Engineering Free Volume within Frontal Ring-Opening Metathesis Polymerization via Pendant Plasticization.

ABSTRACT: Frontal ring-opening metathesis polymerization (FROMP) enables rapid, energy-efficient access to high-performance thermosets and thermoplastics, but the range of accessible properties remains constrained by the rigidity of norbornene-type backbones. Here we introduce a side-chain plasticization strategy for FROMP, wherein norbornene esters bearing n-alkyl groups of varying length (n = 8, 12, 16) are copolymerized with dicyclopentadiene (DCPD) or hydrogenated DCPD (DCPD-H₂). Systematic incorporation of these pendants tunes free volume, resulting in predictable reductions in glass transition temperature (T_g), decreased moduli, and a transition from rigid thermosets to elastomers exceeding 800% elongation at break. Free-volume analysis via dynamic mechanical analysis and

SUBMITTER: Stewart KA 

PROVIDER: S-EPMC12910533 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature