TW200538495A - Bromine, chlorine or iodine functional polymer electrolytes crosslinked by e-beam - Google Patents

Bromine, chlorine or iodine functional polymer electrolytes crosslinked by e-beam Download PDF

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TW200538495A
TW200538495A TW093134363A TW93134363A TW200538495A TW 200538495 A TW200538495 A TW 200538495A TW 093134363 A TW093134363 A TW 093134363A TW 93134363 A TW93134363 A TW 93134363A TW 200538495 A TW200538495 A TW 200538495A
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fluoropolymer
polymer
electron beam
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Michael Andrew Yandrasits
Steven Joseph Hamrock
Nai-Yong Jing
Kai Helmut Lochhaas
Arne Thaler
Tatsuo Fukushi
Klaus Hintzer
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3M Innovative Properties Co
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Description

200538495 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種藉由將電子束輻射應用於高度氟化之 含氟聚合物來製造交聯聚合物電解質之方法，該交聯聚合 物電解質典型地以膜形式用作諸如燃料電池之電解電池中 的聚合物電解質膜，其中該含氟聚合物包括··部分衍生自 四氟乙烯單體之主鏈；包含根據式-S〇2X之基團的第一側接 基團，其中X為F、CM、Br、OH或-0-M+，其中M+為一價陽 離子；及包含Br、C1或I之第二側接基團。 【先前技術】 據稱美國專利第4,470,889號揭示了 一種由氟化之聚合物 膜分成陽極室與陰極室的電解電池，其中該膜包括：（心至 少60莫耳百分數之[CFX_CF2]，其中X=I^C1 ; (b)至少6〇〇 的離子交換當量重；（c)附掛之磺醯基離子交換基團；及（句 附掛的經大體上氟化之碳基團，其不具有離子交換官能 性。不具有離子交換官能性的經大體上氟化之附掛碳基團 可包括Br。 據稱美國專利公開案第US 2003/0181615 A1號揭示了特 定的氟磺化之含氟單體、特定的溴化之含氟單體及非四I 乙烯（TFE)單體的聚合物。（，615在第234段及64-68段）。據 稱該文獻揭示了特定交聯方法。 據稱美國專利第5,260,351號揭示了在沒有固化劑存在下 藉由輻射而固化的全氟彈性體。據稱該文獻係關於完全氟 化之聚合物（例如自四氟乙烯、全氟烧基、全氟乙浠崦製備 97021.doc 200538495 的彼等全就化之聚合物）的固化，且係關於固化位點或在所 得三聚物中提供腈、全氟苯基、溴或碘中之至少一種物質 的交聯單元。 【發明内容】 簡言之’本發明提供一種製造交聯聚合物之方法，其包 括以下步驟：a)提供高度氟化之含氟聚合物，其包括：部 分衍生自四氟乙烯單體之主鏈；包含根據式-S〇2X之基團的 第一側接基團，其中X為F、Cl、Br、OH或-CTM+，其中M+ 為一價陽離子；及包含Br、C1或1(典型地為Br)之第二側接 基團，及b)曝露該含氟聚合物於電子束輻射下以便導致形 成交聯。