Circular Polymer Designed by Regulating Entropy: Spiro-Valerolactone-Based Polyesters with High Gas Barriers and Adhesion Strength

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

Опубликована: Янв. 27, 2025

Enthalpy is often the focal point when designing monomers for polymer circularity, but much less explored on how entropy can be exploited to create polymers with synergistic circularity and properties. Here, we design a series of spiro-lactones (SLs) closed-chain cycloalk(en)yl substituents at α,α-position δ-valerolactone (δVL), which, combined parent δVL gem-α,α-dialkyl-substituted open-chain alkyl groups, provide desired platform exploring circular by focusing change polymerization. These SLs exhibit finely balanced (de)polymerizability that regulated chiefly differentiation, allowing both facile synthesis polyester PSLs (Mn up 1000 kg mol–1) in living fashion selective depolymerization completely recover under mild conditions (using recyclable catalyst 100 °C). One such PSL semicrystalline (Tm = 134 °C), strong (ultimate strength 43 MPa), hard (modulus 1.85 GPa), modestly flexible. notable mechanical properties are bolstered its superior barriers oxygen moisture permeation compared common packaging materials. In addition, this postfunctionalized OH-containing shows higher adhesion than comparative commercial adhesives.

Язык: Английский

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Synthesis of Telechelic Isotactic Polypropylenes for Circular Polypropylene-like Materials via Chain Transfer Polymerization

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

Опубликована: Янв. 27, 2025

While synthesizing circular polymers with telechelic polyolefin building blocks recently emerged as a promising strategy for addressing conventional polyethylenes' sustainability challenges, the lack of iPP (tPP) sufficient difunctional purity polycondensation has been limiting development polypropylenes iPP-like structures and properties. Here we described combined approach coordinative chain transfer polymerization transition-metal-catalyzed quenching reaction various acyl chlorides, affording tPPs high ratio (up to ∼99%) broad end functional group scope. The steric effect polymeryl-Zn species role Pd catalyst were revealed by DFT. This method also solved low challenge polyethylenes. Ester-linked iPPs structure thermomechanical properties PE/iPP multiblock copolymers synthesized resulting tPPs.

Язык: Английский

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Recyclable and Degradable Poly(p-dioxanone)-based Copolymer with Enhanced Mechanical Properties by Microphase-separated Interface Crystallization

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

Опубликована: Янв. 25, 2025

Язык: Английский

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Ultratough Thermoplastic Elastomers Based on Chemically Recyclable Cycloalkyl-Substituted Polyhydroxyalkanoates

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7788 - 7798

Опубликована: Фев. 20, 2025

It remains a long-standing challenge for chemical recycling of polyhydroxyalkanoates (PHAs) to propiolactone-based monomers due the high ring strain and many inevitable side reactions. In this contribution, novel α-spiro-cyclohexyl-propiolactone (SHPL) has been designed with reactivity toward ring-opening polymerization even at catalyst loading <1 ppm. The resulting poly(3-hydroxy-2-spiro-cyclohexylpropionate) (P3HSHP) exhibited thermal stability Td 364 °C Tm 272 °C. Meanwhile, it could be depolymerized back SHPL in 86% yield without decarboxylation or elimination products. Notably, exploited construct high-performance thermoplastic elastomers (TPEs) via one-pot copolymerization ε-caprolactone (CL). Particularly, gradient P(CL2000-grad-SHPL500) showcased an ultimate tensile strength 58.8 ± 4.0 MPa, stretchability 1959 53%, record toughness 600 MJ/m3, elastic recovery (>90%). This superior performance advance development new sustainable TPEs.

Язык: Английский

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Closed-Loop Recyclable Solid-State Polymer Electrolytes Enabled by Reversible Lithium Salt Catalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7624 - 7633

Опубликована: Фев. 24, 2025

The rapid expansion in lithium battery production and disposal presents considerable sustainability challenges, emphasizing the critical need for recycling. However, current methods predominantly focus on metals from cathodes, while electrolytes have rarely been recycled. Here, we propose an innovative closed-loop design solid polymer (SPEs), enabled by reversible catalysis of bis(trifluoromethane) sulfonimide (LiTFSI) both polymerization depolymerization. formation a hydrogen-bonded adduct between TFSI- alcohol initiates situ ring-opening Li+-activated trimethylene carbonate (TMC), generating well-defined SPEs. With delicate structural optimization, SPE achieves outstanding ionic conductivity 1.62 × 10-3 S cm-1 at room temperature with robust high-voltage stability up to 4.7 V. assembled Li||NCM811 demonstrates promising cycling 88% capacity retention over 100 cycles. Upon end-of-life, LiTFSI facilitates selective depolymerization polycarbonate-based 180 °C without introducing external catalysts, recovering TMC monomer (>90%) (>98%) reuse. This work highlights significant advance recyclable SPEs vital step toward sustainable technology.

