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Effect of Aromatic Amines on the Properties of Formaldehyde-Based Xerogels

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This study investigates the synthesis of formaldehyde-based xerogels using alternative aromatic precursors, with comparison to traditional resorcinol-formaldehyde analogues, in order to alter the chemical composition of the resulting gels. By replacing resorcinol with aromatic amine molecules, i.e., ammeline, melamine and melem, each expected to undergo similar reactions with formaldehyde as the substituted species, we found that for all substituted gels, at low additive contents, the gel structure was compromised and non-porous materials were formed, as opposed to the most abundant monomers, and therefore, these additives seem to act as impurities at low levels. Working towards higher additive contents, melem monomers exhibited low solubility (~5%), even at elevated temperatures, thereby limiting the range to which melem could act as a substitute, while melamine could be incorporated up to ~40% under acidic conditions, with enhanced microporosity over this range. Pure gels were successfully synthesised from ammeline, but their performance was inferior to resorcinol-formaldehyde gels, while melamine-formaldehyde analogues required acidic reaction conditions but shrank considerably on sub-critical drying, adversely affecting the gel properties and demonstrating their lack of potential as sorbents. This demonstrates the potential for the inclusion of aminated aromatics within resorcinol-based gel systems, however, only as partial substitutes and not complete replacements.
Title: Effect of Aromatic Amines on the Properties of Formaldehyde-Based Xerogels
Description:
This study investigates the synthesis of formaldehyde-based xerogels using alternative aromatic precursors, with comparison to traditional resorcinol-formaldehyde analogues, in order to alter the chemical composition of the resulting gels.
By replacing resorcinol with aromatic amine molecules, i.
e.
, ammeline, melamine and melem, each expected to undergo similar reactions with formaldehyde as the substituted species, we found that for all substituted gels, at low additive contents, the gel structure was compromised and non-porous materials were formed, as opposed to the most abundant monomers, and therefore, these additives seem to act as impurities at low levels.
Working towards higher additive contents, melem monomers exhibited low solubility (~5%), even at elevated temperatures, thereby limiting the range to which melem could act as a substitute, while melamine could be incorporated up to ~40% under acidic conditions, with enhanced microporosity over this range.
Pure gels were successfully synthesised from ammeline, but their performance was inferior to resorcinol-formaldehyde gels, while melamine-formaldehyde analogues required acidic reaction conditions but shrank considerably on sub-critical drying, adversely affecting the gel properties and demonstrating their lack of potential as sorbents.
This demonstrates the potential for the inclusion of aminated aromatics within resorcinol-based gel systems, however, only as partial substitutes and not complete replacements.

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