該方法可在該步驟b)之前另外包括步驟·· c)將含氟 聚合物形成膜。典型地，膜具有90微米或更小、更典型地 為60微米或更小且最典型地為30微米或更小之厚度。高度 氟化之含氣聚合物典型地為全氟化的。第一側接基團典型 地為根據式-0-(CF2)4_S〇2X之基團，且X典型地為OH。典型 地曝露含氟聚合物於大於1 Mrad(兆拉德）之電子束輻射 下’更典型地曝露於大於3 Mrad之電子束輻射下。 在另一態樣中，本發明提供根據任何本發明之方法製造 的交聯聚合物。 本發明提供一種藉由使用電子束輻射來交聯高度氟化之 含氟聚合物的方法，該方法在此項技術中先前未有描述， 該高度氟化之含氟聚合物包括：部分衍生自四氟乙稀單體 之主鍵；包含根據式- S〇2X之基團的第一側接基團，其中X 為F、a、Br、OH或-0-M+，其中M+為一價陽離子；及包含 97021.doc 200538495
Br、Cl或I之第二側接基團，該聚合物典型地為用作聚合物 電解質膜之膜。 在此應用中： 聚合物之”當量重”（EW)意謂中當量鹼所需的聚合物 聚合物之”水合乘積”（HP)意謂由存在於膜中的每當量磺 酸基所吸收的水之當量數（莫耳）與聚合物之當量重的乘 π高度氟化π意謂含有量為40重量％或更多、典型地為5〇 重量％或更多且更典型為60重量％或更多的氟。 【實施方式】 本發明提供一種製造交聯聚合物之方法。待交聯之聚合 物包括：部分衍生自四氟乙烯（TFE)單體之主鏈；包含根據 式-S02X之基團的第一側接基團，其中乂為F、Cl、B卜 或-0-M+，其中M+為一價陽離子；及包含汾、^或〗之第二 側接基團。該等聚合物可適用於製造聚合物電解質膜 (PEM)，例如可用於諸如燃料電池之電解電池中。、 自根據本發明之交聯聚合物製造的pEM可用於製作用於 燃料電池中的膜電極組（MEA)。MEA為諸如氫燃料電池之
與陽極電極層接觸且其相反的_ 因體1：解質。PEM之一面 面與陰極電極層接觸。各 97021.doc 200538495 電極層包含電化學催化劑，其典型地包含鉑金屬。氣體擴 散層（GDL)有利於氣體傳輸至陽極與陰極電極材料及自該 等材料傳輸及傳導電流。GDL亦可稱為流體傳輸層（FTL)或 擴散器/集電器（DCC)。陽極與陰極電極層可以催化劑油墨 形式塗覆至GDL，且以PEM夹住所得之經塗覆GDL以形成 一 5層MEA。或者，陽極與陰極電極層可以催化劑油墨形式 塗覆至PEM的相反面，且以兩層GDL夾住所得的經催化劑 塗覆之膜（CCM)以形成一 5層MEA。該5層MEA之5層依次 為：陽極GDL、陽極電極層、PEM、陰極電極層及陰極GDL。 在典型之PEM燃料電池中，質子經由氫氧化作用在陽極上 形成且被傳輸穿過PEM至陰極與氧反應，從而引起電流在 連接電極之外部電路中流動。PEM在反應氣體之間形成一 層持久的、無孔的、電學上非傳導的機械障壁，然而其亦 易於傳遞H+離子。 待交聯之聚合物包括可為分枝或未分枝之主鏈，但典型 地為未分枝。主鏈係經高度氟化且更典型地係經全氟化。 主鏈包括衍生自四氟乙烯（TFE)之單元（即，典型地為 -CF2-CF2-單元）及衍生自輔單體之單元，典型地包含至少一 個根據式CF2=CY-R之辅單體，其中Y典型地為F但亦可為 CF3，且其中R為包含根據式-S02X之基團的第一侧接基 團，其中X為F、Cl、Br、OH或-0_M+，其中M+為一價陽離 子，典型地為諸如Na+之鹼金屬陽離子。X最典型地為ΟΗ。 在一替代實施例中，第一側基R可藉由接枝而添加至主鏈 上。典型地，第一側基R係經高度氟化且更典型地係經全氟 97021.doc 200538495 化R可為芳族或非芳族。R典型地為_ri_s〇2X，其中…為 分枝或未分枝之全氟烧基或全氟Μ基，其包括b15個碳原 子及0-4個氧原子。R1典型地為_〇劣2_，其中R2為分枝或未 为枝之全氟烷基或全氟醚基，其包括1-15個碳原子及〇_4個 氧原子。R1更典型地為-0-R、，其中R3為包括卜15個碳原子 的全氟烷基。