Journal
MACROMOLECULES
Volume 45, Issue 10, Pages 4142-4151Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma300533k
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Funding
- EPSRC
- Commonwealth Scholarship in the United Kingdom
- Fellowship Program in the United Kingdom
- EPSRC [EP/G060738/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/G060738/1] Funding Source: researchfish
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We present the synthesis, purification, and characterization of all-conjugated block copolymers comprising poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)- 2,1,3-benzothiadiazole]-2',2 ''-diyl) (PF8TBT) and poly(3-hexylthiophene) (P3HT). Suzuki step-growth polycondensation is used for the synthesis of PF8TBT, which is subsequently terminated via the addition of narrow-distributed, monobrominated P3HT-Br. Purification via preparative GPC is carried out to reduce polydispersity and to remove excess P3HT. Wavelength-dependent GPC and careful NMR end group analysis, assisted by model compounds, reveal pure diblock copolymers of PF8TBT-b-P3HT. Insight into structure formation is given by temperature-dependent UV-vis absorption, DSC, and X-ray scattering. These indicate that PF8TBT-b-P3HT does not microphase-separate within the investigated range of composition and molecular weight. The critical role of introducing sufficient dissimilarity between the segments in all-conjugated block copolymers in order to induce phase separation is discussed, with the conclusion that careful tuning of side chains is crucial for achieving self-organization.
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