CN1526758A - 含离子的或可离子化基团的非全氟聚合物树脂及其产品 - Google Patents
含离子的或可离子化基团的非全氟聚合物树脂及其产品 Download PDFInfo
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- CN1526758A CN1526758A CNA2004100040433A CN200410004043A CN1526758A CN 1526758 A CN1526758 A CN 1526758A CN A2004100040433 A CNA2004100040433 A CN A2004100040433A CN 200410004043 A CN200410004043 A CN 200410004043A CN 1526758 A CN1526758 A CN 1526758A
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- polyelectrolyte
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- 238000010189 synthetic method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
描述了非全氟聚合物,它含有至少一种丙烯酸类树脂或乙烯基树脂,它们具有至少一个离子的或可离子化基团和任选地至少一种加成聚合物。优选的聚合物在许多应用中是有用的,包括形成在电池组和燃料电池等中有用的薄膜。还描述了制备聚合物掺合物的方法。
Description
发明背景
本发明涉及聚合树脂,尤其涉及含离子和/或可离子化基团(也称为“非全氟的聚电解质)的非全氟聚合树脂,它们在许多产品中是有用的,比如聚电解质薄膜和其它热塑性材料。本发明还涉及制备这些树脂及使用这些树脂的方法。
全氟化碳离子交换薄膜提供高的阳离子迁移,已广泛用作离子交换薄膜。聚合的离子交换薄膜可称作固体聚合物电解质或聚合物交换薄膜(PEM)。由于严格的要求,大多数通常使用的薄膜,以及市场上出售的薄膜,由全氟代磺化的Nafion和Aciplix聚合物制备。然而,报告和文献将这些薄膜描述为:虽然很好,但有一些限制,它们阻碍进一步商业化的技术开发。另外,它们与气体燃料一起的操作优于液体燃料,这主要由于削弱电池性能的燃料渗透。膜的耐化学物质性和机械强度,是燃料电池应用的重要性质。确实,薄膜经常受到高的压差,水合-脱水循环,以及其它状况。而且,在薄膜变得非常薄时,比如低于50微米,机械强度就变得重要。此外,用于燃料电池或电池组时,薄膜处于温度高达200℃的非常酸性的介质中,由于金属离子的存在和有时候溶剂的存在,处于氧化和/或还原环境中。这环境要求薄膜是耐化学物质的和耐电化学的,并且是热稳定的。
目前,许多含氟薄膜有下列缺点的一个或几个:
1)液体和气体透过薄膜的渗透率高;
2)氟化聚合物和其它聚合物之间的不均匀掺合,导致不良的性质;
3)在一些液体燃料存在下不充分的耐化学物质性;
4)不良的耐电化学性;
5)缺乏磺化基团的不均匀分布;
6)不良的机械性能;和/或
7)不良的热稳定性。
美国专利4295952(de Nora等人)涉及阳离子薄膜,它们具有部分磺化的苯乙烯三聚物,二乙烯基苯,以及至少2-乙基吡啶,4-乙基吡啶之一,和/或丙烯酸。
美国专利5679482(Ehrenberg等人)涉及与离子基团的离子导电薄膜结合的燃料电池。形成薄膜的聚合物包含用磺化试剂磺化的苯乙烯。磺化可以用单体或聚合物实现。
美国专利5795668描述了含有用NafionTM型聚合物增强的聚合离子交换薄膜(PEM)MEA。PEM是基于氟化的多孔支撑层和当量约500-2000的增强离子交换薄膜,优选离子交换能力0.5-2meq/g干树脂。多孔支撑层由某些PTFE和PTFE的共聚物制成。薄膜是侧链含-CF2CF2SO3H的全氟化聚合物。从文献知道,Nafion型聚合物在甲醇燃料电池中有机械故障及液体透过问题。
WO 97/41168(Rusch)涉及具有离子交换树脂的多层化的离子交换组合物薄膜,如氟化的或非氟化的聚苯乙烯基的磺酸酯和磺化的聚四氟乙烯。
WO 98/20573 A1描述了含高氟化锂离子交换聚合物电解质薄膜(PEM)。PEM是基于吸入质子溶剂的离子交换薄膜。
WO 98/22989描述含聚苯乙烯磺酸和聚(偏氟乙烯)的聚合薄膜,它降低直接甲醇燃料电池(DMFC)使用中的甲醇透过。然而,所述的聚合物掺合过程不能提供可接受的掺合,并且磺化步骤是复杂的。
