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用于制备阻燃、机械强度高、坚韧且透明环氧树脂的磷修饰倍半硅氧烷的设计

Design of P-decorated POSS towards flame-retardant, mechanically-strong, tough and transparent epoxy resins.

作者信息

Wu Tao, Yang Feihao, Tao Jie, Zhao Hai-Bo, Yu Chuanbai, Rao Wenhui

机构信息

College of Materials Science and Engineering, Guilin University of Technology (GUT), Guilin 541004, China.

The Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials (MoE), National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), College of Chemistry, Sichuan University, Chengdu 610064, China.

出版信息

J Colloid Interface Sci. 2023 Jun 15;640:864-876. doi: 10.1016/j.jcis.2023.03.022. Epub 2023 Mar 7.

Abstract

Epoxy resins (EPs) are known for their durability, strength, and adhesive properties, which make them a versatile and popular material for use in a variety of applications, including chemical anticorrosion, small electronic devices, etc. However, EP is highly flammable due to its chemical nature. In this study, phosphorus-containing organic-inorganic hybrid flame retardant (APOP) was synthesized by introducing 9, 10-dihydro-9-oxa-10‑phosphaphenathrene (DOPO) into cage-like octaminopropyl silsesquioxane (OA-POSS) via Schiff base reaction. The improved flame retardancy of EP was achieved by combining the physical barrier of inorganic Si-O-Si with the flame-retardant capability of phosphaphenanthrene. EP composites containing 3 wt% APOP passed the V-1 rating with a value of LOI of 30.1% and showed an apparent reduction in smoke release. Additionally, the combination of the inorganic structure and the flexible aliphatic segment in the hybrid flame retardant provides EP with molecular reinforcement, while the abundance of amino groups facilitates a good interface compatibility and outstanding transparency. Accordingly, EP containing 3 wt% APOP increased in tensile strength, impact strength, and flexural strength by 66.0 %, 78.6 %, and 32.3 %, respectively. The EP/APOP composites had a bending angle lower than 90°, and their successful transition to a tough material highlights the potential of this innovative combination of the inorganic structure and the flexible aliphatic segment. In addition, the relevant flame-retardant mechanism revealed that the APOP promoted the formation of a hybrid char layer containing P/N/Si for EP and produced phosphorus-containing fragments during combustion, showing flame-retardant effects in both condensed and vapor phases. This research offers innovative solutions for reconciling flame retardancy & mechanical performances and strength & toughness for polymers.

摘要

环氧树脂(EPs)以其耐久性、强度和粘合性能而闻名,这使其成为一种用途广泛且受欢迎的材料,可用于各种应用,包括化学防腐、小型电子设备等。然而,由于其化学性质,EP具有高度易燃性。在本研究中,通过席夫碱反应将9,10-二氢-9-氧杂-10-磷杂菲(DOPO)引入笼状八氨基丙基倍半硅氧烷(OA-POSS)中,合成了含磷有机-无机杂化阻燃剂(APOP)。通过将无机Si-O-Si的物理屏障与磷杂菲的阻燃能力相结合,实现了EP阻燃性能的提高。含有3 wt% APOP的EP复合材料通过了V-1等级,极限氧指数(LOI)值为30.1%,并且烟雾释放明显减少。此外,杂化阻燃剂中无机结构和柔性脂肪族链段的结合为EP提供了分子增强作用,而大量的氨基有助于良好的界面相容性和出色的透明度。因此,含有3 wt% APOP的EP的拉伸强度、冲击强度和弯曲强度分别提高了66.0%、78.6%和32.3%。EP/APOP复合材料的弯曲角度低于90°,它们成功转变为韧性材料突出了这种无机结构与柔性脂肪族链段创新组合的潜力。此外,相关的阻燃机理表明,APOP促进了EP形成含P/N/Si的杂化炭层,并在燃烧过程中产生含磷碎片,在凝聚相和气相中均表现出阻燃效果。本研究为协调聚合物的阻燃性与机械性能以及强度与韧性提供了创新解决方案。

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