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.
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.
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.
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.
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).
Multicatalysis from renewable resources: a direct route to furan-based polyesters
Gauvin, Régis M.,Guillaume, Lucie,Marshall, Adam,Ni, Pingping,Niessen, Nicolas,Thomas, Christophe M.
supporting information, p. 6931 - 6935 (2021/09/28)
Here we present a multicatalytic route to produce 2,5-bis(hydroxymethyl)furan and the corresponding (co)polymers from stable 2,5-furanedicarboxylic acid. This approach combines the use of several commercial catalysts and in particular allows to quantitatively obtain two key furan intermediates, not contaminated by humins.