Holmberg等人(J.Material Chem.(1996 6(8),1309)描述了通过照射苯乙烯的接枝到PVDF膜上,接着通过用氯磺酸磺化,制备质子导电薄膜。在本发明中,磺化步骤是不需要的,因为磺化的基团可用磺化的单体被结合进来。
美国专利6252000涉及氟化离子交换/无官能聚合物的掺合。特殊的例子包括全氟化的磺酰氟聚合物/聚(CTFE-共-全氟二氧戊环)掺合物。
WO 99/67304涉及芳族全氟的离子交联聚合物,它通过磺化的芳族全氟单体与丙烯酸单体的共聚制备。存在的磺化基团在聚合物氟化的芳链中。
美国专利6025092涉及全氟离子交联聚合物,其中,VDF单体与磺化的单体聚合。
此外,磺化的丙烯酸聚合物或磺化的乙烯基聚合物被描述为用在高吸水性吸收剂,尿布和隐形眼镜中,例如(J.Meter.Chem.1996,6(a),1309和Ionics3,214(1997)。然而,这种类型产品不被描述作为聚电解质薄膜等的薄膜应用。所有专利,出版物和上面提到的应用及贯穿这应用,全部结合供参考,并形成本应用的一部分。
因此,存在克服一个或多个限制并开发用在液体燃料电池应用中薄膜的需求。尤其,存在开发非全氟聚电解质需求,直接从含水的和非水的分散液制备薄膜。而且,存在提供组合物和合成方法需求,以及使用具有磺化的或其他官能性的非全氟聚电解质的水或非水分散液方法的需求。此外,存在提供更便利和不影响环境方法的需求。另外,本领域的技术人员优选具有较高耐化学物质性和机械强度的聚电解质薄膜。
发明概述
所以,本发明的特点是提供非全氟聚电解质,具有离子的官能度。
本发明的另一个特点是提供具有高耐化学物质性和/或机械强度的非全氟聚电解质薄膜。
本发明的另一个特点是提供聚合物,它们能作为非全氟聚电解质薄膜中的一个组分,这些薄膜避免上面所述的一个或多个缺点,例如避免高的液体透过薄膜。
本发明的另一个特点是提供薄膜,它们能从聚合物的分散液直接制备。
本发明的另一个特点是提供非全氟聚电解质,而没有单独的磺化步骤。
为了达到这些和其他的优点,并根据本发明的目的,如这里具体和广泛描述的,本发明涉及聚合物或含至少一种丙烯酸类树脂和/或乙烯基树脂的聚合物掺合物,这里,丙烯酸类树脂和/或乙烯基树脂具有至少一个离子或可离子化的基团,如磺化的基团,这里聚合物具有的当量从约200-约4000。
本发明还涉及组合物,它包括掺合下列物质的聚合产物:a)至少一种具有丙烯酸和/或乙烯基单元和至少一个离子的或可离子化基团的聚合物;b)任选至少一种加聚物,其中,a)和b)是不同的。加聚物可以是任何兼容的聚合物,如热塑性聚合物(例如,热塑性的非-氟聚合物或氟聚合物)。
本发明还涉及包括聚合物产品的组合物:a)至少一种可聚合的丙烯酸和/或含乙烯基单体和至少一个包括至少一个离子或可离子化基团的单体,或两者;在分散介质存在下,其中聚合物具有EW从约200-约4000,优选约200-约1400。
另外,本发明涉及在上述组合物的优选方法,包括至少一个可聚合的丙烯酸和/或含乙烯基单体和在分散介质中至少一个含至少一个离子的或可离子化基团的单体。
本发明还涉及含聚合物或本发明组合物的非全氟聚电解质薄膜,还涉及燃料电池和含本发明薄膜的电池。
另外,本发明涉及包括上述薄膜的薄膜电极组件,涉及使用这薄膜电极组件的燃料电池。
本发明详细说明
用全氟聚电解质薄膜提供高的阳离子迁移,已广泛用作离子交换薄膜。聚合的离子交换薄膜被称为固体聚合物电解质或聚合物交换薄膜(PEM)。
最常用的薄膜和市场上有售的是Nafion和Aciplex。但是,在文献中很少有描述非全氟聚电解质薄膜。这是由于这样一个事实:薄膜的耐化学物质性,耐电化学性和机械强度是燃料电池应用的重要性质。确实,薄膜经常受到高的压差。另外,当膜很薄(小于50微米)时,机械强度变成很重要。在用于燃料电池和电池组应用时,薄膜位于可达200℃温度的非常酸性的介质中,在金属离子,溶剂等的存在下,需要高的耐化学物质性以及耐电化学性。这些要求在使用氟化基时经常可以满足,因为氟化材料具固有的耐化学物质和耐电化学性。然而,这些薄膜显示一些限制,包括但不限于,在高温时(70-200℃)不良的机械性能,透过,以及在反复水合-脱水循环后的机械故障。另外,制备这些全氟聚电解质需要几步,并包括引起高成本的化学过程。开发容易和便宜的化学过程将进一步减轻燃料电池的商品化的障碍。
