This study aimed to enhance the synthesis of carboxymethyl starch (CMS) by induced electric field (IEF). Corn starch was alkalized, pumped into IEF system, and then reacted with monochloroacetic acid at excitation voltages of 0–400 V. IEF enhanced the carboxymethylation by accelerating the rate of OH− and ClCH2COO− attacking starch particles and slightly intensifying the thermal effect by ~7.1 °C (30 min). Compared with the control (0 V), IEF increased the degree of substitution and reaction efficiency by 0.056–0.148 and 9.37–24.56 %, caused more destruction in starch granular and crystal structure, and thus increased its water solubility, swelling power, and paste transparency. Furthermore, some new crystals were formed during IEF treatment, which enhanced the thermostability of CMS, showing an increase of the maximum decomposition temperature by 16–26 °C. Overall, the results classified that IEF could improve the carboxymethylation and enhance the thermostability of products, which provided guides for the applications of electro-techniques in starch modification involving charged species.
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