- Synthesis of a ZIF-derived hollow yolk-shell Co@CN catalyst for the oxidative esterification of 5-hydroxymethylfurfural
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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.
- Sun, Kang-Kang,Chen, Shu-Jie,Li, Ze-Lin,Lu, Guo-Ping,Cai, Chun
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- Synthesis and characterization of novel renewable polyesters based on 2,5-furandicarboxylic acid and 2,3-butanediol
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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.
- Gubbels,Jasinska-Walc,Koning
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- Effective Strategy for High-Yield Furan Dicarboxylate Production for Biobased Polyester Applications
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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.
- Kim, Minjune,Su, Yaqiong,Aoshima, Takayuki,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka
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- Dimethyl 2,5-furandicarboxylate synthesis from 2,5-furanodicarboxylic acid and dimethyl carbonate in presence of MgO-Al2O3 and tetrabutylammonium bromide
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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.
- Li, Zhenhuan,Meng, Chunyu,Su, Kunmei,Zhang, Maliang
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- On the process for furfural and HMF oxidative esterification over Au/ZrO2
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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.
- Menegazzo, Federica,Fantinel, Tania,Signoretto, Michela,Pinna, Francesco,Manzoli, Maela
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- The synergistic catalysis on Co nanoparticles and CoNx sites of aniline-modified ZIF derived Co@NCs for oxidative esterification of HMF
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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.
- Rui, Tao,Lu, Guo-Ping,Zhao, Xin,Cao, Xun,Chen, Zhong
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- A facile method to synthesize high-molecular-weight biobased polyesters from 2,5-furandicarboxylic acid and long-chain diols
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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.
- Tsanaktsis, Vasilios,Papageorgiou, George Z.,Bikiaris, Dimitrios N.
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- Utilizing Furfural-Based Bifuran Diester as Monomer and Comonomer for High-Performance Bioplastics: Properties of Poly(butylene furanoate), Poly(butylene bifuranoate), and Their Copolyesters
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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.
- Kainulainen, Tuomo P.,Hukka, Terttu I.,?zeren, Hüsamettin D.,Sirvi?, Juho A.,Hedenqvist, Mikael S.,Heiskanen, Juha P.
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- Porous cobalt@N-doped carbon derived from chitosan for oxidative esterification of 5-Hydroxymethylfurfural: The roles of zinc in the synthetic and catalytic process
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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.
- Lin, Yamei,Lu, Guo-Ping,Zhao, Xin,Cao, Xun,Yang, Lele,Zhou, Baojing,Zhong, Qin,Chen, Zhong
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- Carboxyl Methyltransferase Catalysed Formation of Mono- and Dimethyl Esters under Aqueous Conditions: Application in Cascade Biocatalysis
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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).
- Ashbrook, Chloe,Carnell, Andrew J.,Goulding, Ellie,Hatton, Harry,Johnson, James R.,Kershaw, Neil M.,McCue, Hannah V.,Rigden, Daniel J.,Ward, Lucy C.
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supporting information
(2022/02/21)
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- FLOW CHEMISTRY SYNTHESIS OF ISOCYANATES
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The disclosure provides, inter alia, safe and environmentally-friendly methods, such as flow chemistry, to synthesize isocyanates, such as methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tetramethylxylene diisocyanate.
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Paragraph 0175; 0186-0187; 0349-0351
(2021/06/22)
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- Multicatalysis from renewable resources: a direct route to furan-based polyesters
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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.
- Gauvin, Régis M.,Guillaume, Lucie,Marshall, Adam,Ni, Pingping,Niessen, Nicolas,Thomas, Christophe M.
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supporting information
p. 6931 - 6935
(2021/09/28)
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- Ultrafine Copper Oxide Particles Dispersed on Nitrogen-Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass-Derived 5-Hydroxymethylfurfural
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One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/N?C?HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N?C?HNSs was prepared through a template protection-sacrifice strategy using SiO2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m2/g, the CuO/N?C?HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP3C?H bond functionalization is also demonstrated using the same catalyst.
- Gupta, Shyam Sunder R.,Vinu, Ajayan,Kantam, Mannepalli Lakshmi
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p. 259 - 269
(2021/03/01)
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- Method for producing furandicarboxylic acid and derivatives thereof from furfural
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The invention discloses a method for producing furandicarboxylic acid and derivatives thereof from furfural. The method comprises the following steps: furfural is reduced to 2-methylfuran under the hydrogen condition; acetylation reaction is carried out on 2-methylfuran to obtain 5-methyl-2-acetylfuran; 5-methyl-2-acety furan reacts with ester to obtain methyl 5-methyl-2-furanformate, methyl 5-methyl-2-furanformate is oxidized into monomethyl 2,5-furandicarboxylate under the oxygen condition, and monomethyl 2,5-furandicarboxylate is hydrolyzed into monomethyl 2,5-furandicarboxylate or furtheresterified with methyl alcohol to generate dimethyl 2,5-furandicarboxylate. The cheap five-carbon furan compound furfural is used as a raw material, and the 2 5-furandicarboxylic acid and the derivatives thereof are prepared by a strategy of increasing a carbon chain, so that the cost of the raw material is greatly reduced. The product provided by the invention has high purity and can be directlyused as a polymerization monomer of PET polyester.
