Anionic polymerization of butadiene was conducted in cyclohexane using 1,1,4,4-tetraphenyl-1,4-dilithium butane (TPB-DiLi) as initiator and dipiperidinoethane (DPE) as modifier. The polymer design effects of DPE/TPB-DiLi (simplified as DPE/Li) and polymerization temperature on the 1,2 content of polybutadiene (PB) were examined and 1,2-polybutadiene (1,2-PB) with a nearly 100% 1,2 content was obtained. 1,2-1,4-1,2-Stereotriblock polybutadiene (STPB) can be synthesized easily by means of one feed reaction. DSC and DMA analyses showed that STPB with the designed molecular structure (molecular weight, block ratio, and 1,2 content in 1,2 blocks) has two T-g's and two loss moduli and exhibits microphase separation. Studies on reaction kinetics established the polymerization kinetics equation of 1,4-PB as -d[M]/dt = 0.356[C](0.5)[M], indicating the first-order relationship between polymerization rate and monomer concentration. At 50degreesC, the addition of the strong polar modifier DPE into the system increased the reaction rate. The apparent propagating activating energies before and after DPE addition were also determined in this study. (C) 2003 Wiley Periodicals, Inc.