In this study, a new type of hydrophobic cationic polyacrylamide P (AM-DMC-DABC) (PADD) was synthesized by ultrasonic (US)-initiated polymerization, which is used for the separation and removal of coal mine wastewater. The acrylamide (AM), methacryloyloxyethyl trimethyl ammonium chloride (DMC) and acryloyloxyethyl dimethylbenzyl ammonium chloride (DABC) were used as monomers to prepare). The factors that affecting the US initiated polymerization of PADD were analyzed. Fourier transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (1H NMR) and scanning electron microscopy (SEM) were used to characterize the chemical structure, thermal decomposition performance and surface morphology of the polymers. FT-IR and 1H NMR results showed that PADD was successfully synthesized. In addition, irregular porous surface morphology of PADD were observed by SEM analysis. Under the optimum conditions (pH = 7.0, flocculant dosage = 16.0 mg/L), the excellent flocculation performance (turbidity removal rate (TR) = 98.8%), floc size d50 = 513.467 μm, fractal dimension (Df) = 1.61, flocculation kinetics (KN0) = 27.24 × 10−3·s−1) was obtained by using high-efficiency flocculant PADD. Zeta potential analysis was used to further explore the possible flocculation mechanism of removal. The zeta potential and flocculation analytical results displayed that the flocculation removal process of coal mine wastewater mainly included hydrophobic effect, adsorption, bridging and charge neutralization, and electric patching when PADD was used. The PADD showed more excellent coal mine wastewater flocculation performance than PAD, commercial cationic polyacrylamide (CPAM) CCPAM and PAM. Thus PADD, with its good flocculation effect on coal mine wastewater under relatively wide pH range, had bright practical application value.