1281283 V i 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種質子傳導膜及其製法，尤係關於一 種以含氟陽離子交換基為質子傳導基之高分子質子傳導膜 及其製法。 【先前技術】 直接曱醇進料型燃料電池（Direct Methanol Fuel Cell， DMFC)係使用曱醇-水溶液作為電池之燃料（fuel)，經由陽 極觸媒反應產生電子和質子，電子進入外電路，質子則經 由質子傳導膜（proton exchange membrane，PEM)傳送到陰 極，與氧氣及來自外電路之電子結合，再經由觸媒反應生 成水。 目前，存在於直接曱醇進料型燃料電池之質子傳導膜 之最大問題在於，曱醇為與水高度相容者且易與質子形成 錯合物。氫離子（proton)為不含電之裸質子，由於其缺乏屏 蔽原子核的電荷，質子會與其周圍環境產生強烈交互作用 而形成共價鍵。因此，DMFC所使用的曱醇燃料容易在電 池陽極與質子結合，經傳導穿過PEM，而造成陽極燃料的 流失，穿透過PEM之曱醇燃料並會在陰極消耗觸媒與氧 氣，毒化陰極觸媒，進而降低電極活性，此現象一般係稱 為曱醇穿透（Methanol Crossover)，為造成DMFC之效能未 臻理想的重要原因之一。 一般而言，PEM若需具備高質子傳導性，則其化學結 構會形成強烈親水性（Hydrophilic)環境，而親水性環境也 5 18321(修正本) 1281283 是曱醇相當容易與水發生反應的環境，使甲醇穿透現象會 益發明顯。因此，解決的方法之一為降低結構的親水性， 或減少PEM離子基高親水團簇（cluster)的體積。然而，現 有文獻顯示，當PEM結構的親水性降低時，會伴隨質子的 導電度下降。因此，一個理想的質子傳導膜必須同時具備 高效率的質子傳導能力，且對小分子曱醇具高選擇性。但 就化學結構而言，降低甲醇穿透現象與提高質子導電度實 為相互矛盾之情況，現存之單一材料遂無法滿足適用於直 接曱醇進料型燃料電池之質子傳導膜之要求。 目前市售商品中以杜邦（Du Pont)公司所開發之 Nafion®(全氟碳磺酸聚合物），為目前較具實用性之質子交 換材料。其係藉由高分子親/疏水相分離結構形成之奈米微 相空間，該空間中之磺酸根所集結形成之團簇結構藉由吸 收水分而形成水通路，由所包含的水分子帶動質子進行傳 導，此一高分子結構雖為燃料電池電解質研究帶來突破性 的發展，但在直接曱醇進料型燃料電池之應用上卻發現有 燃料大量滲透流失的問題（Methanol Crossover)。而且 Najfion⑧的價格昂貴（$800-100Ο/m2)，使曱醇進料型燃料電 池即使大量生產亦無法有效降低製造成本。因此，極需要 開發適用於直接曱醇進料型電池系統，同時具備低曱醇穿 透性與高質子傳導能力，且能以低成本大量製造之質子傳 導膜。 除上述者，針對DMFC中PEM的改進，目前尚有多 種不同的方案提出，其中之一係著眼於PEM中離子基濃度 6 18321(修正本) 1281283 , 的降低。PEM中離子基的濃度（Ion Exchange Capacity)為決 定PEM質子導電度的重要因素，然而，高離子基濃度之 PEM亦易在其結構中形成親水團鎮（hydrophilic cluster)， 造成甲醇穿透PEM之現象。因此乃有利用不同離子基的濃 度之PEM做成積層結構，或利用含苯環之高分子加以石黃酸 化，以控制系統中離子基的濃度來降低曱醇穿透PE1V[之技 術提出。例如，美國專利第5525436號、第5716727號、 第 6025085 號、第 6099988 號、第 6124060 號及第 5599639 號等所揭示之利用咪唑化合物之雜環提供質子傳導性；第 6444343號美國專利等所揭示之以聚磺酸苯乙烯 (Polystyrene Sulfonic Acid, PSSA)與聚偏 乙稀 (polyvinylidene fluoride; PVDF)交聯反應形成薄膜；又， 美國專利第6365294號等所揭示之以聚磷腈 (polyphosphazene)為基材之PEM。上述美國專利揭露之技 術雖以降低PEM材料的離子基濃度或選用其他PEM替代 材料，使所形成之PEM之甲醇穿透率降低，但上述技術之 實施大多需於高溫或無水的環境下操作始有較佳的質子導 '電度，且其質子導電度會隨著甲醇穿透率的降低而降低。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a proton conducting membrane and a method for preparing the same, and more particularly to a proton conducting membrane having a fluorine-containing cation exchange group as a proton conducting group and a method for preparing the same . [Prior Art] Direct Methanol Fuel Cell (DMFC) uses a decyl alcohol-water solution as a fuel for a battery to generate electrons and protons through an anode catalyst reaction, and electrons enter an external circuit, protons. Then, it is sent to the cathode via a proton exchange membrane (PEM), combined with oxygen and electrons from an external circuit, and then reacted to generate water via a catalyst. At present, the biggest problem with the proton conducting membranes present in direct sterol feed fuel cells is that sterols are highly compatible with water and tend to form complexes with protons. Hydrogen ions (protons) are bare electric protons that do not contain electricity. Due to their lack of electric charge that shields the nucleus, protons interact strongly with their surroundings to form covalent bonds. Therefore, the sterol fuel used in the DMFC is easy to combine with the proton at the anode of the battery, and is transmitted through the PEM, causing the loss of the anode fuel. The sterol fuel penetrating the PEM will consume the catalyst and oxygen at the cathode, poisoning the cathode. The medium, which in turn reduces the activity of the electrode, is generally referred