环己酮绿色氧化制备ε-己内酯的研究进展

doi:10.16085/j.issn.1000-6613.2017.04.036

摘要/Abstract

摘要： ε-己内酯是一种新型聚酯单体，其聚酯具有良好的生物相容性和生物降解性，被广泛应用于生物医学工程、降解塑料等领域。在ε-己内酯的众多制备方法中，环己酮绿色氧化制备ε-己内酯越来越受到人们的关注。本文从氧气和过氧化氢为氧化剂的共氧化和非共氧化体系方面，综述了近年来环己酮绿色氧化制备ε-己内酯的研究进展，从催化剂和副产物处理等方面介绍了各工艺的优缺点，分析了工业化现状和发展趋势，指出以H₂O₂为氧化剂的非共氧化法来合成ε-己内酯是目前最经济、最具发展潜力的合成方法，应该重点研究此方法中涉及的高效稳定的催化剂、反应过程中的高效除水技术。同时展望了使用氧气共氧化法的副产物循环路线和合成ε-己内酯的最理想发展方向应该是分子氧无共氧化剂直接氧化法。

关键词: Bayer-Villiger氧化法, 氧化, ε-己内酯, 环己酮

Abstract: ε-caprolactone is a new kind of polyester monomer. Polyester made from it possess excellent biocompatibility and biodegradability and is used in many fields such as biomedical engineering and biodegradable plastics. Green oxidation cyclohexanone to caprolactone is a research hot topic for preparation of ε-caprolactone. The recent laboratory investigation progress in cyclohexanone green oxidation was reviewed from the aspects of cooxidation and in-cooxidation with oxygen and hydrogen peroxide as oxidizing agents. The merit and demerit were introduced based on the catalyst and coproducts treatment,and the development status and tendency of its industrialization were analyzed. The method of in-cooxidation with hydrogen peroxide is the most economical and of development potential at present,but the key points are the efficient and stable catalyst as well as efficient dehydration technology for the reaction. The cycle route of the coproduction in cooxidation with oxygen was prospected,which should be the optimal way of production ε-caprolactone.

Key words: Bayer-Villiger Dxidation, oxidation, ε-caprolactone, cyclohexanone

中图分类号:

TQ314

闫捷, 赵立红, 宋灿, 蒋元力, 魏灵朝. 环己酮绿色氧化制备ε-己内酯的研究进展[J]. 化工进展, 2017, 36(04): 1424-1428.

YAN Jie, ZHAO Lihong, SONG Can, JIANG Yuanli, WEI Lingchao. Research progress in preparation of ε-caprolactone by cyclohexanone green oxidation[J]. Chemical Industry and Engineering Progress, 2017, 36(04): 1424-1428.

