CN1263787C - 酸碱聚合物共混物和它们在膜制品中的用途 - Google Patents
酸碱聚合物共混物和它们在膜制品中的用途 Download PDFInfo
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- CN1263787C CN1263787C CNB99805173XA CN99805173A CN1263787C CN 1263787 C CN1263787 C CN 1263787C CN B99805173X A CNB99805173X A CN B99805173XA CN 99805173 A CN99805173 A CN 99805173A CN 1263787 C CN1263787 C CN 1263787C
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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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
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- Conductive Materials (AREA)
Abstract
本发明涉及由聚合物磺酸和含有伯、仲或叔胺基的聚合物形成的聚合物共混物和聚合物共混物膜,它们是通过将聚合物磺酸的盐与含有伯、仲或叔胺基的聚合物进行混合而制得。本发明进一步涉及聚合物共混物在膜燃料电池、聚合物电解质膜燃料电池(PEM燃料电池)或直接甲醇燃料电池(DMFC)中,在隔膜电解法中,在含水或非含水的电渗析中,在扩散透析中,在链烯烃从链烯烃/链烷烃混合物中的全抽提分离中(此时该膜是SO3Ag形式,其中Ag+与链烯烃形成可逆的配合物(→促进传输)),在水从水/有机物混合物中全蒸发分离中或在气体分离中的用途。
Description
技术领域
本发明涉及由聚合物磺酸和含有伯、仲或叔胺基的聚合物形成的聚合物共混物和聚合物共混物膜,它们是通过将聚合物磺酸的盐与含有伯、仲或叔胺基的聚合物进行混合而制得。本发明进一步涉及聚合物共混物在膜燃料电池、聚合物电解质膜燃料电池(PEM燃料电池)或直接甲醇燃料电池(DMFC)中,在隔膜电解法中,在含水或非含水的电渗析中,在扩散透析中,在链烯烃从链烯烃/链烷烃混合物中的全抽提(perstractive)分离中(此时该膜是SO3Ag形式,其中Ag+与链烯烃形成可逆的配合物(→促进传输),在水从水/有机物混合物中全蒸发分离中或在气体分离中的用途。
背景技术
PEM燃料电池的关键成本组成是它的质子传导性膜。已经可以商购的全氟化离聚物Nafion®(Grot,W.G.:全氟化离子交换聚合物和它们在研究和工业中的用途,Macromolecular Symposia,82,161-172(1994))满足化学稳定性的要求,该稳定性是这些膜用于PEM燃料电池中所必须要求的(Ledjeff,K.;Heinzel,A.;Mahlendorf,F.;Peinecke,V.:Die reversible Membran-Brennstoffzelle,Dechema-Monographien Band 128,VCH Verlagsgesellschaft,103-118(1993))。然而,它具有各种缺点使得需要寻找代用材料:它很昂贵(DM1400.-/m2),并涉及非常复杂的生产过程包括高毒性的中间体(参见Grot,W.G.)。Nafion®的环境相容性必须严格评估:作为全氟化聚合物,它很难降解。Nafion®的回用性成为问题。
当在直接甲醇燃料电池中使用Nafion®时,人们发现它显示出很高的甲醇渗透性,尤其当使用纯甲醇时(Surampudi,S.,Narayanan,S.R.;Vamos,E.;Frank,H.;Halpert,G.;LaConti,A.;Kosek,J.;Surya Prakash,G.K.;Olah,G.A.:直接氧化式甲醇燃料电池的进展,J.Power Sources,47,377-385(1994)),它通过混合电位的形成大大降低了DMFC的能量效率。
