Hexamethylenetetramine as both a ligand and a reducing agent in AGET atom transfer radical batch emulsion polymerization

Cheap and commercially available hexamethylenetetramine (HMTA) as both a ligand and a reducing agent has been successfully applied in activator generated by electron transfer (AGET) atom transfer radical batch emulsion polymerization (ATREP) for the first time. Both methyl methacrylate (MMA) and butyl acrylate (BA) can be polymerized in a controlled way according to the kinetic studies. Block copolymer of MMA and BA (PMMA- b -PBA) has been prepared in one pot to further prove the living/controlled characteristics of the reaction. Hundred ppm levels of Cu(II) residue was left in the polymer product after 95% of Cu(II) was removed by simply decomposing HMTA-Cu(II) complex under acidic conditions. This method features use of cheap ligand/reducing agent, environmentally benign water-based reaction medium, fast reaction rate, and simple removal of undesired Cu(II) residue.