Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

Stawiasz, Katherine J.; Wendell, Chloe I.; Suslick, Benjamin A.; Moore, Jeffrey S.

doi:10.1021/acsmacrolett.2c00248

Cited by 18 publications

(23 citation statements)

References 27 publications

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“…One such reaction motif, frontal ring-opening metathesis polymerization (FROMP), is an attractive alternative to traditional batch curing. − In this technique, an initial localized stimulus ( i . e ., thermal − or photo , ) promotes highly exothermic catalytic ring-opening reactions by a Grubbs-type complex (Scheme A). The heat generated by the ring-opening of highly strained cyclic olefins (such as dicyclopentadiene, DCPD ) induces additional catalytic events in proximity to highly reactive regions.…”

Section: Introductionmentioning

confidence: 99%

Storable, Dual-Component Systems for Frontal Ring-Opening Metathesis Polymerization

et al. 2022

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Frontal ring-opening metathesis polymerization (FROMP) catalyzed by Grubbs-type Ru complexes enables new, rapid, and energy-efficient syntheses of high-performance, structural plastics. Ideal catalysts survive the extended time periods associated with resin preparation, storage, and transportation. Current catalysts, however, induce premature polymerization within hours to days under ambient conditions. In this work, a thermally latent bis-N-heterocyclic carbene complex provides exceedingly robust resins, which are viable for 8 weeks. When mixed with CuI coreagents, precatalyst activation primes the system for rapid reactivity after thermal initiation. In this study, more than 40 dual-component formulations successfully catalyzed FROMP of dicyclopentadiene. The polymerization process parameters (front temperatures and velocities), resin storability, and resultant polymer properties (e.g., T g) were determined for each composition. Intriguingly, the Cu to Ru ratio dramatically impacts the observed frontal velocity and temperature, as well as the polymer glass-transition temperature; slower, colder reaction fronts result from formulations with large Cu to Ru ratios. The resultant polymers display lower T g values. Mechanistic analysis of a related model system demonstrated that an excess Cu reagent decreases the activation and polymerization rates.

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Section: Introductionmentioning

confidence: 99%

Storable, Dual-Component Systems for Frontal Ring-Opening Metathesis Polymerization

et al. 2022

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“…In FROMP, Grubbs-type Ru catalysts rapidly transform liquid or gel-state resins of dicylopentadiene ( DCPD ) into thermoset materials. After an initial thermal ,− or photo , trigger, the heat generated by ring-opening drives subsequent catalytic events in advance of the reaction zone. The resultant polymerization front traverses through the monomer resin with a well-defined monomer to polymer interface at a steady-state velocity (ν f ).…”

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Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

2022

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“…Indeed, photo-ignition presents interesting possibilities for controlled multi-front FROMP, as well as high-resolution patterning applications. In a subsequent report, Stawiasz et al 162 investigated photoactivated dual-component FROMP system with the bis(NHC) complex described previously by Suslick et al 163 This work cleverly employed a photoredox mediator (e.g., pyrylium or acridinium salts) to transform Cu II species into Cu I in situ after irradiation with blue light (λmax = 455 nm). Catalyst activation then occurs via NHC transmetalation.…”

Section: Non-thermal Initiation Methodsmentioning

confidence: 99%

“…Apart from ATRP and polyurethanes, which have not been thoroughly investigated, only FROMP occurs catalytically with the use of the commercial Grubbs-type ruthenium alkylidene complexes (e.g., G1 and G2). 32,41,49,66,69,70,73,102,106,124,[145][146][147]151,152,160,162,163 Highly strained, cyclic olefins undergo living catalytic polymerization; frontally derived polymers of dicyclopentadiene (DCPD) exhibit desirable mechanical properties via extensive crosslinking during catalysis. Perhaps counterintuitively to most catalyst design principles, FROMP and polyurethane-based systems 68,72,[193][194][195] require worse catalysts to circumvent rapid background polymerization.…”

Section: Large-scale Fabrication and 3d-printingmentioning

confidence: 99%

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

Suslick

Hemmer

Groce

et al. 2022

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The synthesis and processing of thermoplastics and thermoset polymeric materials rely on energy-inefficient and environmentally burdensome manufacturing methods. Frontal polymerization has emerged as an attractive, scalable alternative due to its exploitation of the heat of polymerization, which generally is wasted as unutilized heat-loss. The only external energy needed for frontal polymerization is an initial thermal (or photo) stimulus that locally ignites the reaction. The subsequent reaction exothermicity provides local heating; the transport of this thermal energy to neighboring monomers in either a liquid or gel-like state results in a self-perpetuating reaction zone that provides fully-cured polymeric thermosets and thermoplastics. Propagation of this polymerization front continues through the unreacted monomer media until either all reactants are consumed or sufficient heat-loss stalls further reaction. Several different polymerization mechanisms support frontal processes, including free-radical, cat- or anionic, amine-cure epoxides, and ring-opening metathesis polymerization. The choice of monomer, initiator/catalyst, and additives dictates how fast the polymer front traverses the reactant medium, as well as the maximum temperature achievable. Frontal polymerization enables the preparation of moldable thermoplastics derived from linear polymers. When crosslinking is involved, polymeric networks (e.g., rigid thermosets) are obtainable through a related process best described as a frontal curing reaction. Numerous applications of frontally-generated polymers and thermosets exist, ranging from the reinforcement of porous substrates to the design of patterned composite materials. In this review, we examine in detail the physical and chemical phenomena that govern frontal polymerization, as well as outline the existing applications.

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Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

Cited by 18 publications

References 27 publications

Storable, Dual-Component Systems for Frontal Ring-Opening Metathesis Polymerization

Storable, Dual-Component Systems for Frontal Ring-Opening Metathesis Polymerization

Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

Frontal Polymerizations: From Chemical Perspectives to Macroscopic Properties and Applications

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