Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Nian, Shifeng; Fan, Zhouhao; Freychet, Guillaume; Zhernenkov, Mikhail; Redemann, Stefanie; Cai, Li-Heng

doi:10.1021/acs.macromol.1c01911

Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Journal Article · Tue Oct 05 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c01911· OSTI ID:1890195

^[1]; Fan, Zhouhao ^[1]; Freychet, Guillaume ^[2]; ^[2]; Redemann, Stefanie ^[1]; ^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding is that the domain spacing is limited by the contour length of the polymer backbone. Here, using a combination of molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, and electron tomography, we discover that this molecular picture does not hold for architecturally semiflexible BCPs. For strongly segregated linear–semiflexible bottlebrush–linear triblock copolymers, the size of the bottlebrush domain can be twice the bottlebrush backbone contour length. The mechanism of such anomalous self-assembly is likely that the interfacial repulsion between the incompatible blocks is large enough to pull a part of the linear end blocks into the bottlebrush domain. This effectively increases the bottlebrush domain size. Moreover, the semiflexible bottlebrush widens the regime for the cylinder morphology that is associated with the volume fraction of the end blocks fC^SFB ∈ (0.10, >0.41). This window is much wider than that for flexible linear BCPs, fC^F ∈ (0.14, 0.35), and that predicted by the recent self-consistent field theory for linear-bottlebrush BCPs of the same chemistry and molecular architecture. Finally, our experimental findings reveal previously unrecognized mechanisms for the self-assembly of architecturally complex BCPs.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); ACS Petroleum Research Fund (PRF)

Grant/Contract Number:: SC0012704

OSTI ID:: 1890195

Report Number(s):: BNL-222349-2021-JAAM

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 20 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

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