耐高温含氢乙烯基有机硅树脂的合成及改性

中国塑料 ›› 2025, Vol. 39 ›› Issue (1): 31-36.

耐高温含氢乙烯基有机硅树脂的合成及改性

何文峰,赵彤杰,谢于辉,梅毅,谢德龙

昆明理工大学

收稿日期:2024-04-25 修回日期:2024-05-13 出版日期:2025-01-26 发布日期:2025-01-26
基金资助:
云南省基础研究计划项目;国家自然科学基金地区基金

Synthesis and modification of high-temperature hydrogen-containing vinyl silicone resins

Received:2024-04-25 Revised:2024-05-13 Online:2025-01-26 Published:2025-01-26

摘要/Abstract

摘要： 随着国防工业、电子信息工业以及航空航天等领域的快速发展，对性能优异的耐高温材料的需求不断增加。为此，以含有硅-氢键和硅-乙烯键的烷氧基硅烷为原料，采用简单的两步法在酸性条件下成功制备出了热稳定性较好的含氢乙烯基有机硅树脂。研究了改性有机硅树脂的合成条件，通过红外光谱和热重分析仪表征了其化学结构和热稳定性，并采用热重-红外光谱联用分析了其热解机理。结果显示，三乙氧基硅烷和乙烯基三乙氧基硅烷以摩尔比5/1投料，控制盐酸水溶液的pH值为1、水解温度为30℃、水解时间为3小时制备的有机硅树脂在800℃下残炭质量达到97.84%，远高于一般有机硅树脂的耐高温性能。对有机硅树脂的热解机理分析表明，含氢乙烯基有机硅树脂主要经历两个热分解阶段：首先是253℃左右的由有机硅树脂侧链连接部分引起的乙烯基氧化降解；其次是578℃左右有机硅树脂末端的硅羟基回咬导致有机硅树脂骨架的随机断裂和重排。

Abstract: Silicone resin is a kind of high temperature resistant material with excellent properties, and has broad application prospects in the field of heat resistance With the high-speed silicone resin thermal protection coating in national defense industry, it is difficult to meet the current needs Therefore, it is of great strategic value to improve the high temperature resistance of silicone resin. Thermally stable vinyl silicone resin containing hydrogen was successfully prepared from alkoxysilane containing silicon-hydrogen bond and silicon-ethylene bond by a simple two-step method under acidic conditions The synthesis conditions of modified silicone resin were studied by infrared spectroscopy TG, its chemical structure and thermal stability TG-IR, and its thermal decomposition mechanism The results showed that the synthesis conditions were as follows: triethoxysilane and vinyl triethoxysilane as monomer, ethanol and hydrochloric acid as organic solvent, pH 1, hydrolysis temperature 30 ℃ and hydrolysis time 3 h The remaining 97.84% of silicone resin at 800 ℃ was synthesized under the optimum conditions, and its high temperature resistance was far higher than that of ordinary silicone resin Hydrogen-containing vinyl silicone resin mainly includes two thermal decomposition stages: the first stage occurs at about 253 ℃, which is mainly the oxidative degradation of partial vinyl of side-linked branches of silicone resin; The second stage appeared at 578 ℃, which was mainly caused by the random fracture and rearrangement of SR skeleton caused by the back bite of silicone hydroxyl groups at the end of silicone resin.

何文峰赵彤杰谢于辉梅毅谢德龙. 耐高温含氢乙烯基有机硅树脂的合成及改性[J]. 中国塑料, 2025, 39(1): 31-36.

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