氨丙基低聚硅倍半氧烷及其酰胺化产物的合成与表征  

Synthesis and characterization of aminopropyl oligomeric silsesquioxane and its amidation products

作　　者：董佑邦 张泽祺 杨荣杰 DONG Youbang;ZHANG Zeqi;YANG Rongjie(National Engineering Technology Research Center of Flame Retardant Materials,School of Materials,Beijing Institute of Technology,Beijing 100081,China;Zhongyuan Research Center for Flame Retardant Materials,Beijing Institute of Technology,Xuchang 461000,China)

机构地区：[1]北京理工大学材料学院,国家阻燃材料工程技术研究中心,北京100081 [2]北京理工大学,中原阻燃材料研究中心,河南许昌461000

出　　处：《中国塑料》2022年第8期1-9,共9页China Plastics

基　　金：国家自然科学基金(22075020)。

摘　　要：由3⁃氨基丙基三甲氧基硅烷(NH_(2)⁃propyl⁃silane)出发,在碱催化条件下采用水解缩合一锅法合成了笼形氨丙基硅倍半氧烷(NH_(2)⁃propyl⁃POSS)。红外光谱、核磁共振、电喷雾飞行质谱(ESI⁃TOF)表征结果表明,合成产物NH_(2)⁃propyl⁃POSS是不同大小笼形结构的混合物,其中T8、T9、T10笼形结构含量较高。由NH_(2)⁃propyl⁃POSS分别与乙酸和丙炔酸进行酰胺化反应,进一步合成了乙酰基丙基POSS(CH_(3)⁃CONH⁃POSS)和丙炔酰基丙基POSS(CH≡C—CONH⁃POSS),并通过红外光谱、氢谱、碳谱分析表征了其结构。X射线衍射分析结果表明,3种POSS均为非晶态结构。通过热重分析可知,NH_(2)⁃propyl⁃POSS具有较高的热稳定性。将NH_(2)⁃propyl⁃POSS用于提高环氧树脂(EP)的热稳定性,添加量为5%(质量分数,下同)时,EP/NH_(2)⁃propyl⁃POSS共混物的玻璃化转变温度(T_(g))提高至180.7℃,极限氧指数(LOI)为25.2%。Caged aminopropylsilsesquioxane(NH_(2)⁃propyl⁃POSS)was synthesized through one⁃pot hydrolysis⁃condensation under alkali⁃catalyzed conditions using 3⁃aminopropyltrimethoxysilane as a raw material.The obtained products were characterized using infrared spectroscopy,nuclear magnetic resonance,and electrospray ionization⁃time of flight mass spectrometry.The results indicated that the synthesized NH_(2)⁃propyl⁃POSS was a cage⁃structured mixture with different sizes,and the contents of cage structured T8,T9 and T10 were relatively high.Acetylpropyl POSS and propynoyl POSS were further synthesized through the amidation of NH_(2)⁃propyl⁃POSS with acetic acid and propiolic acid,respectively,and their structures were characterized using infrared spectroscopy,^(1)H⁃NMR spectroscopy,and ^(13)C⁃NMR spectroscopy.X⁃ray diffraction analysis indicated that the three POSSs were all amorphous structures.According to the thermal decomposition characteristics obtained from thermogravimetric analysis,NH_(2)⁃propyl⁃POSS showed the highest thermal stability among the three POSSs.NH_(2)⁃propyl⁃POSS was used for epoxy resin(EP)to improve its thermal stability.The EP/NH_(2)⁃propyl⁃POSS blends exhibited a glass transition temperature of 180.7℃ and a limiting oxygen index of 25.2 vol%with the addition of 5 wt%POSS.

关 键 词：氨基硅倍半氧烷 笼型结构 热性能 酰胺化 

分 类 号：TQ322.4[化学工程—合成树脂塑料工业]