CN1823114A - 非对称聚合物薄膜,它的制备方法及其应用 - Google Patents
非对称聚合物薄膜,它的制备方法及其应用 Download PDFInfo
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- CN1823114A CN1823114A CNA2004800200036A CN200480020003A CN1823114A CN 1823114 A CN1823114 A CN 1823114A CN A2004800200036 A CNA2004800200036 A CN A2004800200036A CN 200480020003 A CN200480020003 A CN 200480020003A CN 1823114 A CN1823114 A CN 1823114A
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- aryl
- heteroaryl
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及一特别是以聚吡咯为基础的非对称的聚合物薄膜,其制备方法以及它的应用。按本发明的以聚吡咯为基础的非对称的聚合物薄膜具有一平整面和一粗糙面,基于它们构造能快速和均匀地掺杂酸,成为传导质子的膜。按本发明的以聚吡咯为基础的非对称的聚合物薄膜由于它的优异的化学、热和力学性能可用于诸多方面,特别适用于制造所谓PEM-燃料电池的聚合物电解质膜(PEM)。
Description
本发明涉及一特别是以聚吡咯为基础的非对称的聚合物薄膜,其制备方法以及它的应用。
按本发明的聚合物薄膜由于它的优异的化学、热和力学性能可用于诸多方面,尤其适于在所谓的PEM-(聚合物电解质膜)燃料电池中用作聚合物电解质膜。
聚吡咯膜必须用酸进行掺杂才能适用于在PEM-燃料电池中,为此目的将碱性的聚吡咯膜用浓磷酸或硫酸处理,使其在所谓的聚合物电解质膜燃料电池(PEM-燃料电池)中起到质子导体或隔板的作用。
基于聚吡咯-聚合物的优异性能,这种聚合物电解质膜能加工成膜-电极-单元(MEE),在高于100℃,尤其是高于120℃的连续工作温度时在燃料电池中获得应用,这种高的连续工作温度能提高在膜-电极-单元(MEE)中所含贵金属催化剂的活性,特别是应用在所谓由烃类构成的转化物中,在转化的气体中含有相当数量的一氧化碳,它通常需经过一昂贵的气体处理或气体净化过程除去,而通过提高工作温度的方式可以长期容许有较高浓度的CO-杂质存在。
通过使用以聚吡咯聚合物为基础的聚合物电解质膜,一方面可以部分地省去昂贵的气体处理或气体净化过程;而另一方面还可减少膜-电极-单元中的催化剂负荷,二者对于PEM-燃料电池大批量使用都是必不可少的前提,否则的话PEM-燃料电池体系的应用成本就会太高。
聚合物膜用强酸掺杂往往得与巨额费用相联系的,因为膜的平面表面吸收酸进行得很慢,所以常常需通过膜的横截面进行非均质的酸掺杂,它往往会导致再现性不够满意。
在迄今为止已知的聚吡咯为基础的聚合物膜一经掺杂酸后应用于上述目的一其力学性能也是不足,这种力学不稳定性表现为低E-模数,较小的撕裂强度和低的断裂韧性。
为了使PEM-燃料电池能获得应用,特别是在汽车领域和固定方式的应用,对所使用的膜希望达到高的再现性,对迄今已知的方法还需改进。
因而本发明的任务是制成一种以聚吡咯为基础的聚合物膜,它一方面能保证在膜的整个横截面上进行均匀的酸掺杂,并同时又能达到一在技术上可行的工艺方法。
令人惊喜的发现,以聚吡咯为基础的一种非对称聚合物膜,它既有一平整的面,又有一粗糙的面,它能在掺杂酸时相当快速和均匀地吸收酸,从而能较经济地,即在短时间内制成具有高再现性的膜,此外,用本发明的方法制备的掺杂聚合物膜具有良好的力学性能和优异的质子传导性。
本发明的对象是一种以聚吡咯为基础的非对称聚合物膜,它有一平整的和粗糙的面,其平整面的粗糙度<2μm,特别是<1μm;而粗糙面的粗糙度在3至10μm之间,优选在4至8.5μm,尤其是在4至7μm之间。
按本发明的聚合物薄膜的粗糙度是用扫描电子显微照相法(REM)测定的,粗糙度是指凹穴(层厚)的深度。从图1中可观察到,按本发明的聚合物薄膜具有明显的不同表面,平整面为一以平面结构为主,只能观察到有很小的深度<2μm的,尤其是<1μm的不平整性。而薄膜的粗糙面的层厚(深度)在3至10μm之间,优选在4至8.5之间,特别是在4至7μm之间。