部分氟化的离聚物目前正在研究中。在这一点上可提及G.G.Scherer的研究工作(Scherer,G.G.:燃料电池的聚合物膜,Ber.Bunsenges.Phys.Chem.94,1008-1014(1990));(Scherer,G.G.;Buchi,F.N.;Gupta,B.;Rouilly,M.;Hauser,P.C.;Chapiro,A.:辐射接枝和磺化(FEP-g-聚苯乙烯)-PEM燃料电池的全氟化膜的替代品?第27届能量转换工程国际协会会议的会议记录IECEC-92(Proceedingsof the 27th Intersociety Energy Conversion Engineering ConferenceIECEC-92),San Diego,USA,Aug.3-7,3.419-3.424(1992));(Gupta,B.;Buchi,F.N.;Scherer,G.G.:有机固体质子导体固态离子学的材料研究方面(Materials Research Aspects of Organic Solid Proton ConductorsSolid State Ionics)61,213-218(1993)),通过使用γ辐射可在全氟化聚合物箔中形成自由基并将苯乙烯接枝到所形成的自由基上。然后,将所形成的全氟聚合物-聚苯乙烯IPN(互穿聚合物网络)的聚苯乙烯链加以磺化。当用于PEM燃料电池中时这些聚合物膜显示出良好的使用性能。然而,所使用的合成方法似乎不适合于这一类型膜的大批量生产。加拿大公司Ballard已经开发了从磺化聚(α,β,β-三氟苯乙烯)制得的部分氟化质子传导膜(Wei,J.;Stone,C.;Steck,A.E.:三氟苯乙烯和取代三氟苯乙烯共聚物组合物和从其形成的离子交换膜,WO95/08581,Ballard Power Systems)。这种膜的缺点是它的高价格,因为单体α,β,β-三氟苯乙烯的复杂生产方法(Livingston,D.I.;Kamath,P.M.;Corley,R.S.:聚α,β,β-三氟苯乙烯,聚合物科学杂志,20,485-490(1956))以及因为聚(α,β,β-三氟苯乙烯)被磺化的能力差。
在文献中,发现了与亚芳基主链聚合物用于PEM燃料电池有关的一些参考资料。最重要的文章在下面提及:
聚苯并咪唑-磷酸
工程热塑性塑料聚苯并咪唑的膜用磷酸浸泡(Wainright,J.S.;Wang,J.-T.;Savinell,R.F.;Litt,M.;Moaddel,H.;Rogers,C.:酸掺杂的聚苯并咪唑,新聚合物电解质,电化学协会,春季会议,旧金山,5月22-27日,详细文摘,94-1卷,982-983页(1994))-磷酸用作质子导体。磷酸分子通过氢桥和通过咪唑结构部分的质子化形成盐H2PO4 -+HN聚合物来保持在膜中。然而,这些膜的危险是,在操作过程中磷酸逐渐被燃料电池中所形成的水从聚苯并咪唑基质中洗出来,因为在这些聚合物共混物中磷酸分子与咪唑结构部分的的比例是大约3∶1。
磺化聚醚砜
Ledjeff的文章(Nolte,R.;Ledjeff,K.;Bauer,M.;Mulhaupt,R.:部分磺化聚(亚芳基醚砜)-现代能量转换技术中的多功能质子传导膜材料,膜科学杂志83,211-220(1993))建议使用交联的磺化聚醚砜离聚物(通过聚醚砜的亲电子磺化制得)在PEM燃料电池中作为质子导体。然而,在该篇文章中没有给出所述膜的电流电压特性曲线,这使得评价这一离聚物对PEM燃料电池的适合性变得困难。
磺化PEEK
在专利文献中能够见到与磺化聚醚酮(PEEK)的膜用于PEM燃料电池中相关的论述(Helmer-Metzmann,F.;Ledjeff,K.;Nolte,R.等人:Polymerelektrolyt-Membran und Verfahren zu ihrer Herstellung,EP 0574 791A2)。这些聚合物据说在PEM燃料电池中显示出良好的性能和化学稳定性。然而,这些膜显示出高溶胀值,尤其在高的质子传导率和因此高的离子交换容量(为PEM燃料电池所需要)下,这将损害它们的机械性能和因此缩短它们在燃料电池中的使用寿命。另外,尤其当PEEK不均匀磺化时,将会遇到的一个危险是聚合物部分再结晶(未改性PEEK是部分结晶性的),导致脆性。
磺化聚亚苯基类
