Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium ...Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.展开更多
The seleno substituted aromatic compounds were prepared via the Diels-Alder reaction of seleno substituted 3-sulfolenes with dimethyl acetylenedicarboxylate followed by DDQ dehydrogenation.
The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to ...The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism展开更多
This study reports the synthesis of size-controlled Fe-MFI （Fe-substituted zeolites with the MFI topology） and their catalytic performances for DTO （dimethyl ether-to-olefins） reaction. The amount of HC1 and aging...This study reports the synthesis of size-controlled Fe-MFI （Fe-substituted zeolites with the MFI topology） and their catalytic performances for DTO （dimethyl ether-to-olefins） reaction. The amount of HC1 and aging temperature were decisive factors to control the particle size of Fe-MFI in the range of 50 nm to 600 nm. The introduction of Fe3＋ ions into the zeolitic framework was confirmed by UV （ultraviolet）-visible spectroscopy. In addition, it was observed that the strength of acid site in prepared Fe-MFI was weaker than that of commercial ZSM-5. With decrease in the particle size, the amount of deposited coke decreased so that the catalyst life for the DTO reaction was well promoted. The present catalysts showed the higher light-olefin selectivity （C2= ＋ C3= ＋ C4=） than commercial ZSM-5 catalysts mainly due to the suppression of the formation of paraffins; however, the Fe-MFI catalysts were deactivated rapidly because of their low activity for the cracking of alkenes.展开更多
The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the react...The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.展开更多
Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 m...Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 molar ratio on the conversion of dimethyl ether and the product selectivity were investigated under the same catalyst formulation.Results showed that a maximum conversion of dimethyl ether was obtained when a mixture consisting of 0.3 mol dimethyl ether and 120 ml acetic acid was reacted at 180 ℃ and 3.0 MPa for 10 h at a stirring speed of 600 rpm under a syngas flow with a CO/H2 molar ratio of 2.5,which was catalyzed by a catalyst mixture comprising 0.3 g RhI3,6 g PPh3 and 1.3 g CH3I.The selectivity of ethylidene diacetate increased with temperature,decreased with the CO/H2 molar ratio and exhibited a maximum with pressure.展开更多
A series of CuO-ZnO catalysts （with different Cu/Zn molar ratios） were prepared, and evaluated under the reaction conditions of syngas-to-dimethyl ether （DME） with three sorts of feed gas and different space veloc...A series of CuO-ZnO catalysts （with different Cu/Zn molar ratios） were prepared, and evaluated under the reaction conditions of syngas-to-dimethyl ether （DME） with three sorts of feed gas and different space velocity. The catalysts were characterized by X-ray diffraction （XRD） and temperatureprogrammed reduction （TPR）. The experiment results showed that the reaction conditions of syngas-to- DME process greatly affected the methanol synthesis and WGS reaction. The influence caused by Cu/Zn molar ratio was quite different on the two reactions; increasing of percentage of CO2 in feed gas was unfavorable for catalyst activity, and also inhibited both reactions; enhancement of reaction space velocity heavily influenced the performance of the catalyst, and the benefits were relatively less for methanol synthesis than for the WGS reaction.展开更多
A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)(4)] was proposed. Na[Co(CO)(4)] was synthesized in situ in the presence of Na2S2O3 and iron powder. The eff...A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)(4)] was proposed. Na[Co(CO)(4)] was synthesized in situ in the presence of Na2S2O3 and iron powder. The effects of some reaction parameters such as temperature. CO pressure and the concentrations of catalyst on the yields of dimethyl malonate were discussed. The kinetic data were studied and a possible reaction mechanism was proposed.展开更多
An efficient process for the conversion of dimethyl oxalateinto ethylene glycol with high selectivity and high yield over CuO was investigated. In situ formed Cu as a true catalytically active species showed a good ca...An efficient process for the conversion of dimethyl oxalateinto ethylene glycol with high selectivity and high yield over CuO was investigated. In situ formed Cu as a true catalytically active species showed a good catalytic performance for DMO conversion to produce EG in 95% yield.展开更多
We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with m...We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with methyl 2-perfluoroalkynoates(2).展开更多
基金supported by the National Key Research and Development Program of China(2022YFB4101800)National Natural Science Foundation of China(22278077,22108040)+2 种基金Key Program of Qingyuan Innovation Laboratory(00221004)Research Program of Qingyuan Innovation Laboratory(00523006)Natural Science Foundation of Fujian Province(2022J02019)。
文摘Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.
