Libraries of 3-aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolact one) (PCL-PDMS-PCL) triblock copolymers were synthesized. Preliminary experiments were carried out to select an appropriate catalyst and route for the poly(dimethylsiloxane) synthesis, and trial experiments were conducted to verify the successful synthesis of the intended polymer compositions. Then, a series of APT-PDMS oligomers were synthesized with an automated combinatorial high-throughput synthesis system to cover a molecular weight range of 2500-50,000 g/mol. Trial PCI-PDMS-PCL triblock copolymers were synthesized with the automated reactor system and characterized in detail with rapid gel permeation chromatography, high-throughput Fourier transform infrared, nuclear magnetic resonance, and differential scanning calorimetry. Finally, two library synthesis experiments were carried out in which the lengths of both the poly(dimethylsiloxane) and poly(E-caprolactone) blocks in the PCI-PDMS-PCL triblock copolymers were varied. The results obtained from these experiments demonstrated that it was possible to synthesize libraries of well-defined APT-PDMS oligomers and PCL-PDMS-PCL triblock copolymers with an automated high-throughput system. (c) 2006 Wiley Periodicals, Inc.