Synthesis and Alcoholysis of Bio-Based Poly（ethylene 2，5-furandicarboxylate） Catalyzed by Ti-MOF

doi:10.19894/j.issn.1000-0518.240122

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (11): 1596-1604.DOI: 10.19894/j.issn.1000-0518.240122

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Synthesis and Alcoholysis of Bio-Based Poly（ethylene 2，5-furandicarboxylate） Catalyzed by Ti-MOF

Li-Xin LIU¹^,², Shu-Hua YAO¹(), Xuan CAO¹, Guan-Nan ZHOU², Rui WANG², Lu LI²()

^1.Liaoning Engineering Research Center for Treatment and Recycling of Industrially Discharged Heavy Metals，Shenyang University of Chemical Technology，Shenyang 110142，China
^2.Division of Energy Materials （DNL 22），Dalian Institute of Chemical Physics，Chinese Academy of Sciences，Dalian 116023，China

Received:2024-04-12 Accepted:2024-08-30 Published:2024-11-01 Online:2024-12-04
Contact: Shu-Hua YAO,Lu LI
About author:lilu528@dicp.ac.cn
yaoshuhua@syuct.edu.cn；
Supported by:
the National Key Research and Development Programme of China(2022YFC2105800);the Science and Technology Programme of Liaoning Province(2022JH24/10200024);the Basic Research Project of the Department of Education of Liaoning Province(JYTQN2023373);the Medical-Industrial Joint Innovation Fund(DMU-1&DICP UN202210)

Abstract

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 M_n=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.

Key words: Polyester catalyst, Metal-organic frameworks, Poly（ethylene 2, 5-furandicarboxylate）, Alcoholysis

CLC Number:

O643.3

Li-Xin LIU, Shu-Hua YAO, Xuan CAO, Guan-Nan ZHOU, Rui WANG, Lu LI. Synthesis and Alcoholysis of Bio-Based Poly（ethylene 2，5-furandicarboxylate） Catalyzed by Ti-MOF[J]. Chinese Journal of Applied Chemistry, 2024, 41(11): 1596-1604.

Figures/Tables 8

Fig.1 Schematic diagram of the preparation process of MIL-125

Fig.2 XRD analysis of MIL-125 （A）； FT-IR spectrum of MIL-125 （B）； TGA for MIL-125 （C）； SEM image of MIL-125 （D）； EDS analysis for MIL-125 （E）

Fig.3 （A） NH3-TPD analysis of MIL-125；（B） The N2 adsorption/desorption isotherms analysis for MIL-125；（C） XPS analysis for MIL-125；（D） EPR analysis for MIL-125

Table 1 Comparison of catalytic performances of MIL-125 with TBT catalysts in PEF synthesis

No.	Compound	T_d-5%/℃	T_g/℃	φ（DEGF）/%	M_n	M_w	PDI
1	PEF/MIL-125-230	375.7	87.6	3.0	3.8×10⁴	7.2×10⁴	1.9
2	PEF/MIL-125-235	373.8	85.6	3.3	3.7×10⁴	7.4×10⁴	2.0
3	PEF/MIL-125-240	371.0	86.4	5.0	3.2×10⁴	6.6×10⁴	2.0
4	PEF/MIL-125-0.01%	375.7	87.6	3.0	3.8×10⁴	7.2×10⁴	1.9
5	PEF/MIL-125-0.05%	373.1	85.6	4.1	3.2×10⁴	5.7×10⁴	1.7
6	PEF/MIL-125-0.1%	370.0	87.3	4.7	3.0×10⁴	5.6×10⁴	1.8
7	PEF/TBT	361.5	86.4	5.1	2.6×10⁴	6.3×10⁴	2.4

Fig.4 （A） TGA graph of the effect of polycondensation temperature on the thermal decomposition temperature of PEF；（B） TGA graph of the effect of catalyst dosage on the thermal decomposition temperature of PEF；（C） DSC secondary heating curve of the effect of polycondensation temperature on the thermal performance of PEF；（D） DSC secondary heating curve of the effect of catalyst dosage on the thermal performance of PEF

Fig.5 1H NMR spectra of the effect of polymerization temperature （A） and catalyst dosage （B） on PEF structure

Fig.6 UV-visible light transmission performance curve of PEF

Fig.7 （A） Catalytic ethylene glycol alcoholysis test of PEF/MIL-125-0.01%， 1H NMR；（B） 13C NMR；（C） MS of the intermediate BHEFDC；（D） Intuitive product diagram

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Synthesis and Alcoholysis of Bio-Based Poly（ethylene 2，5-furandicarboxylate） Catalyzed by Ti-MOF

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