作为在本发明意义上的聚吡咯是如通式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII),含有重复出现的吡咯单元的聚合物。
其中Ar是相同或不同的,为一单核或多核的四键的芳基或杂芳基,
Ar1是相同或不同的,为一单核或多核的二键的芳基或杂芳基,
Ar2是相同或不同的,为一单核或多核的二或三键的芳基或杂芳基,
Ar3是相同或不同的,为一单核或多核的三键的芳基或杂芳基,
Ar4是相同或不同的,为一单核或多核的三键的芳基或杂芳基,
Ar5是相同或不同的,为一单核或多核的四键的芳基或杂芳基,
Ar6是相同或不同的,为一单核或多核二键的芳基或杂芳基,
Ar7是相同或不同的,为一单核或多核二键的芳基或杂芳基,
Ar8是相同或不同的,为一单核或多核三键的芳基或杂芳基,
Ar9是相同或不同的,为一单核或多核二一或三一或四键的芳基或杂芳基,
Ar10是相同或不同的,为一单核或多核二一或三键的芳基或杂芳基,
Ar11是相同或不同的,为一单核或多核二键的芳基或杂芳基,
X是相同或不同的,为氧、硫或氨基,它带有一氢原子,一1~20碳原子的基团,优选是一支化或非支化的烷基或烷氧基或一芳基作为另外的基,
R是相同或不同的,为氢、一烷基和一芳基,其中在式(XX)中的R基氢是不同的,
n,m为一整数,大于等于10,优选大于等于100,
优选芳基或杂芳基是由苯、萘、联(二)苯、二苯基醚、二苯基甲烷、二苯基二甲基甲烷、Bisphenon、二苯基砜、喹啉、吡啶、二吡啶、哒嗪、嘧啶、吡嗪、三嗪、四嗪、吡咯、吡唑、蒽、吲哚、苯并***、苯并氧硫(杂环)二唑、苯并噁二唑、苯并吡啶、苯并吡嗪、Benzopyrazidin、苯并嘧啶、苯并三嗪、吲嗪、喹嗪、吡啶并吡啶、咪唑并嘧啶、吡嗪并嘧啶、咔唑、吖啶、吩嗪、苯并喹啉、吩噁嗪、吩噻嗪、吖啶嗪、苯并蝶啶、菲咯啉和菲衍生出的,它们往往是可以取代的。
此处Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11的取代模式是任意的,例如在亚苯基情况下Ar1、Ar2、Ar3、Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11可以是邻-、间-和对-亚苯基,尤其优选基团是由苯基和亚苯基衍生出的,它们往往是可以取代的。
优选的烷基是带有1至4碳原子短链的烷基,例如甲基、乙基、正-或异-丙基和叔丁基。
优选的芳基是苯基或萘基,烷基和芳基是可以取代的。
优选的取代基是卤素原子,例如氟、氨基、羟基或短链的烷基,例如甲基或乙基。
优选聚吡咯是重复出现的式(I)单元,其中X基在一重复出现的单元中是相同的。
原则上聚吡咯也可具有不同重复出现的单元,例如它们的X基是不同的,优选还是在重复单元上具有相同的X基。
其它优选的聚吡咯一聚合物是聚咪唑、聚苯并噻唑、聚苯并噁唑、聚噁二唑、聚喹喔啉、聚硫杂二唑、聚吡啶、聚嘧啶和聚四氮杂芘。
在本发明的另外的实施模式中含有重复吡咯单元的聚合物是一共聚物和一共混物,它含有至少式(I)至(XXII)的两个互相不同的单元,该聚合物可以是嵌段聚合物(二嵌段、三嵌段),统计共聚物、循环共聚物和/或交替聚合物。
在本发明的特别优选的实施模式中含有重复出现的吡咯单元的聚合物是一仅含有式(I)和/或式(II)单元的聚吡咯。
在聚合物中重复出现的吡咯单元的数目优选是大于等于10的一整数,特别优选是至少含有100重复出现吡咯单元的聚合物。
在本发明的范围内,优选是含有重复出现的苯并咪唑单元的聚合物,通过下式给出最适用的含有重复出现苯并咪唑单元的聚合物若干实例:
其中n和m是大于等10的一整数,优选是大于等于100。
所使用的聚吡咯,尤其是聚苯并咪唑具有较高的分子量,以特性粘度进行测定,至少为0.8dl/g,优选至少为1.1dl/g。
按本发明聚合物薄膜的制备是经过下列步骤实现的:
A)将在溶剂中含有聚吡咯一聚合物的溶液和/或悬浮液加到一载体上,形成一平面层,该载体表面用这样方法打毛,使其具有所要求的粗糙度,
B)按步骤A)形成的薄层进行干燥和
C)将干燥好的聚合物薄膜与载体分离。
按目前的技术水平对以聚吡咯为基础的聚合物溶液的制法曾详细进行了描述,如EP-A-0816415对应用N,N-二甲基乙酰胺作为极性的非质子传递溶剂在温度260℃以上溶解以聚吡咯为基础聚合物的方法作了叙述,在德国专利申请10052237.8中公布了一种用非常柔和的、具有保护作用的方法制备以聚吡咯为基础的溶液。