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Paragraph 0068-0070
(2020/06/05)
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- Quaternary ammonium salt surfactant, preparation method and applications thereof
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The invention provides a quaternary ammonium salt surfactant, a preparation method and applications thereof, wherein the structure of the quaternary ammonium salt surfactant is represented by a formula (I), and each group is defined in the specification. The quaternary ammonium salt surfactant disclosed by the invention can be used as an efficient and low-consumption wetting agent in the field oftertiary oil recovery, and can effectively convert the surface of a carbonate oil reservoir wrapped by crude oil into water wettability or neutral wettability in the tertiary oil recovery process to achieve wetting reversal, so that the oil washing efficiency can be improved.
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Paragraph 0123-0127
(2020/05/08)
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- BIFURAN COPOLYESTERS AND A METHOD FOR PREPARATION THEREOF
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The present invention is directed to bifuran copolyesters comprising 2,2'-bifuran-5,5'- dicarboxylic monomer residues. The present invention is further directed to films, coatings or articles comprising said bifuran copolyesters. Also production methods for said bifuran copolyesters are provided. The invention is also directed to a use of a 2,2'-bifuran-5,5'- dicarboxylic monomers in preparing copolyesters having ultraviolet light (UV) blocking properties.
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Page/Page column 12
(2021/01/22)
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- Process for Preparing Furan-2,5-diakylcarboxylate
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The present invention (i) provides II a process for the preparation of a (oxidation) compound represented by III the following formula, (ii) comprising reacting III a compound N- represented (N-bromosuccinimide, NBS) by the above IV formula with an alcohol; in (iii) the presence IV of a catalyst, in the presence of a catalyst to obtain a (alkoxy carbonylation) compound represented by the general I formula 2,5- (FDAC) and then reacting. the compound of the formula with an alcohol and carbon monoxide in the presence of a catalyst and a base to obtain the compound represented by the general formula (I). (by machine translation)
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- Preparation method of 2, 5-dimethyl furandicarboxylate
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The invention discloses a preparation method of 2, 5-dimethyl furandicarboxylate. The method comprises the following steps: under the catalytic action of an alkali metal or alkaline-earth metal compound and a phase transfer catalyst, using a polar or non-polar organic compound as a solvent and dimethyl carbonate as a methylation reagent at the temperature of 25-200 DEG C under the conditions of normal pressure and no water to convert 2, 5-furandicarboxylic acid into the 2, 5-dimethyl furandicarboxylate. According to the method, the dimethyl carbonate is used as a methylation reagent so that the method is green and environment-friendly, the reaction process of anhydrous generation under a weak base condition is realized, more byproducts are prevented from being generated due to furan ring opening caused by the existence of water, the reaction selectivity and the yield are improved, and the 2, 5-dimethyl furandicarboxylate with high yield is prepared.
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Paragraph 0025-0028; 0030-0031; 0032-0033; 0034-0144
(2020/12/30)
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- SYNTHESIS OF FURANDICARBOXYLIC ACID AND ESTER THEREOF
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According to an example aspect of the present invention, there is provided both a continuous method and a batch method for producing furandicarboxylic acid (FDCA) and furandicarboxylic acid ester (FDCAE) from aldaric acid ester by utilizing cheap and available catalysts and bio-based solvents in an efficient manner.