本发明涉及非全氟聚电解质,它含有至少一个丙烯酸类树脂和/或乙烯基树脂或聚合物,而这些树脂或聚合物有至少一个离子或可离子化的基团,如磺化的和/或磷酸化的基团。聚合物或其掺合物不含全氟聚合物,优选不含氟聚合物。在一个实施例中,非全氟聚电解质是以无其他聚合物出现(即,它不是作为掺合物存在,或者以另一种方式说,非全氟聚电解质是单独使用)。在另一实施例中,非全氟聚电解质是与一个或多个其他聚合物一起出现,例如,作为如与热塑的非全氟聚合物的掺合物。用全氟,可理解为:所有连接到碳原子的氢完全由氟取代。在本发明中,不是这种情况。作为选择,有些氢可用氟取代,但不是所有。这样,部分氟化是可能的或根本无氟化。
本发明还涉及从掺合a)和b)形成产品,a)具有丙烯酸或乙烯基单元或两者的非全氟聚电解质,至少一个离子或可离子化基团,和b)至少一个加聚物,其中,a)和b)是相互不同的。
本发明还涉及一种组合物,它包含至少一个含可聚合乙烯基和/或丙烯酸的单体和至少一个包含至少一个离子或可离子化基团或两者的单体,其中聚合优选在含水分散液存在下发生。
关于丙烯酸类树脂或聚合物,这聚合物或树脂优选含有或带有一个或多个离子或可离子化基团,丙烯酸类树脂的例子包括丙烯酸,甲基丙烯酸,这些酸的酯,或丙烯腈的聚合物(包括共聚物,三聚物,低聚物等)。丙烯酸类树脂也可含有其他重复单元以及不同丙烯酸烷基酯,甲基丙烯酸烷基酯,丙烯酸,甲基丙烯酸和丙烯腈的组合。为了本发明,丙烯酸类树脂可包括其他聚合的单体,或者可以是两个或多个不同丙烯酸类树脂的混合物,或者可另外包括非丙烯酸类树脂,比如乙烯基单体和苯乙烯单体。
可用在非全氟聚电解质中的乙烯基单体的例子包括,但不限于,苯乙烯,乙酸乙烯酯,乙烯基醚,乙烯基酯,如VeoVa 9和VeoVa 10(Shell出品),丙酸乙烯酯,新戊酸乙烯酯,苯甲酸乙烯酯,硬脂酸乙烯酯等,以及它们的组合。
而且,非全氟聚电解质含至少一个离子的(例如磺酸盐或膦酸盐)或可离子化的基团,比如磺化的或磷酸化的基团或磺酰基。可离子化基团是可形成离子基团的基团,如环氨基酸,磺内酯,马来酸酐,硫醇,硫化物,磷杂烷(phosphalanes)等。以任何方式,这些基团可是非全氟聚电解质的一部分,比如:在一个或多个含离子或可离子化基团单体存在下,掺合丙烯酸和/或乙烯基的树脂。另外,用于形成非全氟聚电解质的一个或多个单体,可含有离子的或可离子化的基团。
除了上面提到的关于丙烯酸和/或乙烯树脂的组分外,在一个或多个加成单体另外存在下,丙烯酸和/或乙烯树脂可含有或形成任何类型的官能团,只要这些单体与丙烯酸和/乙烯基树脂的全面形成相容。
如前面所述,优选丙烯酸或乙烯树脂是几个单体聚合的结果,其中之一含离子的或可离子化基团,其他的含有丙烯酸和/或乙烯树脂的丙烯酸和/或乙烯单元。更优选,丙烯酸和或乙烯树脂聚合自:(1)丙烯酸烷基酯,(2)甲基丙烯酸烷基酯,(3)一个或多个可共聚的、与(1)和(2)不同的单体,(4)具有至少一个官能团的单体,(5)含离子的或可离子化基团的单体,如磺化或膦酸化的单体。
丙烯酸酯(1)的例子包括:丙烯酸乙酯,丙烯酸甲酯,丙烯酸丁酯,丙烯酸丙酯,丙烯酸异丁酯,丙烯酸戊酯,丙烯酸2-乙基己酯,丙烯酸己酯,丙烯酸氟烷基酯,以及它们的组合。
甲基丙烯酸酯(2)的例子包括:甲基丙烯酸乙酯,甲基丙烯酸甲酯,甲基丙烯酸丁酯,甲基丙烯酸丙酯,甲基丙烯酸异丁酯,甲基丙烯酸戊酯,甲基丙烯酸2-乙基己酯,甲基丙烯酸己酯,丙烯酸氟烷基酯,以及它们的组合。
官能单体(4)的例子包括,但不限于,α,β不饱和羧酸(例如,丙烯酸,甲基丙烯酸,富马酸,巴豆酸,衣康酸);乙烯酯化合物,酰胺化合物(例如丙烯酰胺,甲基丙烯酰胺,N-甲基甲基丙烯酰胺,N-羟甲基甲基丙烯酰胺,N-烷基丙烯酰胺,N-烷基丙烯酰基甲酰胺,N-二烷基甲基丙烯酰胺,N-二烷基丙烯酰胺);含羟基的单体(例如甲基丙烯酸羟乙酯,丙烯酸羟乙酯,丙烯酸羟丙酯,甲基丙烯酸羟丙酯,二甘醇乙醚丙烯酸酯);含环氧基的单体(例如,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯),含硅烷醇的单体(例如,γ-三甲氧基硅烷甲基丙烯酸酯,γ-三乙氧基甲基丙烯酸酯);含醛的单体(例如,丙烯醛),烯基氰化物(例如,丙烯腈,甲基丙烯腈)。包括在(4)中的单体是可交联的。可交联的可共聚化单体的例子包括:异丁基甲基丙烯酰胺,甲基丙烯酸缩水甘油酯,二甘醇二甲基丙烯酸酯,和三甲氧基硅烷甲基丙烯酸酯。交联可能是改良机械性能和耐溶剂性能所需要的。
对于一些特殊的应用,可使用低分子量可共聚的聚合物或低聚物。而且,在使用丙烯酸烷基酯(1)和甲基丙烯酸烷基酯(2)的混合物时,可适当调节它们的比例,以达到要求的性质。
含至少一个离子的或可离子化基团的单体(5)的例子包括,但不限于,丙烯酰胺磺酸丙酯,乙烯膦酸,乙烯磺酸,甲基丙烯酸磺基丙酯,甲基丙烯酸磺基乙酯。这些单体优选以它们的酸形式使用或作为盐衍生物使用。例如,在接种乳液聚合中,磺化的单体可在第一步或第二步,或在两步中被掺入。离子基团的量优选约200-2500EW,更优选约200-约1100EW,这里EW是当量,并且是每磺化单元中聚合物的克数。