从有机溶剂可溶的磺化的、化学和热稳定的聚亚苯基类制得的膜用作代用材料来代替Nafion®用于PEM燃料电池中已经由Matejcek,L.;Nolte,R.;Heinzel,A.;Ledjeff,K.;Zerfass,T.;Mulhaupt,R.;Frey,H.建议:Die Membranbrennstoffzelle:Untersuchungen an anMembran/Elektrodeneinheite,Jahrestagung 1995 der FachgruppeAngewandte Elektrochemie der GDCH,Duisburg,27.-29.Sept.1995,Abstract Poster Nr.20(1995)。然而,这些膜在PEM燃料电池中的研究迄今为止还没有见到。
磺化聚苯硫醚
Miyatake,K.;Iyotani,H.;Yamamoto,K.;Tsuchida,E.:经由聚(锍阳离子)合成作为热稳定的质子传导聚合物的聚(苯硫醚磺酸)(Synthesis of Poly(phenylene sulfide sulfonic acid)via Poly(sulfonium cation)as a Thermostable Proton-Conducting Polymer),Macromolecules 1996,29,6969-6971(1996),报道了经由聚锍阳离子中间体制备化学和热稳定性磺化聚苯硫醚的方法。该制备方法的缺点是它比较复杂和因此花费大。
基于乙烯基聚合物的酸碱聚合物共混物常常在有关文献中提到(Bazuin,C.G.:离聚物(共混物的相容化),在下面书籍中:聚合物材料大全(主编J.C.Salomone),5(H-L)卷,CRC出版社(Boca Raton,New York,London,Tokyo)3454-3460(1996)),例如,含有聚甲基丙烯酸酯作为酸性组分和聚乙烯基吡啶盐作为碱性组分的酸碱共混物(Zhang,X.;Eisenberg,A.:在聚苯乙烯/聚(丙烯酸乙酯)共混物中利用离子相互作用的溶混性增强的NMR和动态力学研究,J.Polym.Sci.:部分B:聚合物物理,28,1841-1857(1990))。这些酸碱共混物已经就酸性和碱性共混物组分之间的相容性进行了考察。这些酸碱聚合物共混物的实际应用迄今为止还没有报道。
如上所述,为电-膜过程、尤其为膜燃料电池提供化学稳定的离聚物膜是重要的研究领域。该离聚物膜应该选自亚芳基主链聚合物膜,因为这些聚合物显示出仅次于全氟化聚合物的最高化学稳定性。基于PEEK的酸碱共混物描述在Keyes,J.;Cui,W.;Wagner,N.;Schnumberger,W.;Eigenberger,G.:A.7 Entwicklung von Membranenfur die Elektrolyse und fur Membranbrennstoffzellen,Vortrag,“Jahreskolloquium 1997 des Sonderforschungsbereichs 270-Energietrager Wasserstoff”,Sept.29,1997,Berichtsband p.169-193(1997);ISBN:3-00-001796-8;Cui,W.;Keyes,J.;Eigenberger,G.:离子离子交换聚合物共混物膜的发展和特征,Poster,Euromembrane′97,“膜科学和技术的进展”,University of Twente,1997年6月23-27日,摘要p.181(1997).聚合物共混物是通过将聚(醚-醚-酮磺酸)(PEEKSO3H)和聚(醚-砜-邻-砜二胺)(PSU-NH2)在偶极非质子溶剂中聚合,随后蒸发溶剂来制备。该出版物描述了这些特殊聚合物共混物就离子导电、溶胀、选择通透性和热阻而言的特征,以及这些膜当中的一种单独在电渗析中的使用。对于所述的方法(聚合物磺酸与聚合物胺的混合),只有那些酸碱共混物能够制备,它们具有非常弱碱性的胺组分如聚(醚-砜-邻-砜二胺)。较强的聚合物碱在与聚合物磺酸接触后立即形成不溶性的聚合电解质配合物。
原则上,当干燥时,例如当它们以间歇条件用于燃料电池中时,所有磺化的芳基聚合物显示出高脆性。磺化芳基聚合物离聚物的脆性的降低对于它们进一步的发展以长时间用于PEM燃料电池中是首要的。
发明内容
在本发明的第一个实施方案中,以上目的是通过制备离子交换膜的方法实现的,其特征在于使具有以下通式的聚合物磺酸盐的溶液:
聚合物-SO3X,
