酸基導入獲得之嵌段共聚物的方法。 磺酸化可利用習知的磺酸化方法進行。如此的方法，例如 製備嵌段共聚物之有機溶劑溶液或懸浮液並添加磺酸化劑 混合之方法’或對於嵌段共聚物直接添加氣體狀磺酸化劑 之方法等。 使用的磺酸化劑，例如：硫酸、硫酸與脂肪族酸酐之混 合物系、氯磺酸、氯磺酸與氯化三甲基矽烷的混合物系、 三氧化硫、三氧化硫與磷酸三乙酯的混合物系，及以2,4,6 -三甲基苯磺酸爲代表之芳香族有機磺酸等。又，使用之 有機溶劑，例如二氯甲烷等鹵化烴類、己烷等直鏈式脂肪 族烴類、環己烷等環式脂肪族烴類等，也可視需要，從多 數組合中適當選擇使用。 就從得到的含有嵌段共聚物的磺酸化物的反應溶液， 將磺酸化物以固體物的形式取出的方法而言，例如有於水 中注入反應溶液使磺酸化物沉澱後，將溶劑於常壓餾去的 -34- 201131857 方法，或於反應溶液中緩慢加入停止劑的水而使其懸浮， 使磺酸化物析出後將溶劑以常壓餾去的方法等，但是從磺 酸化物微分散化且之後以水的清洗效率提高的觀點來看， 較佳爲於反應溶液中緩慢添加停止劑的水並使其懸浮，使 磺酸化物析出的方法。 其次敘述於獲得之嵌段共聚物導入膦酸基的方法。膦 酸化，可利用習知的膦酸化方法進行。具體而言，例如製 備嵌段共聚物的有機溶劑溶液或懸浮液，於無水氯化鋁存 在下，使該共聚物與氯甲醚等反應，於芳香環導入鹵甲基 後，於其中加入三氯化磷與無水氯化鋁並使其反應，再進 行水解反應而導入膦酸基之方法等。或，對於該共聚物添 加三氯化磷與無水氯化鋁使其反應，於芳香環導入次膦酸 基後，利用硝酸將次膦酸基氧化而成膦酸基之方法等。 磺酸化或膦酸化的程度，如既述者，較理想爲磺酸化 或膦酸化成使嵌段共聚物的離子交換容量較佳爲 0.40meq/g以上，更佳爲 0.50meq/g以上，進一·步更佳爲 0.60meq/g以上，另一方面，較佳爲4.5meq/g以下，更佳 爲4.0meq/g以下，進一步更佳爲3.5meq/g以下。藉此，可 得到實用的離子傳導性能。經磺酸化或膦酸化的嵌段共聚 物的離子交換容量或嵌段共聚物中的芳香族乙烯基系化合 物中的磺酸化率或膦酸化率，可使用酸價滴定法、紅外分 光光譜測定、核磁共振光譜Ch—nmr光譜）測定等分析方 法計算。 -35- 201131857 離子傳導性基’也可利用以適當金屬離子（例如鹼金屬 離子）或相對離子（例如銨離子）中和的鹽的形式導入。例如 利用以適當方法進行離子交換，能獲得使磺酸基成爲鹽型 的嵌段共聚物。 本發明之高分子電解質，只要不損及本發明的效果也 可含有各種添加劑，例如軟化劑、安定劑、光安定劑、抗 靜電劑、脫模劑、難燃劑、發泡劑、顏料、染料、增白劑 等各自單獨或2種以上的組合。 軟化劑例如：石蠟系、環烷系或芳香系的加工油等石油 系軟化劑、石蠟、植物油系軟化劑、可塑劑等。 安定劑包含苯酚系安定劑、硫系安定劑、磷系安定劑 等’具體例例如：2,6 -二—第三丁基對甲酚 '肆[3 —（3，5 -二—第三丁基一4 —羥基苯基）丙酸新戊四醇酯]、1，3,5 —三 甲基—2，4,6-參（3,5 —二—第三丁基一 4 —羥基苄基）苯、3 —(3,5_二—第三丁基—4_羥基苯基）丙酸十八酯、三乙二 醇—雙[3— (3 —第三丁基一 5 —甲基—4一羥基苯基）丙酸 酯]、2,4 —雙一（正辛基硫）—6— (4 —羥基—3，5-二一第三 丁基苯胺基）一 1，3,5_三阱、2,2_硫一二伸乙基雙[3 — (3,5 —二一第三丁基—4 -羥基苯基）丙酸酯]、N，N’ —六亞甲基 雙（3,5—二—第三丁基—4 —羥基—氫桂皮醯胺）、3,5 —二 —第三丁基一 4 —羥基一苄基膦酸二乙酯、參—（3, 5 —二— 第三丁基一 4 一羥基苄基）—異三聚氰酸酯、3,9 —雙{ 2_[3 —(3 —第三丁基—4—羥基—5—甲基苯基）丙醯氧基]一 1，1 -36- 201131857 -二甲基乙基}一 2,4,8，l〇 —四氧雜螺[5·5]十一烷等苯酚系 安定劑；新戊四醇基肆（3_月桂基硫丙酸酯）、3，3’一硫二 丙酸二硬脂酯、3,3，一硫二丙酸二月桂酯、3,3’一硫二丙酸 二肉豆蔻酯等硫系安定劑；參壬基苯基亞磷酸酯、參（2,4 -二-第三丁基苯基）亞磷酸酯、新戊四醇二亞磷酸二硬脂 酯、雙（2,6_二一第三丁基一4 —甲基苯基）新戊四醇二亞磷 酸酯等磷系安定劑。 本發明之高分子電解質中，嵌段共聚物的含量由離子 傳導性的觀點來看，以50重量°/〇以上較佳，70重量％以上 更佳，90重量％以上又更佳。 適於固體高分子型燃料電池用途等的本發明的高分子 電解質膜，由膜電阻、膜強度、操作性等觀點來看，其膜 厚以約5至300μηι較佳，約6至200μπι更佳，約7至ΙΟΟμηι 進一步更佳。欲使膜電阻降低時，較佳爲7至30μιη，欲使 膜電阻維持爲低且具有膜強度時，較佳爲20至60μιη，重 視膜強度時，以50至1 ΟΟμιη較佳。 該高分子電解質膜之製備方法，只要是用於製備的通 常方法均可採用，例如將構成高分子電解質膜的嵌段共聚 物或該嵌段共聚物及如上述之添加劑與適當溶劑混合，製 備5重量％以上的該嵌段共聚物的溶液或懸浮液或乳化液 後’使用塗布機或塗抹器等塗布在完成脫模處理的PET薄 膜等後，於適當條件下將溶劑除去，藉此，獲得具有希望 厚度之高分子電解質膜的溶液塗布方法，或者，將5重量 -37- 201131857 %以下的該嵌段共聚物的溶液或懸浮液或乳化液澆鑄在聚 四氟乙烯片材等後’花費1至數日將溶劑緩慢除去，藉此 得到具有希望厚度的高分子電解質膜的澆鑄法，或使用熱 壓成形、輥成形、擠壓成形等習知方法進行成膜之方法等， 但由容易製備具有良好強度及柔軟性的高分子電解質膜的 觀點來看，宜採用溶液塗布方法。 又’也可在獲得的高分子電解質膜層上，重新塗布相 同或不同的嵌段共聚物溶液並乾燥而使其積層化。又，也 可將如上述方式獲得之相同或不同的高分子電解質膜彼此 利用熱輥成形等壓接並積層化。 將高分子電解質膜以均勻溶液系製備時使用的溶劑， 只要是不破壞嵌段共聚物的構造而可製備能進行溶液塗布 程度的黏度的溶液者即可’無特別限制。具體而言，例如： 二氯甲烷、氯苯等鹵化烴類、甲苯、二甲苯、苯等芳香族 烴類、己烷、庚烷等直鏈式脂肪族烴類、環己烷等環式脂 肪族烴類、四氫呋喃等醚類、甲醇、乙醇、丙醇、異丙醇、 丁醇、異丁醇等醇類、或該等之混合溶劑等。可因應嵌段 共聚物的構成、分子量、離子交換容量等，由上述例示的 溶劑當中適當選用1種或2種以上的組合，但尤其從容易 製備具有良好強度及柔軟性的高分子電解質膜的觀點來 看’較佳爲甲苯與異丁醇的混合溶劑 '甲苯與異丙醇的混 合溶劑、環己烷與異丙醇的混合溶劑、環己烷與異丁醇的 混合溶劑、四氫呋喃、四氫呋喃與甲醇的混合溶劑、氯苯， -38- 201131857 尤佳爲甲苯與異丁醇的混合溶劑、甲苯與異丙醇的混合溶 劑、氯苯。 其次敘述以乳化液系製備高分子電解質膜的情形。具 有離子傳導性基的芳香族乙烯基系聚合物嵌段（A)爲親水 性、脂肪族乙烯基系聚合物嵌段（B)爲疏水性，因此有保護 膠體形成能力’可不使用界面活性劑而獲得乳化液。又， 藉由使用水等極性溶劑，可輕易製造外殻有高極性的離子 傳導性基的粒子。 製作上述乳化液的方法可使用習知方法，但是由能使 分散粒徑的分布狹窄的觀點來看，宜應用轉相乳化法。亦 即，一面將使該嵌段聚合物溶解於適當有機溶劑而成的溶 液以乳化機等攪拌一面添加水等極性溶劑。起初，水等極 性溶劑處於會以粒子的形式分散在有機溶劑系中的狀態， 但是若極性溶劑超過某個量則會成爲共連續狀態，黏度急 劇上升。又若進一步添加極性溶劑，則極性溶劑會成爲連 續相、有機溶劑成爲微粒，黏度急劇下降。使用該方法可 獲得分散粒徑整齊一致的乳化液。 乳化液的分散粒徑爲超過1 μιη的大粒徑時，於粒子內 嵌段聚合物成爲相分離的構造，全部的離子傳導性基未露 出外殻，因此無法有效使用離子傳導性基。因此，使用嵌 段聚合物時，雖也視使用的聚合物的分子量或嵌段的比例 而不同，但是微粒化至使平均分散粒徑成爲ΐμπι以下爲理 想。許多情形，由於上述預乳化的平均分散粒徑成爲1 μηι -39- 201131857 以上’因此’需要進一步微分散化。微分散化的方法可使 用習知方法’但是於防止雜質混入的觀點，較佳爲不使用 於球磨機中的粉碎用球的介質的方法。具體例，例如高壓 碰撞法等。 又’溶液塗布方法中的溶劑除去條件，只要是嵌段共 聚物的礦酸基等離子傳導性基會脫落的溫度以下且可將溶 劑完全除去的條件即可任意選擇。爲了展現所望的物性， 可將多數溫度任意組合或將通風下與真空下等任意組合。 具體而言’於約60至100 °C的熱風乾燥花費4分鐘以上將 溶劑除去之方法’或於約100至1401：的熱風乾燥以2至4 分鐘將溶劑除去之方法，或於約25 °C進行約1至3小時預 備乾燥後於約100 °C的熱風乾燥花費數分鐘進行乾燥之方 法’或於約2 5 °C進行約1至3小時預備乾燥後於約2 5至 40 °C的氣體氣體環境下以真空乾燥進行約1至12小時乾燥 的方法等。由容易製備具有良好強度與柔軟性的高分子電 解質膜的觀點來看，以約60至1〇〇。(：的熱風乾燥花費4分 鐘以上將溶劑除去之方法，或於約2 5。(：進行約1至3小時 預備乾燥後以約100 °C的熱風乾燥花費數分鐘進行乾燥的 方法，或於約2 5 °C進行約1至3小時預備乾燥後於約2 5 至4 0 °C的氣體氣體環境下以真空乾燥進行約1至12小時乾 燥的方法等較佳。 其次’敘述使用由本發明之高分子電解質製作之高分 子電解質膜的本發明的膜-電極接合體。對於膜一電極接 -40- 201131857 合體的製造無特別限制，可適用習知方法，例如將含有離 子傳導性黏結劑的觸媒糊劑利用印刷法或噴塗法，塗布在 氣體擴散層上並乾燥，形成觸媒層與氣體擴散層的接合 體’接著，將1對接合體分別以觸媒層作爲內側，利用熱 壓於高分子電解質膜的兩側等使其接合的方法，或將上述 觸媒糊劑利用印刷法或噴塗法塗布於高分子電解質兩側， 並乾燥使形成觸媒層，再利用熱壓等使氣體擴散層壓接於 各別的觸媒層的方法。又，其他製造方法，例如有將含有 離子傳導性黏結劑的溶液或懸浮液，塗布在高分子電解質 膜的兩面及/或1對氣體擴散電極的觸媒層面，並使高分子 電解質膜與觸媒層面貼合，利用熱壓接等予以接合的方 法。於該情形，可將該溶液或懸浮液塗布在高分子電解質 膜及觸媒層面的其中一面，也可塗布於兩面。又，就其他 製造方法而言，有以下方法：首先將上述觸媒糊劑塗布於聚 四氟乙烯（PTFE)製等基材薄膜並乾燥形成觸媒層，接著， 將1對該基材薄膜上的觸媒層利用加熱壓接轉印於高分子 電解質膜的兩側並將基材薄膜剝離，藉此，獲得高分子電 解質膜與觸媒層的接合體，並利用熱壓將氣體擴散層壓接 於各觸媒層的方法。在該等方法之中，也可將離子傳導性 基形成與鈉等金屬的鹽的狀態進行，並利用接合後的酸處 理進行使其返回質子型的處理。 構成上述膜-電極接合體的離子傳導性黏結劑，可使 用例如由「Nafion」（註冊商標、杜邦公司製）或「Gore — -41 - 201131857 select」（註冊商標’ Gore公司製）等既有的全氟磺酸系聚合 物構成之離子傳導性黏結劑、由磺酸化聚醚颯或磺酸化聚 醚酮構成之離子傳導性黏結劑、由含浸於磷酸或硫酸的聚 苯并咪唑構成的離子傳導性黏結劑等。又，也可由構成本 發明的高分子電解質膜的嵌段共聚物製作離子傳導性黏結 劑。又’爲了更加提高高分子電解質膜與氣體擴散電極的 密合性’較佳爲使用與構成高分子電解質膜的高分子電解 質爲同種的材料，更佳爲相同材料形成的離子傳導性黏結 劑。高分子電解質膜由多層構造等多數材料構成時，較佳 爲使用與構成高分子電解質膜的氣體擴散電極相接之面的 高分子電解質、或與爲該面之主要構成成分的高分子電解 質爲同種材料，更佳爲相同材料形成的離子傳導性黏結劑。 上述膜-電極接合體的觸媒層的構成材料，就導電材 料/觸媒載體而言無特別限制，例如碳材料。碳材料例如： 爐黑、槽製碳黑（〇1^111^1151“1〇、乙炔黑等碳黑、活性碳' 石墨等，該等可單獨使用或混合2種以上使用。觸媒金屬， 只要是可促進氫或甲醇等燃料的氧化反應及氧的還原反應 的金屬均可，例如鉛、金、銀、鈀、銥、铑、釕、鐵、鈷、 鎳、鉻、鎢、錳、鈀等，或此等的合金例如鈾一釕合金。 其中常使用鉑或鉛合金。成爲觸媒的金屬的粒徑，通常爲 10至3〇〇埃。該等觸媒載持於碳等導電材/觸媒載體者，可 減少觸媒使用量，於成本上爲有利。又，觸媒層中視需要 也可含有撥水劑。撥水劑，例如聚四氟乙烯、聚偏二氟乙 烯、苯乙烯丁二烯共聚物、聚醚醚酮等各種熱可塑性樹脂。 -42- 201131857 上述膜-電極接合體的氣體擴散層，例如由具有導電 性及氣體透過性的材料構成’該材料例如由碳紙或碳布等 碳纖維構成之多孔性材料。又’爲了提高撥水性，也可對 該材料施以撥水化處理。 藉由將如上述方法獲得的膜-電極接合體，插入於兼 作爲極室分離及對於電極的氣體供給流路的作用的導電性 分離件材料之間，可獲得固體高分子型燃料電池。本發明 之膜一電極接合體，可使用氫作爲燃料氣體之純氫型、使 用將甲醇改質而獲得之氫之甲醇改質型、使用將天然氣改 質而獲得之氫之天然氣改質型、使用將汽油改質而獲得之 氫之汽油改質型、直接使用甲醇之直接甲醇型等固體高分 子型燃料電池用膜-電極接合體使用。 由本發明之高分子電解質構成之高分子電解質膜，於 低濕度下具有高質子傳導性，且顯示低電阻’藉由將含有 該高分子電解質膜而成之膜-電極接合體用於以氫作爲燃 料的固體高分子型燃料電池，即使於低濕度下也能獲得高 輸出特性，且因爲水所致的膨潤少’與電極的接合性亦優 異。 [實施例] 以下舉實施例及比較例更具體說明本發明’但本發明 不限定於該等實施例。 -43- 201131857 (嵌段共聚物之離子交換容量之測定方法） 將嵌段共聚物秤量（秤量値a(g))於可將試樣密閉的玻 璃容器中，添加過量的氯化鈉飽和水溶液（（300至 500)xa(ml))並攪拌12小時。以酚酞作爲指示劑，以o.oiN 的NaOH標準水溶液（滴定率f)滴定（滴定量b(ml))滴定水中 產生的氯化氫。 離子交換容量以下式求取。 離子交換容量（meq/g)= (0.01 xbxf)/a (嵌段共聚物之數量平均分子量之測定方法） 數量平均分子量，利用凝膠滲透層析（G P C )法以下列條 件測定。(wherein R1 is a hydrogen atom or a hospital group having a carbon number of 1 to 4, and R2 to R4 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but at least one of them represents an alkyl group having 1 to 8 carbon atoms. One of the methods for producing a polymer electrolyte of the present invention, for example, a method of introducing an ion conductive group after producing a block copolymer having no ion conductive group. For example, when a sulfonic acid group is introduced as an ion conductive group, the sulfonation reaction of polystyrene preferentially occurs in the para position of the aromatic ring, and therefore, when the main repeating unit of the aromatic vinyl polymer block is the above 4- 4-position (para) substitution of methylstyrene unit, 4-tert-butylstyrene unit, α,4-dimethylstyrene unit, α-methyl-4-t-butylstyrene unit In the case of the styrene structure, the sulfonation reaction for the corresponding aromatic vinyl-based polymer block is less likely to occur (the sulfonation reaction rate is lowered or not reacted at all). Therefore, it is difficult to introduce a sulfonic acid group into the aromatic vinyl polymer block, and it is advantageous for the aromatic vinyl polymer block to be an aromatic vinyl compound unit having no ion conductive group. In particular, in the case of a configuration in which four substituents are substituted with a large volume of substituents, -28-201131857 is more advantageous, such as isopropyl, second butyl, tert-butyl' and 4 - second. The butyl styrene unit is more advantageous. In this manner, the aromatic vinyl polymer block (C) is obtained by polymerization of an aromatic vinyl compound (for example, a substituted aromatic ethylenic compound) in which an ion conductive group is not easily introduced, and is used for at least a composition. The aromatic vinyl compound (for example, an unsubstituted aromatic vinyl compound) of the aromatic vinyl polymer block (A) has a sufficiently low reactivity of the ion-conductive group introduction reaction. The method of introducing an ion conductive group after the production of the block copolymer having an ion conductive group is advantageous in producing the polymer electrolyte of the present invention. In the method of introducing the ion conductive group in the block copolymer, in the production of the polymer electrolyte of the present invention, the block copolymer before introduction of the ion conductive group corresponds to an aromatic vinyl polymer block (C). The aromatic vinyl polymer block is very difficult to introduce an ion conductive group than the aromatic vinyl polymer block corresponding to the aromatic vinyl polymer block (A). The ion conductive group introduction ratio of the group vinyl polymer block (A) is remarkably higher than that of the aromatic vinyl polymer block (C) in each case. The ion conductive group of the aromatic vinyl polymer block (A) is preferably at least 85 % or more based on the total ion conductive group of the block copolymer, more preferably 90% or more, and 95% or more. Better. In view of the function of the restraint, the aromatic vinyl compound unit is a main repeating unit of the aromatic vinyl polymer block (C) and is more than 50% by weight. Further, it accounts for 70% by weight or more and more preferably 90% by weight. /. The above is even better. -29- 201131857 The molecular weight of the aromatic vinyl polymer block (C) can be appropriately selected depending on the properties of the polymer electrolyte, the required