酸性离子液体的制备及在生物基聚2,5-呋喃二甲酸乙二醇酯合成中的催化性能  

Preparation of Acidic Ionic Liquids and Their Catalytic Performance in Synthesis of Biobased Poly(ethylene 2,5-furandicarboxylate)

作　　者：周俏 赵园园 郭立颖[1] 史亚飞 郑荣荣 ZHOU Qiao;ZHAO Yuanyuan;GUO Liying;SHI Yafei;ZHENG Rongrong(School of Petrochemical Engineering,Shenyang University of Technology,Liaoyang 111003,China)

机构地区：[1]沈阳工业大学石油化工学院,辽阳111003

出　　处：《高等学校化学学报》2024年第5期155-164,共10页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22278271,52103225);辽宁省“揭榜挂帅”科技计划项目(批准号:2023JH1/10400062)资助.

摘　　要：制备了5种酸性离子液体催化剂([DA-2PS][X]_(2)),利用红外光谱仪、核磁共振波谱仪、紫外光谱仪和热重分析仪对其化学结构、Brønsted酸性和热性能进行了表征与测试.用其代替传统金属催化剂催化2,5呋喃二甲酸(FDCA)与乙二醇(EG)直接酯化反应合成聚2,5-呋喃二甲酸乙二醇酯(PEF),讨论了Brønsted酸性强弱对催化性能的影响,其中Brønsted酸性最强的[DA-2PS][HSO_(4)]_(2)催化性能最好.通过正交实验获得了最佳工艺参数,即催化剂用量为FDCA摩尔数的0.10%,n(EG)∶n(FDCA)=2∶1,酯化温度为210℃,缩聚温度为240℃,缩聚时间为6h.在最佳工艺参数下,FDCA转化率为98.1%,PEF的特性黏度为0.63dL/g,数均分子量达到25592.PEF的结构表征和热性能测试结果表明,所合成的物质为目标产物,且具有与传统金属催化剂合成的PEF相当的热性能.Five acidic ionic liquid catalysts,[DA-2PS][X]_(2),were prepared,characterized and tested for their chemical structures,Brønsted acidity and thermal properties using a Fourier transform infrared(FTIR)spectrometer,a nuclear magnetic resonance instrument(1H NMR),an ultraviolet(UV-Vis)spectrosmeter,and a thermal gravimetric analyser(TGA).The acidic ionic liquid catalysts were then used to replace conventional metal catalysts to catalyze the direct esterification of 2,5-furanodicarboxylic acid(FDCA)with ethylene glycol(EG)to poly(ethylene 2,5-furandicarboxylate)(PEF),and the effect of the strength of Brønsted acidity on the catalytic performance was discussed,in which the[DA-2PS][HSO_(4)]_(2) with the strongest Brønsted acidity had the best catalytic performance.The optimal parameters obtained from orthogonal tests are as follows:the catalyst dosage was 0.10%of the molar number of FDCA,the feeding ratio was n(EG)∶n(FDCA)=2∶1,the esterification temperature was 210℃,the poly-condensation temperature was 240℃,and the polycondensation time was 6 h.Experiments were carried out under the optimal conditions process parameters,and the conversion rate of FDCA was 98.1%,the intrinsic viscosity of PEF was 0.63 dL/g,the number average molecular weight of PEF reached 25592.The structural characterization and thermal properties of PEF were tested by FTIR,1H NMR,TGA and differential scanning calorimetry(DSC)analyzer,and the results showed that the synthesized substance is the target product,and it had the comparable thermal properties to those of PEF synthesized by the traditional metal catalysts.

关 键 词：离子液体 直接酯化法 生物基聚2 5-呋喃二甲酸乙二醇酯 

分 类 号：O631[理学—高分子化学]