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2012 , Vol. 70 >Issue 04: 429 - 435

DOI: https://doi.org/10.6023/A1110211

研究论文

多面体低聚八氨基苯基硅倍半氧烷合成方法改进及其表征

  • 范海波 ,
  • 杨荣杰 ,
  • 李定华
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  • 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

收稿日期: 2011-10-21

  修回日期: 2011-11-24

  网络出版日期: 2011-11-30

基金资助

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

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

  • Fan Haibo ,
  • Yang Rongjie ,
  • Li Dinghua
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  • School of Materials, Beijing Institute of Technology, National Laboratory of Flame Retardant Materials, Beijing 100081

Received date: 2011-10-21

  Revised date: 2011-11-24

  Online published: 2011-11-30

Supported by

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

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摘要

以八硝基苯基硅倍半氧烷(ONPS)为原料, 5% Pd/C 和FeCl3 为催化剂, 水合肼为还原剂, 在四氢呋喃溶液中反应 1 h 合成了八氨基苯基硅倍半氧烷(OAPS). 相比文献中已有的其它合成方法, 该方法合成过程简单且稳定, 催化效率高、产率高、周期短. 通过FTIR, 1H NMR, GPC 对产物进行了表征, 证明了硝基已完全转化. 通过催化剂的控制, 分离出ONPS 向OAPS 转化过程中的一种含有羟胺和二羟胺基团的中间体. 分析了OAPS 合成机理, 提出了ONPS 和水合肼的反应历程. 认为ONPS 中的硝基先经过2 电子转移转化为二羟胺化合物, 然后经过脱水加氢生成羟胺化合物, 最后再经过脱水加氢生成OAPS; 在有ONPS 存在的情况下, 水合肼主要转化为氮气和氢气, 待ONPS 完全转化为OAPS 后, 水合肼转化为氮气和氨气.

关键词： 八氨基苯基硅倍半氧烷; 八硝基苯基硅倍半氧烷; 水合肼; 催化

本文引用格式

范海波 , 杨荣杰 , 李定华 . 多面体低聚八氨基苯基硅倍半氧烷合成方法改进及其表征[J]. 化学学报, 2012 , 70(04) : 429 -435 . DOI: 10.6023/A1110211

Abstract

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

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