4282-32-0Relevant articles and documents
Synthesis of a ZIF-derived hollow yolk-shell Co@CN catalyst for the oxidative esterification of 5-hydroxymethylfurfural
Sun, Kang-Kang,Chen, Shu-Jie,Li, Ze-Lin,Lu, Guo-Ping,Cai, Chun
, p. 1602 - 1608 (2019)
A newly developed template protection-sacrifice (TPS) strategy is developed for the synthesis of hollow yolk-shell Co@CN with a large surface area and high pore volume. The catalyst exhibits excellent catalytic efficiency in base-free oxidative esterification of 5-hydroxymethylfurfural under mild conditions with excellent selectivity at a high concentration (2 M) of the reactant.
Synthesis and characterization of novel renewable polyesters based on 2,5-furandicarboxylic acid and 2,3-butanediol
Gubbels,Jasinska-Walc,Koning
, p. 890 - 898 (2013)
Novel polyesters from 2,5-furandicarboxylic acid or 2,5-dimethyl- furandicarboxylate and 2,3-butanediol have been synthesized via bulk polycondensation catalyzed by titanium (IV) n-butoxide, tin (IV) ethylhexanoate, or zirconium (IV) butoxide. The polymers were analyzed by size exclusion chromatography, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy (FTIR), matrix-assisted laser ionization-desorption time-of-flight mass spectrometry, electrospray ionization time-of-flight mass spectrometry, electrospray ionization quadruple time-of-flight mass spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Fully bio-based polyesters with number average molecular weights ranging from 2 to 7 kg/mol were obtained which can be suitable for coating applications. The analysis of their thermal properties proved that these polyesters are thermally stable up to 270-300 °C, whereas their glass transition temperature (T g) values were found between 70 and 110 °C. Furthermore, a material was prepared with a molecular weight of 13 kg/mol, with a Tg of 113 °C. This high Tg would make this material possibly suitable for hot-fill applications.
Effective Strategy for High-Yield Furan Dicarboxylate Production for Biobased Polyester Applications
Kim, Minjune,Su, Yaqiong,Aoshima, Takayuki,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka
, p. 4277 - 4285 (2019)
A unique strategy for the formation of furan-2,5-dicarboxylic acid (FDCA)-derived esters with methanol and ethylene glycol in concentrated solutions was reported using a six-membered ring acetal of (5-hydroxymethyl)furfural (HMF) with 1,3-propanediol in order to improve the economics for the production of polyethylene 2,5-furandicarboxylate (PEF), a biobased polyester. Aerobic oxidative esterification with methanol and ethylene glycol in the presence of a CeO2-supported Au catalyst gave 80-95% yields of methyl furan-2,5-dicarboxylate and bis(2-hydroxyethyl)furan-2,5-dicarboxylate from concentrated HMF-acetal solutions (10-20 wt %). Kinetic studies combined with density functional theory (DFT) calculations were used to identify two key steps for the conversion of the cyclic acetal ring to the corresponding methyl ester: (i) partial hydrolysis of the acetal ring by OH- ions and (ii) subsequent oxidation of the hemiacetal in solution by molecular O2 on Au nanoparticles. These results represent a significant contribution not only to cutting-edge conversion technology for renewable biomass feedstocks to PEF-based applications but also to opportunities for the efficient conversion of substrates with a reactive formyl group in high yield.
Dimethyl 2,5-furandicarboxylate synthesis from 2,5-furanodicarboxylic acid and dimethyl carbonate in presence of MgO-Al2O3 and tetrabutylammonium bromide
Li, Zhenhuan,Meng, Chunyu,Su, Kunmei,Zhang, Maliang
, (2021)
2,5-furandicarboxylic acid (FDCA) and dimethyl 2,5-furandicarboxylate (DMFDCA) are attracting increasing attention as important biomass-based chemical feedstocks. Considering the physicochemical properties of FDCA with high polarity, poor solubility and easy decarboxylation, the synthesis of DMFDCA from FDCA is especially necessary. However, how to synthesize DMFDCA in case of avoiding a series of side reactions such as furan ring opening and double bond addition is a huge challenge. Herein, we used FDCA and dimethyl carbonate (DMC) to synthesize DMFDCA in presence of MgO-Al2O3 and tetrabutylammonium bromide (TBAB), and the optimized yield and selectivity of DMFDCA came up to 76.38% and 80.19%, respectively. In addition, the used catalysts were characterized by SEM, XRD, BET, XPS and CO2-TPD analysis, and the structure, composition, morphology and basic site distribution of catalyst were well studied, and the relationship between catalyst structure and catalytic performance in the esterification of FDCA into DMFDCA thorough organic acid exchange reaction method was also analyzed. This work provides a promising solution for the preparation of furan-based polyester monomers.