本发明的含至少一个丙烯酸或乙烯基树脂的或两者含有至少一个离子或可离子化基团的的聚合物,就丙烯酸或乙烯基树脂而论,有些具有当量约200-4000,更优选约200-1400。这优选的当量范围,就薄膜形成而论,提供了优选的性质,并且提供避免需要氟聚合物的能力。本发明的聚合物可作为掺合物任选地形成。优选地,本发明的聚合物用常规的交联技术交联。
交联可通过常规方法进行,包括但不限于,自缩合,加入第二交联剂,或辐射交联。这些在文献中有描述,并在工艺上是熟知的。能进行自缩合交联的单体的例子包括N-羟甲基丙烯酰胺,异丁氧基甲基丙烯酰胺,N-亚甲基双丙烯酰胺和甲基丙烯酸缩水甘油酯。第二交联剂的例子包括异氰酸酯,蜜胺,环氧化物,羧酸酯,烷氧基硅烷,硅酮,氮丙啶和碳二亚胺。辐射交联的例子包括电子束,紫外线和伽马射线。
含单体可聚合乙烯和/或丙烯酸混合物的聚合,可分开进行,然后与一个或多个聚合物掺合,或在一个或多个聚合物存在下聚合。含单体乙烯基和/或丙烯酸的聚合,可通过溶液聚合,本体聚合,乳液聚合制备,或任何其他已知的聚合方法制备。
如果含单体可聚合乙烯和/或丙烯酸混合物的聚合分开进行,然后与一个或多个聚合物掺合,掺合可通过各种常用的方法进行,包括但不限于,溶液掺合,挤出掺合,胶乳掺合等。对于溶液掺合,聚合物可溶解或分散在溶剂中。用于聚合物的溶剂可与用于含丙烯酸/乙烯基离子聚合物的溶剂类似或不同。例如,掺合可包含两种溶剂的溶液/分散液,或加到溶剂溶液/分散液中的粉末,或在同一溶剂中的两个聚合物,或任何其他组合。使用的典型溶剂包括四氢呋喃,丙酮,二甲亚砜,二甲基甲酰胺,N-甲基吡咯烷酮。对于熔融挤出掺合,典型的挤出温度范围在约100℃-约300℃之间,优选约150-250℃。材料可挤压成丸或膜的形状。在胶乳掺合的情况下,混合可在各种常规方法下进行:丙烯酸/乙烯基胶乳可与聚合物胶乳混合,或丙烯酸/乙烯基聚合物可分散或溶解在聚合物胶乳中,或已知的任何其它混合方法。混合可包括两种以上胶乳。每种胶乳的量和性质可以这样的方法调节:得到希望的物理和化学性质,得到预期的EW。在水性薄膜的情况下(例如通过直接胶乳制备的情况),一个或多个胶乳的粒径和固体含量可适合希望性质的要求。
对于溶剂聚合,聚合可用常规的技术进行。在与另一个聚合物掺合的情况下,用于聚合物掺合的溶剂可与用于丙烯酸/乙烯基聚合物的溶剂类似或不同。例如,掺合可包括两种溶剂溶液/分散液,或加入到溶剂溶液/分散液中的粉末,或两个聚合物在同一溶剂中,或任何其他组合。使用的典型溶剂包括二甲亚砜,二甲基甲酰胺,N-甲基吡咯烷酮,异丙醇,甲醇等。
乳液聚合可在与常规乳浊液聚合相同的条件下进行。优选将表面活性剂,聚合引发剂,链转移试剂,pH调节剂,最后,最好加入溶剂和螯合剂到接种乳液中去,反应在足够的压力,温度和时间的适合反应条件下进行,比如,在大气压下,约0.5-6小时,在温度一般约20-150℃,更优选从约40-80℃。
粒子的粒径约90-500纳米,更优选约50-300纳米,这里,聚合物的量约5-95重量%,丙烯酸或乙烯基树脂的量约95-5重量%。乳液聚合可按照标准方法进行:从开始用单体分散液的分批聚合;半连续聚合,这里,部分的单体混合物是连续地加入或分批加入;连续聚合,这里单体混合物是连续加入,或者在反应期间以含水聚合物分散液分批加入。
表面活性剂可以是阴离子的,阳离子的,和/或非离子的表面活性剂,和/或两性表面活性剂。表面活性剂可分开使用或者两个或多个组合使用。阴离子表面活性剂的例子包括高碳醇硫酸盐的盐类(例如,烷基磺酸的钠盐,烷基苯磺酸的钠盐,丁二酸的钠盐,丁二酸二烷酯磺酸的钠盐,烷基二苯基醚二磺酸的钠盐)。阳离子表面活性剂的例子包括烷基吡啶鎓氯化物或烷基铵氯化物。非离子表面活性剂的例子包括聚氧乙烯烷基苯基醚,聚氧乙烯烷基酯,聚氧乙烯烷基苯基酯,甘油酯,脱水山梨醇烷基酯,以及它们的衍生物。两性表面活性剂的例子包括月桂基甜菜碱。也可使用反应乳化剂,它们可与上面提到的单体共聚(例如苯乙烯磺酸钠,烷基磺酸钠,芳基烷基磺酸钠等)。通常使用表面活性剂的量约0.05-5份重量/100份重量总聚合物颗粒,虽然可使用其他量。
