Qiunan Xie, Xiaohan Li, Jieying Lin, Feiyu Zhu, Jingcheng Liu, Xiaojie Li, Wei Wei
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Abstract
Although epoxy resin (EP) has been widely used in many fields, it is still urgent to effectively improve its flame retardancy by halogen-free strategies. Herein, a silicon-containing cyclotriphosphazene derivative (HEP-Si) was synthesized by nucleophilic substitution and silicon–hydrogen addition reaction using eugenol, hexachlorophosphazene and triethylsilane as raw materials. Then it served as a halogen-free flame retardant for an EP/4,4′-diaminodiphenylmethane system, and its performance was compared with that of commercial flame retardant hexaphenoxycyclotriphosphazene (HPP). The results showed that although the initial thermal decomposition temperature (T 5% ) of the cured products of EP/HEP-Si was slightly lower than that of pure EP, T 5% did not decrease further as the amount of HEP-Si increased, indicating that good thermal stability was maintained. In addition, the char yield of the cured products of EP/HEP-Si was significantly increased (more than 20 wt%) compared to that of pure EP. The cured EP with the addition of HPP and HEP-Si both achieved a V-0 rating in UL-94 vertical burning test at 0.5 wt% phosphorus content, while the limiting oxygen index of the EP/HEP-Si system was higher, reaching 33.2%. From cone calorimetric test results, the peak heat release rate, total heat release and total smoke production of the cured products of EP/HEP-Si decreased by 61.5%, 37.1% and 26.2%, respectively, compared with that of pure EP. The cured EP/HEP-Si materials also exhibited good thermomechanical and mechanical properties. Therefore, HEP-Si is suggested to be a promising P/N/Si-containing halogen-free flame retardant for EP. © 2024 Society of Industrial Chemistry.
用于环氧树脂阻燃改性的含硅环三磷嗪衍生物的合成
尽管环氧树脂(EP)已被广泛应用于多个领域,但通过无卤策略有效提高其阻燃性能仍是当务之急。本文以丁香酚、六氯磷唑和三乙基硅烷为原料,通过亲核取代和硅氢加成反应合成了一种含硅的环三磷唑衍生物(HEP-Si)。然后将其作为 EP/4,4′-二氨基二苯甲烷体系的无卤阻燃剂,并将其性能与商用阻燃剂六苯氧基环三磷嗪(HPP)进行了比较。结果表明,虽然 EP/HEP-Si 固化产物的初始热分解温度(T5%)略低于纯 EP,但随着 HEP-Si 用量的增加,T5% 并没有进一步降低,这表明其保持了良好的热稳定性。此外,与纯 EP 相比,EP/HEP-Si 固化产物的焦炭产率显著提高(超过 20 wt%)。在含磷量为 0.5 wt% 的 UL-94 垂直燃烧测试中,添加了 HPP 和 HEP-Si 的固化 EP 均达到了 V-0 级,而 EP/HEP-Si 系统的极限氧指数更高,达到了 33.2%。从锥量热测试结果来看,与纯 EP 相比,EP/HEP-Si 固化产品的峰值放热率、总放热量和总产烟量分别降低了 61.5%、37.1% 和 26.2%。固化后的 EP/HEP-Si 材料还具有良好的热机械性能和机械性能。因此,HEP-Si 被认为是一种很有前景的含 P/N/Si 的 EP 无卤阻燃剂。本文受版权保护。
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