Department of Chemistry, Graduate School of Science, Kyoto University , Kitashirakawa, Sakyo-ku, Kyoto 606-8502, Japan.
Institute for Chemical Research, Kyoto University , Gokasho, Uji-city, Kyoto 611-0011, Japan.
Langmuir. 2016 Dec 20;32(50):13427-13434. doi: 10.1021/acs.langmuir.6b03249. Epub 2016 Dec 8.
Transparent, monolithic aerogels with nanosized colloidal skeletons have been obtained from a single precursor of 1,2-bis(methyldiethoxysilyl)ethane (BMDEE) by adopting a liquid surfactant and a two-step process involving strong-acid, followed by strong-base, sol-gel reactions. This precursor BMDEE forms the ethylene-bridged polymethylsiloxane (EBPMS, O(CH)Si-CHCH-Si(CH)O) network, in which each silicon has one methyl, two bridging oxygens, and one bridging ethylene, exhibiting an analogous structure to that of the previously reported polymethylsilsesquioxane (PMSQ, CHSiO) aerogels having one methyl and three bridging oxygen atoms. Obtained aerogels consist of fine colloidal skeletons and show high visible-light transparency and a flexible deformation behavior against compression without collapse. Similar to the PMSQ aerogels, a careful tuning of synthetic conditions can produce low-density (0.19 g cm) and highly transparent (76% at 550 nm, corresponding to 10 mm thick samples) xerogels via ambient pressure drying by solvent evaporation due to their high strength and resilience against compression. Moreover, EBPMS aerogels exhibit higher bending strength and bending strain at break against the three-point bending mode compared to PMSQ aerogels. This improved bendability is presumably derived from the introduced ethylene-bridging parts, suggesting the potential for realizing transparent and bendable aerogels in such polysiloxane materials with organic linking units.
采用液体表面活性剂和两步法(强酸性,然后是强碱性),从 1,2-双(甲基二乙氧基硅基)乙烷(BMDEE)的单一前体制备出具有纳米胶体骨架的透明整体气凝胶。这种前体 BMDEE 形成了乙烯桥接聚甲基硅氧烷(EBPMS,O(CH)Si-CHCH-Si(CH)O)网络,其中每个硅原子都有一个甲基、两个桥接氧原子和一个桥接乙烯,其结构类似于之前报道的具有一个甲基和三个桥接氧原子的聚甲基倍半硅氧烷(PMSQ,CHSiO)气凝胶。得到的气凝胶由精细的胶体骨架组成,表现出对可见光的高透明度和对压缩的柔性变形行为而不会塌陷。类似于 PMSQ 气凝胶,通过溶剂蒸发在常压下干燥可以精细调节合成条件,以产生低密度(0.19 g cm)和高透明度(550nm 处为 76%,对应于 10mm 厚的样品)的干凝胶,这是由于其高强度和抗压回弹性。此外,与 PMSQ 气凝胶相比,EBPMS 气凝胶在三点弯曲模式下表现出更高的弯曲强度和断裂弯曲应变。这种改善的柔韧性可能源自引入的乙烯桥接部分,表明在具有有机连接单元的此类聚硅氧烷材料中实现透明和可弯曲气凝胶的潜力。