Hollow polymer particles with large voids were prepared with styrene (St) as the main component and in the presence of a small amount of N,N'-dimethylaminoethyl methacrylate (DMAEMA) via a glass-membrane emulsification technique and a subsequent suspension polymerization. A mixture of the monomer, hexadecane (HD), and N,N'-azobis(2,4-dimethylvaleronitrile) as an initiator was used as a dispersed phase (oil phase). By the careful pushing of the dispersed phase through the pores of the glass membrane into the aqueous phase, an emulsion of fairly monodisperse monomer droplets was formed. Then, the polymerization was performed by temperature being elevated to 70degreesC. The aqueous phase (continuous phase) contained poly(N-vinyl pyrrolidone) as a stabilizer, sodium lauryl sulfate as a surfactant, Na2SO4 as an electrolyte, and sodium nitrite (NaNO2) as a water-soluble inhibitor. Results related to the effects of the HD content, DMAEMA, and the composition of the comonomer, including the crosslinker and flexible segment, on the features of the hollow particles were investigated. When the content of DMAEMA was higher than 1.0 wt% based on the total monomer, small, secondary particles were generated in the aqueous phase, but the generation was effectively prevented when DMAEMA was limited to 0.5 wt%. Hollow particles, with an average diameter of around 7 gm, were obtained with an St-DMAEMA system. The void size of the hollow particles was controlled by the HD content. When, the HD content was lower (<25 wt% based on the oil phase), unbroken hollow particles were easily obtained. However, they tended to break into halves after drying when the HD content was increased to 50 wt%. A soft segment, lauryl acrylate, and a crosslinker, ethylene glycol dimethacrylate, were added to overcome this problem. (C) 2002 Wiley Periodicals, Inc.