基于含萘基团侧链型磺化聚芳醚酮类用于质子交换膜燃料电池的膜材料的制备与性能研究

发布时间：2018-04-22 19:01

本文选题：质子交换膜 + 磺化聚芳醚酮　；参考：《吉林大学》2014年博士论文

【摘要】：质子交换膜是燃料电池的最核心部件，在燃料电池的工过程中起着传导质子，阻绝燃料的作用。针对目前质子膜材料存在高磺化度下膜尺寸稳定性差与化学稳定性低等问题，本论文以合成制备高综合性能的质子交换膜为目的，采用多种方法提高膜的综合性能，并对膜的其他性能进行了测试，努力突破膜稳定性差等技术障碍，为实现工业化应用提供实验基础。成功制备了一种新型含有三甲氧基的聚芳醚酮，利用三溴化硼作为去甲氧基试剂，成功的制备了每个结构单元中含有三个羟基的新型的聚芳醚酮。首先，成功的制备了一系列磺化度可控的侧链型磺化聚芳醚酮SQNPAEK-x。对该系列膜进行性能测试，低磺化度下的磺化聚芳醚酮具有良好的综合性能，但是在高磺化下，其高的吸水率以及较差的阻醇性能限制了其在燃料电池领域的应用。为了降低膜的吸水率，，提高膜的阻醇性能，同时保持质子传导率处于较高水平，我们通过采用交联的方法：（1）首先，成功合成了四甲基联苯二酚型环氧树脂TMBP小分子交联剂，利用磺化聚芳醚酮上剩余的羟基与环氧基团的反应，成功的制备了一系列交联膜SQNPAEK/TMBP-xx。该系列的交联膜表现出了良好的阻醇性能，较高的尺寸稳定性与适宜的质子传导率。（2）然后，成功合成制备了含烯丙基的新型可自交联的磺化聚芳醚酮SQNPAEK-AC-x，制备了一系列自交联的磺化聚醚醚酮SC-SQNPAEK-x。该方法不需要引入交联剂与催化剂，工艺简单方便。（3）最后，成功合成制备了含有羧基的磺化聚芳醚酮SPAEK-COOH-x作为大分子交联剂，制备了一系列的交联膜SQNPAEK/COOH-x，利用交联剂上的磺酸基团作为催化剂，使得羧基与苯环发生交联反应。此法得到的交联膜，交联程度大，质子传导率高。该方法适用于多类聚合物膜的改性。
[Abstract]:Proton exchange membrane (PEM) is the most important component of fuel cell. In view of the problems of poor dimensional stability and low chemical stability of proton membrane materials with high sulfonation degree, this paper aims at synthesizing proton exchange membranes with high comprehensive properties and using various methods to improve the comprehensive properties of the membranes. The other properties of the membrane were tested to break through the technical obstacles such as poor stability of the membrane and to provide the experimental basis for the realization of industrial application. A novel poly (aryl ether ketone) containing trimethoxy was successfully prepared. A novel polyaryl ether ketone containing three hydroxyl groups was successfully prepared by using boron tribromoxide as a demethoxyl reagent. Firstly, a series of side chain sulfonated poly (aryl ether ketones) SQNPAEK-xwere successfully prepared. It was found that the sulfonated poly (aryl ether ketone) with low sulfonation degree had good comprehensive performance, but its high water absorption and poor alcohol resistance limited its application in fuel cell field. In order to reduce the water absorption of the membrane, improve the alcohol resistance of the membrane and keep the proton conductivity at a high level, we successfully synthesized a small molecular crosslinking agent of tetramethyl dihydroxybenzene epoxy resin (TMBP) by using crosslinking method: 1). A series of cross-linking membranes SQNPAEK / TMBP-xx were successfully prepared by the reaction of the remaining hydroxyl groups on sulfonated poly (aryl ether ketones) with epoxy groups. This series of cross-linking membranes exhibit good alcohol resistance, high dimensional stability and appropriate proton conductivity. A novel sulfonated poly (aryl ether ketone) SQNPAEK-AC-x containing allyl group was successfully synthesized and a series of self-crosslinked sulfonated polyether ketones SC-SQNPAEK-xwere prepared. This method does not need to introduce crosslinking agent and catalyst, and the process is simple and convenient. Finally, sulfonated poly (aryl ether ketone) SPAEK-COOH-x containing carboxyl group was successfully synthesized as macromolecular crosslinking agent. A series of cross-linking membranes SQNPAEK / COOH-x were prepared. The sulfonic group on the crosslinking agent was used as catalyst to make the carboxyl group cross-link with benzene ring. The crosslinking membrane obtained by this method has high crosslinking degree and high proton conductivity. This method is suitable for the modification of multi-class polymer membranes.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2014
【分类号】：O631;TM911.4

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