Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms

Macromolecules, Год журнала: 2024, Номер 57(14), С. 6727 - 6740

Опубликована: Июль 9, 2024

An understanding of monomer sequence is required to predict and engineer the properties copolymers. In stochastic polymerizations involving more than one monomer, typically inferred or determined from reactivity ratios, which are measured through copolymerization experiments. The accurate determination ratios copolymerizations where both monomers undergo reversible propagation, however, has been complicated by difficulty in solving underlying population balance equations, presence myriad copolymer equations literature derived under varying assumptions simplifications, lack an easy-to-fit integrated model. Here, we rectify assert consistency between previously reported disparate forms, introduce a new method explicitly solve perform simulations evaluate ability these three methods produce consistent comonomer consumption predictions fits simulated data. We find that all given same input parameters, implies accuracy precision when modeling copolymerization, fitting experimental data, making sequence. Considering this consistency, make recommendation use numerical integration appropriate equation fit real data due its ease implementation. further identify minimum number parameters for suggest ways measure other information ex situ expedite fitting. Finally, practical utility developed herein demonstrated seven distinct sets, span wide range reactivities.

Язык: Английский

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Mechanochemically Promoted Functionalization of Postconsumer Poly(Methyl Methacrylate) and Poly(α‐Methylstyrene) for Bulk Depolymerization

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Июль 15, 2024

We describe a methodology of post-polymerization functionalization to enable subsequent bulk depolymerization monomer by utilizing mechanochemical macro-radical generation. By harnessing ultrasonic chain-scission in the presence N-hydroxyphthalimide methacrylate (PhthMA), we successfully chain-end functionalize polymers promote bulk, achieving up 82 % poly(methyl methacrylate) (PMMA) and poly(α-methylstyrene) (PAMS) within 30 min. This method yields high-purity that can be repolymerized. Moreover, as compared most common methods depolymerization, this work is efficient with ultra-high molecular weight (UHMW) polymers, establishing potential address highly persistent, non-degradable all-carbon backbone plastic materials. Lastly, demonstrate expansion commercial cell cast PMMA, high degrees from post-consumer waste. first demonstration applying PhthMA-promoted strategies homopolymer PMMA PAMS prepared conventional polymerization methods.

Язык: Английский

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Harnessing Non-Thermal External Stimuli for Polymer Recycling

Macromolecules, Год журнала: 2025, Номер 58(5), С. 2210 - 2223

Опубликована: Фев. 18, 2025

Polymeric materials have become indispensable due to their versatility and low cost, yet environmental impact presents a significant global challenge. Traditional chemical recycling methods typically rely on heat as stimulus; for instance, pyrolysis is popular methodology which faces limitations high energy consumption, product selectivity, the generation of undesirable byproducts. In response, recent advances in promotion depolymerization degradation through alternative stimuli such light, electrochemistry, mechanical force, shown promising potential more efficient selective polymer breakdown, yielding either starting monomers or valuable small molecules. This perspective explores key examples these emerging strategies, highlighting improve upon current protocols offer pathways under milder conditions, while identifying challenges that future research must address translate chemistry into viable broadly applicable strategies.

Язык: Английский

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Backbone Degradable Polymers via Chain-growth Radical Polymerization

Chinese Journal of Polymer Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 24, 2025

Язык: Английский

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Tailored synthesis of circular polyolefins

Nature Sustainability, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Язык: Английский

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Low Viscous Imidazolium Ionic Liquid Infused Polyvinyl Alcohol Polymer Electrolyte for Light‐Emitting Electrochemical Device

Energy Storage, Год журнала: 2025, Номер 7(3)

Опубликована: Март 20, 2025

ABSTRACT The burgeoning demand for efficient energy storage systems requires advancements in electrolyte materials, with particular emphasis on improving ionic conductivity and electrochemical stability. Room‐temperature liquids (RTILs) have emerged as promising options due to their distinctive physicochemical characteristics, including high conductivity, low vapor pressure, wide windows. This analysis focuses the integration of RTILs into polymeric matrices create liquid‐based electrolytes (ILPEs), emphasizing potential revolutionize systems. use addresses critical drawbacks traditional liquid solid‐state electrolytes, such limited poor thermal We describe methods by which boost transport within networks, thereby overall performance devices, using a comprehensive review recent advances. article seeks encourage further research innovation materials offering assessment current status future possibilities RTIL‐based polymer electrolytes.

Язык: Английский

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Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Permanently cross-linked polymer networks-thermosets-are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands thermosets using comonomers as additives can facilitate thermoset deconstruction without replacement permanent cross-links, but such monomers lead reduced thermomechanical properties and require high loadings function effectively, motivating design new optimal additives. Here, we introduce "strand-fusing cross-linkers" (SFCs), which fuse two network via a four-way cross-link. SFCs enable model polydicyclopentadiene (pDCPD) with little one-fifth molar loading needed achieve traditional comonomers. under oven curing well low-energy frontal ring-opening metathesis polymerization (FROMP) conditions improved properties, for example, glass transition temperatures, compared prior comonomer designs. This work motivates development increasingly compromising material performance.

Язык: Английский

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Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Abstract Permanently cross‐linked polymer networks—thermosets—are often difficult to chemically deconstruct. The installation of cleavable bonds into the strands thermosets using comonomers as additives can facilitate thermoset deconstruction without replacement permanent cross‐links, but such monomers lead reduced thermomechanical properties and require high loadings function effectively, motivating design new optimal additives. Here, we introduce “strand‐fusing cross‐linkers” (SFCs), which fuse two network via a four‐way cross‐link. SFCs enable model polydicyclopentadiene (pDCPD) with little one‐fifth molar loading needed achieve traditional comonomers. under oven curing well low‐energy frontal ring‐opening metathesis polymerization (FROMP) conditions improved properties, for example, glass transition temperatures, compared prior comonomer designs. This work motivates development increasingly compromising material performance.

Язык: Английский

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Multi-Generation Recycling of Thermosets Enabled by Fragment Reactivation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

Thermosets are used in numerous industrial applications due to their excellent stabilities and mechanical properties; however, covalently cross-linked structures limit chemical circularity. Cleavable comonomers (CCs) offer a practical strategy impart new end-of-life opportunities, such as deconstructability or remoldability, thermosets without altering critical properties, cost, manufacturing workflows. Nevertheless, CC-enabled recycling of has so far been limited one cycle with 25% recycled content. Here, we introduce "fragment reactivation" strategy, wherein the oligomeric fragments obtained from thermoset deconstruction activated functional groups that improve fragment solubility reactivity for subsequent rounds recycling. Using polydicyclopentadiene (pDCPD), an hydrocarbon material, containing low loadings siloxane-based CC, first demonstrate two by incorporating 40 wt % norbornene silyl ether-reactivated derived prior generation's deconstruction. Then, show two-step sequence reactivation can be unified into single-step process, referred "deconstructive reactivation." this approach, three 40-45 incorporated per while maintaining key material properties deconstructability. These generations effectively extend lifespan deconstructable pDCPD ∼2.6 times. Combined CCs, presents promising potentially generalizable efficiency thermosets.

Язык: Английский

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Understanding synthesis and degradation of backbone deconstructable (co)polymers by radical ring-opening polymerization through theoretical calculation and numerical simulation

Current Opinion in Chemical Engineering, Год журнала: 2025, Номер 48, С. 101131 - 101131

Опубликована: Апрель 17, 2025

Язык: Английский

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