应用化学 ›› 2011, Vol. 28 ›› Issue (07): 759-763.DOI: 10.3724/SP.J.1095.2011.00458

• 研究论文 • 上一篇    下一篇

碳酸氢钠活化过氧化氢对烯烃的环氧化

冯树波*,王珊珊,孙雅楠,郑二丽   

  1. (河北科技大学化学与制药工程学院 石家庄 050018)
  • 收稿日期:2010-08-17 修回日期:2010-11-25 出版日期:2011-07-10 发布日期:2011-07-10
  • 通讯作者: 冯树波,研究员; Tel:0311-88632291; Fax:0311-88632242; E-mail:fengsb@263.net; 研究方向:催化反应过程与工艺和清洁化工

Epoxidation of Olefins in Bicarbonate-activated Hydrogen Peroxide System

FENG Shubo*, WANG Shanshan, SUN Yanan, ZHENG Erli   

  1. (College of Chemical and Pharmaceutical Engineering,Hebei University of
    Science and Technology,Shijiazhuang, 050018)
  • Received:2010-08-17 Revised:2010-11-25 Published:2011-07-10 Online:2011-07-10

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。

关键词: 碳酸氢钠, H2O2活化, 烯烃环氧化, 绿色工艺

Abstract:

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 C=C bond.

Key words: bicarbonate, H2O2 activation, olefin epoxidation, green process

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