其中X=单价金属阳离子,NH4 +,NH3R+,NH2R2 +,NHR3 +,NR4 +,吡啶鎓R=任何烷基和/或芳基,与含有伯、仲或叔氮的聚合物在偶极非质子溶剂中反应,所获得的聚合物磺酸盐/碱共混物在贮存之后在20-100℃下在热的稀无机酸中进行后处理。
至少本发明的聚合物共混物膜中的聚合物磺酸或磺酸盐由亚芳基主链聚合物(例如聚醚砜、聚醚酮、聚苯醚、聚苯基砜和聚苯硫醚)组成,据此获得了具有高度机械、化学和热稳定性的聚合物共混物,这使得本发明的膜成为目前主要用于PEM燃料电池和DMFCS中的Nafion®型全氟化离聚物膜的合理替代品。
本发明中与含氮聚合物反应的携带磺酸或磺酸盐基团的聚合物选自以结构式(R1)或(R2)的芳族核结构作为重复单元的聚合物,
其中
R3是氢,三氟甲基或CnH2n+1,n=1-10,
R4是氢,CnH2n+1,n=1-10,或苯基,和
x=1,2或3
它们经过桥接基团R5、R6、R7或R8相连,其中
R5是-O-,
R6是-SO2-,
R7是>C=O,和
R8是-S-。
优选,本发明中与含氮聚合物反应的携带磺酸或磺酸盐基团的聚合物选自:
聚醚醚酮:[R5-R2-R5-R2-R7-R2]n;R2中:x=1,R4=H;
聚醚砜:[R1-R5-R2-R6-R2-R5]n;R2中:x=1,R4=H;
聚醚砜:[R2-R6-R2-R5]n;R2中:x=1,R4=H;
聚苯基砜:[(R2)2-R5-R2-R6-R2]n;R2中:x=2,R4=H;
聚醚醚砜:[R5-R2-R5-R2-R6]n-[R5-R2-R6-R2]m;R2中:x=1,R4=H,n/m=0.18;
聚苯硫醚:[R2-R8]n;R2中:x=1,R4=H;
聚苯醚:[R2-R5]n;R4=CH3。
已经发现,通过将聚合物磺酸,例如,以下通式I的聚(醚-砜-磺酸),或聚(醚-酮-磺酸盐)
即每个重复单元具有两个磺酸基的聚(醚砜磺酸)PSU Udel®;它可根据Kerres,J.;Cui,W.;Reichle,S.:金属化途径获得的新磺化工程聚合物.I.金属化-亚磺化-氧化途径获得的磺化聚(醚砜)(PSU Udel®),聚合物科学杂志,Part A:聚合物化学34,2421-2438(1996)来获得,或以下通式II的聚(醚-醚-酮-磺酸)
即每重复单元有一个磺酸基团的聚(醚-酮-磺酸);根据Helmer-Metzmann等人的方法制得,
与通式III的聚(醚砜-邻-砜-二胺)
即每个重复单元有2个伯氨基的聚(醚砜-邻-砜-二胺),根据Guiver,M.D.;Robertson,G.P.;Foley,S.:聚砜的化学改性II:在芳族链高分子上引入伯胺基的有效方法28,7612-7621(1995)来制得,进行混合,得到聚合物共混物,它令人惊奇地以下述性能为特征:
(1)与各自的纯聚合物磺酸相比,脆性高度降低;
(2)由于共混物组分的聚合物链之间的相互作用,水溶性的聚合物磺酸在与聚合物碱性氮化合物混合后令人惊奇地丧失了它们的水溶性;
(3)从水溶性的聚合物磺酸盐或磺酸制得的此类酸碱共混物显示出高达2.7meq SO3H/g聚合物的令人惊奇的高离子交换容量(这一容量的磺化聚合物一般易溶于水),这导致极低的电阻(实施例11:Ra,H+=0.05Ω.cm2,Rsp,H+=5.88Ω.cm)。
(4)令人惊奇地,该酸碱共混物显示出与Nafion®相比减少了60-250个系数的甲醇渗透性,这很可能使它们能够理想地用于DMFC;
(5)令人惊奇地,该酸碱共混物在H2-PEFC和DMFC中显示出优异的性能;
如上所述,当与聚合物磺酸混合物时,非常弱的聚合物碱如聚(醚砜-邻-砜-二胺)在偶极非质子溶剂如N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、N,N-二甲基甲酰胺(DMF)、环丁砜或二甲亚砜(DMSO)中的溶液中没有发生聚合电解质络合物的沉淀。然而,当使用较强的聚合物碱时,在该碱在偶极非质子溶剂中的溶液与聚合物磺酸在偶极非质子溶剂中的溶液进行混合时形成聚合物盐而发生聚合电解质络合物的沉淀。与聚合物磺酸形成聚合电解质络合物的聚合物碱的例子包括聚(4-乙烯基吡啶)。聚电解质形成反应如下:
