Rapid Gelation of Dicyclopentadiene Resins for Additive Manufacturing of Thermoset Polymers DOI

Pranav Krishnan,

Jacob J. Lessard, Jeffrey S. Moore

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 570 - 575

Published: April 23, 2025

Thermoset resins of dicyclopentadiene were viscosity-modified to achieve the rheology necessary for Direct Ink Writing, with deposited ink solidified on-the-fly by frontal polymerization. This rapid modification strategy incorporated ruthenium-based Grubbs' third-generation catalyst and a ligand exchange reaction decrease gelation time under 10 min, an order magnitude less than existing strategies. The gelled are rheologically stable retain their reactivity over 500 days. Viscosity enables 3D-printing these resins, producing polymers thermomechanical properties that match or surpass those from more slowly. Replacing solvent eliminates reduction in glass transition temperature plasticization while maintaining extended resin pot life.

Language: Английский

Active Learning Guided Optimization of Frontal Ring-Opening Metathesis Polymerization via Alkylidene Modification DOI
Ignacio Arretche, Jacob J. Lessard, Parmeet Kaur

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 525 - 531

Published: April 11, 2025

Frontal ring-opening metathesis polymerization (FROMP) offers an energy-efficient method for manufacturing high-performance thermoset resins. However, the background reaction attributed to (ROMP) results in a complex trade-off between resin shelf life─necessary practical manufacturability─and front velocity. Here, we study influence of alkylidene ligand selection Grubbs' second-generation Ru-initiators on kinetics FROMP and ROMP. We reveal that identity differentially affects ROMP reactivity, enabling tunable control over pot life speed. Leveraging this insight, use active learning with multiobjective Bayesian optimization efficiently explore design space identify superior formulations. This work advances rational resins, expanding range accessible formulations accelerating discovery materials applications.

Language: Английский

Citations

0
Photochemical Activation of Ruthenium Complexes Containing Unsymmetrical Unsaturated N-Heterocyclic Carbenes for Olefin Metathesis DOI
Mathieu Rouen, Marc Mauduit, Antonio Del Vecchio

et al.

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Abstract Olefin metathesis is a fundamental transformation in organic chemist’s toolbox. Herein we report methodological study on set of bench stable, latent, ruthenium-indenylidene catalysts bearing two unsymmetrical unsaturated N-heterocyclic carbene (NHC) ligands. These complexes are successfully ‘activated’ and applied to ring-closing (RCM), cross-metathesis (CM), ring-opening cross (ROCM) upon light irradiation the presence an photoactivator. The transformations could be performed at lower catalytic loading (down 1 mol%) compared state-of-the-art photochemical activation methods, providing good yields shorter reaction time

Language: Английский

Citations

0
Rapid Gelation of Dicyclopentadiene Resins for Additive Manufacturing of Thermoset Polymers DOI

Pranav Krishnan,

Jacob J. Lessard, Jeffrey S. Moore

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 570 - 575

Published: April 23, 2025

Thermoset resins of dicyclopentadiene were viscosity-modified to achieve the rheology necessary for Direct Ink Writing, with deposited ink solidified on-the-fly by frontal polymerization. This rapid modification strategy incorporated ruthenium-based Grubbs' third-generation catalyst and a ligand exchange reaction decrease gelation time under 10 min, an order magnitude less than existing strategies. The gelled are rheologically stable retain their reactivity over 500 days. Viscosity enables 3D-printing these resins, producing polymers thermomechanical properties that match or surpass those from more slowly. Replacing solvent eliminates reduction in glass transition temperature plasticization while maintaining extended resin pot life.

Language: Английский

Citations

0