properties, and other polymer components. When the molecular weight is large, the mechanical properties of the polymer electrolyte tend to be improved. However, if the molecular weight is too large, formation of the block copolymer and film formation become difficult, and when the molecular weight is too small, the mechanical properties tend to be lowered, and the necessary molecular weight is required. The selection system is important. In terms of the average molecular weight in terms of standard polystyrene, it is usually preferred to choose between 800 and 500,000, preferably between 2,000 and 150,000, and between 3,000 and 50,000. The block copolymer used in the present invention is composed of an aromatic vinyl polymer block (C), an aromatic vinyl polymer block (A), and an aliphatic vinyl polymer block (B). The structure of the block copolymer is not particularly limited, but for example, for example, A - B ~ C - A tetrablock copolymer, B - A - B - C tetra block copolymer, A - B - C-B tetrablock copolymer, C-B-C-A tetrablock copolymer, A_B-A-C tetrablock copolymer, A ~C-B-C-A pentablock copolymer, C- A-B-A-C pentablock copolymer, A-C-B-C-A pentablock copolymer, C-B-A-B-C pentablock copolymer 'A-B-C-A - B pentablock copolymer, A-B-C~A_C pentablock copolymer, A-B_C-B-C pentablock copolymer, A-B_A-B-C pentablock copolymer, A-B — A—C—B pentablock copolymer, B—A—B—A—C pentablock copolymer, B—A—B—C—A pentablock copolymer, B—A—B—C— B pentablock copolymer, C-A-C-B-C pentablock copolymer, and the like. From a restraint point of view, it is preferred to have a plurality of C-inserted -30-201131857 segments, especially having C blocks at both ends. Further, when the polymer electrolyte of the present invention is used by emulsifying, it is preferable to have an A block at both ends from the viewpoint of easiness in preparing an emulsion. Further, from the viewpoint of solubility and dispersibility in an organic solvent, a C-A-C-B_C pentablock copolymer is preferred. The block copolymer used in the present invention also contains a part containing a graft bond. A part of the block copolymer containing a graft bond, for example, a part of the constituent polymer block is graft-bonded to a main portion of the block copolymer (e.g., a main chain). The method for producing the block copolymer in the polymer electrolyte which can be used in the present invention is not particularly limited, and a conventional method can be used. It is preferred to produce a block copolymer having no ion conductive group and then ion-conducting. The method of sex-based bonding. In the block copolymer having no ion-conductive group, a polymer block having no ion-conductive group corresponding to the aromatic vinyl-based polymer block (A) is polymerized as an aromatic vinyl group. The block (A)' will be described. The aromatic vinyl polymer block (A)' according to the type and molecular weight of the monomer constituting the aromatic vinyl polymer block (A)' or the aliphatic vinyl polymer block (B) The method for producing the aliphatic vinyl polymer block (B) can be appropriately selected from a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a coordination polymerization method, etc., but from the viewpoint of industrial easiness, selection The radical polymerization method, the anionic polymerization method, and the cationic polymerization method are preferred. In particular, from the viewpoints of molecular weight control, molecular weight distribution control, polymer structure control, and ease of bonding of the aromatic vinyl-based polymer block (A)' to the aliphatic vinyl-based 201131857 polymer block (B), It is preferred to use a so-called active method, and specifically, a living radical polymerization method, an active anion method, or a living cationic polymerization method is preferred. In the specific example of the production method, an aliphatic group composed of an aromatic group-based polymer block (A)' having a 4-ethylidene group or the like as a main repeating unit and a conjugated diene is described. A method for producing a block copolymer in which a vinylate block (B) is a component. In this case, from the viewpoints of industrial ease, molecular weight, and molecular weight, the ease of bonding of the aromatic vinyl-based polymer block (A)' and the aliphatic vinyl-based polyblock (B), etc. The living anionic polymerization method is preferably carried out, for example, the following specific synthesis examples. (1) An anionic polymerization initiator is used in a toluene solvent, and an aromatic vinyl compound such as 4-vinylbiphenyl is polymerized at a temperature of 1 Torr, and then a conjugated diene, 4 - A method in which an arylene-based compound such as vinylbiphenyl is sequentially polymerized to obtain a block of A'-B-A' type. (2) An anionic polymerization initiator is used in a toluene solvent, and an aromatic vinyl compound such as 4-vinylbiphenyl is polymerized at a temperature of 1 Torr, and then the conjugated diene is polymerized and then added. A benzoic acid benzene coupling agent, a method of obtaining an A'-B-A' type block copolymer. In the specific example of the production method, an aromatic vinyl-based polymer block (C) or 4-vinylbiphenyl having an aromatic vinyl compound such as tetrabutylethylene or the like is used as a main repeating unit. Group B polymerization polymerization of styrene-based poly cloth, compound production of 40 °C compounding fragrance polymer 40 ° C compound ester and other base benzene scent base -32- 201131857 system compound as the main repeat unit of aromatic The polymer block (B) composed of the vinyl polymer (A)' and the conjugated diene is used as a method for producing the constituent segment copolymer. In this case, the living anion polymerization method is preferable from the industrial ease of the amount 'molecular weight distribution, the polymer block (C), (B) and (A), and the like, for example, as follows Specific examples can be adopted/applied. (3) An anionic polymerization initiator is used in a toluene solvent to polymerize an aromatic ethyl compound such as 4-butenylstyrene at a temperature of 1 Torr, and then to obtain a conjugated diene, 4 - A method in which a group of B-based compounds such as vinyl biphenyl are sequentially polymerized to obtain a C-B-A' type block is ugly. (4) An anionic polymerization initiator is used in a toluene solvent, and an aromatic vinyl compound such as 4-tert-butyl styrene is polymerized under the temperature conditions to give a fragrance such as 4-vinylbiphenyl. A method of obtaining a C-A'_B-A'-C type block copolymer by adding a benzoic acid benzene vinegar or the like after successively polymerizing the α-element and the common-type storage. (5) An anionic polymerization initiator is used in a toluene solvent, and an aromatic vinyl compound such as 4-tert-butylstyrene is polymerized at a temperature of 1 Torr to give a fragrance such as 4-vinylbiphenyl. An aromatic vinyl compound such as a group B compound, a conjugated diene or a 4-vinylbiphenyl or an aromatic vinyl compound such as 4-tert-butylstyrene is combined to obtain C - A' - B - A'-C type block copolymer method. Block intercalation, easy to synthesize 40 ° C base aromatic polymer 40 ° C base alkenyl coupling 40 ° C base alkenyl group secondary poly-33- 201131857 block copolymer produced in this way The product is supplied with a hydrogenation reaction of a double bond constituting a conjugated diene unit having 4 to 8 carbon atoms of the aliphatic vinyl polymer block (B). In the method of the hydrogenation reaction, for example, a solution of a block copolymer obtained by anionic polymerization or the like is placed in a pressure-resistant container, and a hydrogenation reaction is carried out in a hydrogen gas atmosphere using a Ziegler-based hydrogenation catalyst such as Ni/Al. Next, a method of bonding an ion conductive group to the obtained block copolymer will be described. First, a method of introducing a sulfonic acid group into the obtained block copolymer will be described. The sulfonation can be carried out by a conventional sulfonation method. Such a method, for example, a method of preparing an organic solvent solution or suspension of a block copolymer and adding a sulfonating agent, or a method of directly adding a gaseous sulfonating agent to the block copolymer, or the like. The sulfonating agent used, for example, sulfuric acid, a mixture of sulfuric acid and an aliphatic acid anhydride, a mixture of chlorosulfonic acid, chlorosulfonic acid and trimethylsulfane chloride, sulfur trioxide, sulfur trioxide and triethyl phosphate The mixture is an aromatic organic sulfonic acid represented by 2,4,6-trimethylbenzenesulfonic acid. Further, the organic solvent to be used, for example, a halogenated hydrocarbon such as dichloromethane, a linear aliphatic hydrocarbon such as hexane, or a cyclic aliphatic hydrocarbon such as cyclohexane, may be appropriately selected from most combinations as necessary. . From the obtained reaction solution of the block copolymer-containing sulfonate, the method of taking out the sulfonate as a solid, for example, after injecting a reaction solution into water to precipitate a sulfonate, the solvent is often used. -34-201131857 method, or slowly adding water to the reaction solution in the reaction solution to suspend it, to precipitate the sulfonate, and then to distill the solvent at atmospheric pressure, etc., but slightly dispersed from the sulfonate Further, from the viewpoint of