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Page/Page column 9
(2020/07/07)
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- Method for preparing 5 - by catalyzing 2-hydroxymethylfurfural oxidation esterification and 5 -furandicarboxylic acid dimethyl ester (by machine translation)
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To the method, 5 - hydroxymethyl furfural is contacted with a transition metal catalyst under the condition of an oxidizing atmosphere, and 2 5 - 5 - 2 5 - furandicarboxylic acid dimethyl ester is obtained. To the method, 5 - hydroxymethyl furfural is efficiently and selectively catalytically oxidized and esterified to 2 and 5 - furandicarboxylic acid dimethyl ester without an alkali additive. (by machine translation)
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Paragraph 0095-0108; 0115-0122
(2020/07/02)
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- Copper-catalyzed oxidative methyl-esterification of 5-hydroxymethylfurfural using TBHP as an oxidizing and methylating reagent: A new approach for the synthesis of furan-2,5-dimethylcarboxylate
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Catalytic conversion of 5-hydroxymethylfurfural (HMF) into furan-2,5-dimethylcarboxylate (FDMC) is of great significance in the production of polyethylene furanoate (PEF), a renewable biomass-derived polymer that can replace the fossil dependent polyethylene terephthalate (PET). Herein, for the first time, we report the synthesis of FDMC from oxidative methyl-esterification of HMF using tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent catalyzed by mesoporous alumina nanospheres-embedded with CuO nanoparticles (CuO/m-Al2O3). The CuO/m-Al2O3 catalysts with different copper contents were prepared by evaporation-induced self-assembly of a structure-directing agent (Pluronic P-123). The decomposition of P-123 during calcination in air results into the formation of a mesoporous structure with highly dispersed CuO nanoparticles. The as-prepared 6-CuO/m-Al2O3 exhibits excellent catalytic activity towards oxidative methyl-esterification of HMF into FDMC with 92% yield and turnover frequency (TOF) of 0.56 h?1. Furthermore, oxidative methyl-esterification of a range of substrates through SP3 C[sbnd]H bond functionalization has also been demonstrated using the same catalyst.
- Gupta, Shyam Sunder R.,Kantam, Mannepalli Lakshmi,Vinu, Ajayan
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p. 259 - 269
(2020/06/27)
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- Direct Alkoxycarbonylation of Heteroarenes via Cu-Mediated Trichloromethylation and in Situ Alcoholysis
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We report an efficient approach for direct alkoxycarbonylation of furans as well as other heteroarenes via a one-step copper-mediated reaction of three components (i.e., heteroarene, alcohol, and CHCl3). The copper additive was confirmed to simultaneously promote the reaction in three pathways: oxidant cracking, single electron transfer, and alcoholysis. By means of this protocol, various functionalized furancarboxylates and other heteroarenecarboxylates were facilely obtained in moderate to good yields.
- Jiang, Huanfeng,Jiang, Kai,Li, Yingwei,Luo, Wenkun,Yin, Biaolin
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- Oxidative Esterification of 5-Hydroxymethylfurfural under Flow Conditions Using a Bimetallic Co/Ru Catalyst
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Furanic di-carboxylate derivatives of 5-Hydroxymethylfurfural (HMF) are nowadays important in the polymer industry as they are used as building blocks for bio-based polyesters. The high reactivity of HMF compels to avoid harsh synthetic conditions. Therefore, developing mild catalytic processes for its selective oxidation is a challenging task. Herein, we report the first oxidative esterification of HMF to dimethyl furan-2,5-dicarboxylate (FDCM) under flow conditions using oxygen as oxidant. For that purpose, a new series of nitrogen-doped carbon-supported bimetallic Co/Ru heterogeneous catalysts were prepared and characterized by XRD, XPS and N2 physisorption. These analyses revealed that the porosity of the materials and order of impregnation of the metals to the carbon supports lead to varying catalytic activities. Under optimized conditions the flow reactor showed a 15-fold increase on the production of FDCM compared to batch conditions.
- Salazar, Abel,Linke, Alexander,Eckelt, Reinhard,Quade, Antje,Kragl, Udo,Mejía, Esteban
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p. 3504 - 3511
(2020/05/16)
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- NOVEL ESTERIFICATION CATALYST AND USES THEREOF
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Tin (II) glucarate is found to be effective alone and in combination with other tin compounds for catalyzing the reaction of carboxylic acids such as furan-2,5-dicarboxylic acid, terephthalic acid and adipic acid with alcohols such as the C1-C3 alcohols.
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Page/Page column 0026; 0030-0031
(2020/07/07)
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- Oxidative Esterification of 5-Hydroxymethylfurfural with an N-doped Carbon-supported CoCu Bimetallic Catalyst
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The direct fabrication of furan-2,5-dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass-derived 5-hydroxymethylfurfural (HMF) is a cutting-edge process. In this contribution, an elaborately designed N-doped carbon-supported CoCu bimetallic catalyst (CoxCuy-NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 percent under mild and base-free conditions (Co7Cu3-NC, 2 bar O2, 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo?1 h?1 was achieved over Co7Cu3-NC, which represents the highest catalytic efficiency so far among Co-based catalytic systems. It has been demonstrated that Cu-doping in Co7Cu3-NC catalyst brings about more active sites (Co-Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7Cu3-NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio-based polymer monomers.
