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过程工程学报 ›› 2019, Vol. 19 ›› Issue (2): 413-418.DOI: 10.12034/j.issn.1009-606X.218235

• 材料工程 • 上一篇    下一篇

萘磺酸型磺化聚砜的制备及质子交换膜基本性能

乔宗文1*， 孟 龙1， 陈 涛2   

  1. 1. 陕西国防工业职业技术学院化工学院，陕西 西安 710300 2. 中北大学化工学院，山西 太原 030000
  • 收稿日期:2018-06-21 修回日期:2018-08-16 出版日期:2019-04-22 发布日期:2019-04-18
  • 通讯作者: 乔宗文 qiaozongwen@126.com

Preparation and properties of naphthalenesulfonic acid type polysulfone proton exchange membrane

Zongwen QIAO1*, Long MENG1, Tao CHEN2   

  1. 1. Department of Chemical Engineering, Shaanxi Institute of Technology, Xi'an, Shaanxi 710300, China 2. Department of Chemical Engineering, North University of China, Taiyuan, Shanxi, 030000, China
  • Received:2018-06-21 Revised:2018-08-16 Online:2019-04-22 Published:2019-04-18

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摘要： 以1,4-二氯甲氧基丁烷(BCD)为氯甲基化试剂，通过Fridel?Crafts烷基反应在双酚A型聚砜主链上引入氯甲基基团，制备氯甲基化聚砜(CPS)；以2-萘酚-6,8-二磺酸钾(HNS)为小分子试剂，通过大分子反应制备了侧链含萘环的磺化芳香聚合物 PS-NS，对其结构进行了红外光谱和核磁氢谱表征，优化了反应条件。通过注膜方法制备功能聚合物质子交换膜PEMs，考察了PS-NS膜的吸水率和质子传导率。结果表明，合成反应是单分子亲核取代反应，极性大的二甲基亚砜为适宜的溶剂，在100℃下反应40 h，磺酸基团键合量可达1.51 mmol/g。由于亲水基团远离疏水主链，强化了相分离结构，使PEMs具有较好的吸水率和质子传导率，随磺酸基团含量增加，PEMs的吸水率和溶胀率增加，室温时的吸水率和质子传导率最高达21.3%和0.049 S/cm，满足燃料电池的实际应用要求，与商业化Nafion117膜的性能十分接近。

关键词: 聚砜, 萘磺酸, 尺寸稳定性, 吸水率

Abstract: With 1,4-bischloromethyoxyl butane as chloromethylated reagent, the chloromethylated polysulfone (CPS) was obtained by introducing chloromethyl group onto main chain of bisphenol type A polysulfones (PS) according to Fridel?Crafts alkylation reaction. Subsequently with 2-naphthol-6,8-disulfonic acid dipotassium (HNS) as nucleophilic reagent, the naphthalenesulfonic acid type side chain sulfonated polysulfones (PS-NS) were prepared by nucleophilic substitution reaction. Their chemical structures were characterized by FT-IR and 1H-NMR. The relationship between nucleophilic substitution reaction and factors was explored and the appropriate reaction conditions were found. The corresponding proton exchange membranes (PEMs) were fabricated by solution casting method and the basic properties of PEMs including water uptaking and proton conductivity were explored. The results showed that the nucleophilic substitution reaction was SN1 reaction. The appropriate reaction solvent was dimethyl sulfoxide (DMSO) which had strong polarity, the appropriate reaction temperature was 100℃ and the appropriate reaction time was 40 h. The bonding amount of sulfonate acid group reached up to 1.51 mmol/g at the appropriate reaction conditions. The corresponding PEMs indicated excellent water uptaking and proton conductivity due to the side chains structure enhancing the degree of micro-phase by locating the sulfonic acid groups far away from the hydrophobic polysulfone main chains. The water uptaking and proton conductivity of PEMs increased with the bonding amount of sulfonic acid group increasing. The water uptaking and proton conductivity of PEMs reached up to 21.3% and 0.049 S/cm at room temperature, respectively. The properties of PEMs could meet the demand of actual application of proton exchange membrane fuel cells, and these properties were very close to the commercialized Nafion117 series proton exchange membranes.

Key words: Polysulfone, Naphthalenesulfonic acid, Dimensional stability, water uptake