能产生适合在优选温度约20-100℃下水性介质中自由基聚合的游离基的任何类型引发剂,可用作聚合引发剂。它们可单独使用或结合还原试剂使用(例如二亚硫酸氢钠(sodium hydrogenobisulfite),硫代硫酸钠,亚硫酸氢钠(sodiumhydrogenosulfite))。例如,过硫酸盐和氢过氧化物可用作水溶的引发剂,氢过氧化枯烯,过氧基碳酸二异丙酯,过氧化苯甲酰,2,2’偶氮二甲基丁腈,2,2’-偶氮二异丁腈,1,1’-偶氮二环己烷-1-腈,异丙苯过氧化氢可用作油溶的引发剂。优选的引发剂包括2,2’偶氮二甲基丁腈和1,1’-偶氮二环己烷-1-腈。油溶引发剂优选溶解在单体混合物或少量溶剂中。使用的引发剂的量约01-2份重量/加入的100份的单体混合物重量。
可使用任何适合的链转移试剂的类型,优选不明显减慢反应的。可使用的链转移试剂包括,硫醇(例如十二烷硫醇,辛硫醇),卤化烃(例如四氯化碳,氯仿),黄原酸基(例如二甲基黄原酸基二硫化物)等。使用的链转移试剂量约0-5份重量/加入的100份单体混合物重量。
在反应中可加入少量溶剂,例如,为了帮助晶种颗粒被单体溶胀(如果这是使用的)(所以,在分子水平增加混合)和改进膜形成。加入溶剂的量在这样的范围:可操作,环境安全,生产安全,和/或不影响防止火灾。使用的溶剂包括丙酮,甲乙酮,N-甲基吡咯烷酮,甲苯,二甲亚砜等。
本发明的一个优点是:至少一个离子的或可离子化体,比如磺化体,引入到聚合物,通过在聚合物含水分散液存在下,共聚含离子的或可离子化基团的单体与其他单体。因此,在本发明中,离子的或可离子化的官能度化学地通过聚合连接到聚合物链,由此避免接枝技术。
另外,本发明使两个或多个聚合物在分散液中(例如含水分散液)的均质掺合,优选使用接种聚合方法。因此,形成的树脂可是至少一个聚合物和至少一个有离子或可离子化基团聚合物的均质掺合物。这样,可避免接枝技术以及使用不影响环境的溶剂溶液的需求。而且,不需要用酸,比如硫酸和磺酸或它们的衍生物,进行树脂的后磺化,这是因为离子的或可离子化基团,例如磺化基团已在单体上的缘故。而且,由于离子的或可离子化基团是优选聚合的,它沿聚合物链的分布,容易通过工艺上常规方法控制,如注射加成(shot addition),连续进料,晚加成等。从而,使得从聚合物掺合物形成的薄膜中,形成的离子的或可离子化基团的分布,比以前更容易控制。因此,可完成各种性质的设计,如均匀的,随机的,非均匀的等。
由于上述优点,本发明的应用可包括,但不限于,薄膜,燃料电池,涂层,离子交换树脂,采油,生物薄膜,电池组等。
聚合的离子膜或聚电解质膜可由本发明的聚合物制造。聚合的离子膜可用常规的薄膜制备方法制备,如熔融挤出,溶剂流铸,胶乳流铸等。膜电极组件可由本发明的膜制备,并可制备用这膜电极组件的燃料电池。在使用本发明的聚合物形成薄膜时,聚合物可具有任何当量,相对于聚合物中存在的离子丙烯酸或乙烯基树脂,优选具有当量约200-4000,优选约200-1500,更优选约200-1400。
更详细地,本发明的组合物在燃料电池,电池等中特别有用。除了使用本发明组合物形成聚合的离子交换薄膜外,在燃料电池和电池组中使用的设计和元件,与传统的燃料电池和电池组相同。所以,如美国专利5795668和PCT出版物WO98/22989及WO 98/20573所述的设计和制造燃料电池和电池组的方法,可用在本发明中,并全部结合在此供参考。膜可单独使用或与常用的填料(如硅石等)一起使用。燃料电池可使用液体或气体燃料,如像甲醇的液态烃。本发明的燃料电池可在很宽的操作条件下操作。本发明的燃料电池可有多孔的承载层和离子交换树脂,其中,离子交换树脂被担载在至少多孔支撑层的一侧上。本发明可在直接甲醇燃料电池或其他燃料电池中有用。优选地,本发明的燃料电池具有低的燃料透过,高的导电性,和/或高的机械强度。薄膜的厚度可是常规的,但优选约1-10密耳,更优选约3-5密耳。而且,薄膜优选具有当量约200-2500,更优选约200-1400。多孔支撑层用常规材料制备,如含氟聚合物或其他含聚合物的烃,如聚烯烃。多孔支撑层具有常规的孔径,孔隙率和厚度参数。本发明的燃料电池优选具有极佳的电性质和相对低的电阻。
本发明通过下列实施例进一步澄清,这些实施例旨在纯粹解释本发明。
实施例
在所有表格中,单体的量是以重量份给出,除非另行规定。
本发明的组合物用下列材料和反应条件制作。
原材料
单体(ATOFINA Chemicals,Inc.,Aldrich),引发剂(Aldrich,DuPont),表面活性剂(Aldrich)和缓冲剂(Aldrich),不经进一步纯化被使用。
反应
过硫酸铵0.3克,十二烷基硫酸钠1克,去离子水300克,预先放在500毫升的四颈釜中,它装有冷凝器,高纯度氮气和单体入口和机械搅拌器,反应器加热到65℃,用注射泵以要求的速率将单体混合物[甲基丙烯酸甲酯(MMA)46克和甲基丙烯酸磺丙基酯(sulfopropyl methacrylate)9克]加入反应器。任选地在反应前将部分单体混合物预先加入。残余的单体通过保持反应温度和搅拌120分钟被聚合。然后将介质冷却到室温,排出,最后的分散液通过纱罩过滤。最后的固体含量是15重量%。
