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Acta Chimica Sinica >

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

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

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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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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

Cite this article

Fan Haibo , Yang Rongjie , Li Dinghua . Synthesis Improvement and Characterization of Polyhedral Oligomeric Octa(aminophenyl)silsesquioxane[J]. Acta Chimica Sinica, 2012 , 70(04) : 429 -435 . DOI: 10.6023/A1110211

References

1 Lickiss, P. D.; Rataboul, F. Adv. Organomet. Chem. 2008, 57, 1.  

2 Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Chem. Rev. 2010, 110, 2081.  

3 Du, J.-K.; Yang, R.-J. Fine Chem. 2005, 6, 409 (in Chinese). (杜建科, 杨荣杰, 精细化工, 2005, 6, 409.)

4 Nagendiran, S.; Alagar, M.; Hamerton, I. Acta Mater. 2010, 58, 3345.  

5 Iyer, P.; Coleman, M. R. J. Appl. Polym. Sci. 2008, 108, 2691.  

6 Choi, J.; Kim, S. G.; Laine, R. M. Macromolecules 2004, 37, 99.  

7 Asuncion, M. Z.; Laine, R. M. Macromolecules 2004, 40, 555.

8 Liu, H. Z.; Zheng, S. X. Macromol. Rapid Commun. 2005, 26, 196.  

9 Guo, H. Q.; Meador, M. A. B.; Mccorkle, L.; Quade, D. J.; Guo, J.; Hamilton, B.; Cakmak, M.; Sprowl, G. ACS Appl. Mater. Interfaces 2011, 3, 546.  

10 Cho, H. S.; Liang, K. W.; Chatterjee, S.; Pittman, C. U. J. Inorg. Organomet. Polym. 2006, 15, 541.

11 Tamaki, R.; Tanaka, Y.; Asuncion, M. Z.; Choi, J.; Laine, R. M. J. Am. Chem. Soc. 2001, 123, 12416.  

12 Ervithayasuporn, V.; Wang, X.; Gacal, B.; Gacal, B. N. J. Organomet. Chem. 2011, 696, 2193.  

13 Du, J.-K. Ph.D. Dissertation, Beijing Institute of Technology, Beijing, 2006 (in Chinese). (杜建科, 博士论文, 北京理工大学, 北京, 2006.)  

14 Zhang, J.; Xu, R. W.; Yu, D. S. J. Appl. Polym. Sci. 2007, 103, 1004.  

15 Ye, C.-C.; Yin, Z.-H.; Gao, H.-L.; Meng, W.; Sun, H. Z. Journal of Central South University of Forestry & Technology 2008, 28, 160 (in Chinese). (叶翠层, 殷作虎, 高海丽, 孟维, 孙汗洲, 中南林业科技 大学学报, 2008, 28, 160.)

16 Fu, G.-Y; Zhang, G.-H; He, X.; Huang, B. New Chem. Mater. 2009, 3, 88 (in Chinese). (付桂云, 张国辉, 何旭, 黄斌, 化工新型材料, 2009, 3, 88.)

17 Chen, M.-W.; Gan, L.-Z. J. East China Institute of Chemical Technology 1985, 11, 105 (in Chinese). (陈敏为, 甘礼骓, 华东化工学院学报, 1985, 11, 105.)

18 Wiener, H.; Sasson, Y.; Blum, J. J. Mol. Catal. 1986, 35, 277.  

19 Larsen, J. W.; Freund, M.; Kim, K. Y.; Sidovar, M.; Stuart, J. L. Carbon 2000, 38, 655.  

20 Zhao, B.; Han, W.-F.; Huo, C.; Liu, H.-Z. J. Zhejiang Univ. Technol. 2004, 32, 131 (in Chinese). (赵波, 韩文峰, 霍超, 刘化章, 浙江工业大学学报, 2004, 32, 131.)

21 Chen, Y.-J. Chemical Reaction Engineering and Technology 2002, 18, 275 (in Chinese). (陈筱金, 化学反应工程与工艺, 2002, 18, 275.)
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