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化学进展 2023, Vol. 35 Issue (8): 1191-1198 DOI: 10.7536/PC221209 前一篇   后一篇

• 综述 •

1,6-己二醇选择氧化内酯化制备ε-己内酯

申小雨1, 杜中田1,*(), 郭百睿1, 郭忠旭1, 梁长海1,2,*()   

  1. 1 大连理工大学化工学院 盘锦 124221
    2 大连理工大学精细化工国家重点实验室 大连 116023
  • 收稿日期:2022-12-15 修回日期:2023-05-08 出版日期:2023-08-24 发布日期:2023-07-18
  • 作者简介:

    杜中田 毕业于中国科学院大连化学物理研究所,获理学博士学位,现就职于大连理工大学。主要从事选择氧化和催化新材料方面的应用基础研究,已在相关领域发表研究论文30余篇,并有多项中国发明专利获得授权。先后主持承担了国家自然科学基金项目3项、辽宁省自然科学基金项目2项,参与企业项目多项。

  • 基金资助:
    国家自然科学基金项目(22172010); 中央高校基本科研业务费(DUT2021TD103)
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Selective Oxidative Lactonization of 1,6-Hexanediol into ε-Caprolactone

Xiaoyu Shen1, Zhongtian Du1(), Bairui Guo1, Zhongxu Guo1, Changhai Liang1,2()   

  1. 1 School of Chemical Engineering, Dalian University of Technology,Panjin 124221, China
    2 State Key Laboratory of Fine Chemicals, Dalian University of Technology,Dalian 116023, China
  • Received:2022-12-15 Revised:2023-05-08 Online:2023-08-24 Published:2023-07-18
  • Contact: *e-mail: duzhongtian@dlut.edu.cn(Zhongtian Du);changhai@dlut.edu.cn(Changhai Liang)
  • Supported by:
    National Natural Science Foundation of China(22172010); Fundamental Research Funds for the Central Universities(DUT2021TD103)

ε-己内酯是合成聚己内酯(PCL)等聚合物的关键单体,相关高分子材料具有良好的生物降解性和兼容性,在生物医药、环保材料等领域具有重要应用。ε-己内酯的绿色廉价制备是制约这类材料广泛使用的重要因素,其中1,6-己二醇选择氧化内酯化制备ε-己内酯有待进一步发展。本文分析对比了环己酮Baeyer-Villiger氧化法和1,6-己二醇氧化内酯化法制备ε-己内酯的优缺点,按照反应体系中是否加入电子受体(氧化剂)分类介绍了国内外1,6-己二醇选择氧化内酯化制备ε-己内酯相关的研究进展,并对相应反应体系、所用催化剂的优缺点进行了评述,最后对该转化过程的发展趋势进行了展望。

关键词： 聚己内酯, ε-己内酯, 1,6-己二醇, 催化氧化, 催化脱氢, 分子氧

ε-Caprolactone is a key monomer for the synthesis of poly(ε-caprolactone) (PCL) with good biocompatibility and biodegradability, and relevant polymer materials could be applied in pharmaceutical, medicinal, and packaging applications. Green and economic synthesis of ε-caprolactone is vital to popularize such eco-friendly polymers, and selective oxidative lactonization of 1,6-hexanediol into ε-caprolactone remains to be developed. In this review, different routes for the synthesis of ε-caprolactone such as Baeyer-Villiger oxidation of cyclohexanone and oxidative lactonization of 1,6-hexanediol are comparatively analyzed. According to whether electron acceptors (oxidants) are added to the reaction systems, the related advances of oxidative lactonization of 1,6-hexanediol are summarized, and the advantages and disadvantages of the corresponding reaction systems and catalysts are reviewed. The development trend of oxidative lactonization of 1,6-hexanediol into ε-caprolactone is also proposed.

Contents

1 Introduction

2 Catalytic oxidation processes

2.1 Carbonyl compounds act as electron acceptors

2.2 Molecular oxygen acts as the electron acceptor

2.3 H2O2 acts as the oxidant

3 Catalytic dehydrogenation

3.1 Homogeneous catalysts

3.2 Heterogeneous catalysts

4 Conclusion and outlook

Key words: poly(ε-caprolactone), ε-caprolactone, 1,6-hexanediol, catalytic oxidation, catalytic dehydrogenation, molecular oxygen
()
图1 有机过氧酸氧化环己酮制备ε-己内酯
Fig. 1 Oxidation of cyclohexanone into ε-caprolactone via Baeyer-Villiger oxidation
图2 从结构和组成角度对比分别从1,6-己二醇和环己酮制备ε-己内酯的路线
Fig. 2 The preparation routes of ε-caprolactone from 1,6-hexadiol and cyclohexanone compared from the perspective of structure and composition
图3 1,6-己二醇氧化内酯化制备ε-己内酯常见的反应路径
Fig. 3 Reaction pathway from 1,6-hexanediol to ε-caprolactone
图4 [{Ru(cymene)Cl2}2]/DPPF催化氧化1,6-己二醇制备ε-己内酯[26,27]
Fig. 4 [{Ru(cymene)Cl2}2]/DPPF catalyzed oxidation of 1,6-hexanediol to ε-caprolactone[26,27]
图5 环己酮和1,6-己二醇耦合氧化生成ε-己内酯[32]
Fig. 5 The coupled oxidation of 1,6-hexanediol and cyclohexanone to produce ε-caprolactone[32]
图6 从5-羟甲基糠醛出发制备ε-己内酯[37]
Fig. 6 Preparation of ε-caprolactone from 5-hydroxymethylfurfural[37]
图7 仿生催化氧化1,6-己二醇制备ε-己内酯[39]
Fig. 7 Biomimetic aerobic oxidation of 1,6-hexanediol into ε-caprolactone[39]
图8 Co@C-N(800)催化1,6-己二醇转化为ε-己内酯反应[43]
Fig. 8 Co@C-N(800) catalyzed oxidative lactonization of 1,6-hexanediol into ε-caprolactone[43]
图9 氯化十六烷基吡啶/磷钨酸催化1,6-己二醇制备ε-己内酯反应[45]
Fig. 9 Cetylpyridinium chloride/tungstophosphate-catalysed 1,6-hexanediol to ε-caprolactone[45]
图10 1,6-己二醇催化脱氢内酯化示意图
Fig. 10 Catalytic dehydrogenative lactonization of 1,6-hexanediol
图11 Fe-MACHO-BH催化1,6-己二醇制备ε-己内酯[47]
Fig. 11 Fe-MACHO-BH catalyzed dehydrogenative lactonization of 1,6-hexanediol to ε-caprolactone[47]
表1 1,6-己二醇氧化内酯化为ε-己内酯反应的原子经济性、理论副产物、可能安全隐患的对比1)
Table 1 Comparison of atom economy, theoretical by-products, and possible safety hazards in oxidative lactonization of 1,6-hexanediol into ε-caprolactone1)
Electron acceptors Atom utilization [%] Theoretical by-product Possible safety hazards
Methyl isobutyl ketone2) 35.8% 4-Methyl-2-pentanol Volatile solvent
O2 87.7% H2O O2 and organic mixture
H2O2 44.2% H2O Storage and transport of H2O2
Electron acceptor-free (Dehydrogenation reaction) 96.6% H2 Explosion limit of H2
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