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

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 25, 2025

Language: Английский

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Impact of solvolysis on the decomposition efficiency of poly(lactic acid) materials with insight into their non-uniform architecture

International Journal of Biological Macromolecules, Journal Year: 2025, Volume and Issue: unknown, P. 140529 - 140529

Published: Jan. 1, 2025

Language: Английский

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