可借助已知的措施(浇注、喷射、涂刮)制成薄层,它们从目前的技术水平用于制造聚合物膜都是熟知的,这样制成的薄层的厚度在15和4000μm之间,优选在20和3500μm,特别优选在30和2000μm之间。
在该条件下所有呈隋性的载体都适用于作为载体,常用的是金属带。也可以使用所有在该条件下呈隋性的、并能达到所要求粗糙度的其它材料,此外,应用金属带还可使其在表面形成合金层。
为了获得粗糙的表面,以便按本发明可在其上涂加聚合物溶液,最好是将带板进行打毛处理,处理的方法例如是将金属带喷砂或打磨,这些方法专业人员都是熟知的。
在载体上形成的薄层按着按B)步骤进行干燥直到所形成的薄膜能自行提起。不与载体相接触的薄膜面按已知的方法仍是平整的面;而与载体相接触的薄膜面的结构则类似于载体,具有一粗糙的表面。
扫描电子显微(REM)照相显示出薄膜的粗糙面和平整面结构有明显的差别,按B)步骤薄膜的干燥是在室温至300℃之间实施的,干燥可在常压或减压下进行,干燥的时间与形成薄膜的厚度有关,可在10秒和24秒之间。按步骤B)已干燥的薄膜能自行提起并继续加工,干燥过程可借助在薄膜工业中常用的干燥方法。
如果应用的是一极性的、非质子传递溶剂,则借助B)步骤所进行的干燥过程将其大部分除去,通常干燥后极性的、非质子传递溶剂的剩余含量在10-23重量%之间。
通过干燥使聚合物薄膜的厚度变小,干燥后的厚度在10和3500μm之间,优选在15和3000μm之间,特别是在25和1800μm之间。
通过提高干燥温度和干燥时间可使剩余溶剂的含量继续降低至2重量%以下,但它会使而后进行的薄膜掺杂过程,例如用磷酸,明显增加难度。
为了改善作为聚合物电解质膜应用的效率特性,按本发明方法的聚合物薄膜可接着用一附加程序将剩余溶剂除去,相应的方法在WO02/071518中作了说明。
按步骤C)所生成的以聚吡咯为基础的非对称聚合物薄膜可以继续处理,其中特别是指表面的交联,这可以借助空气中的氧在表面作用来实现,薄膜表面的硬化进一步改善了膜的性能。
另外,也可通过IR或NIR的作用来实现交联(IR=红外,即大于700μm波长的光线;NIR=近IR,即约为700至2000μm波长区的光线或在约0.6至1.75ev区的能量),另一方法是采用β-射线照射,辐照剂量在5至200KGY之间。
按步骤C)所得到的薄膜为达到掺杂目的,可用一掺杂剂浸润或将膜置入其中,作为按本发明聚合物膜的掺杂剂,可优选采用所有路易斯酸和质子酸,特别是无机的路易斯酸和质子酸。
除了上述酸外,也可加入缩多酸,特别是同多酸和杂多酸以及不同酸的混合物,此处按本发明意义的杂多酸是指含有至少两个不同中心原子的无机缩多酸,它们分别由一种金属(优选Cr、Mo、V、W)和一种非金属(优选As、I、P、Se、Si、Te)的弱多碱基的含氧酸生成的部分混合酸酐,属于这一类的有12-钼酸基磷酸和12-钨酸基磷酸。
特别优选的掺杂剂是硫酸和磷酸,非常特别优选的掺杂剂是磷酸(H3PO4)。
在按本发明的薄膜掺杂时,令人惊喜的显示,在薄膜粗糙表面上的酸能很快地被吸收。
如果将一滴磷酸(85%的磷酸)加到粗糙的表面上,磷酸显示非常快速地被吸入薄膜,在薄膜中随着液滴下陷的增大,接触角连续减小,在本发明的薄膜中可观察到接触角的减小值在滴加液滴后1分钟之内<10°。
相反,在磷酸液滴加到平整表面上时,液滴只呈现展开的趋势,接触角减少得很慢,10分钟后接触角还>35°,而磷酸仍未被薄膜完全吸收。
按本发明的非对称聚合物薄膜在粗糙面上掺杂时,酸的吸收是呈均匀性的,另一优点是,与传统薄膜相比,上述薄膜的掺杂有较好的再现性并能节省掺杂过程的时间,这对于大规模制造聚合物电解质膜是有意义的。
优选按本发明的非对称的聚合物薄膜是经掺杂的。在本发明范围内经掺杂的聚合物膜显示出的特性是这类聚合物膜由于掺杂剂的存在,与非掺杂聚合物膜相比,提高了质子的传导性。
制备掺杂聚合物膜的工艺方法是已知的。按本发明的一种优选的实施模式是将所涉及的聚合物薄膜优选在1分钟-96小时,特别优选在10分钟-50小时,在室温和温度100℃之间,往往在提高的压力下,如上述用浓酸,优选用高浓度磷酸浸润。按本发明的膜的掺杂过程可以缩短时间到原来用时的1/5,因为在粗糙的膜面上酸的吸收大大加速。
掺杂度可影响本发明聚合物膜的导电性,其中导电性随着掺杂剂浓度的提高而增大达到一极限值,按本发明掺杂度是以每Mol聚合物重复单元的Mol酸给出的,在按本发明的范围内掺杂度优选在3和15之间,特别是在6和12之间。