to as Methanol Crossover, and is one of the important reasons for the unsatisfactory performance of the DMFC. In general, if PEM is required to have high proton conductivity, its chemical structure will form a strong hydrophilic environment, and the hydrophilic environment is also 5 18321 (Revised) 1281283 is an environment where sterols are relatively easy to react with water. In order to make methanol penetration phenomenon, it will be obvious. Therefore, one of the solutions is to reduce the hydrophilicity of the structure, or to reduce the volume of the PEM ion-based high hydrophilic cluster. However, current literature shows that as the hydrophilicity of the PEM structure decreases, the conductivity of the protons decreases. Therefore, an ideal proton conducting membrane must have both high-efficiency proton conductivity and high selectivity to small molecule sterols. However, in terms of chemical structure, the reduction of methanol penetration and the improvement of proton conductivity are contradictory. The existing single material cannot meet the requirements of a proton conducting membrane suitable for a direct sterol feed fuel cell. Nafion® (perfluorocarbon sulfonic acid polymer) developed by Du Pont is currently a commercially available proton exchange material. The nano-phase space formed by the polymer affinity/hydrophobic phase separation structure, wherein the cluster structure formed by the sulfonate group in the space forms a water passage by absorbing water, and the proton is driven by the water molecules contained therein. Conducting, this polymer structure has brought about a breakthrough in the research of fuel cell electrolytes, but in the application of direct sterol-feeding fuel cells, it has been found that there is a problem of large amount of fuel permeation (Methanol Crossover). Moreover, Najfion8 is expensive ($800-100Ο/m2), which makes it impossible to effectively reduce manufacturing costs even if it is produced in large quantities. Therefore, it is highly desirable to develop a proton conducting membrane which is suitable for a direct sterol feed type battery system, has low sterol permeability and high proton conductivity, and can be mass-produced at a low cost. In addition to the above, there are many different proposals for the improvement of PEM in DMFC, one of which focuses on the reduction of ionic base concentration 6 18321 (corrected) 1281283 in PEM. The concentration of Ion Exchange in PEM is an important factor in determining the proton conductivity of PEM. However, PEM with high ionic concentration also easily forms a hydrophilic cluster in its structure, causing methanol to penetrate PEM. phenomenon. Therefore, a PEM having a concentration of different ionic groups is used to form a laminated structure, or a benzene ring-containing polymer is used for the acidification of the phenyl group to control the concentration of the ionic group in the system to reduce the penetration of sterol into the PE1V [technique]. For example, a heterocyclic ring using an imidazole compound disclosed in U.S. Patent Nos. 5,525,436, 5,716, 727, 6,0,0,058, 6, 599, 988, 6, 214, 050, and 5, 599, 639 Polystyrene sulfonate (PSSA) and polyvinylidene fluoride (PVDF) are cross-linked to form a film; and U.S. Patent No. 6,365,294 discloses polyphosphazene as a polyphosphazene. The PEM of the substrate. Although the technique disclosed in the above U.S. patent reduces the ionic concentration of the PEM material or selects other PEM substitute materials, the methanol permeability of the formed PEM is lowered, but most of the above techniques are required to be operated in a high temperature or no water environment. There is a better proton conductivity, and its proton conductivity decreases as the methanol permeability decreases.
