Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

doi:10.1016/j.cjche.2022.04.024

Chinese Journal of Chemical Engineering ›› 2023, Vol. 55 ›› Issue (3): 192-201.DOI: 10.1016/j.cjche.2022.04.024

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Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

Qiongna Xiao^1,2,3, Yuyan Jiang^1,2,3, Weiqiang Yuan^1,3, Jingjing Chen^1,2,3, Haohong Li^3,4, Huidong Zheng^1,2,3

1. College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. Qingyuan Innovation Laboratory, Quanzhou 362801, China;
3. Engineering Research Center of Advanced Manufacturing Technology for Fine Chemicals, Fujian Province University, Fuzhou University, Fuzhou 350116, China;
4. College of Chemistry, Fuzhou University, Fuzhou 350116, China

Received:2021-12-15 Revised:2022-04-25 Online:2023-06-03 Published:2023-03-28
Contact: Huidong Zheng,E-mail:youngman@fzu.edu.cn
Supported by:
This study was financial supported by the National Natural Science Foundation of China (22078065), Key Program of Qingyuan Innovation Laboratory (00221001) and Quanzhou City Science & Technology Program of China (2020C008R).

Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

Qiongna Xiao^1,2,3, Yuyan Jiang^1,2,3, Weiqiang Yuan^1,3, Jingjing Chen^1,2,3, Haohong Li^3,4, Huidong Zheng^1,2,3

1. College of Chemical Engineering, Fuzhou University, Fuzhou 350116, China;
2. Qingyuan Innovation Laboratory, Quanzhou 362801, China;
3. Engineering Research Center of Advanced Manufacturing Technology for Fine Chemicals, Fujian Province University, Fuzhou University, Fuzhou 350116, China;
4. College of Chemistry, Fuzhou University, Fuzhou 350116, China

通讯作者: Huidong Zheng,E-mail:youngman@fzu.edu.cn
基金资助:
This study was financial supported by the National Natural Science Foundation of China (22078065), Key Program of Qingyuan Innovation Laboratory (00221001) and Quanzhou City Science & Technology Program of China (2020C008R).

Abstract

Abstract: Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry, and the deep insight into catalyst deactivation will help to develop new epoxidation process. In this work, series of quaternary ammoniums bearing different cationic sizes, i.e. MTOA⁺ (methyltrioctylammonium, [(C₈H₁₇)₃CH₃N]⁺), HTMA⁺(hexadecyltrimethylammonium, [(C₁₆H₃₃)(CH₃)₃N]⁺) and DMDOA⁺ (dimethyldioctadecylammonium, [(C₁₈H₃₇)₂(CH₃)₂N]⁺) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs), which were used in the styrene epoxidations. Among them, (MTOA)₃PW₄O₂₄ exhibits the best catalytic performance judged from the highest styrene conversion rate (52%) and styrene oxide selectivity (93%), during which the styrene epoxidation conditions were optimized. Meanwhile, the deactivation mechanism of this kind of PTCs was proposed firstly, i.e. in the case of low H₂O₂ content, the oxidant can only be used in the styrene epoxidation, in which the catalyst can transform into stable Keggin-type POM. But when the content of H₂O₂ is higher, the excess H₂O₂ can re-activate the Keggin-type POM into active (PW₄O₂₄)^3- anions, which can trigger the ring-opening polymerization of styrene oxide. Consequently, the catalyst is deactivated by adhered poly(styrene oxide) irreversibly, which was determined by NMR spectra. In this situation, the active moiety {PO₄[WO(O₂)₂]₄}^3- in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides. This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.

Key words: Phosphotungstic acid phase-transfer catalyst, Styrene epoxidation, Catalyst deactivation mechanism, Cation size effect

摘要： Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry, and the deep insight into catalyst deactivation will help to develop new epoxidation process. In this work, series of quaternary ammoniums bearing different cationic sizes, i.e. MTOA⁺ (methyltrioctylammonium, [(C₈H₁₇)₃CH₃N]⁺), HTMA⁺(hexadecyltrimethylammonium, [(C₁₆H₃₃)(CH₃)₃N]⁺) and DMDOA⁺ (dimethyldioctadecylammonium, [(C₁₈H₃₇)₂(CH₃)₂N]⁺) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs), which were used in the styrene epoxidations. Among them, (MTOA)₃PW₄O₂₄ exhibits the best catalytic performance judged from the highest styrene conversion rate (52%) and styrene oxide selectivity (93%), during which the styrene epoxidation conditions were optimized. Meanwhile, the deactivation mechanism of this kind of PTCs was proposed firstly, i.e. in the case of low H₂O₂ content, the oxidant can only be used in the styrene epoxidation, in which the catalyst can transform into stable Keggin-type POM. But when the content of H₂O₂ is higher, the excess H₂O₂ can re-activate the Keggin-type POM into active (PW₄O₂₄)^3- anions, which can trigger the ring-opening polymerization of styrene oxide. Consequently, the catalyst is deactivated by adhered poly(styrene oxide) irreversibly, which was determined by NMR spectra. In this situation, the active moiety {PO₄[WO(O₂)₂]₄}^3- in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides. This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.

关键词: Phosphotungstic acid phase-transfer catalyst, Styrene epoxidation, Catalyst deactivation mechanism, Cation size effect

Qiongna Xiao, Yuyan Jiang, Weiqiang Yuan, Jingjing Chen, Haohong Li, Huidong Zheng. Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism[J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 192-201.

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Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

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