Covalent metal–organic porous polymer on ZIF-67 realize anti-UV and highly stressed flame retardant epoxy composites

IF 13.3 1区工程技术 Q1 ENGINEERING, CHEMICAL

Chemical Engineering Journal Pub Date : 2024-11-19 DOI:10.1016/j.cej.2024.157758

Jin Cao, Shangxian Chen, Zhengde Han, Ye-Tang Pan, Yichao Lin, Wei Wang, Rongjie Yang

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Abstract

Ferrocene (Fc) and metal–organic frameworks (MOFs) are established as effective functional additives in polymer composites, known for their synergistic effects. However, simple physical mixing does not fully harness their potential. To optimize their performance, we developed a method to graft ferrocene onto zeolitic imidazolate frameworks (ZIFs) via a Schiff base structure, followed by constructing a ferrocene-based covalent metal–organic porous polymer (CMOPP) network using Friedel-Crafts alkylation. This approach addresses the mesoporous structure limitation in ZIFs. During this process, the imidazole ligands are etched, yielding a yolk-shell structured, hierarchically nanoporous flame retardant. The synergy between ferrocene and ZIF significantly enhances the UV protection of epoxy resin, with a 99.1% reduction in UV transmittance. Additionally, ferrocene improves the filler-matrix compatibility, increasing tensile strength by 15.1%. This combination of flame-retardant elements and the porous structure’s adsorption capacity imparts exceptional flame retardancy and smoke suppression to the epoxy resin, evidenced by a Limiting Oxygen Index of 28.3% and a V-0 rating in the UL-94 test. Notable reductions include 56.5% in peak heat release rate, 55.1% in peak smoke production rate, and 71.6% in peak carbon monoxide production. This work introduces a novel strategy for designing high-performance multifunctional flame retardants.

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ZIF-67 上的共价金属有机多孔聚合物实现抗紫外线和高应力阻燃环氧复合材料

二茂铁（Fc）和金属有机框架（MOFs）是聚合物复合材料中有效的功能添加剂，以其协同效应而闻名。然而，简单的物理混合并不能充分发挥它们的潜力。为了优化二茂铁的性能，我们开发了一种方法，通过席夫碱结构将二茂铁接枝到沸石咪唑框架（ZIF）上，然后利用弗里德尔-卡夫烷基化技术构建基于二茂铁的共价金属有机多孔聚合物（CMOPP）网络。这种方法解决了 ZIF 的介孔结构限制。在这一过程中，咪唑配体被蚀刻，产生了卵黄壳结构的分层纳米多孔阻燃剂。二茂铁和 ZIF 的协同作用显著增强了环氧树脂的紫外线防护能力，紫外线透过率降低了 99.1%。此外，二茂铁还能改善填料与基体的相容性，使拉伸强度提高 15.1%。阻燃元素与多孔结构的吸附能力相结合，使环氧树脂具有优异的阻燃性和抑烟性，其极限氧指数为 28.3%，在 UL-94 测试中达到 V-0 级。值得注意的是，这种材料的峰值热释放率降低了 56.5%，峰值烟雾产生率降低了 55.1%，峰值一氧化碳产生率降低了 71.6%。这项研究为高性能多功能阻燃剂的设计引入了一种新策略。

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来源期刊

Chemical Engineering Journal 工程技术-工程：化工

CiteScore

21.70

自引率

9.30%

发文量

6781

审稿时长

2.4 months

期刊介绍： The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.