- Liu, Huai,Ding, Ning,Wei, Junnan,Tang, Xing,Zeng, Xianhai,Sun, Yong,Lei, Tingzhou,Fang, Huayu,Li, Tianyuan,Lin, Lu
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p. 4151 - 4158
(2020/07/10)
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- Method for preparing dimethyl furan-2,5-dicarboxylate through catalytic oxidation of 5-hydroxymethylfurfural
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The invention discloses a method for preparing dimethyl furan-2,5-dicarboxylate by catalytic oxidation of 5-hydroxymethylfurfural, and the method comprises the following steps: in an oxygen-containingatmosphere, contacting a raw material containing methanol and the 5-hydroxymethylfurfural with a catalyst, and reacting to obtain the dimethyl furan-2,5-dicarboxylate, wherein the catalyst comprisesa metal oxide modified by a nitrogen-containing compound. The method is simple in process, mild in preparation condition and high in raw material utilization rate, and a target product can be obtainedwith high selectivity.
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Paragraph 0048-0109
(2020/11/05)
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- METHOD FOR PREPARING 2, 5-FURANDIMETHYLCARBOXYLATE FROM HYDROXYMETHYLFURFURAL
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An embodiment of the present invention provides a method of preparing 2,5-furandimethylcarboxylate (FDMC), including preparing 2,5-furandimethylcarboxylate (FDMC) by subjecting a reaction mixture including 5-hydroxymethylfurfural (HMF), air, and an alcohol solvent to oxidative esterification in the presence of a gold (Au)-nanoparticle-supported catalyst, in which the gold (Au)-nanoparticle-supported catalyst includes a support and gold (Au) nanoparticles supported on the support.
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Paragraph 0080-0098; 0109-0110; 0117-0129
(2020/06/07)
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- Thermal decomposition kinetics and mechanism of in-situ prepared bio-based poly(propylene 2,5-furan dicarboxylate)/graphene nanocomposites
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Bio-based polyesters are a new class of materials that are expected to replace their fossil-based homologues in the near future. In this work, poly(propylene 2,5-furandicarboxylate) (PPF) nanocomposites with graphene nanoplatelets were prepared via the in-situ melt polycondensation method. The chemical structure of the resulting polymers was confirmed by 1H-NMR spectroscopy. Thermal stability, decomposition kinetics and the decomposition mechanism of the PPF nanocomposites were studied in detail. According to thermogravimetric analysis results, graphene nanoplatelets did not affect the thermal stability of PPF at levels of 0.5, 1.0 and 2.5 wt.%, but caused a slight increase in the activation energy values. Pyrolysis combined with gas chromatography and mass spectroscopy revealed that the decomposition mechanism of the polymer was not altered by the presence of graphene nanoplatelets but the extent of secondary homolytic degradation reactions was increased.
- Terzopoulou, Zoi,Tarani, Evangelia,Kasmi, Nejib,Papadopoulos, Lazaros,Chrissafis, Konstantinos,Papageorgiou, Dimitrios G.,Papageorgiou, George Z.,Bikiaris, Dimitrios N.
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- A tunable precious metal-free system for selective oxidative esterification of biobased 5-(hydroxymethyl)furfural
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Oxidative esterification of biomass-derived 5-(hydroxymethyl) furfural (HMF) and furfural and their derivatives has been performed using a simple MnO2/NaCN system. The developed method allows the selective one-pot transformation of HMF to dimethyl furan-2,5-dicarboxylate (FDME) in 83% isolated yield without the formation of a free acid. Simplification of FDME production provides the missing link for manufacturing sustainable value-added materials from biomass. Addition of water to the oxidative system allows fine-tuning of reaction selectivity to obtain the previously difficult-to-access pure methyl 5-(hydroxylmethyl)furan-2-carboxylate in one step directly from the unprotected HMF without chromatographic separation.
- Kozlov, Kirill S.,Romashov, Leonid V.,Ananikov, Valentine P.
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supporting information
p. 3464 - 3468
(2019/06/24)
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- Synthesis method of dialkyl 2,5-furan dicarboxylate
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The invention belongs to the technical field of five-membered ring compounds, which are not condensed with other rings and contain one oxygen atom taken as the only heterocyclic atom, and specificallyrelates to a synthesis method of dialkyl 2,5-furan dicarboxylate. The synthesis method comprises following steps: step A, taking spinel type copper aluminate as a catalyst to oxidize furfural to obtain furoic acid; and step B, sequentially introducing furoic acid, carbonate, and alcohols into a high pressure reactor, closing the reactor, blowing the reactor by nitrogen for three times, filling carbon dioxide into the reactor until the pressure reaches 1 to 4 MPa, and carrying out reactions for 6 to 24 hours at a reaction temperature of 200 to 240 DEG C. The adopted raw materials are abundantand can be obtained massively; the reaction conditions are mild, the yield of the target product can reach 90-95%; target product selectivity can reach 100%; the reaction time is short, the catalyst and the reaction system are easy to separate, the catalyst can be repeatedly used, and the preparation method can be applied to industrial production.
