CN1427739B - 有机-无机膜 - Google Patents

有机-无机膜 Download PDF

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CN1427739B
CN1427739B CN018089690A CN01808969A CN1427739B CN 1427739 B CN1427739 B CN 1427739B CN 018089690 A CN018089690 A CN 018089690A CN 01808969 A CN01808969 A CN 01808969A CN 1427739 B CN1427739 B CN 1427739B
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约享·克雷斯
托马斯·翰翎
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Universitaet Stuttgart
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Abstract

本发明涉及有机/无机杂化聚合物共混物和杂化聚合物共混物膜，它们包括：一种含有SO2X，POX2或-COX基团(X＝F，Cl，Br，I)的聚合酰基卤，一种元素或金属氧化物或氢氧化物，其是通过在膜形成过程中元素和/或有机金属化合物的水解和/或溶胶/凝胶反应，和/或随后在酸性、碱性或中性的水性电解液中处理该膜得到的。本发明还涉及含有带SO3H，PO3H2和/或COOH基团的聚合物的杂化共混物和杂化共混物膜，其是通过在聚合物共混物或聚合物共混物膜中含有的聚合酰基卤的中性、碱性或酸性水解得到的。本发明还涉及生产所述杂化共混物和杂化共混物膜的方法。

Description

有机-无机膜
1.发明主题
本发明涉及有机/无机杂化聚合物共混物和杂化聚合物共混物膜，它们包括：
·含有-SO2X，-POX2或-COX基团的聚合酰基卤(X＝F，Cl，Br，I)
·元素氧化物或元素氢氧化物或金属氧化物或金属氢氧化物，其是通过在膜形成过程中元素有机化合物和/或金属有机化合物的水解和/或溶胶/凝胶反应，和/或随后在酸性、碱性或中性的水性电解液中处理该膜得到的。
本发明还涉及含有带SO3H，PO3H2和/或COOH基团的聚合物的杂化共混物和杂化共混物膜，其是通过在聚合物共混物或聚合物共混物膜中含有的聚合酰基卤的中性、碱性或酸性水解得到的。
本发明还涉及生产所述杂化共混物和杂化共混物膜的方法。
2.技术状况及其缺点
在下列文献中公开了关于酰基氯/无机杂化复合材料的技术状况：
将Nafion磺酰基氟化物前体膜在全氟氢菲中预溶胀并浸渍在3-氨基丙基三乙氧基硅烷中。然后用EtOH洗掉过量的硅烷。形成杂化物，其中通过硅烷水解和通过硅烷与SO2F基团反应，在膜基质中形成与聚合物部分交联的SiO2网状物(Chemical modification of a nafion sulfonyl fluorideprecursor via in situ sol-gel reactions，A.J.Greso，R.B.Moore，K.M.Cable，W.L.Jarrett，K.A.Mauritz Polymer 38，1345-1356(1997))。
所述体系的缺点为：溶胶/凝胶反应在预成型的膜中进行，因此不能任意设定通过水解聚合物复合材料形成的无机聚合物相的含量。
在下列文献中还分别描述了非离子聚合物和各金属元素氧化物的杂化体系：
(e)聚甲基丙烯酸正丁酯和氧化钛的复合材料，它是在蒸发掉溶剂后由烷氧基钛在聚合物基质中进行水蒸气水解制得的，所述烷氧基钛被加入到聚甲基丙烯酸正丁酯聚合物溶液的醇溶液中(Novel Poly(n-ButylMethacrylate)/Titanium Oxide Alloys Produced by the Sol-Gel process forTitanium Alkoxides，K.A.Mauritz，C.K.Jones，J.Appl.Polym.Sci.40，1401-1420(1990))。
(f)聚醚酰亚胺和纳米分散的氧化硅的复合材料，其是通过向聚醚酰亚胺的NMP溶液中加入0.15M的HCl溶液水解TEOS制得的。水解后，由该聚合物溶液制得致密的或相反转的膜。通过另外加入3-氨基丙基三甲氧基硅烷(AS)获得无机相与有机相的相容性(Membranes of poly(etherimide)and nanodispersed silica，S.P.Nunes，K.V.Peinemann，K，Ohlrogge，A.Alpers，M.Keller，A.T.N.Pires J.Memb.Sci.157(1999)219-226.)。