- 部分針對PEM材料改質之專利，乃著眼於提高PEM 在高溫使用的飽水性，或降低氫氧氣的穿透現象。研究乃 利用簡單的合成反應將無機金屬氧化物填充於PEM材料 的團簇（cluster)中，或直接與PEM材料摻混，期望藉此增 強PEM在高溫環境中質子之導電穩定性或降低燃料的穿 透率。例如，美國專利第5849428號等已揭示出於聚四氟 7 18321(修正本) 1281283 I f 乙烯（Polyterafluoroethylene;PTFE)與氧化結石粦（ZrOP)之多 孔膜中加入無機氧化物之技術；美國專利第5849428號等 所揭示之於PEM中沉積ZrOP的方法；美國專利第5919583 號等所揭示之於PEM中加入無機質子導體之方法；美國專 利第6059943號、第63 87230號等所揭示之以溶膠_凝膠方 法使PEM於高溫下與ZrOP結合，以提高其導電度；美國 專利第5795496號等揭示之以聚醚醚酮（Poly(ether ether ketone); s-PEEK)、聚醚楓（P〇ly(ether sulfone); s-PES)與沸 石（H-zeolite)，利用高性能工程塑膠之磺酸化，使高分子 薄膜具質子導電度，並加入沸石以降低甲醇穿透率。然而 上述方法雖能縮減傳統PEN[材料之親水團簇（cluster)之體 積，而部分降低PEM之甲醇穿透率，但通常並未能有效改 善，且因為降低PEM材料中親水團簇之體積，也會同時減 少質子的傳導路徑，而造成導電度的下降。 另一改善方案在於改變質子傳導的方式。改變質子傳 導的方式，係將質子從原來在PEM中以離子基形態進行傳 導的方式改為利用無機物固態酸基的質子跳躍機制 (Hopping Mechanism)進行傳導。例如，美國專利弟4594297 號等所提出之以聚乙烯醇（pVA)與雜聚酸（Heter〇p〇1yacid) 於氣相中反應時，改變質子傳遞方式；美國專利第4380575 號所提示之以雜聚酸固體電解質於氣相使用；W0 9852243號專利等提示出完全以沸石作為電解質。然而， 礙於有機材料較難具備此一特性，而無機材料在成膜加工 性上有其先天限制，同時，室溫下具高質子導電度之無機 8 18321(修正本) 1281283 ι « i才料纽且多為溶於水者，因此應用該方法於贿之改 吾’目别並無突破性的進展。 【發明内容】 有鑑於此，本發明之主要目的即在提 醇進料燃料電池之低甲醇穿透性用於直接τ 丨牙職之貝子傳導膜及其製法。 為達成上述及其他目的，本發明所提 ==先將含氣苯乙婦單體接枝於高分子膜材子= if氟本乙烯基之高分子膜材朗，然後以含陽離子 ί苯化該膜’以將該陽離子交換基取代於該含 質t專=本核上。本發明並提供—種以上述製法製成之 具體而言，本發明之質子傳導膜之製法係 ==氣t乙稀單體接枝於如聚偏氣乙婦樹脂0>VDF) 代上，再經酸化後，使陽離子交換基取 η 苯環上而製得本發明之質子傳導膜。 的單|^接==例巾，本發㈣酸化之含氟苯乙烯 膜至爾乙咖叫。s_她 之偏ΐΓ將含氟苯乙烯單體接枝於如聚偏氟乙婦樹脂 以：：=子膜材之製造’只要不影響反應之進行，可 σ種自知之物理或化學方法為之。 方法進行，其—為先以χ ^ 处兩種 日刀如^g h 卞來 r射線或電漿箄 ne)單趙接枝到經活化之稀系高者分 製 18321(修正本) 9 1281283 , 得氟苯乙稀基接枝之聚偏氟i乙稀樹脂。另一種方法係以自 由基聚合法將含氟苯乙烯單體直接接枝到如聚偏氟乙烯樹 脂之高分子膜材上，以製得含氟苯乙烯基接枝之高分子膜 材。 在前述照射法中，控制照射劑量與單體之使用量可改 變接枝度，適當的接枝度可使樹脂保留原有之機械性能， 並有適合之溶劑溶解性，此種溶解性有利於膜之製造或是 後續改質過程的進行。在自由基聚合法中則可以起始劑的 種類、添加量、單體之使用量及此項技術領域中熟知之聚 合條件等來控制接枝度。 無論以何種方法製備接枝有含氟苯乙烯基之偏氟系 高分子膜材，含氟苯乙烯基的接枝度以10至lOOwt%((接 枝後總重-原始高分子膜材重量）/原始高分子膜材重量）為 宜，在此種接枝度下所得到的接枝產物及酸化後的離子聚 合物有較佳的機械性質。 本發明之含氟苯乙烯單體上之氟原子可接枝於苯環 上之任意位置，而其中以接枝於對位（para)或間位（meta)者 ‘為佳。舉例而言，本發明之以含氟苯乙烯單體接枝之如聚 -偏氟乙烯樹脂之偏氟系高分子膜材較佳實例為對位-氟-聚 苯乙烯基接枝之聚偏氟乙烯樹脂（PVDF-g-PS-p-F或 PVDF-g-PS-4-F)或間位-氟-聚苯乙烯接枝之聚偏氟乙烯樹 脂（PVDF-g_PS-m-F 或 PVDF-g-PS-3-F)。 上述以含氟聚苯乙烯單體接枝之高分子膜材隨而係 以適當之陽離子化試劑或含陽離子交換基之酸液處理，以 10 1832U修正本) 1281283 製得具陽離子交換基之含氟苯乙烯接枝之高分子膜材。適 用於本發明之陽離子基可為磺酸基、羧基、磷酸基、亞醯 胺基、磺亞醯胺基或磺醯胺基等，而其中以解離度及酸度 較佳之磺酸酯基為佳（PVDF-g-SPS-4-F)。該等陽離子化試 劑之選擇，可依反應所需而加以適當選擇，以磺酸酯基化 試劑為例，可使者包括例如濃硫酸、氯續酸、三氧化硫、 發煙硫酸、乙醯磺酸鹽等。而所成之具陽離子交換基之含 氟苯乙烯接枝之偏氟系高分子膜材中，陽離子交換當量至 少為0·lmmol/g，較佳為0· 1至1 Ommol/g，尤以0· 1至 2.5mmol/g 為更佳。 為了進一步提升膜的抗化性、耐熱性與機械性質，本 發明之質子傳導膜内亦可添加其他樹脂成分或結合他種電 子傳導膜以形成複合膜。該其他樹脂成分可為含氟樹脂或 不含氟樹脂。含氟樹脂可為單聚物或共聚物，例如聚偏二 氟乙稀、聚偏二氟乙烯/六氟丙烯共聚合物、聚偏二氟乙稀 / 一氯三氟乙稀共聚合物、聚偏二氟乙烯/六氟丙烯/四氟乙 稀三聚合物或聚一氯三氟乙稀等。碳氫類樹脂可為例如聚 丙烯酸S旨（polyacrylate)、聚酯（polyester)、聚醚醚酮 (polyether ether ketone)、聚石黃酸 g旨（polysulfonate)、聚醚 (polyether)、聚臨胺（polyamide)、聚苯醚（polyphenylene oxide)及聚環氧乙烧（polyethylene oxide)等傳統熟知之碳 氫樹脂。而上述其他樹脂成分之添加量以具陽離子交換基 之含氟苯乙烯接枝之偏氟系高分子膜材之重量計算為0至 50重量％間較佳（添加樹脂之重量除以具陽離子交換基之 11 18321(修正本) 1281283 含氟接枝之偏氟系高分子膜材與樹脂之重量和）。 甲西， 中所使用之溶劑可為非質子溶劑，如二甲兵 甲酉遊月女（Dlmethyiformamide)、i 甲土、 等，亦可添加少量二二f，methyls， 合物=高分子膜材及其他添加劑等成份之混 膜即能以刮刀塗佈方式成膜。