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Paragraph 0032; 0038-0041
(2019/07/04)
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- PET hydrolysing enzymes catalyse bioplastics precursor synthesis under aqueous conditions
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Poly(ethylene terephthalate) hydrolase (PETase) was used to catalyse a double transesterification to convert FDCA dimethyl ester to the bioplastics precursor bis-butandiol ester in good yield under aqueous conditions. The presence of high water content was important for high transesterification selectivity. CAL-A and CAL-B lipases showed low activity or extensive hydrolysis. The PETase bioconversion was demonstrated at gram scale and the transesterification products can be selectively extracted for use in polymerisation reactions.
- Parisi, Daniele,Riley, Christopher,Srivastava, Abhishek S.,McCue, Hannah V.,Johnson, James R.,Carnell, Andrew J.
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supporting information
p. 3827 - 3833
(2019/07/31)
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- AuPd-Fe3O4 Nanoparticle-Catalyzed Synthesis of Furan-2,5-dimethylcarboxylate from 5-Hydroxymethylfurfural under Mild Conditions
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Efficient one-pot oxidative esterification of 5-hydroxymethylfurfural (HMF) to furan-2,5-dimethylcarboxylate (FDMC) was achieved under extremely mild reaction conditions by using AuPd alloy nanoparticles (NPs) supported on Fe3O4. A high yield of FDMC (92 %) was obtained at room temperature under atmospheric O2. The reaction proceeded through the synergistic effects of the AuPd heterobimetallic catalyst system. The most effective molar ratio of noble metal contents for HMF oxidation was 1.00:1.18. If Au-Fe3O4 NPs were used as the catalyst, selective synthesis of 5-hydroxymethylfuroic acid methyl ester (HMFE) was achieved. Additionally, the AuPd-Fe3O4 catalyst could be successfully reused.
- Cho, Ahra,Byun, Sangmoon,Cho, Jin Hee,Kim, Byeong Moon
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p. 2310 - 2317
(2019/04/30)
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- Preparation method of 2,5-furan dicarboxylate compounds
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The invention belongs to the field of fine chemical raw materials, and particularly relates to a preparation method of 2,5-furan dicarboxylate compounds. The method comprises steps as follows: a component shown in the description, ROH, an initiator and a catalyst are added to chloroform and subjected to a reflux reaction, and the 2,5-furan dicarboxylate compounds can be obtained. According to the method, expensive 5-hydroxymethylfurfural is not required to be used as a raw material, an alcoxyl acylation reagent is chloroform, other solvents are not needed, besides, strict anhydrous condition and low-temperature operation are not needed, expensive strong base such as butyl lithium and the like is not required, and the method is simple to operate and low in cost and has broad industrial application prospects.
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Paragraph 0105-0110
(2019/05/08)
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- Method for preparation of 2, 5-furandicarboxylic acid diester compound from 5-hydroxymethylfurfural
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The invention discloses a method for preparation of a 2, 5-furandicarboxylic acid diester compound from 5-hydroxymethylfurfural. The method uses a cheap and specific non-noble metal as the catalyst, and adopts cheap and easily available oxygen or air as an oxygen source to prepare high purity dimethyl furan-2, 5-dicarboxylate at high efficiency under mild reaction conditions, thus solving the problems of low reaction efficiency, low product yield, high cost and the like in the prior art, and has good application prospects.
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Paragraph 0019-0024; 0027-0033
(2019/12/31)
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- Preparation method of 2,5-furandicarboxylic diester
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The invention discloses a preparation method of 2,5-furandicarboxylic diester. 5-hydroxymethylfurfural is catalyzed by ZIF-67C to prepare the 2,5-furandicarboxylic diester. The ZIF-67C adopted as a catalyst is simple to prepare, has a low price, and can be easily recovered by magnetrons due to the self magnetism. The preparation method has the advantages of simple reaction system, mild reaction conditions and high product yield. The problem of high price of a noble metal used as the catalyst and the problem of low product yield of a non-noble metal used as the catalyst in existing researches are solved in the invention.
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Paragraph 0021-0035
(2019/02/13)
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- Solvent-dependent selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under neat conditions
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An eco-friendly and economical route for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with atmospheric dioxygen as the sole oxidant under acid-, base-, metal-, and external initiator-free conditions in minimal solvent was reported. In the present reaction, the 1,2-diethoxyethylane has a dual role: reaction medium and free-radical initiator. The FDCA easily crystallizes during the reaction and was simple purified via recrystallization to provide the pure FDCA.
