Metallo-supramolecular complexes mediated thermoplastic elastomeric block copolymer

Orthogonal multi-phase strategy has been applied to generate a novel type of thermoplastic elastomeric block copolymer which was obtained via anionic polymerization. Functional terpyridine groups which can potentially form metallo-supramolecular complexes with a variety of metal ions has been introduced to the polystyrene-b-polyisoprene (PS-PI) living chain ends through the termination reaction in an optimized condition. Iron(II), cobalt(II) and zinc(II) metal ions have been used to form metal-ligand complexes with the terpyridine end groups, which can phase separate from the polymer matrix to form hybrid clusters. The formation of metallo-supramolecular hybrid clusters have dramatic effects on the micro-phase separated structures of the PS-PI diblock copolymer, which have been characterized by transmission electron microscopy, small-angle X-ray scattering and atomic force microscopy. This type of hybrid material containing hard PS nanophase and metal-ligand clusters exhibit distinct mechanic properties such as increased modulus, higher yield strength and improved toughness, which is further discussed in light of nature of the metal-ligand bonds and the liability of the clusters. The utilization of metallo-supramolecular complex and its high tunability is potential to fabricate new types of supramolecular nanocomposite materials.