为了进一步提高其应用技术性能,可在膜或薄膜中再加入添加物,特别是质子传导性的添加物以及附加酸类,通常是在A)步骤中加入。
对以聚吡咯为基础的质子传导性添加物的非限定性实例优选是:
硫酸盐如:CsHSO4、Fe(SO4)2、(NH4)3H(SO4)2、LiHSO4、NaHSO4、KHSO4、RbSO4、LiN2H5SO4、NH4HSO4,
磷酸盐如:Zr3(PO4)、Zr(HPO4)2、HZr2(PO4)3、UO2PO4·3H2O、H8UO2PO4、Ce(HPO4)2、Ti(HPO4)2、KH2PO4、NaH2PO4、LiH2PO4、NH4H2PO4、CsH2PO4、CaHOP4、MgHPO4、HSbP2O8、HSb3P2O14、H5Sb5P2O20,
缩多酸如:H3PW12O40·nH2O(n=21-29)、H3SiW12O40·nH2O(n=21-29)、HxWO3、HSbWO6、H3PMo12O40、H2Sb4O11、HTaWO6、HNbO3、HTiNbO5、HTiTaO5、HSbTeO5、H5Ti4O9、HSbO3、H2MoO4,
***盐和砷化物如(NH4)3H(SeO4)2、UO2ASO4、(Mf4)3H(SeO4)2、KH2ASO4、Cs3H(SeO4)2、Rb3H(SeO4)2,
氧化物如Al2O3、Sb2O5、ThO2、SnO2、ZrO2、MoO3,
硅酸盐如沸石、沸石(NH4 +)、层状硅酸盐、骨架硅酸盐、H-钠沸石、H-丝光沸石、NH4-方沸石、NH4-方钠石、镓酸铵、H-高岭石,
酸类如HClO4、SbF5
添加物如碳化钙,特别为SiC、Si3N4、纤维,特别为玻璃纤维,玻璃粉和/或聚合物纤维。
此外,该薄膜也可含全氟磺酸助剂(0.1-20重量%,优选为0.2-15重量%,非常优选为0.2-10重量%),这种助剂能改善效率,在阴极附近提高氧溶解性和氧的扩散和减少在铂上磷酸和磷酸盐的吸附(Electrolyte additives for phosphoric Acid fuel cells.Gang,Xiao;Hjuler,H.A.;Olsew,c.;Berg,R.W.;Bjerrum,N.J..Chem.Dep,A,Tech.Univ.Denmark,Lyngly,Dew,J.Electrochem.Soc.(1993),140(4),896-902 andPerfluorosulfonimid as an additive in Phosphoric Acid fuel cell,Razaq,M.Razaq,A.;Yeager,E.;DesMarteaw,Darryl D.;Singh,S.Case Cent.Electrochem.Sci.Case west.Reserve Univ.,Cleveland,OH,USA.J.Electrochem.soc.(1989),136(2)385-90)。
全氟磺酸化助剂的非限制性实例是:
三氟甲烷磺酸、三氟甲烷磺酸钾、三氟甲烷磺酸钠、三氟甲烷磺酸锂、三氟甲烷磺酸铵、全氟己烷磺酸钾、全氟己烷磺酸钠、全氟己烷磺酸锂、全氟己烷磺酸铵、全氟己烷磺酸、九氟丁烷磺酸钾、九氟丁烷磺酸钠、九氟丁烷磺酸锂、九氟丁烷磺酸铵、九氟丁烷磺酸铯、全氟己烷磺酸三乙铵、全氟磺基亚酰胺和全氟磺酸离子交换树脂。
此外,膜或薄膜也可含在工业上氧还原时截获(即一次抗氧剂)或破坏(二次抗氧剂)产生的过氧化物自由基的助剂,从而如在JP2001118591A2中所描述的改善了膜和膜电极单元的寿命和稳定性。这类助剂的作用原理和分子结构在F.Gugumus in Plastics Additives,Hanser Verlag 1990;N.S.Allew,M.Edge Fundamentals of PolymerDegradation and stafility,Elsevier,1992;oder H.Zweifel,Stafilization ofPolymeric Materials,Springer,1998中作了说明。
这类助剂非限定性的实例是:
双(三氟甲基)硝基氧化物,2,2-二苯基-1-苦味碱基-偕腙肼、酚、烷基酚、空间位阻烷基酚,例如Irganox(抗氧剂商品名)、芳族胺、空间位阻胺,例如Chimassorl(商品名),空间位阻羟胺、空间位阻烷基胺,空间位阻羟胺、空间位阻羟胺醚、亚磷酸酯例如Irgafos(商品名)、亚硝基苯、甲基-2-亚硝基-丙烷、二苯甲酮、苯甲醛-叔-丁基硝酸灵、半胱胺、三聚氰胺、氧化铅、氧化锰、氧化镍、氧化钴。