improving the cleaning efficiency of water, a method in which water of a stopper is slowly added to the reaction solution and suspended to precipitate a sulfonate is preferred. Next, a method of introducing a phosphonic acid group into the obtained block copolymer will be described. Phosphonation can be carried out using conventional phosphonation methods. Specifically, for example, an organic solvent solution or suspension of a block copolymer is prepared, and the copolymer is reacted with chloromethyl ether or the like in the presence of anhydrous aluminum chloride, and after the halogen ring is introduced into the aromatic ring, three are added thereto. A method in which phosphorus chloride and anhydrous aluminum chloride are reacted, and a hydrolysis reaction is carried out to introduce a phosphonic acid group. Alternatively, a method in which phosphorus trichloride is added to the copolymer to react with anhydrous aluminum chloride, and a phosphinic acid group is oxidized by nitric acid after introducing a phosphinic acid group into the aromatic ring is used. The degree of sulfonation or phosphonation, as described above, is preferably sulfonated or phosphonated such that the ion exchange capacity of the block copolymer is preferably 0.40 meq/g or more, more preferably 0.50 meq/g or more. The step is more preferably 0.60 meq/g or more, and on the other hand, it is preferably 4.5 meq/g or less, more preferably 4.0 meq/g or less, still more preferably 3.5 meq/g or less. Thereby, practical ion conductivity can be obtained. The ion exchange capacity of the sulfonated or phosphonated block copolymer or the sulfonation ratio or phosphonic acidification rate in the aromatic vinyl compound in the block copolymer can be determined by acid titration, infrared spectrometry, Nuclear magnetic resonance spectrum Ch-nmr spectrum) determination and other analytical methods are calculated. -35- 201131857 The ion-conducting group ' can also be introduced in the form of a salt neutralized with a suitable metal ion (for example, an alkali metal ion) or a counter ion (for example, an ammonium ion). For example, a block copolymer in which a sulfonic acid group is a salt type can be obtained by performing ion exchange by an appropriate method. The polymer electrolyte of the present invention may contain various additives such as a softener, a stabilizer, a photosetter, an antistatic agent, a mold release agent, a flame retardant, a foaming agent, a pigment, and the like, without impairing the effects of the present invention. The dye, the whitening agent, and the like are each used singly or in combination of two or more kinds. The softening agent is, for example, a petroleum softener such as a paraffinic, naphthenic or aromatic processing oil, a paraffin wax, a vegetable oil softener, a plasticizer or the like. The stabilizer contains a phenol-based stabilizer, a sulfur-based stabilizer, a phosphorus-based stabilizer, etc. 'Specific examples, for example, 2,6-di-t-butyl-p-cresol' 肆[3—(3,5-di-third Butyl 4- 4-hydroxyphenyl) propionic acid pentaerythritol], 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxyl Benzyl)benzene, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, triethylene glycol-bis[3-(3-t-butyl-5- Methyl-4-hydroxyphenyl)propionate], 2,4-di-(n-octylsulfanyl)-6-(4-hydroxy-3,5-di-t-butylphenylamino)- 1, 3,5_Tri-trap, 2,2-sulfanyl-diethylethyl [3-(3,5-di-di-t-butyl-4-hydroxyphenyl)propionate], N,N'- Methylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamate), diethyl 3,5-di-t-butyl- 4-hydroxy-benzylphosphonate, ginseng —(3, 5 —di-t-butyl-1,4-hydroxybenzyl)-iso-isocyanate, 3,9-double { 2_[3 —(3 —t-butyl-4-hydroxy-5 —methylphenyl)propenyloxy ]1,1 -36- 201131857 - dimethylethyl}- 2,4,8,l〇-tetraoxaspiro[5·5]undecane and other phenolic stabilizers; pentaerythritol ruthenium (3_lauryl thiopropionate), 3,3'-distearyl dithiolate, 3,3, dilauryl dithiodipropionate, 3,3'-thiodipropionate dimyristyl Sulfur-based stabilizer such as ester; decyl phenyl phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, neopentyl glycol diphosphonate, bis (2) , 6_di-tert-butyl-4-methyl-phenyl) neopentyl glycol diphosphite and other phosphorus-based stabilizers. In the polymer electrolyte of the present invention, the content of the block copolymer is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more, from the viewpoint of ion conductivity. The polymer electrolyte membrane of the present invention which is suitable for use in a polymer electrolyte fuel cell or the like has a film thickness of about 5 to 300 μm, preferably about 6 to 200 μm, from the viewpoints of film resistance, film strength, handleability and the like. , about 7 to ΙΟΟμηι is even better. When the film resistance is to be lowered, it is preferably 7 to 30 μm, and it is preferably 20 to 60 μm when the film resistance is kept low and has a film strength, and 50 to 1 μm is preferable for the film strength. The method for preparing the polymer electrolyte membrane can be used as long as it is a usual method for preparation, for example, a block copolymer constituting a polymer electrolyte membrane or the block copolymer and an additive as described above are mixed with a suitable solvent to prepare a method. After 5% by weight or more of the solution or suspension or emulsion of the block copolymer is applied to a PET film or the like which has been subjected to release treatment using a coater or an applicator, the solvent is removed under appropriate conditions, whereby Obtaining a solution coating method of a polymer electrolyte membrane having a desired thickness, or casting a solution or suspension or emulsion of the block copolymer of 5 to 37-201131857% or less after the polytetrafluoroethylene sheet or the like The method of slowly removing the solvent from 1 to several days to obtain a polymer electrolyte membrane having a desired thickness, or a method of forming a film by a conventional method such as hot press forming, roll forming, or extrusion molding, etc., but From the viewpoint of easily preparing a polymer electrolyte membrane having good strength and flexibility, a solution coating method is preferably employed. Further, the same or different block copolymer solutions may be recoated on the obtained polymer electrolyte membrane layer and dried to be laminated. Further, the same or different polymer electrolyte membranes obtained as described above may be pressure-bonded to each other by heat roll forming or the like. The solvent to be used in the preparation of the polymer electrolyte membrane in a uniform solution is not particularly limited as long as it can prepare a solution having a viscosity at a solution coating degree without destroying the structure of the block copolymer. Specific examples include halogenated hydrocarbons such as dichloromethane and chlorobenzene, aromatic hydrocarbons such as toluene, xylene, and benzene, linear aliphatic hydrocarbons such as hexane and heptane, and cyclic fats such as cyclohexane. An ether such as a hydrocarbon or tetrahydrofuran; an alcohol such as methanol, ethanol, propanol, isopropanol, butanol or isobutanol; or a mixed solvent thereof. Depending on the composition, the molecular weight, the ion exchange capacity, and the like of the above-mentioned block copolymer, one or a combination of two or more kinds may be appropriately selected from the above-exemplified solvents, but in particular, it is easy to prepare a polymer electrolyte membrane having good strength and flexibility. From the viewpoint of 'preferably a mixed solvent of toluene and isobutanol', a mixed solvent of toluene and isopropyl alcohol, a mixed solvent of cyclohexane and isopropyl alcohol, a mixed solvent of cyclohexane and isobutanol, tetrahydrofuran, tetrahydrofuran Mixed solvent with methanol, chlorobenzene, -38- 201131857 Especially preferred is a mixed solvent of toluene and isobutanol, a mixed solvent of toluene and isopropanol, and chlorobenzene. Next, a case where a polymer electrolyte membrane is prepared by an emulsion system will be described. The aromatic vinyl polymer block (A) having an ion conductive group is hydrophilic, and the aliphatic vinyl polymer block (B) is hydrophobic, so that it has a protective colloid forming ability. And get the emulsion. Further, by using a polar solvent such as water, particles having an ion conductive group having a high polarity can be easily produced. A conventional method can be used for the method for producing the above emulsion, but from the viewpoint of narrowing the distribution of the dispersed particle diameter, a phase inversion emulsification method is preferably employed. In other words, a solution obtained by dissolving the block polymer in a suitable organic solvent is added with a polar solvent such as water while stirring with an emulsifier or the like. Initially, a polar solvent such as water is in a state of being dispersed in an organic solvent system as particles. However, if the polar solvent exceeds a certain amount, it becomes a co-continuous state, and the viscosity rapidly increases. Further, when a polar solvent is further added, the polar solvent becomes a continuous phase, the organic solvent becomes fine particles, and the viscosity sharply decreases. Using this method, an emulsion having a uniform dispersion particle size can be obtained. When the dispersed particle diameter of the emulsion is a large particle diameter of more than 1 μm, the intragranular block polymer has a phase separation structure, and all the ion