磺化侧苯基杂萘联苯聚醚酮酮的合成与性能

Synthesis and Properties of Sulfonated Poly(phthalazinone ether ketone ketone)s Containing Pendant Phenyl Groups

以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ-P)、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)和1,4-二(4'-氟苯甲酰基)苯(BFBB)为原料,经溶液亲核取代缩聚反应,通过调节DHPZ-P和DHPZ的比例,合成了一系列侧苯基杂萘联苯聚醚酮酮(PPEKK-P),然后以浓硫酸为磺化剂,制备出一系列磺化侧苯基杂萘联苯聚醚酮酮(SPPEKK-P).利用傅里叶变换红外光谱(FTIR)和氢核磁共振谱(1H NMR)对聚合物结构进行表征,结果表明,磺酸基团引入到聚合物链的侧苯基上.采用溶液浇铸法制备SPPEKK-P质子交换膜.SPPEKK-P膜的吸水率、溶胀率和质子传导率均随离子交换容量(IEC)的增加而增加,且具有较好的耐氧化性.IEC最高的SPPEKK-P-100膜的质子传导率在95℃能达到7.44×10-2S/cm,且甲醇渗透系数为5.57×10-8cm2/s,阻醇性能优于Nafion117膜.

Poly（phthalazinone ether ketone ketone）s with pendant phenyl groups（PPEKK-P） were synthesized via high temperature polycondensation from 4-（4-hydroxyphenyl）-2,3-phthalazin-1-ketone, 4-（3-phenyl-4-hydroxyphenyl）-2,3-phthalazin-1-ketone and 1,4-bi（4-fluorobenzoyl）benzene（BFBB）. A series of sulfonated poly（phthalazinone ether ketone ketone）s containing pendant phenyl groups（SPPEKK-P） was prepared from PPEKK-P with concentrated sulfuric acid as the sulfonating agent. The chemical structures of PPEKK-P and SPPEKK-P were characterized by FTIR and 1H NMR. SPPEKK-Ps proton exchange membranes were obtained by solution casting method. Water uptake, swelling ratio and proton conductivities of SPPEKK-Ps membranes increased with the increase of ion exchange capacity. The membranes exhibited good oxidative stability. The methanol permeability values of SPPEKK-Ps membranes were much lower than that of Nafion117 membrane. The proton conductivity of SPPEKK-P-100 membrane reached 7.44×10^-2 S/cm at 95℃.