令人惊奇地,现已发现,将聚合物磺酸盐(例如:聚(醚-醚-酮磺酸锂)或聚(醚-砜磺酸锂))的溶液与含有伯、仲或叔氮的聚合物(例如:聚(醚-砜-邻-砜-二胺),聚(4-乙烯基吡啶),聚(乙烯亚胺),聚(苯胺))的溶液混合能够生产单相溶液;在蒸发掉溶剂之后,它们形成清澈、透明及机械和热稳定的聚合物共混物膜。当这样的聚合物共混物膜在制备之后用稀无机酸在20-100℃的温度下进行后处理时,即使那些由于聚电解质沉淀,不能通过将聚合物磺酸与聚合物胺混合直接获得的那些酸碱共混物也可以得到。由该方法,例如能够获得聚(4-乙烯基吡啶)与聚(醚-砜-磺酸)的相容性共混物,由于聚电解质沉淀,它们不能直接从聚(4-乙烯基吡啶)和聚(醚-砜-磺酸)获得。
在本发明的一个优选实施方案中,将聚合物磺酸溶于偶极非质子溶剂中,在此之后添加对应于聚合物中的SO3H基团含量为等摩尔量的低分子量伯、仲或叔胺,然后将含有伯、仲或叔碱性氮基团的另一种聚合物溶解于所获得的聚合物溶液中。
由上述迂回路线,几乎任何聚合物磺酸/任何聚合物磺酸盐能够与几乎任何聚合(伯/仲/叔)胺混合,至少得到相容性聚合物共混物。各种酸碱共混物的性能能够通过适当选择反应对象来确定。
酸碱共混物的这些有益性能归因于共混物组分的聚合物链之间的特定相互作用。(参见Bazuin,C.G.;Zhang,X.;Eisenberg,A.:聚苯乙烯/聚(丙烯酸乙酯)共混物中离子相互作用导致的混溶性增强的NMR和动态力学研究(NMR and Dynamic Mechanical Studies of MiscibilityEnhancement via Ionic Interactions in Polystyrene/poly(ethyl Acrylate)Blends),J.Polym.Sci.:Part B:聚合物物理,28,1841-1857(1990)):
·氢桥
·酸碱相互作用
·离子-偶极子相互作用
这些特定的相互作用导致聚合物磺酸/聚合物磺酸盐与聚合碱性氮化合物的相容性和部分导致分子混溶性。
除了早已提及的应用即直接甲醇和H2膜燃料电池外,该酸碱共混物能够理想地用于其它膜过程:
·聚合物电解质膜电解
·含水或不含水的电渗析
·扩散透析
·经过气体分离法、全蒸发法或全抽提法(perstraction)从链烯烃/链烷混合物中分离链烯烃(这里膜处于SO3Ag形式,其中Ag+可逆地与链烯烃配合并因此有选择地携带它通过该膜(→促进传输)(van Zyl,A.J.;Linkov,V.M.;Bobrova,L.P.;Timofeev,S.V:用于分离石油化工混合物的全氟磺酸盐离聚物膜,J.Mat.Sci.Lett.,15,1459(1996)),以及
·透析、超滤、纳米过滤或反渗析
实施例
参考实施例
从磺化PEEK和胺化PSU制备酸碱共混物(类似于J.Kerres等人,见前文)
根据Helmer-Metzmann等人的方法制备聚(醚-醚-酮磺酸)Victrex®。该聚合物显示出1.66meq SO3H/g的离子交换容量。胺化聚砜Udel®通过已知的方法制备(类似于Guiver等人,见上文)。这一聚合物具有两个氨基/每个重复单元。聚(醚醚酮磺酸)和胺化聚砜按照不同的混合比例进行混合(表1),所获得的混合物溶解于N-甲基吡咯烷酮中得到15重量%的溶液。在它的制备之后,将溶液过滤和脱气。随后将聚合物溶液铺展在载体(例如,玻璃板)上形成薄膜,然后在有循环空气的烘箱中于125℃蒸发溶剂或在真空干燥箱中蒸发溶剂。在蒸发溶剂之后,将有聚合物膜的玻璃板放置在有去离子水的水槽中。在1/2小时后,该膜已经与玻璃板分离开。该膜首先在1N HCl中后处理48小时,然后在去离子水中处理48小时,每次在60℃下进行。随后,表征它的性能。表征结果列在表1中。
表1:磺化PEEK和胺化PSU的共混物膜的组成和性能
实施例号 | 组成 | 溶胀率[%] | IEC[meq/g] | 选择渗透性[%] | Ra[Ω·cm2] | Rsp[Ω·cm] |
1 | 4.25g PEEK(SO3H)0.50.75g PSU(NH2)2 | <40 | 1.34 | 0.109 | 18.2 | |
2 | 4.5g PEEK(SO3H)0.50.5g PSU(NH2)2 | <50 | 1.58 | 0.101 | 34.8 | |
3 | 4g PEEK(SO3H)0.51g PSU(NH2)2 | 23.81 | 1.4 | 94.44 | 0.25 | 46.41 |
4 | 4.25g PEEK(SO3H)0.50.75g PSU(NH2)2 | 29.5 | 1.63 | 97.1 | 24.8 | |