conductive groups are not exposed to the outer shell, so that the ion conductive group cannot be effectively used. Therefore, when a block polymer is used, it differs depending on the molecular weight of the polymer to be used or the ratio of the block. However, it is desirable to atomize the particles to have an average dispersed particle diameter of ΐμπι or less. In many cases, since the average dispersed particle diameter of the above pre-emulsified is 1 μηι -39 - 201131857 or more, "there is a need for further microdispersion." The method of microdispersion can be carried out by a conventional method, but from the viewpoint of preventing the incorporation of impurities, a method of not using a medium for pulverizing balls in a ball mill is preferred. Specific examples include a high pressure collision method and the like. Further, the solvent removal conditions in the solution coating method can be arbitrarily selected as long as the temperature at which the mineral-conductive group of the ortho-acid group of the block copolymer falls off and the solvent can be completely removed. In order to exhibit the desired physical properties, most of the temperatures can be arbitrarily combined or arbitrarily combined with a vacuum or the like. Specifically, 'the method of removing the solvent by hot air drying at about 60 to 100 ° C for 4 minutes or more' or the method of removing the solvent by drying with hot air of about 100 to 1401 for 2 to 4 minutes, or about 25 ° C is carried out after about 1 to 3 hours of preliminary drying and drying at about 100 ° C for several minutes to dry - or about 2 to 5 ° C for about 1 to 3 hours after preliminary drying at about 25 to 40 ° C A method of drying in a gas atmosphere under vacuum for about 1 to 12 hours, and the like. From the viewpoint of easily preparing a polymer electrolyte membrane having good strength and flexibility, it is about 60 to 1 Torr. (: The hot air drying method takes 4 minutes or more to remove the solvent, or about 25). (: After drying for about 1 to 3 hours, it is dried by hot air at about 100 ° C for several minutes to dry, or Preferably, it is preferably dried at about 25 ° C for about 1 to 3 hours, and dried in a gas atmosphere of about 25 to 40 ° C in a vacuum gas atmosphere for about 1 to 12 hours. The membrane-electrode assembly of the present invention is a polymer electrolyte membrane produced by a polymer electrolyte. The membrane-electrode assembly is not particularly limited, and a conventional method can be applied, for example, an ion-conducting binder is used. The catalyst paste is applied to the gas diffusion layer by a printing method or a spray coating method and dried to form a bonded body of the catalyst layer and the gas diffusion layer. Next, the pair of bonded bodies are respectively made of the catalyst layer as the inner side, and the hot pressing is performed. a method of bonding the two sides of the polymer electrolyte membrane or the like, or applying the above-mentioned catalyst paste to both sides of the polymer electrolyte by a printing method or a spray coating method, and drying to form a catalyst layer, and then using the same. a method of diffusing a gas to a respective catalyst layer by pressure, etc. Further, other manufacturing methods include, for example, coating a solution or suspension containing an ion conductive adhesive on both sides of a polymer electrolyte membrane and/or a method in which a polymer layer of a gas diffusion electrode is bonded to a catalyst layer and bonded to a catalyst layer by thermocompression bonding, etc. In this case, the solution or suspension can be applied to a polymer electrolyte membrane. One of the catalyst layers may be applied to both sides. Further, in other manufacturing methods, the following method may be employed: first, applying the above-mentioned catalyst paste to a substrate film such as polytetrafluoroethylene (PTFE) and drying it. The catalyst layer is formed, and then the catalyst layer on the base film is transferred to both sides of the polymer electrolyte membrane by heat and pressure bonding, and the base film is peeled off, whereby the polymer electrolyte membrane and the contact are obtained. a method of diffusing and bonding a gas to each catalyst layer by hot pressing, and forming an ion conductive group into a state of a salt of a metal such as sodium, and use The acid treatment after the bonding is carried out to return to the proton type. The ion conductive adhesive constituting the membrane-electrode assembly can be, for example, "Nafion" (registered trademark, manufactured by DuPont) or "Gore — -41 - 201131857 select" (registered trademark 'Gore Co., Ltd.), an ion conductive adhesive composed of an existing perfluorosulfonic acid polymer, an ion conductive adhesive composed of a sulfonated polyether oxime or a sulfonated polyether ketone, An ion conductive adhesive composed of polybenzimidazole impregnated with phosphoric acid or sulfuric acid, etc. Further, an ion conductive adhesive can be produced from a block copolymer constituting the polymer electrolyte membrane of the present invention. The adhesion between the molecular electrolyte membrane and the gas diffusion electrode is preferably a material of the same kind as the polymer electrolyte constituting the polymer electrolyte membrane, and more preferably an ion conductive binder formed of the same material. When the polymer electrolyte membrane is composed of a plurality of materials such as a multilayer structure, it is preferred to use a polymer electrolyte that is in contact with a gas diffusion electrode that constitutes the polymer electrolyte membrane, or a polymer electrolyte that is a main constituent of the surface. The same material, more preferably an ion conductive adhesive formed of the same material. The constituent material of the catalyst layer of the membrane-electrode assembly is not particularly limited in terms of the conductive material/catalyst carrier, such as a carbon material. The carbon material is, for example, furnace black, grooved carbon black (〇1^111^1151"1〇, carbon black such as acetylene black, activated carbon' graphite, etc., and these may be used alone or in combination of two or more. Catalyst metals, Any metal that can promote the oxidation reaction of hydrogen or methanol and the reduction reaction of oxygen, such as lead, gold, silver, palladium, rhodium, iridium, ruthenium, iron, cobalt, nickel, chromium, tungsten, manganese, palladium. Etc., or such alloys such as uranium-niobium alloys. Platinum or lead alloys are often used. The particle size of the metal to be a catalyst is usually 10 to 3 angstroms. The catalysts are supported on a conductive material such as carbon. / Catalyst carrier, can reduce the amount of catalyst used, which is advantageous in terms of cost. In addition, the catalyst layer may also contain a water repellent agent as needed. Water repellent such as polytetrafluoroethylene, polyvinylidene fluoride, benzene Various thermoplastic resins such as a vinyl butadiene copolymer and a polyether ether ketone. -42- 201131857 The gas diffusion layer of the membrane-electrode assembly is made of, for example, a material having conductivity and gas permeability. a porous material made of carbon fiber such as paper or carbon cloth. The water-repellent treatment may be applied to the material. The membrane-electrode assembly obtained by the above method is inserted into the conductivity which functions as a gas separation and a gas supply flow path to the electrode. A solid polymer fuel cell can be obtained between the separator materials. The membrane-electrode assembly of the present invention can be a pure hydrogen type using hydrogen as a fuel gas, and a methanol-modified type using hydrogen obtained by reforming methanol. Membrane-electrode assembly for a polymer electrolyte fuel cell using a natural gas-modified type of hydrogen obtained by upgrading natural gas, a gasoline-modified type using hydrogen obtained by upgrading gasoline, and a direct methanol type using methanol directly The polymer electrolyte membrane comprising the polymer electrolyte of the present invention has high proton conductivity at low humidity and exhibits low electrical resistance by using a membrane-electrode assembly comprising the polymer electrolyte membrane. A polymer electrolyte fuel cell using hydrogen as a fuel can obtain high output characteristics even under low humidity, and has less swelling due to water' entanglement with an electrode [Embodiment] The present invention will be more specifically described below by way of Examples and Comparative Examples. However, the present invention is not limited to the examples. -43-201131857 (Method for measuring ion exchange capacity of block copolymer) Block Copolymer weighing (weighing 値a (g)) In a glass container in which the sample can be sealed, an excess saturated aqueous solution of sodium chloride ((300 to 500) x a (ml)) was added and stirred for 12 hours. To dilute the hydrogen chloride produced in water by titration with a NaOH standard aqueous solution (titer ratio f) of o. oiN (titration amount b (ml)). The ion exchange capacity is obtained by the following formula: Ion exchange capacity (meq/g) = (0.01 xbxf /a (Method for measuring the number average molecular weight of the block copolymer) The number average molecular weight is measured by a gel permeation chromatography (GPC) method under the following conditions.