按本发明的聚合物薄膜的可能应用领域为用作过滤介质,特别是在气体过滤和分离及气体净化以及在反渗透方面,在电子工业中作为基底,特别是在晶体管、电容器和其它电子器件中用于柔性电路、印刷电路,作为电池隔板,作为电缆的保护薄膜,作为电子器件和设备如电容器中的绝缘子,作为保护薄膜用于金属和其它表面。
按本发明的经掺杂的聚合物膜的可能应用领域,是在燃料电池、电解、在电容器和电池体系等方面的用途。根据其性能特点经掺杂的聚合物膜优选是用在燃料电池中。
本发明还涉及一种至少具有按本发明非对称的经掺杂的聚合物膜的膜-电极-单元。关于膜-电极-单元的其它信息资料可参阅专业文献,特别是US-A-4191618,US-A-4212714和US-A-4333805专利。在上述的文章中(US-A-4191618,US-A-4212714和US-A-4333805)揭示的关于膜-电极-单元的制备和构造内容也是属于说明书的组成部分。
下面将通过实例和对比例子对本发明作进一步阐明,但本发明并非是局限于这些实例。
实例:
图1a和1b表示按本发明的非对称聚吡咯膜的粗糙面的扫描电子显微照片。如所观察到的,该膜的粗糙化的层厚(深度)为4.775μm(图1b)或6350μm(图1a)。
为与此相对比,图2表示聚吡咯膜平整面的扫描电子显微照片。与图1a和图1b相比,此处看到的主要是一平整表面,细微的不平整性只在增加放大倍数时才能清楚地观察到,而其层厚不超过2μm。
图3a和3b再次表示通过整个直径的本发明非对称膜。在此处也可看出打毛的和平整的膜面的明显差别。
例1:
接触角的测定
在按本发明制备的非对称聚吡咯的平整面和粗糙面上对比磷酸的浸入速度。
在膜表面上形成一磷酸液滴,并借助光显微镜测量接触角,从液滴的轮廓分析中由在空气薄膜/磷酸界面上的两条切线的平均值给出此角。
在按本发明得到的一非对称聚吡咯薄膜的粗糙面上加一滴85%的磷酸,可清楚看到,酸滴很快被吸入粗糙的表面,接触角在1分钟内即降到<10°值。同样试验在两个平整面的聚吡咯膜面上进行,与前所做的试验区别在于,液滴只在膜表面上展开,即便在10分钟后酸滴进入膜表面的程度也无足轻重,10分钟后的接触角一直还>35°。
采用Krss公司产型号为G10/DAS10的接触角测定仪从一液滴轮廓分析中测定接触角作为时间的函数。
图4表示在平整的和粗糙的膜表面上作为时间函数接触角的降低可明显看出,经过一定时间后达到一恒定值并不再有值得一提的液体吸收。在薄膜的粗糙表面上酸的吸收不仅速度快的多,而且也较为完全。
Claims (15)
1.以聚吡咯为基础的聚合物薄膜具有平整面和粗糙面,其中平整面的粗糙度<2μm,而粗糙面的粗糙度在3~10μm之间。
2.按权利要求1的聚合物薄膜,其特征在于,聚吡咯涉及包括通式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII)重复出现的吡咯单元,
其中Ar是相同或不同的,为单核或多核的四键的芳基或杂芳基,
Ar1是相同或不同的,为单核或多核的二键的芳基或杂芳基,
Ar2是相同或不同的,为单核或多核的二或三键的芳基或杂芳基,
Ar3是相同或不同的,为单核或多核的三键的芳基或杂芳基,
Ar4是相同或不同的,为单核或多核的三键的芳基或杂芳基,
Ar5是相同或不同的,为单核或多核的四键的芳基或杂芳基,
Ar6是相同或不同的,为单核或多核二键的芳基或杂芳基,
Ar7是相同或不同的,为单核或多核二键的芳基或杂芳基,
Ar8是相同或不同的,为单核或多核三键的芳基或杂芳基,
Ar9是相同或不同的,为单核或多核二-或三-或四键的芳基或杂芳基,
Ar10是相同或不同的,为单核或多核二-或三键的芳基或杂芳基,
Ar11是相同或不同的,为单核或多核二键的芳基或杂芳基,
X是相同或不同的,为氧、硫或氨基,它带有氢原子,1~20碳原子的基团,优选是支化或非支化的烷基或烷氧基或芳基作为另外的基团,
R是相同或不同的,为氢、烷基和芳基,其中在式(XX)中的R基氢是不同的,
n,m为整数,大于等于10,优选大于等于100。
4.按权利要求1的聚合物薄膜的制造方法,包括下列步骤:
A)将含有聚吡咯聚合物的溶液和/或悬浮液加到载体上,形成平面层,载体表面用一种方法打毛,使其符合所要求的粗糙度,
B)干燥按A)步骤形成的薄层,和
