Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides

ZHANG Xiangnan; MA Hongfang; QIAN Weixin; ZHANG Haitao; YING Weiyong

doi:10.12434/j.issn.2097-2547.20240139

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Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides

- Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides
  增强出版
- Vol. 50, Issue 1, Pages: 20-26(2025)
- 作者机构：
  
  华东理工大学化工学院大型工业反应器工程教育部工程研究中心化学工程联合国家重点实验室，上海 200237
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240139
  CLC： TQ426
- Published：25 January 2025，
  
  Received：03 April 2024，
  
  Revised：23 April 2024，
- 稿件说明：
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ZHANG XIANGNAN, MA HONGFANG, QIAN WEIXIN, et al. Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 20-26.
DOI：

ZHANG XIANGNAN, MA HONGFANG, QIAN WEIXIN, et al. Application of bifunctional Mn-based catalysts in cycloaddition reaction of carbon dioxide and epoxides. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 20-26. DOI： 10.12434/j.issn.2097-2547.20240139.

摘要

二氧化碳（CO

）和环氧化物环加成反应是目前合成环状碳酸酯的有效方法之一。催化剂对活化该反应中的CO

和环氧化物具有重要意义。以2

2’-联吡啶及其衍生物为配体，Mn(CO)

Br为金属源，乙醚为溶剂制备了一系列双功能Mn基催化剂L

Mn(CO)

Br（

= 1~6）。通过

H NMR、

C NMR、HR-MS和FT-IR等对L

Mn(CO)

Br的化学结构、相对分子质量和化学基团等进行了表征。研究了L

Mn(CO)

Br在CO

和环氧氯丙烷环加成反应中的催化性能，及L

Mn(CO)

Br对一系列环氧化物底物的适应性。结果表明，L

Mn(CO)

Br中给电子基团（甲氧基、叔丁基和甲基）的给电子性能和吡啶环上甲基的位置均对其催化性能有影响；对于CO

和环氧氯丙烷环加成反应，在L

Mn(CO)

Br投加量（物质的量分数）为0.05%、反应温度为125 ℃和反应压力为3.0 MPa的条件下反应1 h，L

Mn(CO)

Br的环氧氯丙烷转化率和催化剂转换频率分别为42%和840 h

-1

；L

Mn(CO)

Br对多种环氧化物作底物的环加成反应具有适应性，且底物的空间位阻效应对其催化性能有较大影响。

Abstract

The cycloaddition reaction of carbon dioxide (CO

) and epoxides is an effective method to synthesize cyclic carbonates. Catalysts are important for the activation of CO

and epoxides in the reaction. A series of bifunctional Mn-based catalysts L

Mn(CO)

Br (

= 1~6) were prepared by 2

2’-bipyridine with its derivatives as the ligands

Mn(CO)

Br as the metal source and ethyl ether as the solvent. The chemical structures

molecular weights and chemical groups of L

Mn(CO)

Br were characterized by

H NMR

C NMR

HR-MS and FT-IR

etc. The catalytic performances of L

Mn(CO)

Br in the cycloaddition reaction of CO

and epichlorohydrin and the adaptability of L

Mn(CO)

Br to a series of epoxide substrates were studied. The results show that the electron donating properties of electron donating groups (methoxy group

tertiary butyl and methyl group) in L

Mn(CO)

Br and the positions of methyl group on the pyridine ring have influences on their catalytic performances. For the cycloaddition reaction of CO

and epiglorohydrin

under the conditions of L

Mn(CO)

Br dosage (mole fraction) of 0.05%

reaction temperature of 125 ℃ and reaction pressure of 3.0 MPa for 1 h

the epiglorohydrin conversion rate and catalyst turnover frequency of L

Mn(CO)

Br are 42% and 840 h

-1

respectively. L

Mn(CO)

Br has adaptability to the cycloaddition reaction of several epoxides. And the steric hindrance effects of the substrates have great influences on catalytic performance of L

Mn(CO

)Br.

关键词

环状碳酸酯双功能Mn基催化剂二氧化碳环氧化物环加成反应

Keywords

cyclic carbonatesbifunctional Mn-based catalystscarbon dioxideepoxidescycloaddition reaction

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