交联型哌啶功能化聚芳醚阴离子交换膜的制备与性能  

Preparation and Properties of Cross-Linked Piperidine Functionalized Polyarylether Anion Exchange Membranes

作　　者：丁梦茹 苏王天慧 周维阳 王磊[2] 李香丹[1] DING Mengru;SU Wangtianhui;ZHOU Weiyang;WANG Lei;LI Xiangdan(College of Chemistry and Materials Science,South-Central Minzu University,Wuhan 430074,China;CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety,National Center for Nanoscience and Technology,Beijing 100190,China)

机构地区：[1]中南民族大学化学与材料科学学院,武汉430074 [2]国家纳米科学中心纳米生物效应与安全性重点实验室,北京100190

出　　处：《功能高分子学报》2022年第4期379-386,I0005,共9页Journal of Functional Polymers

基　　金：国家自然科学基金资助项目(51573031);中南民族大学中央高校项目(CZD19014)。

摘　　要：将氯甲基化率为150%的聚芳醚砜(PSF)依次与对羟基苯甲醇、二氯亚砜反应,通过哌啶季铵化、碱化制备侧链型哌啶功能化聚芳醚砜阴离子交换膜(QPSF-Pip150)。控制交联剂与哌啶的比例,制备不同交联度的交联型阴离子交换膜(cQPSF-Pipx-TAPy)。通过核磁共振氢谱(1HNMR)、傅里叶变换红外光谱(FT-IR)、热重分析(TGA)等对聚合物的结构及性能进行了表征与测试。结果表明:所制得的交联型阴离子交换膜在80℃下的离子传导率最高可达到131.5 mS/cm,而溶胀率仅有19.7%,在60℃、1 mol/L NaOH溶液中浸泡20 d,其离子传导率仍保持初始的73.1%~85.9%。交联有效提高了阴离子交换膜的力学性能、热稳定性、尺寸稳定性和碱性稳定性。Poly(aryl ether sulfone)with chloromethylation rate of 150%(CMPSF150)was synthesized,and then CMPSF150 was reacted with p-hydroxybenzyl alcohol to synthesize side-chain poly(aryl ether sulfone)(PSF-HBA150).Side chain chloromethylated poly(aryl ether sulfone)(PSF-CM150)was synthesized by reaction of PSF-HBA150 with thionyl chloride.PSF-CM150 was quaternized with piperidine and alkalized to prepare side-chain piperidine-functionalized poly(aryl ether sulfone)anion exchange membrane(QPSF-Pip150).Finally,crosslinked anion exchange membrane with different crosslink degree(cQPSF-Pipx-TAPy,x was the mole percentage of functional cation,y was the mole percentage of 2,4,6-tris(dimethylaminomethyl)phenol(TAP))were prepared by controlling the ratio of the crosslinking agent TAP to piperidine.The polymer structure was characterized by 1H-NMR.cQPSF-Pipx-TAPy were insoluble in any solvent,the initial decomposition temperature and tensile strength of cQPSF-Pipx-TAPy increased up to 18°C and 14.7 MPa higher than QPSF-Pip150,respectively.QPSF-Pip150 was completely damaged after soaking in distilled water at 80℃for 48 h,but cQPSF-Pipx-TAPy were intact.The water absorption rates of cQPSF-Pip130-TAP20 and cQPSF-Pip120-TAP30 were 87.4%and 72.5%,the swelling rates of cQPSF-Pip130-TAP20 and cQPSF-Pip120-TAP30 were only 19.7%and 16.4%,respectively.The ionic conductivity of cQPSF-Pip130-TAP20 was up to 131.5 mS/cm at 80℃,while the swelling rate is only 19.7%.Ion exchange capacity and ionic conductivity of cQPSF-Pip130-TAP20 and cQPSF-Pip120-TAP30 still remain 81.7%-91.1%and 73.1%-85.9%after soaking in 1 mol/L NaOH at 60°C for 20 d,respectively.The mechanical properties,thermal stability,dimensional stability and alkaline stability of anion exchange membranes were effectively improved by crosslinking.

关 键 词：交联 聚芳醚砜 哌啶盐 侧链型 阴离子交换膜 

分 类 号：O631[理学—高分子化学]