应用化学2024，Vol.41Issue(11)：1596-1604,9.DOI:10.19894/j.issn.1000-0518.240122
Ti-MOF催化合成生物基聚2,5-呋喃二甲酸乙二醇酯及醇解
Synthesis and Alcoholysis of Bio-Based Poly(ethylene 2,5-furandicarboxylate)Catalyzed by Ti-MOF
摘要
Abstract
The green and non-toxic Ti-MOF(MIL-125)titanium catalyst was prepared by the oil bath thermal reflux method and was successfully used in the synthesis of bio-based poly(ethylene 2,5-furandicarboxylate)(PEF)and alcoholysis.The structural morphology and elemental composition of MIL-125 were characterized and analyzed by powder X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR)and field emission scanning electron microscopy(SEM).The catalyst surface was also revealed to be rich in acid sites by means of Ammonia programmed temperature desorption test(NH3-TPD),which showed high catalytic activity in both catalytic synthesis of PEF and catalytic alcoholysis of PEF reactions.Under the condition that the catalyst dosage is only 0.01％of the molar amount of 2,5-furandicarboxylic acid(FDCA),the esterification stage reaches clarity and transparency(the end of the esterification reaction)at 210 ℃ and 55 min.When the polycondensation stage is maintained at 230 ℃ for 3 h,the number average molecular mass of PEF/MIL-125-230 can reach Mn=3.8×104,and the synthesized PEF relative molecular mass distribution is narrow PDI=1.9;In addition,MIL-125 not only plays a catalytic role,but also endows PEF with good UV shielding and anti-blue light capabilities,shielding up to 87％of UV light and 34％of blue light.Alcoholysis experiments show that the residual MIL-125 in PEF has the ability to catalyze the alcoholysis of ethylene glycol from PEF to the monomer ethylene glycol furandicarboxylate(BHEFDC).This study broadens the catalytic field of MOFs and opens up a new way for the recycling of bio-based polyesters.关键词
聚酯催化剂/金属有机骨架材料/聚2,5-呋喃二甲酸乙二醇酯/醇解Key words
Polyester catalyst/Metal-organic frameworks/Poly(ethylene 2,5-furandicarboxylate)/Alcoholysis分类
化学化工引用本文复制引用
刘利鑫,姚淑华,曹旋,周冠男,王瑞,李璐..Ti-MOF催化合成生物基聚2,5-呋喃二甲酸乙二醇酯及醇解[J].应用化学,2024,41(11):1596-1604,9.基金项目
国家重点研发计划(No.2022YFC2105800)、辽宁省科技计划(No.2022JH24/10200024)和医工联合创新基金(No.MU-1&DICP UN202210)资助 Supported by the National Key Research and Development Programme of China(No.2022YFC2105800),the Science and Technology Programme of Liaoning Province(No.2022JH24/10200024),the Basic Research Project of the Department of Education of Liaoning Province(No.JYTQN2023373)and the Medical-Industrial Joint Innovation Fund(No.DMU-1&DICP UN202210) （No.2022YFC2105800）
