Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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

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 http://dx.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 (Mn 6800 g mol–1, PDI 1.15) was treated with poly(6-O-methacryloyl mannose) (Mn 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.


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