利用4,4?-二氟二苯砜(DFDPS)、9,9?-双(4-羟苯基)芴(BHPF)、2,2?-二(4-羟基苯基)丙烷(双酚A)及4,4?-(六氟异丙叉)双酚(双酚AF)为原料,制备了2类具有不同主链刚性的聚醚砜材料.以聚醚砜及其氯甲基化产物按一定质量比采用溶液浇铸法,制备了2类新型共混阴离子交换膜,并避免了成膜过程中的相分离现象.在高分子主链上通过引入双酚芴(BQPAES系列)及双酚A(BQPES系列)结构调整主链的刚性,探讨了主链刚性对性能的影响;表征了共混膜的离子交换容量(IEC)、吸水及溶胀特性与离子电导率,并考察了它们的耐水解和耐碱稳定性.结果表明:2种聚合物相容性良好,共混膜质地均一,柔韧透明,吸水率和溶胀率适中,均随着温度的升高逐渐增加、随着聚醚砜含量增加逐渐减小;在90?C时,离子电导率最高达到89 m S/cm.经过沸水处理24 h后,均保持高机械强度,失重率低于5%;经2 mol/L的Na OH溶液30?C处理168~240 h后离子电导率仍可保持65%~80%.由于含双酚芴结构的高分子主链具有更高的刚性,在类似IEC条件下,BQPAES膜显示了比BQPES膜更好的尺寸稳定性和化学稳定性,同时维持了较高的电导率水平.由此表明,复合处理及适度提高高分子主链的刚性,有利于提高膜的性能.
Two series of poly(aryl ether sulfone)s with different rigidity are synthesized by the polymerization of bis(4-fluorophenyl) sulfone(DFDPS) with 9,9?-bis(4-hydroxyphenyl) fluorine(BHPF) or 2,2?-bis(4-hydroxy phenyl) propane(BPA)/2,2-bis(4-hydroxyphenyl) hexafluoropropane(6FBPA). Two novel types of blend anion exchange membranes(AEMs) are prepared through solution casting by co-dissolving the synthesized poly(aryl ether sulfone) and its chloromethylated products with various weight ratios, while the phase-separation is avoided successfully during membrane formation. The rigidity of the polymer main chains is adjusted by introducing the monomers of BHPF(BQPAES series) and BPA(BQPES series), respectively, and their influence on membrane properties is studied in details. The ion exchange capacity(IEC), water absorbing and swelling properties, as well as ion conductivity of the obtained blend AEMs are characterized, and the hydrolytic and alkaline stability are investigated. The precursory and corresponding chloromethylated polymers show fine compatibility and their resultant blend AEMs are uniform, ductile and transparent, with moderate water uptakes and dimensional changes. Both the water uptakes and the dimensional change increase along with temperature and decrease with poly(aryl ether sulfone) content. The ion conductivity of the blend AEMs reaches the maximum of 89 m S/cm at 90 ?C. After aging in hot water for 24 h, they still retain high mechanical strength with mass loss less than 5%; they also maintain 65% ~ 80% of the original ion conductivity after treated with 2 mol/L Na OH solutions for 168 ~ 240 h at 30 ?C. Because of the higher rigidity of BHPF moieties, the BQPAES series blend membranes show better dimensional stability and chemical stability than those of the BQPES series at similar IEC level, while maintaining high ionic conductivity. The results imply that the blend treatment and appropriate enhancement in rigidity in the polymer ma