磺化杂萘联苯聚醚酮酮醚酮质子交换膜材料的合成与表征

Synthesis and Characterization of Sulfonated Poly(Phthalazinone Ether Ketone Ketone Ether Ketone)s for Proton Exchange Membrane Materials

以1,4-二(3-磺酸钠-4-氟代苯甲酰基)苯(SBFBB)和4,4’-二氟二苯酮(DFK)为二卤单体,与杂萘联苯类双酚进行溶液亲核缩聚反应,通过调控SBFBB与DFK的比例,制备了一系列具有不同磺化度的高分子量磺化杂萘联苯聚醚酮酮醚酮(SPPEKKEKs)。采用红外光谱、核磁共振谱、示差扫描量热分析等对SPPEKKEKs的结构和性能进行了表征,随着磺化度增加,SPPEKKEKs的玻璃化转变温度增大。以氮甲基吡咯烷酮为溶剂制备质子交换膜,随着SPPEKKEKs的磺化度增加,质子交换膜的含水率和质子传导率增加,95℃时,质子交换膜的质子传导率均达到10-2S.cm-1,SPPEKKEKs质子交换膜具有较好的耐氧化性能。

Sulfonated Poly（phthalazinone ether ketone ketone ether ketone）s（SPPEKKEKs） were synthesized from 1,4-bis（3-sodium sulfonate-4-fluorobenzoxy）benzene（SBFBB）,4,4＇-difluorodiphenylketone and 4-（4-hydroxyphenyl）-1-phthalazinone in sulfolane via direct polymerization.The degree of sulfonation can been controlled by changing the ratio of SBFBB.High molecular weight sulfonated polymers with different degrees of sulfonation were obtained.The structure and the properties of SPPEKKEKs were characterized with FT-IR,~1H-NMR and DSC.Glass transition temperature of SPPEKKEKs increased with increasing the degree of sulfonation.Membranes were obtained by casting 10% solution in N-methyl-2-pyrrolidinone of SPPEKKEKs.Water uptake and proton conductivity of SPPEKKEKs increased with increasing of degree of sulfonation.SPPEKKEKs membranes show proton conductivities higher than 10-2 S·cm-1at 95℃.SPPEKKEKs membranes show good oxidative stability.