本文選題：聚砜 + 氫氧根離子交換膜��； 參考：《大連理工大學(xué)》2015年碩士論文

【摘要】：陰離子交換膜是氫氧燃料電池的核心部件,研發(fā)高離子傳導(dǎo)率、優(yōu)良化學(xué)、機(jī)械性能的高性能陰離子交換膜成為現(xiàn)階段氫氧燃料電池研究的重點(diǎn)。現(xiàn)有研究思路主要集中在設(shè)計(jì)聚合物主鏈及堿性功能基團(tuán)側(cè)鏈兩個(gè)方面,如功能化單體聚合形成嵌段聚合物以及強(qiáng)堿性、穩(wěn)定性好的堿性功能基團(tuán)的改性研究。本文以性能優(yōu)良的熱塑性工程塑料聚砜為主鏈,提出三甲胺均相季銨化,以及烏洛托品、K支鏈醚鍵咪唑作為新型堿性功能基團(tuán)的方法,制備性能優(yōu)良的聚砜基陰離子交換膜。針對(duì)非均相法制備的陰離子交換膜反應(yīng)不均勻、離子傳導(dǎo)率不高的問(wèn)題,開發(fā)混合溶劑,實(shí)現(xiàn)氯甲基化聚砜與三甲胺的均相季銨化反應(yīng),成功制備了一系列三甲胺聚砜陰離子交換膜。均相法和非均相法制備的膜,離子交換容量分別可達(dá)到0.52-1.13 mmolg-1和0.56-1.28 mmolg-1與非均相膜相比,均相季銨化膜中季銨基團(tuán)更多(離子交換容量,IEC約增加10%),膜的含水量約提高8.8%,氫氧根傳導(dǎo)率的提高程度遠(yuǎn)大于離子交換容量和含水量的提高程度,常溫下離子傳導(dǎo)率最大可提高29.3%,透射電鏡(TEM)顯示均相法制備的膜具有更好的微觀相分離結(jié)構(gòu)。盡管均相法制備聚砜膜電導(dǎo)率有一定程度提高,但沒能解決提高季銨基團(tuán)數(shù)量造成過(guò)度溶脹和高溫強(qiáng)堿下降解問(wèn)題。針對(duì)上述問(wèn)題,選用含有四個(gè)氮、金剛烷結(jié)構(gòu)的烏洛托品作為新的季銨化試劑,成功合成烏洛托品季銨化聚砜陰離子交換膜(CPSF-QuOH),通過(guò)核磁共振確定了季銨化程度及交聯(lián)度。CPSF-QuOH膜的離子交換容量從1.39-2.23mmol g-1,交聯(lián)度在15-26%,水吸收率和溶脹度分別保持在30%和20%以下,30℃時(shí)離子傳導(dǎo)率從18.2 mS cm"1增大到40mS cm-1,表明CPSF-QuOH膜具有較高的氫氧根離子傳導(dǎo)率和良好的機(jī)械穩(wěn)定性。CPSF-QuOH膜初始分解溫度高達(dá)204℃,具有良好的熱穩(wěn)定性；60℃下1MKOH強(qiáng)堿溶液中浸泡7天,離子傳導(dǎo)率衰減很小(最大衰減14.4%),測(cè)試證明具有很好的化學(xué)穩(wěn)定性。為進(jìn)一步提高陰離子交換膜的穩(wěn)定性,首先合成氯化1-(2-羥乙基)-3-甲基咪唑摀鹽為季銨化試劑,然后通過(guò)威廉姆森成醚反應(yīng),成功合成了醚鍵接枝咪唑筠化聚砜(EPSF-ImCl),進(jìn)而澆鑄成膜,制備了理論IEC為1.37-1.95mmolg-1的EPSF-ImOH膜。20℃時(shí),EPSF-ImOH 1.22(理論IEC為1.95mmol g-1)的氫氧根離子傳導(dǎo)率達(dá)到27.4 mScm-’,60℃時(shí)升高到72mScm-1。EPSF-ImOH膜初始分解溫度169℃,高于三甲銨基團(tuán)的熱初始分解溫度120℃,表明具有良好的熱穩(wěn)定性；80℃下1MKOH強(qiáng)堿溶液中浸泡144h,離子傳導(dǎo)率僅衰減1.2%,測(cè)試證明具有很好的化學(xué)穩(wěn)定性。
[Abstract]:Anion exchange membrane is the core component of hydrogen oxygen fuel cell. The research and development of high ionic conductivity, excellent chemical and mechanical properties of high performance anion exchange membrane has become the focus of research on hydrogen oxygen fuel cell. The existing research ideas mainly focus on the design of polymer main chain and basic functional group side chain, such as functionalized monomer polymerization to form block polymer and strong alkaline, good stability of basic functional groups modification. In this paper, using thermoplastic engineering plastics polysulfone as main chain, trimethylamine homogeneous quaternization and Ulotropine K branched chain ether imidazole as new basic functional groups were proposed to prepare polysulfone based anion exchange membranes with excellent properties. Aiming at the problems of heterogeneous anion exchange membrane reaction and low ion conductivity, a mixed solvent was developed to realize the homogeneous quaternary ammonium reaction of chloromethylated polysulfone with trimethylamine. A series of trimethylamine polysulfone anion exchange membranes were successfully prepared. The ion exchange capacities of the membranes prepared by homogeneous and heterogeneous methods are 0.52-1.13 mmolg-1 and 0.56-1.28 mmolg-1, respectively. In homogeneous quaternary ammonium film, there were more quaternary ammonium groups (ion exchange capacity increased by about 10%, water content of membrane increased about 8.8%, the increase of hydrogen oxygen conduction rate was much greater than that of ion exchange capacity and water content. The maximum ionic conductivity can be increased by 29.3% at room temperature. Transmission electron microscopy (TEM) shows that the membrane prepared by homogeneous phase method has a better microstructure. Although the conductivity of polysulfone membrane prepared by homogeneous method has been improved to some extent, it has not solved the problem of excessive swelling and degradation under high temperature and strong alkali caused by increasing the number of quaternary ammonium groups. To solve the above problems, Ulotropine with four nitrogen and adamantane structures was selected as a new quaternary ammonium reagent. Urotropine quaternary ammonium polysulfone anion exchange membrane (CPSF-QuOHH) was successfully synthesized. The degree of quaternary ammonium conversion and crosslinking degree. CPSF-QuOH membrane ion exchange capacity was determined from 1.39-2.23mmol g-1, crosslinking degree was 15-26%, water absorptivity and swelling degree were kept at 30% and 30%, respectively. The ionic conductivity increases from 18.2mScm "1 to 40mS cm-1 at 30 鈩，

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