TW200530285A - Polymer electrolytes crosslinked by e-beam - Google Patents
Polymer electrolytes crosslinked by e-beam Download PDFInfo
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- TW200530285A TW200530285A TW093133943A TW93133943A TW200530285A TW 200530285 A TW200530285 A TW 200530285A TW 093133943 A TW093133943 A TW 093133943A TW 93133943 A TW93133943 A TW 93133943A TW 200530285 A TW200530285 A TW 200530285A
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- fluoropolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
200530285 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種製造交聯聚合物之方法及如此製造之 聚合物,該方法包含以下步驟··提供一種高氟化之含氟聚 合物,普遍為全氟化之含氟聚合物,其包含側基,側基包 括如式-S02x之基團,其中X為F、a、Br、〇H或_0-M+(其 中M+為單價陽離子),且將該含氟聚合物曝露於電子束輻射 下以至於導致形成交聯。 【先前技術】 美國專利案第4,230,549號據稱揭示藉由輻射接枝 (radiation grafting)技術所產生用於電化學電池之聚合物 膜。 ^ 吳國專利案第6,225,368號及6,387,964號據稱揭示藉由輕 射交聯及接枝所製造之單體接枝交聯聚合物。在某些^ 實施例中,該單體接枝交聯聚合物可為—種含敦聚:物。 在-些具體實施例中,該單體接枝交聯聚合物可隨後經綠 化且用作一種電化學電池中的離子交換膜。 美國專利案第6,255,370號據稱揭示一種固體聚合電解質 燃料電池’其包含一種固體聚合電解質膜,其中該聚合電 解質膜之水含量更接近於負電極。在巾, 控制膜中之交聯程度來控制水含量。 里本參照案聲明,,當將側 鍵引入至主鏈共聚物之膜時,用於 4 W ^之物質或交聯物 質僅與該膜之一表面接觸,藉以 、、升y成於膜中之該側錢 的濃度或於膜中交聯之程度可用五 j用吾人所需之方式控制。 96834.doc 200530285 π(’3 70, c〇l· 5, Ins· 5 7-61)。在該處理之後為磺化作用。(,37〇, col· 6, Ins· 31-48)。 美國專利案弟5,2 6 0,3 5 1號據稱揭示一種藉由在無固化劑 存在下輕射所固化之全氟彈性體。該參照案據稱係關於全 氟化聚合物(例如由四氟乙烯、全氟化烷基全氟化乙烯醚所 製備之聚合物)之固化,及固化部位或交聯單元(其在所得三 聚物中提供至少一種腈、全氟化苯基、溴或碘)。 【發明内容】 簡而言之,本發明係提供一種製造交聯聚合物之方法, 其包含以下步驟··提供一種包含侧基之高氟化的含氟聚合 物’曰遍為全氟化之含氟聚合物,其中該等側基包括如式 -S02x之基團,其中χ為F、α、Br、〇11或_〇^+(其中M+為 單價陽離子);及將該含氟聚合物曝露於電子束輻射下形成 交聯。該側基-般如式_r、s〇2X,其中Rl為包含i七個碳 原子及〇·4個氧原子之分枝或未分枝之純化燒基或全敦 化乙喊基,且最普遍為如式办(CM·。一般而言,根 據=明:方法額外包含以下步驟:將該含氟聚合物形成 有90微米或更小之厚度,更普遍為6。微 予又,且最普遍為30微米或更小之厚度。—浐 而言,該電子束輻射為4 或以上之劑 又 ^或以上之劑量,且最普遍W或以上之劑日量為 般而,,該電子束輻射為低於難㈣之劑 低於10 Mrad之劑量。 S k為 製 在另一態樣中,本發明提供根據本發明之任何方法所 96834.doc 200530285 得之交聯聚合物。 本發明提供一種在先前技術中未描述之交聯一種聚合物 (其包含側基,側基包括如式-S02X之基團,其中X為F、c卜
Br、OH或-〇M勺之方法,一般為交聯-種用作聚合物電解 質膜之膜的方法,其使用電子束輻射。 在本申請案中: 一種聚合物之”當量"(EW)意謂該聚合物中和一當量鹼之 重量; 一種聚合物之"水合產物"(HP)意謂存在於膜中之膜每當 量磺酸基所吸收的水之當量數(莫耳)乘以該聚合物之當^ 數;且 θ 局氟化”意謂其含有氟之量為40重量%或以上,一般為5〇 重置%或以上,且更普遍為6〇重量%或以上。 【實施方式】 本發明提供一種製造交聯聚合物之方法。待交聯聚合物 包含側基,側基包括如S_s〇2X之基團,其中X為F、c卜 OH或OM (其中μ為單價陽離子,一般為驗金屬陽離 子,例如Na+,但最普遍為〇Η)。該等聚合物可用於聚合物 電解質膜(ΡΕΜ)之製造,例如用於諸如燃料電池之電解電 池。 由根據本發明之交聯聚合物所製造的ρΕΜ可用於燃料電 池之膜電極套組(ΜΕΑ)的製造。ΜΕΑ為質子交換膜燃料電 池(例如氫燃料電池)之中心元件。燃料電池為藉由催化組合 一種燃料(例如氫)及一種氧化劑(例如氧)產生可利用電流 96834.doc 200530285 之電化學電池。一般的MEA包含一種聚合物電解質膜 (PEM)(亦稱為一種離子導電膜(ICM)),其係作為固體電解 質。該PEM之一面與陽極層接觸且反面與陰極層接觸。每 個電極層均包括電化學催化劑,其一般包括鉑金屬。氣體 擴散層(GDL)係促進氣體進出陽極與陰極材料的傳輸且傳 導電流。該GDL亦可稱作流動傳輸層(FTL)或擴散體/集電體 (DCC) 〇陽極及陰極層可以催化劑墨水之形式塗布於GDL· 上,且所得經塗布之氣體擴散層夾雜PEM以形成一五層 MEA。或者陽極及陰極層可以催化劑墨水之形式塗布於該 PEM之反面,且所得經催化劑塗布之膜(CCM)夾雜兩層GDL 以形成一五層MEA。該五層MEA之五層按順序為:陽極 GDL、陽極層、PEM、陰極層及陰極GDL。在一般PEM燃 料電池中,質子在陽極係經由氫之氧化而形成且通過該 PEM傳輸至陰極以與氧反應,引起電流在與電極相聯之外 電路中流動。該PEM在反應氣體之間形成一種耐用的、無 孔的、不導電的機械障壁,但H+亦可容易地通過該膜。 待交聯之聚合物係包含一主結構,其可分枝或未分枝, 但一般為未分枝。該主結構係高度氟化且更普遍為全氟 化。該主結構可包含衍生自四氟乙烯(TFE)之單元及衍生自 共聚單體之單元,其一般至少包括一種如式CF2=CY-R之單 元,其中Y—般為F,但亦可為CF3,且其中R為側基,該側 基係包括一種如式-S02X之基團,其中X為F、Cl、Br、OH 或如式-CTM+之基團,其中M+為單價陽離子,一般為鹼金屬 陽離子,例如Na+。X最普遍為OH。在另一具體實施例中, 96834.doc 200530285 側基R可藉由接枝加至該主結構。一般而言,側基r是高度 :化且更普遍為全氟化。时為芳香基或非芳香基。一般而 δ ’ R為-R S02X,纟中Rl為分枝或未分枝包含個碳原 子及0-4個氧原子之全氟化烷基或全氟化鱗基。…一般為 -(CF2)n-其中 η為 1、2、 12、13、14 或 15 咖2-,其中R2為分枝或未分枝包含⑷個碳原子及0_4個 乳原子之全氟化烧基或全氟㈣基。