Thermodynamics and kinetics of transesterification reactions to produce diphenyl carbonate from dimethyl carbonate catalyzed by tetrabutyl titanate and dibutyltin oxide

Abstract

The transesterification reactions to diphenyl carbonate (DPC) from dimethyl carbonate (DMC) and phenol are the key steps to the green production of polycarbonate polymers (PC). The transesterification equilibrium constants were determined under temperatures from 453.2 to 493.2 K, and the reaction kinetics catalyzed by single tetrabutyl titanate, dibutyltin oxide, and their combinations was measured. By taking into account the effect of catalyst, the simplified kinetic model was developed involving the transesterification of DMC and methyl phenyl carbonate (MPC) with phenol, the disproportionation of MPC, and the formation of byproduct anisole. The kinetic model fitted experiments well under various temperatures and had an excellent predictive ability on the effect of catalyst concentrations. The reverse reaction of MPC transesterification with phenol, as well as that of the disproportionation of MPC, was found to be independent of temperatures within the investigated conditions. The thermodynamic information and kinetic model reported here will provide valuable insight into the understanding of the transesterification process from DMC to DPC.

Stable Organic Titanium Catalysts and Reactive Distillation Used for the Transesterification of Dimethyl Carbonate with Phenol

“…On the other hand, a homogeneous catalyst has higher activity and selectivity, which is closer to industrial application. Among the homogeneous catalysts such as organic titanium compounds [14][15][16], organotin compounds [17], and samarium diiodide [18], titanium alkoxides show high activity for this reaction. However, most titanium alkoxides are sensi-tive to water and easily deactivated by hydrolysis.…”

Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

“…[22] Various important studies have been reported in the case of thermodynamics and kinetics for reaction mixture of organic carbonates and liquid phase reactions. [23][24][25][26][27][28] However, no study of thermodynamics has been performed comparing various routes for DEC synthesis. Considering this, a comprehensive effort was carried out for estimation of equilibrium constants at standard temperature and pressure.…”

“…Various important studies have been reported in the case of thermodynamics and kinetics for reaction mixture of organic carbonates and liquid phase reactions . However, no study of thermodynamics has been performed comparing various routes for DEC synthesis.…”

Comparative thermodynamic analysis of CO2 based dimethyl carbonate synthesis routes

“…It requires a significant amount of energy to enhance its reactiveness and transform it into valuable products. [ 11–18 ]…”

“…It requires a significant amount of energy to enhance its reactiveness and transform it into valuable products. [11][12][13][14][15][16][17][18] Dimethyl carbonate (DMC) is one of the most promising members of dialkyl carbonate due to its nontoxicity and low bioaccumulation behaviour. [19,20] The term bioaccumulation is used for describing the ecotoxicity behaviour of chemical substances and it is generally defined as the accumulation and enrichment of contaminants in organisms, relative to that in the environment.…”