1917-64-2Relevant articles and documents
5-Hydroxymethyl-2-vinylfuran: A biomass-based solvent-free adhesive
Han, Miaomiao,Liu, Xiao,Zhang, Xiaosa,Pang, Yuanyuan,Xu, Peng,Guo, Jianwei,Liu, Yadong,Zhang, Shuangyan,Ji, Shengxiang
, p. 722 - 728 (2017)
5-Hydroxymethylfurfural (HMF) is an important platform chemical derived from biomass. Tremendous efforts have been made to transform HMF into valuable chemicals for applications in biofuels, materials science, and pharmaceuticals. Here we report the conversion of HMF into 5-hydroxymethyl-2-vinylfuran (HMVF), a versatile adhesive. HMVF can bond to a variety of substrates, e.g. metal, glass, plastics and rubber, under heating or acid treatment at room temperature. Mechanistic studies show that the vinyl group undergoes free radical polymerization and the hydroxyl group dehydrates to form an ether linkage to crosslink HMVF under either heating or acid treatment. The bonding strength (τ) of HMVF cured by heating (h-HMVF) is close to that of Krazy Glue (Loctite 401, cyanoacrylate) and higher than that of white glue (Pattex No. 710, PVA) and Pattex PKME15C epoxy glue. The outstanding adhesive performance of HMVF is attributed both to the interaction of hydroxyl groups with substrates and crosslinking by etherification between hydroxyl groups. Similar to Krazy Glue, HMVF is also used in its monomer form, which eliminates the use of solvents. Cells show good adhesion on crosslinked HMVF, which makes HMVF a potential bio-adhesive.
Facile and high-yield synthesis of methyl levulinate from cellulose
Huang, Yao-Bing,Yang, Tao,Lin, Yu-Ting,Zhu, Ying-Zhi,Li, Li-Cheng,Pan, Hui
, p. 1323 - 1334 (2018)
Efficient production of chemicals from cellulose provides sustainable routes for the utilization of natural renewable resources to meet the requirements of human society. Herein, we reported a highly efficient and simple metal salt catalyst, Al2(SO4)3, for cellulose conversion to methyl levulinate (ML) under microwave conditions. A highest ML yield of 70.6% was obtained at 180 °C within a very short time of 40 min. The introduction of water could reduce humin/coke formation and solvent consumption, and could also switch the reaction pathway via the more reactive intermediate glucose. Kinetic and mechanistic studies of the subreactions showed that both cellulose hydrolysis and alcoholysis pathways were involved in the cellulose conversion to ML, with the former as the main route in the presence of water. The Lewis acid species [Al(OH)x(H2O)y]n+ and the Br?nsted acid species H+, generated by in situ hydrolysis of Al2(SO4)3, were responsible for the reaction conversions. The reaction with microwave heating showed accelerated reaction rates of 25 times the reaction with conventional oil heating, and even more times for the rates of glucose and methyl glucoside (MG) dehydration, resulting in higher reaction selectivity toward ML production. The catalyst was also successfully recycled and applied to the conversion of cellulose to other alkyl levulinates, as well as the conversion of raw biomass to ML with high yields. The homogeneous nature of Al2(SO4)3, together with its high efficiency and excellent recyclability, make it a potential catalyst for the large-scale production of ML in industry.
Synergistic Production of Methyl Lactate from Carbohydrates Using an Ionic Liquid Functionalized Sn-Containing Catalyst
Wang, Fenfen,Wen, Yi,Fang, Yanxiong,Ji, Hongbing
, p. 4154 - 4161 (2018)
Considerable progress has been made recently in the catalytic conversion of renewable biomass resources to methyl lactate (MLA). However, conceiving eco-friendly and effective catalytic systems for the production of MLA from biomass carbohydrates remains a key challenge. Herein, we report a multifunctional catalyst Sn(salen)/IL, consisting of a Sn(salen) complex and an imidazolium-based ionic liquid (IL), which acts via an intramolecular synergistic effect to convert carbohydrates to MLA in methanol. The versatile properties of the resultant catalyst were revealed to be responsible for the conversion of fructose to MLA and the efficient suppression of undesired side reactions. This catalyst displayed outstanding catalytic activity, high selectivity, and excellent recyclability, giving an MLA yield of up to 68.9 % at 160 °C after 2 h. The results of this study will contribute to new approaches for designing synergistic catalysts for producing liquid fuels and chemicals from biomass resources.
Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents
Zhu, Hong,Cao, Quan,Li, Chunhu,Mua, Xindong
, p. 2016 - 2018 (2011)
Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system.
Etherification of 5-hydroxymethylfurfural using a heteropolyacid supported on a silica matrix
Casella, Mónica,Lick, Daniela I.,Luque, Rafael,Martínez, José J.,Portilla-Zu?iga, Omar M.,Romanelli, Gustavo P.,Sathicq, ángel G.
, (2020/08/06)
In this work, Preyssler-type heteropolyacids and their silica-included counterparts were employed in the etherification reaction of HMF and n-BuOH. Materials were synthesized with a Preyssler acid load of 12.5percent w/w using the sol-gel technique, which improved surface areas and modulated their acid strength. Prepared materials were used as heterogeneous solid acid catalysts in the selective etherification of 5-hydroxymethylfurfural (HMF) to 5-butoxymethylfurfural (5BMF). The high catalytic performance of the bulk Preyssler acids is related to their high acid strength, while selectivity related to the decrease in acidity by the inclusion effects. Different reaction parameters were optimized, with PWMo(12.5percent)&at;SiO2 exhibited the highest catalytic activity with 89percent of HMF conversion and 73percent of 5BMF selectivity. The catalyst is reusable up to five cycles without noticeable decrease in selectivity.
Importance of the synergistic effects between cobalt sulfate and tetrahydrofuran for selective production of 5-hydroxymethylfurfural from carbohydrates
Dong, Dehua,Hu, Xun,Li, Qingyin,Li, Xueli,Shao, Yuewen,Sun, Kai,Wang, Yi,Ye, Zhengmao,Zhang, Lijun,Zhang, Shu
, p. 2293 - 2302 (2020/04/20)
In this study, an effective catalytic system (CoSO4·7H2O/THF) for selective conversion of fructose to 5-hydroxymethylfurfural (HMF; yield: 88%) was developed. The synergistic effects among Co2+, SO42-, crystal water and tetrahydrofuran (THF) were crucial for achieving selective dehydration of fructose to HMF. Co2+ worked as a Lewis acid for catalyzing mainly dehydration of fructose to HMF but not the further decomposition of HMF to levulinic acid. THF could help to retain HMF while CoSO4 could coordinate with HMF, enhancing the thermal stability of HMF in THF. The crystal water in cobalt sulfate could help to coordinate with fructose, which facilitated the conversion of fructose via dehydration reactions. The CoSO4·7H2O/THF catalytic system could also catalyze the conversion of inulin and cellulose into HMF. The main advantages of the CoSO4·7H2O/THF catalytic system are the low cost, the easy recycling of the CoSO4·7H2O catalyst and the easy separation of HMF from volatile THF.
