Journal
POLYMER CHEMISTRY
Volume 9, Issue 18, Pages 2382-2388Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7py01196b
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Funding
- University of Warwick
- Lubrizol Corporation
- Syngenta
- MRSEC program of the National Science Foundation [DMR-1121053, DMR-1205194]
- PREM program of the National Science Foundation [DMR-1121053, DMR-1205194]
- MRSEC Program of the NSF [DMR 1121053]
- NSF
- Global Marie Curie Fellowship [BINAMA EC 705041]
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The controlled radical polymerization of methacrylates via Cu(0)-mediated RDRP is challenging in comparison to acrylates with most reports illustrating higher dispersities, lower monomer conversions and poorer end group fidelity relative to the acrylic analogues. Herein, we present the successful synthesis of poly(methyl methacrylate) (PMMA) in DMSO by judicious selection of optimal reaction conditions. The effect of the initiator, ligand and temperature on the rate and control of the polymerization is investigated and discussed. Under carefully optimized conditions enhanced control over the molecular weight distributions is obtained furnishing methacrylic polymers with dispersities as low as 1.10, even at very high conversions. A range of methacrylates were found to be tolerant to the optimized polymerization conditions including hydrophobic, hydrophilic and functional methacrylates including methyl and benzyl methacrylate, ethylene glycol methyl ether methacrylate and glycidyl methacrylate. The control retained during the polymerization is further highlighted by in situ chain extensions yielding well-defined block polymethacrylates.
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