Microporous materials derived from two- and three-dimensional hyperbranched conjugated polymers by thermal elimination of substituents
作者:Norifumi Kobayashi、Masashi Kijima
DOI:10.1039/b707925g
日期:——
Symmetrical and multivalent monomers having thermally degradable alkoxyl groups such as 1,3,5-triethynylbenzene and tetra(4-bromophenyl)silane derivatives were polymerised by certain appropriate methods, i.e. Hay or Sonogashira coupling, which gave hyperbranched poly(phenylenebutadiynylene)s and poly(phenyleneethynylene)s having rigid macrocyclic frameworks in high yields. By heat treating the polymers at about 400 °C, the degradable side chains were selectively eliminated resulting in microporous pyrolytic polymers that showed surface areas of ca. 800 m2 g−1. This result suggests that the spaces resulting from the elimination of the side chains contribute to the generation of the pores of the pyrolytic polymers. In addition, most of the pyrolytic polymers retained their microporosity after further heat treatments at 900 °C, affording microporous carbon.
具有热降解烷氧基(如 1,3,5-三乙炔基苯和四(4-溴苯基)硅烷衍生物)的对称和多价单体通过某些适当的方法(如干草偶联或 Sonogashira 偶联)进行聚合,从而得到高产率的超支化聚(亚苯基丁二炔基)和具有刚性大环框架的聚(亚苯基乙炔基)。通过在 400 °C 左右的温度下对聚合物进行热处理,可降解侧链被选择性地消除,从而产生了微孔热解聚合物,其表面积约为 800 m2 g-1。这一结果表明,消除侧链产生的空间有助于热解聚合物孔隙的形成。此外,大多数热解聚合物在 900 °C下进一步热处理后仍能保持其微孔性,从而产生微孔碳。