Polymers, from DNA, cellulose, to poly-olefins, are ubiquitous to human existence. Polymer synthesis, however, has been limited to a set of methodologies with kinetics playing a critical role in the quality of material obtained. For hydrocarbon-based polymers, the use of initiator moieties—often needed to induce asymmetry in the electron density, is the first challenge in their synthesis. In free-radical chain growth, for example, addition of a single electrons to an olefin introduces an odd-electron activated monomer albeit with an appended initiator fragment. The initiator moeity can, however, be eliminated by use of a free-electron initiator. Use of free (solvated) electrons in co-polymerization of so-called ‘armed-disarmed’ monomer pairs will be discussed. Exploiting solubility and quantum mechanics dominated properties of the free electrons, challenges in diffusion limited reactivity can be overcome. This coupled approach allows for rapid polymerization where the odd-symmetry in electron density can be exploited in a bimechanistic (concurrent radical and anionic) reaction. We extended this approach to synthesis of block co-polymers of complex architecture that given unprecedented neoteric micro-structures.

Rapid bimechanistic synthesis and self-assembly of block co-polymers using free electron initiators

256th National Meeting (2018)

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