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芳基氨基磷腈作为阻燃剂及苯并恶嗪聚合催化剂的合成与应用

Synthesis and Application of Arylaminophosphazene as a Flame Retardant and Catalyst for the Polymerization of Benzoxazines.

作者信息

Bornosuz Natalia V, Gorbunova Irina Yu, Kireev Vyacheslav V, Bilichenko Yulya V, Chursova Larisa V, Svistunov Yuri S, Onuchin Denis V, Shutov Vyacheslav V, Petrakova Viktoria V, Kolenchenko Alexander A, Nguyen Duong T, Pavlov Nikolay V, Orlov Alexey V, Grebeneva Tatyana A, Sirotin Igor S

机构信息

Mendeleev University of Chemical Technology of Russia, 125047 Moscow, Russia.

Prepreg-ACM JSC (Part of UMATEX, Rosatom State Corporation), 109316 Moscow, Russia.

出版信息

Polymers (Basel). 2021 Jan 14;13(2):263. doi: 10.3390/polym13020263.

Abstract

A novel type of phosphazene containing an additive that acts both as a catalyst and as a flame retardant for benzoxazine binders is presented in this study. The synthesis of a derivative of hexachlorocyclotriphosphazene (HCP) and meta-toluidine was carried out in the medium of the latter, which made it possible to achieve the complete substitution of chlorine atoms in the initial HCP. Thermal and flammability characteristics of modified compositions were investigated. The modifier catalyzes the process of curing and shifts the beginning of reaction from 222.0 °C for pure benzoxazine to 205.9 °C for composition with 10 phr of modifier. The additive decreases the glass transition temperature of compositions. Achievement of the highest category of flame resistance (V-0 in accordance with UL-94) is ensured both by increasing the content of phenyl residues in the composition and by the synergistic effect of phosphorus and nitrogen. A brief study of the curing kinetics disclosed the complex nature of the reaction. An accurate two-step model is obtained using the extended Prout-Tompkins equation for both steps.

摘要

本研究介绍了一种新型磷腈,其含有一种添加剂,该添加剂对苯并恶嗪粘合剂兼具催化剂和阻燃剂的作用。六氯环三磷腈(HCP)与间甲苯胺的衍生物合成是在后者的介质中进行的,这使得初始HCP中的氯原子能够完全被取代。研究了改性组合物的热性能和燃烧性能。该改性剂催化固化过程,并使反应起始温度从纯苯并恶嗪的222.0℃转变为含有10 phr改性剂的组合物的205.9℃。该添加剂降低了组合物的玻璃化转变温度。通过增加组合物中苯基残基的含量以及磷和氮的协同作用,确保达到最高阻燃等级(符合UL - 94标准的V - 0级)。对固化动力学的简要研究揭示了反应的复杂性。使用扩展的Prout - Tompkins方程对两个步骤均获得了精确的两步模型。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/81f8/7830697/287d4ab7c671/polymers-13-00263-g001.jpg

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