Varying the hydrophobicity of humic matter by a phase-transfer-catalyzed O-alkylation reaction

An O-alkylation reaction catalyzed by tetrabutylammonium hydroxide (TBAH) as a phase-transfer agent was applied to a humic acid (HA) to modify its hydrophobic properties. The carboxyl and hydroxyl functional groups of HA acted as nucleophiles in substitution reactions (Sn²) with methyl iodide, pentyl bromide and benzyl bromide added in amounts equimolar to 20, 60 and 80% of HA total nucleophilic sites. The occurrence of O-alkylation was shown by DRIFT spectrometry, NMR spectroscopy, High Performance Size Exclusion Chromatography (HPSEC) and elemental analysis of reaction products. DRIFT spectra showed changes in C–H stretching and bending regions following the insertion of methyl and pentyl groups, while the incorporation of benzyl groups revealed the characteristics aromatic C–H stretching bands. Both liquid- and solid-state NMR spectra revealed characteristic signals for alkyl/aryl esters and ethers. HPSEC chromatograms of alkylated materials invariably displayed an increase in hydrodynamic volume in respect to the original HA, thereby suggesting that the enhanced hydrophobicity conveyed further associations among humic molecules. Analytical, HPSEC and spectroscopic results suggest that benzylation was the most effective reaction at all percentages of HA total nucleophilicity, followed, in the order, by pentylation and methylation, The benzylation reaction was used to improve reaction and work-up conditions and show that HA could be efficiently alkylated also with substantial reduction of TBAH amount, with no THF addition, increase of reaction time and of washing cycles to remove catalyst impurities. These findings indicate that the hydrophobicity of humic substances can be modulated through a mild O-alkylation reaction under a phase-transfer catalysis according to the extent of exposed HA nucleophilic sites. Such a structural modification of humic matter may have multiple chemical, environmental and biological applications.