Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.
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http://dx.doi.org/10.1021/acsmacrolett.7b00270 | DOI Listing |
J Am Chem Soc
August 2024
Department of Aerospace Engineering, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction-diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations.
View Article and Find Full Text PDFAdv Mater
September 2024
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana - Champaign, Urbana, IL, 61801, USA.
Frontal ring-opening metathesis polymerization (FROMP) presents an energy-efficient approach to produce high-performance polymers, typically utilizing norbornene derivatives from Diels-Alder reactions. This study broadens the monomer repertoire for FROMP, incorporating the cycloaddition product of biosourced furan compounds and benzyne, namely 1,4-dihydro-1,4-epoxynaphthalene (HEN) derivatives. A computational screening of Diels-Alder products is conducted, selecting products with resistance to retro-Diels-Alder but also sufficient ring strain to facilitate FROMP.
View Article and Find Full Text PDFACS Omega
June 2024
University of Sassari, Department of Chemical, Physical, Mathematical, and Natural Sciences, Via Vienna 2, 07100 Sassari, Italy.
Among the different polymerization techniques, frontal polymerization (FP) has gained high interest from the scientific community because of its peculiar characteristics: in particular, compared to classic polymerization reactions, FP allows for a better exploitation of the heat of polymerization involved, without requiring any external energy input apart from an initial photo or thermal ignition that triggers the reaction. The latter usually propagates in a few tenths of seconds or (at most) minutes through a hot self-sustaining polymerization front, giving rise to the formation of fully cured thermosetting networks or thermoplastic polymers. Furthermore, different polymerization mechanisms can be involved in FP reactions, comprising cationic or anionic, ring-opening metathesis, and free-radical polymerization, among others.
View Article and Find Full Text PDFJ Am Chem Soc
June 2024
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States.
The rate of frontal ring-opening metathesis polymerization (FROMP) using the Grubbs generation II catalyst is impacted by both the concentration and choice of monomers and inhibitors, usually organophosphorus derivatives. Herein we report a data-science-driven workflow to evaluate how these factors impact both the rate of FROMP and how long the formulation of the mixture is stable (pot life). Using this workflow, we built a classification model using a single-node decision tree to determine how a simple phosphine structural descriptor () can bin long versus short pot life.
View Article and Find Full Text PDFAdv Mater
July 2024
Beckman Institute for Advanced Science and Technology, University of Illinois Urbana-Champaign, Urbana, IL, 61801, USA.
While valued for their durability and exceptional performance, crosslinked thermosets are challenging to recycle and reuse. Here, inherent reprocessability in industrially relevant polyolefin thermosets is unveiled. Unlike prior methods, this approach eliminates the need to introduce exchangeable functionality to regenerate the material, relying instead on preserving the activity of the metathesis catalyst employed in the curing reaction.
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