Post-Functionalized Vinyl-Addition Polynorbornenes as Modular Platforms for Anion Exchange Membranes: Structure–Property Relationships

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-19 DOI:10.1021/acs.macromol.6c01487

Seungbae Jeon,Eun Woo Lee,Kyulee Jung,Seungjae Lee,Yeongsik Kim,Woohwa Lee,Taehyoung Kim,Hyun Kim,Chang-Geun Chae,Dong-Gyun Kim,Jae Hun Lee,Sungmin Park

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Abstract

Abstract Fully hydrocarbon-based anion exchange membranes (AEMs) were developed through a facile post-polymerization strategy using vinyl-addition polynorbornene (VA-PNB) backbones. A high-molecular-weight poly(5-vinyl-2-norbornene) (PVNB) precursor was synthesized via chemoselective vinyl-addition polymerization, followed by hydrobromination to introduce tunable brominated functionalities. Subsequent thermal treatment enabled crosslinking through residual vinyl groups without additional crosslinkers. By systematically varying the brominated norbornene content (30–90 mol %), the relationships among ionic composition, crosslinking structure, hydration behavior, mechanical properties, and electrochemical performance were investigated. SAXS and TEM analyses revealed phase-separated ionic aggregates with characteristic d-spacings of approximately 1 nm. Increasing ionic-site density enhanced hydroxide transport but also induced excessive swelling and deterioration of mechanical properties under hydrated conditions. Among the membranes investigated, P(VNB-r-NBQA)50 exhibited a balanced combination of dimensional stability, mechanical properties, and electrochemical performance, showing a low area-specific resistance (0.060 Ω·cm2 at 50 °C) and superior alkaline water electrolysis single-cell performance compared with a commercial FAA membrane. The membrane achieved a current density of 3.06 A/cm2 at 2.0 V and 60 °C, which is approximately 15% higher than that of the commercial FAA membrane (2.66 A/cm2) under identical conditions. Although excessive hydration limited long-term operational stability, this study demonstrates that post-functionalized VA-PNBs provide a versatile platform for designing hydrocarbon-based AEMs and offers important insights into balancing ionic conductivity, swelling behavior, and mechanical stability.

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后功能化乙烯加成聚降冰片烯作为阴离子交换膜的模块化平台：结构-性能关系

摘要以乙烯加成聚降冰片烯（VA-PNB）为骨架，通过简单的后聚合策略制备了全烃基阴离子交换膜（AEMs）。采用化学选择性乙烯加成聚合法制备了高分子量聚（5-乙烯基-2-降冰片烯）（PVNB）前驱体。随后的热处理可以通过残余的乙烯基进行交联，而无需额外的交联剂。通过系统地改变溴化降冰片烯的含量（30 ~ 90 mol %），研究了离子组成、交联结构、水化行为、力学性能和电化学性能之间的关系。SAXS和TEM分析显示，相分离的离子聚集体具有约1nm的特征d-间距。离子位密度的增加增强了氢氧化物的输运，但在水合条件下也会引起过度膨胀和力学性能的恶化。在所研究的膜中，P(VNB-r-NBQA)50表现出尺寸稳定性、力学性能和电化学性能的平衡组合，与商用FAA膜相比，具有低的面积比电阻（50°C时0.060 Ω·cm2）和优越的碱性水电解单电池性能。该膜在2.0 V和60℃条件下的电流密度为3.06 a /cm2，比商用FAA膜（2.66 a /cm2）在相同条件下的电流密度高约15%。尽管过度水化限制了长期的运行稳定性，但该研究表明，后功能化va - pnb为设计烃基AEMs提供了一个通用平台，并为平衡离子电导率、膨胀行为和机械稳定性提供了重要见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.