Simultaneous Dual Living Polymerizations: A Novel One-Step Approach to Block and Graft Copolymers

The Use of e-Caprolactone as a Polymerizable Solvent for the Atom Transfer Radical Polymerization of MMA at Low Temperature

“…[22,23] This strategy can be implemented in one or two steps. In the sequential twostep method, the first block is isolated and purified after polymerization and used as a macro-initiator for the second polymerization.…”

Novel Macromolecular Architectures Based on Aliphatic Polyesters: Relevance of the “Coordination-Insertion” Ring-Opening Polymerization

“…Quite interestingly, we introduced the original concept of performing simultaneous dual living polymerizations as a novel one-step approach to block copolymers [83]. For example, from a hydroxy functionalized alkoxyamine initiator, both living ROP of εCL catalyzed by Sn(OCt) 2 and controlled free radical polymerization of styrene take place without the need for any intermediate steps (Scheme 24).…”

“…In a very similar way, hydroxy functionalized ATRP initiators such as 2,2,2-tribromoethanol can be used for the simultaneous polymerization of εCL and MMA (Scheme 25) [83]. Purposely, the ROP of εCL is promoted by Al(OzPr) 3 added in catalytic amount so that the rapid alcohol-alkoxide exchange reaction (see Sect.…”

Metal complexes with polymeric ligands: Chelation and metalloinitiation approaches to metal tris(bipyridine)-containing materials

“…Recently, it has also been shown that ␣-halo ester-functionalized Ru complexes (18)(19)(20) serve as effective initiators for acrylate polymerizations 42,47 with the Ni(PPh 3 ) 2 Br 2 catalyst previously explored by Sawamoto et al 48 and Jérôme et al 49 Molecular weights up to approximately 320,000 were obtained with control (PDI ϭ 1.29) for Ru-centered six-arm stars generated by the reaction of MMA with the hexafunctional tertiary halide initiator 18 in a toluene solution. For this system, linear first-order kinetics and M n /percentage of monomer conversion plots were observed that were consistent with a controlled polymerization.…”