应用化学 ›› 2023, Vol. 40 ›› Issue (6): 833-844.DOI: 10.19894/j.issn.1000-0518.230005

• 研究论文 • 上一篇    下一篇

结晶型聚苯乙烯/氢化聚(苯乙烯-丁二烯-苯乙烯)阴离子交换膜的制备、结构及性能

王芙琳, 赵忠夫(), 梁一鸣, 黄见恩, 张春庆()   

  1. 大连理工大学化学工程学院,精细化工国家重点实验室,大连 116024
  • 收稿日期:2023-01-09 接受日期:2023-04-06 出版日期:2023-06-01 发布日期:2023-06-27
  • 通讯作者: 赵忠夫,张春庆

Preparation, Structure and Properties of Crystalline Homo-Polystyrene/Hydrogenated Poly(styrene-b-butadiene-b-styrene) Anion Exchange Membrane

Fu-Lin WANG, Zhong-Fu ZHAO(), Yi-Ming LIANG, Jian-En HUANG, Chun-Qing ZHANG()   

  1. State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Chain

摘要:

以低数均相对分子质量均聚聚苯乙烯(hPS)和氢化聚(苯乙烯-丁二烯-苯乙烯)(HSBS)为原材料,经氯甲基化、季胺化和碱化步骤制备以聚丁二烯加氢得到的结晶相为支撑结构的复合型阴离子交换膜(AEMs),并通过hPS用量调节复合膜的组成、结构及性能。随hPS用量增加,拉伸强度有所降低,杨氏模量由14.68 MPa大幅提升至69.35 MPa,吸水率从17.9%增加到54.3%,而溶胀度仅从4.1%增加到10.2%,借助HSBS结晶结构的支撑,体系的力学性能及尺寸稳定性优于多数聚(苯乙烯-(乙烯-丁二烯)-苯乙烯)(SEBS)基AEMs; 同时,AEMs结晶微区之间的距离增大,离子传输通道拓宽,离子交换容量值从0.82 mmol/g增大至1.94 mmol/g,耐碱稳定性增强; 然而,由于hPS在HSBS中的相容性受HSBS中聚苯乙烯(PS)含量的制约,AEMs的离子电导率值随hPS含量增加呈现出先升后降的变化趋势,其中,氯甲基化HSBS与氯甲基化hPS以质量比8∶2共混制备的AEMs具有最好的离子传输性能,在80 ℃时离子电导率高达101.3 mS/cm,远高于PS含量相同的SEBS体系,在70 ℃下其极化和功率密度曲线开路电压高达0.970 V,功率密度随着电流密度的增加呈现出先升后降的变化趋势,在188 mA/cm2的电流密度下实现了高达299 mW/cm2的功率密度。

关键词: 聚(苯乙烯-丁二烯-苯乙烯), 低数均相对分子质量均聚聚苯乙烯, 阴离子交换膜

Abstract:

Composite anion exchange membranes (AEMs) supported by crystalline poly(ethylene-co-butadiene) phase are prepared from low molecular mass homo-polystyrene (hPS) and hydrogenated poly?(styrene-b-butadiene-b-styrene) (HSBS) by chloromethylation, quaternization and alkalization. The composition, structure and properties of the composite membranes are adjusted by the amount of hPS. The results show that with the increase of hPS content, the tensile strength decreases, the Young′s modulus increases significantly from 14.68 MPa to 69.35 MPa, water uptake (WU) increases from 17.9% to 54.3%, and swelling ratio (SR) increases only from 4.1% to 10.2%. With the support of HSBS crystal structure, the mechanical properties and dimensional stability of the system are better than other poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) based AEMs. Meanwhile, the distance between AEMs′ crystalline micro regions increases, the ion transport channel broadens, the ion exchange capacity (IEC) increases from 0.82 mmol/g to 1.94 mmol/g, and the alkali resistance stability is enhanced. However, because the compatibility of hPS in HSBS is restricted by PS content, CHM-OH-8∶2 has the best ion transport performance (101.3 mS/cm@80 ℃), which is much higher than SEBS system with the same PS content. Its open circuit voltage at 70 ℃ is 0.970 V, and the power density of 299 mW/cm2 is achieved at a current density of 188 mA/cm2.

Key words: Poly(styrene-b-butadiene-b-styrene), Low molecular mass homo-polystyrene, Anion exchange membrane

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