Aliphatic tertiary amino-group N-substituted acrylamides, N-acryl-N′-methylpiperazine (AMP)and N-methacryl-N′-methylpiperazine (MAMP) were synthesized directly from N-methylpiperazinewith corresponding acryloyl chlorides and characterized by elementary analysis of their picrates,1H-NMR, IR and MS. AMP did not polymerize with benzoyl peroxide (BPO), but could poly-merize with lauroyl peroxide (LPO). The rate equation of the polymerization was given as RP=KP [AMP]1.5[LPO]0.5 and the overall activation energy of this polymerization system was 10.8Kcal/mol.The redox nature of LPO with the monomer itself was suggested.Even though AMP and MAMP hardly proceed the polymerization initiated with BPO,but under lower concentration would form redox system with BPO to initiate the polymerization of MMA readily.The rate equation of the polymerization of MMA initiated with MAMP-BPO system was given as Rp=Kp[MMA][MAMP]0.5[BPO]0.5 and the overall activation energy was 10.2 Kcal/mol.The analysis of the obtained polymers confirmed that MAMP not only initiated the polymerization of MMA by combining with BPO,but also took part in the polymer chains imparting them with better biocompatibility.