5 | 4g PEEK(SO3H)0.51g PSU(NH2)2 | 28.4 | 1.54 | 95 | 23.6 | |
6 | 3.5g PEEK(SO3H)0.51.5g PSU(NH2)2 | 21.4 | 1.42 | 98.2 | 50.3 | |
7 | 2.4g PEEK(SO3H)0.51.6g PSU(NH2)2 | 16.7 | 1.13 | 99.5 | 105.5 |
实施例1-11:
从磺化PSU和胺化PSU合成酸碱共混物
根据Kerres等人的方法制备聚(醚砜磺酸)Udel®。聚合物具有2.6meq SO3H/g(水溶性的)的离子交换容量,或1.7meq SO3H/g(水不溶性)的离子交换容量。胺化聚砜Udel®根据Guiver等人的方法制备。这一聚合物具有两个氨基/每个重复单元。聚(醚砜磺酸)和胺化聚砜按照不同的混合比例进行混合(表2),所获得的混合物溶解于N-甲基吡咯烷酮中得到15重量%的溶液。在它的制备之后,将溶液过滤和脱气。随后将聚合物溶液铺展在载体(例如,玻璃板)上形成薄膜,然后在有循环空气的烘箱中于125℃蒸发溶剂或在真空干燥箱中蒸发溶剂。在蒸发溶剂之后,将有聚合物膜的玻璃板放置在有去离子水的水槽中。在1/2小时后,该膜已经与玻璃板分离开。该膜首先在1N HCl中后处理48小时,然后在去离子水中处理48小时,每次在60℃下进行。随后,表征它的性能。表征结果列在表2中。
表2:磺化和胺化PSU的共混物膜的组成和性能
实施例号 | 组成 | 溶胀率[%] | IEC[meq/g] | 选择渗透性[%] | Ra[Ω·cm2] | Rsp[Ω·cm] |
1 | 3g PSUSO3H1g PSU(NH2)2 | 26.83 | 1.44 | 97.25 | 0.261 | 70.41 |
2* | 2.8g PSUSO3Li0.7g PSU(NH2)2 | 20.22 | 1.27 | 99.18 | 0.68 | 65.34 |
3 | 4.2g PSUSO3H1.8g PSU(NH2)2 | 17.04 | 1.09 | 99.74 | 0.966 | 148.61 |
4 | 5.4g PSUSO3H0.6g PSU(NH2)2 | 40.54 | 1.59 | 92.14 | 0.139 | 13.93 |
5 | 4.8g PSUSO3H1.2g PSU(NH2)2 | 30.6 | 1.54 | 97.05 | 0.28 | 29.09 |
6 | 3g PSUSO3H3g PSU(NH2)2 | 11.70 | 0.42 | 99.58 | - | - |
7 | 3.6g PSUSO3H2.4g PSU(NH2)2 | 13.86 | 0.97 | 99.24 | 3.21 | 401.1 |
8 | 4.2g PSU(SO3H)1.61.8g PSU(NH2)2 | 42.07 | 2.1 | - | 0.094 | 14.46 |
9 | 4.8g PSU(SO3H)1.61.2g PSU(NH2)2 | 63.27 | 2.31 | - | 0.057 | 7.92 |
10 | 5.28g PSU(SO3H)1.60.72g PSU(NH2)2 | 120.77 | 2.57 | - | 0.0475 | 5.52 |
11 | 5.58g PSU(SO3H)1.60.42g PSU(NH2)2 | 306.25 | 2.66 | - | 0.05 | 5.88 |
*该膜是通过将PSU磺酸锂和胺化PSU混合制得
实施例12:
从磺化PSU和聚(4-乙烯基吡啶)制备酸碱共混物
将5.7g属于SO3Li形式的磺化PSU(IEC=1.6meq/g)溶于24g的N-甲基吡咯烷酮(NMP)中。随后,称取0.3g的聚(4-乙烯基吡啶)(MW=200,000g/mol)并溶于该溶液中。在它的制备之后,将溶液过滤和脱气。随后将聚合物溶液铺展在载体(例如,玻璃板)上形成薄膜,然后在有循环空气的烘箱中于125℃蒸发溶剂或在真空干燥箱中蒸发溶剂。在蒸发溶剂之后,将有聚合物膜的玻璃板放置在有去离子水的水槽中。在1/2小时后,该膜已经与玻璃板分离开。该膜首先在1N HCl中后处理48小时和然后在去离子水中处理48小时,每次在70℃下进行。随后,表征它的性能。
表征结果:
