Synthesis of New Cellobiose-Based Glycopolysiloxanes and their Use as Polymer Stabilizers in Miniemulsion Polymerisation Solenn Berson, D. Viet, Sami Halila, Hugues Driguez, Etienne Fleury, Thierry Hamaide * Introduction Green Chemistry for sustainable development implies new constraints that are to be taken into account in order to reduce the waste and protect fragile environments. Environmental regulations lead to favour environmentally friendly waterborne systems. This point is particularly true in the field of the polymerisation or stabilisation of polymer nanoparticles in dispersed media, for which emulsifiers are required to get particle latex and disper- sions displaying both controlled particle sizes and colloidal stability over a long-time storage. Polymer surfactants display some obvious advantages with respect to molecular ones, particularly their surface properties at lower concentrations, as well as their better adsorption on surfaces that leads to a lower residual concentration in the aqueous phase. [1] In addition, their hydrophilic-lipophilic balance (HLB) can be tuned from the control of both the hydrophobic and hydrophilic parts. The well-known non-ionic poly(ethylene oxide)-block-poly- (propylene oxide) (PEO-block-PPO) or poly(ethylene oxide)- block-polycaprolactone (PEO-block-PCL) block copolymers constitute a good illustration of this concept. Unlike Full Paper S. Berson, T. Hamaide Universite ´ de Lyon 1, CNRS-UMR5223, Inge ´nierie des Mate ´riaux Polyme `res, Laboratoire des Mate ´riaux Polyme `res et Biomate ´riaux, F-69622 Villeurbanne, France E-mail: thierry.hamaide@univ-lyon1.fr S. Berson, E. Fleury Universite ´ de Lyon 1, CNRS-UMR5223, Inge ´nierie des Mate ´riaux Polyme `res, Laboratoire des Mate ´riaux Macromole ´culaires, F-69622 Villeurbanne, France D. Viet, S. Halila, H. Driguez CERMAV (UPR-CNRS 5301) Universite ´ Joseph Fourier and Institut de Chimie Mole ´culaire de Grenoble, BP 53. 38041 Grenoble Cedex 9, France New glycopolysiloxanes were synthesized from cellobiose and commercially available reac- tive silicone oils or MD 0 M precursors. Their synthesis is based on the hydrosilylation of allyl- functionalized cellobiose onto the reactive silicone oil, after protection of the hydroxyl functions. The subsequent deprotection step leads to a redistribution of the silicon chain to yield oligomers with around 5 or 6 silicon atoms. Two water-dispersible glycosiloxanes were used for the steric stabilisation of vinyl acetate (VAc) miniemulsion polymerisation with up to 10% Miglyol 1 as the hydrophobic component. The best performances were obtained by using a mixture of non-ionic triblock copolymer and glycopolysiloxane. Poly(vinyl acetate) (PVAc) latex with particle sizes around 200 nm were obtained, displaying colloidal stabilisation upon long-time storage. 1814 Macromol. Chem. Phys. 2008, 209, 1814–1825 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/macp.200800194