Ultra high molar mass poly[2-(dimethylamino)ethyl methacrylate] via atom transfer radical polymerization

Well-defined high molecular weight poly[2-(dimethylamino)ethyl methacrylates] [poly(DMAEMA)s] with molar masses up to ∼1×10⁶ g/mol were successfully synthesized via atom transfer radical polymerization (ATRP). This was achieved by using p-toluenesulfonyl chloride(p-TsCl)/CuCl/1,1,4,7,10,10-hexamethyl-triethylenetetramine(HMTETA) initiator/catalyst complex in methanol/water mixture. Well-controlled/‘living’ behavior was demonstrated throughout the reaction, up to high monomer conversion. The PDI value remained low at 1.26 even for a polymer with very high molecular weight at 1.1×10⁶ g/mol. We believe this is the first successful case where controlled ATRP produces a polymer with molar mass exceeding a million!