Controlled ATRP synthesis of novel linear- dendritic block copolymers and their directed self- assembly in breath figure arrays

Herein, we report the formation and characterization of novel amphiphilic lineardendritic block copolymers (LDBCs) composed of hydrophilic dendritic poly(ether-ester), PEE, blocks and hydrophobic linear poly(styrene), PSt. The LDBCs are synthesized via controlled atom transfer radical polymerization (ATRP) initiated by a PEE macroinitiator. The copolymers formed have narrow molecular mass distributions and are designated as LGn-PSt M_n, in which LG represents the PEE fragment, n denotes the generation of the dendron (n = 1-3), and M_n refers to the average molecular mass of the LDBC (M_n = 3.5-68 kDa). The obtained LDBCs are utilized to fabricate honeycomb films by a static "breath figure" (BF) technique. The copolymer composition strongly affects the film morphology. LDBCs bearing acetonide dendron end groups produce honeycomb films when the PEE fraction is lower than 20%. Pore uniformity increases as the PEE content decreases. For LDBCs with hydroxyl end groups, only the first generation LDBCs yield BF films, but with a significantly smaller pore size (0.23 μm vs. 1-2 μm, respectively). Although higher generation LDBCs with free hydroxyl end groups fail to generate honeycomb films by themselves, the use of a cosolvent or addition of homo PSt leads to BF films with a controllable pore size (3.7- 0.42 μm), depending on the LDBC content. Palladium complexes within the two triazole groups in each of the dendron's branching moieties can also fine-tune the morphology of the BF films.