环梯形聚苯基硅倍半氧烷的硝化研究

doi:10.6023/cjoc201612043

有机化学 ›› 2017, Vol. 37 ›› Issue (7): 1870-1876.DOI: 10.6023/cjoc201612043 上一篇下一篇

研究简报

环梯形聚苯基硅倍半氧烷的硝化研究

吴义维, 范海波, 杨荣杰

北京理工大学材料学院国家阻燃材料工程技术研究中心北京 100081

收稿日期:2016-12-14 修回日期:2017-01-20 发布日期:2017-03-03
通讯作者: 杨荣杰 E-mail:yrj@bit.edu.cn
基金资助:
国际科技交流合作（No.S2014ZR0465）、国家自然科学基金（No.51273022）资助项目.

Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane

Wu Yiwei, Fan Haibo, Yang Rongjie

School of Materials Science & Engineering, National Engineering Technology Research Center of Flame Retardant Materials, Beijing Institute of Technology, Beijing 100081

Received:2016-12-14 Revised:2017-01-20 Published:2017-03-03
Contact: 10.6023/cjoc201612043 E-mail:yrj@bit.edu.cn
Supported by:
Project supported by the International Science&Technology Cooperation Program of China (No.S2014ZR0465) and the National Natural Science Foundation of China (No.51273023).

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摘要/Abstract

以环梯形聚苯基硅倍半氧烷（CL-PPSQ）为原料，采用HNO₃-（CH₃CO）₂O硝化体系，在不同的条件下对其进行硝化，制备得到含硝基基团的NO₂-PPSQ.使用GPC、TGA、¹H NMR、FTIR、元素分析等测试手段对硝化产物进行表征.结果表明，75% HNO₃-（CH₃CO）₂O硝化过程温和，硝化能力适中，制备得到分子链不断裂且实现了苯基完全一硝化的硝化产物.对不同硝化试剂的硝化机理进行了分析，在发烟硝酸、HNO₃-H₂SO₄、KNO₃-H₂SO₄中，NO₂⁺为硝化活化剂，硝化能力强，会导致CL-PPSQ分子链断裂；对于HNO₃-（CH₃CO）₂O体系，CH₃COONO₂为主要的硝化活化剂，硝化能力适中.

关键词: 有机-无机杂化材料, 环梯形聚苯基硅倍半氧烷, 硝化反应机理

How to promote polyhedral oligomeric silsesquioxanes (POSS) compatibility with polymers is always the key point of the research on POSS. Introduction of nitro groups into the POSS by nitration is an important method for improving the compatibility between POSS and other polymers. GPC, TGA, ¹H NMR, FTIR and element analysis were used to characterize the structures of the products nitrated from cyclic ladder polyphenylsilsesquioxane (CL-PPSQ) by several kinds of nitration agents, including fuming nitric acid, HNO₃-H₂SO₄, KNO₃-H₂SO₄ and HNO₃-(CH₃CO)₂O. The results showed that NO₂-CL-PPSQ was prepared using 75% HNO₃-(CH₃CO)₂O through a moderate nitration process, meanwhile the cyclic structure of PPSQ was remained, and NO₂-CL-PPSQ of one nitryl group on every phenyl could be prepared. At the same time, the nitration mechanisms using different nitration reagents were analyzed. NO₂⁺, which broke the chemical structure of CL-PPSQ, could be found in the fuming nitric acid and H₂SO₄-HNO₃ (KNO₃) systems. With regard to the HNO₃-(CH₃CO)₂O system, the main activator was CH₃COONO₂ which had appropriate nitration ability. In brief, cyclic ladder polynitrophenylsilsesquioxanes have good solubility in organic solvent, good dispersion in the resin matrix and nitro groups with reaction activity at the same time. The successful synthesis of this polymer provides a precursor for subsequent amination, alkynyl, azide reaction.

Key words: inorganic-organic hybrid materials, cyclic ladder polyphenylsilsesquioxane, nitration mechanism

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吴义维, 范海波, 杨荣杰. 环梯形聚苯基硅倍半氧烷的硝化研究[J]. 有机化学, 2017, 37(7): 1870-1876.

Wu Yiwei, Fan Haibo, Yang Rongjie. Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane[J]. Chin. J. Org. Chem., 2017, 37(7): 1870-1876.

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环梯形聚苯基硅倍半氧烷的硝化研究

Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane

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