Preparation of macroporous, monodisperse, functionalized styrene–divinylbenzene copolymer beads: Effect of the nature of the monomers and total porogen volume on the porous properties

The staged templated suspension polymerization method was used for the preparation of 5 μm beads from mixtures of styrene and several substituted styrene monomers, including 4-methylstyrene, 4-aminostyrene, 3-aminostyrene, 4-acetoxystyrene, and 4-tert-butoxycarbonyl oxystyrene, with divinylbenzene in the presence of various amounts of linear polystyrene and dibutyl phthalate as porogens. The nature of the monomer as well as the total percentage of porogenic compounds in the polymerization mixture have a large effect on the porous properties and surface morphology of the monodisperse beads. Beads with large pores can only be obtained once the percentage of porogen in the mixture exceeds a threshold value that varies with the type of monomers involved in the polymerization. The level of incompatibility of the functional polymer chains formed during the crosslinking polymerization with the linear polystyrene porogen that is present in the polymerization mixture is another variable that also affects both the porous properties and the morphology of the beads. Because better compatibility is achieved, this effect is less pronounced if unfunctionalized styrene is used as a monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 597–607, 1998