Bifunctionalized poly(butyl acrylate) and poly(methyl methacrylate) were synthesized by the polymerization of butyl acrylate or methyl methacrylate using an organosamarium complex, [SmMe(C5Me5)(2)(CH2-CH-CHCH2)](2), as an initiator followed by the insertion of aldehydes. The polymerization proceeds quantitatively to afford the hydroxy-end functionalized polymer (M-n >4120) with narrow molecular weight distributions (M-w/M-n < 1.13). The attempted chain elongation of the resulting polymer with 4,4'-methylenebis(phenylisocyanate) has however failed, while the chain extension was realized by the reaction of poly(-caprolactone-co-butyl acrylate-co-epsilon -caprolactone) (M-n > 15,200, M-w/M-n <1.23) with a diisocyanate affording the desired high solid paint with M-n of 87,600 using a limited amount of THF as a solvent. (C) 2000 Elsevier Science B.V. All rights reserved.