Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found...Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.展开更多
Special proton-gradient-transfer acid complexes （PGTACs） in which the bonded protons are not equivalent and have gradients in transfer ability, acidity, and reactivity were reported. The acidity gradient of the prot...Special proton-gradient-transfer acid complexes （PGTACs） in which the bonded protons are not equivalent and have gradients in transfer ability, acidity, and reactivity were reported. The acidity gradient of the protons gave the PGTACs excellent catalytic activity and selectivity in the esterifica- tion of terpenols. These PGTACs are ＂reaction-induced self-separation catalysts＂ and can be easily reused. The kinetics with PGTACs as catalyst in the esterification of geraniol were also studied for use in engineering design.展开更多
2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification proce...2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.展开更多
基金Natural Science Foundation of China (Project number: 20074017)
文摘Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.
基金supported by the National Natural Science Foundation of China (21376115, 21576129)~~
文摘Special proton-gradient-transfer acid complexes （PGTACs） in which the bonded protons are not equivalent and have gradients in transfer ability, acidity, and reactivity were reported. The acidity gradient of the protons gave the PGTACs excellent catalytic activity and selectivity in the esterifica- tion of terpenols. These PGTACs are ＂reaction-induced self-separation catalysts＂ and can be easily reused. The kinetics with PGTACs as catalyst in the esterification of geraniol were also studied for use in engineering design.
基金The financial support from National Natural Science Foundation of China(21776074,21861132019 and 21978096)is greatly acknowledged
文摘2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.
