Study on the mechanism of the formation of polyhedral oligomeric silsesquioxanes by the 2D correlation infrared spectral
Study on the mechanism of the formation of polyhedral oligomeric silsesquioxanes by the 2D correlation infrared spectral
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二维相关红外光谱研究多面体低聚倍半硅氧烷的形成机理
DOI：
10.1002/app.36489
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发表时间：
2012-09
影响因子：
3
通讯作者：
Li, Jiali
中科院分区：
文献类型：
--
作者：
Qu, Yanbin;Huang, Guangsu;Wang, Xiaoan;Li, Jiali
利用三官能团有机硅烷[如RSiCl3或RSi(or)3]的水解缩合反应合成多面体低聚硅氧烷（POSS）可能已经取得成功。然而，POSS的确切形成机制，特别是反应的演化过程仍不清楚。在这项工作中，进行了实时FTIR跟踪POSS的合成过程。结果表明，该反应生成了线性硅氧烷、环状硅氧烷和笼状聚硅氧烷。借助广义二维相关分析，我们得到了三种硅烷的精确顺序变化，线性硅最初形成。接着是环状硅氧烷的出现，最后是笼状聚硅氧烷。因此，我们不仅证明了线性硅氧烷和环状硅氧烷的存在，而且准确地检测了过程中硅氧烷的顺序变化，展示了完整而直观的POSS形成演化过程。在此基础上，提出了反应机理。最后，通过29Si-NMR和GPC进一步表征笼状产物的化学结构。(C) 2012 Wiley期刊公司应用高分子学报，2012
Synthesis of polyhedral oligomeric silsesquioxanes (POSS) by the hydrolytic condensation reaction of trifunctional organosilanes [e.g., RSiCl3 or RSi(OR)3] may have achieved success. However, the exact formation mechanism of POSS, especially, an evolution process in the reaction still remains unclear. In this work, a real-time FTIR was carried out to trace the synthesis process of POSS. It was found that linear siloxanes, cyclic siloxanes, and cage-like polysiloxanes were formed during the reaction. With the help of generalized two-dimensional (2D) correlation analysis, we obtained exact sequential change among the three siolxanes, with the linear silicons formed initially. Following this was the emergence of cyclic siloxanes, and finally the cage-like polysiloxanes. Consequently, we not only proved the existence of the linear and cyclic siloxanes but also accurately detected the sequential change of the siloxanes in the process, which exhibited an intact and visual evolution process of POSS formation. Based on this, the reaction mechanism is presented. Finally, the chemical structure of cage-like products was further characterized by 29Si-NMR and GPC measurements. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
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影响因子：
2.3
作者：
Hoflund, GB;Gonzalez, RI;Phillips, SH
通讯作者：
Phillips, SH
影响因子：
2.9
作者：
T. Kudo;M. Gordon
通讯作者：
T. Kudo;M. Gordon
影响因子：
2.3
作者：
Yu. A. Molodtsova;Yulia A. Pozdniakova;K. Lyssenko;I. Blagodatskikh;D. Katsoulis;O. Shchegolikhina
通讯作者：
Yu. A. Molodtsova;Yulia A. Pozdniakova;K. Lyssenko;I. Blagodatskikh;D. Katsoulis;O. Shchegolikhina
影响因子：
6.2
作者：
Lligadas, Gerard;Ronda, Joan C.;Cadiz, Virginia
通讯作者：
Cadiz, Virginia
影响因子：
3.8
作者：
Noda, Isao
通讯作者：
Noda, Isao