Frontal Polymerization of Stereoisomers: Distinct Microstructures and Properties in Endo- and Exo-Dicyclopentadiene Thermosets

Wang, Hanlin M.; Suslick, Benjamin A.; Lessard, Jacob J.; Yu, Christina H.; Saengow, Chaimongkol; Ewoldt, Randy H.; Moore, Jeffrey S.

doi:10.1021/acs.macromol.3c02177

Frontal Polymerization of Stereoisomers: Distinct Microstructures and Properties in Endo- and Exo-Dicyclopentadiene Thermosets

Journal Article · Tue Dec 19 00:00:00 EST 2023 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c02177· OSTI ID:2339599

^[1]; ^[2]; ^[2]; Yu, Christina H. ^[2]; ^[2]; ^[2]; ^[2]

University of Illinois at Urbana-Champaign, IL (United States); REMAT EFRC, University of Illinois Urbana-Champaign
University of Illinois at Urbana-Champaign, IL (United States)

This study explores the relationship between monomer stereochemistry and the materials properties of thermosets generated by frontal ring-opening metathesis polymerization (FROMP). The exo- and endo-stereoisomers of dicyclopentadiene (DCPD) undergo rapid FROMP to fabricate robust thermosets within seconds. The exo-isomer provides significant benefits compared to the commonplace endo-DCPD resins; exo-DCPD supports faster fronts (≈3 times faster) than the endo-analogue and is an easier-to-handle liquid at room temperature. This work is among the first to explore the materials properties of p(exo-DCPD) thermosets. Here, we demonstrate a significant decrease in T_g for products derived from exo-DCPD, despite having a similar rubbery plateau compared to p(endo-DCPD). Soluble oligomers were synthesized as models to probe the microstructural features affected by the monomer stereochemistry. Interestingly, hydrogenated oligomers of endo-DCPD exhibit slight differences in stereoregularity compared to their exo-counterparts. Finally, we incorporated a bisnorbornenyl cross-linker in exo-DCPD resins to boost the polymer T_g, while also maintaining fronts that propagate faster than endo-DCPD.

View Accepted Manuscript (DOE)

Research Organization:: University of Illinois Urbana-Champaign, IL (United States)

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

Grant/Contract Number:: SC0023457

OSTI ID:: 2339599

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 1 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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