Glycerol acetals and ketals as bio-based solvents: positioning in Hansen and COSMO-RS spaces, volatility and stability towards hydrolysis and autoxidation

Moity, Laurianne; Benazzouz, Adrien; Molinier, Valérie; Nardello‐Rataj, Véronique; Elmkaddem, Mohammed Kamal; de, Pascale; Thiébaud‐Roux, Sophie; Gerbaud, Vincent; Marion, P; Aubry, Jean‐Marie

doi:10.1039/c4gc02377c

Cited by 66 publications

(51 citation statements)

References 57 publications

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“…We studied the reductive conversion of solketal (the best known glycerol derivative) into a mixture of GIPEs. Solketal is a convenient intermediate in the chemistry of glycerol: it can be easily prepared by the ketalization of glycerol, it has a free hydroxyl group, which makes it possible to perform selective alkylation (acylation), and the protective ketal group can be readily removed by acid hydrolysis.…”

Section: Introductionmentioning

confidence: 99%

“…Because there are no reliable data on glycerol etherification with isopropanol (particularly the reaction regioselectivity) in the scientific literature, we performed the direct alkylation of glycerolw ith isopropanol over an Am-berlyst36i on-exchange resin, which is as uitable catalyst for glyceroletherification. [2,13,17,20,44] We studied the reductivec onversion of solketal( the best known glycerol derivative) [1,[45][46][47][48] into am ixture of GIPEs.S olketal is ac onvenient intermediate in the chemistry of glycerol:i t can be easily prepared by the ketalization of glycerol, it has af ree hydroxyl group, which makes it possible to perform selective alkylation (acylation), and the protective ketal group can be readily removed by acid hydrolysis. Solketali ss oluble in hydrocarbons, and it possesses ah igh octane number, [49,50] its viscosity is lower and its volatility is considerably higher than those of glycerol;t herefore, it is ap otentialf uel component.…”

Section: Introductionmentioning

confidence: 99%

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Glycerol Isopropyl Ethers: Direct Synthesis from Alcohols and Synthesis by the Reduction of Solketal

et al. 2017

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The catalytic reduction of solketal ((2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methanol) over bifunctional heterogeneous palladium catalysts is proposed as an alternative to the synthesis of glycerol isopropyl ethers by the etherification of glycerol. The direct synthesis of glycerol isopropyl ethers from isopropanol and glycerol requires severe conditions (T=130–150 °C, p(H2)=20–35 bar) and a large excess of isopropanol to reach a considerable yield. The main reaction products in the catalytic reduction of solketal are glycerol mono‐ and di‐isopropyl ethers and solketal isopropyl ether. Solketal conversion over Al‐HMS‐supported palladium catalysts (T=120 °C and p(H2)=20 bar) affords a mixture of ethers with a high degree of conversion (87 %), 78 % selectivity, and excellent regioselectivity between isomeric ethers. Zeolite‐BEA‐supported palladium catalysts also exhibit high activity but much lower selectivity because of intense acetone aldol condensation. The effects of Si/Al ratios in BEA zeolites and Al‐HMS aluminosilicates and the amounts of supported palladium (1 and 2 wt %) on the properties of the catalysts at different reaction temperatures and hydrogen pressures are considered.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Glycerol Isopropyl Ethers: Direct Synthesis from Alcohols and Synthesis by the Reduction of Solketal

et al. 2017

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“…Solketal and glycerol formal are the products of acid-catalyzed acetone and formaldehyde reactions with glycerol, respectively [41], and currently solketal is sold commercially under the name Augeo™ SL 191. It is used as a solvent in interiorscenting products and household cleaners [42].…”

Section: Glycerol and Its Derivativesmentioning

confidence: 99%

Bio-Solvents: Synthesis, Industrial Production and Applications

Oklu¹,

Matsinha²,

Makhubela³

2020

Solvents, Ionic Liquids and Solvent Effects

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Solvents are at the heart of many research and industrial chemical processes and consumer product formulations, yet an overwhelming number are derived from fossils. This is despite societal and legislative push that more products be produced from carbon-neutral resources, so as to reduce our carbon footprint and environmental impact. Biomass is a promising renewable alternative resource for producing bio-solvents, and this review focuses on their extraction and synthesis on a laboratory and large scale. Starch, lignocellulose, plant oils, animal fats and proteins have been combined with creative synthetic pathways, novel technologies and processes to afford known or new bio-derived solvents including acids, alkanes, aromatics, ionic liquids (ILs), furans, esters, ethers, liquid polymers and deep eutectic solvents (DESs)-all with unique physiochemical properties that warrant their use as solvation agents in manufacturing, pharmaceutical, cosmetics, chemicals, energy, food and beverage industries, etc. Selected bio-solvents, conversion technologies and processes operating at commercial and demonstration scale including (1) Solvay's Augeo™ SL 191 renewable solvent, (2) Circa Group's Furacell™ technology and process for making levoglucosenone (LGO) to produce dihydrolevoglucosenone (marketed as Cyrene™), (3) Sappi's Xylex ® technology and demonstration scale processes that aim to manufacture precursors for biosolvents and (4) Anellotech's Bio-TCat™ technology and process for producing benzene, toluene and xylenes (BTX) are highlighted.

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“…Solvent selectioni su sually performed on a" like-for-like"s ubstitution basis, [14] but history tells us such as imple approach is never likely to allow users to completely escape the toxicity,s afety issues, or environmental impact of one type of solvent. [16] In this informatives tudy of commercial products,t he solvents were characterized, but as pecific application was not sought. [3] Similarly,a to ne time NMP was claimed to be nontoxic [15] but it is now recognizedt ob er eprotoxic and, therefore, aSVHC.…”

Section: Introductionmentioning

confidence: 99%

“…This combination of techniques was used previously by Moity et al to describe four glycerold erivatives. [16] In this informatives tudy of commercial products,t he solvents were characterized, but as pecific application was not sought. By contrast, in this work, we have identified an ew class of solvents from the screening of more than 100 candidates and we found ar elevant application for them based on the strength of their properties.…”

Section: Introductionmentioning

confidence: 99%

Intelligent Approach to Solvent Substitution: The Identification of a New Class of Levoglucosenone Derivatives

et al. 2016

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With the increasing restriction and control of hazardous solvents, safer alternatives need to be identified. Here a contemporary approach to solvent selection and substitution is presented that offers a more scientific alternative to the simple "like-for-like" exchange. A new family of levoglucosenonederived compounds is proposed, modeled to determine their solvent properties, synthesized, and tested. These new molecules show promise as replacements for polar aprotic solvents that have chronic toxicity issues, such as dichloromethane, nitrobenzene, and N-methylpyrrolidinone. The success of this approach makes it possible for academia and industry to make calculated, intelligent choices for solvent substitution in the future.

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Glycerol acetals and ketals as bio-based solvents: positioning in Hansen and COSMO-RS spaces, volatility and stability towards hydrolysis and autoxidation

Abstract: Hansen and COSMO-RS approaches show that glycerol ketals and acetals can be effective alternatives to certain harmful petro-sourced solvents.

Cited by 66 publications

References 57 publications

Glycerol Isopropyl Ethers: Direct Synthesis from Alcohols and Synthesis by the Reduction of Solketal

Glycerol Isopropyl Ethers: Direct Synthesis from Alcohols and Synthesis by the Reduction of Solketal

Bio-Solvents: Synthesis, Industrial Production and Applications

Intelligent Approach to Solvent Substitution: The Identification of a New Class of Levoglucosenone Derivatives

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