裝置：東曹（股）製、商品名：HLC- 8220GPC 溶離液：THF 管柱：將東曹（股）製、商品名：TSK — GEL(TSKgel G3000HxL(內徑 7.6mm、有效長度 30cm)l 支、TSKgel Super Multipore HZ — Μ(內徑4.6mm、有效長度15cm)2支，共計 3支以串.連連接） 管柱溫度：4〇°C 檢測器：RI 送液量：〇_35ml /分 數量平均分子量計算··標準聚苯乙烯換算 -44- 201131857 <參考例1 > (製造由聚（4 一乙烯基聯苯）、氫化聚異戊二烯及聚（4 -第三丁基苯乙烯）構成之嵌段共聚物） 於lOOOmL熱壓釜中加入脫水甲苯43 5ml及第二丁基 鋰（1.05M—環己烷溶液）1.71ml後，逐次添加4 —第三丁基 苯乙烯7.6ml、4 一乙烯基聯苯25.3g、4 —第三丁基苯乙烯 7.1ml、異戊二烯26.4ml、4_第三丁基苯乙烯6.6ml，並於 4〇 °C使其逐次聚合，而合成聚（4 一第三丁基苯乙烯）-b -聚 (4 -乙烯基聯苯）一b—聚（4 —第三丁基苯乙烯）一b —聚異 戊二烯一 b —聚（4 —第三丁基苯乙烯）（以下簡稱爲 tBSVBtBSItBS)。獲得的tBSVBtBSItBS的數量平均分子量 (GPC測定、標準聚苯乙烯換算）爲35,000，由1H-NMR測 定求得的1 , 4 —鍵結量爲9 3 · 0 %，4 —乙烯基聯苯單元的含 量爲36.6重量％，4 —第三丁基苯乙烯單元的含量爲30.4 重量％。 製備經合成的tBSVBtBSItBS的環己烷溶液，裝入經過 充分氮取代的耐壓容器後，使用Ni/Al系Ziegler系氫化觸 媒’於氫氣氣體環境下於7 0 °C進行8小時氫化反應，獲得 聚（4 —第三丁基苯乙烯）—b -聚（4 —乙烯基聯苯）—b-聚 (4 —第三丁基苯乙烯）—b-氫化聚異戊二烯一 b-聚（4_第 三丁基苯乙烯）（以下簡稱爲tBSVBtBSEPtBS)。以1H—NMR 光譜測定計算獲得的t B S V B t B S E P t B S的氫化率，結果未檢 測到來自於聚異戊二烯的雙鍵的峰部。 -45- 201131857 <參考例2 > (製造由（聚（4 —乙烯基聯苯）、氫化聚異戊二烯及聚（4 -第三丁基苯乙烯）構成之嵌段共聚物） 於lOOOmL熱壓釜加入脫水甲苯435ml及第二丁基鋰 (1_2〇 Μ-環己烷溶液）1.0ml後’添加4—第三丁基苯乙烯Device: Tosoh Co., Ltd., trade name: HLC-8220GPC Dissolution: THF Pipe column: Tosoh (stock), trade name: TSK — GEL (TSKgel G3000HxL (inner diameter 7.6mm, effective length 30cm) l Branch, TSKgel Super Multipore HZ — Μ (inner diameter 4.6mm, effective length 15cm) 2 pieces, total 3 pieces in series. Connection) Column temperature: 4〇 °C Detector: RI Liquid volume: 〇_35ml / Calculation of the number average molecular weight··Standard polystyrene conversion-44- 201131857 <Reference example 1 > (Manufactured from poly(4-vinylbiphenyl), hydrogenated polyisoprene, and poly(4-third) Block copolymer composed of styrene). After adding 5 ml of dehydrated toluene and 1.71 ml of second butyllithium (1.05 M-cyclohexane solution) in a 1000 mL autoclave, 4 to 3 butylbenzene was added successively. 7.6 ml of ethylene, 25.3 g of 4-vinylbiphenyl, 7.1 ml of 4-tert-butylstyrene, 26.4 ml of isoprene, 6.6 ml of 4_t-butylstyrene, and allowed to make it at 4 ° C. Sequential polymerization, and synthesis of poly(4-butylbutyl styrene)-b-poly(4-vinylbiphenyl)-b-poly(4-t-butylstyrene)-b-polymer Pentadiene a b - poly (4 - tertiary butylstyrene) (hereinafter abbreviated as tBSVBtBSItBS). The number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSVBtBSItBS was 35,000, and the amount of 1,4 - linkage determined by 1H-NMR was 9 3 · 0 %, and the 4-vinylbiphenyl unit was obtained. The content was 36.6 wt%, and the content of the 4-tert-butylstyrene unit was 30.4 wt%. A cyclohexane solution of the synthesized tBSVBtBSItBS was prepared, and after being filled into a pressure-resistant container which was sufficiently nitrogen-substituted, a Ni/Al-based Ziegler-based hydrogenation catalyst was used for hydrogenation at 70 ° C for 8 hours under a hydrogen atmosphere. Obtaining poly(4-t-butylstyrene)-b-poly(4-vinylbiphenyl)-b-poly(4-t-butylstyrene)-b-hydrogenated polyisoprene-b- Poly(4_t-butylstyrene) (hereinafter referred to as tBSVBtBSEPtBS). The hydrogenation rate of t B S V B t B S E P t B S obtained by 1H-NMR spectroscopy was measured, and as a result, no peak derived from the double bond of polyisoprene was detected. -45- 201131857 <Reference Example 2 > (Production of block copolymer composed of (poly(4-vinylbiphenyl), hydrogenated polyisoprene, and poly(4-t-butylstyrene)) Adding 4 - tert-butyl styrene after adding 435 ml of dehydrated toluene and 1.0 ml of second butyl lithium (1 2 〇Μ-cyclohexane solution) in a 1000 mL autoclave
10.3ml、4_乙烯基聯苯22.8g、異戊二烯36.8ml，於4(TC 進行聚合，並添加苯甲酸苯酯137mg使其偶合，藉此合成 聚（4 -第三丁基苯乙稀）一b—聚（4 一乙嫌基聯苯）—b—聚 異戊二稀一 b —聚（4 —乙燃基聯苯）—b —聚（4 —第三丁基苯 乙烯）（以下簡稱爲tBSVBIVBtBS)。獲得的tBSVBIVBtBS 的數量平均分子量（GPC測定，標準聚苯乙烯換算）爲 1 5 8,000，由1H— NMR測定求得的1，4 一鍵結量爲94.0%， 4 一乙烯基聯苯單元的含量爲33·9重量％，4 —第三丁基苯 乙烯單元的含量爲22.0重量％。 製備經合成的tBSVBIVBtBS的環己烷溶液，裝入經過 充分氮取代的耐壓容器後，使用Ni/Al系Ziegler系氫化觸 媒，於氫氣氣體環境下於7 0 °C進行8小時氫化反應，獲得 聚（4 —第三丁基苯乙烯）一b —聚（4 —乙烯基聯苯）—b —氫 化聚異戊二烯—b-聚（4_乙烯基聯苯）—b—聚（4 —第三丁 基苯乙烯）（以下簡稱爲tBSVBEPVBtBS)。以1H-NMR光譜 測定計算獲得的tBSVBEPVBtBS的氫化率，未檢測到來自 於聚異戊二烯的雙鍵的峰部。 -46- 201131857 <參考例3 > (製造由聚苯乙烯、氫化聚異戊二烯及聚（4 -第三丁基 苯乙烯））構成之嵌段共聚物） 於l4〇OmL熱壓釜加入脫水環己烷8 2 0ml及第二丁基 鋰（1.25M-環己烷溶液）l.7ml後，逐次添加4—第三丁基 苯乙烯19.8ml、苯乙烯27.7ml，於5〇t：使其逐次聚合，接 著，逐次添加異戊二烯80.4ml、苯乙烯26.6ml、及4一第 三丁基苯乙烯18.1ml，於60 °C使其逐次聚合藉此合成聚（4 —第三丁基苯乙烯）_b —聚苯乙烯一 b —聚異戊二烯一 b — 聚苯乙烯—b -聚（4 -第三丁基苯乙烯）（以下簡稱爲 tBSSIStBS)。獲得的tBSSIStBS的數量平均分子量（GPC測 定，標準聚苯乙烯換算）爲86,000，由1H—NMR測定求得 的1，4 一鍵結量爲94.0%，苯乙烯單元的含量爲32.9重量 %，4一第三丁基苯乙烯單元的含量爲29.8重量％。 製備經合成的tBSSIStBS的環己烷溶液，放入經過充 分氮取代的耐壓容器後，使用Ni/A1系ziegler系氫化觸 媒，於氫氣氣體環境下於70 °C進行8小時氫化反應’獲得 聚（4 —第三丁基苯乙烯）一 b-聚苯乙烯- b_氫化聚異戊 二稀—b-聚苯乙烧—b—聚（4一第二丁基苯乙嫌）（以下簡 稱爲tBSSEPStBS)。以1H—NMR光譜測定計算獲得之 tBSSEPStBS的氫化率，未檢測到來自於聚異戊二烯的雙鍵 的峰部 -47- 201131857 <參考例4 > (製造由聚苯乙烯、氫化聚異戊二烯及聚（4 一第三丁基 苯乙烯）構成之嵌段共聚物） 於1 400mL熱壓釜加入脫水環己烷76 8 ml及第二丁基 鋰（1·25Μ_環己烷溶液）1.76ml後，逐次添加4 一第三丁基 苯乙烯60.7ml、苯乙烯55.6 ml，並於50 °C使其逐次聚合， 接著，逐次添加異戊二嫌2〇2ml'苯乙稀54.1ml、及4 —第 三丁基苯乙烯56.7ml，並於60 °C使其逐次聚合，藉此合成 聚（4 -第三丁基苯乙烯）一b -聚苯乙烯一b —聚異戊二烯 —b —聚苯乙烯-b-聚（4 -第三丁基苯乙烯）（以下簡稱爲 tBSSIStBS)。獲得的tBSSIStBS的數量平均分子量（GPC測 定，標準聚苯乙烯換算）爲72,000，由1H—NMR測定求得 之1，4_鍵結量爲94.0%，苯乙烯單元的含量爲29.4重量 %，4一第三丁基苯乙烯單元的含量爲30.0重量％。 製備經合成的tBSSIStBS的環己烷溶液，放入經過充 分氮取代的耐壓容器後，使用Ni/Al系Ziegler系氫化觸 媒，於氫氣氣體環境下於7 0 °C進行8小時氫化反應，獲得 聚（4-第三丁基苯乙烯）-b—聚苯乙烯_b —氫化聚異戊 二烯一 b -聚苯乙烯—b-聚（4 一第三丁基苯乙烯）（以下簡 稱爲tBSSEPStBS)。利用1H— NMR光譜測定計算獲得的 tBSSEPStBS的氫化率，結果未檢測到來自於聚異戊二烯之 雙鍵的峰部。 -48- 201131857 <參考例5 > (製造由聚苯乙烯、氫化聚異戊二烯及聚（4-第三丁基 苯乙烯）構成之嵌段共聚物） 於1400mL熱壓釜加入脫水環己烷593ml及第二丁基 鋰（1.00M—環己烷溶液）2.9ml後，逐次添加4_第三丁基 苯乙烯22.9m卜苯乙烯32.6ml並於50 °C使其逐次聚合，接 著，逐次添加異戊二烯59.0ml、苯乙烯29.3ml、及4—第 三丁基苯乙烯20.3ml，並於60 °C使其逐次聚合，藉此合成 聚（4-第三丁基苯乙烯）一 b-聚苯乙烯—b-聚異戊二烯 一 b —聚苯乙嫌一 b —聚（4 —第二丁基本乙嫌）（以下簡稱爲 tBSSIStBS)。獲得之tBSSIStBS的數量平均分子量（GPC測 定，標準聚苯乙烯換算）爲64,000，由1H—NMR測定求得 的1,4 -鍵結量爲94.2%，苯乙烯單元的含量爲41.2重量 %，4 —第三丁基苯乙烯單元的含量爲29.4重量％。 製備經合成的tBSSIStBS的環己烷溶液，放入經過充 分氮取代的耐壓容器後，使用Ni/Al系Ziegler系氫化觸 媒，於氫氣氣體環境下於70。(：進行8小時氫化反應’獲得 聚（4_第三丁基苯乙烯）—b-聚苯乙烯_b 一氫化聚異戊 二烯—b -聚苯乙烯一 b —聚（4_第三丁基苯乙烯）（以下簡 稱爲t B S S E P S t B S )。利用1 Η — N M R光譜測定計算獲得的 tBSSEPStBS的氫化率，結果未檢測到來自於聚異戊二烯的 雙鍵的峰部。 -49- 201131857 <製造例1 > (合成嵌段共聚物（磺酸化 tBSVBtBSEPtBS)，該嵌段共 聚物係由以下所構成：主要由磺酸化4一乙烯基聯苯單元構 成之芳香族乙烯基系聚合物嵌段（A)、主要由氫化異戊二烯 單元構成之脂肪族乙烯基系聚合物嵌段（B)及主要由4-第 三丁基苯乙烯構成之芳香族乙烯基系聚合物嵌段（C)) 將參考例1獲得的嵌段共聚物（tBSVBtBSEPtBS)5g於 附攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著 進行氮取代後，加入二氯甲烷200ml，於室溫攪拌使其溶 解。溶解後，花費30分緩慢滴加二氯甲烷50ml、氯磺酸 3 · 5 m 1的混合溶液。於室溫攪拌4 〇小時後，添加作爲停止 劑的蒸餾水10ml。之後，於攪拌下將25 0ml的蒸餾水緩緩 地注入聚合物溶液中，使聚合物凝固析出。將二氯甲烷於 常壓餾去除去後進行過濾。將過濾獲得的固體成分移到燒 杯中，加入蒸餾水1 L，於攪拌下進行清洗後，進行過濾回 收。反複該清洗及過濾的操作直到清洗水的pH沒有變化爲 止，最後將濾集的聚合物進行真空乾燥，獲得本發明的高 分子電解質，即磺酸化tBSVBtBSEPtBS。獲得的磺酸化 tBSVBtBSEPtBS的具有磺酸基的芳香族乙烯基系聚合物嵌 段（A)，即含有經過磺酸基改性的4 -乙烯基聯苯單元的聚 合物嵌段，其每一重複單元的磺酸基含量’從滴定的結果 爲1 . 9 6個，該高分子電解質的離子交換容量爲3 · 0 m e q / g。 -50- 201131857 <製造例2 > (合成嵌段共聚物（磺酸化tBSVBtBSEPtBS)，該嵌段共 聚物係由以下所構成：主要由磺酸化4 一乙烯基聯苯單元構 成之芳香族乙烯基系聚合物嵌段（A)、主要由氫化異戊二烯 單元構成之脂肪族乙烯基系聚合物嵌段（B)及主要由4一第 三丁基苯乙烯單元構成之芳香族乙烯基系聚合物嵌段（C)) 將參考例1獲得的嵌段共聚物（tBSVBtBSEPtBS)5g，於 附攪拌機的玻璃製反應容器.中進行1小時真空乾燥，接著 進行氮取代後，加入二氯甲烷200ml，於室溫攪拌使其溶 解。溶解後花費30分鐘緩緩滴加二氯甲烷50ml、氯磺酸 2.8ml的混合溶液。於室溫攪拌7小時後，添加作爲停止劑 的蒸餾水10ml。之後，於攪拌下將250ml蒸餾水緩慢注入 聚合物溶液，使聚合物凝固析出。將二氯甲烷於常壓餾去 除去後進行過濾。將過濾獲得的固體成分移到燒杯，並加 入蒸餾水1 L，於攪拌下進行清洗後，進行過濾回收。反複 該清洗及過濾的操作直到清洗水的P Η無變化爲止，最後將 濾集的聚合物進行真空乾燥，獲得本發明的高分子電解 質，即磺酸化 tBSVBtBSEPtBS 。得到的磺酸化 tBSVBtBSEPtBS的芳香族乙烯基系聚合物嵌段（A)，即含有 經過磺酸基改性的4 -乙稀基聯苯單元的聚合物嵌段，其 每一重複單元的磺酸基含量，由滴定的結果爲1.76個，該 高分子電解質的離子交換容量爲2.77meq/g。 -5 1- 201131857 <製造例3 > (合成嵌段共聚物（磺酸化tBSVBEPVBtBS)，該嵌段共 聚物由以下所構成：主要由磺酸化4 -乙烯基聯苯單元構成 的芳香族乙烯基系聚合物嵌段（A)、主要由氫化異戊二烯單 元構成的脂肪族乙烯基系聚合物嵌段（B)及主要由4一第三 丁基苯乙烯單元構成的芳香族乙烯基系聚合物嵌段（C)) 將參考例2獲得的嵌段共聚物（tBSVBEPVBtBS)5g，於 附攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著 進行氮取代後，加入二氯甲烷1 8 0m 1，於室溫攪拌使其溶 解。溶解後花費30分鐘緩慢滴加二氯甲烷40ml、氯磺酸 2.8ml的混合溶液。於室溫攪拌4小時後，添加作爲停止劑 的蒸餾水1 Oml。之後於攪拌下將220ml蒸餾水緩慢注入聚 合物溶液中，使聚合物凝固析出。將二氯甲烷於常壓餾去 除去後進行過濾。將過濾獲得的固體成分移到燒杯，添加 蒸餾水1 L，於攪拌下進行清洗後，進行過濾回收。反複該 清洗及過濾的操作直到清洗水的pH無變化爲止，最後將濾 集的聚合物進行真空乾燥，獲得本發明的高分子電解質磺 酸化tBSVBEPVBtBS。獲得的磺酸化tBSVBEPVBtBS的芳 香族乙烯基系聚合物嵌段（A)，即含有經過磺酸基改性的4 -乙烯基聯苯單元的聚合物嵌段，其每一重複單元的磺酸 基含量，由滴定的結果爲1·54個，該高分子電解質的離子 父換谷量爲2.33meq/g。 -52- 201131857 <製造例4 > (合成嵌段共聚物（磺酸化tBSSEPStBS)，該嵌段共聚物 由以下所構成：主要由磺酸化苯乙烯單元構成之芳香族乙 烯基系聚合物嵌段（A)、主要由氫化異戊二烯單元構成之脂 肪族乙烯基系聚合物嵌段（B)及主要由4 一第三丁基苯乙烯 單元構成之芳香族乙烯基系聚合物嵌段（C)) 將參考例3獲得的嵌段共聚物（tBSsEPStBS)40g，於附 攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著進 行氮取代後’加入二氯甲烷5 OOm卜於室溫攪拌使其溶解。 溶解後，於〇°C將使乙酸酐61.4ml與硫酸27.5ml反應獲得 之磺酸化試藥’花費5分鐘緩慢滴加於二氯甲烷123ml中。 於室溫攪拌7 2小時後’添加作爲停止劑的蒸餾水2 〇m !。 之後，將〇 · 7 L蒸餾水緩慢注入聚合物溶液中使聚合物凝固 析出。將二氯甲烷於常壓餾去除去後進行過濾。將過濾獲 得的固體成分移到燒杯，添加蒸餾水1 · 3 L，於攪拌下進行 清洗後’進行過濾回收。反複該清洗及過濾的操作直到清 洗水的pH無變化爲止’最後將濾集的聚合物進行真空乾燥 得到不屬於本發明的高分子電解質，即橫酸化^ tBSSEPStBS。獲得的擴酸化tBSSEPStBS的含有經過磺酸 基改性的苯乙嫌單兀的聚合物嵌段的每一重複單元的磺酸 基含量’由1H — NMR分析的結果爲κ00個，該高分子電 解質的離子交換容量爲2.52meq/g。 -53- 201131857 <製造例5 > (合成嵌段共聚物（磺酸化tBSSEPStBS)，該嵌段共聚物 由以下所構成：主要由磺酸化苯乙烯單元構成之芳香族乙 烯基系聚合物嵌段（A)、主要由氫化異戊二烯單元構成之脂 肪族乙烯基系聚合物嵌段（B)及主要由4 一第三丁基苯乙烯 單元構成之芳香族乙烯基系聚合物嵌段（C)) 將參考例3獲得的嵌段共聚物（tBSSEPStBS)40g，於附 攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著進 行氮取代後，加入二氯甲烷452ml，於室溫攪拌使其溶解。 溶解後，於二氯甲烷1 1 1 m 1中，於0 °C使乙酸酐5 5 . 5 m 1與 硫酸24. Sml反應獲得的磺酸化試藥，花費5分鐘緩慢滴 加。於室溫攪拌 7 2小時後，添加作爲停止劑的蒸餾水 2 0ml。之後，將0.7 L蒸餾水緩緩注入聚合物溶液中，使聚 合物凝固析出。將二氯甲烷於常壓餾去除去後進行過濾。 將過濾獲得的固體成分移到燒杯，並添加蒸餾水1 . 3 L，於 攪拌下清洗後，進行過濾回收。反複該清洗及過濾的操作 直到清洗水的pH沒有變化爲止，最後將濾集的聚合物進行 真空乾燥’得到不屬於本發明的高分子電解質磺酸化 tBSSEPStBS。獲得的磺酸化tBSSEPStBS的經過磺酸基變 性的含有苯乙烯單元的聚合物嵌段每一重複單元的磺酸基 含量’由1H_ NMR分析的結果爲ι·〇〇個，該高分子電解 質的離子交換容量爲2.30meq/g。 -54- 201131857 <製造例6 > (合成嵌段共聚物（磺酸化tBSVBtBSEPtBS)，該嵌段共 聚物由以下所構成··主要由磺酸化4 -乙烯基聯苯單元構成 之芳香族乙烯基系聚合物嵌段（A)、主要由氫化異戊二烯單 元構成之脂肪族乙烯基系聚合物嵌段（B)及主要由4 一第三 丁基苯乙烯單元構成之芳香族乙烯基系聚合物嵌段（c)) 將參考例1獲得的嵌段共聚物（tBSVBtBSEPtBS)5g，於 附攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著 進行氮取代後’加入二氯甲烷200ml，於室溫攪拌使其溶 解。溶解後花費30分鐘緩慢滴加二氯甲烷50ml、氯磺酸 2 · 8ml的混合溶液。於室溫攪拌7小時後，添加作爲停止劑 的蒸餾水l〇ml。之後，於攪拌下緩慢將2 50mi蒸餾水注入 聚合物溶液中’使聚合物凝固析出。將二氯甲烷於常壓餾 去除去後進行過濾。將過濾獲得的固體成分移到燒杯，添 加蒸餾水1L’於攪拌下進行清洗後，進行過濾回收。