4740-78-7Relevant academic research and scientific papers
An efficient method for the refinement of 1,3-methyleneglycerol via bridged acetal exchange and the synthesis of a symmetrically branched glycerol trimer
Hattori, Hatsuhiko,Matsushita, Tsuyoshi,Yoshitomi, Kohsuke,Katagiri, Ayato,Nemoto, Hisao
, p. 2365 - 2373 (2012)
Acid-catalyzed equilibrium of a mixture of 1,2- and 1,3-methyleneglycerol in 1,4-dioxane affords predominantly the 1,3-isomer via bridged acetal exchange. The minor 1,2-isomer is removed via sequential pivaloylation and tritylation to afford the desired 1,3-isomer in >99.5% purity. A symmetrically branched triglycerol is efficiently synthesized starting from the purified 1,3-isomer. Georg Thieme Verlag Stuttgart · New York.
Glycerol acetalization with formaldehyde using water-tolerant solid acids
Chen, Lin,Nohair, Bendaoud,Kaliaguine, Serge
, p. 143 - 152 (2016)
The acid-catalyzed reaction of glycerol with aqueous formaldehyde was studied using various heterogeneous catalysts for the production of glycerol formal. Owing to the high amount of water involved in the reaction medium, three types of water-tolerant heterogeneous catalysts namely acid functionalized periodic mesoporous organosilicas (PMOs), zeolite ZSM-5 and a heteropoly compound Cs2.5H0.5PW12O40 as well as commercial catalyst Amberlyst-15 were used for glycerol acetalization. The activity of Cs2.5H0.5PW12O40 was found superior to that of the other catalysts and the glycerol conversion was over 70% within 60 min of reaction time. The effects of different parameters including temperature, feed composition and catalyst content, were studied as well. The distribution of the two glycerol formal isomers could be controlled by changing reaction parameters. Optimum reactive parameters were studied to control the distribution of the acetal isomers aiming to reach a high selectivity to the six-member ring isomer.
Mesoporous Zr-SBA-16 catalysts for glycerol valorization processes: Towards biorenewable formulations
Gonzalez-Arellano, Camino,Parra-Rodriguez, Leticia,Luque, Rafael
, p. 2287 - 2292 (2014)
Zr-containing SBA-16 materials were utilized in glycerol valorization for the production of esters (via reaction with levulinic acid) and glycerol formal (GF) via acetalisation with paraformaldehyde. The materials were found to be highly active and selective for the production of valuable compounds from glycerol using benign by design solventless protocols which employ mild reaction conditions. Certain materials were also found to be highly reusable and stable under the investigated conditions.
Biomass alcoholysis method for petroleum-based plastic POM
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Paragraph 0030-0052, (2021/05/01)
The invention discloses a biomass alcoholysis method for petroleum-based plastic POM. According to the method, simple biomass derivative alcohol and the petroleum-based plastic POM are allowed to generate a cyclic acetal product through dehydration condensation under catalytic conditions; low reaction cost and high added value are realized, and only water is byproduced and is easy to separate; and an obtained product has high added value, can be used for preparing organic solvents such as lignin and chromatographic analysis solvents, metal surface treatment agents or medical intermediates and monomers, realizes green, efficient and low-cost recovery, and has a high practical application value.
Interaction of triols with formaldehyde and acetone: Experimental and theoretical study
Sultanova, Rimma,Borisevich, Sophia,Raskil'dina, Gulnara,Borisova, Julianna,Baykova, Irina,Spirikhin, Leonid,Khursan, Sergey,Zlotsky, Simon
, p. 1144 - 1151 (2020/02/25)
Experimental and theoretical aspects of the condensation of glycerol and its homologs (1,2,3- and 1,2,4-butanetriols) with formaldehyde and acetone are studied under conditions of acid catalysis. Calculation of the thermodynamic parameters of the resulting products by the composite method CBS-QB3 shows that the six-membered heterocycles, the products of the interaction of triols with formaldehyde, are thermodynamically more stable than the five-membered acetals, while the reaction of the same triols with acetone is preferable for the formation of the five-membered acetals. This is due to the fact that the regioselectivity of the studied reactions is determined by the structural features and reactivity of the carbocations formed in a condensed medium during the course of the reaction. According to the theoretical data obtained experimentally, during the condensation of glycerol and 1,2,4-butanetriol with formaldehyde in the most stable form of the six-membered cyclic carbocation, intramolecular hydrogen bonding and anomeric stabilization due to the axially oriented hydroxyl group take place. As a result, cation 1b–1 is 1.2–1.6 kJ/mol more stable than its five-membered isomers (1a–1 and 1b–2). It leads to the predominant formation of 1,3-dioxane (3b). However, upon condensation of butanetriol-1,2,3 with formaldehyde, the intermediate cation 4a–1 turns out to be significantly more stable than the other isomers due to the strong intramolecular hydrogen bond in the six-membered ring with the participation of the hydroxyl group of the substituent and the hydroxyl group of the cationic center, leading to the predominant formation of the dioxolane 6a.
