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1、-范文最新推荐-1 / 13含联苯结构的三磺化聚芳醚氧膦质子交换膜的制备及性能测试摘要随着经济快速发展，人们的物质生活水平不断提高，同时对能源的需求也日益增大。要满足这样的能源需求已经是十分艰巨的任务，因此我们急需寻找到一种清洁，安全，高效的能源利用技术。目前，各国科学家均在致力于寻找一些能够提高能源利用率、减少环境污染的新方法或新途径。燃料电池作为一种高效、清洁的新能源发电技术，显示出了广阔、诱人的研究价值及市场前景。质子交换膜是燃料电池的核心组成部件之一，在燃料电池中起着分隔燃料和氧化剂，传导 质子、对电子绝缘等作用，是一种致密的选择性透过功能高分子膜。常见的质子交换膜分类有含氟质子交换膜
2、和非氟质子交换膜。全氟磺酸膜的结构由疏水的氟碳主链和亲水性的磺酸基团侧链两部分组成， 氟碳主链能使膜保持较好的机械性能，而含水的磺酸基团起着传导质子的作用。因此，这类膜材料具有电导率高、强度好、化学及电化学稳定性好、使用寿命长等优点，但同时也有价格高、 高温下质子传导率急剧下降和甲醇透过率高等缺点。全氟磺酸膜在实际应用中存在的一些问题及昂贵的生产成本制约了该类膜在燃料电池中的进一步发展。因此，开发新型非氟质子交换膜已成为研究的主要方向。12575本拟通过直接缩聚的方法，合成含联苯结构的三磺化聚芳醚氧膦质子交换膜，通过调整膜中磺酸基团的分布方式达到改变膜的性能的目的。第二章，从分子设计着手，以二
3、(4-氟苯基)苯基氧膦为原料，合成了含三个磺酸基的一种磺化单体，即二（3-磺酸钠-4- 氟苯基）-3′- 磺酸钠苯基氧膦（ TSPPO） 。再将六氟双酚 A 和二(4-氟苯基)苯基氧膦与这种磺化单体缩聚，合成了三系列的磺化聚芳醚氧膦，其主链骨架相同，但磺酸基分布方式各异，分别为单磺化、二磺化或三磺化的聚芳醚氧膦（msPEPOF-x, dsPEPOF-x 和 tsPEPOF-x，其中 x 为磺化度） ，其磺化度（或 磺酸基的含量）通过反应物配比来调节。也就是说，通过分子设计方法合成了磺酸基的分布方式和含量可调的多种磺化聚芳醚氧膦。SAXS 和 STEM 结果表明这-范文最新推荐-3
4、/ 13些磺化聚芳醚氧膦膜中具有明显的亲水/疏水微相分离结构，离子通道尺寸及连通性由磺酸基的分布方式和含量决定。当磺 化度相同时，二磺化聚芳醚氧膦与单磺化聚芳醚氧膦相比，离子通道尺寸略增大，但连通性变差；三磺化聚芳醚氧膦与二磺化聚芳醚氧膦相比，离子通道尺寸急剧增大，连通性显著变差。 相对应的是，从单磺化到二磺化，再到三磺化聚芳醚氧膦膜，疏水相的尺寸和连通性均增大。 因此，当磺化度相同时，从单磺化到二磺化，再到三磺化聚芳醚氧膦膜，尺寸稳定性增加，耐氧化稳定性大幅增加，电导率下降。另一方面，对于同系列膜，随着磺化度的增加，离子通道尺寸增大，连通性增加，电导率增大。因此，上述由于磺酸基的分布方式导致
5、的电导率降低可通过提高磺化度来补偿，甚至进一步提高，并且还能保持优异的尺寸稳定性和耐氧化稳定性。 换句话说，通过调节磺酸侧基的分布方式和含量，磺化聚芳醚氧膦质子交换膜的尺寸稳定性、 电导率和耐氧化性能同时改善，综合性能优良。 Proton exchange membrane fuel cell is one of the core components, in play a space of fuel and oxidant, fuel cells conducting proton, for electrical insulation effect, and the selective th
6、rough functional polymer film is a kind of. Common classification of proton exchange membrane are proton exchange membrane and non fluoride fluorine proton exchange membrane. Nafion membrane structure consists of the main chain of the fluorocarbon hydrophobic and hydrophilic sulfonic acid group side
7、 chain of two parts, the main chain of the fluorine carbon can make membrane to keep good mechanical properties, and the water cut of sulfonic acid groups to play the role of a proton conduction. Therefore, this kind of membrane materials with high conductivity and good strength, good chemical and e
8、lectrochemical stability, long life and other advantages, but also has a high price, high temperature proton conductivity and methanol transmittance sharply declining higher shortcomings. Nafion membrane in some of the problems existing in the practical application and the production cost of expensi
9、ve restricted the further development of this kind of membranes in fuel cells. Therefore, development of new type non fluorine proton -范文最新推荐-5 / 13exchange membrane has become the main direction of research.This thesis proposed by direct polycondensation method, synthetic containing biphenyl struct
10、ure of three sulfonated poly (aryl ether oxygen proton exchange membrane, phosphine sulfonic acid groups by adjusting the film distribution mode to achieve the purpose of changing the performance of the membrane. The second chapter, begin from molecular design, with 2 (4 - fluorinated phenyl) phenyl
11、 phosphine oxygen as raw material, synthesized containing sulfonic group of the three kinds of sulfonated monomer, i.e. (3-4 - fluorinated phenyl sulfonate -) - 3 - oxygen phenyl phosphine sulfonic acid sodium (TSPPO). Then six fluorine bisphenol A and two (4 - fluorinated phenyl) phenyl phosphine o
12、xygen and condensation, the sulfonated monomer synthesized three series of sulfonated poly (aryl ether oxygen phosphine, its main chain skeleton is the same, but different sulfonic group distribution way, single sulfonated respectively, sulfonated or sulfonated poly (aryl ether oxygen phosphine (msP
13、EPOF - x, dsPEPOF - x and tsPEPOF - x, where x is sulfonated degrees), the degree of sulfonation (or the content of sulfonic group) to adjust by the ratio of reactants. That is to say, sulfonic acid was synthesized by molecular design method base adjustable the distribution and content of the variet
14、y of sulfonated poly (aryl ether oxygen phosphine. SAXS and STEM result shows that the sulfonated poly (aryl ether oxygen phosphine has obvious in membrane hydrophilic/hydrophobic micro phase separation structure, ion channel size and connectivity is decided by the distribution and content of the su
15、lfonic group. When the sulfonated coefficent phase at the same time, two sulfonated poly (aryl ether oxygen phosphonic compared with single oxygen sulfonated aromatic ether phosphine, ion channel size increases slightly, but connectivity variation; Three sulfonated poly (aryl ether oxygen were compared with the sulfonated aromatic ether oxygen phosphine, ion channel size increases sharply, connectivity significantly worse