Язык: Английский

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Modular Access from Acrylate to a Sustainable Polyester Platform with Large-Span Tunability and Chemical Circularity under Mild Conditions

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

Опубликована: Март 4, 2025

Making polyesters with conventional vinyl monomers is one of the most economical ways to develop sustainable polymeric materials. For polar vinyls, while their transformation into lactones has been studied extensively, there exists no further access synthesizing polyesters, presumably due nonstrained and nonpolymerizable nature obtained lactones. Herein, we report first facile synthesis that originated from critical classes vinyls-acrylates. Specifically, a series modular six-membered were rationally designed synthesized methyl acrylate together malonic esters containing diverse functional groups formaldehyde. The underwent ring-opening polymerization (ROP) yield acrylate-derived which constitute unique polymer platform large scope potential functionalities performances as well easy chemical circularity under mild conditions. Notably, are rare example featuring tunable on side ester whose impact certain material properties (e.g., glass transition temperature) similar polyacrylates, implying replacement between polyacrylates. In addition, by presenting special geminal disubstitutions originally monomers' γ-position for time, also exhibited unprecedentedly enhanced thermal recycling properties: Variation offers large-span modulation completely amorphous high-level crystalline materials, melting temperature high crystallinity was drastically increased 84 °C compared reported monosubstituted counterpart. At same other required harsh conditions (>150 vacuum), gem-disubstituted in this work can undergo complete much milder (80 ambient pressure). This study informs design future high-performance derived vinyls.

Язык: Английский

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Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones

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

Опубликована: Янв. 22, 2025

Degradable chalcogenide polyesters, e.g., polythioesters (PTEs), typically exhibit improved thermal, mechanical, and optical properties. Anionic ring-opening polymerization (ROP) of thionolactones, an intrinsically promising yet underexplored approach to accessing PTEs, however, is still limited by: intolerance metal catalysts, inadequate control over chain growth, the absence aromatic system. Monomer design-boosted mechanistic studies may address above challenges. Here, we present a new highly reactive thionolactone synthesized from 1,1'-binaphthyl-2,2'-diol (BINOL). Our investigations into kinetics thermodynamics have underscored importance rapid initiation, eventually leading discovery tetrabutylammonium 2-naphthyl-thiocarboxylate as distinctive initiator that enables genuinely controlled living thionolactones. Ultimately, atropisomerism inherent in BINOL has resulted creation axially chiral PTE materials with tailored molecular weights, enantiomeric compositions, topologies.

Язык: Английский

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Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

Abstract Degradable chalcogenide polyesters, e.g., polythioesters (PTEs), typically exhibit improved thermal, mechanical, and optical properties. Anionic ring‐opening polymerization (ROP) of thionolactones, an intrinsically promising yet underexplored approach to accessing PTEs, however, is still limited by: intolerance metal catalysts, inadequate control over chain growth, the absence aromatic system. Monomer design‐boosted mechanistic studies may address above challenges. Here, we present a new highly reactive thionolactone synthesized from 1,1′‐binaphthyl‐2,2′‐diol (BINOL). Our investigations into kinetics thermodynamics have underscored importance rapid initiation, eventually leading discovery tetrabutylammonium 2‐naphthyl‐thiocarboxylate as distinctive initiator that enables genuinely controlled living thionolactones. Ultimately, atropisomerism inherent in BINOL has resulted creation axially chiral PTE materials with tailored molecular weights, enantiomeric compositions, topologies.

Язык: Английский

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Readily Degradable and Recyclable High Molecular Weight Thiosalicylic Acid-based Copolyesters

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

Опубликована: Янв. 25, 2025

Язык: Английский

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Tough and Closed‐Loop Recyclable Thermoplastic Elastomers From Sequential Ring‐Opening Copolymerization of Bio‐Renewable β‐Methyl‐δ‐Valerolactone and δ‐Valerolactone

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Abstract Despite the great successes achieved for closed‐loop recyclable polymers in last decade, thermoplastic elastomers (TPEs) with recyclability and good mechanical performances are largely underexplored. In this contribution, preparation of PδVL‐ b ‐PβMVL‐ ‐PδVL triblock copolymers via one‐pot sequential ring‐opening copolymerization bio‐renewable β‐methyl‐δ‐valerolactone (βMVL) δ‐valerolactone (δVL) is achieved. The obtained behave as TPEs that exhibit superior tensile strength toughness well comparable elasticity to most previously reported polyester‐based commercial styrenic copolymer‐based TPEs. Remarkably, these can be depolymerized recover pristine monomers a high yield by simply heating materials under reduced pressure presence stannous octoate catalyst. recovered separated or directly used prepare original TPEs, thus establishing life cycle.

Язык: Английский

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