钴卟啉-四丁基溴化铵串联催化苯乙烯在氧气和二氧化碳中合成碳酸苯乙烯酯

陈亚举; 梁中秀; 周贤太; 纪红兵

doi:10.11949/0438-1157.20200248

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钴卟啉-四丁基溴化铵串联催化苯乙烯在氧气和二氧化碳中合成碳酸苯乙烯酯

南京大学化工学院院庆专栏 | 更新时间：2026-07-24

- 钴卟啉-四丁基溴化铵串联催化苯乙烯在氧气和二氧化碳中合成碳酸苯乙烯酯
- CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂
- 化工学报 2020年71卷第11期页码：4981-4989
- 作者机构：
  
  1.广东石油化工学院化学学院，广东茂名 525000
  2.中山大学化学学院精细化工研究院，广东广州 510275
- 作者简介：
  
  陈亚举（1989—），男，博士，讲师，chenyaju970@126.com
  纪红兵（1970—），男，博士，教授，jihb@mail.sysu.edu.cn
- 基金信息：
  
  国家自然科学基金项目(21938001;21961160741);广东省基础与应用基础研究基金项目(2019A1515010612);广东石油化工学院科研基金项目(2019rc049);广东省“珠江人才计划”本土创新科研团队项目(2017BT01C102);广东石油化工学院科研创新团队项目
- DOI：10.11949/0438-1157.20200248
  中图分类号： O 643
- 收稿：2020-03-11，
  
  修回：2020-05-18，
  
  网络首发：2020-11-03，
  
  纸质出版：2020-11-05
- 稿件说明：
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陈亚举, 梁中秀, 周贤太, 纪红兵. 钴卟啉-四丁基溴化铵串联催化苯乙烯在氧气和二氧化碳中合成碳酸苯乙烯酯[J]. 化工学报, 2020, 71(11): 4981-4989

CHEN Yaju, LIANG Zhongxiu, ZHOU Xiantai, JI Hongbing. CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂[J]. CIESC Journal, 2020, 71(11): 4981-4989 DOI: 10.11949/0438-1157.20200248.
陈亚举, 梁中秀, 周贤太, 纪红兵. 钴卟啉-四丁基溴化铵串联催化苯乙烯在氧气和二氧化碳中合成碳酸苯乙烯酯[J]. 化工学报, 2020, 71(11): 4981-4989 DOI： 10.11949/0438-1157.20200248.

CHEN Yaju, LIANG Zhongxiu, ZHOU Xiantai, JI Hongbing. CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂[J]. CIESC Journal, 2020, 71(11): 4981-4989 DOI: 10.11949/0438-1157.20200248. DOI：

摘要

通过仿生催化，将苯乙烯、氧气（O

）和二氧化碳（CO

）直接合成环状碳酸酯在现代化学中极具学术研究意义和工业应用价值。采用钴卟啉-四丁基溴化铵为双组分催化剂，以2-氧代环戊烷羧酸甲酯为助剂，在O

和CO

条件下，直接将苯乙烯转化为碳酸苯乙烯酯。系统考察了催化剂用量等因素对催化性能的影响。在最佳反应条件下，苯乙烯的转化率高达99%，环状碳酸酯的收率可达35%。利用在线紫外与在线红外探讨了该串联反应可能的机理。结果表明，钴中心与2-氧代环戊烷羧酸甲酯的环内氧原子配位后活化氧气形成过氧活性物种，进而形成高价钴-氧中间体，其通过传递氧原子给苯乙烯而生成环氧苯乙烷。而后，环氧苯乙烷在四丁基溴化铵的催化作用下开环，并通过CO

插入反应和分子内闭环反应最终生成环状碳酸酯。

Abstract

The direct synthesis cyclic carbonate from styrene

and CO

is of great academic attraction and industrial value in modern chemistry. The metalloporphyrin/tetrabutylammonium bromide was employed as binary catalyst for this reaction in the presence of O

and CO

by using methyl 2-cyclopentanone-carboxylate as co-catalysts. The effects of reaction parameters on catalytic performance were investigated systematically. Under the optimal reaction conditions

conversion of styrene (99%) and selectivity to cyclic carbonate (35%) were obtained. The possible mechanism of cascade reaction was proposed by using

situ

ultraviolet and infrared spectroscopy. The results show that the cobalt center is coordinated with the ring oxygen atom of methyl 2-oxocyclopentanecarboxylate to activate oxygen to form a peroxy active species

thereby forming a high-valent cobalt-oxygen intermediate

which passes oxygen atoms to styrene and generate epoxy styrene. Then

styrene oxide opened ring under the catalysis of tetrabutylammonium bromide

and finally formed cyclic carbonate through CO

insertion reaction and intramolecular ring-closing reaction.

关键词

Keywords

references

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