Domain Structures of Poly(3-dodecylthiophene)-Based
Block Copolymers Depend on Regioregularity
Posted on 2018-05-18 - 18:33
Microphase-separation behavior of
conjugated–amorphous block
copolymers (BCPs) is driven by a complex interplay between Flory–Huggins
interaction (χ), liquid crystalline (LC) interaction, and crystallization.
Herein, in order to elucidate the influence of LC interaction on the
morphology of the BCPs, we report the effects of regioregularity (RR)
on the microphase separation and molecular packing structures of poly(3-dodecylthiophene)-block-poly(2-vinylpyridine) (P3DDT-b-P2VP). To decouple the effect of LC interactions from crystallization
kinetics, we investigate the morphological behavior of the P3DDT-b-P2VP at above the melting temperature of P3DDT (∼160
°C). Both electron microscopy and X-ray scattering show an abrupt
reduction in the domain spacing of both lamellar and cylindrical phases
as the RR of P3DDT block increases. Specifically, lower RR (i.e.,
85, 79, and 70%) BCPs have larger domain spacings than high RR (94%)
by 50% (lamellar) or 80% (cylindrical), even though the overall molecular
weights and P2VP volume fractions were similar for each RR. We propose
that the RR-driven transition in domain spacing is caused by a change
in P3DDT conformations and interchain interactions. When RR is low,
the system assembles into a typical bilayer structure like other semiflexible
and flexible block copolymer systems. When RR is high, the less flexible
P3DDT chains are extended, driving their assembly into an LC monolayer.
Significantly, this study demonstrates that tunable RR provides a
simple route to manipulate melt state self-assembly of conjugated–amorphous
materials.
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Kim, Jin-Seong; Han, Junghun; Kim, Youngkwon; Park, Hyeonjung; Coote, Jonathan P.; Stein, Gila E.; et al. (2018). Domain Structures of Poly(3-dodecylthiophene)-Based
Block Copolymers Depend on Regioregularity. ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.8b00795