Development of an Efficient Thionolactone for Radical Ring-Opening Polymerization by a Combined Theoretical/Experimental Approach

Luzel, Bastien; Gil, Noémie; Désirée, Patrick; Monot, Julien; Bourissou, Didier; Siri, Didier; Gigmes, Didier; Martin-Vaca, Blanca; Lefay, Catherine; Guillaneuf, Yohann

doi:10.1021/jacs.3c08610

Cited by 7 publications

(4 citation statements)

References 40 publications

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“…While previous studies have reported predictions of deconstruction efficiency, they have only considered small sets of reactivity ratio pairs, which precludes the analysis of general trends and trade-offs. We find that when copolymerization behavior is near random, , the smallest deconstruction fragments are produced (i.e., r 1 ≈ r CCA ≈ 1, which is in-line with previous heuristics relating optimal deconstructability to “random” CCA incorporation , ); however, this optimal behavior is further maintained even when the CCA copolymerizes with a strong alternating tendency (i.e., r CCA < 1). To rationalize this reactivity/deconstructability trend we present two arguments.…”

supporting

confidence: 90%

Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives

Lundberg,

Ko,

Kilgallon

et al. 2024

ACS Macro Lett.

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The incorporation of cleavable comonomers as additives into polymers can imbue traditional polymers with controlled deconstructability and expanded end-of-life options. The efficiency with which cleavable comonomer additives (CCAs) can enable deconstruction is sensitive to their local distribution within a copolymer backbone, which is dictated by their copolymerization behavior. While qualitative heuristics exist that describe deconstructability, comprehensive quantitative connections between CCA loadings, reactivity ratios, polymerization mechanisms, and deconstruction reactions on the deconstruction efficiency of copolymers containing CCAs have not been established. Here, we broadly define these relationships using stochastic simulations characterizing various polymerization mechanisms (e.g., coltrolled/living, free-radical, and reversible ring-opening polymerizations), reactivity ratio pairs (spanning 2 orders of magnitude between 0.01 and 100), CCA loadings (2.5% to 20%), and deconstruction reactions (e.g., comonomer sequence-dependent deconstruction behavior). We show general agreement between simulated and experimentally observed deconstruction fragment sizes from the literature, demonstrating the predictive power of the methods used herein. These results will guide the development of more efficient CCAs and inform the formulation of deconstructable materials.

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supporting

confidence: 90%

Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives

Lundberg,

Ko,

Kilgallon

et al. 2024

ACS Macro Lett.

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“…Recent work of Lefay and Guillaneuf indicates that the development of novel thionolactone monomers can be accelerated through synergies with theoretical chemistry. [82] The reported approach was based on DFT calculations to analyze the radical reactivity of existing thionolactones, especially the transfer rate constant and its ratio with the propagation rate constant. Based on this analysis of existing systems, variations in ring size and substitutions were introduced in the calculations and the most promising candidate, 7-Phenyloxepane-2-thione (POT), was synthesized (Figure 3).…”

Section: Thionolactonesmentioning

confidence: 99%

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Sbordone,

Frisch

2024

Chemistry A European J

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Radical polymerization is the most widely applied technique in both industry and fundamental science. However, its major drawback is that it typically yields polymers with non‐functional, non‐degradable all‐carbon backbones—a limitation that radical ring‐opening polymerization (rROP) allows to overcome. The last decade has seen a surge in rROP, primarily focused on creating degradable polymers. This pursuit has resulted in the creation of the first readily degradable materials through radical polymerization. Recent years have witnessed innovations in new monomers that address previous design limitations, such as ring strain and reactivity ratios. Furthermore, advances in integrating rROP with reversible deactivation radical polymerization (RDRP) have facilitated the incorporation of complex, customizable chemical payloads into the main polymer chain. This short review discusses the latest developments in monomer design with a focused analysis of their limitations in a broader historical context. Recently evolving strategies for compatibility of rROP monomers with RDRP are discussed, which are key to precision polymer synthesis. The latest chemistry surveyed expands the horizon beyond mere hydrolytic degradation. Now is the time to explore the chemical potential residing in the previously inaccessible polymer backbone.

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“…To the best of our knowledge, this is the first example where a computational tool was employed to analyze the copolymerization between TLs and methacrylates. We note that Guillaneuf and co-workers recently reported on their elegant use of DFT calculations to aid in the development of a TL with improved reactivity for styrene and acrylate monomers. Their approach involved defining a composite rate constant that combines the multistep process of radical addition to TLs, which they have proven beneficial for evaluating and predicting the reactivity of CCs when there are known molecules that copolymerize with the monomer of interest as reference points, as is the case with styrene and acrylates.…”

Section: Introductionmentioning

confidence: 99%

“…TLs have proven to be successful as CCs for various vinyl polymers. A notable example is the TL molecule dibenzo[c,e]oxepine-5(7H)-thione, commonly referred to as “DOT,” which has demonstrated favorable copolymerization reactivity with various acrylate, ,− acrylamide, ,, and styrenic ,− , monomers; however, there have been no successful instances of TLs copolymerizing with methacrylates without exhibiting negligible reactivity or pronounced compositional gradients, which can be attributed to their reactivity ratios being far from optimal.…”

Section: Introductionmentioning

confidence: 99%

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate)

Ko,

Lundberg,

Johnson

et al. 2024

J. Am. Chem. Soc.

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The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for the introduction of backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues for the selective deconstruction of multiple classes of vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize with methacrylates to an appreciable extent to enable polymer deconstruction. Here, we overcome this challenge through the design of a new class of benzyl-functionalized thionolactones (bDOTs). Guided by detailed mechanistic analyses, we find that the introduction of radical-stabilizing substituents to bDOTs enables markedly increased and tunable copolymerization reactivity with methyl methacrylate (MMA). Through iterative optimizations of the molecular structure, a specific bDOT, F-p-CF 3 PhDOT, is discovered to copolymerize efficiently with MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, M n > 120 kDa) with low percentages of F-p-CF 3 PhDOT (1.8 and 3.8 mol%) are prepared using industrially relevant bulk free radical copolymerization conditions. The thermomechanical properties of dPMMA are similar to PMMA; however, the former is shown to degrade into low molar mass fragments (<6.5 kDa) under mild aminolysis conditions. This work presents the first example of a radical ring-opening CC capable of nearly random copolymerization with MMA without the possibility of cross-linking and provides a workflow for the mechanism-guided design of deconstructable copolymers in the future.

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Development of an Efficient Thionolactone for Radical Ring-Opening Polymerization by a Combined Theoretical/Experimental Approach

Cited by 7 publications

References 40 publications

Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives

Defining Reactivity–Deconstructability Relationships for Copolymerizations Involving Cleavable Comonomer Additives

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate)

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