Poly(caprolactone) containing highly branched segmented poly(ester urethane)s via A₂ with oligomeric B₃ polymerization

Highly branched, poly(caprolactone) (PCL) containing segmented poly(ester urethane)s were synthesized via polymerization of A₂ and oligomeric B₃ type monomers. An isocyanate functional butanediol-based A ₂ hard segment was synthesized and immediately reacted with a poly(caprolactone)-based trifunctional (B₃) soft segment. Characterization of thermal properties using DMA and DSC analysis demonstrated that the PCL segment remained amorphous in branched poly(ester urethane)s. Conversely, the crystallinity of PCL segment was retained to some extent in a linear analogue with equivalent soft segment molecular weight. Tensile testing revealed a slight decrease in Young's modulus and tensile strength for the highly branched polymers compared with a linear analogue. However, highly branched poly(ester urethane)s demonstrated lower hysteresis. In addition to synthesis of highly branched polymers, poly(ester urethane) networks were synthesized from a highly branched hydroxyl-terminated precursor and a low molar mass diisocyanate as the crosslinking agent.