Tailoring Phase Behavior and Mechanical Properties in Thermoplastic Elastomers through Block Sequence and Macromolecular Architecture

Block copolymers exhibit unique properties which depend not only on the identities of the constituent blocks but also the block sequence and macromolecular architecture. Thermoplastic elastomers (TPEs) are a prime example. In TPEs the arrangement of glassy end blocks flanking a long rubbery midblock gives rise to a physically cross-linked, elastic solid. Exchanging the glassy blocks for crystalline blocks can improve the processability and solvent resistance, but adversely affects the mechanical performance. The block sequence crystalline-glassy-rubbery-glassy-crystalline has been developed to combine the advantages of both crystalline and glassy blocks. Careful selection of block lengths produces materials in which the order-disorder transition temperature lies below the melting point of the crystalline block, ensuring that the melt will be homogeneous above the melting point. Access to single-phase melts provides a large reduction in viscosity and elasticity over conventional TPEs, which remain microphase-separated in the melt. Inserting the glassy blocks between the crystalline and rubbery blocks produces a vitreous layer surrounding the crystalline domains, which improves the room-temperature mechanical performance. Incorporating the crystalline-glassy-rubbery motif into the arms of star block copolymers adds another level of control. The star architecture introduces a permanent cross-link at the center of the star without appreciably affecting the phase behavior.