3.发明目的
本发明的一个目的是提供含有另外的无机元素/金属氧化物/氢氧化物相的聚合酰基卤的复合材料和复合材料膜，其改善了下列的膜性能：
·机械稳定性
·热稳定性
·改善的持水能力，即使在＞100℃的温度下，这一点是重要的，特别是对于在＞100℃的温度范围内在膜燃料电池中的应用。
在根据本发明的方法中，元素/金属氧化物/氢氧化物的有机前体被引入到聚合物溶液中(烷氧化物/酯，乙酰丙酮化物等)。
在离子交联聚合物中无机相的形成发生在通过在酸性、碱性和/或中性水环境下水解形成膜之后，而任选发生在聚合酰基卤可被水解为酸基团的同时或另一步中。
4.本发明解决的目标(发明内容)
已令人惊奇地发现，如果将在1-丙醇中的70重量％的丙醇锆(IV)Zr(OCH2CH2CH3)4引入到PSU磺酰氯的四氢呋喃溶液中，丙醇锆(IV)在聚合物溶液中不会水解或形成保守的可溶的络合物，但当溶剂蒸发时形成膜基质。如果将丙醇锆(IV)的丙醇溶液和PSU磺酰氯(或PSU磺酸或PSU磺酸盐)在偶极非质子溶剂例如N-甲基吡咯烷二酮中的溶液混合，丙醇锆(IV)将立刻水解或沉淀。已令人惊奇地发现，通过连续地在碱性水溶液和/或水和/或酸中后处理膜，可将有机锆化合物水解成在膜基质中纳米分散的二氧化锆或氧化锆氢氧化物。采用EDX在膜基质中可检测到该无机锆化合物。其它的有机金属化合物，如Ti(acac)2(OiPr)2也可与PSU磺酰氯在醚溶剂中的溶液混合，而不会在聚合物溶液中水解并通过蒸发溶剂形成膜基质。
具体地说，本发明提供了如下方面：
1.一种含有至少一种聚合酰基卤的膜的制备方法，其特征在于：
在偶极非质子溶剂中使如下组分混合：聚合酰基卤，其中所述聚合酰基卤具有SO2X，POX2或COX或BX2基团，其中X是指F，Cl，Br或I；至少一种选自Ti，Zr，Sn，Si，B，或Al的烷氧化物、乙酰丙酮化物、有机氨基化合物、或酯的化合物或这些的混合化合物；
将所述聚合物溶液浇铸到载体上形成薄膜，所述溶剂在80-150℃的常压或真空下蒸发，其中所述溶剂选自：N-甲基吡咯烷二酮，N，N-二甲基乙酰胺，N，N-二甲基甲酰胺，二甲亚砜，环丁砜，四氢呋喃，二噁烷，甘醇二甲醚，二甘醇二甲醚，三甘醇二甲醚；和
对所述薄膜进行如下后处理，其中后处理步骤的顺序可以改变，并可任选省略掉步骤(1)和/或(2)和/或(3)，但不能同时省略掉步骤(1)、(2)和(3)：
(1)在T＝50-100℃的水中后处理，
(2)在T＝50-100℃的1-100％的无机酸中后处理，和/或
(3)在1-50％的碱性水溶液中后处理。
2.根据方面1的方法，其中所述聚合酰基卤是芳基主链聚合物并包括SO2X，POX2，COX或BX2基团，其中X选自F，Cl，Br或I。
3.根据方面1的方法，其中所述聚合酰基卤选自聚醚砜，聚砜，聚苯基砜，聚醚醚砜，聚醚酮，聚醚醚酮，聚苯醚，聚二苯基苯醚，聚苯硫，或为含有这些组分中至少一种的共聚物。
4.根据方面1的方法，其中所述载体是玻璃板、金属板、薄纸，织物，非织物，羊毛，多孔膜。
5.根据方面4的方法，其中所述多孔膜为多孔聚合物膜。
6.根据方面1-5中任一项的方法获得的膜。
可制备根据本发明的下列复合材料。复合材料含有：
·至少一种带-SO2X，-POX2和/或-COX基团的聚合酰基卤，其中X是指F，Cl，Br或I，优选含有芳基主链聚合物骨架，和
·至少一种盐，元素氧化物或元素氢氧化物或金属氧化物或金属氢氧化物，其是通过在膜形成过程中水解下列种类的元素有机化合物和/或金属有机化合物，和/或通过在酸性、碱性或中性的水性电解液中后处理膜得到的：
·Ti，Zr，Sn，Si，B，Al的金属/元素烷氧化物/酯
·金属乙酰丙酮化物，例如Ti(acac)4，Zr(acac)4
·金属/元素烷氧化物和金属乙酰丙酮化物的混合化合物，例如Ti(acac)2(OiPr)2等
·Ti，Zr，Sn，Si，B，Al的有机氨基化合物
采用相同的后处理步骤或采用另一种水性的酸性、碱性或中性后处理步骤，酰基卤基团可由此任选水解成相应的酸基团，得到含有另外的纳米分散分布的无机相的离子交联聚合物(共混物)膜。
根据本发明可采用下列溶剂制备膜：偶极非质子溶剂，例如N-甲基吡咯烷二酮(NMP)，N，N-二甲基乙酰胺(DMAc)，N，N-二甲基甲酰胺(DMF)，二甲亚砜(DMSO)或环丁砜，或醚溶剂，例如四氢呋喃，二噁烷，甘醇二甲醚，二甘醇二甲醚，三甘醇二甲醚。