- Liu, Kai-Jian,Zeng, Tang-Yu,Zeng, Jia-Le,Gong, Shao-Feng,He, Jun-Yi,Lin, Ying-Wu,Tan, Jia-Xi,Cao, Zhong,He, Wei-Min
-
supporting information
p. 2304 - 2308
(2019/11/26)
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- Method for preparing dimethyl furan-2,5-dicarboxylate by oxidizing and esterifying 5-hydroxymethyl furfural
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The invention discloses a method for preparing dimethyl furan-2,5-dicarboxylate by oxidizing and esterifying 5-hydroxymethyl furfural. The method comprises the following steps: using air and/or oxygenas an oxidant and using methanol as a solvent and a reactant without adding alkali or bromine; using a gold-based catalyst for catalyzing oxidation and esterification of 5-hydroxymethylfurfural to synthesize dimethyl furan-2,5-dicarboxylate. The method provided by the invention has high selectivity for dimethyl furan-2,5-dicarboxylate, and can ensure that a conversion rate of 5-hydroxymethyl furfural is greater than 95% and the selectivity of dimethyl furan-2,5-dicarboxylate is greater than 99%.
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Paragraph 0065-0067; 0070
(2019/09/05)
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- Valorization of 2,5-furandicarboxylic acid. Diels-Alder reactions with benzyne
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Biomass-derived 2,5-furandicarboxylic acid was valorized by conversion to 1,4-naphthalenedicarboxylic acid via benzyne-cycloaddition and reductive aromatization in 66% overall yield (four steps). Two novel bicyclic intermediates were isolated in 80% and 98% yield. These advances diversify the potential end uses of renewable terephalic acid analogs and other furanics available from cellulose biorefinery.
- Serum, Eric M.,Selvakumar, Sermadurai,Zimmermann, Nicolas,Sibi, Mukund P.
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supporting information
p. 1448 - 1454
(2018/04/12)
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- PRODUCTION METHOD OF CARBOXYLIC ACID ESTER OR CARBOXYLIC ACID
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PROBLEM TO BE SOLVED: To provide a production method of carboxylic acid ester or carboxylic acid, which can obtain carboxylic acid ester or carboxylic acid that is a target at a high yield while suppressing a side reaction and has excellent long term operation stability when producing the carboxylic acid ester or carboxylic acid having a furan skeleton derived from a biomass raw material. SOLUTION: When producing a carboxylic acid ester or carboxylic acid having a furan skeleton derived from a biomass raw material, a production method of the carboxylic acid ester or carboxylic acid via a cyclic acetal intermediate is provided. The carboxylic acid ester or carboxylic acid having a furan skeleton is produced by producing the cyclic acetal intermediate and by undergoing its oxidation reaction step. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2018,JPO&INPIT
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- PROCESS FOR MAKING ESTERS OF 2,5-FURANDICARBOXYLIC ACID
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The present invention relates to a process for making the esters of 2,5-furandicarboxylic acid, and particularly the dimethyl, diethyl or dipropyl esters of FDCA for use as monomers in the production of polyesters and other types of polymers with biobased content, comprising: reacting an aqueous feed comprising glucaric acid with a high boiling first alcohol in the presence of an acid catalyst and with removing water during the reaction, to form a first product mixture comprising a first ester of FDCA and the high boiling first alcohol; removing unreacted high boiling first alcohol from the first product mixture; combining the first ester of FDCA and the high boiling first alcohol with a lower boiling second alcohol selected from the group consisting of methanol, ethanol, isopropanol and n-propanol; transesterifying the first ester with the lower boiling second alcohol to form a second product mixture comprising a second ester of FDCA with the lower boiling second alcohol; and recovering the second ester of FDCA with the lower boiling second alcohol.
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Paragraph 0060; 0061
(2019/01/10)
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- METHOD FOR PREPARING FDMC FROM HMF USING GOLD-PALLADIUM BIMETALLIC NANOPARTICLES SUPPORTED ON AN ANION EXCHANGE RESIN
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The present invention relates to a method for producing 2,5-furandimethylcarboxylate (FDMC), wherein the method comprises a step of producing FDMC represented by chemical formula 2 by oxidation methylation of hydroxy methyl fulfural (HMF) represented by chemical formula 1 by using a catalyst in a solvent. The catalyst includes an anion exchange resin and gold palladium bimetallic nanoparticles supported on the anion exchange resin. By adjusting a gold (Au)-palladium (Pd) ratio, FDMC having a high yield of 90% or more can be obtained. A gold (Au)-palladium (Pd) bimetallic nanoparticle catalyst supported on an anion exchange resin has a high activity maintained even when being reused.COPYRIGHT KIPO 2018
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Paragraph 0133-0195
(2019/01/15)
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- Aerobic Oxidation and Oxidative Esterification of 5-Hydroxymethylfurfural by Gold Nanoparticles Supported on Nanoporous Polymer Host Matrix
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The aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural (HMF) catalyzed by gold nanoparticles (AuNPs) supported on a semicrystalline nanoporous multiblock copolymer matrix consisting of syndiotactic poly(styrene)-cis-1,4-poly(butadiene) (sPSB) have been investigated. Depending on the reaction parameters (support nanoporosity, presence of water, solvent, temperature, cocatalyst, oxygen pressure), the conversion of HMF can be finely addressed to the formation of the desired oxidation product, such as 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (FFCA), methyl 5-(hydroxymethyl)furan-2-carboxylate (MHMFC), dimethyl furan-2,5-dicarboxylate (DMFC), and furan-2,5-dicarboxylic acid (FDCA), under optimized reaction conditions. The AuNP–sPSB catalyst is highly effective and selective because the polymer support acts as a conveyor and concentrator of the reactants toward the catalytic sites.
