RAFT Chemistry and Huisgen 1,3-Dipolar Cycloaddition: A Route to Block Copolymers of Vinyl Acetate and 6-O-Methacryloyl Mannose?

S. R. Simon Ting; Anthony M. Granville; Damien Quémener; Thomas P. Davis; Martina H. Stenzel; Christopher Barner-Kowollik

doi:10.1071/CH07089

RESEARCH FRONT

RAFT Chemistry and Huisgen 1,3-Dipolar Cycloaddition: A Route to Block Copolymers of Vinyl Acetate and 6-O-Methacryloyl Mannose?

S. R. Simon Ting ^A , Anthony M. Granville ^A , Damien Quémener ^A ^B , Thomas P. Davis ^A , Martina H. Stenzel ^A and Christopher Barner-Kowollik ^A ^C

+ Author Affiliations

- Author Affiliations

^A Centre for Advanced Macromolecular Design, School of Chemical Sciences and Engineering, University of New South Wales, Sydney, NSW 2052, Australia.

^B Current address: Laboratoire de Chimie Physique Macromoléculaire, UMR CNRS-INPL 7568, ENSIC, 1 rue Grandville, BP 20451, 54 001 Nancy Cedex, France.

^C Corresponding author. Email: camd@unsw.edu.au

Australian Journal of Chemistry 60(6) 405-409 https://doi.org/10.1071/CH07089
Submitted: 28 March 2007 Accepted: 20 April 2007 Published: 18 June 2007

Abstract

The present communication explores a novel avenue to glycopolymer-block-poly(vinyl acetate) polymers by a combination of reversible addition fragmentation chain transfer (RAFT) chemistry and Huisgen 1,3-dipolar cycloaddition (i.e., so-called ‘click’ chemistry) under mild reaction conditions. Such block copolymers are—because of the strongly disparate reactivity of the two monomers—otherwise not obtainable. Poly(vinyl acetate) that has an azide end group (M_n 6800 g mol^–1, PDI 1.15) was treated with poly(6-O-methacryloyl mannose) (M_n 7600 g mol^–1, PDI 1.11) in the presence of 1,8-diaza[5,4,0]bicycloundec-7-ene and copper(i) iodide. The resulting poly(vinyl acetate)-block-poly(6-O-methacryloyl mannose) had a number-average molecular weight of 15 400 g mol^–1 and a PDI of 1.48, which indicates that while the cycloaddition had occurred the resulting polymer distribution featured a considerable width. The resulting slightly amphiphilic block copolymer was subsequently investigated with regard to its self-assembly in aqueous solution. Dynamic light scattering studies indicated a hydrodynamic diameter of close to 200 nm. Transmission electron microscopy studies indicate the formation of rods as well as spheres with transitions between these two phases. However, the segregation between core and shell in the spheres is not pronounced; such behaviour is expected for weakly amphiphilic block copolymers.

Acknowledgments

C.B.-K. and M.H.S. acknowledge receipt of a Discovery Grant (ARC). C.B.-K. also acknowledges receipt of an Australian Professorial Fellowship (ARC). T.P.D. acknowledges receipt of a Federation Fellowship. The authors thank Dr Leonie Barner and Mr Istvan Jacenyik for their excellent management of the Centre for Advanced Macromolecular Design (CAMD).

References

RAFT Chemistry and Huisgen 1,3-Dipolar Cycloaddition: A Route to Block Copolymers of Vinyl Acetate and 6-O-Methacryloyl Mannose?

Abstract

Acknowledgments

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