离子交换容量:IEC=1.2meq SO3H/g聚合物
厚度:d=65um
溶胀率(H2O,RT,H+形式):SW=32.2%
表面电阻(RT,H+形式)0.144Ω.cm2(在0.5N HCl中测量)
电阻率(RT,H+形式):22.1Ω.cm
实施例13:
从磺化PSU和聚乙烯亚胺制备酸碱共混物
将3g属于SO3Li形式的水溶性磺化聚砜Udel®(离子交换容量2.5meq SO3H/g聚合物)溶于17g的N,N-二甲乙酰胺(DMAc)中。随后将0.322g的50重量%的聚乙烯亚胺水溶液(ALDRICH;产品号No.18,197-8)滴加到该溶液中。在它的制备之后,将溶液过滤和脱气。随后将聚合物溶液铺展在载体(例如,玻璃板)上形成薄膜,然后在有循环空气的烘箱中于125℃蒸发溶剂或在真空干燥箱中蒸发溶剂。在蒸发溶剂之后,将有聚合物膜的玻璃板放置在有去离子水的水槽中。在1/2小时后,该膜已经与玻璃板分离开。该膜首先在1N HCl中后处理48小时和然后在去离子水中处理48小时,每次在70℃下进行。随后,表征它的性能。
表征结果:
离子交换容量:IEC=1.65meq SO3H/g聚合物
厚度:d=110um
溶胀率(H2O,RT,H+形式):SW=160%
表面电阻(RT,H+形式):0.0623Ω.cm2(在0.5N HCl中测量)
电阻率(RT,H+形式):5.67Ω.cm
参考实施例8:
酸碱共混物膜在H2-PEFC中的应用
两种膜(参考实施例2,图1中的上曲线,和参考实施例1,下曲线)以氧模式和以空气模式在H2-PEFC中进行测试。该膜上镀敷了Pt含量为4mg Pt/g的SIEMENS电极。
在O2/H2模式中的实验条件是:
压力:2巴(绝对压力)
λ:2
温度:80℃
以O2/H2模式获得的电流-电压特性曲线示于图1中。
在空气/H2模式中的实验条件是:
压力:1.5巴(绝对压力)
λ:10
温度:65℃
在空气/H2模式中获得的电流-电压特性曲线示于图2中。
从图1和2能够看出,在H2燃料电池中检验的膜的性能在O2模式和在空气模式中都表现优异。
实施例14
酸碱共混物膜在DMFC中的应用
这些膜当中的一种(参考实施例1)按空气模式在直接甲醇燃料电池(DMFC)中进行测试。该膜上镀敷了SIEMENS电极。在甲醇/水混合物中甲醇的浓度是0.5mol/l。
在空气/甲醇模式中的实验条件如下:
压力:1.5/1.5巴(绝对压力)
流速:100ml/min
空气温度:80℃
以空气/甲醇模式获得的电流-电压特性曲线示于图3中。
从图3中能够看出,膜的性能令人惊奇地几乎与Nafion®117一样好。通过引入较高水平的胺化PSU使膜的厚度进一步减少和/或甲醇渗透性减少,甚至可以获得比Nafion更好性能的膜。
Claims (11)
1.制备酸碱聚合物共混物膜的方法,其特征在于使具有下式的聚合物磺酸或磺酸盐的溶液
聚合物-SO3X,其中X=H+,单价金属阳离子,NH4 +,NH3R+,NH2R2 +,NHR3 +,NT4 +,吡啶鎓,R=任何烷基或芳基,与含有伯、仲或叔氮的聚合物在偶极非质子溶剂中反应,将获得的酸碱聚合物共混物溶液铺展在载体上形成薄膜,蒸发除去溶剂,使膜与载体分离,然后在20-100℃于热的稀无机酸中进行后处理。
2.根据权利要求1的方法,其特征在于所述的与含有伯、仲或叔氮的聚合物反应的聚合物选自聚醚醚酮,聚醚砜,聚苯基砜,聚苯硫醚和/或聚苯醚。
3.根据权利要求1的方法,其特征在于与含氮聚合物反应的携带磺酸或磺酸盐基团的聚合物选自以结构式(R1)或(R2)的芳族核结构作为重复单元的聚合物,
其中
R3是氢,三氟甲基或CnH2n+1,n=1-10,
R4是氢,CnH2n+1,n=1-10,或苯基,和
x=1,2或3
它们经过桥接基团R5、R6、R7或R8相连,其中
R5是-O-,
R6是-SO2-,
R7是>C=O,和
R8是-S-。
4、根据权利要求3的方法,其特征在于与含氮聚合物反应的携带磺酸或磺酸盐基团的聚合物选自:
聚醚醚酮:[R5-R2-R5-R2-R7-R2]n;R2中:x=1,R4=H;
聚醚砜:[R1-R5-R2-R6-R2-R5]n;R2中:x=1,R4=H;
聚醚砜:[R2-R6-R2-R5]n;R2中:x=1,R4=H;
聚苯基砜:[(R2)2-R5-R2-R6-R2]n;R2中:x=2,R4=H;