反複 進行該清洗及過濾的操作直到清洗水的pH沒有變化爲 止，最後將濾集的聚合物進行真空乾燥，獲得不屬於本發 明的高分子電解質，即磺酸化tBSVBtBSEPtBS。得到的磺 酸化tBSVBtBSEPtBS的含有經過磺酸基改性的4 -乙烯基 聯苯單元的苯環的聚合物嵌段，其每一重複單元的磺酸基 含量，由滴定的結果爲1.30個，該高分子電解質的離子交 換容量爲2.1 7meq/g。 -55- 201131857 <製造例7 > (合成嵌段共聚物（磺酸化tBSSEPStBS)，該嵌段共聚物10.3ml, 22.8g of 4-vinylbiphenyl, 36.8ml of isoprene, and polymerized at 4 (TC, and 137mg of phenyl benzoate was added to couple it, thereby synthesizing poly(4-tert-butylbenzene) Dilute)-b-poly(4-i-ethyl phenyl)-b-polyisoprene-b-poly(4-ethoxyphenylbiphenyl)-b-poly(4-t-butylstyrene) (hereinafter referred to as tBSVBIVBtBS) The number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSVBIVBtBS is 15 8,000, and the number of 1,4 bonds determined by 1H-NMR measurement is 94.0%, 4 The content of the vinyl biphenyl unit is 33.9% by weight, and the content of the 4-tert-butylstyrene unit is 22.0% by weight. The cyclohexane solution of the synthesized tBSVBIVBtBS is prepared and charged with a sufficient nitrogen substitution pressure. After the vessel, a Ni/Al-based Ziegler-based hydrogenation catalyst was used to carry out a hydrogenation reaction at 70 ° C for 8 hours under a hydrogen atmosphere to obtain poly(4-t-butylstyrene)-b-poly(4-ethylene). Base phenyl)-b-hydrogenated polyisoprene-b-poly(4-vinylbiphenyl)-b-poly(4-t-butyl styrene (hereinafter referred to as tBSVBEPVBtBS) The hydrogenation rate of the obtained tBSVBEPVBtBS was calculated by 1H-NMR spectroscopy, and the peak of the double bond derived from polyisoprene was not detected. -46- 201131857 <Reference Example 3 > (manufacturing a block copolymer composed of polystyrene, hydrogenated polyisoprene and poly(4-t-butylstyrene)) in an autoclave of l4〇OmL, adding dehydrated cyclohexane 8 2 0 ml and After 1. 7 ml of dibutyllithium (1.25 M-cyclohexane solution), 19.8 ml of 4-tert-butylstyrene and 27.7 ml of styrene were successively added, and the mixture was successively polymerized at 5 〇t: successively, successively added. 80.4 ml of isoprene, 26.6 ml of styrene, and 18.1 ml of 4-tert-butylstyrene were successively polymerized at 60 ° C to synthesize poly(4-t-butylstyrene)_b-polyphenylene. Ethylene-b-polyisoprene-b-polystyrene-b-poly(4-t-butylstyrene) (hereinafter abbreviated as tBSSIStBS). The number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 86,000, the 1,4 bond amount determined by 1H-NMR measurement was 94.0%, and the styrene unit content was 32.9 wt%, 4 The content of a third butyl styrene unit was 29.8% by weight. A cyclohexane solution of the synthesized tBSSIStBS was prepared, placed in a pressure-resistant container which was sufficiently nitrogen-substituted, and subjected to a hydrogenation reaction at 70 ° C for 8 hours under a hydrogen gas atmosphere using a Ni/A1 ziegler-based hydrogenation catalyst. Poly(4-t-butylstyrene)-b-polystyrene-b_hydrogenated polyisoprene-b-polyphenylene bromide-b-poly(4-butylbutene benzene) Referred to as tBSSEPStBS). The hydrogenation rate of the obtained tBSSEPStBS was calculated by 1H-NMR spectroscopy, and the peak of the double bond derived from polyisoprene was not detected -47-201131857 <Reference Example 4 > (manufactured by polystyrene, hydrogenated poly Block copolymer composed of isoprene and poly(4-butyl butyl styrene) was added to dehydrocyclohexane 76 8 ml and second butyl lithium (1·25 Μ_cyclohexyl) in a 1 400 mL autoclave After 1.76 ml of alkane solution, 60.7 ml of 4-butyl butyl styrene and 55.6 ml of styrene were successively added, and they were successively polymerized at 50 ° C. Then, isoamyl 2, 2 ml of styrene was added successively. 54.1 ml, and 4 to 3 butyl styrene 56.7 ml, and successively polymerized at 60 ° C, thereby synthesizing poly(4-butylbutyl styrene)-b-polystyrene-b-poly Pentadiene-b-polystyrene-b-poly(4-t-butylstyrene) (hereinafter abbreviated as tBSSIStBS). The number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 72,000, the number of 1,4_bonds determined by 1H-NMR was 94.0%, and the content of styrene units was 29.4% by weight, 4 The content of a third butyl styrene unit was 30.0% by weight. A cyclohexane solution of the synthesized tBSSIStBS was prepared, placed in a pressure-resistant container which was sufficiently nitrogen-substituted, and subjected to a hydrogenation reaction at 70 ° C for 8 hours under a hydrogen gas atmosphere using a Ni/Al-based Ziegler-based hydrogenation catalyst. Obtaining poly(4-tert-butylstyrene)-b-polystyrene_b-hydrogenated polyisoprene-b-polystyrene-b-poly(4-butylated styrene) (hereinafter referred to as For tBSSEPStBS). The hydrogenation rate of the obtained tBSSEPStBS was calculated by 1H-NMR spectroscopy, and as a result, no peak derived from the double bond of polyisoprene was detected. -48- 201131857 <Reference Example 5 > (Production of block copolymer composed of polystyrene, hydrogenated polyisoprene, and poly(4-tert-butylstyrene)) Dehydration was carried out in a 1400 mL autoclave After 593 ml of cyclohexane and 2.9 ml of a second butyllithium (1.00 M-cyclohexane solution), 42.6 ml of 4_3 butylstyrene 22.9 m of styrene was successively added and polymerized at 50 ° C successively. Next, 59.0 ml of isoprene, 29.3 ml of styrene, and 20.3 ml of 4-t-butylstyrene were successively added, and they were successively polymerized at 60 ° C to synthesize poly(4-tert-butylbenzene). Ethylene)-b-polystyrene-b-polyisoprene-b-polyphenylene is a b-poly (4-second butyl-B) (hereinafter referred to as tBSSIStBS). The number average molecular weight (GPC measurement, standard polystyrene conversion) of the obtained tBSSIStBS was 64,000, the 1,4 -bond amount determined by 1H-NMR measurement was 94.2%, and the styrene unit content was 41.2% by weight, 4 The content of the t-butylstyrene unit was 29.4% by weight. A cyclohexane solution of the synthesized tBSSIStBS was prepared and placed in a pressure-resistant container which was substituted with nitrogen, and then a Ni/Al-based Ziegler-based hydrogenation catalyst was used at 70 in a hydrogen gas atmosphere. (: 8 hours hydrogenation reaction to obtain poly(4_t-butylstyrene)-b-polystyrene_b-hydrogenated polyisoprene-b-polystyrene-b-poly (4_third Butylstyrene) (hereinafter abbreviated as t BSSEPS t BS ). The hydrogenation rate of the obtained tBSSEPStBS was calculated by 1 Η-NMR spectroscopy, and as a result, no peak of the double bond derived from polyisoprene was detected. - 201131857 <Production Example 1 > (Synthesis block copolymer (sulfonated tBSVBtBSEPtBS), which is composed of an aromatic vinyl group mainly composed of a sulfonated 4-vinylbiphenyl unit a polymer block (A), an aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and an aromatic vinyl polymer mainly composed of 4-tert-butyl styrene Block (C)) 5 g of the block copolymer (tBSVBtBSEPtBS) obtained in Reference Example 1 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and then 200 ml of dichloromethane was added thereto at room temperature. Stir it to dissolve it. After dissolving, it takes 30 minutes to slowly drop. 50 ml of dichloromethane and a mixed solution of chlorosulfonic acid 3 · 5 m 1 . After stirring at room temperature for 4 hours, 10 ml of distilled water as a stopper was added. Thereafter, 250 ml of distilled water was slowly injected into the polymer with stirring. In the solution, the polymer was coagulated and precipitated, and the dichloromethane was removed by atmospheric distillation, and then filtered. The solid component obtained by filtration was transferred to a beaker, and 1 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation is repeated until the pH of the washing water does not change, and finally the filtered polymer is vacuum dried to obtain the polymer electrolyte of the present invention, that is, sulfonated tBSVBtBSEPtBS. The obtained sulfonated tBSVBtBSEPtBS has a sulfonic acid group. Aromatic vinyl-based polymer block (A), that is, a polymer block containing a sulfonic acid group-modified 4-vinylbiphenyl unit, the sulfonic acid group content of each repeating unit 'from titration The result was 1.96, and the ion exchange capacity of the polymer electrolyte was 3 · 0 meq / g. -50 - 201131857 <Production Example 2 > (Synthesis block copolymer (sulfonated tBSVBt) BSEPtBS), the block copolymer is composed of an aromatic vinyl-based polymer block (A) mainly composed of a sulfonated 4-vinylbiphenyl unit, mainly composed of hydrogenated isoprene units. An aliphatic vinyl polymer block (B) and an aromatic vinyl polymer block (C) mainly composed of a 4-t-butylstyrene unit. The block copolymer obtained in Reference Example 1 ( 5 g of tBSVBtBSEPtBS) was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and then 200 ml of dichloromethane was added thereto, followed by stirring at room temperature to dissolve. After the dissolution, it took 30 minutes to slowly add a mixed solution of 50 ml of dichloromethane and 2.8 ml of chlorosulfonic acid. After stirring at room temperature for 7 hours, 10 ml of distilled water as a stopper was added. Thereafter, 250 ml of distilled water was slowly poured into the polymer solution under stirring to cause the polymer to coagulate and precipitate. The dichloromethane was distilled off under normal pressure and then filtered. The solid component obtained by filtration was transferred to a beaker, and 1 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation was repeated until the P Η of the washing water did not change, and finally the filtered polymer was vacuum dried to obtain the polymer electrolyte of the present invention, i.e., sulfonated tBSVBtBSEPtBS. The obtained aromatic vinyl-based polymer block (A) of the sulfonated tBSVBtBSEPtBS, that is, a polymer block containing a sulfonic acid group-modified 4-ethylenebiphenyl unit, the sulfonic acid of each repeating unit The basis content was 1.76 as a result of titration, and the ion exchange capacity of the polymer electrolyte was 2.77 meq/g. -5 1-201131857 <Production Example 3 > (Synthesis block copolymer (sulfonated tBSVBEPVBtBS), which is composed of aromatic vinyl mainly composed of sulfonated 4-vinylbiphenyl units Base polymer block (A), aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and aromatic vinyl group mainly composed of 4-t-butylstyrene unit Polymer block (C)) 5 g of the block copolymer (tBSVBEPVBtBS) obtained in Reference Example 2 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and then dichloromethane was added. 