Poly(aryl ether ketone)s with carboxylic acid groups: synthesis, sulfonation and crosslinking
作者:Baijun Liu、Wei Hu、Gilles P. Robertson、Michael D. Guiver
DOI:10.1039/b806690f
日期:——
Carboxylic acid-containing poly(aryl ether ether ketone) (PFEEK–COOH) and poly(aryl ether ether ketone ketone) (PFEEKK–COOH) were synthesized from the monomer 9,9-bis(4-hydroxyphenyl)-fluoren-4-carboxylic acid. The latter polymer, PFEEKK–COOH, was post-sulfonated to yield SPFEEKK–COOH whereby the site and the degree of sulfonation (DS from 0 to 3) could be controlled. The reaction progress and structures of the resulting sulfonated polymers were identified by 1D and 2D NMR techniques. The carboxylic acid group was used as to crosslink SPFEEKK–COOH by reaction with poly(vinyl alcohol) (PVA) to prepare crosslinked membranes. The proton conductivity of a crosslinked SPFEEKK–COOH-1.6/PVA membrane was ∼0.15 S cm−1 at 65 °C, while maintaining acceptable dimensional stability in water. Thermal stability, water uptake and proton conductivity of carboxylated, carboxylated/sulfonated, and crosslinked membranes were investigated.
利用单体 9,9-双(4-羟基苯基)-芴-4-羧酸合成了含羧酸的聚(芳基醚醚酮)(PFEEK-COOH)和聚(芳基醚醚酮)(PFEEKK-COOH)。后一种聚合物 PFEEKK-COOH 经过后磺化处理后得到 SPFEEKK-COOH,磺化的部位和程度(DS 从 0 到 3)可以控制。通过一维和二维核磁共振技术,确定了反应的进展情况和生成的磺化聚合物的结构。利用羧酸基团与聚乙烯醇(PVA)反应交联 SPFEEKK-COOH,制备交联膜。交联的 SPFEEK-COOH-1.6/PVA 膜在 65 °C 时的质子传导率为 0.15 S cm-1,同时在水中保持了可接受的尺寸稳定性。研究了羧化膜、羧化/磺化膜和交联膜的热稳定性、吸水性和质子传导性。