Atom transfer radical polymerization of alkyl methacrylates using T‐triazine as ligand

A new multidentate amine ligand, 1,3,5‐tris[(3‐dimethylamino)propyl]‐hexahydro‐1,3,5‐triazine (T‐triazine) was developed for the atom transfer radical polymerization of methacrylates (dimethylaminoethyl methacrylate (DMAEMA) and methyl methacrylate (MMA)). It was found that with T‐triazine as ligand, CuBr mediated a living polymerization of DMAEMA and MMA, producing polymers with controlled molecular weight and narrow polydispersity. The DMAEMA bulk polymerization and MMA solution polymerization in THF and γ‐butyrolactone (γBL) followed first order kinetics with respect to the monomer. At lower temperature, both polymerizations had an induction period and the induction time decreased with increasing temperature. The measured apparent active energy was 67.8 kJ/mol for DMAEMA polymerization. The NMR spectra confirmed that the polymerizations proceeded via an atom transfer radical process.