R丨更普遍為_〇_r3_,其 tR3為包含1-15個碳原子之全氟化烷基。Rl之實例包含: 9 、 10 、 11 (-0?20卩(^?3)-)11其中11為1、2、3、4或5 (-0?(0?3)€卩2-)11其中11為1、2、3、4或5«172€17 (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-CF2CF2CF2-)n其中 η為 1、2、3、4或 5 (-0-CF2CF2CF2CF2-)n其中 η為 1、2 或 3 (-0-CF2CF(CF3)-)n其中 η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 -〇-(CF2)n-其中 η為1、2、3、4、5、6、7、8、9、10、11、 96834.doc -10- 200530285 12、13或 14 R 一般為-〇-CF2CF2CF2CF9 v 4、 rF PP ^2^S02X ^ -〇.CF2-CF(CF3).〇- 2 FVS02X且最普遍為_〇 為 F、C1 R A CWf2CF2-S02X,其中 x 為F C】、Br、0H或為·〇-Μ'但最普遍為〇H。 、二:之氣化單體可藉由任何適當之手段來合成,盆包括 吳國專利案第M24,328號所揭示之方法。 待交聯之聚合物可藉由# …人4 何適當之方法來製得,其包括 礼化t合、擠壓聚合、在 d界—减碳中聚合、溶解或 類似的分批進行或連續進行之聚合。 酸性官能侧基一般存在足夠量以產生-種高於15,_, 更普遍高於18,刚’更普遍高於22,_,且最普遍高於 25,_之水合產物(HP)。一般而言’更高之Hp與更高之離 子導電率有關。 酸性官能側基-般存在足夠量以產生低於1200,更普遍 低於1100’且更普遍低於嶋,且更普遍低於_之當量 (EW) 〇 一般而言,該聚合物在交聯之前形成一種膜。可使用任 何形成該膜之適當方法。該聚合物一般由一種懸浮液鑄造 而成。可使用任何適當之鑄造方法,其包括棒塗法、噴塗 法、縫塗法、刷塗法及類似塗法。或者,該膜可用諸如擠 壓法之熔合法由一種純聚合物所形成。該膜可於形成之後 退火,一般在120°c或以上之溫度下,更普遍在13(rc或以 上之溫度下,最普遍在150°c或以上之溫度下。一般而言, 該膜具有90微米或更小之厚度,更普遍為60微米或更小之 96834.doc -11 - 200530285 2二=?:ΓΓ之厚度。一種更_ 一 仏更小的阻力。在用於燃料電池時,其可導致 更冷之運行及輸出更多可利用能量。t薄的膜必須藉由可 在使用中維持膜結構完整之材料來製得。 、交聯步驟包含將氟化聚合物曝露於電子束輻射下以至於 導致,成交聯。—般而言,該電子束輻射為4 或以上 之劑量’更普遍為5 Mr_以上之劑量’且最普遍為請㈣ 或=上之劑;t。—般而言’該電子束輻射為低於心㈣之 劑1 ’更普遍為低於1GMrad之劑量。可使用任何適當之裝 置。持績曝露之方法可用於處理滾筒式良膜。 視情況可加入一種交聯劑。該交聯劑可以任何適當之方 法加入丨包括在I成膜及將該交聯劑施加於膜之前與聚 口物摻合,例如,藉由浸入一種交聯劑之溶液中。一般的 交聯劑可包括多官能化合物,例如多官能烯、乡官能丙又烯 酸脂、多官能基乙烯醚及類似之可非敦化或較低程度氟化 (但其更普遍為高氟化及更普遍為全氟化)之多官能化合物。 在另一具體實施例中,可將該聚合物於交聯之前吸入至 多孔支撐基質内,-般以-種薄膜之形式,該膜具有90微 米或更小之厚度,更普遍為60微米或更小之厚度,且最普 遍為30微米或更小之厚度。可使用任何將該聚合物吸入至 支撐基質内之適當方法,其包括超壓力、真空、芯吸、浸 沒及類似之方法。該摻合物經由交聯而深入至基質内。可 使用任何適當之支撐基質。該支撐基質一般不導電。一般 而言’該支撐基質由-種含說聚合物組成,其更普遍為全 96834.doc 12 200530285 氟化身又的基負包括多孔聚四敦乙烯(PTFE),例如雙軸 拉伸聚四氟乙烯網。 吾人應瞭解根據本發明之方法所製得之聚合物及膜在化 學結構上不同於其它方法製得之聚合物及膜(交聯位置、酸 ί·生吕月b基位置、側基上存在或不存在交聯或交聯上存在或 不存在酸性官能基,及類似方面)。 本發明用於強化聚合物電解質膜之製造,該膜用於諸如 燃料電池之電解電池。 本發明之目標及優勢藉由以下實例來做進一步閣述,但 是在該等實例中所引用之特殊材料及量,以及其它條件及 細節,不應理解為對本發明之不當限制。 實例 除非另外說明,否則所有試劑均獲自或構自紐⑽ Chemical Co·,Milwaukee,WI,或可由已知方法合成。 聚合物 本實例所用之聚合物電解質係藉由將四氟乙烯(tfe)與 CF2=CF-〇-(CF2)4-S〇2F(MV4S)之乳化共聚合作用來製得, 其係藉由美國專利案第6,624,328號所揭示之方法所合成。 在咼度剪切(24,000 rpm)下,利用ULTRA-TURRAX⑧ Model T 25分散劑 S25KV-25F(IKA_Werke GmbH & Co· KG,
Staufen,Germany)將MV4S以APFO乳化劑(全氟辛酸銨, GF^COONH4)於水中預乳化2分鐘。將去離子水裝載至配 有葉輪攪拌器系統之聚合鍋中。將該鍋加熱高達5〇c^,然 後將該預乳化液裝載至無氧聚合鍋中。在5〇t下另外在今 96834.doc -13- 200530285 鍋中裝載入氣體四氟乙烯(TFE)達到6巴之絕對反應壓力。 在50°C及240 rpm攪拌速度下,藉由添加亞硫酸氫鈉及過硫 酉文叙開啟4聚合反應。在反應過程期間,將反應溫度保持 在50°C。藉由於氣相中饋入額外之TFE使反應壓力保持在絕 對6巴。如上所述,製備第二部分的%¥43_預乳化液。在反 應過程期間’將該第二預乳化液部分連續地饋人液相中。 在饋入額外之TFE後,關閉該單體閥及中斷單體的饋入。 連續聚合反應使單體氣相之壓力降低至約2巴。同時,排放 反應益且用氮氣沖洗之。 將如此獲得之聚合物分散液與2_3當量之^^^丑及2當量之 LhCO3(基於磺醢氟濃度之當量)及足量水混合以製備 水口物固體混合物。將該混合物加熱至25〇它並歷時4小 時。在該等條件下大部分該聚合物(>95%)變分散其中。將 該分散液過渡以移除LiF及未分散之聚合物,並接著在⑺升 Mitsubishi Diaion SKT離子交換樹脂上進行離子交換以得 到酸形式之離子聚合物。所得之聚合物電解質為一種具有 如式之酸性側鏈的全氟化聚合物,。所得之 混合物為一種具有18至19%聚合物固體之酸性分散液。將 該分散液與正丙醇混合,並接著在真空中濃縮以得到所需 於水/正丙醇之溶劑混合物(其中約3〇%水/7〇%正丙醇)中= 20%固體分散液。該鹼性分散液係用於鑄造膜。 膜 用於檢測之聚合物膜樣本藉由到刀塗法將含有2〇%固體 之水/丙醇懸浮液(40%水/60%正丙醇)塗覆於玻璃板上來鑄 96834.doc 14 200530285 造,在8〇°C下乾燥10分鐘,在2〇〇°C下退火l〇分鐘。所得膜 旱又大、为為3〇彳政米。並接著從玻璃板上移除該膜,將其 切成條帶’放於聚乙烯袋中及用氮氣淨化。 電子束 將該膜樣本曝露於電子束源下。(Energy Sciences cB3〇〇, gy Sciences, Inc·, Wilmington,Massachusetts)。將劑量 控制為每次通過21^1^(1。