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Toward Uniform Nanofibers with a π‑Conjugated Core: Optimizing the “Living” Crystallization-Driven Self-Assembly of Diblock Copolymers with a Poly(3-octylthiophene) Core-Forming Block
journal contribution
posted on 2018-07-03, 16:29 authored by Ulrich Tritschler, Jessica Gwyther, Robert L. Harniman, George R. Whittell, Mitchell A. Winnik, Ian MannersCrystalline poly(3-alkylthiophene)
(P3AT) nanofibers are promising
materials for a myriad of device applications, but nanofiber length
control and colloidal stability are difficult to achieve. We report
an in-depth study of the solution self-assembly of regioregular poly(3-octylthiophene)-b-poly(dimethylsiloxane) (P3OT-b-PDMS)
diblock copolymers with a crystallizable π-conjugated core-forming
block. Use of the “living” crystallization-driven self-assembly
(CDSA) seeded-growth method in solvents selective for PDMS allowed
access to relatively low length dispersity, colloidally stable P3OT-b-PDMS fiber-like micelles with a crystalline, tape-like
P3OT core, a PDMS corona, and lengths up to ca. 600 nm under optimized
conditions. Significantly, the presence of a small percentage of common
solvent and the use of slightly elevated temperature (35 °C)
were found to enhance the length control. Analogous studies for P3OT-b-PS (PS = polystyrene) suggest that solvent composition
and temperature represent key parameters for the general optimization
of fiber formation by living CDSA for P3AT block copolymers.
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600 nmPDMS fiber-like micellesDiblock Copolymerslength dispersityP 3AT nanofibersP 3OT bcore-forming blockcrystallizable π-tape-like P 3OT corediblock copolymersP 3AT block copolymersoptimized conditionsCDSAlength controlfiber formationPDMS coronadevice applicationssolution self-assemblyseeded-growth methodUniform NanofibersPSnanofiber length controlAnalogous studies
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