A straightforward method for the preparation of polysiloxanes grafted with carbohydrate side groups is described. Two kinds of backbones have been functionalized, namely one-dimensional, linear polysiloxanes, and hyperbranched poly(siloxysilane)s based on cyclotetrasiloxanes. The method enables us to keep a good integrity of the polysiloxane backbone. The introduction of intermediate activated esters as side groups on the polysiloxane backbone ensures a complete homogeneity of the reaction medium during sugar grafting in dimethyl sulfoxide, and consequently an easy grafting with the unprotected amino sugar. Solubility of the resulting polysiloxanes has been tested in various solvents. The sugar-grafted polysiloxanes are good candidates for applications such as silicone formulations, hydrophilic silicone elastomers, interactions with metallic nanoparticles, and suspension stabilization, or as starting point for the design of more complex polysiloxanes for molecular recognition. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3607–3618
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