Liquid–liquid equilibria of ternary mixtures of dimethyl carbonate, diphenyl carbonate, phenol and water at 358.15 K

doi:10.1016/j.fluid.2010.11.012

Fluid Phase Equilibria

Volume 301, Issue 1, 15 February 2011, Pages 18-21

https://doi.org/10.1016/j.fluid.2010.11.012 Get rights and content

Abstract

The ternary liquid–liquid equilibria (LLE) of the following systems were analytically determined at 358.15 K at atmospheric pressure using stirred and thermo-regulated cells: {dimethyl carbonate (DMC) + diphenyl carbonate (DPC) + water}, {DMC + phenol + water} and {DPC + phenol + water}. The experimental ternary LLE data were correlated with the NRTL and UNIQUAC activity coefficient models. Additionally, the Bachman–Brown correlation was used to ascertain the reliability of the experimental data for each system.

Introduction

The viscosity of suitable polymers is preferably from 3 to 120 centipoises measured according to DIN 53,015.

Alkyl carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), and diphenyl carbonate (DPC) are excellent solvents for cellulose ethers, esters and salts, and also in the industry of pharmaceutical and cosmetics, natural and synthetic resins and polymers [1]. DMC is a carbonate ester and is used as a methylating agent and a benign fuel additive in unleaded gasoline. DPC is a very useful chemical intermediate in the synthesis of aromatic and aliphatic polycarbonates and industrially significant polymers. DPC has several desirable properties, such as good electrical insulation, a high heat of distortion, transparency, and impact resistance. DMC is usually synthesized from CO, methanol, and O₂. High-purity DMC, CO₂, and water are the reaction products. In this process, when DMC reacts with phenol and bisphenol A by trans-esterification, DPC and methanol to be produced. This newly developed DPC synthesis process is considered to be a “green process” because it does not use phosgene, a highly toxic environmental pollutant. However, to date, relatively very few investigations of the phase equilibria and mixture properties of systems containing DPC have been reported [2].

In the present work, we analytically determined the ternary liquid–liquid equilibria (LLE) at 358.15 K and at atmospheric pressure using stirred and thermo-regulated cells of the following systems: {DMC + DPC + water}, {DPC + phenol + water} and {DMC + phenol + water}. We chose these systems because they may be encountered in the environmentally friendly DPC synthesis process. The experimental LLE data for the above ternary systems were correlated using two activity coefficient models: the NRTL and the UNIQUAC models. Additionally, Bachman–Brown [3] correlations were used to examine the reliability of the experimental data for each system.

Section snippets

Chemicals

Commercial-grade analytical chemicals were used in this investigation. Water (H₂O, M = 18.02 g mol⁻¹, CAS-RN 7732-18-5, 99.9%) was provided by J.T Baker Chemical Co. DMC (C₃H₆O₃, M = 90.08 g mol⁻¹, CAS-RN 616-38-6, 99.9%), DPC (C₁₃H₁₀O₃, M = 214.22 g mol⁻¹, CAS-RN 102-09-0. 99.0%) and phenol (C₆H₆O, M = 94.11 g mol⁻¹, CAS-RN 108-95-2, 99.9%) were obtained from Aldrich Co. All chemicals were dried using molecular sieves with a pore diameter of 0.4 nm. The water content of the chemicals, determined using a

Results and discussion

The experimental ternary LLE data for the ternary systems {DMC + DPC + water}, {DMC + phenol + water} and {DPC + phenol + water} at 358.15 K are given in Table 2. These ternary LLE data were correlated using the NRTL and UNIQUAC models. The binary parameters of each constituent were regressed by minimizing the differences between the experimental and calculated mole fractions for each component of both liquid phases over all of the measured systems. The objective function (OF) used was $O F = \min \sum_{i} \sum_{α} \sum_{k} (x_{i k}^{α (\exp)} -$

Conclusions

Ternary liquid–liquid equilibrium (LLE) data for the systems {DMC + DPC + water}, {DMC + phenol + water} and {DPC + phenol + water} at 358.15 K were analytically determined at atmospheric pressure. The systems {DMC + phenol + water} and {DPC + phenol + water} exhibited Treybal's Type I LLE behavior, while the system {DMC + DPC + water} showed Treybal's Type II behavior. The experimental LLE data were correlated using two activity coefficient models: NRTL and UNIQUAC. The NRTL model gave slightly better correlation

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Liquid–liquid equilibria of ternary mixtures of dimethyl carbonate, diphenyl carbonate, phenol and water at 358.15 K

Abstract

Introduction

Section snippets

Chemicals

Results and discussion

Conclusions

Fluid Phase Equilib.

Fluid Phase Equilib.

Encyclopedia of Chemical Technology

J. Phys. Chem. B

Ind. Eng. Chem.