Rod-coil type miktoarm star copolymers consisting of polyfluorene and polylactide : precise synthesis and structure-morphology relationship

A series of rod-coil miktoarm star copolymers consisting of poly[2,7-(9,9-dihexylfluorene)] (PF) and polylactide (PLA) arms as the rod and coil segments, respectively, were synthesized by combining the chain-growth Suzuki-Miyaura coupling polymerization and living ring-opening polymerization (ROP). First, PFs having a hydroxyl group at the alpha-chain end (PF-BnOH) were prepared by the polymerization of 2-(7-bromo-9,9-dihexyl-9H-fluorene-2-yl) 4,4,5,5-tetramethyl-1,2,3-dioxaborolane using the initiating system of 4-(tetrahydropyran-2'-yloxymethyl)-iodobenzene/Pd-2(dba)(3)/t-Bu3P. After a couple of chain end modifications, PFs having one, two, and three hydroxyl groups at the alpha-chain end (PF-OH, PF-(OH)(2), and PF-(OH)(3), respectively) were obtained with dispersity (D) values of less than 1.29. The obtained PF-OH, PF-(OH)(2), and PF-(OH)(3) were used as the initiators for the organic base-catalyzed ROP of rac-lactide to produce the AB type linear diblock (PF-b-PLA) and AB(2) and AB(3) type miktoarm star copolymers (PF-b-(PLA)(2) and PF-b-(PLA)(3), respectively). The self-assembled nanostructures in the thermally-annealed PF-b-(PLA)(x)s (x = 1, 2, and 3) were evaluated in the bulk by synchrotron small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The PF-b-PLA, PF-b-(PLA)(2), and PF-b-(PLA)(3) with the PF weight fractions of 0.52-0.56 were found to form poorly ordered PLA cylindrical structures in the PF matrix due to a strong rod-rod interaction of the PF segment. On the other hand, these BCPs with the PF weight fractions of 0.22-0.23 exhibited the hexagonally close-packed cylinder (Hex) morphologies, in which the cylindrical PF phase was embedded in the PLA matrix. More interestingly, the domain-spacing (d) values for the Hex morphologies decreased with the increasing PLA arm number despite each BCP having a comparable molecular weight and PF weight fraction: d = 26.4 nm for PF-b-PLA, d = 21.7 nm for PF-b-(PLA)(2), and d = 18.6 nm for PF-b-(PLA)(3)