80 m 1 , stir at room temperature to dissolve. After the dissolution, it took 30 minutes to slowly add a mixed solution of 40 ml of dichloromethane and 2.8 ml of chlorosulfonic acid. After stirring at room temperature for 4 hours, 10 ml of distilled water as a stopper was added. Thereafter, 220 ml of distilled water was slowly poured into the polymer solution under stirring to cause the polymer to coagulate and precipitate. The dichloromethane was distilled off under normal pressure and then filtered. The solid component obtained by filtration was transferred to a beaker, and 1 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation was repeated until the pH of the washing water did not change, and finally, the filtered polymer was vacuum dried to obtain the polymer electrolyte sulfonated tBSVBEPVBtBS of the present invention. The obtained aromatic vinyl-based polymer block (A) of the sulfonated tBSVBEPVBtBS, that is, a polymer block containing a sulfonic acid group-modified 4-vinylbiphenyl unit, the sulfonic acid group of each repeating unit The content was titrated to 1.54, and the amount of ionic fathers of the polymer electrolyte was 2.33 meq/g. -52-201131857 <Production Example 4 > (Synthesis block copolymer (sulfonated tBSSEPStBS), which is composed of an aromatic vinyl polymer mainly composed of a sulfonated styrene unit Segment (A), an aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and an aromatic vinyl polymer block mainly composed of 4 -butyl butyl styrene units (C) 40 g of the block copolymer (tBSsEPStBS) obtained in Reference Example 3 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and then added dichloromethane at 50,000 m at room temperature. Stir to dissolve. After the dissolution, the sulfonated reagent obtained by reacting 61.4 ml of acetic anhydride with 27.5 ml of sulfuric acid at ° °C was slowly added dropwise to 123 ml of dichloromethane for 5 minutes. After stirring at room temperature for 7 hours, 'distilled water 2 〇m ! as a stopper was added. Thereafter, 〇·7 L of distilled water was slowly poured into the polymer solution to solidify and precipitate the polymer. The dichloromethane was removed by atmospheric distillation and filtered. The solid component obtained by the filtration was transferred to a beaker, and 1·3 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation was repeated until the pH of the washing water did not change. Finally, the filtered polymer was vacuum dried to obtain a polymer electrolyte not belonging to the present invention, i.e., cross-acidified tBSSEPStBS. The obtained sulfonic acid group content of the repeating unit of the polymer block of the phenylsulfonate-modified styrene-fluoride-modified tBSSEPStBS obtained by 1H-NMR analysis was κ00, and the polymer electrolyte The ion exchange capacity was 2.52 meq/g. -53-201131857 <Production Example 5 > (Synthesis block copolymer (sulfonated tBSSEPStBS), which is composed of an aromatic vinyl polymer mainly composed of a sulfonated styrene unit Segment (A), an aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and an aromatic vinyl polymer block mainly composed of 4 -butyl butyl styrene units (C) 40 g of the block copolymer (tBSSEPStBS) obtained in Reference Example 3 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and then 452 ml of dichloromethane was added and stirred at room temperature. Let it dissolve. After the dissolution, the sulfonated reagent obtained by reacting acetic anhydride 5 5 . 5 m 1 with sulfuric acid 24. S ml at 0 ° C in 1 1 1 m 1 was slowly added dropwise over 5 minutes. After stirring at room temperature for 7 hours, 20 ml of distilled water as a stopper was added. Thereafter, 0.7 L of distilled water was slowly poured into the polymer solution to coagulate and precipitate the polymer. The dichloromethane was removed by atmospheric distillation and filtered. The solid component obtained by filtration was transferred to a beaker, and 1.3 L of distilled water was added thereto, and after washing with stirring, it was collected by filtration. This washing and filtering operation was repeated until the pH of the washing water did not change, and finally the filtered polymer was vacuum dried to obtain a polymer electrolyte sulfonated tBSSEPStBS which is not in the present invention. The sulfonic acid group content of each of the repeating units of the sulfonic acid-denatured styrene unit-containing polymer block of the obtained sulfonated tBSSEPStBS was analyzed by 1H_NMR, and the polymer electrolyte ions were obtained. The exchange capacity is 2.30 meq/g. -54-201131857 <Production Example 6 > (Synthesis block copolymer (sulfonated tBSVBtBSEPtBS), which is composed of the following: · Aromatic ethylene mainly composed of sulfonated 4-vinylbiphenyl units The base polymer block (A), the aliphatic vinyl polymer block (B) mainly composed of hydrogenated isoprene units, and the aromatic vinyl group mainly composed of 4 -butyl butyl styrene units Polymer block (c)) 5 g of the block copolymer (tBSVBtBSEPtBS) obtained in Reference Example 1 was vacuum dried in a glass reaction vessel equipped with a stirrer for 1 hour, followed by nitrogen substitution, and '200 ml of dichloromethane was added. Stir at room temperature to dissolve. After the dissolution, it took 30 minutes to slowly dropwise add a mixed solution of 50 ml of dichloromethane and 2 · 8 ml of chlorosulfonic acid. After stirring at room temperature for 7 hours, 1.0 ml of distilled water as a stopper was added. Thereafter, 2 50 mi of distilled water was slowly poured into the polymer solution under stirring to cause the polymer to coagulate and precipitate. The dichloromethane was distilled off under normal pressure and then filtered. The solid component obtained by filtration was transferred to a beaker, and 1 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation was repeated until the pH of the washing water did not change. Finally, the filtered polymer was vacuum dried to obtain a polymer electrolyte not belonging to the present invention, i.e., sulfonated tBSVBtBSEPtBS. The polymer block of the obtained sulfonated tBSVBtBSEPtBS containing a benzene ring of a sulfonic acid group-modified 4-vinylbiphenyl unit, and the sulfonic acid group content per repeating unit is 1.30 by titration. The ion exchange capacity of the polymer electrolyte was 2.1 7 meq/g. -55-201131857 <Production Example 7 > (Synthesis block copolymer (sulfonated tBSSEPStBS), the block copolymer
I 由以下所構成：主要由磺酸化苯乙烯單元構成之芳香族乙 烯基系聚合物嵌段（A)、主要由氫化異戊二烯單元構成之脂 肪族乙烯基系聚合物嵌段（B)及主要由4 -第三丁基苯乙烯 單元構成之芳香族乙烯基系聚合物嵌段（C)) 將參考例5獲得的嵌段共聚物（tBSSEPStBS)40g，於附 攪拌機的玻璃製反應容器中進行1小時真空乾燥，接著進行 氮取代後，加入二氯甲烷54〇ml，於室溫攪拌使溶解。溶解 後，將於二氯甲烷44.5 ml中於0°C使乙酸酐89.0ml與硫酸 5 1.8 ml反應獲得的磺酸化試藥，花5分鐘緩慢滴加。於室溫 攪拌72小時後，添加作爲停止劑的蒸餾水20ml。之後，將 0.6 L蒸餾水緩慢注入聚合物溶液中，使聚合物凝固析出。 將二氯甲烷於常壓餾去除去後進行過濾。將過濾獲得的固 體成分移到燒杯，添加蒸餾水1 .3 L，於攪拌下進行清洗後， 進行過濾回收。反複該清洗及過濾的操作直到清洗水的pH 沒有變化爲止，最後將濾集的聚合物進行真空乾燥，得到 不屬於本發明的高分子電解質，即磺酸化tBSSEPStBS。獲 得的磺酸化tBSS EPS tBS的含有經過磺酸基改性的苯乙烯單 元的聚合物嵌段，其每一重複單元的磺酸基含量，由1Η -NMR分析的結果爲1.00個，該高分子電解質的離子交換容 量爲 2.99meq/g。 -56- 201131857 <實施例1 > (高分子電解質膜之製作） 製備製造例1獲得的磺酸化tBSVBtBSEPtBS(離子交換 容量3.0meq/g)的25重量％的甲苯/異丁醇（重量比6/4)溶 液，塗布於完成脫模處理的PET薄膜[東洋紡（股）製「東洋 紡酯薄膜K 1 5 04」]上，使其厚度爲約25 0μπι，以熱風乾燥 機於l〇〇°C使其乾燥4分鐘，得到厚度35μιη的膜。 <實施例2 > (高分子電解質膜之製作） 製備製造例2獲得之磺酸化188¥8183£?183(離子交換 容量2.77meq/g)的30重量％的甲苯/異丁醇（重量比6/4)溶 液，塗布在完成脫模處理的PET薄膜[東洋紡（股）製「東洋 紡酯薄膜K1504」]上，使其厚度爲約150μιη，以熱風乾燥 機於l〇〇°C使其乾燥4分鐘，得到厚度20μιη的膜。 <實施例3 > (高分子電解質膜之製作） 製備製造例3獲得的磺酸化183乂8£?乂8183(離子交換 容量2.33meq/g)的1重量％的氯苯溶液，澆鑄於以聚四氟乙 烯片材製作的容器後，花費1至數日將溶劑緩慢除去，藉 此獲得厚度29μπι的膜。 -57- 201131857 <比較例1 > (高分子電解質膜之製作） 製備製造例4獲得的磺酸化tBS SEP StBS的1 8重量％ 的甲苯/異丙醇（重量比5/5)溶液，塗布於完成脫模處理的 PET薄膜[東洋紡（股）製「東洋紡酯薄膜K1504」]上使其厚 度爲約350μιη，於lOOt乾燥4分鐘後，從PET薄膜剝離， 藉此得到厚度30μιη的膜。 <比較例2 > (高分子電解質膜之製作） 製備製造例5獲得的磺酸化tBSSEPStBS的19重量％ 的甲苯/異丙醇（重量比5/5)溶液，塗布於完成脫模處理的 PET薄膜[東洋紡（股）製「東洋紡酯薄膜K1504」]上，使其 厚度爲約350μιη，於100°C乾燥4分鐘後，從PET薄膜剝 離，藉此獲得厚度31 μιη的膜。 <比較例3 > (高分子電解質膜之製作） 製備製造例6獲得的磺酸化tBSVBtBSEPtBS(離子交換 容量2.17meq/g)的30重量％的甲苯/異丁醇（重量比6/4)溶 液，塗布於完成脫模處理的PET薄膜[東洋紡（股）製「東洋 紡酯薄膜K1504」]上，使其厚度爲約250μιη，以熱風乾燥 機於l〇〇°C乾燥4分鐘，得到厚度33μιη的膜。 -58- 201131857 <比較例4 > (高分子電解質膜之製作） 製備製造例7獲得的擴酸化tBSSEPStBS(離子交換容 量2.99meq/g)的18重量％的甲苯/異丙醇（重量比5/5)溶 液，塗布於完成脫模處理的PET薄膜[東洋紡（股）製「東洋 紡酯薄膜K1504」]上’使其厚度爲約350μηι，於100T：乾 燥4分鐘後，從PET薄膜剝離，獲得厚度30μιη的膜。 (實施例及比較例的高分子電解質膜的性能試驗及其 結果） 如以下方式進行各實施例或比較例獲得之由磺酸化嵌 段共聚物構成之高分子電解質膜的性能試驗。 (離子傳導度的測定） 將lcmx4cm的高分子電解質膜以1對鈾電極夾持，安 裝在開放系小室。將測定小室設置於調整在溫度8 0 °C及相 對濕度3 0 %的恆溫恆濕器內，利用交流阻抗法測定上述膜 的離子傳導度。 (線膨脹率的測定） 將lcm X 4 cm的試樣於室溫浸泡於蒸餾水4小時後，計 測長邊方向的長度（X)，並以下列算式計算線膨脹率。 線膨脹率（％)= (X- 4)/4χ100 表1顯示關於實施例1至3及比較例1至4使用的高 分子電解質及製作的高分子電解質膜的離子傳導度及線膨 脹率的測定結果。 -59- 201131857 [表i] 高分子電解質 每一(A)的 重複單元的 離子傳導性 基(個） 高分子 電解質 中之(A) (重量％) (A海lg的離 子傳導性基 含量 (meq/g) 離子交換容量 (meq/g) 離子傳導度 (S/cm) (相對濕度 30%) 線膨脹 率(％) (室溫、 水中4 小時） 實施例1 磺酸化 tBSVBtBSEPtBS 1.96 36.3 5.82 3.00 1.2χ1〇·2 52 實施例2 磺酸化 tBSVBtBSEPtBS 1.76 36.3 5.48 2.77 Ι.