综合采用红外光谱(FTIR)、核磁碳谱(13 C NMR)、差示扫描量热(DSC),热失重测试(TGA)等多种表征手段,研究了聚硅芳炔(PAR)和聚硅乙炔(PMR)两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明:PAR和PMR树脂的...综合采用红外光谱(FTIR)、核磁碳谱(13 C NMR)、差示扫描量热(DSC),热失重测试(TGA)等多种表征手段,研究了聚硅芳炔(PAR)和聚硅乙炔(PMR)两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明:PAR和PMR树脂的固化机理不同,PAR主要通过炔基间的加成和Diels-Alder反应实现分子间的固化交联,并最终形成由苯环和稠芳环组成的芳构网络;PMR则主要通过硅氢基、炔基、烯基之间的加成反应实现固化,并成形饱和的碳硅Si—C(sp3)网络结构。固化成型的芳构网络和Si—C(sp3)网络结构分别赋予了PAR和PMR树脂固化物良好的热稳定性能,它们的热分解温度Td5均大于600℃,900℃残重率均达到85%以上。展开更多
Poly（silanylenediethynylanthracene） （PSDEA） exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The s...Poly（silanylenediethynylanthracene） （PSDEA） exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G（d） level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also decrease in the presence of the electron-withdrawing group on the anthracene ring. The 13C chemical shifts and nucleus independent chemical shifts （NICS） at the anthracene ring center in the oligomers were calculated at B3LYP/6-31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.展开更多
文摘综合采用红外光谱(FTIR)、核磁碳谱(13 C NMR)、差示扫描量热(DSC),热失重测试(TGA)等多种表征手段,研究了聚硅芳炔(PAR)和聚硅乙炔(PMR)两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明:PAR和PMR树脂的固化机理不同,PAR主要通过炔基间的加成和Diels-Alder反应实现分子间的固化交联,并最终形成由苯环和稠芳环组成的芳构网络;PMR则主要通过硅氢基、炔基、烯基之间的加成反应实现固化,并成形饱和的碳硅Si—C(sp3)网络结构。固化成型的芳构网络和Si—C(sp3)网络结构分别赋予了PAR和PMR树脂固化物良好的热稳定性能,它们的热分解温度Td5均大于600℃,900℃残重率均达到85%以上。
文摘Poly（silanylenediethynylanthracene） （PSDEA） exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G（d） level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also decrease in the presence of the electron-withdrawing group on the anthracene ring. The 13C chemical shifts and nucleus independent chemical shifts （NICS） at the anthracene ring center in the oligomers were calculated at B3LYP/6-31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.
