@article{
 title = {Copper(I)-Mediated Living Radical Polymerization in the Presence of Oxyethylene Groups: Online 1 H NMR Spectroscopy To Investigate Solvent Effects},
 type = {article},
 year = {2000},
 keywords = {QD Chemistry},
 pages = {8246-8251},
 volume = {33},
 websites = {http://wrap.warwick.ac.uk/12808/%5Cnhttp://pubs.acs.org/doi/abs/10.1021/ma001097c},
 publisher = {ACS Publications},
 id = {c5e9fef3-12dc-3661-b00d-db6be072d05f},
 created = {2024-01-02T14:09:39.100Z},
 file_attached = {false},
 profile_id = {36921318-7a81-32e6-acca-75b835acd8f1},
 group_id = {f2d52f92-0a5a-3712-a53b-a4492da8da5f},
 last_modified = {2024-01-02T14:09:39.100Z},
 read = {false},
 starred = {false},
 authored = {false},
 confirmed = {true},
 hidden = {false},
 citation_key = {haddleton2000copper},
 source_type = {article},
 private_publication = {false},
 abstract = {The use of oxyethylene methacrylate monomers, initiators, and 1,2-diethoxyethane as a cosolvent in the living radical polymerization mediated by copper(I) pyridylmethanimine complexes has been studied. Online H-1 NMR monitoring of the reaction has been used to investigate the living radical polymerizations. Polymerization of poly(ethylene glycol) methyl ether methacrylate macromonomer (MeO(PEG)MA; M-n = 480) was carried out in toluene mediated by a copper(I) bromide/N-(n-propyl)-2-pyridylmethanimine catalyst, using phenyl alpha -bromoisobutyrate (1) as initiator. The measured number-average molar mass, M-n, of the product increases linearly with monomer conversion in close agreement to the theoretical M-n, with low polydispersity products (PDI < 1.2) achieved in all cases, as expected for a living polymerization. The overall rate of polymerization was very fast (ca. 90% conversion after 1 h at 90 <degrees>C) when compared to polymerization of benzyl methacrylate (BzMA) under similar conditions, indicating high values for k(p)[R*], where R* = active propagating species. The origin of this dramatic rate enhancement was investigated by carrying out the polymerization of MeO(PEG)MA over a range of temperatures and by the polymerization of alkyl methacrylates with a MeO(PEG)-derived macroinitiator. Polymerization of BzMA was carried out in I,2-diethoxyethane as solvent, which showed an enhanced rate when compared to polymerization in nonpolar/noncoordinating solvents. The high value of k(p)[R*] is ascribed to complexation of the oxyethylene groups at the copper in a dynamic state with the pyridylmethanime ligand complexation, which results in a more active catalyst.},
 bibtype = {article},
 author = {Haddleton, David M and Perrier, Sébastien and Bon, Stefan A F},
 doi = {10.1021/ma001097c},
 journal = {Macromolecules},
 number = {22}
}

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Online H-1 NMR monitoring of the reaction has been used to investigate the living radical polymerizations. Polymerization of poly(ethylene glycol) methyl ether methacrylate macromonomer (MeO(PEG)MA; M-n = 480) was carried out in toluene mediated by a copper(I) bromide/N-(n-propyl)-2-pyridylmethanimine catalyst, using phenyl alpha -bromoisobutyrate (1) as initiator. The measured number-average molar mass, M-n, of the product increases linearly with monomer conversion in close agreement to the theoretical M-n, with low polydispersity products (PDI < 1.2) achieved in all cases, as expected for a living polymerization. The overall rate of polymerization was very fast (ca. 90% conversion after 1 h at 90 <degrees>C) when compared to polymerization of benzyl methacrylate (BzMA) under similar conditions, indicating high values for k(p)[R*], where R* = active propagating species. The origin of this dramatic rate enhancement was investigated by carrying out the polymerization of MeO(PEG)MA over a range of temperatures and by the polymerization of alkyl methacrylates with a MeO(PEG)-derived macroinitiator. Polymerization of BzMA was carried out in I,2-diethoxyethane as solvent, which showed an enhanced rate when compared to polymerization in nonpolar/noncoordinating solvents. 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