樣本經受〇、1或3次通過對應〇、2 或6 Mrad之總電子束劑量。 分析 _ 藉由動態力學分析(DMA)來量測曝露於〇、2或6 Mrad之 電子束劑量下的樣本之Tg。在DMA中,以一種應用擺動力 且量測該樣本之最終位移之測試裝置夾住待測試之聚合物 樣本。該方法於溫度可控之環境下進行。溫度隨測量進行 而勻變上升。由該資料可知,該裝置一般計算、記錄及展 現彈性模數(E’)、損耗模數(E”)及該樣本之阻尼因子(tan δ) 作為溫度之函數。將Tg作為tan δ之最大值。 在本貫例中,在1赫茲頻率(6.28 rad/秒)下使用流變性固 體分析器 RSAII(TA Instruments,New Castle,Delaware, USA)。測試到一種樣本之薄條,測量為約65mm寬,約乃 nim長。在25 C至200 C之溫度範圍下於拉緊狀態時進行測 量。 圖1係為顯示每種劑量下之DMA結果圖表。跡線a代表〇 Mrad(比較性的),跡線B代表2 Mrad(比較性的),跡線c代 表6Mrad(發明物)。圖2係為顯示每種劑量下之Tg圖表,其 96834.doc 15 200530285 中將Tg作為圖1所代表之tan δ資料之最大值。Tg於樣本曝露 在6 Mr ad之電子束輻射下時升高,表示交聯已經發生。 對於熟習此項技術者,未脫離本發明之範疇及原理之各 種修正及變更將變得顯而易見,且應瞭解本發明不過度侷 限於以上所舉之說明性具體實施例。 【圖式簡單說明】 圖1為表示兩種比較聚合物(A及B)及一種根據本發明之 聚合物(C)的動態力學分析(DMA)結果圖。 圖2為表示兩種比較聚合物(0 Mrad及2 Mrad)及一種根據 本發明之聚合物(6 Mr ad)之Tg圖。 96834.doc 16-
Claims (1)
- 200530285 十、申請專利範圍: 1· 一種製造交聯聚合物之方法,其包含以下步驟: (a) 提供一包含側基之高度氟化的含氟聚合物,其中該 等側基包括一如式-S〇2X之基團,其中又為F、α、仏、 〇H或-〇·Μ+,其中M+為單價陽離子;及 (b) 將δ亥含氟聚合物曝露於電子束輻射下以至於導致交 聯的形成。 2·如請求項1之方法,其中該方法在該步驟…之前額外包含 步驟: (c) 將該含氟聚合物形成膜。 3. 如請求項2之方法,其中該膜具有9〇微米或更小之厚度。 4. 如晴求項2或3之方法,其中步驟勾包含將該含氟聚合物吸 入至一多孔支撐基質内。 5. 如請求項4之方法,其中該多孔支撐基質為一多孔聚四氟 乙浠網。 6·如請求項1至3中任一項之方法,其中將該含氟聚合物曝 露於電子束輻射下之該步驟包含將該含氟聚合物曝露於 高於4 Mrad之電子束輻射下。 7.如請求項1至3中任一項之方法,其中該高度氟化之含氟 聚合物為全氟化。 8·如請求項1至3中任一項之方法,其中該等側基係如式 -R -S〇2X ’其中R1為一分枝或未分枝包含5個碳原子及 0-4個氧原子之全氟化烷基或全氟化醚基,且其中X為ρ、 Cl、Br、OH或,其中M+為單價陽離子。 96834.doc 200530285 9. 10. 如請求項1至3中任一項之方法,其中該側基為如式-O-(CF2)4-S02X之基圑,其中X為 F、C卜 Br、OH 或-0-ΊΜ+, 其中M +為單價陽離子。 一種聚合物電解質膜,其包含如請求項1至3中任一項之 方法所製得之交聯聚合物。96834.doc
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US7265162B2 (en) * | 2003-11-13 | 2007-09-04 | 3M Innovative Properties Company | Bromine, chlorine or iodine functional polymer electrolytes crosslinked by e-beam |
US7060756B2 (en) | 2003-11-24 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolyte with aromatic sulfone crosslinking |
US7112614B2 (en) * | 2003-12-08 | 2006-09-26 | 3M Innovative Properties Company | Crosslinked polymer |
US7060738B2 (en) * | 2003-12-11 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolytes crosslinked by ultraviolet radiation |
US7173067B2 (en) * | 2003-12-17 | 2007-02-06 | 3M Innovative Properties Company | Polymer electrolyte membranes crosslinked by direct fluorination |
JP4854284B2 (ja) * | 2005-12-02 | 2012-01-18 | 日東電工株式会社 | 高分子電解質膜の製造方法 |
EP2055758A1 (en) * | 2007-10-31 | 2009-05-06 | S.A. Imperbel N.V. | A bituminous glue. |
CN102066468B (zh) | 2008-04-24 | 2015-01-28 | 3M创新有限公司 | 质子传导材料 |
US20130056415A1 (en) * | 2009-02-27 | 2013-03-07 | Mikhail Kozlov | Negatively charged porous medium for removing protein aggregates |
CN102753253B (zh) | 2009-08-26 | 2016-04-13 | 伊沃夸水技术私人有限公司 | 离子交换膜 |
WO2011149732A2 (en) | 2010-05-25 | 2011-12-01 | 3M Innovative Properties Company | Reinforced electrolyte membrane |
WO2012051608A1 (en) | 2010-10-15 | 2012-04-19 | Siemens Industry, Inc. | Anion exchange membranes and process for making |
EA023933B1 (ru) | 2010-10-15 | 2016-07-29 | ЭВОКУА УОТЕР ТЕКНОЛОДЖИЗ ЭлЭлСи | Способ получения катионообменной мембраны |
EP2652049A4 (en) * | 2010-12-17 | 2016-01-13 | 3M Innovative Properties Co | FLUORINATED OLIGOMERS HAVING FRACTIONS CONTAINING PENDING BROMINE |
US9711816B2 (en) | 2011-08-04 | 2017-07-18 | 3M Innovative Properties Company | Low equivalent weight polymers |
CA2884791C (en) | 2012-10-04 | 2021-09-07 | Evoqua Water Technologies Llc | High-performance anion exchange membranes and methods of making same |
SG11201502697YA (en) | 2012-10-11 | 2015-05-28 | Evoqua Water Technologies Llc | Coated ion exchange membranes |
EP3079808B1 (en) | 2013-12-12 | 2020-05-27 | EMD Millipore Corporation | Method of separating monomeric protein from protein agregates with a porous membrane comprising a co-polymer of benzyl acrylamide and acrylamide |
JP7252521B2 (ja) | 2020-06-29 | 2023-04-05 | トヨタ自動車株式会社 | 車両用制振制御装置及び方法 |
CN116387612B (zh) * | 2023-02-13 | 2023-12-15 | 北京纯锂新能源科技有限公司 | 一种聚合物电解质膜、制备方法及金属锂电池 |
Family Cites Families (109)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3282875A (en) * | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
GB1184321A (en) | 1968-05-15 | 1970-03-11 | Du Pont | Electrochemical Cells |
US3635926A (en) * | 1969-10-27 | 1972-01-18 | Du Pont | Aqueous process for making improved tetrafluoroethylene / fluoroalkyl perfluorovinyl ether copolymers |
US3784399A (en) * | 1971-09-08 | 1974-01-08 | Du Pont | Films of fluorinated polymer containing sulfonyl groups with one surface in the sulfonamide or sulfonamide salt form and a process for preparing such |
US4000356A (en) * | 1972-06-19 | 1976-12-28 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of thermoplastically workable fluoro-olefin polymers |
US3853828A (en) * | 1973-11-21 | 1974-12-10 | Us Army | Process for crosslinking fluorocarbon polymers |
US4169023A (en) * | 1974-02-04 | 1979-09-25 | Tokuyama Soda Kabushiki Kaisha | Electrolytic diaphragms, and method of electrolysis using the same |
US4035565A (en) * | 1975-03-27 | 1977-07-12 | E. I. Du Pont De Nemours And Company | Fluoropolymer containing a small amount of bromine-containing olefin units |
US4073752A (en) | 1975-06-02 | 1978-02-14 | The B. F. Goodrich Company | High normality ion exchange membranes containing entrapped electrostatically bulky multicharged ions and method of production |
GB1518387A (en) | 1975-08-29 | 1978-07-19 | Asahi Glass Co Ltd | Fluorinated cation exchange membrane and use thereof in electrolysis of an alkali metal halide |
US4508603A (en) * | 1976-08-22 | 1985-04-02 | Asahi Glass Company Ltd. | Fluorinated cation exchange membrane and use thereof in electrolysis of an alkali metal halide |
JPS5329291A (en) | 1976-09-01 | 1978-03-18 | Toyo Soda Mfg Co Ltd | Cation exchange membrane and production of the same |
JPS5397988A (en) | 1977-02-08 | 1978-08-26 | Toyo Soda Mfg Co Ltd | Production of cation exchange membrane |
FR2387260A1 (fr) | 1977-04-12 | 1978-11-10 | Rhone Poulenc Ind | Membranes echangeuses d'ions |
JPS53134088A (en) | 1977-04-28 | 1978-11-22 | Asahi Glass Co Ltd | Production of fluorocopolymer having ion exchange groups and its crosslinked article |
US4230549A (en) * | 1977-05-31 | 1980-10-28 | Rai Research Corporation | Separator membranes for electrochemical cells |
JPS53149881A (en) * | 1977-06-03 | 1978-12-27 | Asahi Glass Co Ltd | Strengthened cation exchange resin membrane and production thereof |
JPS6026145B2 (ja) | 1977-10-04 | 1985-06-21 | 旭硝子株式会社 | 改良された含フツ素陽イオン交換膜 |
EP0008894B1 (en) * | 1978-09-05 | 1983-02-23 | Imperial Chemical Industries Plc | Sulphonated polyarylethersulphone copolymers and process for the manufacture thereof |
US4281092A (en) * | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
US4242498A (en) * | 1979-04-09 | 1980-12-30 | Frosch Robert A | Process for the preparation of fluorine containing crosslinked elastomeric polytriazine and product so produced |
JPS5672002A (en) | 1979-11-16 | 1981-06-16 | Asahi Glass Co Ltd | Production of fluorine-containing polymer containing iodine |
US4330654A (en) * | 1980-06-11 | 1982-05-18 | The Dow Chemical Company | Novel polymers having acid functionality |
US4470889A (en) * | 1980-06-11 | 1984-09-11 | The Dow Chemical Company | Electrolytic cell having an improved ion exchange membrane and process for operating |
DE3023455A1 (de) * | 1980-06-24 | 1982-01-14 | Hoechst Ag, 6000 Frankfurt | Verfahren zur fluorierung von polymeren und perfluorierte ionenaustauscher |
US4334082A (en) | 1980-09-26 | 1982-06-08 | E. I. Du Pont De Nemours And Company | Dialkyl perfluoro-ω-fluoroformyl diesters and monomers and polymers therefrom |
US4414159A (en) * | 1980-09-26 | 1983-11-08 | E. I. Du Pont De Nemours & Co. | Vinyl ether monomers and polymers therefrom |
ZA818207B (en) * | 1980-11-27 | 1982-10-27 | Ici Australia Ltd | Permselective membranes |
US4391844A (en) * | 1981-06-26 | 1983-07-05 | Diamond Shamrock Corporation | Method for making linings and coatings from soluble cross-linkable perfluorocarbon copolymers |
US4440917A (en) * | 1981-12-14 | 1984-04-03 | E. I. Du Pont De Nemours & Company | Vinyl ethers monomers and polymers therefrom |
US4454247A (en) * | 1981-12-14 | 1984-06-12 | E. I. Du Pont De Nemours & Company | Ion exchange membranes |
JPS5952690A (ja) * | 1982-05-08 | 1984-03-27 | Mitsubishi Paper Mills Ltd | ノ−カ−ボン記録紙用顕色剤シ−ト |
JPS60250009A (ja) | 1984-05-25 | 1985-12-10 | Asahi Glass Co Ltd | スルホン酸型官能基を有するパ−フルオロカ−ボン重合体の製造方法 |
WO1986000624A1 (fr) * | 1984-07-13 | 1986-01-30 | Societe Atochem | Nouveau polymere fluore ionique, son procede de preparation et les membranes d'electrolyse formees a partir de ce polymere |
JPH0641494B2 (ja) * | 1984-08-31 | 1994-06-01 | 旭化成工業株式会社 | 架橋可能な含フツ素共重合体 |
US4686024A (en) * | 1985-02-01 | 1987-08-11 | The Green Cross Corporation | Novel perfluoro chemicals and polyfluorinated compounds and process for production of the same |
US4743419A (en) * | 1985-03-04 | 1988-05-10 | The Dow Chemical Company | On-line film fluorination method |
US4755567A (en) * | 1985-11-08 | 1988-07-05 | Exfluor Research Corporation | Perfluorination of ethers in the presence of hydrogen fluoride scavengers |
JPS62288617A (ja) | 1986-06-06 | 1987-12-15 | Asahi Glass Co Ltd | スルホン酸型官能基を有するパ−フルオロカ−ボン重合体を製造する方法 |
JPH0637416B2 (ja) | 1987-06-26 | 1994-05-18 | 徳山曹達株式会社 | フルオロジビニルエ−テル化合物及びその製造方法 |
JP2750594B2 (ja) | 1989-02-01 | 1998-05-13 | 旭化成工業株式会社 | 高分子量ポリイミドイルアミジンとその製造法および用途 |
US5693748A (en) * | 1989-02-01 | 1997-12-02 | Asahi Kasei Kogyo Kabushiki Kaisha | High molecular weight polyimidoylamidine and a polytriazine derived therefrom |
US5260351A (en) * | 1989-04-24 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Radiation curing of perfluoroelastomers |