表1:含磺化单体树脂的代表性合成数据
实施例 | MMA | TPMS | BA | S | ISMA | HEMA | SPM | EW |
1 | 56.6 | 24 | 2.2 | 17.2 | 1140 | |||
2 | 40 | 39 | 2.4 | 18.5 | 1330 | |||
3 | 28.6 | 19 | 19 | 9.5 | 23.8 | 1035 | ||
4 | 31.5 | 21.1 | 21.1 | 10.5 | 15.8 | 1560 | ||
5 | 28.6 | 19 | 19 | 9.5 | 23.8 | 1035 | ||
6 | 31.7 | 21 | 21 | 10.5 | 15.8 | 1560 | ||
7 | 31.6 | 21 | 21 | 10.5 | 15.8 | 1535 | ||
8 | 39.9 | 39.2 | 2.4 | 18.5 | 1330 | |||
9 | 37.8 | 3.4 | 11.8 | 27.5 | 19.5 | 1266 | ||
10 | 33 | 32.5 | 2 | 32.5 | 758 |
表2:实施例的1质子导电性测量
实施例 | 浇铸类型 | 质子导电性mS/cm |
5 | 胶乳流铸 | 25 |
6 | 胶乳流铸 | 34 |
7 | 胶乳流铸 | 22 |
8 | 胶乳流铸 | 13 |
9 | 溶剂流铸 | 20 |
10 | 溶剂流铸 | 60 |
2 | 溶剂流铸 | 9 |
试验:
导电性测试是用四个探头配置,通过电化学阻抗谱进行。测量用Gamay仪器在5×105和1Hz之间进行(Potensiostat-Galvanostat ZRAPC4/750和EIS 300软件)。这里出现的值是在室温浸入条件下得到的。
配方制备如下:
胶乳配制进行如下:
2克Baybond 116和1克Acrysol 275溶解在4克TPM中。溶液与2克TEP混合,在恒定搅拌下,将形成的溶液慢慢加入到100克胶乳中去。用刮涂器在玻璃底物上流铸薄膜,在温度范围80-100℃的烘箱中固化1-15分钟。
溶剂配方制备如下:
干燥丙烯酸乳胶,回收形成的粉末。然后,10-20克丙烯酸粉末溶解在100克DMSO中。Desmodur BL-3175A以各种异氰酸酯羟基比率加入DSMO溶液,以得到最大交联效率。用二月桂酸二丁锡催化异氰酸酯交联。
这系统的交联剂包括嵌段异氰酸酯,单体异氰酸酯,蜜胺,硅烷,环氧化物或羧酸。对具体交联化学,选择催化剂,但最普通的是有机锡,磺酸或胺。
用刮涂器在玻璃底物上流铸薄膜,在温度范围150-200℃的烘箱固化1-15分钟。
Baybond 116是基于己二异氰酸酯(Bayer)的水性交联剂。Acrysol 275是疏水改性的亚乙基-氧化物基氨基甲酸乙酯嵌段共聚物(HEUR)(Rohm & Haas)。
Desmodur BL-3175A是用甲基乙基酮肟嵌段的己二异氰酸酯低聚物,并且是Bayer Corp.的产品。
符号表:
MMA | 甲基丙烯酸甲酯 |
TPMS | 三-异丙氧基硅烷甲基丙烯酸酯 |
S | 苯乙烯 |
HEMA | 甲基丙烯酸羟乙酯 |
IBMA | 异丁氧基甲基丙烯酰胺 |
SPM | 甲基丙烯酸磺基丙酯 |
BA | 丙烯酸丁酯 |
TPM | 三甘醇单甲基醚 |
TEP | 磷酸三乙酯 |
DSMO | 二甲亚砜 |
Claims (34)
1.非全氟聚电解质,包含:
a)至少一种丙烯酸类树脂和/或乙烯基树脂,或者两者,所述树脂具有至少一个离子的或可离子化基团且EW为约200-4000,以及可选地,
b)至少一种加成聚合物,其中,a)和b)是不同的。
2.如权利要求1所述的非全氟聚电解质,其特征在于:所述的非全氟聚电解质是共聚物。
3.如权利要求1所述的非全氟聚电解质,其特征在于:所述的非全氟聚电解质包含丙烯酸,甲基丙烯酸,这些酸的酯或丙烯腈的聚合物。
4.如权利要求1所述的非全氟聚电解质,其特征在于:所述的非全氟聚电解质包含丙烯酸乙酯,丙烯酸甲酯,丙烯酸丁酯,丙烯酸丙酯,丙烯酸戊酯,丙烯酸2-乙基己酯,丙烯酸己酯,丙烯酸氟烷基酯及其它们的组合。
5.如权利要求1所述的非全氟聚电解质,其特征在于:所述的离子的或可离子化的基团是磺化基团或磷酸化基团,或者两者。
6.如权利要求1所述的非全氟聚电解质,其特征在于:存在所述的加成聚合物,且所述加成聚合物是芯,所述的丙烯酸类树脂和/或乙烯基树脂至少部分包着所述的芯。
