Glen R. Jones

Cu(0)-RDRP of methacrylates in DMSO: importance of the initiator

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.

MALDI-LID-ToF/ToF analysis of statistical and diblock polyacrylate copolymers

We report the use of MALDI-LID-ToF/ToF utilising the laser induced dissociation (LID) fragmentation technique, which has been almost exclusively applied to protein/peptide analysis to date. MALDI-LID-ToF/ToF is used as a powerful tool to give information of monomer distributions in synthetic co-poly(acrylates). Analysis of a range of poly(acrylate) homopolymers by LID have found slight improvement over CID, with less rearrangements in the poly(butyl acrylate) fragmentation and more backbone cleavages. Analysis of both block and statistical copolymers, when compared to homopolymer analogues, yield markedly different spectra which can be correlated to give some monomer sequence information, thus achieving a wealth of structural information from two samples which would otherwise be identical by single stage MALDI-ToF analysis. The determination of fragmentation pathways of polymers with varying end group lability and monomer structure has allowed for high-resolution microstructural determination at the block boundary, showing even small amounts of mixing at the block boundary.