A series of NCO terminated polyurethane (PU)-imide copolymers were synthesized by a systematic three-step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG-1000) with hard segments like 2,4-tolylene-diisocyanate (TDI) or isophorone-diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess-NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. (c) 2006 Wiley Periodicals, Inc.