高等学校化学学报

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (11): 1792.

• 论文 • 上一篇    下一篇

聚丙烯酸甲酯及其模型化合物与O2的初始暗氧化反应

董宇平, 丘坤元, 冯新德   

  1. 北京大学化学与分子工程学院, 北京, 100871
  • 收稿日期:1995-11-20 出版日期:1996-11-24 发布日期:1996-11-24
  • 通讯作者: 董宇平,男,32岁,博士,副研究员,现在北京理工大学工作.
  • 作者简介:董宇平,男,32岁,博士,副研究员,现在北京理工大学工作.

The Oxidation of Polymethyl Acrylate and Its Model Compound by Molecular Oxygen in Dark

DONG Yu-Ping, QIU Kun-Yuan, FENG Xin-De   

  1. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871
  • Received:1995-11-20 Online:1996-11-24 Published:1996-11-24

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摘要： 聚丙烯酸甲酯及其模型化合物2-甲基丁酸甲酯与O2能够形成不稳定的接触电荷转移复合物(CCT).在无光照条件下,通O2放置一段时间以后再通N2,CCT吸收峰不再完全消失,其残留峰的强度随存放时间的延长、温度的升高而增加,峰形和峰位与原CCT相似。通过对2-甲基丁酸甲酯氧化产物的分析,证明过氧化反应发生在α-H位置,并有2-甲基丁烯酸甲酯生成。

关键词: 聚丙烯酸甲酯, 2-甲基丁酸甲酯, 接触电荷转移复合物, 初始氧化反应

Abstract: The oxidation of polymethyl acrylate(PMA) and its model compound methyl 2-methylbutyrate with molecular oxygen in dark have been studied.The experimental results showed that the two esters could form a contact charge transfer complex(CCT)with O2 respectively.When O2 was bubbled to solution of ester and kept for several hours and then N2 was bubbled to the solution again,the UVabsorption of the CCTcould not completely disappear and a remaining peak was formed, and the strength of the remaining peak increased with the increasing of time.It indicated that the new compound was produced,and CCT played an important role in the oxidation of the two esters with O2.Furthermore from IR and NMR spectra it was found that the hydroperoxide was formed at the a-Cof methyl 2-methylbutyrate.As well as the unsaturated methyl 2-methylbutenate which was produced in the further oxidation of methyl 2-methylbutyrate with O2.

Key words: Polymethyl acrylate(PMA), 2-Methylbutyrate(MMB), Contact charge transfer complex(CCT), Initial oxidation

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