CN114945627A - 由含有高度氟化的芳族基团的聚合物通过亲核取代制备的阳离子交换和阴离子交换聚合物和(共混)膜 - Google Patents
由含有高度氟化的芳族基团的聚合物通过亲核取代制备的阳离子交换和阴离子交换聚合物和(共混)膜 Download PDFInfo
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
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Abstract
本发明涉及由含有高度氟化的芳族基团的聚合物借助亲核取代制备的新型阴离子交换聚合物和(共混)膜,以及借助亲核芳族取代制备它们的方法及其在膜过程、特别是在电化学膜过程如燃料电池、电解和氧化还原液流电池中的应用领域。
Description
本发明涉及由含有高度氟化的芳族基团的聚合物通过亲核取代制备的新型阴离子交换聚合物和(共混)膜,以及通过亲核芳族取代制备它们的方法及其在膜过程,特别是在电化学膜过程如燃料电池、电解和氧化还原液流电池中的应用领域。
从文献中已知全氟亚芳基可以进行亲核取代反应。在最近的出版物中已经表明,含有全氟芳基化的结构单元的聚合物可以在聚合物类似物反应中被化学改性;C.R.Becer,K.Babiuch,D.Pilz,S.Hornig,T.Heinze,M.Gottschaldt and U.S.Schubert,Macromolecules 2009,42,2387-2394;C.R.Becer,K.Kokado,C.Weber,A.Can,Y.Chujo,U.S.Schubert,Journal of Polymer Science:Part A:Polymer Chemistry,2010,48,1278–1286。作者还通过硫醇基亲核试剂与聚(五氟苯乙烯)之间的“点击”反应证明了全氟化结构单元在C-F键上的活化作用。对含F芳族化合物进行亲核芳族取代反应的另一个实例是十氟联苯和4,4'-硫代二苯硫酚(其中S-桥先前已经用H2O2氧化成砜桥)的聚合物与NaSH的反应,在该反应中聚合物的八氟联苯结构单元的所有F已经被SH基团替代。然后在下一个反应步骤中,用H2O2将SH基团氧化成SO3H基团,其中获得超磺化芳族聚合物;ShogoTakamuku,Andreas Wohlfarth,Angelika Manhart,Petra Patric Jannasch,Polym.Chem.,2015,6,1267-1274。侧链中的芳族F被活化用于亲核取代的聚合物的亲核取代的实例是Guiver,Kim等人的出版物,其中4-氟磺酰基侧基的F被强N-碱四甲基胍亲核取代(Dae Sik Kim,Andrea Labouriau,Michael D.Guiver,Yu Seung Kim,Chem.Mater.2011,23,3795-3797)。从文献(L.I.Goryunov,J.Grobe,V.D.Shteingarts,B.Krebs,A.Lindemann,E.-U.Wüthwein,Chr.Mueck-Lichtenfeld,Chem.Eur.J.2000,6,24,4612-4622;R.M.Bellabarba,M.Nieuwenhuyzen and G.C.Saunders,Organometallics2003,22,1802-1810;B.Hoge and P.Panne,Chem.Eur.J.2006,12,9025–9035)中已知全氟化亚芳基与亲核有机膦化合物形成亲核C-P键的几个实例,包括其中聚合物聚(五氟苯乙烯)上的4-F被三(三甲基甲硅烷基)亚膦酸酯亲核取代,并且接着聚合的膦酸甲硅烷基酯被水水解成游离的膦酸的研究(V.Atanasov,J.Kerres,Macromolecules 2011,44,6416–6423)。另一项研究涉及借助NaSH由SH基团取代聚(五氟苯乙烯)的4-F,随后用过氧化氢将SH基团氧化成磺酸基团SO3H(V.Atanasov,M.Bürger,S.Lyonnard,G Gebel,J.Kerres,Solid State Ionics,2013,252,75-83)。
在本发明的上下文中,令人惊讶地发现,全氟化亚芳基(低分子量化合物、低聚物和聚合物)的活化芳族C-F键的F的亲核取代可以获得阴离子交换聚合物,其特征在于高化学稳定性,因此可以有利地用于电化学应用,例如碱性或酸性燃料电池、碱性或酸性电解池或氧化还原液流电池。
因此,本发明的目的的特征在于具有权利要求中所述特征的实施方案。
附图示出了:
图1示出了根据本发明的全氟化芳基与强有机仲N-碱的反应。
图2示出了根据本发明可使用的全氟化低分子量芳烃的非限制性实例。
图3示出了根据本发明可使用的全氟化高分子量芳烃(聚合物)的非限制性实例。
图4示出了与全氟化芳烃进行SN Ar反应的强N-碱的非限制性实例。
图5示出了基于聚(五氟苯乙烯)的具有胍鎓基团的阴离子交换聚合物的制备;a)用四甲基胍部分取代PPFSt的4-F,随后烷基化;b)用4-氟苯硫酚取代PPFSt的4-F,随后氧化,随后与四甲基胍反应,随后烷基化。
图6示出了碱金属氨化物与全氟化芳烃的反应(SN Ar),随后用烷基化剂(卤代烷烃、苄基卤、硫酸二烷基酯等)季铵化所形成的叔氨基团。
图7示出了与全氟化芳烃进行SN Ar反应的氨基锂的非限制性实例。
图8示出了聚(五氟苯乙烯)与2,2,6,6-四甲基哌啶-1-氨基锂的反应(a)以及4-氟苯硫酚取代并且随后氧化的聚(五氟苯乙烯)与2,2,6,6-四甲基哌啶-1-氨基锂的反应(b),随后将这些聚合物烷基化。
图9示出了全氟芳烃与仲或叔N-碱或仲N-氨化物和第二亲核试剂反应的反应方案。
图10示出了PPFSt与己硫醇的反应,随后氧化,随后与四甲基胍反应,随后用硫酸二甲酯烷基化。
图11示出了聚(五氟苯乙烯)与四甲基胍的反应,随后与1-(2-二甲基氨基乙基)-5-巯基四唑反应,随后用甲基碘季铵化(a),或者与4-氟苯硫酚反应,随后用H2O2氧化,随后用亚膦酸三(三甲基甲硅烷基)酯膦化(b)。
图12示出了作为“一锅反应”的聚(五氟苯乙烯)与2,2,6,6-四甲基哌啶-1-氨基锂和Na2S的反应,随后用碘己烷烷基化。
图13示出了根据本发明的聚合物和叔N-碱性基团与卤代甲基化聚合物进行季铵化和共价交联的反应。
图14示出了根据本发明的聚合物和N-碱性基团与卤代甲基化聚合物和磺化聚合物形成共价和离子交联位点的共混。
图15示出了PPFSt-TMG(顶部)和PPFSt(底部)的19F-NMR谱。
图16示出了M-PPFST-TMG(顶部)和PPFST-TMG(底部)的1H-NMR谱。
图17示出了用四甲基胍修饰PPFSt及其甲基化。
图18示出了M-PPFSt-TBF-OX-TMG的合成。
图19示出了PPFSt(顶部)和PPFSt-TBF(底部)的19F-NMR谱。
图20示出了PPFSt-TBF-OX(顶部)和PPFSt-TBF(底部)的1H-NMR谱。
图21示出了PPFSt-TBF-OX-TMG(顶部)和M-PPFSt-TBF-OX-TMG(底部)的1H-NMR谱。
图22示出了制备的混合膜的照片。
图23示出了共混膜和Nafion 212膜的CE(a)、VE(b)和EE(c)。
图24示出了混合膜和Nafion 212膜的自放电时间。
图25示出了共混膜和Nafion 212膜的长期循环测试。
图26示出了PPFSt-MTZ-TMG(顶部)和PPFSt-MTZ(底部)的1H-NMR光谱。
图27示出了用于生产交联膜的反应方案(a)和交联的PPFSt-MTZ膜的照片(b)。
图28示出了用巯基己基和四甲基胍单元对PPFSt进行后修饰。
图29示出了PPFSt-TH的19F-NMR谱。
图30示出了PPFSt-TH的1H-NMR谱。
图31示出了PPFSt-TH-TMG的1H-NMR谱。
图32示出了M-PPFSt-TH-TMG的1H-NMR谱。
图33示出了制备的M-PPFSt-TH-TMG膜的照片。
图34示出了膜的PA掺杂结果。
图35示出了聚合物的热稳定性。
图36示出了聚合物的FT-IR光谱。
图37示出了m-PBI(a)和M-PPFSt-TH-TMG(b)的燃料电池性能。
图38示出了M-PPFSt-TH-TMG膜随时间的特性曲线。
图39示出了在燃料电池中在恒定电流密度下M-PPFSt-TH-TMG的短期稳定性。
本发明的第一实施方案涉及全氟化芳基与强有机仲或叔N-碱的反应,其中全氟化芳基可以是小分子量化合物、低聚物或聚合物。图1中示出了本发明的第一实施方案。当仲胺与氟化芳烃反应时,1个或任意个F与胺亲核交换,其中在SN Ar反应期间分离的H+使另外的胺分子质子化。在第二步中,用烷基化剂将所得叔氨基基团季铵化。烷基化剂可以具有低分子量,然后选自卤代烷烃(CnH2n+1Hal,n=1-20,苄基卤,PhCH2Hal,Hal=I、Br、Cl)或硫酸二烷基酯R2SO4(R=烷基CnH2n+1,n=1-12,苄基)或二卤代烷烃(CnH2nHal2,Ph(CH2Hal)2,n=1-20,Hal=I、Br、Cl)。烷基化剂也可以具有高分子量,然后是具有卤代甲基CH2Hal,Hal=Cl、Br、I的任意选择的聚合物。如果使用二卤代烷烃或具有卤代甲基的聚合物进行季铵化,则根据本发明的聚合物通过季铵化同时交联。如果叔胺(低或高分子量)用于与氟化芳烃的SN Ar反应,则在仅一步中形成季铵盐作为阴离子交换基团。在分子中具有至少两个叔氨基的胺(低分子量或高分子量)的情况下,由于SN Ar反应而形成交联的阴离子交换膜。
图2示出了合适的低分子量全氟化亚芳基的非限制性实例,并且图3示出了聚合的全氟化亚芳基的非限制性实例。图4示出了合适的仲或叔N-碱的非限制性实例。
图5示出了基于聚(五氟苯乙烯)的具有胍鎓-阴离子交换基团的阴离子交换聚合物的制备。在步骤a)中,示出了聚(五氟苯乙烯)与四甲基胍的反应,随后进行胍改性的聚合物的烷基化的反应。在步骤b)中,首先使聚(五氟苯乙烯)与4-氟苯硫酚反应,随后用过氧化氢将S-桥氧化成SO2桥,随后与四甲基胍反应,最后用硫酸二甲酯进行烷基化。
本发明的第二实施方案涉及强N-碱,其中NH键被N-碱金属键替代。这些碱金属-氮化合物是碱金属氨化物。碱金属可以是Li、Na、K、Rb或Cs,优选Li。碱金属氨化物与全氟化芳烃(低分子量、低聚物或聚合物)反应进行亲核碱金属-F-交换(SN Ar),如图6所示。在第二步中,然后用烷基化剂将所形成的叔碱性N-化合物烷基化。烷基化剂的选择原则上是任意的,优选卤代烷烃、苄基卤和硫酸二烷基酯作为烷基化剂。
原则上,任何碱金属氨化物可以与根据本发明的全氟芳烃反应。在本发明中优选氨基锂。在图7中示出了氨基锂的非限制性选择。
图8示出了本发明的第二实施方案,其使用了聚(五氟苯乙烯)与2,2,6,6-四甲基哌啶-1-氨基锂的反应实例(步骤a),以及用4-氟苯硫酚取代、随后用2,2,6,6-四甲基哌啶-1-氨基锂氧化聚(五氟苯乙烯)的反应实例(步骤b),其中被哌啶取代的聚(五氟苯乙烯)在最后的步骤中被烷基化以得到阴离子交换聚合物。这些聚合物的特别优点在于1,2,2,6,6-五甲基哌啶鎓阳离子的甲基对季铵化的N具有良好的空间屏蔽,这使得这些聚合物在碱性介质(如果抗衡离子是OH-)中具有非常好的稳定性,使得它们成为碱性阴离子交换膜电解(AEME)或碱性阴离子交换膜燃料电池(AEMFC)中的优异且长期稳定的阴离子导体。
本发明的第三实施方案涉及用其它亲核试剂取代含有叔氨基或季铵基团的低分子量、低聚或高聚全氟芳烃中的另外的F。原则上,取代F的一种或多种亲核试剂的类型不受限制,但与全氟芳烃反应进行F的亲核交换的所有亲核试剂都是合适的。图9示出了当含有叔氨基或季铵盐的低分子量、低聚或聚合化合物与第二亲核试剂反应时,在本发明的第三实施方案中获得的低分子量、低聚和聚合物质的示意图。
然而,优选以下亲核试剂(在此不限制亲核试剂的选择):
-R-SH、[R-S]-[C+](R=任何烷基或芳基残基,C+=1价阳离子,例如金属阳离子、铵离子、吡啶鎓离子、咪唑鎓离子、胍鎓离子等)。亲核试剂还可以含有多于1个的SH或SC基团。R-SH的非限制性实例是烷基硫醇CnH2n+1SH(n=2-20),RSC的非限制性实例是具有碱金属阳离子(碱金属=Li、Na、K、Rb、Cs)或任何铵离子作为抗衡离子的烷基或芳基或苄基硫醇盐。含有多个SH或SC基团的化合物的非限制性实例是(邻-、间-或对-)苯二硫酚、萘二硫醇、二苄基二硫醇、烷二硫醇HS-CnH2n-SH(n=2-20)或其与金属或铵抗衡离子的盐,对抗衡(阳)离子的性质没有限制。
-P(OSi(CH3)3)3(三(三甲基甲硅烷基)亚膦酸酯)
-AL2S和ALSH(AL=碱金属抗衡离子)
用于获得根据本发明的低分子量、低聚和聚合化合物的第三实施方案可以按以下顺序获得:
(1)低分子量、低聚或聚合的全氟芳烃首先与第二亲核试剂反应。如果第二亲核试剂是RSH或RSC,则所得的硫醚桥可以被氧化成砜桥。如果亲核试剂是AL2S或ALSH,则所得的SH基团可以被氧化成SO3H基团。其随后与仲或叔N-碱或仲N-氨化物反应,随后在仲N-碱或仲N-氨化物的情况下进行烷基化。在图10中该反应顺序通过聚(五氟苯乙烯)与己硫醇反应,随后将硫桥氧化成砜桥,随后与四甲基胍反应,随后用硫酸二甲酯季铵化的非限制性实例示出。这种聚合物的特殊优点在于己基砜基团用作该聚合物的一体化“增塑剂”官能团,这显著降低了阴离子交换聚合物的脆性,这对于这种阴离子交换聚合物在膜燃料电池中的应用是非常有利的。烷基链越长,烷基砜基团的增塑剂作用越强。
(2)低分子量、低聚或聚合的全氟芳烃首先与仲或叔碱性N-化合物或仲N-氨化物反应,任选地随后N-烷基化成季N-盐,随后与第二亲核试剂反应。该反应顺序通过三个非限制性实例来说明:(a)在图11中,部分氟化的芳族聚砜与四甲基胍反应,随后与三(三甲基甲硅烷基)亚膦酸酯进行膦化,和(b)聚(五氟苯乙烯)与四甲基胍反应,随后与1-(2-二甲基氨基乙基)-5-巯基四唑反应,随后用甲基碘季铵化,和(c)通过使聚(五氟苯乙烯)与四甲基胍反应,随后使聚(五氟苯乙烯)的剩余4-F与4-氟苯硫酚反应,随后用H2O2将聚合物的硫桥氧化成砜桥,随后膦化苯砜侧链的4-F。使用ACD软件计算膦酸基团的pKA值表明,由于砜桥的强-I效应,分子中该点处的膦酸基团是强酸基团,这使得该聚合物由于膦酸基团的固有导电性而成为用于高温燃料电池(温度范围100-250℃)的有前景的质子导体。
(3)低分子量、低聚或聚合的全氟芳烃同时与仲或叔N-碱或仲N-氨化物反应。该反应在图12中示出为“一锅反应”,使用聚(五氟苯乙烯)和部分氟化的芳族聚砜与2,2,6,6-四甲基哌啶-1-氨基锂和Na2S的反应的非限制性实例。
还令人惊讶地发现,在所有上述三个实施方案中,根据本发明的新型聚合物可以容易地与其它合适的聚合物进行转化以形成共混膜。
以下列出了根据本发明的共混膜的非限制性选择:
-将第一和第二实施方案的聚合物(具有季N-碱性基团的聚合的全氟化芳烃(参见图1和图6))与碱性聚合物以任意混合比率共混,碱性聚合物的选择不受限制,但优选聚苯并咪唑,因为其高的机械和热稳定性以及化学稳定性。获得了阴离子交换共混物,其中碱性共混物组分用于机械、热和化学稳定共混物。
-将第一和第二实施方案的聚合物(具有叔N-碱性基团的聚合的全氟化芳烃(参见图1和图6))与阳离子交换聚合物以任意混合比率共混,其中阳离子交换聚合物的选择不受限制,并且阳离子交换聚合物可以具有磺酸根基团(-SO3 -G+)、膦酸根基团(PO3 2-(G+)2)或羧酸根基团(COO-G+),其中G+=抗衡离子=H+、金属阳离子、铵、胍鎓、吡啶鎓、咪唑鎓……,其中磺酸根和膦酸根基团优选作为阳离子交换基团。
-将第一和第二实施方案的聚合物(具有叔N-碱性基团的聚合的全氟化芳烃(参见图1和图6))与含有CH2Hal基团(Hal=Cl、Br、I)的聚合物以任意混合比率共混。第一和第二实施方案的聚合物的叔N-碱性基团与卤代甲基化聚合物之间的季铵化反应导致这些共混膜的共价交联(图13)。
-将第一和第二实施方案的聚合物(具有季N-碱性基团的聚合的全氟化芳烃(参见图1和图6))与磺化、膦化或羧化阳离子交换聚合物以及与卤代甲基化聚合物以任意混合比率共混。卤代甲基与叔氨基之间的季铵化反应导致共价交联,同时导致阴离子交换基团的形成,其又与阳离子交换聚合物共混物组分的阳离子交换基团形成离子交联点(图14)。
-将第三实施方案的聚合物(具有季N-碱性官能团和其它亲核引入的官能团的全氟芳烃(参见图9))与碱性聚合物共混,可能的碱性聚合物的选择不受限制,但优选聚苯并咪唑。在这些共混物中,碱性聚合物用于化学、机械和热稳定共混物组分。
-用阳离子交换聚合物(磺化、膦化、羧化聚合物)和/或碱性聚合物和/或用含有卤代甲基-CH2Hal(Hal=Cl、Br、I)的聚合物共混制备第三实施方案的聚合物(具有叔N-碱性官能团和其它亲核引入的官能团的全氟芳烃(参见图9))。如果将卤代甲基化聚合物用作共混物组分,则卤代甲基与叔N-碱性基团的反应导致季铵化以及因此共混膜的共价交联(参见上文)。
通过以下实施例更详细地解释本发明,但不限于此。
1.聚(五氟苯乙烯)与四甲基胍反应,随后用硫酸二甲酯将取代的聚合物烷基化
1.1 M-PPFSt-TMG的合成方法
1.1.1四甲基胍改性的PPFSt(PPFSt-TMG)
在配备有冷凝器、氩气入口和出口的三颈圆底烧瓶中,在130℃下,将PPFSt(1g,5.15mmol)分散在DMAc(20mL)中2小时。冷却至室温后,向反应溶液中加入四甲基胍(2.97g,25.8mmol)。将反应溶液在130℃下搅拌24小时。然后通过将聚合物溶液滴入水中沉淀聚合物。将获得的聚合物用大量水洗涤数次并在烘箱中在60℃下干燥24小时。通过19F-NMR确认100%的取代度,其中显示反应后有2个峰(邻位和间位)(图15)。
1.1.2 PPFSt-TMG的季铵化(M-PPFSt-TMG)
PPFSt-TMG的季铵化通过使用硫酸二甲酯的甲基化进行。在配备有隔膜、冷凝器、氩气入口和出口的圆底烧瓶中,在室温下在氩气气氛下,将PPFSt-TMG(1g,3.45mmol)溶解在20mL的DMAc中3小时。完全溶解后,通过注射器缓慢加入硫酸二甲酯(1mL,10.4mmol)。将反应混合物在90℃下搅拌16小时。冷却至室温后,将聚合物溶液在丙酮中沉淀。将获得的聚合物用丙酮洗涤两次,并在60℃下烘箱干燥24小时。通过1H-NMR确认100%DOS,显示甲基(N-CH3(a),2.5ppm至2.9ppm)的完全峰位移,并且通过甲基化鉴定新峰可以指定(b)N-CH3。
1.1.3合成的聚合物的溶解度测试
表1:合成的聚合物在各种溶剂中的溶解度
DMSO | DMAc | THF | 丙酮 | 甲醇 | 水 | 氯仿 | |
PPFSt | + | + | ++ | ++ | - | - | - |
PPFSt-TMG | - | ++ | ++ | ++ | ++ | - | |
M-PPFSt-TMG | ++ | ++ | - | - | ++ | ++ | - |
++可溶;+部分可溶;-不溶
1.2 M-PPFSt-TBF-OX-TMG的合成
PPFSt-TBF的合成:在配备有氩气入口、出口和冷凝器的100mL三颈烧瓶中,将PPFSt(1g,5.2mmol)溶解在40mL的甲基乙基酮(MEK)中。在PPFSt完全溶解后,将三乙胺(7.82g,15当量,相对于PPFSt)和4-氟苯硫酚(1.65mL,相对于PPFSt的3当量)加入聚合物溶液中。然后将反应混合物在75℃保持24小时。通过在甲醇中沉淀获得合成的聚合物。将聚合物用甲醇洗涤数次,并在烘箱中在60℃下干燥18小时;通过19F NMR测定几乎完全取代。
PPFSt-TBF-OX的合成:在配备有冷凝器的烧瓶中,将PPFSt-TBF(3g,10mmol)分散在60mL的三氟乙酸中。然后将10mL的过氧化氢(30%水溶液,100mmol)滴加到反应烧瓶中。将反应溶液在30℃下搅拌72小时,然后在110℃下搅拌1小时。冷却至室温后,将反应溶液倒入水中以获得聚合物。将获得的聚合物用水洗涤数次,并在烘箱中在60℃下干燥18小时;芳族区域的化学位移表明从硫化物成功氧化成砜。
PPFSt-TBF-OX-TMG的合成:在配备有氩气入口、出口和冷凝器的三颈烧瓶中,将PPFSt-TBF-OX(3.34g,10mmol)溶解在DMAc中。完全溶解后,将TMG(10mL,80mmol)加入聚合物溶液中,并在130℃下搅拌20小时。然后通过在水中沉淀分离聚合物。将获得的聚合物用水洗涤数次,并在烘箱中在60℃下干燥24小时;由1H-NMR确认部分胍化:由于四甲基胍基团的N-CH3,芳香区中有3个峰并且最强峰在2.6ppm处。
M-PPFSt-TBF-OX-TMG的合成:用硫酸二甲酯(DMS)在DMAc中进行PPFSt-TBF-OX-TMG的甲基化。将PPFSt-TBF-OX-TMG溶解在DMAc中。在完全溶解后,将DMS加入聚合物反应溶液中并将温度升高至90℃。在该温度下机械搅拌反应20小时。然后通过在丙酮中沉淀获得聚合物。用丙酮洗涤聚合物,并在烘箱中在60℃下干燥24小时;由于甲基化,四甲基胍峰的化学位移从2.6至3.7ppm并且新峰在3.4ppm处。
2.由反应产物4.1和F6PBI制备共混膜
2.1共混膜制剂
将M-PPFSt-TMG聚合物溶解在DMSO中作为5wt%聚合物溶液。在80℃下将F6PBI溶解在DMSO中作为5wt%溶液。将两种聚合物溶液以表中所述的特定比率混合在一起。将聚合物共混物溶液流延到玻璃板上并置于对流烘箱中在80℃下持续24小时以蒸发溶剂。通过浸入去离子水中将所得混合膜从玻璃板上剥离。将混合膜储存在拉链袋中以供后续使用。以相同方式制备M-PPFSt-TBF-OX-TMG与F6PBI的混合膜。
表2:M-PPFST-TMG与F6PBI的共混膜制剂
膜 | M-PPFSt-TMG/F<sub>6</sub>PBI(w/w) | 观测结果 |
M-PPFSt-TMG 80-20 | 80/20 | 过多溶胀 |
M-PPFSt-TMG 70-30 | 70/30 | 可伸展的 |
M-PPFSt-TMG 60-40 | 60/40 | 可伸展的 |
M-PPFSt-TMG 50-50 | 50/50 | 可伸展的 |
表3:M-PPFSt-OX-TBF-TMG与F6PBI的共混膜制备
2.2共混膜特性
表4:共混膜特性
-由于过度溶胀而省略
2.3钒氧化还原液流电池性能
2.3.1库仑效率(CE)、电压效率(VE)和能量效率(EE)
共混膜和Nafion 212膜的库仑效率(CE)(a)、电压效率(VE)(b)和能量效率(EE)(c)示于图23中。
2.3.2自放电测试
混合膜和Nafion 212膜的自放电测试可以在图24中找到。
2.3.3长期循环测试
共混膜和Nafion 212膜的长期循环测试的结果可以在图25中找到。
3.聚(五氟苯乙烯)与1-(2-二甲基氨基乙基)-5-巯基四唑的反应,随后与四甲基胍的反应
3.1聚(五氟苯乙烯)与1-(2-二甲基氨基乙基)-5-巯基四唑的反应
根据文献(如果公开,取代度:30%)将1-(2-二甲基氨基乙基)-5-巯基四唑接枝到聚(五氟苯乙烯)上。将四甲基胍引入到部分接枝的PPFSt-MTZ上。将1g的部分取代的PPFSt-MTZ溶解在配备有冷凝器、氩气入口和氩气出口的20ml的DMAc中。在90℃下完全溶解1小时后,将四甲基胍加入聚合物溶液中,并在130℃下保持24小时。聚合物溶液在水中沉淀。将获得的聚合物(PPFSt-MTZ-TMG)用水洗涤数次并在烘箱中在60℃下干燥24小时。
甲基化:在90℃下用硫酸二甲酯进行甲基化。然而,在该温度下观察到沉淀。
4.部分改性的PPFSt和1,6-己二硫醇的交联膜
4.1交联膜(XL-M-PPFSt-MTZ)的制备
在玻璃小瓶中,将0.3g的M-PPFSt-MTZ(根据文献制备,如果公布,41%DOS)溶解在10ml的DMSO中。在完全溶解后,将三乙胺(0.27g)和1,6-己二硫醇(0.19g)加入聚合物溶液中。均化后,将混合溶液倒入皮氏培养皿中。将其置于60℃的密闭烘箱(或具有皮氏培养皿盖)中以确保1天的反应时间,随后在120℃下真空8小时以去除残余化学品。如图(b)所示,获得机械稳定的交联膜。XL-M-PPFSt-MTZ的IEC为0.28mmol/g并且在1M H2SO4中测量的电导率为1.77±0.18mS/cm。甚至IEC和电导率与混合膜相比更低。使用二硫醇化合物的交联是获得机械稳定的膜的可能的制造路线,因为均聚-M-PPFSt-MTZ聚合物膜是机械不稳定的。
5.使聚(五氟苯乙烯)与1-己硫醇反应,随后与四甲基胍反应
5.1聚(五氟苯乙烯)与1-己硫醇的反应
在配备有回流冷凝器以及氩气入口和出口的500mL三颈圆底烧瓶中,在氩气流下,将PPFSt(10g,51.5mmol)溶解在THF(200mL)中,在90℃下保持1小时。在该温度下加入1-己硫醇(3.8mL,27.1mmol)和DBU(8mL,52.5mmol)并搅拌15小时。冷却至室温后,将粘性溶液缓慢倒入异丙醇中,形成微黄色沉淀。将所得聚合物用异丙醇洗涤数次并在对流烘箱中在60℃下干燥24小时。
产量:9.8g
19F NMR(400MHz,CDCl3,ppm):-134(s,2.8F),-143(s,4.9F),-154(s,1F).-161(s,2.1F)(图29)
1H NMR(400MHz,CDCl3,ppm):0.90(t,1.8H),1.27–1.54(m,ca.5H),1.99(s,2H),2.41(s,0.8H),2.88(s,1.2H))(图30)
5.2 4.5.1的产物(PPFSt-TH)与四甲基胍之间的反应
在具有冷凝器和氩气流的500mL三颈烧瓶中,将PPFSt-TH(8g,31.6mmol)溶解在DMAc(200mL)中,在130℃下保持2小时。冷却至室温后,将TMG(19.8ml,158mmol)滴加到聚合物溶液中,并在130℃下反应24小时。冷却后,将褐色反应溶液在去离子水中逐滴沉淀,得到聚合物。通过过滤分离聚合物并用去离子水洗涤数次。将最终聚合物在对流烘箱中在60℃下干燥24小时。
产量:9.04g
图31显示1H NMR(400MHz,THF-d8,ppm)。
5.3 4.5.2的产物(PPFSt-TH-TMG)与硫酸二甲酯(DMS)之间的甲基化反应
将PPFSt-TH-TMG(7g,24mmol)溶解在DMAc(150mL)中。完全溶解后,用注射器将DMS(20.5mL,72.1mmol)加入反应溶液中。在剧烈搅拌下将反应在90℃保持12小时。然后将反应溶液滴加到乙醚中,用乙醚洗涤两次,用去离子水洗涤一次。将所得聚合物在真空烘箱中在60℃下在1mbar下干燥24小时。
产量:7.5g
图32显示1H NMR(400MHz,THF-d8,ppm)。
5.4膜制造
将m-PBI以5.2重量%溶解在DMAc中。将m-PBI溶液流延到玻璃板上,并将溶剂在对流烘箱中在80℃下蒸发24小时。然后通过在水浴中浸泡将膜从玻璃板上剥离。将所得膜在90℃下干燥12小时并在使用前储存在拉链袋中。通过溶解在DMAc中制备M-PPFSt-TH-TMG的5wt%聚合物溶液。将溶液倾倒在Teflon片材上并置于60℃的对流烘箱中24小时以蒸发溶剂。通过浸入水中将膜从玻璃载体上去除。将所得膜在60℃下用10wt%氯化钠水溶液调节3天,然后在60℃下浸入DI水中1天,用DI水广泛洗涤,然后储存在拉链锁袋中以备后用(图33)。
5.5膜的PA掺杂
通过测定在不同浓度的PA水溶液中掺杂前后的重量来进行PA掺杂。在PA掺杂之前,将膜在6℃下干燥24小时,随后测量它们的干质量。将干燥的膜样品在室温下浸入PA溶液中24小时。从PA溶液中取出膜样品并用纸巾吸干以去除表面上的磷酸。然后称量掺杂的膜(图34)。
掺杂水平(%)=[(W后-W干)/W干]×100
W后:PA掺杂后的膜重量,W干:PA掺杂前的膜重量酸掺杂水平(ADL)PA/官能团=[(W后-W干)×0.85/97.99]/[(W干/膜的IEC)×1000]
W后:PA掺杂后的膜重量
W干:膜干重
IEC:离子交换容量
由NMR光谱中的取代和未取代的芳环之间的积分比计算取代度。膜的理论离子交换容量(CEC)由IEC与取代度(从NMR获得)的函数计算。
5.6热稳定性(TGA)
为了研究合成的聚合物的热稳定性,使用与FT-IR偶联的NETZSCH TGA,型号STA499C进行热重分析(TGA)。在混合的氧气和氮气气氛(氧气:56mL/min,氮气:24mL/min)下以每分钟20℃的加热速率升高温度(图35)。
5.7 FT-IR光谱
对于聚合物的结构分析,使用Nicolet iS5 FTIR光谱仪在室温下以64次扫描和衰减全反射(ATR)模式记录作为从4000至400cm-1的波数范围的函数的FTIR光谱(图36)。
5.8燃料电池测试
为了制造膜电极组件(MEA),将磷酸掺杂的膜夹置在两个电极之间。气体扩散电极(GDE)由Freudenberg提供并且含有1.5mg Pt/cm2,并且在阳极侧和阴极侧使用相同的电极,有效面积为23.04cm2。将MEA安装在可商购的单电池中,其已经用3Nm的扭矩密封。使用商业测试站(Scribner 850e,Scribner Associates Inc.)进行燃料电池测试。研究了在环境压力下在阳极侧和阴极侧上的非加湿气体的燃料电池性能。阳极处的H2流速和阴极处的空气流速分别为0.25L/min和1.25L/min(图37、图38和图39)。
Claims (15)
5.含有季铵化N-碱性官能团和其它官能团的部分或全氟化的低分子量或高分子量芳族化合物,其特征在于,它们能通过与含有仲和/或叔N-碱性基团的化合物和其它能够导致亲核取代的有机低分子量或高分子量化合物的亲核取代反应以下方式获得:
1.全氟芳烃与仲N-氨化物和第二亲核试剂的反应,随后季铵化:
2.全氟芳烃与仲N-碱性化合物和第二亲核试剂的反应,随后季铵化:
3.全氟芳烃与叔N-碱性化合物和第二亲核试剂的一步反应(一锅反应):
x:任意,1至m
n:任意,1至n
m:任意,1至m
x≥(n+m)
AL=Li,Na,K,Rb,Cs
NU:能够F-NU-交换的所有亲核试剂
R:任意烷基和/或芳基残基
Ry:任意烷基和/或芳基残基
AN-:烷基化剂的抗衡离子(例如,Hal-(Hal=F,Cl,Br,I)或SO4 2-)。
6.根据权利要求1至5中任一项所述的化合物,其特征在于,所述有机化合物是分子量为1kDa至10,000kDa的高分子量化合物。
10.由根据前述权利要求1至9中一项或多项所述的低聚物或聚合物制成的任选离子和/或共价交联的共混膜,其特征在于,将单独溶解在溶剂中的所述低聚物和/或聚合物与以下聚合物的溶液以任何混合比率混合:
-磺化和/或膦化和/或羧化的聚合物,
-碱性聚合物,其中所述碱性聚合物可以在侧链或主链中具有伯、仲或叔N-碱性基团,
-卤代甲基化聚合物,其中所述卤代甲基基团可以用作共价交联基团。
11.根据权利要求10所述的共混膜的制备方法,其特征在于,将所述共混物组分单独溶解在偶极-非质子溶剂和/或醚溶剂和/或质子(醇)溶剂中,然后将所述溶液以任何混合比率彼此混合,之后将所述混合溶液刮刀涂布、喷涂或印刷在基材上,在30至180℃的升高的温度下在真空烘箱或对流烘箱中蒸发所述溶剂(混合物),然后将形成的膜从基材上分离,并且任选地在如下的各种步骤中进行后处理以将其活化,其中所述后处理的顺序是任意的并且可以包含以下列出的所有后处理液体或仅其一部分:
-在0至100℃的温度下用去离子水,
-在0至130℃的温度下用任意浓度的无机酸溶液,
-在0至100℃的温度下用任意浓度的碱金属碱液,
-用纯形式或作为在水中的溶液、在醇和/或醚和/或偶极-质子溶剂中的溶液的任何液体叔N-碱,
-在0至100℃的温度下在任意浓度的水性或醇性金属盐溶液中。
12.根据权利要求10和11的共混膜的制备方法,其特征在于,作为所述共混物组分的溶剂,优选偶极-非质子溶剂,例如二甲亚砜、二甲砜、二苯砜、环丁砜、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲酰胺和碳酸二甲酯。
13.根据权利要求10至12的共混膜的制备方法,其特征在于,优选任意浓度的硫酸、磷酸或盐酸作为无机酸用于所述共混膜的所述后处理/掺杂。
14.根据权利要求10所述的任选地离子和/或共价交联的共混膜,其特征在于,以下聚合物类型用作权利要求1至9的聚合物的共混物组分:
-作为磺化、膦化或羧化聚合物,根据权利要求7的聚合物,基于非氟化、部分氟化或全氟化的乙烯基烃聚合物,非氟化、部分氟化或全氟化的聚苯乙烯或芳基主链聚合物,包括聚苯、聚苯醚、聚醚砜、聚醚酮、聚砜、聚酮、聚乙烯基咔唑、聚苯氧化膦,
-作为碱性聚合物,聚咪唑或聚苯并咪唑类型的聚合物,其中所述咪唑基团或苯并咪唑基团可以存在于所述聚苯并咪唑或聚苯并咪唑的主链或侧链中,
-作为卤代甲基化聚合物,氯代或溴代甲基化聚合物,包括溴代甲基化聚苯醚、氯代甲基化聚乙烯基苄基氯或者氯代或溴代甲基化聚苯。
15.根据权利要求1至14所述的聚合物和共混膜作为电极离聚物的用途,以及在根据权利要求10至14的共混膜中作为离聚物膜在电化学过程中的用途,所述电化学过程例如燃料电池、电解、氧化还原液流电池、扩散渗析、电渗析,还包括作为具有阳离子层和阴离子层的双极膜的用途。
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Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (1)
Title |
---|
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