Novel starlike poly(methyl methacrylate)s by controlled dendritic free radical initiation

Branched starlike polymethyl methacrylate (PMMA) homo and copolymers were synthesized using atom transfer radical polymerization (ATRP) techniques and dendritic initiators. The initiators were obtained by coupling a bromo functionalized first generation dendron of bis(hydroxymethyl)propionic acid to hydroxyl-functionalized precursors. The living free radical character of the ATRP polymerization was supported by the remarkably low polydispersities of the polymers and the close correspondence between the calculated and measured molecular weights. Nuclear magnetic resonance studies on the polymers were consistent with initiation occurring from all initiator arms.