A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers

Till Gruendling; Mathias Dietrich; Christopher Barner-Kowollik

doi:10.1071/CH09080

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A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers

Till Gruendling ^A ^B , Mathias Dietrich ^A ^C and Christopher Barner-Kowollik ^A ^D

+ Author Affiliations

- Author Affiliations

^A Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Universität Karlsruhe (TH)/Karlsruhe Institute of Technology (KIT), 76128 Karlsruhe, Germany.

^B Bioanalytical Mass Spectrometry Facility, UNSW Analytical Centre, The University of New South Wales, Sydney, NSW 2052, Australia.

^C Environmental Engineering Group, Fraunhofer Institute of Chemical Technology, Joseph-von-Fraunhofer-Str. 7, 76327 Pfinztal, Germany.

^D Corresponding author. Email: christopher.barner-kowollik@polymer.uni-karlsruhe.de

Australian Journal of Chemistry 62(8) 806-812 https://doi.org/10.1071/CH09080
Submitted: 9 February 2009 Accepted: 12 March 2009 Published: 13 August 2009

Abstract

We report on the successful quantitative transformation of methacrylate and acrylate-type polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization carrying a dithioester-end-group into hydroxy-functional polymers. The simple reaction procedure involves stirring a solution of the dithioester-capped polymer and an azo-initiator in tetrahydrofuran at elevated temperatures (T = 60°C) in the presence of air. This reaction quantitatively yields hydroperoxide functionalities that can be efficiently reduced to hydroxy groups in a one-pot procedure using triphenylphosphine. Size exclusion chromatography–electrospray mass spectrometry was employed to monitor the progress of the reaction. The new backbone-linked hydroxy group provides a versatile anchor for chemical end-group conversions and conjugation reactions with prepared RAFT polymers, which alleviates problems with the rather limited ability of the dithioester-end-group to undergo non-radical transformations.

Acknowledgements

C.B.-K. acknowledges financial support from the University of Karlsruhe/Karlsruhe Institute of Technology (KIT) in the context of the Excellence Initiative for leading German universities as well as the German Research Council (DFG) and the Ministry of Science and Arts of the state of Baden-Württemberg. T.G. thanks the University of New South Wales for financial support via the University International Postgraduate Award (UIPA). We thank Mr Andrew J. Inglis for the synthesis of pyridine-2-carbodithioate functional poly(isobornyl acrylate).

References

A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers

Abstract

Acknowledgements

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