Easy Synthetic Access to High‐Melting Sulfurated Copolymers and their Self‐Assembling Diblock Copolymers from Phenylisothiocyanate and Oxetane DOI Creative Commons

Jenny Stephan,

Jorge L. Olmedo‐Martínez, Christoph Fornacon‐Wood

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)

Published: March 23, 2024

Abstract Although sulfurated polymers promise unique properties, their controlled synthesis, particularly when it comes to complex and functional architectures, remains challenging. Here, we show that the copolymerization of oxetane phenyl isothiocyanate selectively yields polythioimidocarbonates as a new class sulfur containing polymers, with narrow molecular weight distributions ( M n =5–80 kg/mol Đ ≤1.2; ,max =124 kg/mol) high melting points up 181 °C. The method tolerates different substituent patterns on both isothiocyanate. Self‐nucleation experiments reveal π‐stacking substituents, presence unsubstituted polymer backbones, kinetically linkage selectivity are key factors in maximising points. increased tolerance macro‐chain transfer agents propagation allows synthesis double crystalline amphiphilic diblock copolymers, which can be assembled into micellar‐ worm‐like structures amorphous cores water. In contrast, crystallization driven self‐assembly ethanol gives cylindrical micelles or platelets.

Language: Английский

Copolymerization Involving Sulfur-Containing Monomers DOI
Tian‐Jun Yue, Wei‐Min Ren, Xiao‐Bing Lu

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(24), P. 14038 - 14083

Published: Nov. 2, 2023

Incorporating sulfur (S) atoms into polymer main chains endows these materials with many attractive features, including a high refractive index, mechanical properties, electrochemical and adhesive ability to heavy metal ions. The copolymerization involving S-containing monomers constitutes facile method for effectively constructing polymers diverse structures, readily tunable sequences, topological structures. In this review, we describe the recent advances in synthesis of via or multicomponent polymerization techniques concerning variety monomers, such as dithiols, carbon disulfide, carbonyl sulfide, cyclic thioanhydrides, episulfides elemental (S8). Particularly, significant focus is paid precise control main-chain sequence, stereochemistry, structure achieving high-value applications.

Language: Английский

Citations

47
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

22
Designing Polymer Electrolytes via Ring‐Opening Polymerization for Advanced Lithium Batteries DOI
Shi Wang, Lei Zhang,

Qinghui Zeng

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(3)

Published: Nov. 27, 2023

Abstract Replacing liquid electrolytes with solid‐state polymer (SPEs) can solve the safety hazards of Li metal batteries (LMBs) while increasing their energy density. However, there has been limited success so far in preparing advanced SPEs controllable molecular structure and chemical composition, posing great obstacles to further promoting its application LMBs. Recently, ring‐opening polymerization (ROP), including cationic ROP, anionic metathesis polymerization, become a dazzling new star achieving due mild conditions composition (molecular structure, functional group), etc. Besides, is no small molecule released during process, which means reduced interfacial side reaction. Hence, this review, merits ROP mechanism as well interfering factors, etc are evaluated from perspective synthetic chemistry. Furthermore, review focuses on outlining existing cases related much possible summarize them different ring structures (from triple multivariate ring) methods, hoping provide comprehensive understanding serve strategic guidance for designing high‐performance SPEs. Challenges opportunities regarding burgeoning field also discussed at end.

Language: Английский

Citations

38
Chemically recyclable copolyesters from bio-renewable monomers: controlled synthesis and composition-dependent applicable properties DOI
Wanting Xiong, Gang Wu, Si‐Chong Chen

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(7), P. 2062 - 2069

Published: June 21, 2023

Language: Английский

Citations

37
Emerging Trends in the Chemistry of End-to-End Depolymerization DOI Creative Commons
Zhengyu Deng, Elizabeth R. Gillies

JACS Au, Journal Year: 2023, Volume and Issue: 3(9), P. 2436 - 2450

Published: Aug. 23, 2023

Over the past couple of decades, polymers that depolymerize end-to-end upon cleavage their backbone or activation a terminal functional group, sometimes referred to as "self-immolative" polymers, have been attracting increasing attention. They are growing interest in context enhancing polymer degradability but also recycling they allow monomers be regenerated controlled manner under mild conditions. Furthermore, highly promising for applications smart materials due ability provide an amplified response specific signal, single sensing event is translated into generation many small molecules through cascade reactions. From chemistry perspective, depolymerization relies on principles self-immolative linkers and ceiling temperature (Tc). In this article, we will introduce key chemical concepts foundations field then our perspective recent exciting developments. For example, over few years, new depolymerizable backbones, including polyacetals, polydisulfides, polyesters, polythioesters, polyalkenamers, developed, while modern approaches conventional backbones such polymethacrylates introduced. Progress has made topological evolution systems, introduction fully block copolymers, hyperbranched networks. precision sequence-defined oligomers synthesized studied data storage encryption. Finally, perspectives future opportunities challenges discussed.

Language: Английский

Citations

36
Production of γ-Valerolactone from levulinic acid via selected transfer hydrogenation pathway by FeAl-framework ZSM-5 supporting ZrO2 DOI
Xiaozhou Chen, Hailong Tian,

Longbin Deng

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160796 - 160796

Published: Feb. 1, 2025

Language: Английский

Citations

1
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

1
Fully recyclable and tough thermoplastic elastomers from simple bio-sourced δ-valerolactones DOI Creative Commons
Kai Ma, Haiyan An,

Jiyun Nam

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 10, 2024

Language: Английский

Citations

9
Stereoselective Ring‐opening Polymerization of S‐Carboxyanhydrides Using Salen Aluminum Catalysts: A Route to High‐Isotactic Functionalized Polythioesters DOI

Yinuo Zhu,

Youhua Tao

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 5, 2024

Abstract Polythioesters are important sustainable polymers with broad applications. The ring‐opening polymerization (ROP) of S ‐Carboxyanhydrides (SCAs) can afford polythioesters functional groups that typically difficult to prepare by ROP thiolactones. Typical methods involving organocatalysts, like dimethylaminopyridine (DMAP) and triethylamine (Et 3 N), have been plagued uncontrolled polymerization, including epimerization for most SCAs resulting in the loss isotacticity. Here, we report use salen aluminum catalysts selective various without epimerization, affording functionalized polythioester high molecular weight up 37.6 kDa highest P m value 0.99. Notably, TlaSCA (SCA prepared from thiolactic acid) generates first example a isotactic crystalline poly(thiolactic acid), which exhibited distinct T 152.6 °C. Effective ligand tailoring governs binding affinity between sulfide chain‐end metal center, thereby maintaining activity organometallic reducing occurrence reactions.

Language: Английский

Citations

7
Recycling Polyester and Polycarbonate Plastics with Carbocation Lewis Acidic Organocatalysts DOI

Nan Wang,

Qiao Zhang, Zhiqiang Sun

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 377 - 384

Published: March 8, 2025

The effective management of plastic waste is critical for environmental sustainability. This work explores the use carbocation catalysts recycling common polyesters and polycarbonates through alcoholysis. We demonstrate complete depolymerization end-of-life materials investigate relationship between catalytic reactivity structural features compounds, including cations their counteranions. Carbocations function as Lewis acids, facilitating interaction with carbonyls in polymer chains. Moreover, our approach enables hierarchical degradation polyester blends. research not only elucidates role carbocations alcoholysis these polymers, but also establishes a metal-free process efficient plastics.

Language: Английский

Citations

1