Organocatalytic acetylation of starch: Effect of reaction conditions on DS and characterisation of esterified granules

• Starch acetates were prepared by a novel solvent-free organocatalytic methodology.
• The effect on DS of reaction conditions was evaluated.
• Starch acetates with controlled DS in the 0.03–2.93 range were obtained.
• Starch esters were characterised by SEM, FTIR, TGA and hydrophobicity.

Starch acetates with varying degree of substitution (DS) were prepared by a novel solvent-free organocatalytic methodology. The acetylation protocol involved a non-toxic biobased α-hydroxycarboxylic acid as catalyst, and proceeded with high efficiency in absence of solvents. The effect of reaction conditions including reaction temperature (90–140 °C), catalyst load (0–2.3 g/g starch), acetic anhydride/starch weight ratio (6.5–13.5 g/g), and starch moisture content (0.6–14.8%) on the DS of the esters was evaluated. The analysis performed showed that the increase of temperature and catalyst concentration resulted in higher DS values, and evidenced a beneficial contribution of native starch moisture content on the substitution level achieved. Variation of reaction conditions allowed starch esters to be obtained with DS in the 0.03–2.93 range. Starch esters were characterised in terms of morphology, chemical structure, thermal properties, and distribution in polar/non polar liquid systems.