新型磺化聚酰亚胺膜的合成与表征

2009年第67卷化学学报Vol.67,2009第9期,1013～1018ACTACHIMICASINICANo.9,1013～1018*E-mail:ydhuang.hitl@yahoo.com.cnReceivedJuly26,2008;revisedNovember18,2008;acceptedDecember23,2008.·研究论文·新型磺化聚酰亚胺膜的合成与表征赵亮黄玉东*朴艳梅孟祥丽宋元军龙军(哈尔滨工业大学应用化学系哈尔滨150001)摘要摘要合成了4,4'-二(间氨基苯氧基)联苯-3,3'-二磺酸(mBAPBDS)单体,采用红外光谱和核磁共振等方法对其结构进行了表征.使用mBAPBDS,2-(对胺基苯基)苯并噁唑-5-胺(APBA)和1,4,5,8-萘四甲酸二酐(NTDA)共聚合成了含有噁唑结构的新型磺化聚酰亚胺(NTDA-mBAPBDS/APBA),通过控制磺化二胺与非磺化二胺的比例来控制磺化程度.NTDA-mBAPBDS/APBA共聚物表现出较好的溶解性、成膜性能和良好的热稳定性,其磺酸基团分解温度高于300.℃采用溶液浇铸法制备了磺化聚酰亚胺(SPIs)膜,对膜的吸水率、溶胀度和质子电导率等性能进行了初步的研究.结果表明,SPIs膜具有适当的吸水率和良好的尺寸稳定性,其室温电导率在4.72×10－3和9.60×10－3S/cm之间,接近于相同条件下Nafion®117的电导率(9.80×10－3S/cm).关键词关键词燃料电池;磺化聚酰亚胺;质子交换膜SynthesisandCharacterizationofNovelSulfonatedPolyimideMembranesZhao,LiangHuang,Yudong*Piao,YanmeiMeng,XiangliSong,YuanjunLong,Jun(DepartmentofAppliedChemistry,HarbinInstituteofTechnology,Harbin150001)AbstractThesulfonateddiamine,4,4'-bis(3-aminophenoxy)biphenyl-3,3'-disulfonicacid(mBAPBDS),wassuccessfullysynthesizedandcharacterizedbyFT-IRand1HNMRspectra.Aseriesofnewsulfonatedpolyim-ides(NTDA-mBAPBDS/APBA)containingabenzoxazolestructureweresynthesizedfrommBAPBDS,[5-amine-2-(4-aminophenyl)benzo[d](1,3)oxazol](APBA)and1,4,5,8-naphthalenetetracarboxylicdianhy-dride(NTDA)usingaone-stephightemperaturepolymerizationmethod.ThesulfonationdegreeofNTDA-mBAPBDS/APBAcopolymerswascontrolledthroughvaryingthemolarratioofmBAPBDStoAPBA.TheresultsshowedthattheNTDA-mBAPBDS/APBAcopolymerspossessedgoodsolubilityandfilmprocessingproperty.TGanalysisindicatedthattheSPIcopolymersdisplayedgoodthermalstabilitywiththedecompositiontemperatureabove300℃.TheSPImembraneswerepreparedbycastingfromthepolymersolution,andtheirwateruptake,swellingratioandprotonconductivitywerealsoinvestigated,whichdisplayedadequatewateruptakeandgooddimensionalstability.TheprotonconductivitiesoftheSPImembraneswerebetween4.72×10－3～9.60×10－3S/cmatroomtemperature,whichwasclosetothatofNafion®117membranemeasuredunderthesamecondition(9.8×10－3S/cm).Keywordsfuelcell;sulfonatedpolyimide;protonex