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• Amphiphilic CPAM was fabricated through ultrasonic initiated template polymerization. • Comparative characterizations confirmed the microblock structure and amphiphilicity. • Template copolymerization met bimolecular termination of free radical polymerization. • The effect of NaPAA followed template polymerization I (ZIP) mechanism. • Cationic microblocks produced stronger flocs to form more permeable filter cakes. Flocculation is an important pretreatment technique for sludge dewatering, the performance of employed flocculants is the key factor determine the flocculation efficiency. Herein, an amphiphilic cationic polyacrylamide (CPAM) with microblock structure was synthesized through template copolymerization initiated by ultrasonic. The chemical components and cationic microblock structure of copolymers were confirmed through comparative characterization by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (1H NMR) spectrum. The copolymerization mechanism was investigated through kinetics study and association coefficient (K M) determination. The results indicated that the reaction followed free radical copolymerization and terminated mainly through bimolecular termination. The pre-adsorption between acryloyloxyethyltrimethylammonium chloride (DAC) and sodium polyacrylate (NaPAA) before reaction confirmed the template polymerization met the type I (ZIP) mechanism. Cationic microblocks and hydrophobic association together contributed to the optimal dewaterability (FCMC=67.2 %, SRF=3.84×1012 m·kg−1) using TP(AM-DAC-LA). Hydrophobic association enhanced bridging and sweeping effect to promote the floc size growth. Cationic microblocks produced compacter flocs with stronger mechanical strength through enhanced charge neutralization and patching effects, which acted as skeletons to make filter cakes less compressible and more permeable in mechanical dewatering. This work developed a highly effective flocculant for sludge dewatering, the synthesis and working mechanism of which were also given. [ABSTRACT FROM AUTHOR]