High pressure equilibrium data of CO2/cyclohexene oxide and CO2/limonene oxide systems in the context of polycarbonate synthesis using CO2 as a co-monomer

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria Pub Date : 2025-02-26 DOI:10.1016/j.fluid.2025.114406

Edoardo Vittorio Pasini , Jérôme Durand , Séverine Camy

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Abstract

Polycarbonates are a class of high-performance polymers with a wide range of industrial applications. Traditionally, polycarbonate production involves the use of bisphenol A (BPA) and phosgene (COCl₂), which have raised concerns due to their high toxicity and the overall environmental impact of the process. To address these issues, more sustainable methods such as ring-opening copolymerization (ROCOP) of epoxides and carbon dioxide (CO₂) under supercritical CO₂ (sCO₂) are being developed. Recent research has focused on the synthesis of poly(cyclohexene carbonate) (PCHC) and poly(limonene carbonate) (PLC) from cyclohexene oxide (CHO) and limonene oxide (LO), respectively. Limonene oxide has attracted particular interest due to its non-toxic properties and its derivation from limonene, an available bio-based terpene. Reaction performance is strongly influenced by the initial physical state of the mixture, in particular the composition of the liquid and vapor phases. Therefore, access to this thermodynamic information, represented by phase diagrams, is essential for understanding and predicting reaction behavior. However, there is a lack of equilibrium data for these two systems. The aim of this study is to investigate the phase equilibria of the CO₂/CHO and CO₂/LO binary mixtures, thereby contributing to the advancement of greener polycarbonate production. The experiments were performed in a variable volume view-cell, covering a temperature range from 338.15 K to 363.15 K for the CO₂/CHO mixture and from 303.15 K to 343.15 K for the CO₂/LO system. The molar fraction of CO₂ was varied between 0.189 and 0.967 for the CO₂/CHO case, and between 0.227 and 0.997 for the CO₂/LO mixture. Vapor-liquid bubble point (VLE-BP) and dew point (VLE-DP) were determined for both mixtures, along with mixture critical points for the temperatures studied. The phase behavior was modeled using several equations of state (EoS). In particular, the Peng-Robinson (PR) equation of state with the volume translated Peng-Robinson (VTPR) complex mixing rule and the Wilson model for the activity coefficient provided a highly accurate description of the experimental results.

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以CO2为共聚单体合成聚碳酸酯时CO2/环氧环己烯和CO2/环氧柠檬烯体系的高压平衡数据

聚碳酸酯是一类高性能聚合物，具有广泛的工业应用。传统上，聚碳酸酯的生产涉及到双酚A （BPA）和光气（COCl2）的使用，由于它们的高毒性和整个过程的环境影响而引起了人们的关注。为了解决这些问题，人们正在开发更可持续的方法，例如在超临界二氧化碳（sCO2）下环氧化物和二氧化碳（CO2）的开环共聚（ROCOP）。近年来的研究主要集中在以环氧环己烯（CHO）和环氧柠檬烯（LO）为原料合成聚碳酸环己烯（PCHC）和聚碳酸柠檬烯（PLC）。氧化柠檬烯由于其无毒特性和从柠檬烯（一种可用的生物基萜烯）衍生而来而引起了特别的兴趣。反应性能受混合物的初始物理状态，特别是液相和气相的组成的强烈影响。因此，获得这些由相图表示的热力学信息，对于理解和预测反应行为是必不可少的。然而，这两种系统缺乏平衡数据。本研究的目的是研究CO2/CHO和CO2/LO二元混合物的相平衡，从而促进绿色聚碳酸酯生产。实验在变体积视池中进行，CO2/CHO混合物的温度范围为338.15 K至363.15 K， CO2/LO体系的温度范围为303.15 K至343.15 K。CO2/CHO的摩尔分数在0.189 ~ 0.967之间，CO2/LO的摩尔分数在0.227 ~ 0.997之间。测定了两种混合物的汽液泡点（VLE-BP）和露点（VLE-DP），以及所研究温度下的混合物临界点。用几个状态方程（EoS）对相行为进行了建模。其中，具有体积转换Peng-Robinson （VTPR）复合混合规则的Peng-Robinson （PR）状态方程和活度系数的Wilson模型提供了对实验结果的高度精确描述。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Fluid Phase Equilibria 工程技术-工程：化工

CiteScore

5.30

自引率

15.40%

发文量

223

审稿时长

53 days

期刊介绍： Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results. Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.