Surfactant bilayers adsorbed on silica are used as the reaction site f
or the formation of ultrathin polymer films from coadsorbed or adsolub
ilized monomer. Results from the polymerization of styrene in cetyltri
methylammonium bromide (CTAB), in octylphenoxypoly(ethoxy)ethanol, and
in methyltri(C8-C10)ammonium chloride bilayers show effective convers
ion of adsolubilized styrene monomer to polystyrene. The process has b
een demonstrated effective with amorphous precipitated silica substrat
es having a variety of surface areas and with two types of initiation
schemes. The extractable polymer has been characterized using photoaco
ustic FTIR, UV, and gel permeation chromatography (GPC). Only approxim
ately 25% of the polymer was extractable after refluxing for 4 h in te
trahydrofuran. The impact of the treatment on some industrially import
ant surface properties of the modified silicas has also been determine
d. The process offers a potentially inexpensive method for modifying c
hemical and physical surface properties of various substrates.