由于无机相纳米分散分布在膜基质中，根据本发明其导致酰基卤聚合物(共混物)或传导质子的离子交联聚合物(共混物)的性能与离子交联聚合物(共混物)膜之间的曲线关系被明显改变。质子传导性增加，而溶胀性通常没有相应地增加。
根据纳米分散分布的组分的性质和含量，膜对非离子渗透分子(例如气体)的选择渗透性也会改变。
如果在磷酸中进行水解，或者如果用磷酸进一步后处理膜是在水解后进行的，则产生相应的金属或元素磷酸盐或磷酸氢盐或磷酸二氢盐，其中的一部分对质子传导性有贡献。
5.实施例
5.1离子交联聚合物共混物膜TH785的制备
将每个重复单元含有约1个磺酰氯基团的0.5g PSU磺酰氯溶解在3gTHF中。然后，加入0.5307g 70重量％的丙醇锆(IV)的1-丙醇溶液。对该溶液脱气，然后将其注塑成陪替氏培养皿。在室温下过夜蒸发溶剂。之后，对形成的膜进行如下的后处理：
(1)在80℃的10％NaOH中处理24小时，
(2)在80℃的10％硫酸中处理24小时，
(3)在85℃的水中处理16小时。
结果表征：
IEC[毫克当量SO3H/g]：                      0,77
溶胀[％]：                                 30.9
Rsp H+(0,5N HCl)[Ωcm]：                    28,9
5.2离子交联聚合物共混物膜TH782的制备
将每个重复单元含有约1个磺酰氯基团的0.5g PSU磺酰氯溶解在2.5gTHF中。然后，加入0.8817g 75重量％的双(乙酰丙酮根)二异丙醇钛(IV)的2-丙醇溶液。对该溶液脱气，然后将其注塑成陪替氏培养皿。在室温下过夜蒸发溶剂。之后，对形成的膜进行如下的后处理：
(4)在80℃的10％NaOH中处理24小时，
(5)在80℃的10％硫酸中处理24小时，
(6)在85℃的水中处理16小时。
结果表征：
IEC[毫克当量SO3H/g]：                      0,81
溶胀[％]：                                 39,4
Rsp H+(0.5N HCl)[Ωcm]：                    12
6.发明的新颖性
本发明的新型无机/有机杂化离子交联聚合物(共混物)膜及其制备方法没有在文献中公开过，既没有被申请人公开过，也没有被其它出版物公开过。
7.发明的优点
本发明的新型无机/有机杂化膜显示出优异的性能：
·良好的质子传导性
·良好的热稳定性
·良好的机械稳定性
·有限的溶胀性。
本发明的一些膜显示出改善的持水能力，特别是在T＞80℃的条件下，这是由在膜基质中的无机氧化物/氢氧化物导致的。可以推测无机组分在膜中的纳米分散是其背后的原因。如同在某些出版物中已提议的那样(Comparison of Ethanol and Methanol Oxidation in a Liquid-Feed SolidPolymer Electrolyte Fuel Cell at High Temperature，A.S.Arico，P.Creti，P.L.Antonucci，V.Antonucci，Electrochem.Sol.St.Lett，182)66-68(1998))，通过将氧化物粉末混入离子交联聚合物膜中，不能实现使无机组分在膜基质中象本发明方法那样的精细分布，其中元素有机化合物/金属有机化合物在膜基质中仅水解为氧化物或磷酸(氢)盐。取决于特定的组成，本发明的膜还显示出下列优点：
·降低的甲醇渗透性
·对质子传导性的贡献，特别是在T＞80℃的条件下
·改变带电和非带电颗粒的选择渗透性
·膜是光化学活性的，特别是那些含有纳米分散的二氧化钛的膜
·特定的组成(含有二氧化钛)显示光致发光性
8.关键词
芳基主链聚合物
溶胶/凝胶方法
水解
Ti，Zr，Sn，Si，B，Al的金属和元素烷氧化物
金属和元素乙酰丙酮化物Ti(acac)4，Zr(acac)4
金属/元素烷氧化物和金属乙酰丙酮化物的混合化合物Ti(acac)2(OiPr)2
Ti，Zr，Sn，Si，B，Al的有机氨基化合物
元素氧化物
金属氧化物
元素氢氧化物
金属氢氧化物
含水的氧化物
含水的磷酸盐
持水能力
质子传导性
聚砜
聚醚醚酮
Figure G018089690D00072
聚合酰基卤
阳离子交换聚合物
阳离子交换聚合物膜
聚合物质子导体
质子本身传导性
膜燃料电池
H2燃料电池
直接甲醇燃料电池
膜
膜工艺
应用温度＞80℃
热稳定性。