C)将干燥的聚合物薄膜从载体上分离。
5.按权利要求4的方法,其特征在于,作为溶剂采用极性的非质子传递溶剂,尤其是N,N-二甲基乙酰胺。
6.按权利要求4的方法,其特征在于,在A)步骤产生的薄层的厚度在15和4000μm之间。
7.按权利要求4的方法,其特征在于,在A)步骤采用隋性载体,优选金属带。
8.按权利要求7的方法,其特征在于,载体具有的粗糙度即为聚合物膜的粗糙度。
9.按权利要求4的方法,其特征在于,将C)步骤后的聚合物薄膜进行交联。
10.按权利要求4的方法,其特征在于,在A)步骤加入其它添加物,尤其是传导质子的添加物。
11.按权利要求1的聚合物薄膜的应用,作为过滤介质,特别是气体-过滤和-分离或者气体净化以及在反渗透方面,在电子工业中作为基底,特别是在晶体管、电容器和其它电子器件中用于柔性电路、印刷电路、作为电池隔板、作为电缆的保护膜、在电气元器件和设备中如电容器中作绝缘子、作为金属和其它表面的保护膜、在电池体系和电容器中用于制造电化学电池,尤其是用于燃料电池和电解应用的聚合物电解质膜。
12.至少具有按权利要求1至3之一的聚合物薄膜制造的聚合物膜和至少具有电极的电化学电池。
13.至少具有是由按权利要求1至3之一的聚合物薄膜制造的聚合物膜和至少具有-电极的膜-电极单元。
14.按权利要求13的膜-电极单元,其特征在于,聚合物膜至少用路易斯酸和/或质子酸,优选硫酸和/或磷酸,特别是磷酸进行掺杂。
15.至少具有一按权利要求13的膜-电极-单元的燃料电池。
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JP5005160B2 (ja) * | 2003-12-08 | 2012-08-22 | 三星エスディアイ株式会社 | ゲル電解質及び燃料電池 |
JP2007537317A (ja) * | 2004-05-14 | 2007-12-20 | ペミアス ゲーエムベーハー | 異方性造形体、異方性造形体の製造方法および使用 |
US7736782B2 (en) * | 2004-10-20 | 2010-06-15 | Samsung Sdi Co., Ltd. | Proton conductive solid polymer electrolyte and fuel cell |
KR20060087140A (ko) | 2005-01-28 | 2006-08-02 | 삼성에스디아이 주식회사 | 고분자 전해질막 및 이를 채용한 연료전지 |
EP2339678A1 (en) * | 2006-08-25 | 2011-06-29 | Sumitomo Chemical Co., Ltd. | Polymer electrolyte membrane and laminate thereof |
DE102007018280A1 (de) | 2007-04-18 | 2008-10-23 | Volkswagen Ag | Verfahren zur Herstellung einer Polymerelektrolytmembran für eine Brennstoffzelle sowie nach dem Verfahren hergestellte Membran |
DE102008009437A1 (de) | 2008-02-14 | 2009-09-03 | Volkswagen Ag | Membran-Elektroden-Einheit für eine HT-PEM-Brennstoffzelle sowie ein Verfahren zu ihrer Herstellung |
EP2228857A1 (de) | 2009-03-06 | 2010-09-15 | Basf Se | Verbesserte Membran-Elektrodeneinheiten |
DK2869382T3 (en) | 2013-10-30 | 2019-04-01 | Basf Se | Improved diaphragm electrode devices |
JP6131973B2 (ja) | 2014-03-14 | 2017-05-24 | トヨタ自動車株式会社 | 補強型電解質膜の製造方法、膜電極接合体の製造方法、及び、膜電極接合体 |
