Song, In Young Kim, Jinseck Im, Min Jeong Moon, Byung Joon Park, Taiho Synthesis and Self-Assembly of Thiophene-Based All-Conjugated Amphiphilic Diblock Copolymers with a Narrow Molecular Weight Distribution A series of amphiphilic poly­(3-hexylthiophene-<i>b</i>-3-(2-(2-{2-[2-(2-methoxy–ethoxy)-ethoxy]-ethoxy}-ethyl))­thiophene) (P­(3HT-<i>b</i>-3EGT)) polymers was synthesized via a nickel-catalyzed quasi-living polymerization. Size exclusion chromatograms (SEC) revealed that the molecular weight distributions of the <b>P3HT</b> blocks in the block copolymers were comparable with those of the polystyrene standard (monodisperse). <sup>1</sup>H NMR spectra revealed that the <b>P3HT</b> and <b>PEGT</b> units in the block copolymers were well-defined and did not form compositionally mixed regions at the boundary between the blocks and the highly regioregular <b>P3HT</b> units. The correlations among the block ratio, the amphiphilicity, and the self-assembled nanostructures of the block copolymers in thin films and in solution were examined. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) studies revealed that the crystallinity of the <b>BP93</b> composed of 93 mol % <b>P3HT</b> blocks was higher than the crystallinity of the <b>P3HT</b> alone due to the packing effects caused by repulsion among the hydrophobic hexyl and hydrophilic ethylene glycol oligomer side chains. A long relaxation time was required to observe the ordering among <b>P3HT</b> blocks in the <b>BP26</b> composed of 26 mol % P3HT blocks, suggesting that self-assembly could occur if induced on the molecular level. We demonstrated that the molecular-level self-assembly of <b>BP26</b> (at dilute concentrations) via a slow dialysis method produced highly ordered polymer vesicles 200–250 nm in size under thermodynamic control. The size could be tuned via competitive hydrophobic interactions using polystyrene. In contrast, kinetic control via a rapid precipitation method yielded 5–20 nm micelles. ethylene glycol oligomer side chains;Narrow Molecular Weight DistributionA series;XRD;DSC;P 3HT;regioregular P 3HT units;Size exclusion chromatograms;BP 26;PEGT;P 3HT blocks;SEC;Differential scanning calorimetry;1 H NMR spectra;block copolymers 2016-02-20
    https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Self_Assembly_of_Thiophene_Based_All_Conjugated_Amphiphilic_Diblock_Copolymers_with_a_Narrow_Molecular_Weight_Distribution/2510767
10.1021/ma300771g.s001