A bifunctional catalyst based on Nb and v oxides over alumina: Oxidative cleavage of crude glycerol to green formic acid
Chagas, Poliane,Figueiredo, Marcio P.,Hensen, Emiel J. M.,Oliveira, Henrique S.,Oliveira, Luiz Carlos A.,Sangiorge, Daniel L.,Siqueira, Kisla P. F.
, p. 8538 - 8544 (2020/06/19)
A bimetallic vanadium and niobium oxide catalyst using alumina as support was developed for the conversion of crude glycerol from biodiesel production into formic acid. The high dispersion of the active oxide phase combined with the presence of acid and redox active centers resulted in a high glycerol conversion (>90% for 25 h) with a good selectivity for formic acid (～55%). This process is the first example of a heterogeneous liquid-phase process for the conversion of crude glycerol to formic acid, which is an important chemical intermediate currently derived from petroleum feedstock.
Method for preparing glycerolformal
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Paragraph 0029-0034, (2019/04/11)
The invention discloses a method for preparing glycerolformal. According to the invention, SO42-/Fe2O3-CNTS super acid is used as a catalyst for compounding glycerolformal, so that the method has theadvantages that reaction temperature is low, catalyst activity is high, no new water-carrying agent is brought, yield of reaction products is 95% or above and hexatomic ring products are high in proportion.
Glycerolformal industrial production method
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Paragraph 0029-0032, (2019/05/22)
The invention discloses a glycerolformal industrial production method. The glycerolformal industrial production method achieves synthesis of glycerolformal by taking SO42-/ZrO2-CNTS (carbon nanotubes)super acids as catalysts. The glycerolformal industrial production method is low in reaction temperature, high in activity of catalysts, free from introduction of new water-carrying agent and short in reaction time; the products achieve a yield of higher than 92% and a high proportional ratio of hexatomic ring products.
Method for preparing glycerol benzaldehyde
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Paragraph 0032; 0033, (2019/04/17)
The invention discloses a method for preparing glycerol benzaldehyde. Metal zinc modified strong acid cation exchange resin is used as a catalyst for synthesizing the glycerol benzaldehyde. Owing to modification of metal zinc, the strong acid cation exchange resin has the function of activating aldehydic carbonyl, glycerol conversion rate reaches up to 95% or more, and product yield is 88% or more.
Highly Efficient Glycerol Acetalization over Supported Heteropoly Acid Catalysts
Chen, Lin,Nohair, Bendaoud,Zhao, Dongyuan,Kaliaguine, Serge
, p. 1918 - 1925 (2018/03/28)
The acetalization of glycerol with acetone to yield solketal was catalyzed by Cs2.5H0.5PW12O40 (Cs2.5) supported on mesoporous silica under mild conditions. It gave a high glycerol conversion and selectivity to the targeted product even at room temperature (23 °C). We studied the use of both bulk and supported Cs2.5 as catalysts in another highly efficient glycerol acetalization reaction with paraformaldehyde, which gave much higher activity than with formaldehyde solution. For the reaction with acetone, the supported Cs2.5 showed a higher activity than the bulk material because of the high surface area of the mesoporous support. Interestingly, the supported Cs2.5 gave a lower conversion than the bulk for the reaction with paraformaldehyde. This is probably because of the high viscosity of the reaction system with the solid reagent paraformaldehyde. Overall, there is a complex relationship between catalyst, reaction conditions, which include the molar ratio of reactants and temperature, reaction mechanism and thermodynamics that affects the achieved activity and byproduct formation. A discussion about these interactions is included for each reaction.
