{"title":"具有高离子传导性和化学稳定性的基于多环降冰片烯的阴离子交换膜","authors":"Ting Wang , Yu Wang , Wei You","doi":"10.1016/j.memsci.2024.122747","DOIUrl":null,"url":null,"abstract":"<div><p>Polycyclic norbornene derivatives, dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), have rigid structures with ease of accessibility and high chemical reactivity. After vinylic-addition polymerization, the resultant polynorbornenes (PNBs) possess high thermal stability, excellent mechanical integrity, and chemical inertness due to the retention of the rigid polycyclic norbornene motifs along the polymer backbones. Herein, we first report polycyclic PNBs composing DCPD or TCPD and an alkyl-bromide-substituted norbornene as comonomers to prepare high performance anion-exchange membranes (AEMs). The two double bonds in DCPD/TCPD can be used for vinylic-addition polymerization and thiol-ene click cross-linking reactions, respectively. By comparing with previously reported cross-linked PNB AEMs without polycyclic structures, it is unambiguously confirmed that the involvement of DCPD/TCPD significantly improved the mechanical strength (the stress-at-break of 34 MPa <em>vs</em> 28 MPa), the hydroxide conductivity (212 mS cm<sup>−1</sup> <em>vs</em> 199 mS cm<sup>−1</sup> at 90 °C), and the alkaline stability (93 % <em>vs</em> 81 % conductivity remaining after treating in 1 M KOH at 80 °C for 1200 h). The successful application of the AEMs with excellent durability for over 500 h prove that the involvement of polycyclic structures is a convenient strategy to enhance the performance of aromatic-free AEMs.</p></div>","PeriodicalId":368,"journal":{"name":"Journal of Membrane Science","volume":null,"pages":null},"PeriodicalIF":8.4000,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Polycyclic norbornene based anion-exchange membranes with high ionic conductivity and chemical stability\",\"authors\":\"Ting Wang , Yu Wang , Wei You\",\"doi\":\"10.1016/j.memsci.2024.122747\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Polycyclic norbornene derivatives, dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), have rigid structures with ease of accessibility and high chemical reactivity. After vinylic-addition polymerization, the resultant polynorbornenes (PNBs) possess high thermal stability, excellent mechanical integrity, and chemical inertness due to the retention of the rigid polycyclic norbornene motifs along the polymer backbones. Herein, we first report polycyclic PNBs composing DCPD or TCPD and an alkyl-bromide-substituted norbornene as comonomers to prepare high performance anion-exchange membranes (AEMs). The two double bonds in DCPD/TCPD can be used for vinylic-addition polymerization and thiol-ene click cross-linking reactions, respectively. By comparing with previously reported cross-linked PNB AEMs without polycyclic structures, it is unambiguously confirmed that the involvement of DCPD/TCPD significantly improved the mechanical strength (the stress-at-break of 34 MPa <em>vs</em> 28 MPa), the hydroxide conductivity (212 mS cm<sup>−1</sup> <em>vs</em> 199 mS cm<sup>−1</sup> at 90 °C), and the alkaline stability (93 % <em>vs</em> 81 % conductivity remaining after treating in 1 M KOH at 80 °C for 1200 h). The successful application of the AEMs with excellent durability for over 500 h prove that the involvement of polycyclic structures is a convenient strategy to enhance the performance of aromatic-free AEMs.</p></div>\",\"PeriodicalId\":368,\"journal\":{\"name\":\"Journal of Membrane Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":8.4000,\"publicationDate\":\"2024-04-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Membrane Science\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0376738824003417\",\"RegionNum\":1,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Membrane Science","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0376738824003417","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0
摘要
多环降冰片烯衍生物--二环戊二烯(DCPD)和三环戊二烯(TCPD)--具有刚性结构,易于加工,化学反应活性高。在乙烯基加成聚合后,由于聚合物骨架上保留了刚性多环降冰片烯基团,因此生成的聚降冰片烯(PNB)具有高热稳定性、优异的机械完整性和化学惰性。在此,我们首次报道了以 DCPD 或 TCPD 和烷基溴代降冰片烯为共聚单体的多环 PNB,用于制备高性能阴离子交换膜(AEM)。DCPD/TCPD 中的两个双键可分别用于乙烯基加成聚合反应和巯基烯点击交联反应。通过与之前报道的不含多环结构的交联 PNB AEM 比较,可以明确证实 DCPD/TCPD 的参与显著提高了 AEM 的机械强度(断裂应力为 34 兆帕对 28 兆帕)、氢氧化物电导率(90 °C 时为 212 mS cm-1 对 199 mS cm-1)和碱性稳定性(在 80 °C 的 1 M KOH 中处理 1200 小时后,电导率保持率为 93% 对 81%)。这种 AEM 的成功应用证明,多环结构是提高不含芳烃的 AEM 性能的一种便捷策略。
Polycyclic norbornene based anion-exchange membranes with high ionic conductivity and chemical stability
Polycyclic norbornene derivatives, dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), have rigid structures with ease of accessibility and high chemical reactivity. After vinylic-addition polymerization, the resultant polynorbornenes (PNBs) possess high thermal stability, excellent mechanical integrity, and chemical inertness due to the retention of the rigid polycyclic norbornene motifs along the polymer backbones. Herein, we first report polycyclic PNBs composing DCPD or TCPD and an alkyl-bromide-substituted norbornene as comonomers to prepare high performance anion-exchange membranes (AEMs). The two double bonds in DCPD/TCPD can be used for vinylic-addition polymerization and thiol-ene click cross-linking reactions, respectively. By comparing with previously reported cross-linked PNB AEMs without polycyclic structures, it is unambiguously confirmed that the involvement of DCPD/TCPD significantly improved the mechanical strength (the stress-at-break of 34 MPa vs 28 MPa), the hydroxide conductivity (212 mS cm−1vs 199 mS cm−1 at 90 °C), and the alkaline stability (93 % vs 81 % conductivity remaining after treating in 1 M KOH at 80 °C for 1200 h). The successful application of the AEMs with excellent durability for over 500 h prove that the involvement of polycyclic structures is a convenient strategy to enhance the performance of aromatic-free AEMs.
期刊介绍:
The Journal of Membrane Science is a publication that focuses on membrane systems and is aimed at academic and industrial chemists, chemical engineers, materials scientists, and membranologists. It publishes original research and reviews on various aspects of membrane transport, membrane formation/structure, fouling, module/process design, and processes/applications. The journal primarily focuses on the structure, function, and performance of non-biological membranes but also includes papers that relate to biological membranes. The Journal of Membrane Science publishes Full Text Papers, State-of-the-Art Reviews, Letters to the Editor, and Perspectives.