US5986012A (en) * | 1989-04-24 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Fluorination of radiation crosslinked perfluoroelastomers |
IT1235545B (it) | 1989-07-10 | 1992-09-09 | Ausimont Srl | Fluoroelastomeri dotati di migliore processabilita' e procedimento di preparazione |
US6048952A (en) | 1991-07-10 | 2000-04-11 | 3M Innovative Properties Company | Perfluoroalkyl halides and derivatives |
US5852148A (en) * | 1991-07-10 | 1998-12-22 | Minnesota Mining & Manufacturing Company | Perfluoroalkyl halides and derivatives |
US5264093A (en) * | 1992-04-30 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Irradiation of cation exchange membranes to increse current efficiency and reduce power consumption |
JP3101085B2 (ja) | 1992-05-11 | 2000-10-23 | 日東電工株式会社 | 電池用セパレータの製造法 |
US5264508A (en) * | 1992-06-25 | 1993-11-23 | The Dow Chemical Company | Polymers of haloperfluoro and perfluoro ethers |
US5330626A (en) * | 1993-02-16 | 1994-07-19 | E. I. Du Pont De Nemours And Company | Irradiation of polymeric ion exchange membranes to increase water absorption |
US5608022A (en) * | 1993-10-12 | 1997-03-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Perfluorocarbon copolymer containing functional groups and a method for producing it |
US5466930A (en) * | 1994-02-23 | 1995-11-14 | Florida State University | Solid scintillators for detecting radioactive ions in solution |
US5447993A (en) * | 1994-04-19 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Perfluoroelastomer curing |
JP3298321B2 (ja) * | 1994-08-31 | 2002-07-02 | ダイキン工業株式会社 | ビニリデンフルオライド系共重合体水性分散液、ビニリデンフルオライド系シード重合体水性分散液およびそれらの製法 |
USRE37307E1 (en) | 1994-11-14 | 2001-08-07 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
USRE37701E1 (en) | 1994-11-14 | 2002-05-14 | W. L. Gore & Associates, Inc. | Integral composite membrane |
US6254978B1 (en) * | 1994-11-14 | 2001-07-03 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
US5547551A (en) | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
JPH08239494A (ja) | 1995-03-02 | 1996-09-17 | Mitsubishi Chem Corp | ポリオレフィン系陽イオン交換膜の製造法 |
US5795496A (en) * | 1995-11-22 | 1998-08-18 | California Institute Of Technology | Polymer material for electrolytic membranes in fuel cells |
DE19622337C1 (de) * | 1996-06-04 | 1998-03-12 | Dlr Deutsche Forschungsanstalt | Vernetzung von modifizierten Engineering Thermoplasten |
US5798417A (en) * | 1996-10-15 | 1998-08-25 | E. I. Du Pont De Nemours And Company | (Fluorovinyl ether)-grafted high-surface-area polyolefins and preparation thereof |
US5747546A (en) * | 1996-12-31 | 1998-05-05 | The Dow Chemical Company | Ion-exchange polymers having an expanded microstructure |
JP3538843B2 (ja) * | 1997-03-31 | 2004-06-14 | ダイキン工業株式会社 | パーフルオロビニルエーテルスルホン酸誘導体の製法及びそれからなる共重合体 |
CA2266660C (fr) * | 1997-07-25 | 2012-07-17 | Acep Inc. | Composes ioniques perfluorovinyliques, leurs utilisations comme composants de conducteurs ioniques du type polymere, de membranes selectives, de catalyseurs |
US6248469B1 (en) * | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JPH11111310A (ja) * | 1997-09-30 | 1999-04-23 | Aisin Seiki Co Ltd | 燃料電池用の固体高分子電解質膜およびその製造方法 |
