Group Transfer Polymerization of N,N-Dimethylacrylamide Using Nobel Efficient System Consisting of Dialkylamino Silyl Enol Ether as an Initiator and Strong Brønsted Acid as an Organocatalyst

The combination of (Z)-1-(dimethylamino)-1-trimethylsiloxy-1-propene ((Z)-DATP) and Bronsted acid of trifluoromethanesulfonimide (Tf2NH) was found to act as a highly efficient GTP initiating system for N,N-dimethylmethacrylamide (DMAA) at 0 °C. The Tf2NH-catalyzed GTP of DMAA initiated by (Z)-DATP proceeded in a living manner to produce poly(N,N-dimethylacrylamide)s (PDMAA) with controlled molecular weights and narrow molecular weight distributions. The living nature was confirmed by kinetic measurements and a postpolymerization experiment. Furthermore, the MALDI-TOF MS analysis revealed that the molecular weight of the obtained PDMAA was in perfect agreement with that of PDMAA containing the (Z)-DATP initiator residue and the desilylated chain end, showing that the Tf2NH-catalyzed GTP of DMAA proceeded without any side reactions. The obtained PDMAA was r diad rich and had up to 73% of r diad contents. Glass transition temperatures of PDMAA showed molecular weight dependence below 20 kg mol−1.