Ultra-precise insertion of functional monomers in chain-growth polymerizations

Mirela Zamfir and Jean-François Lutz ()
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Mirela Zamfir: Precision Macromolecular Chemistry Group—icFRC, Institut Charles Sadron, UPR22-CNRS, 23 rue du Loess, BP 84047, Cedex 2, Strasbourg 67034, France.
Jean-François Lutz: Precision Macromolecular Chemistry Group—icFRC, Institut Charles Sadron, UPR22-CNRS, 23 rue du Loess, BP 84047, Cedex 2, Strasbourg 67034, France.

Nature Communications, 2012, vol. 3, issue 1, 1-8

Abstract: Abstract Chain-growth polymerizations are popular methods because they allow synthesis of high-molecular weight polymers in high yields and in short times. However, copolymers prepared by such processes generally exhibit uncontrolled monomer sequences. The controlled radical copolymerization of styrene with N-substituted maleimides is an interesting exception allowing preparation of controlled primary structures. However, because of the statistical nature of chain-growth mechanisms, sequence deviations are still present in these copolymers. Here we describe a specific range of experimental conditions that allows ultra-precise incorporation of a single N-substituted maleimide unit in a polystyrene chain. This occurs in a given kinetic regime where the styrene/N-substituted maleimide comonomer ratio is very low. This situation usually only arises in the later stages of a chain-growth polymerization. Nevertheless, we show that it is possible to restore these particular kinetic conditions multiple times during a single polymerization by using successive feeds of donor and acceptor comonomers.

Date: 2012
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DOI: 10.1038/ncomms2151

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