High molecular weight, high functionality diamino telechelic polybutadienes (TPBs) were synthesized by ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in the presence of a chain transfer agent, 1,8-dicyano-4-octene, followed by lithium aluminum hydride reduction. Melt coupling of diamino TPB with anhydride-terminated polystyrene (PS-anh) resulted in the formation of styrenebutadiene-styrene (SBS) triblock copolymers; ca. 80% maximum conversion of PS-anh was achieved within 30 s. The results from SAXS, TEM, and theological measurements of the coupling products confirmed the formation of SBS triblock copolymers having lamellar morphology. A fluorescent-labeled PS-anh was used to study the coupling kinetics by diluting the reactants by the addition of non-functional PS. (c) 2008 Elsevier Ltd. All rights reserved.