The Development of End-group Functionalized Polyolefin Building Blocks through LCCTP

The development of living coordination chain transfer polymerization utilizing the cationic hafnium monocyclopentadienyl, monoacetamidinate derivative, [(η⁵-C₅Me₅)Hf(Me)[N(Et)C(Me)N(Et)][B(C₆F₅)₄], as the active initiator in the presence of excess equivalents of main-group-metal alkyl ‘surrogate’ chain growth centers has provided a viable path to practical and scalable bulk quantities of structurally-well defined polyolefins that are further characterized by having tunable molecular weight, narrow polydispersity and end-group functionality, including  –OH, -I, -N₃ and –COOH chemical moieties.  These low molecular weight, atactic end-group functionalized polyolefins are further attractive as building blocks for new types of polyolefin materials with novel polymer architectures and properties.   In the present work, the synthetic utility of the -I and -OH end group functionalized polyolefins has been explored to develop several ‘bio-inspired’ self-assembled materials that have been characterized in solution and ultra-thin film state by an arsenal of techniques, including TEM, AFM, GPC, DLS, MALDI-TOF and NMR in order to establish the potential utility in nanotechnology.