基于Oxyma耦合活化低温制备对苯类环保增塑剂  

Preparation of Terephthalate Plasticizers based on Oxyma Low Temperature Activation

作　　者：潘思宇 陆天 刘德蒙 侯德隆 孙献冲 陈意[1] PAN Siyu;LU Tian;LIU Demeng;HOU Delong;SUN Xianchong;CHEN Yi(College of Biomass Science and Engineering,Sichuan University,Chengdu 610065,China;Shandong Chengwu Yixin Environmental Technology Co.,Ltd.,Heze 274200,China)

机构地区：[1]四川大学轻工科学与工程学院,四川成都610065 [2]山东成武易信环保科技有限公司,山东菏泽274200

出　　处：《皮革科学与工程》2025年第3期25-31,共7页Leather Science and Engineering

基　　金：国家重点研发计划(2023YFC3904905)。

摘　　要：对苯二甲酸酯是近年来市场规模增长最快的环保增塑剂之一,可有效替代传统高毒性邻苯二甲酸酯。然而,传统Fischer酯化法须采用200℃以上高温条件,存在能耗大、对设备要求高等问题。文章利用2-肟氰乙酸乙酯(Oxyma)耦合活化方法,以对苯二甲酸及丁醇为模型,探索了在较低酯化温度下合成对苯二甲酸二丁酯的可行性,并借助响应面法对反应条件进行了优化,最终证实最佳反应条件为:对n(苯二甲酸)∶n(丁醇)∶n(Oxyma)=1∶3∶0.81、反应温度33℃、反应时间11.7 h;采用此条件合成了醇碳链长度为4~10的对苯二甲酸酯,产率均可达96.5%以上。同时,该合成方法对再生对苯二甲酸也具有适用性。上述工作为降低对苯二甲酸酯增塑剂生产能耗提供了技术支撑,为再生对苯二甲酸高值利用提供了参考。Terephthalate,an effective alternative to traditional highly toxic phthalate plasticizers,has gradually become one of the fastest-growing environmentally friendly plasticizer in recent years.However,conventional Fischer synthesis methods require temperatures above 200℃,resulting in high energy consumption and stringent equipment requirements.Here,using terephthalic acid and butanol as a representative,this work explored the feasibility of synthesizing dibutyl terephthalate at lower temperature by Oxyma activation method.The reaction conditions were optimized by using the response surface methodology.It was demonstrated that the yields of terephthalates with alcohol carbon chain lengths of 4-10 prepared could be more than 96.5%under the optimal reaction conditions,i.e.,reacting at 33℃for 11.7 h under n(terephthalic acid)∶n(butanol)∶n(Oxyma)=1∶3∶0.81.Furthermore,this study also examined the suitability of the above synthesis technique for regenerating terephthalic acid.The present efforts may provide a technical support for reducing energy consumption in the production of terephthalate plasticizers,and give a reference for the high-value use of recycled terephthalic acid.

关 键 词：对苯二甲酸酯 增塑剂 Oxyma 酯化 响应面法 

分 类 号：TS529.1[轻工技术与工程—皮革化学与工程]