除溶劑法外，製 膜、丄 可以任何傳統熟知之方式’如熱壓法、滾繞薄 膜比、旋轉塗佈法或擠壓法等來製造。 膜之成份内亦可添加如界面活性劑、可塑劑、 ^抗氧化劑等成份來改善膜之加工性與其他性能。此種 硬口版具有良好之耐熱性、耐酸驗性、機械性與可挽曲性， 此膜在PH值i至14範圍内長期儲存時亦無分解現象。 根據本發明所製得之質子傳導膜，其質子導電度至少 為1X10-3至lxl〇-】S/Cm，且其甲醇穿透率為1><1〇_8至2\1〇6 cm2/sec ° 本發明將以下述實施例更詳細說明本發明之質子傳 導膜’惟該等實施例僅為本發明之示例，不應視為任何揭 限本發明之用意。 【實施方式】 實施例1 將20g對位-氟本乙細（p-fiuorodyrene)單體（純度 99.8%)加入40g聚偏氟乙烯樹脂（pVDF)中，攪拌均勻後， 以Co-60進行輻射照射進行接枝反應，照射劑量係控制在 18321(修正本) 12 1281283 二 r 25gGy 〇所得之PVDF-g，PSf F粗產物以乙酸乙酯進行萃 取（Soxhlet extraction)，以除去未反應之單體及苯乙稀均聚 合物。產物於室溫或加熱乾燥下得到白色之PVDF-g-PS產 物，接枝重量百分比為38.5重量％。將PVDF-g-PS-p-F與 1 Omg氟素界面活性劑FO430 —起加入1-曱基-2-D比略咬_ 20ml中（固體含量3至50wt%)，接著以刮刀塗佈法在加熱 下（120°C)成膜。之後，此膜以氯磺酸在25°C下進行磺酸化 反應，反應時間為8小時。續酸化後之膜先後以四氫咲喃 及水清洗，接著在80°C於真空下乾燥6小時，即製得本發 明之質子傳導膜。所製得之質子傳導膜之化學結構示於第 1 (a)圖，其IR分析結果圖示於第1 (b)圖。以AC交流阻抗 方法測試該質子傳導膜之質子導電度為1.3x1 (T2S/cm。 實施例2 將20g間位-氟苯乙婦（m-fluoro-styrene)單體（純度 99.8%)加入40g聚偏氟乙烯樹脂（PVDF)中，攪拌均勻後， 以Co-60進行輻射照射以產生接枝反應，照射劑量係控制 在25gGy。所得之PVDF-g_PS-m-F粗產物以乙酸乙酯進行 萃取（Soxhlet extraction)，以除去未反應之單體及苯乙稀均 聚合物。產物於室溫或加熱乾燥下得到白色之PVDF-g-PS 產物，接枝重量百分比為32.5重量％。將PVDF-g-PS-3-F 與10mg氟素界面活性劑FC-430 —起加入1-曱基-2-D比口各 咬酮20ml中（固體含量3至50wt%)，接著以刮刀塗佈法在 加熱下（130°C)成膜。之後，此膜以氯磺酸在25°C下進行磺 酸化反應，反應時間為8小時。磺酸化後之膜先後以四氫 13 18321(修正本) 1281283 呋鳴及水清洗，接著在8(TC於真空下乾燥6小時，即製得 本發明之質子傳導膜。所製得之質子傳導膜之化 示 於第2圖。以从交流阻抗方法測試該質子傳導膜之質子 導電度為 3.5xl(T3s/cm。 吸水率分t 將乾燥之具賴化之含氟苯乙埽的單體接枝之聚偏 氣乙稀樹脂製成之質子傳導膜在沸水（或甲醇）中者3〇分鐘 後’將之取出並以拭鏡紙將膜表面之水滴拭乾，隨即將拭 乾^質子傳導膜秤重，將膜所吸收之水重除以具續酸化之 =II苯乙稀的單體接枝之聚偏氟乙烯樹脂製成之乾膜之重 量即得到膜的吸水率。 比較試驗 以市售之Nafi〇nll7與本發明實施例i所製得之質子 傳導膜進行導電度、曱⑽透（methanol _SQVei.)、吸水 率及甲醇吸收率之比較試驗，其結果示於表卜 樣 ΏΏ 導電度 (S/cm) 甲醇穿透率 (cm2/s) 吸水率(重量％) 溶劑吸收率 (重量％) ------—/s ^Nafi〇nll7 6xl(T2 —由表1結果可知，本發明之質子傳導膜在導電度不受 Λ貝衫％下具有較市售產品更低之甲醇穿透率、更低之吸 水率及曱醇吸收率。亦即’本發明之質子傳導膜應用於直 接曱#進料型㈣電池中，可降低膜材之甲醇燃料電池中 之膨潤性並明顯降低其曱醇穿透。 14 18321(修正本) 1281283- Part of the patent for the modification of PEM materials, focusing on improving the water saturation of PEM at high temperatures or reducing the penetration of hydrogen and oxygen. The study uses a simple synthesis reaction to fill the inorganic metal oxide in a cluster of PEM materials, or directly blended with the PEM material, in order to enhance the conductive stability of the PEM or the fuel in the high temperature environment. Penetration rate. For example, U.S. Patent No. 5,849,428 et al. discloses the addition of inorganic oxides to a porous film of polytetrafluoro 7 18321 (modified) 1281283 I f ethylene (polygonal fluoroethylene; PTFE) and oxidized stone iridium (ZrOP); A method for depositing ZrOP in a PEM as disclosed in No. 5,849, 428, et al., a method of adding an inorganic proton conductor to a PEM as disclosed in U.S. Patent No. 5,915, 853, and the like, and a sol disclosed in U.S. Patent No. 6,507,943, No. 63,87,230, et al. The gelation method allows PEM to be combined with ZrOP at a high temperature to increase its conductivity; and Polyetheretherketone (Poly(ether ether ketone); s-PEEK), polyether maple (P) disclosed in U.S. Patent No. 5,795,496, et al. 