DE19854728B4 (de) * | 1997-11-27 | 2006-04-27 | Aisin Seiki K.K., Kariya | Polymerelektrolyt-Brennstoffzelle |
US6462228B1 (en) * | 1997-12-22 | 2002-10-08 | 3M Innovative Properties Company | Process for preparation of fluorinated sulfinates |
JPH11204121A (ja) * | 1998-01-19 | 1999-07-30 | Aisin Seiki Co Ltd | 固体高分子電解質型燃料電池 |
JP4477149B2 (ja) * | 1998-01-30 | 2010-06-09 | ハイドロ−ケベック | 架橋したスルホン化ポリマーおよびその製造法 |
IL137932A0 (en) * | 1998-03-03 | 2001-10-31 | Du Pont | Substantially fluorinated ionomers |
JP4150867B2 (ja) | 1998-05-13 | 2008-09-17 | ダイキン工業株式会社 | 燃料電池に使用するのに適した固体高分子電解質用材料 |
US6090895A (en) * | 1998-05-22 | 2000-07-18 | 3M Innovative Properties Co., | Crosslinked ion conductive membranes |
ATE262559T1 (de) * | 1998-05-29 | 2004-04-15 | Du Pont | Färbbare fluorpolymer-fasern |
IL141879A0 (en) * | 1998-09-15 | 2002-03-10 | Regenesys Tech Ltd | A process for the preparation of a monomer-grafted cross-linked polymer |
JP2000119420A (ja) | 1998-10-19 | 2000-04-25 | Nissan Motor Co Ltd | イオン交換膜およびその製造方法 |
US6385769B1 (en) * | 1999-02-03 | 2002-05-07 | International Business Machines Corporation | Text based object oriented program code with a visual program builder and parser support for predetermined and not predetermined formats |
US6255370B1 (en) * | 1999-04-29 | 2001-07-03 | Railroad-Solutions, Llc | Rail spike retention and tie preservation mixture and method |
US6277512B1 (en) * | 1999-06-18 | 2001-08-21 | 3M Innovative Properties Company | Polymer electrolyte membranes from mixed dispersions |
JP4539896B2 (ja) | 1999-09-17 | 2010-09-08 | 独立行政法人産業技術総合研究所 | プロトン伝導性膜、その製造方法及びそれを用いた燃料電池 |
US6423784B1 (en) * | 1999-12-15 | 2002-07-23 | 3M Innovative Properties Company | Acid functional fluoropolymer membranes and method of manufacture |
JP4352546B2 (ja) * | 1999-12-22 | 2009-10-28 | ユニマテック株式会社 | フルオロエラストマー、その製造方法、架橋性組成物およびその硬化物 |
US6780935B2 (en) * | 2000-02-15 | 2004-08-24 | Atofina Chemicals, Inc. | Fluoropolymer resins containing ionic or ionizable groups and products containing the same |
DE10021104A1 (de) | 2000-05-02 | 2001-11-08 | Univ Stuttgart | Organisch-anorganische Membranen |
DE10024576A1 (de) * | 2000-05-19 | 2001-11-22 | Univ Stuttgart | Kovalent und ionisch vernetzte Polymere und Polymermembranen |
US6982303B2 (en) * | 2000-05-19 | 2006-01-03 | Jochen Kerres | Covalently cross-linked polymers and polymer membranes via sulfinate alkylation |
CA2312194A1 (fr) * | 2000-06-13 | 2001-12-13 | Mario Boucher | Elastomeres reticulables fluores bromosulfones a faible tg a base de fluorure de vinylidene et ne contenant ni du tetrafluoroethylene ni de groupement siloxane |
IT1318593B1 (it) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati. |
IT1318669B1 (it) | 2000-08-08 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati solfonici. |
JP4166574B2 (ja) | 2001-02-01 | 2008-10-15 | 旭化成株式会社 | スルホンアミド基を有するパーフルオロビニルエーテルモノマーの共重合体とその製造方法 |
ITMI20010383A1 (it) | 2001-02-26 | 2002-08-26 | Ausimont Spa | Membrane idrofiliche porose |
DE10114243B4 (de) * | 2001-03-22 | 2004-07-29 | Heraeus Kulzer Gmbh & Co. Kg | Verfahren zur Herstellung einer Prothese sowie Prothesenwerkstoff und dessen Verwendung |
