Copolymerization of N,N-Dimethylacrylamide with n-Butyl Acrylate via Atom Transfer Radical Polymerization

The (co)polymerization of N, N -dimethylacrylamide (DMAA) was performed by atom transfer radical polymerization (ATRP). Using methyl 2-chloropropionate/CuCl/Me 6 TREN as the initiating/catalyst system in toluene solution, at room temperature, high molecular weight homopolymers ( M n up to 50 000) with narrow molecular weight distribution ( M w / M n = 1.05−1.13) were prepared. The controlled polymerization of DMAA has been extended to simultaneous copolymerization with n -butyl acrylate ( n BA), which resulted in a comparable rate of conversion for each monomer, indicating formation of a nearly random copolymer. The reactivity ratios of DMAA and n BA in ATRP are similar: r DMAA = 1.16 and r n BA = 1.01. Block copolymers of n BA and DMAA, with two different polymerization degrees of the second block (DP DMAA = 65 and 100), were synthesized using a well-defined P n BA-Br (DP n BA = 140) macroinitiator. The other approach to block copolymer formation using extension of PDMAA-Cl (DP DMAA = 160) with n BA was used, and block copolymers with DP n BA = 50 and 100 were prepared.