〇ly (ether sulfone); s-PES) and zeolite (H-zeolite), using high-performance engineering plastic sulfonation, the polymer film has proton conductivity, and added zeolite to reduce methanol penetration. However, the above method can reduce the volume of the traditional PEN [the hydrophilic cluster of the material, and partially reduce the methanol permeability of the PEM, but generally does not improve effectively, and because the volume of the hydrophilic cluster in the PEM material is reduced, It also reduces the conduction path of protons and causes a decrease in conductivity. Another improvement is to change the way protons are conducted. The way in which proton conduction is altered is to transfer protons from the original PEM to the proton hopping mechanism using the solid state acid group. For example, U.S. Patent No. 4,594,297, et al., the disclosure of which is incorporated herein by reference in its entirety by reference to the disclosure of the disclosure of U.S. Pat. The heteropoly acid solid electrolyte is used in the gas phase; the patent of WO 9852243 and the like suggests that zeolite is completely used as the electrolyte. However, it is difficult for organic materials to have such a characteristic, and inorganic materials have inherent limitations in film forming processability, and at the same time, inorganic protons with high proton conductivity at room temperature 8 18321 (Revised) 1281283 ι « i The material is mostly soluble in water, so there is no breakthrough in the application of this method to the bribery. SUMMARY OF THE INVENTION In view of the above, the main object of the present invention is to provide a low methanol permeability of a methanol feed fuel cell for use in a direct τ 丨 之 贝 传导 传导 传导 及其 及其 及其 。 。 。 。 。 。 。 。 。 。 。 。 。 In order to achieve the above and other objects, the present invention provides that == firstly, the gas-containing phenylethylene monomer is grafted to the polymer film material = if the fluorine-based vinyl polymer film is lang, and then the cation-containing benzoic acid is used. The membrane 'substitutes the cation exchange group on the nucleus t-specific nucleus. The present invention further provides a method for producing a proton conductive membrane of the present invention, wherein the method for producing a proton conductive membrane of the present invention is grafted onto a gas such as a polymetaphorar resin, 0>VDF). After acidification, the cation exchange group is taken on the η benzene ring to prepare the proton conductive membrane of the present invention. Single | ^ connect = = case towel, this hair (four) acidified fluorine-containing styrene film to the end of the bar. S_ Her partiality grafting of fluorinated styrene monomer to, for example, polyvinylidene fluoride resin: := sub-membrane production 'as long as it does not affect the progress of the reaction, σ can be known by physical or chemical methods For it. The method is carried out, which is firstly grafted to the activated rare earther 18321 (amendment) 9 1281283 by two kinds of Japanese knives such as ^ gh 卞 r ray or plasma 箄 ne). a fluorovinylethylene-grafted polyvinylidene fluoride-ethylene resin. In another method, a fluorine-containing styrene monomer is directly grafted onto a polymer film such as a polyvinylidene fluoride resin by a radical polymerization method to obtain a fluorine-containing styrene-based grafted polymer film. In the foregoing irradiation method, controlling the irradiation dose and the amount of the monomer can change the degree of grafting, and the proper degree of grafting can make the resin retain the original mechanical properties and have a suitable solvent solubility, and the solubility is favorable for the solvent. The manufacture of the