参考文献

[1] SINHAMAHAPATRA A,SINHA A,PAHARI S K,et al. Room temperature Baeyer-Villiger oxidation using molecular oxygen over mesoporous zirconium phosphate[J]. Catalysis Science & Technology,2012,2:2375-2382.
[2] ZANG J,DING Y J,PEI Y P,et al. Efficient Co₃O₄/SiO₂ catalyst for the Baeyer-Villiger oxidation of cyclohexanone[J]. Reaction Kinetics Mechanisms and Catalysis,2014,112:159-171.
[3] RAHMAN S,ENJAMURI N,GOMES R,et al. Aerobic Baeyer-Villiger oxidation of cyclic ketones over periodic mesoporous silica Cu/Fe/Ni/Co-HMS-X[J]. Applied Catalysis A:General,2015,505:515-523.
[4] ZHOU X T,JI H B,YUAN Q L.Baeyer-ViIIiger oxidation of ketones catalyzed by iron(Ⅲ) mesotetraplienylporphyrin chloride in the presence of molecular oxygen[J].Journal of Porphyrins and Phthalocyanines,2008,12(2):94-100.
[5] BELAROUI L S,SOROKIN A B,FIGUERAS F,et al.Comparative Baeyer-Villiger oxidation of cyclohexanone on Fe-pillared clays and iron tetrasulfophthalocyanine covalently supported on silica[J]. Comptes. Rendus. Chimie.,2010,13(4):466-472.
[6] JEONG E Y,ANSARI M B,PARK S E.Aerobic Baeyer-Villiger oxidation of cyclic ketones over metalloporphyrins bridged periodic mesoporous organosilica[J]. American Chemical Society Catalysis,2011,l(8):855-863.
[7] LLAMAS R,JIMÉNEZ-SANCHIDRIÁN C,Ruiz J R. Environmentally friendly Baeyer-Villiger oxidation with H₂O₂/nitrile over Mg(OH)₂ and MgO[J]. Applied Catalysis B:Environmental,2007,72(1/2):l8-25.
[8] LLAMAS R,JIMÉNEZ-SANCHIDRIÁN C,Ruiz J R. Metal hydroxides catalysts for the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide[J]. Reaction Kinetics and Catalysis Letters,2007,90(2):309-313.
[9] LI J X,DAI W L,FAN K N. Formation of ordered mesoporous MgO with tunablepore diameter and its application as excellent alkaline catalyst in Baeyer-Villiger oxidation[J]. The Journal of Physical Chemistry C,2008,112(45):17657-17663.
[10] JIMÉNEZ-SANCHIDRIÁN C,HIDALGO J M,LLAMAS R,et al. Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide/benzonitrile over hydrotalcites as catalysts[J]. Applied Catalysis A:General,2006,312(8):86-94.
[11] CHEN C X,PENG J S,LI B,et al. The catalytic Baeyer-Villiger oxidation of cyclohexanone to caprolactone over stibium-containing hydrotalcite[J]. Catalysis Letters,2009,131(3/4):618-623
[12] BERKESSEL A,ANDREAE M R M. Efficient catalytic methods for the Baeyer-Villiger oxidation and epoxidation with hydrogen peroxide[J]. Tetrahedron Letters,2001,42(12):2293-2295.
[13] LI X Z,CAO R,QI L,Solvent-free Baeyer-Villiger oxidation with H₂O₂ as oxidant catalyzed by multi-SO₃H functionalized heteropolyanion-based ionic hybrids[J]. Catalysis Communications,2015,63:79-83.
[14] BRINK G,VIS J,ARENDS I W C E,et al. Selenium-catalyzed oxidations with aqueous hydrogen peroxide and Baeyer-Villiger reactions in homogeneous solution[J]. Journal of Organic Chemistry,2001,66(7):2429-2433.
[15] GOODMAN M A,DETTY M R. Selenoxides as catalysts for epoxidation and Baeyer-Villiger oxidation with hydrogen peroxide[J]. Synlett.,2006,7:1100-1104.
[16] HAO X,YAMAZAKI O,YOSHIDA A,et al. Green Baeyer-Villiger oxidation with hydrogen peroxide:Sn[N(SO₂C₈F₁₇)₂]₄ as a highly selective Lewis acid catalyst in a fluorous biphase system[J]. Green Chemistry,2003,5(5):524-528.