- Buonerba, Antonio,Impemba, Salvatore,Litta, Antonella Dentoni,Capacchione, Carmine,Milione, Stefano,Grassi, Alfonso
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p. 3139 - 3149
(2018/09/14)
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- Aerobic oxidative esterification of 5-hydroxymethylfurfural to dimethyl furan-2,5-dicarboxylate by using homogeneous and heterogeneous PdCoBi/C catalysts under atmospheric oxygen
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The conversion of platform molecule 5-hydroxymethylfurfural (HMF) into many value-added derivatives has attracted significant interest. FDCA and its esters are important derivatives of HMF, which can be used as polyester monomers and pharmaceutical intermediates. In this paper, oxidative esterification of 5-HMF has been carried out by using homogeneous and heterogeneous PdCoBi/C catalysts under atmospheric oxygen. The effect of reaction conditions on product distribution has been studied under both homogeneous and heterogeneous catalytic conditions. The highest yields of oxidative esterification products are obtained at 93% and 96% by using homogeneous and heterogeneous PdCoBi/C catalysts, respectively. The catalysts are characterized by X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (XRD). The catalytic system has better compatibility according to the expansion of the substrate. A reaction mechanism is proposed, and recycle experiments are also conducted.
- Li, Feng,Li, Xing-Long,Li, Chuang,Shi, Jing,Fu, Yao
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supporting information
p. 3050 - 3058
(2018/07/13)
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- Preparation method of dimethyl furan-2, 5-dicarboxylate
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The invention relates to a method for synthesis of dimethyl furan-2, 5-dicarboxylate from 5-hydroxymethylfurfural by means of catalytic oxidation. The method adopts oxygen or air as the oxidant and uses a cheap metal catalyst for efficient and highly selective catalysis of 5-hydroxymethylfurfural oxidation esterification, thus synthesizing dimethyl furan-2, 5-dicarboxylate. The catalytic reactionof the method has simple operation and mild conditions, the reaction system has no need for adding alkali additive, the 5-hydroxymethylfurfural conversion rate reaches 99% or more, and the yield of the product dimethyl furan-2, 5-dicarboxylate can reach 99%.
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Paragraph 0040-0041; 0048
(2018/08/04)
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- ORGANOTIN CATALYSTS IN ESTERIFICATION PROCESSES OF FURAN-2,5-DICARBOXYLIC ACID (FDCA)
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A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0031; 0032-0054
(2018/06/06)
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- OLIGOMERS OF FDCA AND GLYCOLS FROM A ONE-POT ESTERIFICATION-TRANSESTERIFICATION PROCESS USING WATER-TOLERANT METAL TRIFLATE CATALYST
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A method for preparing sugar-based oligomers is described. The process involves sequential (one-pot) esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol and transesterification with a glycol, as catalyzed by relatively low amounts of homogeneous water-tolerant Lewis acid catalysts, which can be retained in the product mixture from the esterification through transesterification.
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Page/Page column 0050; 0051; 0052; 0053
(2017/09/02)
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- NOVEL MONOMERS FROM BIOMASS
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Compounds derived from biomass, e.g., cellulose and lignins, methods of forming such compounds and polymers and products formed using such compounds.
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Paragraph 0130-0133
(2017/09/02)
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- Highly efficient and selective oxidation of 5-hydroxymethylfurfural by molecular oxygen in the presence of Cu-MnO2 catalyst
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The selective oxidation of 5-hydroxymethylfurfural (HMF) to produce value-added chemicals is a hot topic in the utilization of biomass, in which the development of heterogeneous catalyst and the use of O2 as terminal oxidant is desired. In this work, a series of metal ion-doped MnO2 materials are successfully prepared using liquid precipitation method, and employed as catalysts for the aerobic oxidation of HMF in the alcoholic solvents. As a result, it is found that 86.0% conversion of HMF and 96.1% selectivity of 2,5-diformylfuran (DFF) was obtained under suitable conditions. Moreover, the Cu-MnO2 catalyst can keep a high activity after being recycled five times.
