高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (3): 937.doi: 10.7503/cjcu20200470

• 高分子化学 • 上一篇    下一篇

微纳米钙钛矿型羟基锡酸钙的合成及对环氧树脂的阻燃性能

董璐铭1, 苏衍跃1, 王春征1, 乔亚飞1, 陈雅君1,2(), 马海云1,2()   

  1. 1.河北大学化学与环境科学学院, 2. 河北省分析科学技术重点实验室, 3.河北省阻燃材料与加工技术工程技术研究中心, 保定 071002
    4.北京工商大学高分子无卤阻燃剂工程实验室, 北京 100048
  • 收稿日期:2020-07-20 出版日期:2021-03-10 发布日期:2021-03-08
  • 通讯作者: 马海云 E-mail:chenyajun@th.btbu.edu.cn;mahy@hbu.edu.cn
  • 作者简介:陈雅君, 女, 博士, 副教授, 主要从事绿色阻燃体系研究. E-mail: chenyajun@th.btbu.edu.cn
  • 基金资助:
    河北省自然科学基金(E2019201181);北京工商大学高分子无卤阻燃剂工程实验室开放课题(BTBUFR20-5)

Synthesis of Micro- to Nano-scale Perovskite Calcium Hydroxytinate and Its Performance as a Flame Retardant in Epoxy Resin

DONG Luming1, SU Yanyue1, WANG Chunzheng1, QIAO Yafei1, CHEN Yajun1,2(), MA Haiyun1,2()   

  1. 1.College of Chemistry and Environmental Science
    2.Key Laboratory of Analytical Science and Technology of Hebei Province
  • Received:2020-07-20 Online:2021-03-10 Published:2021-03-08
  • Contact: MA Haiyun E-mail:chenyajun@th.btbu.edu.cn;mahy@hbu.edu.cn
  • Supported by:
    ? Supported by the Natural Science Foundation of Hebei Province, China(E2019201181);the Open Project of Engineering Laboratory of Non?halogen Flame Retardants for Polymers, Beijing Technology and Business University, China(BTBUFR20?5)

摘要:

钙钛矿型羟基锡酸盐是近年来出现的新型高效阻燃消烟剂. 本文采用化学共沉淀法合成了微纳米钙钛矿型羟基锡酸钙[CaSn(OH)6, CSH], 并利用扫描电子显微镜、 透射电子显微镜、 X射线衍射仪、 红外光谱仪和X射线光电子能谱仪等对其形貌和结构进行表征. 结果表明合成的CaSn(OH)6为平均粒径500 nm的纯净正六面体, 粒径均一且分散性良好. 将CaSn(OH)6应用于环氧树脂(EP)复合阻燃体系(CSH/EP), 并分别采用热重分析、 极限氧指数和锥形量热测试表征了其热降解行为和燃烧性能. 采用扫描电子显微镜、 红外光谱、 X射线衍射和拉曼光谱对EP复合材料的阻燃成炭机制进行探索. 结果表明, CaSn(OH)6能显著提高EP复合材料的高温稳定性、 热释放速率、 热释放量、 烟释放量和极限氧指数数值. 特别是在很低添加量(0.5%, 质量分数)下, 阻燃消烟性能即得到极大提升, 热释放速率、 总放热量和一氧化碳释放量分别降低45.8%, 25.1%和31.3%. 此外, 由于CaSn(OH)6在EP基体中的良好分散及较强的界面作用, CaSn(OH)6在提升EP复合材料阻燃消烟性的同时还提升了EP复合材料的力学强度. 本文合成的CaSn(OH)6可作为一种多功能的高效阻燃、 消烟和增强剂.

关键词: 环氧树脂, 羟基锡酸钙, 阻燃剂, 钙钛矿

Abstract:

Perovskite hydroxystannate is a new type of flame retardant and smoke suppressant with high efficiency that has appeared in recent years. In this paper, micro- to nano-scale perovskite-type calcium hydroxystannate[CaSn(OH)6, CSH] was synthesized by co-precipitation method. Scanning electron micros-copy, transmission electron microscopy, X-ray diffraction, infrared spectroscopy, and X-ray photoelectron spectroscopy were used to characterize its morphology and structure. The results show that the synthesized CaSn(OH)6 was a pure regular hexahedron with an average particle size of 500 nm, and showed a uniform size and good dispersion. CSH/EP flame retardant composites were prepared by applying CaSn(OH)6 to epoxy resin(EP). Thermogravimetric analysis, limiting oxygen index and cone calorimeter tests were used to characte-rized its thermal degradation behavior and combustion performance, respectively, scanning electron micros-copy, infrared spectroscopy, X-ray diffraction and Raman spectroscopy were used to explore the carbonizing flame retardant mechanism of EP composites. The results show that CaSn(OH)6 could significantly improve the high temperature stability, heat release rate, total heat release, total smoke release and limiting oxygen index value of the EP composites. Especially at very low addition levels(0.5%, mass fraction), the flame retardant and smoke suppression performance were greatly improved, and the heat release rate, total heat release and carbon monoxide release were reduced by 45.8%, 25.1% and 31.3%, respectively. Moreover, due to the good dispersion of CaSn(OH)6 in the EP matrix and the strong interface effect, the addition of CaSn(OH)6 also improved the mechanical strength of the EP composite and enhanced its flame retarancy properties. The CaSn(OH)6 synthesized in this paper can be used as a multi-functional high-efficiency flame retardant, smoke suppression as well as a reinforcing agent for EP resin.

Key words: Epoxy resin, Calcium hydroxystannate, Flame retardant, Perovskite (Ed.: W, K, M)

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