Solvent‐Dependent Sequence‐Controlled Copolymerization of Lactones: Tailoring Material Properties from Robust Plastics to Tough Elastomers DOI Open Access
Chaoqun Weng, Xiao Li, Xiaoyan Tang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract Copolymerization stands as a versatile and potent method for tailoring polymer properties by adjusting structural unit composition sequence distribution. However, achieving sequence‐controlled copolymerization in one‐step one‐pot process remains challenging. This study introduces solvent‐dependent strategy to produce block statistical copolyesters from 4‐phenyl‐2‐oxabicyclo[2.1.1]hexan‐3‐one (4 Ph ‐BL) ϵ ‐caprolactone ( ‐CL). The distinct kinetics of the two monomers enable facile synthesis diblock triblock copolyesters, PCL‐ b ‐P(4 P(4 ‐BL)‐ ‐PCL‐ ‐BL), non‐coordinating solvents, such dichloromethane toluene. Conversely, coordinating solvents like tetrahydrofuran, 2‐methyltetrahydrofuran, 2,5‐dimethyltetrahydrofuran, 1,4‐dioxane, 1,2‐dimethoxyethane facilitate frequent transesterifications, yielding P[CL‐ stat ‐(4 ‐BL)] with varying ratios heterosequences. Density functional theory (DFT) calculations confirmed that stabilize transition state transesterification, thereby validating their role triggering this process. By microstructures compositions, resultant display tunable thermal mechanical properties, evolving robust plastics an ultimate tensile strength up 46.3±3.1 MPa tough elastomers >99.3 % elastic recovery. All exhibit remarkable stability T d,5% =376 °C) maintain desirable chemical circularity (>92 %), supporting closed‐loop life cycle sustainable material economy.

Language: Английский

New sustainable polymers with on-demand depolymerization property DOI
Yangyang Sun, Zesheng An, Yanshan Gao

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(9), P. 2803 - 2841

Published: Aug. 12, 2024

Language: Английский

Citations

17
Ring-Opening Polymerization of α-Diazo Lactones: Access to Diazo-Containing Polyesters and Their Post-Polymerization Modifications DOI

Lefei Yu,

Yisong Wang, Qi Zhou

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(14), P. 6429 - 6438

Published: July 11, 2024

Language: Английский

Citations

4
Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones DOI Open Access

Shaoqiu Zheng,

Shusen Chen,

Yangyang Li

et al.

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

Citations

0
Monomer Design Enables Mechanistic Mapping of Anionic Ring‐Opening Polymerization of Aromatic Thionolactones DOI Open Access

Shaoqiu Zheng,

Shusen Chen,

Yangyang Li

et al.

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

Citations

0
Ultratough Thermoplastic Elastomers Based on Chemically Recyclable Cycloalkyl-Substituted Polyhydroxyalkanoates DOI
Hao‐Yi Huang, Lei Yang, Siqi Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7788 - 7798

Published: Feb. 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.

Language: Английский

Citations

0
Solvent‐Dependent Sequence‐Controlled Copolymerization of Lactones: Tailoring Material Properties from Robust Plastics to Tough Elastomers DOI Open Access
Chaoqun Weng, Xiao Li, Xiaoyan Tang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract Copolymerization stands as a versatile and potent method for tailoring polymer properties by adjusting structural unit composition sequence distribution. However, achieving sequence‐controlled copolymerization in one‐step one‐pot process remains challenging. This study introduces solvent‐dependent strategy to produce block statistical copolyesters from 4‐phenyl‐2‐oxabicyclo[2.1.1]hexan‐3‐one (4 Ph ‐BL) ϵ ‐caprolactone ( ‐CL). The distinct kinetics of the two monomers enable facile synthesis diblock triblock copolyesters, PCL‐ b ‐P(4 P(4 ‐BL)‐ ‐PCL‐ ‐BL), non‐coordinating solvents, such dichloromethane toluene. Conversely, coordinating solvents like tetrahydrofuran, 2‐methyltetrahydrofuran, 2,5‐dimethyltetrahydrofuran, 1,4‐dioxane, 1,2‐dimethoxyethane facilitate frequent transesterifications, yielding P[CL‐ stat ‐(4 ‐BL)] with varying ratios heterosequences. Density functional theory (DFT) calculations confirmed that stabilize transition state transesterification, thereby validating their role triggering this process. By microstructures compositions, resultant display tunable thermal mechanical properties, evolving robust plastics an ultimate tensile strength up 46.3±3.1 MPa tough elastomers >99.3 % elastic recovery. All exhibit remarkable stability T d,5% =376 °C) maintain desirable chemical circularity (>92 %), supporting closed‐loop life cycle sustainable material economy.

Language: Английский

Citations

1
Solvent‐Dependent Sequence‐Controlled Copolymerization of Lactones: Tailoring Material Properties from Robust Plastics to Tough Elastomers DOI Open Access
Chaoqun Weng, Xiao Li, Xiaoyan Tang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract Copolymerization stands as a versatile and potent method for tailoring polymer properties by adjusting structural unit composition sequence distribution. However, achieving sequence‐controlled copolymerization in one‐step one‐pot process remains challenging. This study introduces solvent‐dependent strategy to produce block statistical copolyesters from 4‐phenyl‐2‐oxabicyclo[2.1.1]hexan‐3‐one (4 Ph ‐BL) ϵ ‐caprolactone ( ‐CL). The distinct kinetics of the two monomers enable facile synthesis diblock triblock copolyesters, PCL‐ b ‐P(4 P(4 ‐BL)‐ ‐PCL‐ ‐BL), non‐coordinating solvents, such dichloromethane toluene. Conversely, coordinating solvents like tetrahydrofuran, 2‐methyltetrahydrofuran, 2,5‐dimethyltetrahydrofuran, 1,4‐dioxane, 1,2‐dimethoxyethane facilitate frequent transesterifications, yielding P[CL‐ stat ‐(4 ‐BL)] with varying ratios heterosequences. Density functional theory (DFT) calculations confirmed that stabilize transition state transesterification, thereby validating their role triggering this process. By microstructures compositions, resultant display tunable thermal mechanical properties, evolving robust plastics an ultimate tensile strength up 46.3±3.1 MPa tough elastomers >99.3 % elastic recovery. All exhibit remarkable stability T d,5% =376 °C) maintain desirable chemical circularity (>92 %), supporting closed‐loop life cycle sustainable material economy.

Language: Английский

Citations

0