Preparation and thermal stability of carboxymethyl starch/quaternary ammonium salts complexes

Starch complexes were obtained from activated and pregelatinized cassava starch (AS) or carboxymethyl starch (CMS) by using quaternary ammonium salts (QAS). The synthesis of the CMS was carried out by a single or double step carboxymethylation reaction with monochloroacetic acid. Different parameters were assayed to prepare the ionic complexes: CMS or AS as starting materials, anhydroglucose unit/QAS ratio, and length of the alkyl chain of the alkyltrimethylammonium bromide (CnTAB) salt. The products were characterized by FTIR, 1H and 13C NMR, and the Kjeldhal method. The results indicated a much more favorable complex formation when using CMS, obtaining the highest degree of substitution or complexation (0.72) and reaction efficiency (0.96) when C18TAB was employed. DSC and WAXS experiments evidenced the crystallization of the octadecyl chain introduced in the starch, exhibiting a dependence on sample water content. TGA and TVA analysis showed the stability of the complexes up to ∼150 °C and that degradation takes place in at least two stages with the release of the surfactant moiety in a first stage and the degradation of the starch skeleton in a second stage.