7.如权利要求1所述的非全氟聚电解质,其特征在于:所述的至少一种丙烯酸类树脂和/或乙烯基树脂或两者具有至少一个离子的或可离子化的基团,通过聚合至少一种含有丙烯酸和/或乙烯基或两者的单体,至少一种可共聚单体,至少一种具有至少一个官能基团的单体和至少一种具有离子的或可离子化基团的单体形成,其中各单体是相互不同的。
8.如权利要求7所述的非全氟聚电解质,其特征在于:所述的单体具有的离子的或可离子化基团是磺化或磷酸化的单体。
9.如权利要求1所述的非全氟聚电解质,其特征在于:所述的丙烯酸类树脂或乙烯基树脂是均聚物。
10.如权利要求1所述的非全氟聚电解质,其特征在于:所述的丙烯酸类树脂或乙烯基树脂是共聚物。
11.如权利要求7所述的非全氟聚电解质,其特征在于:所述的丙烯酸类树脂包含丙烯酸烷基酯和甲基丙烯酸烷基酯的聚合物。
12.如权利要求3所述的非全氟聚电解质,其特征在于:所述的甲基丙烯酸的酯包括甲基丙烯酸乙酯,甲基丙烯酸甲酯,甲基丙烯酸丁酯,甲基丙烯酸丙酯,甲基丙烯酸异丁酯,甲基丙烯酸戊酯,甲基丙烯酸2-乙基己酯,甲基丙烯酸己酯,甲基丙烯酸氟烷基酯或它们的组合。
13.如权利要求7所述的非全氟聚电解质,其特征在于:所述的可共聚单体包括异丁基甲基丙烯酰胺,甲基丙烯酸缩水甘油酯,二甲基丙烯酸二乙二醇酯或三甲氧基硅烷甲基丙烯酸酯。
14.如权利要求7所述的非全氟聚电解质,其特征在于:所述的具有至少一个官能基团的单体包括α,β不饱和羧酸乙烯酯化合物,酰胺化合物,含有羟基的单体,含有环氧基团的单体,含有硅烷醇的单体,含醛、烯基氰化物的单体。
15.包含非全氟聚电解质的聚电解质膜,其特征在于:所述的非全氟聚电解质包含至少一种具有至少一个离子的或可离子化的基团的丙烯酸或乙烯基树脂或两者。
16.如权利要求15所述的聚电解质薄膜,其特征在于:所述的非全氟聚电解质的当量为约200-4000。
17.如权利要求15所述的聚电解质薄膜,其特征在于:所述的非全氟聚电解质包含至少一个加成聚合物。
18.包括权利要求15的聚合离子薄膜的膜电极组件。
19.包括权利要求18膜电极组件的燃料电池。
20.包括由聚电解质膜隔开的阳极室和阴极室的燃料电池,其特征在于:所述的薄膜包含非全氟聚电解质,其中,所述的非全氟聚电解质包含至少一种具有至少一个离子的或可离子化基团的丙烯酸类树脂和/或乙烯基树脂或两者。
21.如权利要求20所述的燃料电池,其特征在于:所述的薄膜还包含至少一种填料。
22.如权利要求20所述的燃料电池,其特征在于:还包含至少一个埋入所述薄膜中的多孔支撑层。
23.如权利要求20所述的燃料电池,其特征在于:所述的燃料电池用液体烃燃料操作。
24.如权利要求20所述的燃料电池,其特征在于:所述的燃料电池用甲醇燃料操作。
25.包含用聚电解质膜隔开的阳极室和阴极室的电池,其特征在于:所述的膜包含非全氟聚电解质,其所述的非全氟聚电解质包含至少一种具有至少一个离子的或可离子化基团的丙烯酸类树脂和/或乙烯基树脂或两者。
26.制备权利要求1组合物的方法,包括掺合下列组分:
a)至少一种包含丙烯酸单元、乙烯基单元或两者和至少一个离子的或可离子化的基团的聚合物;
b)至少一种加成聚合物,其中,a)和b)是不同的。
27.如权利要求26所述的方法,其特征在于:所述的掺合通过熔融或挤出掺合,胶乳掺合或溶剂掺合完成。
28.如权利要求26所述的方法,其特征在于:a)聚合物通过乳液聚合,本体聚合或溶液聚合制备。
29.包含权利要求1聚合物的薄膜。
30.包含聚合下列物质得到的聚合物产物的组合物:a)至少一个可聚合的含丙烯酸或乙烯基或两者的单体,至少一个包括至少一个离子的或可离子化基团的单体,或两者;b)至少一个能分散在介质中的加成聚合物的分散液存在,其中,所述的聚合物产物具有当量约200-4000。
31.如权利要求30所述的组合物,其特征在于:所述的当量约200-1400。
32.如权利要求1所述的非全氟聚电解质,其特征在于:所述的非全氟聚电解质具有当量约200-4000。
33.如权利要求15所述的聚电解质薄膜,其特征在于:所述的非全氟聚电解质具有当量约200-1500。
34.如权利要求1所述的非全氟聚电解质,其特征在于:存在所述的加成聚合物。
Applications Claiming Priority (2)
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US10/383,026 US20040175625A1 (en) | 2003-03-06 | 2003-03-06 | Non-perfluorinated resins containing ionic or ionizable groups and products containing the same |
