Three thiol-compounds with different functionalities were synthesized through esterification reaction which was prepared by 1, 4-butanediol, trimethylolpropane, and pentaerythritol and 3-mercapto propionic acid respectively. Thiol-compounds and polyurethane-acrylate prepolymer were blended with addition of photo-initiator in certain proportions in order to form polyurethane curing film under UV irradiation. The structure and properties of the thiol-compounds and the polyurethane curing film were characterized by NMR, FT-IR, and TG. The results showed that the thiol-ene addition reaction between the urethane acrylates and the thiol-compounds was preceeded. With the increase of functionality of mercaptopropionic acid ester, the thermal stability improved, and the T-peel strength enhanced. When the moral ratio of urethane acrylates and trimethylolpropane-3-mercapto propionic acid ester was 1:1, the adhesive showed the best mechanical properties and thermal stability with curing time 40s, T-peel strength 88N/m and 50 % mass loss at 369°C, respectively.