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

doi:10.11949/0438-1157.20200248

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 4981-4989.DOI: 10.11949/0438-1157.20200248

• 南京大学化工学院院庆专栏 • 上一篇下一篇

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¹(),梁中秀²,周贤太²,纪红兵^1,²()

^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

收稿日期:2020-03-11 修回日期:2020-05-18 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 纪红兵
作者简介:陈亚举（1989—），男，博士，讲师，chenyaju970@126.com
基金资助:
国家自然科学基金项目(21938001);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

CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂

Yaju CHEN¹(),Zhongxiu LIANG²,Xiantai ZHOU²,Hongbing JI^1,²()

^1.School of Chemistry, Guangdong University of Petrochemical Technology, Maoming 525000, Guangdong, China
^2.Fine Chemical Industry Research Institute, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2020-03-11 Revised:2020-05-18 Online:2020-11-05 Published:2020-11-05
Contact: Hongbing JI

摘要/Abstract

摘要：

通过仿生催化，将苯乙烯、氧气（O₂）和二氧化碳（CO₂）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O₂和CO₂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CO₂插入反应和分子内闭环反应最终生成环状碳酸酯。

关键词: 金属卟啉, 氧化, 氧气, 二氧化碳, 仿生催化, 环状碳酸酯

Abstract:

The direct synthesis cyclic carbonate from styrene, O₂ and CO₂ 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 O₂ and CO₂ 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 in-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 CO₂ insertion reaction and intramolecular ring-closing reaction.

Key words: metalloporphyrin, oxidation, oxygen, carbon dioxide, biomimetic catalysis, cyclic carbonate

中图分类号:

O 643

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.

Yaju CHEN,Zhongxiu LIANG,Xiantai ZHOU,Hongbing JI. 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.

图/表 13

图1 苯乙烯、O2和CO2直接合成环状碳酸酯

Fig.1 The direct synthesis of styrene to styrene carbonate within O2 and CO2

图2 CoTPP用量对苯乙烯环氧化反应的影响

Fig.2 The effect of amount of CoTPP on styrene epoxidation

图3 MCC用量对苯乙烯环氧化反应的影响

Fig.3 The effect of amount of MCC on styrene epoxidation

图4 反应温度对烯烃环氧化反应的影响

Fig.4 The effect of reaction temperature on styrene epoxidation

图5 反应时间对烯烃环氧化反应的影响

Fig.5 The effect of reaction time on styrene epoxidation

图6 TBAB用量对环氧化物与CO2环加成反应的影响

Fig.6 The effect of amount of TBAB on cycloaddition of styrene epoxide with CO2

图7 反应温度对环氧化物与CO2环加成反应的影响

Fig.7 The effect of reaction temperature on cycloaddition of styrene epoxide with CO2

图8 反应时间对环氧化物与CO2环加成反应的影响

Fig.8 The effect of reaction time on cycloaddition of styrene epoxide with CO2

表1 苯乙烯、O2和CO2直接合成碳酸苯乙烯酯的反应结果

Table 1 Results of the direct synthesis of styrene carbonate from styrene, dioxygen and carbon dioxide①

Entry	CoTPP/mmol	TBAB/mmol	MCC/mmol	Reaction time /h	Conv. ^②/%	Yield ^② /%
Entry	CoTPP/mmol	TBAB/mmol	MCC/mmol	Reaction time /h	Conv. ^②/%	SC	SO	BA
1	0.005	—	5.0	12	99	1	7	13
2	—	0.1	5.0	12	46	5	1	3
3	0.005	0.1	5.0	12	99	20	2	13
4	0.005	0.3	5.0	12	99	20	2	10
5	0.005	0.5	5.0	12	99	21	2	10
6	0.005	0.5	5.0	26	99	21	2	7
7	0.005	0.5	1.0	12	47	14	1	12
8	0.005	0.5	2.0	12	99	35	2	12
9	0.005	0.5	3.0	12	99	34	3	14

图9 苯乙烯、O2和CO2直接合成碳酸苯乙烯酯反应的时间动力学曲线图

Fig.9 Kinetic curve for the direct synthesis styrene carbonate from styrene, O2 and CO2

图10 CoTPP在反应过程中的在线紫外光谱图

Fig.10 In-situ UV-vis spectra of CoTPP during the reaction process

图11 TBAB催化环氧苯乙烷和CO2环加成反应的在线红外光谱三维图(a)；环氧化物和环状碳酸酯中官能团红外特征吸收峰在不同时间的变化(b)

Fig.11 Three-dimensional stack plot of in-situ IR spectra collected every 1 min during the coupling reaction of SO and CO2 over TBAB(a); changes of the epoxide ring and SC vibrational peaks at different time(b)

图12 苯乙烯、O2和CO2直接制备环状碳酸酯可能的反应机理

Fig.12 Plausible reaction mechanism of direct synthesis of styrene carbonate from styrene, CO2 and O2

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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

CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂

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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

CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O2 and CO2

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CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O₂ and CO₂