Two procedures to prepare styrenic reactive surfactants are described. The first one, close to a procedure
of Ito et al., involves the initiation of anionic polymerization of ethylene oxide by an alkyl silanolate. Once
the ethylene oxide is fully consumed, the anion is condensed on a styrenic alkyl bromide. Then the hydroxyl
is recovered by a reaction of deprotection. The second one, on the contrary, starts from the hydrophobic
end group. This anionic polymerization is initiated by vinyl benzyl alcoholate. Successively butylene oxide
and ethylene oxide are polymerized. In the last step, the anion can be used to open the ring of propane
sultone and we produce an anionic reactive surfactant, or the living chain can be hydrolyzed to obtain a
nonionic surfactant. This second procedure gives good control of both hydrophobicity and hydrophilicity.
The physicochemical properties of the corresponding surfactants are measured.
Styrenic block-copolymer polymerizable surfactants, when engaged in emulsion polymerization of core−shell acrylic latexes, are forming copolymers containing a large majority of monomer
units. These copolymers can be extracted, and analyzed, after extensive washing of the particles by
ultrafiltration. Owing to the restricted mobility of the polymer inside the particles, direct 1H NMR analysis,
in normal waterwith water suppressionof the latex itself, in its initial serum, gives selective detection
of the water-solvated species and allows to estimate both the amount of surfmer remaining at the surface
of the particle and their conformation, thus allowing to determine what part of it participates in the
steric and electrosteric stabilization.
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