Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (04): 429-435.DOI: 10.6023/A1110211 Previous Articles     Next Articles

Full Papers


范海波, 杨荣杰, 李定华   

  1. 北京理工大学材料学院 阻燃材料研究国家专业实验室 北京 100081
  • 投稿日期:2011-10-21 修回日期:2011-11-24 发布日期:2011-11-30
  • 通讯作者: 杨荣杰
  • 基金资助:

    国家863 计划新材料领域项目(No. 2007AA03Z538)资助项目.

Synthesis Improvement and Characterization of Polyhedral Oligomeric Octa(aminophenyl)silsesquioxane

Fan Haibo, Yang Rongjie, Li Dinghua   

  1. School of Materials, Beijing Institute of Technology, National Laboratory of Flame Retardant Materials, Beijing 100081
  • Received:2011-10-21 Revised:2011-11-24 Published:2011-11-30
  • Supported by:

    Project supported by the National High Technology Research and Development Program 863 (No. 2007AA03Z538).

On the 5% Pd/C-FeCl3 catalyst, octa(aminophenyl)silsesquioxane (OAPS) was prepared in tetrahydrofuran (THF) using hydrazine hydrate as reductant from octa(nitrophenyl)silsesquioxane (ONPS) in 1 h. Compared with the synthesis methods in the references, this synthetic process was simple and stable, with shortened reaction period, increased yield and promoted catalytic efficiency. The product was characterized by FTIR, 1H NMR and gel permeation chromatography (GPC) and it was found that nitro groups were completely converted to amino groups. An intermediate with N,N-dihydroxyaminophenyl groups and hydroxylaminophenyl groups was obtained when the only 5% Pd/C was used as catalyst. The synthesis mechanism of OAPS from ONPS was studied based on the intermediate compound. In nitro groups reduction, N,N-dihydroxyaminophenyl groups were firstly formed through two-electron transfer, then hydroxylaminophenyl groups were generated through dehydration/hydrogenation and finally aminophenyl groups were produced after further reduction. At the beginning, hydrazine hydrate was mainly oxidated to N2 and H2, but its oxidative products changed to N2 and NH3 when all of the ONPS were completely converted to OAPS.

Key words: octa(aminophenyl)silsesquioxane, octa(nitrophenyl)silsesquioxane, hydrazine hydrate, catalyst