乙烯基醚系列产品合成过程的热力学研究OACSTPCD
Thermodynamic study on synthesis process of vinyl ether series products
乙烯基醚是一类重要的聚合单体,但针对其合成过程的系统热力学分析尚未见报道.分别采用Benson法、Joback法等方法,以经典热力学公式为基础,计算了乙炔与不同醇(甲醇、乙醇、丁醇、异丁醇以及叔丁醇)合成对应乙烯基醚类化合物(乙烯基甲醚、乙烯基乙醚、乙烯基丁醚、乙烯基异丁醚以及乙烯基叔丁醚)的热力学参数,包括在反应温度为283~363 K下的焓变(∆rHθ)、熵变(∆rSθ)、吉布斯自由能(∆rGθ)和反应平衡常数(K).系统分析和总结了不同结构的醇与乙炔发生亲核加成反应过程的难易程度,以及热力学反应参数的变化规律.结果表明,所有反应均为强放热反应且均可自发进行,反应温度越低反应进行得越彻底.即使在近室温(283 K)条件下,乙烯基醚类化合物仍可顺利合成,且反应温度越低,安全性越高.本研究结果可为乙烯基醚工业化生产提供理论指导.
Vinyl ether is an important polymeric monomer,but the systematic thermodynamic analysis of its synthesis has not been reported.By utilizing Benson and Joback method and other methods respectively,based on classical thermodynamic formulas,the thermodynamic parameters of corresponding vinyl ethers compounds(vinyl methyl ether,vinyl ethyl ether,vinyl butyl ether,vinyl isobutyl ether and vinyl tert-butyl ether)synthesized from acetylene with different alcohols(methanol,ethanol,butanol,isobutyl alcohol and tert-butyl alcohol)were calculated,including enthalpy change(∆rHθ),entropy change(∆rSθ),molar Gibbs free energy(∆rGθ)and reaction equilibrium constant(K)at 283 K to 363 K.The difficulty of nucleophilic addition reactions between acetylene and alcohols of different structures,and the thermodynamic reaction rules,were systematically analyzed and summarized.The results show that all the reactions are highly exothermic and can occur spontaneously,and the lower the reaction temperature,the more thorough the reaction will be.Even at near room temperature(283 K)conditions,vinyl ether compounds can still be synthesized smoothly,and the lower the reaction temperature,the higher the safety.The results of this study can provide theoretical guidance for the industrial production of vinyl ethers.
周千惠;魏文胜;张卫海;杨文兵;贾风雷;石磊
沈阳化工大学 资源化工与材料教育部重点实验室,辽宁 沈阳 110142||沈阳化工大学 理学院,辽宁 沈阳 110142沈阳化工大学 资源化工与材料教育部重点实验室,辽宁 沈阳 110142宁夏惟远新能源有限公司,宁夏 银川 750411沈阳化工大学 资源化工与材料教育部重点实验室,辽宁 沈阳 110142||沈阳化工大学 理学院,辽宁 沈阳 110142||宁夏惟远新能源有限公司,宁夏 银川 750411
化学工程
乙烯基醚类热力学分析反应平衡常数
vinyl ethersthermodynamic analysisreaction equilibrium constant
《低碳化学与化工》 2024 (003)
53-62 / 10
辽宁省创新能力联合基金(2021-NLTS-12-02).
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