film or the subsequent modification process. In the radical polymerization method, the degree of grafting can be controlled by the kind of the initiator, the amount of the initiator, the amount of the monomer used, and the polymerization conditions well known in the art. Regardless of the method for preparing a fluorine-doped polymer film grafted with a fluorine-containing styrene group, the degree of grafting of the fluorine-containing styrene group is 10 to 100% by weight ((grafted total weight - original polymer film) The weight/original polymer film weight) is preferred, and the graft product obtained after such grafting degree and the acidified ionic polymer have better mechanical properties. The fluorine atom on the fluorine-containing styrene monomer of the present invention may be grafted at any position on the benzene ring, and it is preferred that it is grafted to a para or meta. For example, a preferred example of the fluorine-based polymer film of the present invention, which is grafted with a fluorine-containing styrene monomer, such as a poly-vinylidene fluoride resin, is a para-fluoro-polystyrene-based graft. Fluoroethylene resin (PVDF-g-PS-pF or PVDF-g-PS-4-F) or meta-fluoro-polystyrene-grafted polyvinylidene fluoride resin (PVDF-g_PS-mF or PVDF-g- PS-3-F). The above-mentioned polymer film grafted with a fluorine-containing polystyrene monomer is treated with an appropriate cationizing agent or a cation-exchange-containing acid solution, and is modified by 10 1832 U. Fluorostyrene grafted polymer film. The cationic group suitable for use in the present invention may be a sulfonic acid group, a carboxyl group, a phosphoric acid group, a sulfonium group, a sulfilimine group or a sulfonamide group, and the like, and a sulfonate group having a better degree of dissociation and acidity is preferred. (PVDF-g-SPS-4-F). The selection of the cationizing reagents may be appropriately selected according to the reaction requirements, and the sulfonate-based reagents may be exemplified, for example, concentrated sulfuric acid, chlorine acid, sulfur trioxide, fuming sulfuric acid, acesulfame Acid salt, etc. The fluorine-containing styrene-grafted fluorine-based polymer film having a cation exchange group has a cation exchange equivalent of at least 0.1 mol/g, preferably from 0.1 to 1 Ommol/g, particularly 0·1 to 2.5 mmol/g is more preferred. In order to further improve the chemical resistance, heat resistance and mechanical properties of the film, other resin components or other kinds of electron conductive films may be added to the proton conductive film of the present invention to form a composite film. The other resin component may be a fluorine-containing resin or a fluorine-free resin. The fluorine-containing resin may be a monomer or a copolymer, such as polyvinylidene fluoride, polyvinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride/monochlorotrifluoroethylene copolymer, Polyvinylidene fluoride / hexafluoropropylene / tetrafluoroethylene tripolymer or polychlorotrifluoroethylene. The hydrocarbon-based resin may be, for example, polyacrylate, polyester, polyether ether ketone, polysulfonate, polyether, polyamine. Traditionally known hydrocarbon resins such as polyamide, polyphenylene oxide and polyethylene oxide. The amount of the other resin component added is preferably