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1、碩士論文多嵌段型磺化聚芳醚砜質(zhì)子交換膜的制備及性能研究摘要成功制備了一系列新型的多嵌段型磺化聚芳醚砜聚合物(bS隊(duì)ES),并通過bSPAES與磺化聚酰亞胺(SPI)復(fù)合,制各了具有雙磺化結(jié)構(gòu)的復(fù)合膜。對它們的離子交換容量(IEC),吸水率(WU),尺寸變化,質(zhì)子導(dǎo)電率(o)及水穩(wěn)定性進(jìn)行了詳細(xì)的研究。在K2C03的存在下,通過溶液縮聚的方法合成了具有親水/疏水鏈段的多嵌段型磺化聚芳醚砜共聚物(SN.bSPAES)。利用1HNMR對低聚體以及多嵌段聚合物的結(jié)構(gòu)進(jìn)行了驗(yàn)證。SIN.bSPAES膜都具有良好的高溫水穩(wěn)定,如mC
2、高達(dá)2.42meq/g的M(6/a)-b(12/8)膜在loooc水中放置24h后,仍表現(xiàn)了較高的機(jī)械強(qiáng)度。SN-bSPAES膜在水中的質(zhì)子導(dǎo)電率都明顯高于Nafionll2,M(4/6)-b(8/12_)在600C水中的質(zhì)子導(dǎo)電率為0.208S/cm,是相同條件下Nafionl12(0.142S/cm)的約1.5倍。當(dāng)IEC相似時(shí),它們的質(zhì)子導(dǎo)電率和吸水率受鏈段長度影響,隨著鏈段長度的增加,質(zhì)子導(dǎo)電率和吸水率也隨著增加。合成了具有高磺W/低磺化鏈段的多嵌段型磺化聚芳醚砜共聚物(SS-bSPAES)。SEM譜圖顯示所有嵌
3、段膜的橫斷面沒有出現(xiàn)明顯相分離區(qū)域。SS-bSPAES膜都具有良好的水穩(wěn)定性,盡管IEC達(dá)到了2.08meq/g,在100oC水中放置200h后,仍保持很好的力學(xué)性能。當(dāng)相對濕度達(dá)到60%以上時(shí),SS-bSPAES膜的質(zhì)子導(dǎo)電率要明顯高于Nafionll2膜。利用溶液澆注法成功制備了一系列的雙磺化型SN-bSPAES/SPI復(fù)合膜。復(fù)合膜質(zhì)地均勻,表面光滑平整。SEM譜圖顯示復(fù)合膜沒有存在明顯的相分離,表明兩者具有很好的相溶性。由于SPI的引入,與純的SN-bSPAES膜相比,復(fù)合膜的尺寸穩(wěn)定性和高溫水穩(wěn)定性方面有了很大
4、的提高。關(guān)鍵詞:質(zhì)子交換膜,磺化聚芳醚砜,多嵌段共聚,。復(fù)合,尺寸穩(wěn)定性,質(zhì)子導(dǎo)電率Abstract碩士論文AseriesofnovelmultibloekSPAESweresuccessfullydeveloped.BlendmembranesfrombSPAESandSPlwel"eprepared.,11leirpropertiessuchasionexchangecapacity(IEC),wateruptake(歷叻,dimensionalchange,protonconductivity(o)aswell弱w
5、aterstabilitywereinvestigatedindetails.Hydrophilic/hydrophobicmultiblockSPAEScopolymers(SN-bSPAESs)weresynthesizedv/astep·growthpolymerizationinthepresenceofpotaSsiumcarbonate.Thestructuresofoligomersandmultiblockcopolymerswereconfirmedby1HNMRspectra.AllbSPAESmem
6、branesshowed900dwaterstability.Forexample,M(6/4)-b(12/8)(IEC=2.42meq/g)stillremainedgoodmechanicalpropertyafteragingtestinwaterat100oCfor24h.AllbSPAESsshowedhigherprotonconductivitiesthanthatofNation12inwater.neprotonconductivityofM(4/6)ob(8/12)inwaterat600cwas0.
7、208S/cm,whichWasabout1.5timestOthatofNation(0.142S/cm).AtthesimilarIECvalue,theirprotonconductivityandwateruptakeweresignificantlyaffectedbytheblocklength,whichoandWUincreasedwiththeincreaseblocklength.Aseriesofhighsulfonateddegree/lowsulfonateddegreemultiblockco
8、polymer(SS-bSPAESs)weresuccessfullysynthesized.SEMmicrographsrevealedthatthereWasnoobviousphaseseparationoccurredinthemembrane.AlloftheSS-bSP:AESsmembranesshow