化学学报 ›› 2012, Vol. 70 ›› Issue (16): 1737-1742.DOI: 10.6023/A12030047 上一篇    下一篇

研究论文

多面体低聚八硝基苯基硅倍半氧烷纯度分析

范海波, 杨荣杰, 李向梅   

  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
  • 收稿日期:2012-03-22 出版日期:2012-08-28 发布日期:2012-06-08
  • 通讯作者: 杨荣杰

Purity Analysis of Polyhedral Oligomeric Octa(nitrophenyl)silsesquioxane

Fan Haibo, Yang Rongjie, Li Xiangmei   

  1. School of Materials, Beijing Institute of Technology, National Laboratory of Flame Retardant Materials, Beijing 100081
  • Received:2012-03-22 Online:2012-08-28 Published:2012-06-08

使用高效液相色谱-电喷雾四级杆飞行时间质谱(HPLC-ESI-Q-TOF MS)联用技术对八硝基苯基硅倍半氧烷(ONPS)纯度进行分析, 从而判定ONPS产物峰及杂质峰的位置, 根据ONPS峰和杂质峰的面积比计算ONPS的纯度. 通过改变HPLC的洗脱梯度和测试时间, 将ONPS产物中的杂质峰完全分开, 测得硝基苯基硅倍半氧烷(NPS)质量分数为97.55%, 其中ONPS的纯度约为92.42%, 产物中含有九硝基八苯基硅倍半氧烷(9-NPS)约5.13%, 其它杂质含量约为2.45%. 通过对ONPS高效液相色谱图峰形和同分异构体极性情况分析, 进一步证明ONPS分子中硝基取代发生于对位和间位. 使用超高效液相色谱(UPLC)对ONPS进行分析, 以更高的分离效率验证了HPLC的结果. 该方法可作为ONPS纯度的分析方法.

关键词: 八硝基苯基硅倍半氧烷, 纯度分析, 高效液相色谱-质谱, 超高效液相色谱

The purity of polyhedral oligomeric octa(nitrophenyl)silsesquioxane (ONPS) was analyzed using high performance liquid chromatography/ESI-Q-TOF MS (HPLC-ESI-Q-TOF MS). The peaks of ONPS and impurities could be distinguished and the purity of ONPS could be calculated. The impurity peaks of HPLC were separated completely through changing the analytical conditions. The best HPLC conditions in the testing were obtained. The analytical time under these conditions was longer than under others. It was obtained that nitrophenylsilsesquioxane (NPS) was in 97.55 wt%. According to the analytical results from MS and the extracted ion chromatogram (EIC) HPLC-MS for ONPS, it could be found that in ONPS there is a little of nonanitro-octaphenylsilsesquioxane (9-NPS), but no 7-NPS and 10-NPS. It was supposed that ONPS and 9-NPS had the same ionization degree because of their very similar chemical structures. It was obtained that ONPS was in a purity of 92.42%, while the 9-NPS was in an amount of 5.13%, and impurities were in 2.45%. It was confirmed that nitro groups on the phenyl groups were at either para- or meta-position in ONPS according to the results of HPLC and the polarity analysis of different isomers. Compared to centrosymmetric structure of octaphenylsilsesquioxane (OPS), ONPS could be non-centrosymmetric due to difference of -NO2 substitution position on the phenyl groups. All of the possible polarity distributions were analyzed for the ONPS. It was pointed that there are seven kinds of different polarity distributions on ONPS molecules, and they are correspondent to the particular peaks of HPLC results, respectively. As well, the purity of ONPS was analyzed using ultra performance liquid chromatography (UPLC) and it provided consistent results with HPLC in high separation efficiency. It is suggested that the HPLC-ESI-Q-TOF MS method can be used to analyze the purity of ONPS.

Key words: octa(nitrophenyl)silsesquioxane, purity analysis, HPLC-MS, UPLC