侧链末端为磺酸根基团的磺化改性聚砜的制备及其阳离子交换膜的基本性能  

Preparation of Sulfonation-Modified Polysulfone Containing Sulfonate End Group on Side-Chain and Basic Property of Cation-Exchange Membrane

作　　者：乔宗文 高保娇[1] 陈涛[1] 

机构地区：[1]中北大学化学工程系,太原030051

出　　处：《功能高分子学报》2014年第4期399-407,共9页Journal of Functional Polymers

基　　金：山西省青年科学基金资助项目(2013021009-1)

摘　　要：采用两步一锅法,在聚砜(PSF)主链上键联了末端基为磺酸根基团的侧链,获得了疏水主链与磺酸根基团"微相分离"结构的磺化改性PSF。以氯乙基异氰酸酯(CEIC)为亲电试剂,使PSF主链上的苯环发生付-克烷基化反应,制得侧链含有活性基团—NCO的中间产物聚合物PSFeic;通过活性基团—NCO与对羟基苯磺酸钠(HBSAS)生成氨基甲酸酯的较快速的反应,获得了侧链末端为磺酸根基团的磺化改性聚砜PSF-sas。采用FT-IR、1 H-NMR及紫外分光光度法对目标产物聚合物PSF-sas的化学结构进行了表征。以PSF-sas为膜材,采用流延法制备了PSF阳离子交换膜,测定了交换膜的基本性能,包括离子交换容量、吸水率及质子传导率。研究结果表明,在路易斯酸催化剂作用下,CEIC与PSF主链上苯环之间的付-克烷基化反应可顺利进行,生成中间聚合物产物PSF-eic;以强极性的二甲基乙酰胺(DMAC)为溶剂,反应24h,PSF-eic分子链中乙基异氰酸酯(eic)的键合量可达2.43mmol/g。在此基础上进行第2步反应,可得到磺酸根基团含量为2.23mmol/g的目标产物PSF-sas,所制备的阳离子交换膜,具有高的离子交换容量,适当的吸水率与高的质子传导率。A side chain with sulfonate group as end group was bonded on the backbone of polysulfone （PSF） by two stepsr!＇one pot＂ method. The sulfonation-modified PSF with a micro-phase separation struc- ture was prepared, in which the hydrophobic main-chain and hydrohilic sulfonate groups were in a separate state by locating the sulfonate groups away from the polymer main chains. The Friedel-Cratfs alkylation reaction on benzene ring of PSF backbone was allowed to be carried out with 2-chloroethylisocyanate （CE- IC） as electrophilic reagent, and the intermediate polymer PSF-eic, in whose chain the active group NCO was as electrophilic reagent, and the intermediate polymer PSF-eic, in whose chain the active group --NCO was contained, was obtained. And then a sulfonation-modified polysulfone PSF-sas, in whose side chain sulfonate group was the end group, was prepared through the fast reaction between the active group --NCO and p-hydroxybenzenesulfonic acid sodium （HBSAS）. The chemical structure of the target poly-mer PSF-sas was fully characterized by FT-IR, 1H-NMR and ultraviolet spectrophotometry. PSF cation- exchange membrane was prepared by solution casting method with PSF-sas as membrane material, and the basic properties of the cation-exchange membrane including ion exchange capacity, water uptake and pro- ton conductivity were determined. The experiment results showed that with the action of Lewis acid cata- lyst, the Friedel-Cratfs alkylation reaction between the benzene ring on the main-chain of PSF and CEIC could be carried smoothly, and the intermediate polymer PSF-eic was formed. The content of ethylisocya- nate （eic） group in PSF-eic macromolecular chain could get up to 2.43 mmol/g with dimethylacetamide （DMAC） having strong polarity as solvent and in a reaction period of 24 h. On this basis, through the second step reaction, the target product PSF-sas with a content of sulfonate of 2. 23 mmol/g could be obtained. The prepared cation-exchange membrane had higher ion exchange capacity, wat

关 键 词：聚砜 微相分离 阳离子交换膜 离子交换容量 质子传导率 

分 类 号：O631[理学—高分子化学]