Acrylic polyols of different hydroxyl numbers consisting of hydroxy ethyl methacrylate, methyl methacrylate, butyl acrylate, and styrene were prepared by free-radical solution as well as suspension polymerization techniques in the presence of benzoyl peroxide initiator. These polyols were crosslinked with butoxy methyl melamine at a ratio of 85 : 15 in the presence of acid catalyst. The thermal stability of polyols and their corresponding crosslinked films was studied by thermogravimetric (TG) technique. The Broido and Coats-Redfern methods were used to calculate the activation energy of thermal decomposition from standard TG curves. Dynamic mechanical thermal analysis was used to study the dynamic mechanical properties and determination of glass-transition temperature of acrylic/melamine crosslinked films. The results indicate that the thermal stability of polyols and crosslinked films strongly depends on the hydroxyl number of the acrylic polyols. It was found that acrylic polyols synthesized by suspension polymerization methods upon crosslinking yield more thermally stable and flexible films than polyols prepared by solution polymerization methods. (C) 2003 Wiley Periodicals, Inc.