- Tong, Xinli,Yu, Linhao,Chen, Hui,Zhuang, Xuli,Liao, Shengyun,Cui, Hongge
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- Method for preparing 2,5-furandicarboxylic acid
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The invention discloses a method for preparing 2,5-furandicarboxylic acid. The method comprises the following steps: preparing the 2,5-furandicarboxylic acid by sequentially performing four-step reaction namely bromination reaction, esterification reaction, carbonylation reaction and hydrolysis reaction on furan-2-carboxylic acid, wherein a compound as shown in Formula 3, a compound as shown in Formula 4 and a compound as shown in Formula 5 are obtained by the bromination reaction, the esterification reaction and the carbonylation reaction respectively. Compared with the prior art, the invention can effectively solve the problem of not high yield or severe reaction condition requirement by improving the key overall process flow of the preparation method and reaction conditions of each step. The structural formulae of the compound as shown in Formula 3, the compound as shown in Formula 4 and the compound as shown in Formula 5 are as shown in the specification respectively.
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- Synthesis of Furandicarboxylic Acid Esters From Nonfood Feedstocks Without Concomitant Levulinic Acid Formation
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5-Hydroxymethylfurfural (HMF) is a versatile intermediate in biomass conversion pathways. However, the notoriously unstable nature of HMF imposes challenges to design selective routes to chemicals such as furan-2,5-dicarboxylic acid (FDCA). Here, a new strategy for obtaining furans is presented, bypassing the formation of the unstable HMF. Instead of starting with glucose/fructose and thus forming HMF as an intermediate, the new route starts from uronic acids, which are abundantly present in many agro residues such as sugar beet pulp, potato pulp, and citrus peels. Conversion of uronic acids, via ketoaldonic acids, to the intermediate formylfuroic acid (FFA) esters, and subsequently to FDCA esters, proceeds without formation of levulinic acid or insoluble humins. This new route provides an attractive strategy to valorize agricultural waste streams and a route to furanic building blocks without the co-production of levulinic acid or humins.
- van der Klis, Frits,van Haveren, Jacco,van Es, Daan S.,Bitter, Johannes H.
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p. 1460 - 1468
(2017/04/14)
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- PROCESS FOR PRODUCING 2,5-FURANDICARBOXYLIC ACID DIALKYL ESTER
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Disclosed herein are processes for producing 2,5-furandicarboxylic acid dialkyl ester. In one embodiment, the process comprises a) contacting 2,5-furan dicarboxylic acid, excess alcohol, and optionally, a catalyst in a reactor at a temperature in the range of from 50°C to 325°C and a pressure in the range of between 1 bar to 140 bar to form a liquid phase composition comprising an ester of 2,5-furan dicarboxylic acid, the alcohol and water; b) lowering the temperature of the liquid phase composition to form a crude crystallized ester of 2,5-furan dicarboxylic acid; c) separating the product of step b) to form a solids phase comprising a purified ester of 2,5-furan dicarboxylic acid and a mother liquor comprising alcohol and water; and d) removing at least a portion of the water from the mother liquor. In one embodiment, the 2,5-furan dicarboxylic acid is contacted with an alcohol source and optionally, a catalyst.
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Page/Page column 26; 27
(2017/02/24)
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- REACTIVE DISTILLATION PROCESS FOR THE ESTERIFICATION OF FURANDICARBOXYLIC ACID
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Disclosed are processes for producing the dialkyl ester of 2,5-furan dicarboxylic acid by contacting a feed containing 2,5-furan dicarboxylic acid and a high boiling solvent with an alcohol in the presence of a solid acid catalyst using reactive distillation.
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Page/Page column 27
(2017/02/24)
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- Highly efficient metal salt catalyst for the esterification of biomass derived levulinic acid under microwave irradiation
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The esterification of levulinic acid (LA) to alkyl levulinates has been investigated in the presence of various metal salt catalysts under microwave irradiation. The reaction obtained 99.4% yield of methyl levulinate (ML) in the presence of Al2(SO4)3 catalyst in methanol solution under microwave conditions. The optimized reaction conditions were 110 °C and 10 minutes with a 20 mol% catalyst loading. Alcohols with longer carbon chains showed lower reactivities in the microwave electromagnetic field due to their poorer abilities to absorb and transmit microwave energy. Moreover, microwave irradiation provided a significantly higher reaction rate compared to conventional oil bath heating. LA aqueous solution was also converted to ML with high yields. The Al2(SO4)3 catalyst was successfully applied to the esterification of other biomass derived organic acids to their corresponding esters in high yields. Finally, the catalyst was recycled 5 times without much decrease in activity.
- Huang, Yao-Bing,Yang, Tao,Cai, Bo,Chang, Xin,Pan, Hui
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p. 2106 - 2111
(2016/01/20)
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