Journal
MACROMOLECULAR RAPID COMMUNICATIONS
Volume 32, Issue 5, Pages 456-461Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/marc.201000641
Keywords
atom transfer radical polymerization; catalysts; living polymerization; microgels; star polymers
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Funding
- Australian Research Council (ARC) [LP0348853]
- Japan Society for the Promotion of Science [19675003]
- Global COE Program
- Australian Government
- University of Melbourne
- ARC Nanotechnology Network
- Australian Research Council [LP0348853] Funding Source: Australian Research Council
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The efficient formation of low polydispersity core cross-linked star (CCS) polymers via controlled/living radical polymerization (LRP) and the arm-first approach was found to be dependant on the mediating catalyst system. The Ru catalyst, Ru(Ind)Cl(PPh3)(2) Cat. 1, and tertiary amine co-catalyst were used to synthesize highly living poly(methyl methacrylate) (PMMA) macroinitiators, which were then linked together with ethylene glycol dimethacrylate (EGDMA) to form PMMA(arm)-PEGDMA(core) CCS polymers. The quantitative and near-quantitative synthesis of CCS polymers were observed for low to moderate molecular weight macroinitiators ((M) over bar (n) = 8 and 20 kDa), respectively. Lower conversions were observed for high-molecular weight macroinitiators ((M) over bar (n) >= 60 kDa). Overall, an improvement of between 10 and 20% was observed when comparing the Cat. 1 system to a conventional Cu-catalyzed system. This significant improvement in macroinitiator-to-star conversion is explained in the context of catalyst system selection and CCS polymer formation.
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