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<p>Para-aramid thin films face distinct environmental stressors depending on their application, yet conventional compositional optimization often yields inconsistent stability. This work proposes a structure-driven, stressor-matched co-monomer design strategy for para-aramid films by incorporating three functionally distinct co-monomers into the backbone: 4,4′-bis(4-aminophenoxy)biphenyl (BABP) for chain rigidity, 4,4′-(piperazine-1,4-diyl)dianiline (PIPE) for metal interaction, and 6-(4-aminophenoxy)pyridin-3-amine (APA) for photostability. The resulting copolymers (BABP-ARP, PIPE-ARP, and APA-ARP) were paired with their dominant targeted stressors: thermal shock cycling (250&#xa0;°C ↔ − 60&#xa0;°C), metal-ion exposure (FeCl<sub>3</sub>, CuCl<sub>2</sub>, ZnCl<sub>2</sub>), and UV-A photo-aging, respectively.</p><p>While baseline thermal decomposition temperatures (<i>T</i><sub>d5</sub>) remained comparable (483–489&#xa0;°C), each system exhibited a unique response mechanism modulated by co-monomer content. After thermal cycling, BABP-ARP films retained their mechanical and structural integrity, with superior retention at higher BABP content (90&#xa0;mol%). PIPE-ARP films (20&#xa0;mol%) exhibited distinct metal uptake. Specifically, XPS analysis revealed a reduction in N 1s binding energy and counter-ion exchange, indicating electrostatic polarization rather than dative coordination. For APA-ARP, higher APA content (60&#xa0;mol%) significantly improved mechanical retention against UV-induced degradation. These findings demonstrate that co-monomer architecture defines the dominant degradation-resistance mechanism, while its content modulates the response strength, providing a framework for designing task-specific aramid films for extreme environments.</p>

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Stressor-matched co-monomer design: a structure-driven framework for para-aramid thin films targeting industry-specific extreme environments

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月29日

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  • Yeonhae Ryu,
  • Hyeonseo Nam,
  • Jaemin Im,
  • Jaeseo Lee,
  • Deockhyeon Kim,
  • Hyun Ho Choi

摘要

Para-aramid thin films face distinct environmental stressors depending on their application, yet conventional compositional optimization often yields inconsistent stability. This work proposes a structure-driven, stressor-matched co-monomer design strategy for para-aramid films by incorporating three functionally distinct co-monomers into the backbone: 4,4′-bis(4-aminophenoxy)biphenyl (BABP) for chain rigidity, 4,4′-(piperazine-1,4-diyl)dianiline (PIPE) for metal interaction, and 6-(4-aminophenoxy)pyridin-3-amine (APA) for photostability. The resulting copolymers (BABP-ARP, PIPE-ARP, and APA-ARP) were paired with their dominant targeted stressors: thermal shock cycling (250 °C ↔ − 60 °C), metal-ion exposure (FeCl3, CuCl2, ZnCl2), and UV-A photo-aging, respectively.

While baseline thermal decomposition temperatures (Td5) remained comparable (483–489 °C), each system exhibited a unique response mechanism modulated by co-monomer content. After thermal cycling, BABP-ARP films retained their mechanical and structural integrity, with superior retention at higher BABP content (90 mol%). PIPE-ARP films (20 mol%) exhibited distinct metal uptake. Specifically, XPS analysis revealed a reduction in N 1s binding energy and counter-ion exchange, indicating electrostatic polarization rather than dative coordination. For APA-ARP, higher APA content (60 mol%) significantly improved mechanical retention against UV-induced degradation. These findings demonstrate that co-monomer architecture defines the dominant degradation-resistance mechanism, while its content modulates the response strength, providing a framework for designing task-specific aramid films for extreme environments.