CN106296796B (zh) | 2015-06-04 | 2019-08-13 | 北京智谷睿拓技术服务有限公司 | 信息处理方法、信息处理装置及用户设备 |
CN116059801B (zh) * | 2023-01-10 | 2024-05-28 | 中南大学 | 一种气体膜分离装置、及气体选择性分离的方法 |
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US4272353A (en) * | 1980-02-29 | 1981-06-09 | General Electric Company | Method of making solid polymer electrolyte catalytic electrodes and electrodes made thereby |
EP0141793A1 (en) * | 1983-06-30 | 1985-05-15 | Monsanto Company | Asymmetric gas separation membranes having increased selectivy, and process for their production |
WO2002004083A2 (en) * | 2000-07-07 | 2002-01-17 | Colorado State University Research Foundation | Surface modified membranes and methods for producing the same |
JP3947994B2 (ja) * | 2000-12-06 | 2007-07-25 | 東レ・デュポン株式会社 | ポリイミドフィルム、その製造方法および用途 |
DE10109829A1 (de) * | 2001-03-01 | 2002-09-05 | Celanese Ventures Gmbh | Polymermembran, Verfahren zu deren Herstellung sowie deren Verwendung |
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2003
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- 2004-07-09 DE DE502004002796T patent/DE502004002796D1/de active Active
- 2004-07-09 EP EP04740851A patent/EP1646674B1/de not_active Not-in-force
- 2004-07-09 JP JP2006518161A patent/JP2007527443A/ja active Pending
- 2004-07-09 WO PCT/EP2004/007570 patent/WO2005007725A1/de active IP Right Grant
- 2004-07-09 CN CNB2004800200036A patent/CN100432121C/zh not_active Expired - Fee Related
- 2004-07-09 AT AT04740851T patent/ATE352579T1/de not_active IP Right Cessation
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JP2007527443A (ja) | 2007-09-27 |
ATE352579T1 (de) | 2007-02-15 |
EP1646674A1 (de) | 2006-04-19 |
DE502004002796D1 (de) | 2007-03-15 |
CN100432121C (zh) | 2008-11-12 |
JP2011190445A (ja) | 2011-09-29 |
WO2005007725A1 (de) | 2005-01-27 |
EP1646674B1 (de) | 2007-01-24 |
DE10331365A1 (de) | 2005-02-10 |
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