Precise control over the location of monomers in a polymer chain has been described as the ‘Holy Grail’ of polymer synthesis. Controlled chain growth polymerization techniques have brought this goal closer, allowing the preparation of multiblock and multisite copolymers with ordered sequences of functional monomers. But the statistical nature of reversible deactivation radical polymerization places strong limits on the structural control that can be obtained. We have shown that monomer locations in highly idealized systems are distributed according to surprisingly simple laws related to standard probability distributions. The degree of control can be quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. Here we present the extension of these results to more realistic systems with slow equilibria between active and dormant species. This analysis establishes experimental requirements for the design of polymeric chains with a controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis.

Limits of precision monomer placement in reversible deactivation radical polymerization

254th National Meeting (2017)

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