from 0 to 50% by weight based on the weight of the fluorine-containing styrene-grafted fluorine-based polymer film having a cation exchange group (the weight of the added resin divided by the cation exchange) Base 11 18321 (amendment) 1281283 Fluorinated grafted fluorine-based polymer film and resin weight and). The solvent used in the company can be an aprotic solvent, such as Dlmethyiformamide, i-soil, etc., or a small amount of di-f, methyls, compounds = polymer membranes and others. A film mixture of additives and the like can be formed by doctor blade coating. In addition to the solvent method, film formation and ruthenium can be produced by any conventionally known method such as hot pressing, roll film ratio, spin coating or extrusion. The components of the film may also be added with components such as surfactants, plasticizers, and antioxidants to improve the processability and other properties of the film. This hard-dip version has good heat resistance, acid resistance, mechanical properties and flexibility. The film does not decompose when stored for a long period of time in the range of pH i to 14. The proton conducting membrane prepared according to the present invention has a proton conductivity of at least 1×10-3 to lxl〇-]S/Cm and a methanol permeability of 1><1〇_8 to 2\1〇6 Cm2/sec ° The present invention will be described in more detail with reference to the following examples to illustrate the proton-conducting membranes of the present invention. However, the examples are merely examples of the invention and should not be construed as limiting the scope of the invention. [Examples] Example 1 20 g of p-fiuorodyrene monomer (purity: 99.8%) was added to 40 g of polyvinylidene fluoride resin (pVDF), stirred uniformly, and irradiated with Co-60. The grafting reaction was carried out by irradiation, and the irradiation dose was controlled at 13321 (Revised) 12 1281283. The obtained PVDF-g of 25 gGy ,, and the crude PSf F product was extracted with ethyl acetate (Soxhlet extraction) to remove unreacted monomers. And styrene homopolymer. The product was obtained as a white PVDF-g-PS product at room temperature or under heating, and the graft weight percentage was 38.5% by weight. Add PVDF-g-PS-pF together with 1 Omg of fluorosurfactant FO430 to 1-mercapto-2-D ratio slightly bite _ 20ml (solid content 3 to 50wt%), followed by knife coating Film formation was carried out under heating (120 ° C). Thereafter, the film was subjected to a sulfonation reaction with chlorosulfonic acid at 25 ° C for a reaction time of 8 hours. The acidified film was washed successively with tetrahydrofuran and water, followed by drying at 80 ° C for 6 hours under vacuum to obtain a proton conductive membrane of the present invention. The chemical structure of the prepared proton conductive membrane is shown in Fig. 1(a), and the results of IR analysis are shown in Fig. 1(b). The proton conductivity of the proton conducting membrane was measured by an AC alternating current impedance method to be 1.3 x 1 (T2S/cm. Example 2 20 g of m-fluoro-styrene monomer (purity 99.8%) was added to 40 g. In a polyvinylidene fluoride resin (PVDF), after uniformly stirring, irradiation with Co-60 was carried out to produce a graft reaction, and the irradiation dose was controlled at 25 g of Gy. The obtained PVDF-g_PS-mF crude