Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Stevens, Kaden C.; Lott, Megan E.; Treaster, Kiana A.; O’Dea, Robert M.; Suresh, Adarsh; Eades, Cabell B.; Thompson, Victoria L.; Bowman, Jared I.; Young, James B.; Evans, Austin M.; Rowan, Stuart J.; Epps, Thomas H.; Sumerlin, Brent S.

doi:10.1021/acscentsci.5c01313

Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Journal Article · Wed Oct 29 00:00:00 EDT 2025 · ACS Central Science

DOI:https://doi.org/10.1021/acscentsci.5c01313· OSTI ID:3010485

Stevens, Kaden C. ^[1]; ^[1]; Treaster, Kiana A. ^[1]; ^[2]; Suresh, Adarsh ^[3]; ^[1]; Thompson, Victoria L. ^[1]; ^[1]; ^[1]; ^[1]; ^[3]; ^[2]; ^[1]

Univ. of Florida, Gainesville, FL (United States)
Univ. of Delaware, Newark, DE (United States)
Univ. of Chicago, IL (United States)

Thermally triggered depolymerization has traditionally been viewed through the lens of sustainability and recycling, not as a constructive tool for materials design. Herein, we show that selective, thermally triggered depolymerization to gaseous monomer serves as a solvent-free strategy for generating porosity in nanostructured polymer materials, offering a means to bypass the mass transport limitations inherent in conventional solution-based etching. As a demonstration platform, we employed polymerization-induced microphase separation (PIMS) to generate disordered bicontinuous block copolymer structures with embedded depolymerizable domains. By incorporating a methacrylate block susceptible to thermal depolymerization within a cross-linked, depolymerization-resistant styrenic matrix, we developed a process we term depolymerization etching of polymerization-induced microphase separations (DEPIMS). This approach enables highly selective and efficient domain removal via reversion to monomer to produce mesoporous materials with high surface areas (>200 m²/g). Subsequent surface functionalization yielded mesoporous adsorbents with tunable uptake kinetics and among the highest dye adsorption capacities reported for PIMS-derived materials, demonstrating the adaptability of the DEPIMS platform for chemical separations. DEPIMS can also be extended to a gram-scale, one-pot approach to yield mesoporous materials with recoverable monomer in under 12 h. These findings reposition thermal depolymerization from a sustainability tool to a broadly enabling strategy for scalable, on-demand fabrication of functional nanostructured materials.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Delaware, Newark, DE (United States)

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

Grant/Contract Number:: SC0021166

OSTI ID:: 3010485

Alternate ID(s):: OSTI ID: 3001043

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Journal Issue: 12 Vol. 11; ISSN 2374-7943; ISSN 2374-7951

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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