One‐Pot Synthesis of Biomass‐Derived Surfactants by Reacting Hydroxymethylfurfural, Glycerol, and Fatty Alcohols on Solid Acid Catalysts

Abstract

A new type of biomass-derived non-ionic surfactants has been obtained by reacting hydroxymethylfurfural (HMF), glycerol, and fatty alcohols. For instance, 5-(octyloxymethyl)furfural glyceryl acetal can be obtained in a one-pot process by etherification of HMF with fatty alcohols followed by acetalization with glycerol. For a successful solid catalyst, acidity and polarity have to be optimized to improve conversion, selectivity, and catalyst deactivation owing to the different adsorption characteristics of the reactant molecules. Accordingly, Beta zeolite with a high Si/Al ratio and practically free of connectivity defects showed good results when dealing with these biomass derivatives, which include a highly polar reactant such as glycerol. The scope of the reaction is good and a variety of new stable surfactant molecules can be obtained that present hydrophilic-lipophilic balance (HLB ) values in the range 4.9 to 6.6, which are of interest for water in oil emulsions.

Effect of Bio‐Based Aldehyde Structure on the Conversion and Selectivity Towards Glycerol Acetal Over Amberlyst‐46 by Using a Solvent‐Free Approach

“…They are shown to have good solubility and stability towards oxidation but hydrolyze in the presence of acid [4] . This class of compound and its derivatives also have shown potential in different applications including as surfactant, [5] fuel additives [6–8] and anti‐freezing agent [9,10] . Dodson et al.…”

“…[3] They are shown to have good solubility and stability towards oxidation but hydrolyze in the presence of acid. [4] This class of compound and its derivatives also have shown potential in different applications including as surfactant, [5] fuel additives [6][7][8] and anti-freezing agent. [9,10] Dodson et al (2014b) showed the anti-oxidant activity exhibited by aromatic glycerol acetal indicated wide range of potential of this class of compound in industrial application including biodiesel industry.…”

Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification

“…5‐Hydroxymethylfurfural (HMF), obtained by dehydration of hexoses, constitutes one of the most important and versatile platform molecules, owing to its broad range of potential applications in the biofuels and chemical industries. Numerous transformations of HMF, such as, oxidation, reduction, etherification, alkylation, aldol condensation, acetalization, hydration, and reductive amination, have been reported in recent years . Among them, the reduction of the formyl group of HMF to afford the symmetrical diol 2,5‐bis(hydroxymethyl)furan (BHMF), has received much attention .…”

5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals

“…[120][121] The acetalization with glycerol was extended to several in situ formed 5-(alkyloxymethyl)furfurals for the preparation of potential surfactant molecules 107 and 108 in a one-pot process. [122] The resulting compounds with HLB values in the range of 4.9 to 6.6 and good thermal and water stability could be useful for industrial applications as W/O emulsifiers.…”