Claims (6)

1.一种含有至少一种聚合酰基卤的膜的制备方法，其特征在于：
在偶极非质子溶剂中使如下组分混合：聚合酰基卤，其中所述聚合酰基卤具有SO2X，POX2，COX或BX2基团，其中X是指F，C1，Br或I；至少一种选自Ti，Zr，Sn，Si，B，或A1的烷氧化物、乙酰丙酮化物、有机氨基化合物、或酯的化合物或这些的混合化合物；
将上述聚合物溶液浇铸到载体上形成薄膜，所述溶剂在80-150℃的常压或真空下蒸发，其中所述溶剂选自：N-甲基吡咯烷二酮，N，N-二甲基乙酰胺，N，N-二甲基甲酰胺，二甲亚砜，环丁砜，四氢呋喃，二噁烷，甘醇二甲醚，二甘醇二甲醚，三甘醇二甲醚；和
对所述薄膜进行如下后处理，其中后处理步骤的顺序可以改变，并可任选省略掉步骤(1)和/或(2)和/或(3)，但不能同时省略掉步骤(1)、(2)和(3)：
(1)在T＝50-100℃的水中后处理，
(2)在T＝50-100℃的1-100％的无机酸中后处理，
(3)在1-50％的碱性水溶液中后处理。
2.根据权利要求1的方法，其中所述聚合酰基卤是芳基主链聚合物并包括SO2X，POX2，COX或BX2基团，其中X选自F，Cl，Br或I。
3.根据权利要求1的方法，其中所述聚合酰基卤选自聚醚砜，聚砜，聚苯基砜，聚醚醚砜，聚醚酮，聚醚醚酮，聚苯醚，聚二苯基苯醚，聚苯硫，或为含有这些组分中至少一种的共聚物。
4.根据权利要求1的方法，其中所述载体是玻璃板、金属板、薄纸，织物，非织物，羊毛，多孔膜。
5.根据权利要求4的方法，其中所述多孔膜为多孔聚合物膜。
6.根据权利要求1-5中任一项的方法获得的膜。
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