R1之實例包含： -(CF2)n- ’ 其中 η為 1、2、3、4、5、6、7、8、9、10、11、 12、13、14 或 15 (-CF2CF(CF3)-)n，其中 η為 1、2、3、4、或 5 (-CF(CF3)CF2-)n，其中 η為1、2、3、4、或5 (-CF2CF(CF3)-)n-CF2- ’ 其中 η為 1、2、3 或 4 (-0-CF2CF2-)n，其中 η為1、2、3、4、5、6或7 (-0-CF2CF2CF2CF2-)n，其中 η為 1、2或 3 (-0-€?20卩(0卩3)-)11，其中11為1、2、3、4、或5 (-0-CF2CF(CF2CF3)-)n，其中 η為 1、2或 3 (-0-CF(CF3)CF2-)n，其中 η為1、2、3、4或5 (-0-CF(CF2CF3)CF2-)n，其中 η為 1、2 或 3 (-0-CF2CF(CF3)-)n-0-CF2CF2-，其中 η為 1、2、3 或 4 (-0-CF2CF(CF2CF3)-)n-0-CF2CF2-，其中 η為 1、2 或 3 (-0-CF(CF3)CF2-)n-0_CF2CF2-，其中 η為 1、2、3 或 4 (-0-CF(CF2CF3)CF2-)n-0-CF2CF2-，其中 η為 1、2 或 3 -0-(CF2)n-，其中 η為 1、2、3、4、5、6、7、8、9、10、 11 、 12 、 13或14 97021.doc -10- 200538495 R典型地為-0-CF2CF2CF2CF2-S02X或轉 CF2-CF2-S02x且最典型地為-0-CF2CF2CF2CF2-S02X，其中 X為F、Cl、Br、OH、或-CTM+，但最典型地為〇H。 提供第一側基R之含氟單體可由任何適當方式合成，包含 美國專利第6,624,328號中所揭示之方法。
另外，含氟聚合物包含第二側接基團Q，其含有Br、C1 或I ’典型地為Br。第二側接基團可衍生自根據式CF2=C y_q 之辅單體，其中Y典型地為F但亦可為CF3，且其中q為包含 Br、C1或I的第二側接基團。在一替代實施例中，第二側接 基團Q可藉由接枝而添加至主鏈上。第二側接基團卩典型地 係經高度氟化且更典型地係經全氟化，除了在溴位置上。Q 典型地為，其中R1係如上所述。或者，卩為汾、〇1或 1，典型地為Br。 含氟聚合物最典型地為TFE、如上所述之cf2=C Y-R及如 上所述之CF2=CY-Q的三聚物。 待父聯之聚合物可以任何適當之方法來製造，該方法包 含乳液聚合、擠壓聚合、超臨界二氧化碳聚合、溶液或懸 浮液聚合及其類似方法，其可以係分批的或連續的。 在實軛例中，鏈轉移劑可用於聚合中以提供以C1、Br 或I為端基的聚合物。若該等端基存在，則可認為其為用於 本發明目的之側接基團。鏈轉移劑之實例包含彼等具有式 RXn之鏈轉移劑，其中R為含有M2個碳原子之n價烷基，其 可、、二氟化或不經氟化，且其中χ係獨立選自C1、价或Ζ。另 外的鏈轉移劑例不於美國專利第4,刪，356號及第6,38〇,337 97021.doc 200538495 號中。另外，如EP 407937中所描述，可在-鹽存在下進 行聚合以引入末端Br或I端基。 酸官能側接基團典型地以足量存在以導致水合乘積（HP) 大於15,000、更典型地大於18,000、更典型地大於22,〇〇〇、 且最典型地大於25,000。一般而言，較高的111>與較高的離 子電導率有關。 酸官能側接基團典型地以足量存在以導致當量重（EW)小 於1200、更典型地小於11〇〇、更典型地小於1〇〇〇、且最典 型地小於900。 聚合物典型地在交聯之前形成膜。可使用任何形成膜之 適當方法。聚合物典型地由懸浮液澆注而來。可使用任何 適S之’/堯注方法，包含桿塗法、喷塗法、切塗法、刷塗法 及其類似方法。或者，膜可在諸如擠壓之熔融過程中由純 聚合物形成。在形成之後，可將膜退火，典型地在120qc或 更高溫度下、更典型地在130。(:或更高溫度下、最典型地在 15 0°C或更高溫度下。膜典型地具有9〇微米或更小、更典型 的為60微米或更小、且最典型地為3〇微米或更小之厚度。 較薄的膜可對離子通過提供較小阻力。在燃料電池之使用 中’其導致較低的運行溫度及較大的可用能量輸出。較薄 的膜必須由能夠在使用中保持其結構完整性的材料來製 得。 交聯步驟包括曝露含氟聚合物於電子束輻射下之步驟以 導致形成交聯。電子束輻射典型地為1 Mrad或更多、更典 型地為3 Mrad或更多、更典型地為5 Mrad或更多、且最典 97021.doc •12- 200538495 型地為15 Mrad或更多之劑量。