Polystyrenes with different molecular weights were chemically modified with maleic anhydride by use of certain cationic catalysts of Lewis acid type (BF3 . OEt(2), AlCl3, TiCl4, ZnCl2, FeCl3, and SnCl4) in chloroform. The effects of molecular weight of polystyrene, as well as type of Lewis acid used, on properties and structure of products were investigated. The interrelation between the molecular weight of polystyrene and content of carboxyl groups in the products was made. A direct relationship between the activity of catalyst used and the number of carboxyl groups was found. For characterization of side-chain functionalized polystyrene, fractional precipitation was applied which yielded carboxyl groups in all fractions. The carboxyl group concentrations were found to be the highest in the case of BF3 . OEt(2). Modified polystyrene samples containing - CO - CH = CH - COOH fragments in side chains are easily crosslinked at 140-150 degrees C and by UV irradiation as proved by IR, DTA, and TGA analyses. Functionalized polymers obtained are characterized by their high thermostability, adhesion, and photosensitivity. (C) 1996 John Wiley & Sons, Inc.