ΟχΙΟ'2 43 實施例3 磺酸化 tBSVBEPVBtBS 1.54 33.5 5.08 2.33 8_7χ10-3 30 比較例1 磺酸化 tBSSEPStBS 1.00 32.9 5.43 2.52 7.0x10'3 41 比較例2 磺酸化 tBSSEPStBS 1.00 29.3 5.43 2.30 6.〇χ10'3 33 比較例3 磺酸化 tBSVBtBSEPtBS 1.30 36.3 4.58 2.17 4.8χ1〇·3 29 比較例4 磺酸化 tBSSEPStBS 1.00 40.9 5.43 2.99 1.0x10-2 65 若比較實施例1與比較例4可知：雖然大約爲相同離子 交換容量，實施例1的離子傳導度爲較高，線膨脹率較低。 亦即，本發明的闻分子電解質膜的離子傳導性較高，於水 中的形狀安定性亦高。實施例3與比較例2的比較也可說 是同樣情形。 又’若將顯示同程度的離子傳導度的實施例2與比較 例4比較’實施例2的線膨脹率遠遠較低，於水中的形狀 安定性優異。 由上述試驗的結果，由本發明之高分子電解質構成之 高分子電解質膜，於低濕度下的離子傳導性優異，因此， 使用該高分子電解質膜的膜一電極接合體及固體高分子型 燃料電池’於低濕度下的輸出特性也可說是優異。又，該 高分子電解質膜由於水所致的膨潤少，於水中的形狀安定 性良好。 -60- 201131857 [產業利用性] 藉由使用本發明之高分子電解質、由該高分子電解質 構成之高分子電解質膜，可提供於低濕度下的輸出特性優 異的膜-電極接合體、及固體高分子型燃料電池。 【圖式簡單說明】 姐。 【主要元件符號說明】 無。 -6 1-I is composed of an aromatic vinyl polymer block (A) mainly composed of a sulfonated styrene unit, and an aliphatic vinyl polymer block mainly composed of hydrogenated isoprene units (B). And an aromatic vinyl polymer block (C) mainly composed of a 4-tert-butylstyrene unit. 40 g of the block copolymer (tBSSEPStBS) obtained in Reference Example 5, in a glass reaction vessel with a stirrer After vacuum drying for 1 hour, followed by nitrogen substitution, 54 ml of dichloromethane was added, and the mixture was stirred at room temperature to dissolve. After the dissolution, the sulfonated reagent obtained by reacting 89.0 ml of acetic anhydride with 5 1.8 ml of sulfuric acid in 44.5 ml of dichloromethane at 0 ° C was slowly added dropwise over 5 minutes. After stirring at room temperature for 72 hours, 20 ml of distilled water as a stopper was added. Thereafter, 0.6 L of distilled water was slowly poured into the polymer solution to coagulate and precipitate the polymer. The dichloromethane was removed by atmospheric distillation and filtered. The solid component obtained by filtration was transferred to a beaker, and 1.3 L of distilled water was added thereto, and the mixture was washed with stirring, and then collected by filtration. This washing and filtering operation was repeated until the pH of the washing water did not change, and finally the filtered polymer was vacuum dried to obtain a polymer electrolyte not belonging to the present invention, i.e., sulfonated tBSSEPStBS. The obtained sulfonated tBSS EPS tBS polymer block containing a sulfonic acid group-modified styrene unit, the sulfonic acid group content per repeating unit was 1.00 by 1 Η-NMR analysis, the polymer The ion exchange capacity of the electrolyte was 2.99 meq/g. -56-201131857 <Example 1> (Production of polymer electrolyte membrane) 25 wt% of toluene/isobutanol (weight ratio) of sulfonated tBSVBtBSEPtBS (ion exchange capacity 3.0 meq/g) obtained in Production Example 1 was prepared. 6/4) The solution was applied to a PET film (Toyobo Epoxy Film K 1 5 04) manufactured by Toyobo Co., Ltd. to a thickness of about 25 μm, and a hot air dryer at 10 °. C was allowed to dry for 4 minutes to obtain a film having a thickness of 35 μm. <Example 2 > (Production of Polymer Electrolyte Membrane) 30% by weight of toluene/isobutanol (weight) of sulfonated 188 ¥8183 183 (ion exchange capacity 2.77 meq/g) obtained in Production Example 2 was prepared. The ratio of the 6/4) solution was applied to a PET film (Toyobo Epoxy Film K1504 manufactured by Toyobo Co., Ltd.) which had been subjected to release treatment to a thickness of about 150 μm, and was dried in a hot air dryer at 10 ° C. After drying for 4 minutes, a film having a thickness of 20 μm was obtained. <Example 3 > (Production of polymer electrolyte membrane) A 1% by weight solution of chlorobenzene having a sulfonated 183 乂 8 乂 8183 (ion exchange capacity of 2.33 meq/g) obtained in Production Example 3 was prepared and cast in After the container made of the polytetrafluoroethylene sheet, the solvent was slowly removed in 1 to several days, whereby a film having a thickness of 29 μm was obtained. -57-201131857 <Comparative Example 1 > (Production of Polymer Electrolyte Membrane) A solution of 18% by weight of toluene/isopropyl alcohol (5/5 by weight) of sulfonated tBS SEP StBS obtained in Production Example 4 was prepared. The film was applied to a PET film (Toyobo Epoxy Film K1504, manufactured by Toyobo Co., Ltd.) having a thickness of about 350 μm, and dried at 100 Torr for 4 minutes, and then peeled off from the PET film to obtain a film having a thickness of 30 μm. <Comparative Example 2 > (Production of Polymer Electrolyte Membrane) A 19% by weight solution of toluene/isopropyl alcohol (5/5 by weight) of the sulfonated tBSSEPStBS obtained in Production Example 5 was prepared and applied to the release treatment. The PET film (Toyobo Epoxy Film K1504, manufactured by Toyobo Co., Ltd.) was dried to a thickness of about 350 μm, and dried at 100 ° C for 4 minutes, and then peeled off from the PET film to obtain a film having a thickness of 31 μm. <Comparative Example 3 > (Production of polymer electrolyte membrane) 30% by weight of toluene/isobutanol (weight ratio 6/4) of sulfonated tBSVBtBSEPtBS (ion exchange capacity 2.17 meq/g) obtained in Production Example 6 was prepared. The solution was applied to a PET film (Toyobo Epoxy Film K1504, manufactured by Toyobo Co., Ltd.) having a thickness of about 250 μm, and dried in a hot air dryer at 1 ° C for 4 minutes to obtain a thickness of 33 μm. Membrane. -58-201131857 <Comparative Example 4 > (Production of polymer electrolyte membrane) 18% by weight of toluene/isopropyl alcohol (weight ratio) of the acid-extended tBSSEPStBS (ion exchange capacity: 2.99 meq/g) obtained in Production Example 7 was prepared. 5/5) The solution was applied to a PET film (Toyobo Epoxy Film K1504 manufactured by Toyobo Co., Ltd.) which was subjected to release treatment to have a thickness of about 350 μm, and was peeled off from the PET film at 100T after drying for 4 minutes. A film having a thickness of 30 μm was obtained. (Performance test and results of the polymer electrolyte membrane of the examples and the comparative examples) The performance test of the polymer electrolyte membrane composed of the sulfonated block copolymer obtained in each of the examples or the comparative examples was carried out in the following manner. (Measurement of ion conductivity) A polymer electrolyte membrane of 1 cm x 4 cm was sandwiched between a pair of uranium electrodes and mounted in an open cell. The measurement chamber was placed in a thermo-hygrostat adjusted to a temperature of 80 ° C and a relative humidity of 30%, and the ion conductivity of the film was measured by an alternating current impedance method. (Measurement of linear expansion ratio) After immersing the sample of 1 cm X 4 cm in distilled water for 4 hours at room temperature, the length (X) in the longitudinal direction was measured, and the linear expansion ratio was calculated by the following formula. Linear expansion ratio (%) = (X-4) / 4 χ 100 Table 1 shows the ionic conductivity and linear expansion ratio of the polymer electrolyte used in Examples 1 to 3 and Comparative Examples 1 to 4 and the produced polymer electrolyte membrane. The measurement results. -59- 201131857 [Table i] Ion-conducting group of each (A) repeating unit of polymer electrolyte (A) (A) (% by weight) of polymer electrolyte (A lg ion-conducting group content ( Meq/g) ion exchange capacity (meq/g) ion conductivity (S/cm) (relative humidity 30%) linear expansion rate (%) (room temperature, water for 4 hours) Example 1 Sulfonated tBSVBtBSEPtBS 1.96 36.3 5.82 3.00 1.2χ1〇·2 52 Example 2 Sulfonated tBSVBtBSEPtBS 1.76 36.3 5.48 2.77 Ι.ΟχΙΟ'2 43 Example 3 Sulfonated tBSVBEPVBtBS 1.54 33.5 5.08 2.33 8_7χ10-3 30 Comparative Example 1 Sulfonated tBSSEPStBS 1.00 32.9 5.43 2.52 7.0x10'3 41 Comparative Example 2 Sulfonated tBSSEPStBS 1.00 29.3 5.43 2.30 6.〇χ10'3 33 Comparative Example 3 Sulfonated tBSVBtBSEPtBS 1.30 36.3 4.58 2.17 4.8χ1〇·3 29 Comparative Example 4 Sulfonated tBSSEPStBS 1.00 40.9 5.43 2.99 1.0x10-2 65 Comparing Example 1 with Comparative Example 4, it is understood that the ion conductivity of Example 1 is relatively high and the coefficient of linear expansion is low, although it is approximately the same ion exchange capacity. That is, the ion conductivity of the molecular electrolyte membrane of the present invention is relatively low. high, The shape stability in water is also high. The comparison between Example 3 and Comparative Example 2 can be said to be the same. Further, if Example 2 showing the same degree of ion conductivity is compared with Comparative Example 4, the line of Example 2 The expansion ratio is much lower, and the shape stability in water is excellent. As a result of the above test, the polymer electrolyte membrane composed of the polymer electrolyte of the present invention is excellent in ion conductivity at low humidity, and therefore, the polymer is used. The membrane-electrode assembly of the electrolyte membrane and the polymer electrolyte fuel cell can be said to have excellent output characteristics under low humidity. Moreover, the polymer electrolyte membrane has less swelling due to water and shape stability in water. -60-201131857 [Industrial Applicability] By using the polymer electrolyte of the present invention and the polymer electrolyte membrane comprising the polymer electrolyte, it is possible to provide a membrane-electrode assembly excellent in output characteristics under low humidity, And solid polymer fuel cell. [Simple description of the diagram] Sister. [Main component symbol description] None. -6 1-