高级检索

  • ISSN 1008-9357
  • CN 31-1633/O6

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

含磺化芴基侧基的聚芳醚氧膦质子交换膜的合成与表征

付志男 谈云龙 肖谷雨 颜德岳

付志男, 谈云龙, 肖谷雨, 颜德岳. 含磺化芴基侧基的聚芳醚氧膦质子交换膜的合成与表征[J]. 功能高分子学报. doi: 10.14133/j.cnki.1008-9357.20210216001
引用本文: 付志男, 谈云龙, 肖谷雨, 颜德岳. 含磺化芴基侧基的聚芳醚氧膦质子交换膜的合成与表征[J]. 功能高分子学报. doi: 10.14133/j.cnki.1008-9357.20210216001
FU Zhinan, TAN Yunlong, XAIO Guyu, YAN Deyue. Synthesis and Characterization of Poly(arylene ether phosphine oxide)s with Pendent Sulfonated Fluorenyl as Proton Exchange Membranes[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20210216001
Citation: FU Zhinan, TAN Yunlong, XAIO Guyu, YAN Deyue. Synthesis and Characterization of Poly(arylene ether phosphine oxide)s with Pendent Sulfonated Fluorenyl as Proton Exchange Membranes[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20210216001

含磺化芴基侧基的聚芳醚氧膦质子交换膜的合成与表征

doi: 10.14133/j.cnki.1008-9357.20210216001
基金项目: 国家自然科学基金(21774073);广东省科技专项资金项目(190805155540379)
详细信息
    作者简介:

    付志男(1994—),女,硕士生,研究方向为质子交换膜的合成与表征。E-mail:chemistryfzn@sjtu.edu.cn

    通讯作者:

    肖谷雨,E-mail:gyxiao@sjtu.edu.cn

  • 中图分类号: O631

Synthesis and Characterization of Poly(arylene ether phosphine oxide)s with Pendent Sulfonated Fluorenyl as Proton Exchange Membranes

  • 摘要: 将9,9-二(4-羟苯基)芴(BHPF)与二(4-氟苯基)苯基氧膦(BFPPO)聚合,合成了含芴基侧基的聚芳醚氧膦(PAEPO),并采用后磺化法,制备了侧链型磺化聚芳醚氧膦(sPAEPO)质子交换膜。通过核磁与红外确定了聚合物的化学结构,用原子力显微镜对sPAEPO的微观结构进行了表征,同时对sPAEPO质子交换膜的尺寸稳定性和质子电导率进行了测试。结果表明,侧基苯环上的磺酸基促使聚合物膜形成亲水相连通性好的微相分离结构,有利于提高质子电导率,并保持低溶胀率,综合性能优良。所得质子交换膜在80 °C下的溶胀率为30%,低于绝大多数非氟质子交换膜的溶胀率,质子电导率为0.075 S/cm,与Nafion 117的质子电导率接近,并且热稳定性与耐氧化性优良。

     

  • 图  1  sPAEPO的合成路线

    Figure  1.  Synthesis route of sPAEPO

    图  2  PAEPO和sPAEPO-100的1H-NMR谱图

    Figure  2.  1H-NMR spectra of PAEPO and sPAEPO-100

    图  3  PAEPO和sPAEPO膜的FT-IR谱图

    Figure  3.  FT-IR spectra of PAEPO and sPAEPO membranes

    图  4  (a)聚合物的热失重曲线;(b)sPAEPO-128的热裂解-气相色谱-质谱图;(c)聚合物的DSC曲线

    Figure  4.  (a) TGA curves of polymers; (b) Pyrolysis-GC-MS spectrum of sPAEPO-128; (c) DSC curves of polymers

    图  5  sPAEPO膜在不同温度下的(a)吸水率和(b)溶胀率

    Figure  5.  (a) Water adsoption and (b) swelling ratio of sPAEPO membranes at various temperatures

    图  6  sPAEPO膜在不同温度下的质子电导率

    Figure  6.  Proton conductivity of sPAEPO membranes at various temperatures

    图  7  (a) sPAEPO-100, (b) sPAEPO-117和(c) sPAEPO-128的AFM相图

    Figure  7.  AFM images of (a) sPAEPO-100, (b) sPAEPO-117, and (c) sPAEPO-128

    表  1  反应物配比及sPAEPO的IEC、磺化度和特性黏度

    Table  1.   Ratios of reactants and IEC, sulfonation degree, and intrinsic viscosity of sPAEPO

