Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

The separation of an oligo(methyl acrylate) distribution, obtained from reversible addition–fragmentation chain transfer (RAFT) polymerization, in a discrete (dispersity=1) oligomeric library (degree of polymerization between 1 and 22) is presented. The properties of this library in terms of diffusivity, glass transition temperature, and viscosity are determined, filling a significant knowledge gap associated with these materials. The obtained oligomer library is used to construct artificial oligomer distributions on demand. These artificial oligomer distributions are used to highlight the potential to tailor physical properties of a material, while concomitantly demonstrating the limitations associated with size-exclusion chromatography analysis of molecular weight and dispersity in particular. The authors are grateful for helpful discussions with PeterNichols regarding DOSY NMR and with Maarten Rubens forthe simulation of SEC number distributions. They would alsolike to kindly acknowledge Kei Saito for granting access totheir DSC instrument. The authors thank Andres CastroVillavicencio for his help with preliminary experiments. J.D.N.is grateful to the Bijzonder Onderzoeks Fonds (BOF) ofHasselt University for providing a scholarship. Funding fromMonash University is also kindly acknowledged.