后磺化法精确可控合成主链型磺化聚苯喹喔啉及其质子交换膜性能研究

引用本文: 刘璐, 陈康成. 后磺化法精确可控合成主链型磺化聚苯喹喔啉及其质子交换膜性能研究[J]. 高分子学报, 2020, 51(4): 393-402. doi: 10.11777/j.issn1000-3304.2019.19203 shu

Citation: Lu Liu, Kang-cheng Chen. Post-sulfonation for Precisely Controllable Preparation of Main-chain Type Sulfonated Poly(phenylquinoxaline)s and Their Properties for Proton Exchange Membrane[J]. Acta Polymerica Sinica, 2020, 51(4): 393-402. doi: 10.11777/j.issn1000-3304.2019.19203 shu

后磺化法精确可控合成主链型磺化聚苯喹喔啉及其质子交换膜性能研究

刘璐 ,
陈康成 ^,

北京理工大学化学与化工学院　北京 102488

通讯作者: E-mail: chenkc@bit.edu.cn

摘要: 以不同摩尔比的4,4′-双(4-(2-苯基乙二酮基)苯氧基联苯、4,4′-双(2-苯基乙二酮基)二苯醚与3,3′,4,4′-四氨基联苯共聚制备聚喹喔啉，经后磺化法得到一系列磺化度可控的磺化聚苯基喹喔啉(SPPQ). 模型化合物确认，磺酸基团精确接入电子云密度较高的含醚键的联苯片段的2,2′-位上，证明通过单体分子结构设计与后磺化法结合，可使磺酸基团在温和条件下，按预想接入到聚合物主链上，达到磺化度和磺化位置精确可控的目的. SPPQ的相对黏度均在3.8 dL/g以上. 通过溶液涂膜法制备的主链型磺化聚苯基喹喔啉质子交换膜(SPPQ PEM)的吸水率都低于39%，尺寸变化率为2.1% ~ 13%，且随着IEC和温度的提高而线性增加. 如，80 ℃下，IEC高达2.21 meq/g的SPPQ-5的膜面和膜厚方向的尺寸变化率仅为11%和13%，具有良好的形状维持能力. 热重分析表明，SPPQ PEM在320 ℃左右脱去磺酸基团，550 ℃左右发生聚合物主链降解，具有良好的热稳定性. Fenton试剂测试表明，SPPQ PEM开始破碎的时间随IEC的增加而缩短，在20 ℃时，IEC较低的SPPQ-1 (1.29 meq/g)破碎时间可达151 h，而IEC较高的SPPQ-5(2.21 meq/g)破碎时间缩短至81 h. PEM的质子传导率随温度和IEC的增加而显著提高，最高可达64 mS/cm，由于磺酸基团和喹喔啉酸碱对的形成以及吸水率偏低的原因，这一数值远低于Nafion.

关键词:

English

Post-sulfonation for Precisely Controllable Preparation of Main-chain Type Sulfonated Poly(phenylquinoxaline)s and Their Properties for Proton Exchange Membrane

Lu Liu ,
Kang-cheng Chen ^,

School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488

Corresponding author: E-mail: chenkc@bit.edu.cn

Received Date: 02 December 2019
Revised Date: 01 January 2020
Available Online: 01 April 2020

Abstract: A series of main-chain type sulfonated poly(phenylquinoxaline) (SPPQ) were prepared by post-sulfonation of PPQs, which were synthesized from copolymerization of 4,4′ -bis(4-(2-phenylethylenedione)phenoxybiphenyl and 4,4′ -bis(2-phenylethylenedione)diphenylether with 3,3′ ,4,4′ -tetraaminobiphenyl under different molar ratios. They were confirmed by the model compounds that sulfonic acid groups were precisely introduced to the 2,2′-position of the biphenyl fragment with high electron cloud density on SPPQ backbone. Therefore, sulfonic acid groups can be predicablely introduced to the polymer main-chain under mild conditions by the combination of monomer molecular structure design and post-sulfonation proceeding. Relative viscosity of these SPPQs was higher than 3.8 dL/g, indicating their high molecular weight. SPPQ-based proton exchange membranes (PEMs) were prepared by solution casting method. Their properties such as ion exchange capacity (IEC), water uptake, swell ratio, oxidative stability, mechanical properties and proton conductivity were investigated. The TGA results indicated that SPPQ PEMs had good thermal stability with the desulfonic acid groups temperature at about 320 °C and the decompose temperature at about 550 °C. All SPPQ PEMs showed water uptake less than 39% and in-plane swelling ratio linearly increased with increasing IEC and temperature, with the values ranging from 2.1% – 13%. For example, SPPQ-5 with the IEC value up to 2.21 meq/g showed excellent dimensional stability with only 11% and 13% in-plane direction and thickness direction of the swelling ratios at 80 °C, respectively. Free radical oxidative stability test in Fenton reagent showed that the breaking time of SPPQ PEMs decreased with increasing IEC. For example, the SPPQ-1 (1.29 meq/g) has breaking time of over 150 h at 20 °C, whereas the value decreased to 81 h for SPPQ-5 (2.21 meq/g). Proton conductivity of SPPQ PEMs were increased obviously with the increase of temperature and IEC, and the maximum proton conductivity reached 64 mS/cm. The proton conductivities are much lower than that of Nafion NR212, due to the formation of acid-base groups between sulfonic acid groups and quinoxaline groups and the obviously low water uptake of the PEM.

Key words:

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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

后磺化法精确可控合成主链型磺化聚苯喹喔啉及其质子交换膜性能研究

通讯作者: E-mail: chenkc@bit.edu.cn

English

Post-sulfonation for Precisely Controllable Preparation of Main-chain Type Sulfonated Poly(phenylquinoxaline)s and Their Properties for Proton Exchange Membrane

Corresponding author: E-mail: chenkc@bit.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

后磺化法精确可控合成主链型磺化聚苯喹喔啉及其质子交换膜性能研究

通讯作者: E-mail: chenkc@bit.edu.cn

English

Post-sulfonation for Precisely Controllable Preparation of Main-chain Type Sulfonated Poly(phenylquinoxaline)s and Their Properties for Proton Exchange Membrane

Corresponding author: E-mail: chenkc@bit.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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