AbstractThe grafting of maleic anhydride onto carbon black surface based on the Diels–Alder addition via ultrasonic irradiation was investigated. Fourier transform infrared spectroscopy (FT‐IR) and thermogravimetric analysis (TGA) were used to determine the chemical structure of the resulting products. The anhydride ring in the modified products can be opened into two carboxylic groups. Accordingly, the carboxylated carbon black was analyzed quantitatively through acid‐based titration to determine the concentration of anhydride ring on the modified carbon black's surface. The grafted molecules amount calculated from the concentration of the anhydride ring was consistent with the results of TGA data. Comparison of zeta potential measurement demonstrated that there were more negative charges attached to the surface of carbon black after ultrasonic modification. TEM observations showed that the conglomeration degree of modified carbon black decreased more than that of initial carbon black. Copyright © 2008 John Wiley & Sons, Ltd.