聚醚醚砜:[R5-R2-R5-R2-R6]n-[R5-R2-R6-R2]m;R2中:x=1,R4=H,n/m=0.18;
聚苯硫醚:[R2-R8]n;R2中:x=1,R4=H;
聚苯醚:[R2-R5]n;R4=CH3。
5.根据权利要求1的方法,其特征在于将聚合物磺酸溶于偶极非质子溶剂中,任选在此之后添加对应于聚合物中的SO3H基团含量为等摩尔量的低分子量伯、仲或叔胺,然后将含有伯、仲或叔碱性氮基团的另一种聚合物溶解于所获得的聚合物溶液中。
6.根据权利要求1-5之一的方法,其特征在于所述的偶极非质子溶剂选自N-甲基吡咯烷酮,N,N-二甲基乙酰胺,N,N-二甲基甲酰胺,环丁砜和二甲亚砜。
7.根据权利要求4的方法,其特征在于携带磺酸或磺酸盐基团的聚合物选自聚醚醚酮和聚醚砜。
8.根据权利要求1-5之一的方法,其特征在于含有伯、仲或叔氮的聚合物选自聚醚砜-邻砜二胺、聚(4-乙烯基吡啶)、聚乙烯亚胺和聚苯胺。
9.可由权利要求1-8之一的方法获得的聚合物共混物膜,其是由聚合物磺酸或磺酸盐的溶液与聚(4-乙烯基吡啶)反应得到的。
10.根据权利要求9的聚合物共混物膜作为质子传导性电解质在膜燃料电池、聚合物电解质膜电解、含水或不含水的电渗析,或扩散透析中的用途。
11.根据权利要求9的聚合物共混物膜在全蒸发、全抽提、气体分离、透析、超滤、纳米过滤或反渗析中的用途。
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-
1998
- 1998-04-18 DE DE19817376A patent/DE19817376A1/de not_active Withdrawn
- 1998-06-12 US US09/096,189 patent/US6194474B1/en not_active Expired - Lifetime
-
1999
- 1999-04-16 EP EP99920762A patent/EP1073690B1/de not_active Expired - Lifetime
- 1999-04-16 WO PCT/EP1999/002756 patent/WO1999054389A1/de active IP Right Grant
- 1999-04-16 CN CNB99805173XA patent/CN1263787C/zh not_active Expired - Fee Related
- 1999-04-16 BR BRPI9909727-3A patent/BR9909727B1/pt not_active IP Right Cessation
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2000
- 2000-09-19 US US09/665,459 patent/US6300381B1/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109862958A (zh) * | 2016-08-18 | 2019-06-07 | Nx过滤控股公司 | 制备带正电的膜的方法 |
CN109862958B (zh) * | 2016-08-18 | 2021-12-03 | Nx过滤控股公司 | 制备带正电的膜的方法 |
Also Published As
Publication number | Publication date |
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US6300381B1 (en) | 2001-10-09 |
CN1297463A (zh) | 2001-05-30 |
US6194474B1 (en) | 2001-02-27 |
EP1073690A1 (de) | 2001-02-07 |
DE19817376A1 (de) | 1999-10-21 |
BR9909727A (pt) | 2000-12-19 |
EP1073690B1 (de) | 2004-01-14 |
WO1999054389A1 (de) | 1999-10-28 |
BR9909727B1 (pt) | 2009-01-13 |
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