A series of alkali-soluble resins were prepared from esterification reaction of styrene-maleic anhydride copolymer (SMA) and four fatty alcohols having different alkyl chains. The critical aggregates concentration of the prepared hemiester was lower than SMA, indicating that modification of SMA resin with long alkyl chains could improve their emulsification efficiency. The detailed experiments of emulsion polymerization of methyl methacrylate and butyl acrylate using these hemiesters as sole surfactants showed that SMA-C12-75, SMA-C14-70, and SMA-C16-65 were good surfactants. In the end, we successfully prepared stable latexes using above three good surfactants with relatively low surfactant concentration and high solid content. Characterization of latexes by Zetasizer and transmission electron microscopy revealed that particles of these latexes have core-shell nanostructure with average particle size below 60 nm. Compared with SMA, the improvement of emulsification efficiency of its hemiesters may come from the better hydrophilic-lipophilic balance and steric stabilization after incorporation of long alkyl chain. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013