高单酯含量的甲基丙烯酸-β-羟乙酯磷酸酯的催化合成

doi:10.11944/j.issn.1000-0518.2015.06.140338

摘要/Abstract

摘要：

采用浸渍法将磷钨酸及其盐[TEAH]₃PW₁₂O₄₀负载到活性炭上制备出HPW/AC和TEAPW/AC 2个系列的催化剂,并用IR、XRD、N₂-吸附脱附和NH₃-TPD等技术手段对它们的结构和酸性进行了表征。进一步,以P₂O₅为磷酸化剂考察了上述催化剂在功能性磷酸酯—甲基丙烯酸-β-羟乙酯磷酸酯合成中的催化性能。结果显示,上述催化剂在该酯化反应中不仅具有很高的活性,而且由于催化剂的微孔结构抑制了双、三酯的生成,明显提高了单酯的选择性。在优化的反应条件和催化剂上,酯化率可达94%,单酯选择性可达95%。且催化剂高度稳定,可以重复使用。该催化剂和催化工艺不仅克服了磷酸酯合成中使用含氯原料的缺点,而且大大提高了产物中单酯的含量。

关键词: 磷酸酯, 多金属氧酸盐, 催化剂, 催化合成

Abstract:

Two series of catalysts, HPW/AC and TEAPW/AC, were prepared by impregnating tungstophosphoric acid and [TEAH]₃PW₁₂O₄₀ solution on active carbon. The structure and acidic property of these catalysts were characterized by IR, XRD, N₂ adsorption-desorption and NH₃-TPD techniques. Then these catalysts were used to catalyze the synthesis of 2-methacryloyloxyethyl phosphate, a functional phosphate, by using P₂O₅ as phosphorylation agent. These catalysts possess not only high activity but also high selectivity for the mono(2-methacryloyloxyethyl) phosphate since the formations of di(2-methacryloyloxyethyl) phosphate and tri(2-methacryloyloxyethyl) phosphate are restricted by the micropores of catalysts. Under the optimum conditions and on the optimal catalyst, the total ester yield and the selectivity of mono(2-methacryloyloxyethyl) phosphate are 94% and 95%, respectively. The catalyst can be isolated and recycled with high stability. This catalytic process not only avoids using chlorine-containing reagent in the synthesis, but also greatly increases monophoshpate content in the product.

Key words: phosphate, polyoxometalates, catalysts, catalytic synthesis

中图分类号:

从云玲, 杨春. 高单酯含量的甲基丙烯酸-β-羟乙酯磷酸酯的催化合成[J]. 应用化学, 2015, 32(6): 658-665.

CONG Yunling, YANG Chun. Catalytic Selective Synthesis of Mono (2-Methacryloyloxyethyl) Phosphate[J]. Chinese Journal of Applied Chemistry, 2015, 32(6): 658-665.

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