任何適當裝置均可使用。持 續的曝露過程可用於處理滾筒良好膜。 可視情況添加交聯劑。交聯劑可以任何適當方法來添 加’包含在聚合物形成膜之前與聚合物摻合及將交聯劑施 力於膜中例如，藉由浸沒於交聯劑溶液中。典型之交聯 劑可包含多官能化合物，例如多官能烯烴、多官能丙烯酸 酉曰、多官能乙烯醚及其類似物，其可未經氟化或經氟化至 低水平，但其更典型地係經高度氟化且更典型地係經全氟 化。 在另一實施例中，可在交聯之前將聚合物吸收入多孔支 撐基質中，該聚合物典型地為具有9〇微米或更小、更典型 地為60微米或更小且最典型地為3〇微米或更小之厚度的薄 膜形式。任何將聚合物吸收入支撐基質之孔中的適當方法 均可使用，包含過壓法、真空法、燈芯作用法、浸沒法及 其類似方法。一旦交聯，該摻合物就包埋於基質中。任何 適當之支撐基質均可使用。支撐基質典型地不具有電傳導 性。支撐基質典型地包括含氟聚合物，其更典型地係經全 氟化。典型的基質包含多孔聚四氟乙烯（PTFE)，例如經雙 軸拉伸之PTFE網。 應瞭解，根據本發明之方法製造的聚合物及膜之化學結 構可在交聯結構、交聯排列、酸官能基之排列、在側接基 團上交聯存在與否或在交聯處酸官能基存在與否、及其類 似方面，不同於彼等以其它方法製得之聚合物及膜。 本發明適用於製造用於諸如燃料電池之電解電池中的於 9702i.doc -13- 200538495 加強之聚合物電解質膜。 本發明之目的及優勢將由以下實例來進一步說明，但在 此等實例中所述之特定材料與其量以及其它條件與細節不 應理解為不適當地限制本發明。 實例 除非另有說明，否則所有試劑均由Aldrich Chemical Co·， Milwaukee，WI獲得或購得，或可以已知方法合成。 聚合物 在本發明之實例中所使用之聚合物電解質係藉由四氟乙 烯（TFE)與 CF2=CF-0-(CF2)4-S02F(MV4S)(其以美國專利第 6,624,328號所揭示之方法來合成）乳化聚合及四氟乙烯 (TFE)與 CF2=CF_0-(CF2)2-Br(MV2Br)乳化聚合來製造。 使用 ULTRA-TURRAX® 型 T 25 分散機 S25KV-25F (IKA-Werke GmbH & Co. KG，Staufen，德國），在高剪切 速率（24,000 rpm)下於水中以15 g APFO乳化劑（全氟辛酸 銨，C7F15COONH4)將130 g MV4S預乳化2分鐘。向配備有 推進器攪拌器系統的4公升聚合鍋中饋入3· 1 kg去離子水。 將鍋加熱至50°C且接著將預製乳液饋入無氧之聚合锅中。 在50oC下向鍋中進一步饋入6 g MV2Br及178 g氣態四氟乙 烯（TFE)直至達到8巴（bar)之絕對反應壓力。在5〇°C及240 rpm攪拌速度下，藉由添加15 g亞硫酸氫納及40 g過氧硫酸 氫銨來起動聚合作用。在反應過程中反應溫度維持在 50°C。反應壓力係藉由向氣相饋入額外之TFE而維持在6.0 巴之絕對壓力下。使用427 g MV4S以同樣方式及上述比例 97021.doc -14- 200538495 來製備第二份MV4S-預製乳液。在反應過程中，將第二份 預製乳液持續地饋入液相中。在反應過程中，額外的26 g MV2Br亦持續地饋入反應器中。 在饋入800 g TFE後，關閉單體閥門且中斷單體進料。持 續的聚合作用使單體氣相壓力降至2·9巴。此時對反應器進 行排放且以氮氣沖洗。 如此獲得之聚合物分散液與2_3當量之Li〇H及2當量之 LizCO3 (以磺醯氟濃度計之當量）及足夠的水混合以製造 〇竓的♦ δ物固體混合物。將此混合物加熱至2 $ 〇。。持續4 小呀。在此等條件下，大部分（>95%)聚合物變得分散。過 渡分散液以移除LiF及未分散之聚合物，且接著在 Mitsubishi Diaion SKT10L離子交換樹脂上交換離子以得到 離子鍵共聚物之酸形式。所得之聚合物電解質為具有根據 式-〇_(CF2)4_s〇3H之酸性側鏈及根據式-0-(CF2)2_Br之側鏈 的王氟化I合物。所得混合物為具有丨8_丨9%之聚合物固體 的S文性为散液。將此分散液與正丙醇混合且接著在真空中 辰縮以彳于到所要的水中之2〇%固體分散液/約水與 醇之正丙醇/谷劑混合物。此驗性分散液用於洗注膜。 