[17] 杨志旺,马振宏,牛棱渊,等. SBA-15负载硅钨酸催化环己酮Baeyer-Villiger氧化[J]. 催化学报,2011,32(3):463-467. YANG Z W,MA Z H,NIU L Y,et al. Baeyer-Villiger oxidation of cyclohexanone catalyzed bu SBA-15 supported silicotungstic acid[J]. Chin. J. Catal.,2011,32:463-467.
[18] MA Q G,XING W Z,XU J H,et al. Baeyer-Villiger oxidation of cyclic ketones with aqueous hydrogen peroxide catalyzed by transition metal oxides[J]. Catalysis Communications,2014,53:5-8.
[19] CORMA A,NEMETH L T,RENZ M,et al. Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations[J]. Nature,2001,412(6845):423-425.
[20] NEMETH L,MOSCOSO J,ERDMAN N,et al. Synthesis and characterization of Sn-Beta as a selective oxidation catalyst[J]. Studies in Surface Science and Catalysis,2004,154(Part C):2626-2623l.
[21] CORMA A,NAVARRO M T,NEMETH L,et al. Sn-MCM-41——a heterogeneous selective catalyst for the Baeyer-Villiger oxidation with hydrogen peroxide[J]. Chemical Communications,2001,7(21):2190-2191.
[22] CORMA A,NAVARRO M T,RENZ M. Lewis acidic Sn(Ⅳ) centers-grafted onto MCM-41 as catalytic sites for the Baeyer-Villiger oxidation with hydrogen peroxide[J]. Journal of Catalysis,2003,219(1):242-246.
[23] NOWAK I,FELICZAK A,NEKOKSOVÁI,et al. Comparison of oxidation properties of Nb and Sn in mesoporous molecular sieves[J]. Applied Catalysis A:General,2007,321(1):40-48.
[24] LEI Z Q,MA G F,JIA C G. Montmorillonite(MMT) supported tin(Ⅱ) chloride:an efficient and recyclable heterogeneous catalyst for clean and selective Baeyer-Villiger oxidation with hydrogen peroxide[J]. Catalysis Communications,2007,8(3):305-309.
[25] YANG Z W,NIU L Y,MA Z H,et al. Fabrication of highly active Sn/W mixed transition-metal oxides as so1id acid catalysts[J]. Transition Metal Chemistry,2011,36(3):269-274.
[26] 韩文君,孙小玲,秦红玲. 环己酮的Baeyer-Villiger氧化[J]. 上海应用技术学院学报(自然科学版),2007(1):23-27. HAN W J,SUN X L,QIN H L. Baeyer-Villiger oxidization of cyclohexanone[J]. Journal of Shanghai Institute of Technology(Natural Science),2007(1):23-27.
[27] 严生虎,韩玲玲,沈卫,等. 微通道中环己酮氧化合成ε-己内酯的连续流工艺[J],化工进展,2014,33(11):3061-3066. YAN S H,HAN L L,SHEN W,et al. Continuous synthesis process of ε-caprolactone from oxidization of cyclohexanone in micro-channel reactor[J]. Chemical Industry and Engineering Progress,2014,33(11):3061-3066.
[28] 张光旭,张红波,任晓聪,环己酮氧化合成ε-己内酯Mg/Sn复合氧化物催化剂的再生研究[J]. 武汉理工大学学报,2014(5):28-31,42. ZHANG G X,ZHANG H B,REN X C. Regeneration of Mg/Sn composite oxide catalyst on synthesis of ε-caprolactone over oxidation of cyclohexanone[J]. Journal of Wuhan University of Technology,2014(5):28-31,42.
[29] 张光旭,欧华强,胡昌林,等. 固体酸催化合成ε-己内酯的研究Ⅰ.催化剂的表征及其催化性能[J]. 石油化工,2011,40(5):486-491. ZHANG G X,OU H Q,HU C L,et al. Synthesis of ε-caprolactone over solid acid catalysts Ⅰ.Characterization and activity of the catalysts[J]. Petrochemical Technology,2011,40(5):486-491.
[30] ZHANG G X,REN X C,ZHANG H B,et al. MgO/SnO₂/WO₃ as catalysts for synthesis of ε-caprolactone over oxidation of cyclohexanone with peracetic acid[J]. Catalysis Communications,2015,58:59-63.
[31] PRALUS M,LECOQ J C,SCHIRMANN J P. Process for the preparation of epsilon-caprolactone:US 4994583[P]. 1991-02-19.
[32] LECOQ J C,PRALUS M,SCHIRMANN J P. Process for the preparation of ε-caprolactone:US 4740603[P]. 1988-04-26.
[33] 黎树根,李长存. ε-己内酯产业现状及其应用[J]. 合成纤维工业,2013,36(1):46-49. LI S G,LI C C. Industry status and application of ε-caprolactone[J]. China Synthetic Fiber Industry,2013,36(1):46-49.