Abstract:

Monovinyl-functionalized silsesquioxane cage, 1,3,5,7,9,11,13-heptacyclopentyl-15-vinyl silsesquioxane(VinylPOSS), was prepared via the corner capping reaction of incompletely condensed silsesquioxanes, (C₅H₉)₇Si₇O₉(OH)₃, with vinyltrichlorosilane.VinylPOSS was characterized by FTIR, ¹H NMR, ²⁹Si NMR, ¹³C NMR, elemental analysis, WAXD and TGA.The yield of VinylPOSS increased with reaction time, when vinyltrichlorosilane reacted with (C₅H₉)₇Si₇O₉(OH)₃ for 10 h, the yield was 90%.VinylPOSS has good solubility in weak polar solvent,and it shows good thermal stability, its temperature with 5% decomposition is 283℃ and the temperature with 56% residue is 800℃.The reactivity of VinylPOSS with high hydrogen-containing silicone fluid (HHSF) was investigated.It can be reacted with HHSF by Michael additions at both α- and β- positions, and the reaction is mainly β-addition.

Key words:

笼型单乙烯基倍半硅氧烷, 热稳定性, 有机-无机杂化材料

摘要：

用环戊基三氯硅烷合成不完全缩合三羟基硅氧烷［(C₅H₉)₇Si₇O₉(OH)₃］，再以乙烯基三氯硅烷和不完全缩合三羟基硅氧烷为原料，以四氢呋喃和三乙胺为混合溶剂，通过“顶角-戴帽”反应合成了笼型单乙烯基倍半硅氧烷，即1,3,5,7,9,11,13-七环戊基-15-乙烯基笼型倍半硅氧烷(VinylPOSS)。利用FTIR、¹H NMR、²⁹Si NMR、¹³C NMR、元素分析、WAXD和TGA表征了VinylPOSS的结构及热稳定性。研究结果表明VinylPOSS的产率随着反应时间的增加而提高，当反应时间为10 h时，产率高达90%；其在弱极性溶剂中具有较好的溶解性，5%失重温度为283℃，800℃残留率为56%，具有较高的热稳定性。研究了VinylPOSS和高含氢硅油(HHSF)的反应性，结果表明VinylPOSS能与含氢硅油发生α、β加成反应, 且以β加成为主。

关键词:

笼型单乙烯基倍半硅氧烷, 热稳定性, 有机-无机杂化材料