Copper mediated living polymerisation remains one of the most widely applied and useful methods of controlling vinyl polymerization. Thus, a greater understanding and development of very well controlled Cu-mediated polymerization in water and other aqueous media is required. All existing protocols are encumbered by important, and often overlooked, competing reactions that can reduce the polymerisation control, broadening PDi values which can generally fall between 1.2->1.4. An observation first seen by Perrier in 2000 has finally been understood and exploited. The prior disproportionation of CuBr/Me6TREN in water is been exploited for the SET-LRP of hydrophilic monomers. Reactions proceed faster and with no induction periods when compared to SET-LRP mediated by commercial Cu(0) sources without any compromise in polymerization control. Thorough analysis of model and reaction mixtures confirmed complete disproportionation of CuBr/Me6TREN in the water system. Attempted polymerization with the separated products of disproportionation revealed the synergistic character of the products of the disproportionation reaction.

Aqueous living radical polymerisation using copper complexes: The Perrier effect

248th National Meeting (2014)

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