product was extracted with ethyl acetate ( Soxhlet extraction) to remove unreacted monomer and styrene homopolymer. The product was obtained at room temperature or under heat to obtain a white PVDF-g-PS product with a graft weight percentage of 32.5% by weight. -PS-3-F with 10 mg of fluorosurfactant FC-430 together with 1-mercapto-2-D ratio in 20 ml of each biting ketone (solid content 3 to 50 wt%), followed by knife coating The film was formed under heating (130 ° C). Thereafter, the film was subjected to sulfonation reaction with chlorosulfonic acid at 25 ° C for 8 hours. The film after sulfonation was successively treated with tetrahydro 13 18321 (amendment) 1281283 Furnishing and water washing, followed by drying at 8 (TC for 6 hours under vacuum) to obtain the proton conducting membrane of the present invention. The proton conductive membrane is shown in Fig. 2. The proton conductivity of the proton conducting membrane was tested by the alternating current impedance method to be 3.5 x 1 (T3 s/cm. The water absorption fraction is t. The proton conductive membrane made of monomer-grafted polyhedral ethylene resin is taken in boiling water (or methanol) for 3 minutes, 'take it out and wipe the water droplets on the surface of the membrane with a mirror paper, and then wipe it off. The dry proton conductive membrane is weighed, and the water absorbed by the membrane is divided by the weight of the dry film made of the monomer-grafted polyvinylidene fluoride resin having the acidified = II styrene to obtain the water absorption of the membrane. The comparative test was conducted by comparing the conductivity, m(10) permeable (methanol _SQVei.), water absorption rate and methanol absorption rate with a commercially available Nafi〇nll7 and a proton conducting membrane prepared in Example i of the present invention, and the results are shown in Table ΏΏ Conductivity (S/cm) Methanol penetration rate (cm2/s) Water absorption rate (% by weight) Solvent absorption rate (% by weight) ------—/s ^Nafi〇nll7 6xl (T2 — It can be seen from the results of Table 1 that the proton conductive membrane of the present invention has a lower methanol permeability than the commercially available product in that the conductivity is not affected by the bristles. Permeability, lower water absorption rate and sterol absorption rate. That is, the proton conductive membrane of the present invention is applied to the direct feed type (four) battery, which can reduce the swelling property of the membrane fuel cell and significantly reduce the swelling property. Its sterol penetration. 14 18321 (Revised) 1281283
4 I 【圖式簡單說明】 第1(a)圖為本發明實施例1之質子傳導膜 (PVDF_g-SPS_p-F)之化學結構圖； 第1(b)圖為本發明實施例1之質子傳導膜 (PVDF-g_SPS-p-F)之 IR 分析結果圖； 第2圖為本發明實施例2之質子傳導膜 (PVDF-g-SPS-m-F)之化學結構圖。 【主要元件符號說明】 本案圖式無元件符號。 15 18321(修正本)4 I [Simple Description of the Drawings] Fig. 1(a) is a chemical structural diagram of a proton conducting membrane (PVDF_g-SPS_p-F) of Example 1 of the present invention; and Fig. 1(b) is a proton of Example 1 of the present invention The IR analysis result chart of the conductive film (PVDF-g_SPS-pF); Fig. 2 is the chemical structure diagram of the proton conductive film (PVDF-g-SPS-mF) of Example 2 of the present invention. [Description of main component symbols] There is no component symbol in this case. 15 18321 (amendment)