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Obtaining Kinetic Information from the Chain-Length Distribution of Polymers Produced by RAFT

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Key Centre for Polymers & Colloids, School of Chemistry, The University of Sydney, NSW 2006, Australia, and School of Chemistry, Monash University, Victoria 3800, Australia
* To whom correspondence should be addressed. Phone: +61 2 9351 3366. E-mail: [email protected]
†The University of Sydney.
‡Monash University.
Cite this: J. Phys. Chem. B 2009, 113, 20, 7086–7094
Publication Date (Web):April 29, 2009
Copyright © 2009 American Chemical Society

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    Abstract Image

    We describe a simple model for the kinetics and chain-length distribution of polymers made by living radical techniques. Living radical methods give good control over the molecular weight of a linear polymer by capping the growing end and forming a dormant chain. The polymer is predominantly capped, and occasionally decaps to form a radical that propagates for a short period before recapping. Our model uses this mechanism to describe the chain-length distribution of polymers made by living radical methods. We focus on oligomers made by reversible addition−fragmentation chain transfer (RAFT) polymerization as model systems. Our model can determine optimal reaction conditions for desired polymer properties and test hypotheses about reaction schemes by using only two parameters, with each parameter related to the kinetics. The first parameter is the mean number of monomers added when a chain decaps. A broad distribution results if many monomers are added upon decapping. The second parameter is the mean number of times a polymer decaps. Many decapping events indicate high monomer conversion. Our model gives kinetic information by directly fitting to an experimental chain-length distribution, which is the reverse of other kinetic models that generate the distribution from rate coefficients. Our approach has also the advantage of being simpler than previously published kinetic schemes, which use many rate coefficients as inputs. Our model was tested against three monomers (acrylic acid, butyl acrylate, and styrene) and two RAFT agents. In each case, we successfully describe the chain-length distribution, and give information about the kinetics, especially the probability of propagation versus deactivation by the RAFT mechanism. This excellent agreement with a priori expectations and quantum calculations makes our model a powerful tool for predicting the structure of polymers obtained by living radical polymerization.

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    Electrospray, MALDI-ToF, and size exclusion analyses of EOSSA mediated RAFT polymerization of acrylic acid. This information is available free of charge via the Internet at

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