US6503378B1 (en) * | 2001-04-23 | 2003-01-07 | Motorola, Inc. | Polymer electrolyte membrane and method of fabrication |
US7045571B2 (en) * | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
TW589759B (en) * | 2001-10-15 | 2004-06-01 | Du Pont | Fuel cell membranes |
US6727386B2 (en) * | 2001-10-25 | 2004-04-27 | 3M Innovative Properties Company | Aromatic imide and aromatic methylidynetrissulfonyl compounds and method of making |
US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
US7348088B2 (en) | 2002-12-19 | 2008-03-25 | 3M Innovative Properties Company | Polymer electrolyte membrane |
US7071271B2 (en) * | 2003-10-30 | 2006-07-04 | 3M Innovative Properties Company | Aqueous emulsion polymerization of functionalized fluoromonomers |
US7074841B2 (en) * | 2003-11-13 | 2006-07-11 | Yandrasits Michael A | Polymer electrolyte membranes crosslinked by nitrile trimerization |
US7259208B2 (en) * | 2003-11-13 | 2007-08-21 | 3M Innovative Properties Company | Reinforced polymer electrolyte membrane |
US7179847B2 (en) | 2003-11-13 | 2007-02-20 | 3M Innovative Properties Company | Polymer electrolytes crosslinked by e-beam |
US7265162B2 (en) * | 2003-11-13 | 2007-09-04 | 3M Innovative Properties Company | Bromine, chlorine or iodine functional polymer electrolytes crosslinked by e-beam |
US7060756B2 (en) * | 2003-11-24 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolyte with aromatic sulfone crosslinking |
US7112614B2 (en) | 2003-12-08 | 2006-09-26 | 3M Innovative Properties Company | Crosslinked polymer |
US7060738B2 (en) * | 2003-12-11 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolytes crosslinked by ultraviolet radiation |
US7173067B2 (en) * | 2003-12-17 | 2007-02-06 | 3M Innovative Properties Company | Polymer electrolyte membranes crosslinked by direct fluorination |
-
2003
- 2003-11-13 US US10/712,361 patent/US7179847B2/en not_active Expired - Fee Related
-
2004
- 2004-10-13 EP EP04795026A patent/EP1689808A1/en not_active Withdrawn
- 2004-10-13 JP JP2006539505A patent/JP5319067B2/ja not_active Expired - Fee Related
- 2004-10-13 CN CN2004800336074A patent/CN1882640B/zh not_active Expired - Fee Related
- 2004-10-13 CA CA002545172A patent/CA2545172A1/en not_active Abandoned
- 2004-10-13 WO PCT/US2004/033807 patent/WO2005052036A1/en active Application Filing
- 2004-10-13 KR KR1020067009296A patent/KR20060117946A/ko not_active Application Discontinuation
- 2004-11-05 TW TW093133943A patent/TW200530285A/zh unknown
-
2007
- 2007-01-29 US US11/668,270 patent/US7514481B2/en not_active Expired - Fee Related
-
2012
- 2012-05-24 JP JP2012118371A patent/JP2012180529A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CN1882640A (zh) | 2006-12-20 |
CA2545172A1 (en) | 2005-06-09 |
WO2005052036A1 (en) | 2005-06-09 |
CN1882640B (zh) | 2010-06-09 |
EP1689808A1 (en) | 2006-08-16 |
JP2007514012A (ja) | 2007-05-31 |
US7179847B2 (en) | 2007-02-20 |
US20050107488A1 (en) | 2005-05-19 |
US20070142563A1 (en) | 2007-06-21 |
KR20060117946A (ko) | 2006-11-17 |
JP2012180529A (ja) | 2012-09-20 |
JP5319067B2 (ja) | 2013-10-16 |
US7514481B2 (en) | 2009-04-07 |
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