US10/383,026 | 2003-03-06 |
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CN1526758A true CN1526758A (zh) | 2004-09-08 |
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US (2) | US20040175625A1 (zh) |
EP (1) | EP1455407A3 (zh) |
JP (1) | JP4864292B2 (zh) |
KR (1) | KR20040079842A (zh) |
CN (1) | CN1526758A (zh) |
CA (1) | CA2456224C (zh) |
TW (1) | TWI343143B (zh) |
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-
2003
- 2003-03-06 US US10/383,026 patent/US20040175625A1/en not_active Abandoned
-
2004
- 2004-01-16 EP EP04290118A patent/EP1455407A3/en not_active Withdrawn
- 2004-01-26 CA CA2456224A patent/CA2456224C/en not_active Expired - Fee Related
- 2004-02-06 CN CNA2004100040433A patent/CN1526758A/zh active Pending
- 2004-02-09 KR KR1020040008364A patent/KR20040079842A/ko not_active Application Discontinuation
- 2004-02-09 TW TW093102930A patent/TWI343143B/zh not_active IP Right Cessation
- 2004-02-20 JP JP2004044732A patent/JP4864292B2/ja not_active Expired - Fee Related
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2007
- 2007-06-26 US US11/768,448 patent/US20070259240A1/en not_active Abandoned
Cited By (3)
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CN101133511B (zh) * | 2005-02-08 | 2010-10-13 | 通用汽车公司 | 用作聚电解质膜的磺化聚(亚苯基硫醚)薄膜 |
CN102432765A (zh) * | 2011-08-15 | 2012-05-02 | 中科院广州化学有限公司 | 一种聚甲基丙烯酸羟乙酯和钒电池用阴离子交换膜 |
CN102432765B (zh) * | 2011-08-15 | 2013-11-06 | 中科院广州化学有限公司 | 一种聚甲基丙烯酸羟乙酯和钒电池用阴离子交换膜 |
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JP4864292B2 (ja) | 2012-02-01 |
TW200418226A (en) | 2004-09-16 |
US20040175625A1 (en) | 2004-09-09 |
KR20040079842A (ko) | 2004-09-16 |
US20070259240A1 (en) | 2007-11-08 |
CA2456224C (en) | 2012-01-24 |
JP2004269875A (ja) | 2004-09-30 |
EP1455407A3 (en) | 2010-04-14 |
EP1455407A2 (en) | 2004-09-08 |
TWI343143B (en) | 2011-06-01 |
CA2456224A1 (en) | 2004-09-06 |
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