臈 、 ;、j Λ之來合物膜樣品係藉由以刮刀將含有固體 的水/丙醇懸洋液（4〇%水/6〇%正丙醇）塗布至玻璃板上而洗 =成’在80oC下乾燥1〇分鐘，且在2〇〇〇c下退火ι〇分鐘。所 传膜之厚度為約3G微米。接著將膜自玻璃板上移除，切割 成T，置於聚乙烯袋中且以氮淨化。 97021.doc 15 200538495 電子束 曝露膜樣品於電子束源下。（Energy Sciences CB300, Energy Sciences，Inc·，Wilmington，Massachusetts) 〇 控制每 次通過之劑量為2 Mr ad。樣品經受總電子束劑量為0、2或6 Mr ad的0、1或3次通過。 分析 藉由動態機械分析（DMA)來量測曝露於0、2或6 Mrad之 電子束劑量下的樣品之Tg。在DMA中，將待測試之聚合物 樣品夾在施加振盪力且量測所得樣品位移的測試裝置上。 在可控溫度環境下進行該過程。在進行量測時溫度呈斜線 上升。該等裝置典型地自此資料計算、記錄及顯示作為溫 度函數的樣品之彈性模數（E’）、損失模數（E”）及阻尼係數 (tan3)。將tan3中之最大值取作Tg。 在本發明之實例中，於1赫茲（6.28拉德/秒）之頻率下使用 Rheometrics 固體分析儀 RSA II (TA Instruments，New Castle，Delaware，美國）。測試薄帶樣品，量測到其寬度 為約6 · 5 mm且長度為約2 5 mm。在拉伸情況下於25°C至 200°C之溫度範圍下進行量測。 圖1為顯示各劑量之DMA結果的圖表。跡線A表示0 Mrad (對照）、跡線B表示2 Mrad (本發明）且跡線C表示6 Mrad (本 發明）。圖2為顯示各劑量之Tg的圖表，其中Tg係視為示於 圖1中之tanS資料中的最大值。就曝露於2 Mrad電子束輻射 下之樣品而言，Tg有所提高，其表明交聯已經發生。就曝 露於6 Mrad電子束輻射下之樣品而言，Tg進一步有所提高。 97021.doc -16- 200538495 在不脫離本發明之範疇及原則的情況下，本發明之各種 修飾及麦更對於熟習此項技術者將變得顯而易見，且應瞭 解本發明不會不適當地限制上文中所述之說明性實施例。 【圖式簡單說明】 圖1為展示一種對照聚合物（A)與兩種根據本發明之聚合 物（B，C)之動態機械分析結果（Dma)的圖表。 圖2為展示一種對照聚合物（〇 Mrad)與兩種根據本發明之 聚合物（2 Mrad，6 Mrad)之Tg的圖表。 97021.doc 17-

Claims (1)

  1. 200538495 十、申請專利範圍： 1· 一種製造交聯聚合物之方法，其包括以下步驟： a) 提供高度氟化之含氟聚合物，其包括：部分衍生自四 氟乙稀單體之主鏈；包含根據式_s〇2X之基團的第一側 接基團’其中X為F、Ch Br、〇11或_〇.M+，其中為 -價陽離子；及包含選自由Β。，組成之群之函素 原子的第二側接基團；及 b) 曝路該含氟聚合物於電子束輻射下以導致形成交聯。 2·如明求項1之方法，其中該方法可在該步驟七）之前另外包 括步驟： C)將該含氟聚合物形成膜。 3·如明求項丨或2之方法，其中步驟c)包括將該含氟聚合物吸 收至多孔支撐基質中。 4· 4叫求項3之方法，其中該多孔支撐基質為多孔聚四氟乙 稀網。 5·如凊求項4之方法，其中該膜具有9〇微米或更小之厚度。 6.如印求項丨或2之方法，其中該曝露該含氟聚合物於電子 束輻射下之步驟包括曝露該含氟聚合物於大於丨Mud之 電子束輻射下。 7·如1晴求項丨或2之方法，其中該等側接基團為根據式 2X之基團’其中R為分枝的或未分枝的全氟燒基 或全氟醚基，其包括^15個碳原子及〇_4個氧原子，且其 中X為F、α、Br、0H或-0-M+,其中M+為一價陽離子。 8·如請求項丨或2之方法，其中該等側接基團為根據式 97021.doc 200538495 -0-(CF2)4_s〇3fi 之基厨。 9· 10. 如請求項1或2之方法，其尹包含在該等第二侧接基團中 之該鹵素原子為Br。 -種聚合物電解質膜，纟包括由請求項15戈2之方法製造 的交聯聚合物。 97021.doc
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