文摘The seleno substituted aromatic compounds were prepared via the Diels-Alder reaction of seleno substituted 3-sulfolenes with dimethyl acetylenedicarboxylate followed by DDQ dehydrogenation.
文摘The kinetics of reaction of bromo-epoxy resin with oleic acid in the presence of dimethylbenzylamine catalyst was studied. The reaction is a zero order reaction with respect to oleic acid, first order with respect to epoxy group and 0. 74 order with respect to dimethylbenzylamine. The reaction rate constants at various temperatures and activation energy were determined. The mechanism of this reaction was discussed. Keywords Tetrabromobisphenol-A, Bromo-epoxy resin, Oleic acid kinetics, Reaction mechanism
文摘This study reports the synthesis of size-controlled Fe-MFI （Fe-substituted zeolites with the MFI topology） and their catalytic performances for DTO （dimethyl ether-to-olefins） reaction. The amount of HC1 and aging temperature were decisive factors to control the particle size of Fe-MFI in the range of 50 nm to 600 nm. The introduction of Fe3＋ ions into the zeolitic framework was confirmed by UV （ultraviolet）-visible spectroscopy. In addition, it was observed that the strength of acid site in prepared Fe-MFI was weaker than that of commercial ZSM-5. With decrease in the particle size, the amount of deposited coke decreased so that the catalyst life for the DTO reaction was well promoted. The present catalysts showed the higher light-olefin selectivity （C2= ＋ C3= ＋ C4=） than commercial ZSM-5 catalysts mainly due to the suppression of the formation of paraffins; however, the Fe-MFI catalysts were deactivated rapidly because of their low activity for the cracking of alkenes.
基金supported by the National Natural Science Foundation of China(NSFC,No.21203220 and 21133011)China Postdoctoral Science Foundation(No.2014M551674)+1 种基金Jiangsu Planned Projects for Postdoctoral Research Funds(No.1302070C)the National Basic Research Program of China(973 Program,No.2011CB201404)
文摘The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.
文摘Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 molar ratio on the conversion of dimethyl ether and the product selectivity were investigated under the same catalyst formulation.Results showed that a maximum conversion of dimethyl ether was obtained when a mixture consisting of 0.3 mol dimethyl ether and 120 ml acetic acid was reacted at 180 ℃ and 3.0 MPa for 10 h at a stirring speed of 600 rpm under a syngas flow with a CO/H2 molar ratio of 2.5,which was catalyzed by a catalyst mixture comprising 0.3 g RhI3,6 g PPh3 and 1.3 g CH3I.The selectivity of ethylidene diacetate increased with temperature,decreased with the CO/H2 molar ratio and exhibited a maximum with pressure.
文摘A series of CuO-ZnO catalysts （with different Cu/Zn molar ratios） were prepared, and evaluated under the reaction conditions of syngas-to-dimethyl ether （DME） with three sorts of feed gas and different space velocity. The catalysts were characterized by X-ray diffraction （XRD） and temperatureprogrammed reduction （TPR）. The experiment results showed that the reaction conditions of syngas-to- DME process greatly affected the methanol synthesis and WGS reaction. The influence caused by Cu/Zn molar ratio was quite different on the two reactions; increasing of percentage of CO2 in feed gas was unfavorable for catalyst activity, and also inhibited both reactions; enhancement of reaction space velocity heavily influenced the performance of the catalyst, and the benefits were relatively less for methanol synthesis than for the WGS reaction.
文摘A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)(4)] was proposed. Na[Co(CO)(4)] was synthesized in situ in the presence of Na2S2O3 and iron powder. The effects of some reaction parameters such as temperature. CO pressure and the concentrations of catalyst on the yields of dimethyl malonate were discussed. The kinetic data were studied and a possible reaction mechanism was proposed.
基金financial support from the State Key Program of National Natural Science Foundation of China(No.21436007)Key Basic Research Projects of Science and Technology Commission of Shanghai(14JC1403100)+2 种基金the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(ZXDF160002)the Projectsponsored by SRF for ROCS,SEM(BG1600002)State Key Laboratory of Fine Chemicals(KF1411)
文摘An efficient process for the conversion of dimethyl oxalateinto ethylene glycol with high selectivity and high yield over CuO was investigated. In situ formed Cu as a true catalytically active species showed a good catalytic performance for DMO conversion to produce EG in 95% yield.
文摘We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with methyl 2-perfluoroalkynoates(2).
