Synchronous modification of ZIF-67 with cyclomatrix polyphosphazene coating for efficient flame retardancy and mechanical reinforcement of epoxy resin

环氧树脂 阻燃剂 材料科学 聚磷腈 双酚A 涂层 复合材料 单体 高分子化学 缩聚物 磷腈 共聚物 双酚 蚀刻(微加工) 化学工程 图层(电子) 聚合物 工程类
作者
Xiaoning Song,Qianlong Li,Zhengde Han,Boyou Hou,Ye‐Tang Pan,Zhishuai Geng,Jing Zhang,Laia Haurie,Rongjie Yang
出处
期刊:Journal of Colloid and Interface Science [Elsevier BV]
卷期号:667: 223-236 被引量:27
标识
DOI:10.1016/j.jcis.2024.04.088
摘要

Cyclomatrix polyphosphazenes have attracted widespread attention in the field of polymer flame retardancy. Nevertheless, the optimal manifestation of their distinctive structural attributes and flame-retardant properties necessitates a judicious selection of condensation monomers and synergistic templates during the fabrication of polyphosphazene flame retardants. In our previous studies, it was discovered that when ZIF-67 is functionalized with polyphosphazene, the by-product HCl from phosphazene polycondensation causes etching on ZIF-67. Based on this "synchronous etching" effect, a series of hybrid materials comprising cyclomatrix polyphosphazene and ZIF-67, denoted as ZIF-67@PDS (PDS, poly-(cyclotriphosphazene-co-4,4'-diaminodiphenyl sulfone)), ZIF-67@PBS (PBS, poly-(cyclotriphosphazene-co-Bisphenol A)), and ZIF-67@PZS (PZS, poly-(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)), was synthesized utilizing DDS (4,4'-diaminodiphenyl sulfone), BPA (Bisphenol A), and BPS (4,4'-sulfonyldiphenol) monomers as precursors, respectively. Upon the incorporation of 2.0 wt.% of ZIF-67@PDS, ZIF-67@PBS, and ZIF-67@PZS, the flame retardant and mechanical characteristics of EP composites exhibited marked enhancement. The distinctive structural characteristics of hybrid and the synergistic effects of Co-P-N contribute to the improvement of comprehensive properties. Compared with pure EP, EP/ZIF-67@PZS has the best enhancement effect, and its pHRR, THR, and TSP decreased by 34.0%, 30.0%, and 40.5% respectively. In terms of mechanical strength, ZIF-67@PZS also increases the flexural strength of EP by 37.42%. Relying on the "synchronous etching" effect, this study explores and verifies the effective combination of ZIF-67 and different types of polyphosphazenes, and obtains a series of ZIF-67-derived cyclomatrix polyphosphazene hybrids with different morphologies and properties in one step. It provides a new idea and strategy for the simultaneous modification of polyphosphazene materials and the preparation of multifunctional flame retardants in the future.
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