title: The limits of precision monomer placement in chain growth polymerization.
abstract: 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 copolymers with ordered sequences of functional monomers. Such structures have promising applications ranging from medicine to materials engineering. Here we show, however, that the statistical nature of chain growth polymerization places strong limits on the control that can be obtained. We demonstrate that monomer locations are distributed according to surprisingly simple laws related to the Poisson or beta distributions. The degree of control is quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. This analysis establishes experimental requirements for the design of polymeric chains with controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis.
authors.affiliation: Department of Chemistry, University of Warwick, Warwick CV4 7AL, UK.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Gody
authors.affiliation: Centre for Advanced Macromolecular Design, School of Chemical Engineering, University of New South Wales, Sydney, New South Wales 2052, Australia.
authors.forename: Per B
authors.initials: PB
authors.lastname: Zetterlund
authors.affiliation: Department of Chemistry, University of Warwick, Warwick CV4 7AL, UK.|Faculty of Pharmacy and Pharmaceutical Sciences, Monash University, Parkville, Victoria 3052, Australia.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Perrier
authors.affiliation: Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique, CNRS UMR5623, Université Paul Sabatier Toulouse III, 118 Route de Narbonne, Toulouse 31062, France.
authors.forename: Simon
authors.initials: S
authors.lastname: Harrisson
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