有机磷阻燃剂插层钙基蒙脱土纳米复合物的制备和表征

doi:10.11868/j.issn.1001-4381.2021.000148

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摘要

采用一种简单直接、绿色无溶剂的制备方法，将三种有机磷小分子阻燃剂(9，10-二氢-9-氧杂-10-膦菲-10-氧杂(DOPO)、磷酸三苯酯(TPP)、季戊四醇磷酸酯(PEPA))分别插层进入到钙基蒙脱土(CaMMT)的片层中，制备了三种有机磷阻燃剂的蒙脱土纳米复合物(DOPO-CaMMT，TPP-CaMMT和PEPA-CaMMT)。X射线衍射(XRD)表明三种含磷小分子成功插层进入了蒙脱土的片层中，透射电子显微镜(TEM)验证了三种蒙脱土纳米复合物中蒙脱土的层间距表现出不同程度的增加，热重分析(TGA)表征了纳米复合物热稳定性的变化。对三种纳米复合物的形成机理进行研究。结果表明，TPP和PEPA均以一步插入到蒙脱土片层中；DOPO按照两步插层蒙脱土，且层间距更大。三种有机磷阻燃剂在插层进入蒙脱土层间形成的纳米复合物，实现了蒙脱土在聚合物中更好的分散性及磷硅协同的阻燃效应。

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	秦建雨
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	杨荣杰

关键词 ：钙基蒙脱土, 9，10-二氢-9-氧杂-10-膦菲-10-氧杂, 磷酸三苯酯, 季戊四醇磷酸酯, 纳米复合物, 插层

Abstract：

Three organophosphorus flame retardants (9, 10-dihydro-9-oxa-10-phosphophenanthrene-10-oxa (DOPO), triphenyl phosphate (TPP) and pentaerythritol phosphate (PEPA)) were intercalated into the layer of calcium-based montmorillonite (CaMMT) by a simple, direct and solvent-free method, and three organophosphorus flame retardant montmorillonite nanocompounds (DOPO-CaMMT, TPP-CaMMT and PEPA-CaMMT) were prepared. X-ray diffraction (XRD) shows that the three phosphorus-containing small molecules are successfully intercalated into the layer of CaMMT. It was verified by transmission electron microscope (TEM) that the interlayer spacing of CaMMT in the three nanocompounds shows different degrees of increase. The change of thermal stability of the nanocompounds was characterized by thermogravimetric analysis (TGA). The formation mechanism of the three nanocompounds was studied. The results show that TPP and PEPA are intercalated into CaMMT in one step, while DOPO is intercalated into CaMMT in two steps with a larger interlayer spacing. The nanocompounds formed by the intercalation of three organophosphorus flame retardants into CaMMT layer are expected to achieve better dispersion of CaMMT in polymer and synergistic flame retardant effect of phosphorus and silicon.

Key words： calcium-based montmorillonite 9, 10-dihydro-9-oxa-10-phosphophenanthrene-10-oxa triph-enyl phosphate pentaerythritol phosphate nanocompound intercalation

收稿日期: 2021-02-22 出版日期: 2022-09-20

中图分类号:

TB332

基金资助:国家重点研究发展规划项目(2016YFB0302101)

通讯作者: 杨荣杰 E-mail: yrj@bit.edu.cn

作者简介: 杨荣杰(1962—)，男，教授，研究方向为阻燃高分子材料以及含能材料，联系地址：北京市海淀区中关村南大街五号北京理工大学材料学院(100081)，E-mail: yrj@bit.edu.cn

引用本文:

秦建雨, 赵翰鹏, 姚金雨, 张文超, 杨荣杰. 有机磷阻燃剂插层钙基蒙脱土纳米复合物的制备和表征[J]. 材料工程, 2022, 50(9): 78-88.
Jianyu QIN, Hanpeng ZHAO, Jinyu YAO, Wenchao ZHANG, Rongjie YANG. Preparation and characterization of intercalated calcium-based montmorillonite nanocompounds with organophosphorus flame retardants. Journal of Materials Engineering, 2022, 50(9): 78-88.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.000148 或 http://jme.biam.ac.cn/CN/Y2022/V50/I9/78

Fig.1 DOPO-CaMMT (a)和TPP-CaMMT (b) 纳米复合物和混合物的XRD对比图

Fig.2 PEPA-CaMMT纳米复合物和混合物的XRD对比图

Fig.3 CaMMT(a)，DOPO3-CaMMT1-8 h(b)，TPP5-CaMMT1-8 h(c)和PEPA10-CaMMT1-1 h(d)纳米复合物的TEM照片

Fig.4 DOPO5-CaMMT1(a)和TPP5-CaMMT1(b)纳米复合物形成过程的XRD图谱

Fig.5 PEPA10-CaMMT1纳米复合物形成过程的XRD图谱

Fig.6 DOPO-CaMMT纳米复合物和混合物的TG(a)和DTG(b)曲线

Table 1 DOPO-CaMMT纳米复合物和混合物的热失重参数

Fig.7 TPP-CaMMT纳米复合物和混合物的TG(a)和DTG(b)曲线

Table 2 TPP-CaMMT纳米复合物和混合物的热失重参数

Fig.8 PEPA-CaMMT纳米复合物和混合物的TG(a)和DTG(b)曲线

Table 3 PEPA-CaMMT纳米复合物和混合物的热失重参数

Fig.9 DOPO5-CaMMT1(a)和TPP5-CaMMT1(b)纳米复合物随时间变化的红外曲线

Fig.10 PEPA10-CaMMT1纳米复合物随时间变化的照片

Fig.11 PEPA10-CaMMT1纳米复合物随时间变化的红外曲线

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