碳酸氢钠活化过氧化氢对烯烃的环氧化  

Epoxidation of Olefins in Bicarbonate-activated Hydrogen Peroxide System

作　　者：冯树波[1] 王珊珊[1] 孙雅楠[1] 郑二丽[1] 

机构地区：[1]河北科技大学化学与制药工程学院,石家庄050018

出　　处：《应用化学》2011年第7期759-763,共5页Chinese Journal of Applied Chemistry

摘　　要：研究了碳酸氢钠活化H2O2(BAP)体系对苯乙烯和不饱和脂肪酸甲酯的环氧化。分别考察了碳酸氢钠、表面活性剂、加料方式、反应时间、H2O2用量和反应温度对BAP体系H2O2分解和烯烃环氧化的影响。在n(苯乙烯)∶n(H2O2)∶n(NaHCO3)=1∶10∶0.25,阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)质量分数1%,水浴冷却控制体系温度35℃以下,搅拌下缓慢滴加30%H2O2,反应6 h,环氧苯乙烷产率可达85%,选择性96%,仅有少量副产物苯甲醛生成。CTAB可携带活性氧物种HCO-4极大促进苯乙烯环氧化反应转化率。但活性氧物种HCO-4的亲电能力不足以环氧化不饱和脂肪酸甲酯分子中直链的缺电子C C烯键。Epoxidations of styrene and unsaturated fatty acid methyl esters（FAMEs） were studied using bicarbonate-activated hydrogen peroxide（BAP） system.The effects of bicarbonate,surfactants,adding modes of feedstocks,reaction time,the amount of H2O2 and reaction temperature on H2O2 decomposition and olefin epoxidation were investigated,respectively.When the molar ratio of n（styrene）∶n（H2O2）∶n（NaHCO3） is 1∶10∶0.25,the adding amount of cation surfactant cetyl trimethylammonium bromide（CTAB） is 1% mass fraction,the reaction temperature is less than 35 ℃,the reaction time is 6 h with slowly adding 30%H2O2 under stirring,the yield and selectivity of styrene oxide were up to 85% and 96%,respectively,and only a minor amount of benzaldehyde was formed.Cation surfactant CTAB,which carries active oxygen species HCO-4,can significantly promote the styrene conversion.However,the electrophilicity of active oxygen species HCO-4 is not enough to epoxide unsaturated FAMEs molecules with straight chains or containing an electron-defect CC bond.

关 键 词：碳酸氢钠 H2O2活化 烯烃环氧化 绿色工艺 

分 类 号：O621.3[理学—有机化学]