膜科学与技术

亲水链段对磺化聚砜质子交换膜性能的影响

作者：乔宗文

单位：陕西国防工业职业技术学院化工学院, 陕西省西安市 710300

关键词：聚砜；萘磺酸；芘磺酸；相分离；尺寸稳定性

出版年,卷(期):页码： 2020,40(4):49-54

摘要：

在前期的研究中，我们制备了氯甲基化聚砜（CMPSF），紧接着氯甲基分别与2-萘酚-6,8-二磺酸钾（NS）和8-羟基-1,3,6-芘三磺酸三钠（TS）通过亲核取代反应，成功制备了含有不同亲水链段结构的PSF-NS（萘磺酸型磺化聚砜）和PSF-TS（芘磺酸型磺化聚砜），在充分表征的基础上，制备了相应的质子交换膜PEM（Proton Exchange Membrane），探讨了在相同的磺酸基团含量下，亲水链段结构对PEM的性能包括WU（WU，Water Uptaking）、吸水溶胀率（SW, Swelling Ratio）、PC（PC, Proton Conductivity）和抗氧化稳定性等的影响。结果显示：由于亲水基团远离聚合物主链，能够在纳米水平形成类似于Nafion膜的相分离结构，PSF-NS 和PSF-TS PEM在高磺化度下保持良好的尺寸稳定性。在相同的磺酸含量下， PSF-TS由于亲水链段少，吸水效率更高，亲水链段的磺酸基团数目多，有利于吸收的水分的聚集，相分离结构越明显， PSF-TS在高WU下的尺寸稳定性、抗氧化稳定性和阻醇性能更好，其中PSF-TS-3膜在25℃和85℃的溶胀性仅为20.3% 和48.1%，室温时的甲醇扩散系数（DK）仅为 7.54×10-7cm2·s-1，优于商业化Nafion115膜在相同条件下的性能（16.8×10-7cm2/s），所制备的质子交换膜膜材有望用于燃料电池的实际应用，结果对于高性能的膜材设计和制备具有重要意义。

Based on the preparation of chloromethylated polysulfone(CMPSF), two kinds of side chain type sulfonated polysulfone, naphthalenesulfonic acid type polysulfone(PSF-NS) and pyrenesulfonic acid type polysulfone（PSF-TS） with different hydrophilic chain segments were successfully prepared via nulecophilic substitution with 2-naphthol-6,8-disulfonic acid dipotassium(NS) and 8-hydroxy-1,3,6-pyrene trisulfonic acid sodium(TS) as reagents, respectively. After characterizing their structure by the FT-IR and 1H-NMR, the corresponding PSF-NS and PSF-TS PEMs were obtained by solution casting method. The effect of hydrophilic segment structure on performance including water sorption, size stability and proton conductivity of PEMs at the same bonding amount of sulfonic group were explored. The result put up PSF-NS and PSF-TS PEMs keep excellent size stability, antioxidative stability and anti-methanol permeability at high water sorption because they could form micro-phase separation structure similar to Nafion membrane due to the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain.With the same bonding amount of sulfonic acid, PSF-TS has a higher water absorption efficiency due to less hydrophilic chain segment and a larger number of sulfonic acid group PSF in the hydrophilic chain segment, which is conducive to the aggregation of absorbed water and the more obvious phase separation structure. It leads to the PSF-TS present better size stability and anti-oxidative at high water sorption. The swelling ratio of PSF-TS-3 PEM was only 20.3% and 48.1%. Meanwhile, the methanol permeability was only 7.54×10-7cm2·s-1 at room temperature, much lower than commercialization Nafion115 PEM (16.8×10-7cm2/s at room temperature) at the same condition. The PEM is expected to be used in the practical application of fuel cell. The research results are of great significance for the design and preparation of high-performance membrane materials.

第一作者简介：乔宗文（1987-），男，江苏连云港人，博士研究生，副教授，研究方向：功能高分子的合成及性能研究，Tel：15929899061, Email:qiaozongwen@126.com

参考文献：

[1] 连文玉,傅荣强,王伟,张晓丽,李晓玉,刘兆明.直接甲醇燃料电池用双重交联结构聚苯醚基质子交换膜的制备及性能[J].膜科学与技术,2019,39(06):38-45.
[2] 陶丹, 向雄志, 王雷. 磺酸基在侧链萘环上的磺化聚芳醚PEMs的制备与性能研究 [J]. 高分子学报, 2014, 3: 326-332.
[3]杨谦,张瑜兰,张秋根,朱爱梅,刘庆林.高耐碱性交联型聚苯醚阴离子交换膜的制备[J]. 膜科学与技术，2020,03(17): 1-11
[4] Zhang Y, Wan Y, Zhao C J, et al. Novel side-chain-type sulfonated poly(arylene ether ketone) with pendant sulfoalkyl grouPSF for direct methanol fuel cells [J]. Polymer, 2009, 50: 4471-4478.
[5] Zhang Y, Wan Y, Zhao C J, et al. Novel side-chain-type sulfonated poly(arylene ether ketone) with pendant sulfoalkyl grouPSF for direct methanol fuel cells [J]. Polymer, 2009, 50: 4471-4478.
[6] Kobayashi T, Rilukawa M, Sanui K, et al. Proton conducting polymers derived from poly(etheretherketone) and poly(4-phenoxybenzoyl-1,4-phenylene) [J]. Solid State Ionic, 1998, 106: 219-225.
[7] 沈斌, 汪称意, 徐常, 等. 一类侧链型磺化聚芳醚砜质子交换膜的合成及表征[J]. 高分子学报, 2016, 10 : 1409-1417
[8] 乔宗文, 孟龙, 陈涛.萘磺酸型磺化聚砜的制备及质子交换膜基本性能[J].过程工程学报, 2019, 19, 02: 413-418.
[9] 王明娟, 高保娇, 杜俊玫. 萘甲酸功能化聚砜的制备及其与Eu(Ⅲ)稀土离子配合物的荧光发射特性 [J]. 应用化学, 2013, 3: 283-289.
[10] 杜瑞奎, 高保娇, 李延斌等. 聚砜阴离子交换膜的制备及结构与性能研究 [J]. 高分子学报, 2010, 7: 121-128.
[11] Bose S, Kuila T, Nguyen T X, et al. Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges [J]. Pro Polym Sci, 2011, 36: 813-843.
[12] ZHU Y Q, MANTHIRAM A. Synthesis and characterization of polysulfone-containing sulfonated side chains for direct methanol fuel cells [J]. J Power Sources, 2011, 196: 7481-7487.
[13] Zhang B P, Ni J P, Tang X Z, et al. Synthesis and properties of reprocessable sulfonated polyimides cross-linked via acid stimulation for use as proton exchange membranes[J]. J Power Sources. 2017, 337(1): 110-117.
[14] Gong X, Yan X M, Li T T, et al.. Design of pendent imidazolium side chain with flexible ether-containing spacer for alkaline anion exchange membrane[J]. J Membr Sci, 2017, 523(1): 216-224.
[15] Ahnab M K, Lee S B, Min C M, et al. Enhanced proton conductivity at low humidity ofproton exchange membranes with triazole moieties in the side chains[J]. J Membr Sci, 2017, 532, 480-486
[16] Kima K, Junga B K, Koa T, et al. Comb-shaped polysulfones containing sulfonated polytriazole side chains for proton exchange membranes[J]. J Membr Sci, 2018, 554 (15): 232-243.

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