On the process for furfural and HMF oxidative esterification over Au/ZrO2
Menegazzo, Federica,Fantinel, Tania,Signoretto, Michela,Pinna, Francesco,Manzoli, Maela
, p. 61 - 70 (2014)
The process for the oxidative esterification of furfural and HMF on Au/ZrO2catalyst has been deeply investigated. Many variables, such as reaction time, temperature, pressure, and nature of the oxidant, have been optimised. For both processes, a considerable effect of the reaction temperature has been evidenced in the range here investigated (60-140 °C). As regards furfural, oxygen pressure can be lowered from 6 to 1 bar without significant changes in the catalytic performances. Molecular oxygen can be replaced by the more economic air, still at very low relative pressure (0.5 bar). In the case of HMF, oxygen pressure can be lowered from 6 to 1 bar without significant changes in the catalytic performances. Data on the reaction mechanism have been also verified by FTIR spectroscopy measurements taken in opportune experimental conditions in order to mimic reaction conditions.
The synergistic catalysis on Co nanoparticles and CoNx sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF
Rui, Tao,Lu, Guo-Ping,Zhao, Xin,Cao, Xun,Chen, Zhong
, p. 685 - 690 (2021)
An efficient, sustainable and scalable strategy for the synthesis of porous cobalt/nitrogen co-doped carbons (Co@NCs) via pyrolysis of aniline-modified ZIFs, has been demonstrated. Aniline can coordinate and absorb on the surface of ZIF (ZIF-CoZn3-PhA), accelerate the precipitation of ZIFs, thus resulting in smaller ZIF particle size. Meanwhile, the aniline on the surface of ZIF-CoZn3-PhA promotes the formation of the protective carbon shell and smaller Co nanoparticles, and increases nitrogen content of the catalyst. Because of these properties of Co@NC-PhA-3, the oxidative esterification of 5-hydroxymethylfurfural can be carried out under ambient conditions. According to our experimental and computational results, a synergistic catalytic effect between CoNx sites and Co nanoparticles has been established, in which both Co nanoparticles and CoNx can activate O2 while Co nanoparticles bind and oxidize HMF. Moreover, the formation and release of active oxygen species in CoNx sites are reinforced by the electronic interaction between Co nanoparticles and CoNx.
A facile method to synthesize high-molecular-weight biobased polyesters from 2,5-furandicarboxylic acid and long-chain diols
Tsanaktsis, Vasilios,Papageorgiou, George Z.,Bikiaris, Dimitrios N.
, p. 2617 - 2632 (2015)
In this study, biobased furan dicarboxylate polyesters have been prepared using 2,5-furandicarboxylic acid (FDCA) and diols with high number of methylene groups (long-chain diols), namely, 8, 9, 10, and 12. Because of the high boiling points of these diols, a modified procedure of the well-known melt polycondensation was applied in this work. According to this, the dimethyl ester of FDCA (DMFD) reacted in the first transesterification stage with the corresponding diols forming bis-hydroxy-alkylene furan dicarboxylates (BHFD). In the second stage, the BHFD reacted with DMFD again at temperatures of 150-170 C (for 4-5 h), and in the final stage, the temperature was raised to 210-230 C (vacuum was applied for 2-3 h). The molecular weight of the polyesters and the content of oligomers, as was verified by gel permeation chromatography analysis, depend on the polycondensation time and temperature. The chemical structure of the polyesters was verified from 1H NMR spectroscopy. All the polymers were found to be semicrystalline, with melting temperatures from 69 to 140 C depending on the diol used. In addition, the mechanical properties also varied with the type of diol. The higher values were observed for poly(octylene 2,5-furanoate), whereas the lowest values were observed for poly(dodecylene 2,5-furanoate) with the higher number of methylene groups in its repeating unit.
