Nondestructive Photo-Cross-Linking of Microphase-Separated Diblock Polymers through Coumarin Dimerization

Sims, Michael B.; Zhang, Bo; Gdowski, Zachary M.; Lodge, Timothy P.; Bates, Frank S.

doi:10.1021/acs.macromol.2c00356

Nondestructive Photo-Cross-Linking of Microphase-Separated Diblock Polymers through Coumarin Dimerization

Journal Article · Fri Apr 15 00:00:00 EDT 2022 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.2c00356· OSTI ID:1874679

^[1]; ^[2]; Gdowski, Zachary M. ^[2]; ^[2]; ^[2]

Univ. of Minnesota, Minneapolis, MN (United States); University of Minnesota Twin Cities
Univ. of Minnesota, Minneapolis, MN (United States)

The effect of long-wavelength ultraviolet photocrosslinking on microphase-separated coumarin-containing block polymers was studied by photo-rheometry and small-angle X-ray scattering. This model system consisted of three photocrosslinkable diblock polymers of poly(methoxyethyl acrylate)-b-poly(hexyl methacrylate-co-coumarin methacrylate) with different volume fractions of the crosslinkable coumarin-containing block, which microphase separated into lamellar and cylindrical morphologies. All polymers stiffened upon exposure to 365 nm light, with much greater relative increases in moduli recorded for lamellae-forming polymers (ca. 3200% increase) compared to the cylinder-forming polymer (ca. 550% increase). Disordering transitions that were evident in uncrosslinked samples were no longer observed after crosslinking in the ordered state, and domain sizes were found to remain stable to heating. The photocrosslinking reaction only proceeded under active irradiation, indicating a high degree of spatiotemporal control over curing in this system. Finally, at constant concentration of couamarin within the crosslinkable block, the cure rate was largely independent of polymer composition, suggesting a constant local concentration of coumarin moieties within the segregated crosslinkable domains. Lastly, these findings establish a set of specific structure-property relationships governing the phase-selective photocrosslinking of diblock polymers that can guide the design of robust nanostructured materials.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Twin Cities, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation

Grant/Contract Number:: SC0017809

OSTI ID:: 1874679

Alternate ID(s):: OSTI ID: 1906368

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 8 Vol. 55; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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