    Polymern(Repeat units)∶ n(HSO3Cl)IEC/(meq·g−1)SD/%[η]/(dL·g−1
    sPAEPO-351∶3.00.54351.25
    sPAEPO-741∶3.51.08741.19
    sPAEPO-1001∶4.01.421001.14
    sPAEPO-1171∶4.51.631171.08
    sPAEPO-1281∶5.01.761280.97
    下载: 导出CSV

    表  2  sPAEPO的热稳定性和氧化稳定性

    Table  2.   Thermal stability and oxidative resistance of sPAEPO

    Polymerτ1/hτ2/hRw/%Td5/°C
    sPAEPO-35386999545
    sPAEPO-74266297420
    sPAEPO-100245095357
    sPAEPO-117233895355
    sPAEPO-12882893316
    下载: 导出CSV
  • [1] HICKNER M A, GHASSEMI H, KIM Y S, et al. Alternative polymer systems for proton exchange membranes (PEMs) [J]. Chemical Reviews,2004,104(51):4587-4612.
    [2] WANG S S, LI Q F, WANG F H. reparation and properties of sulfonated poly (2,6-dimethyl-1,4-phenylene oxide)/ionic liquid/phosphoric acid high temperature proton exchange composite membrane [J]. Polymer-Plastics Technology and Materials,2021,60(6):650-658.
    [3] KANG K, KIM D. Pendant dual-sulfonated poly(arylene ether ketone) multi-block copolymer membranes for enhanced proton conductivity at reduced water swelling [J]. Journal of Membrane Science,2019,578:103-110. doi: 10.1016/j.memsci.2019.02.043
    [4] SHARMA P P, TINH V D C, KIM D, et al. Enhanced ion cluster size of sulfonated poly(arylene ether sulfone) for proton exchange membrane fuel cell application [J]. Polymers,2021,13(7):1111. doi: 10.3390/polym13071111
    [5] DHRA G, BALASUBRAMANIAN A, KANNAN T. Polyelectrolyte proton exchange membranes: Synthesis and characterization of sulfonated polyimide membranes using novel stilbene-containing diamine[J]. Polym Bull, DOI: 10.1007/s00289-021-03586-0.
    [6] FU F Y, XU H L, DONG Y, et al. Polyphosphazene-based copolymers containing pendant alkylsulfonic acid groups as proton exchange membranes [J]. Solid State Ionics,2015,278:58-64. doi: 10.1016/j.ssi.2015.05.018
    [7] LIN G, BAI Z X, HAN M G, et al. Tungstophosphoric acid-doped sulfonated poly(arylene ether nitrile)s composite membranes with improved proton conductivity and excellent long-term stability [J]. Solid State Ionics,2020,357:115487. doi: 10.1016/j.ssi.2020.115487
    [8] CHEN S X, PAN H Y, CHANG Z H, et al. Synthesis and study of pyridine-containing sulfonated polybenzimidazole multiblock copolymer for proton exchange membrane fuel cells [J]. Ionics,2019(25):2255-2265. doi: 10.1007/s11581-018-2610-7
    [9] 郭玉飞, 郭志海, 张崇印, 等. 燃料电池用新型磺化聚(醚酮苯并咪唑)共聚物的合成与性能 [J]. 功能高分子学报,2020,33(5):473-482.

    GUO Y F, GUO Z H, ZHANG C Y, et al. Preparation and properties of novel sulfonated poly(ether ketone benzimidazole) copolymers for fuel cells [J]. Journal of Functional Polymers,2020,33(5):473-482.
    [10] LIAO H Y, ZHANG K, TONG G S, et al. Sulfonated poly(arylene ether phosphine oxide)s with various distributions and contents of pendant sulfonic acid groups synthesized by direct polycondensation [J]. Polymer Chemistry,2014(5):412-422.
    [11] TAN Y L, ZhANG K, LIAO H Y, et al. Sulfonated poly(arylene thioether phosphine oxide)s (sPTPO) and sPTPO/sulfonated polybenzothiazole blends as proton exchange membranes [J]. RSC Advances,2016,6:21367-21375.
    [12] 付志男, 谈云龙, 肖谷雨, 等. 含全氟联苯结构的磺化聚二氮杂萘酮醚氧膦质子交换膜的制备与性能 [J]. 高等学校化学学报,2021,42(8):2635-2642.