Utilizing Furfural-Based Bifuran Diester as Monomer and Comonomer for High-Performance Bioplastics: Properties of Poly(butylene furanoate), Poly(butylene bifuranoate), and Their Copolyesters
Kainulainen, Tuomo P.,Hukka, Terttu I.,?zeren, Hüsamettin D.,Sirvi?, Juho A.,Hedenqvist, Mikael S.,Heiskanen, Juha P.
, p. 743 - 752 (2020)
Two homopolyesters and a series of novel random copolyesters were synthesized from two bio-based diacid esters, dimethyl 2,5-furandicarboxylate, a well-known renewable monomer, and dimethyl 2,2′-bifuran-5,5′-dicarboxylate, a more uncommon diacid based on biochemical furfural. Compared to homopolyesters poly(butylene furanoate) (PBF) and poly(butylene bifuranoate) (PBBf), their random copolyesters differed dramatically in that their melting temperatures were either lowered significantly or they showed no crystallinity at all. However, the thermal stabilities of the homopolyesters and the copolyesters were comparable. Based on tensile tests from amorphous film specimens, it was concluded that the elastic moduli, tensile strengths, and elongation at break values for all copolyesters were similar as well, irrespective of the furan:bifuran molar ratio. Tensile moduli of approximately 2 GPa and tensile strengths up to 66 MPa were observed for amorphous film specimens prepared from the copolyesters. However, copolymerizing bifuran units into PBF allowed the glass transition temperature to be increased by increasing the amount of bifuran units. Besides enhancing the glass transition temperatures, the bifuran units also conferred the copolyesters with significant UV absorbance. This combined with the highly amorphous nature of the copolyesters allowed them to be melt-pressed into highly transparent films with very low ultraviolet light transmission. It was also found that furan-bifuran copolyesters could be as effective, or better, oxygen barrier materials as neat PBF or PBBf, which themselves were found superior to common barrier polyesters such as PET.
Porous cobalt@N-doped carbon derived from chitosan for oxidative esterification of 5-Hydroxymethylfurfural: The roles of zinc in the synthetic and catalytic process
Lin, Yamei,Lu, Guo-Ping,Zhao, Xin,Cao, Xun,Yang, Lele,Zhou, Baojing,Zhong, Qin,Chen, Zhong
, (2020)
A newly developed, facile and sustainable self-sacrifice template strategy, in which zinc and chitosan were used as the sacrificial template and carbon source respectively, has been disclosed for the synthesis of a hollow Co-embedded in nitrogen-doped graphite (Co@CN) structure. This material exhibits excellent catalytic efficiency in the oxidative esterification of 5-hydroxymethylfurfural to 2,5-furandicarboxylicacid dimethyl ester that is a significant raw material for polymer synthesis. According to the experimental and calculation results, zinc as the self-sacrificial template and acid-base site regulator has significantly improved the performance of the catalyst. The high specific surface area owing to the partial evaporation of zinc and the optimization of basic and acid sites in the catalyst prove to be the main reasons for its high activity.
Carboxyl Methyltransferase Catalysed Formation of Mono- and Dimethyl Esters under Aqueous Conditions: Application in Cascade Biocatalysis
Ashbrook, Chloe,Carnell, Andrew J.,Goulding, Ellie,Hatton, Harry,Johnson, James R.,Kershaw, Neil M.,McCue, Hannah V.,Rigden, Daniel J.,Ward, Lucy C.
supporting information, (2022/02/21)
Carboxyl methyltransferase (CMT) enzymes catalyse the biomethylation of carboxylic acids under aqueous conditions and have potential for use in synthetic enzyme cascades. Herein we report that the enzyme FtpM from Aspergillus fumigatus can methylate a broad range of aromatic mono- and dicarboxylic acids in good to excellent conversions. The enzyme shows high regioselectivity on its natural substrate fumaryl-l-tyrosine, trans, trans-muconic acid and a number of the dicarboxylic acids tested. Dicarboxylic acids are generally better substrates than monocarboxylic acids, although some substituents are able to compensate for the absence of a second acid group. For dicarboxylic acids, the second methylation shows strong pH dependency with an optimum at pH 5.5–6. Potential for application in industrial biotechnology was demonstrated in a cascade for the production of a bioplastics precursor (FDME) from bioderived 5-hydroxymethylfurfural (HMF).
