合成聚丁二酸丁二醇酯的热力学分析.pdfVIP

学兔兔 石 油 化 工 2014年第43卷第3期 PETR0CHEMICAL TECHN0L0GY ·293· 合成聚丁二酸丁二醇酯的热力学分析 马 莹 ，杨 琴 ，蒋文伟 (1．四川大学 化学工程学院，四川 成都 610065；2．成都惠恩精细化工有限责任公司，四川 成都 610000) [摘要]采用基团贡献法分别对丁二醇与丁二酸(反应(1))、丁二醇与丁二酸酐(反应(2))和丁二醇与丁二酸二甲酯(反应 (3))合成聚丁二酸丁二醇酯的反应进行了热力学计算与分析，得到了298．15～498．15 K内的反应摩尔焓变、摩尔Gibbs自由 能变以及平衡常数与温度的关系。分析结果表明，反应(1)～(3)均可自发进行；反应(2)放热，反应(1)和(3)在液态时放 热，在气态时吸热；反应(1)～(3)的平衡常数较大，表明反应进行的可行性；反应(2)的摩尔Gibbs自由能变更小，平衡常 数更大，表明该反应更容易发生。 [关键词]聚丁二酸丁二醇酯；丁二醇；丁二酸；热力学分析；基团贡献法 [文章编号]1000—8144(2014)03—0293—06 [中图分类号]TQ 013．1 [文献标志码]A Thermodynamic Analysis on Synthesis of Poly(Butylene Succinate) Ma Ying ，Yang Qin ，Jiang Wenwei (1．Department ofChemical Engineering，Sichuan University，Chengdu Sichuan 610065，China 2．Chengdu Huien Fine Chemical Co．，Ltd．，Chengdu Sichuan 610000，China) [Abstract]Thermodynamic analysis for the synthesis of poly(butylene succinate)from 1，4-butanediol and succinic acid(reaction(1))，1，4一butanediol and succinic anhydride(reaction(2))， or 1，4一butanediol and dimethyl succinate(reaction(3))were conducted by group contribution methods．The relationships between the molar enthalpy changes，molar Gibbs free energy changes and equilibrium constants of the reactions，and temperature in the range of 298．1 5-498．1 5 K were established．The results showed that reactions(1)-(3)could take place spontaneously；reaction(2) was exothermic，and reactions(1)，(3)were exothermic in liquid state and endothermic in gas state； all the equilibrium constants of reaction(1)-(3)were large，which indicated that the reactions were feasible．Moreover，reaction(2)was the easiest due to its small molar Gibbs free energy change and large eq