    FU Z N, TAN Y L, XIAO G Y, et al. Synthesis and properties of sulfonated poly(phthalazinone ether phosphine oxide)s with perfluorobiphenyl moieties for proton exchange membranes [J]. Chemical Journal of Chinese Universities,2021,42(8):2635-2642.
    [13] FU L C, LIAO H Y, XIAO G Y, et al. Sulfonated poly(arylene ether)s with high content of phosphine oxide moieties for proton exchange membranes [J]. Journal of Membrane Science,2012,389:407-415. doi: 10.1016/j.memsci.2011.11.006
    [14] FU L C, XIAO G Y, YAN D Y. High performance sulfonated poly(arylene ether phosphine oxide) membranes by self-protected cross-linking for fuel cells [J]. Journal of Materials Chemistry,2012,22(27):13714-13722. doi: 10.1039/c2jm31659e
    [15] LI N W, WANG C Y, LEE S Y, et al. Enhancement of proton transport by nanochannels in comb-shaped copoly(arylene ether sulfone)s [J]. Angewandte Chemie International Edition,2011,50(39):9158-9161. doi: 10.1002/anie.201102057
    [16] NORSTEN T B, GUIVER M D, MURPHY J, et al. Highly fluorinated comb-shaped copolymers as proton exchange membranes (PEMs): Improving PEM properties through rational design [J]. Advanced Functional Materials,2010,16(14):1814-1822.
    [17] ROWLETT J R, CHEN Y, SHAVER A T, et al. Multiblock poly(arylene ether nitrile) disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes: Part 1 synthesis and characterization [J]. Polymer,2013,54:6305-6313.
    [18] KWON S, Kim T-H. he effect of adjusting the hydrophilicehydrophobic block length in densely sulfonated poly(fluorenyl ether sulfone) block copolymer membranes [J]. International Journal of Hydrogen Energy,2017,42:11845-11856.
    [19] NI C J, WEI Y C, HU Q X, et al. Nanocystalline cellulose reinforced sulfonated fluorenyl-containing polyaryletherketones for proton exchange membranes [J]. Solid State Ionics,2016,297:29-35.
    [20] WANG S J, ZHANG Y F, SHU D, et al. Portable PEMFC stack using sulfonated poly(fluorenyl ether ketone) ionomer as membrane [J]. International Journal of Hydrogen Energy,2012,37:4539-4544.
    [21] FU L C, XIAO G Y, YAN D Y. Sulfonated poly(arylene ether sulfone)s with phosphine oxide moieties: A promising material for proton exchange membranes [J]. ACS Applied Materials & Interfaces,2010,2(6):1601-1607.
    [22] TAN Y L, ZHANG K, LIAO H Y, et al. Trisulfonation approach: To improve the properties of poly(arylene thioether phosphine oxide)s based proton exchange membranes [J]. Journal of Membrane Science,2016,508:32-39. doi: 10.1016/j.memsci.2016.02.020
    [23] 肖磊, 张晨, 何美玉, 等. 后磺化法精确可控制备磺化聚芳醚砜及其质子交换膜性能 [J]. 高等学校化学学报,2018,39(6):1281-1289.

    XIAO L, ZHANG C, HE M Y, et al. Precise controllable post-sulfonation for preparation of sulfonated poly(arylene ether sulfone)s and their properties for proton exchange membrane [J]. Chemical Journal of Chinese Universities,2018,39(6):1281-1289.
    [24] BAE B, YODA T, MIYATAKE K, et al. Proton-conductive aromatic ionomers containing highly sulfonated blocks for high-temperature-operable fuel cells [J]. Angewandte Chemie International Edition,2010,49:317-320. doi: 10.1002/anie.200905355
    [25] SUTRADHAR S C, RAHMAN M M, AHMED F, et al. Improved proton conductive membranes from poly(phenylenebenzophenone)s with pendant sulfonyl imide acid groups for fuel cells [J]. Journal of Power Sources,2019,442:227-233.
  • 加载中
图(7) / 表(2)
计量
  • 文章访问数:  31
  • HTML全文浏览量:  23
  • PDF下载量:  20
  • 被引次数: 0
出版历程
  • 收稿日期:  2021-02-16
  • 网络出版日期:  2021-07-05

目录

    /

    返回文章
    返回