Base-Assisted Polymerizations of Elemental Sulfur and Alkynones for Temperature-Controlled Synthesis of Polythiophenes or Poly(1,4-dithiin)s

Peng, Jianwen; Tian, Tian; Xu, Shuangshuang; Hu, Rongrong; Tang, Ben Zhong

doi:10.1021/jacs.3c10954

Cited by 10 publications

(5 citation statements)

References 59 publications

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“…But if we increase the temperature by more than 150 °C, the reaction mixture could become insoluble in CS 2 due to cross-linking and generate H 2 S. Free radical polymerization is not an easy task to do. Problems that occur in this process are depolymerization, incomplete sulfur consumption, and H 2 S gas generation . Inverse vulcanization is a type of free radical polymerization.…”

Section: Polysulfide Preparation Techniquesmentioning

confidence: 99%

A Comprehensive Exploration of Polysulfides, From Synthesis Techniques to Diverse Applications and Future Frontiers

Amna,

Alhassan

2024

ACS Appl. Polym. Mater.

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The present review offers a concise overview of polysulfides, focusing on various techniques for synthesizing polymers with high sulfur content through direct elemental sulfur polymerization. These methodologies encompass condensation, ionic, and free radical polymerizations. Of particular interest is the extensively discussed free radical polymerization type known as inverse vulcanization. The report delves into the diverse applications of polysulfides, spanning areas such as lithium−sulfur batteries, self-healing materials, IR imaging technology, energy storage, controlled fertilizer, antimicrobial agents, oil spill remediation, water-soluble polymers, and separation science, specifically in metal removal from wastewater. Polysulfides showcase distinctive properties, including optical, thermoresponsive, mechanical, and electrochemical attributes. However, it is crucial to acknowledge that this field is not without its challenges. The review briefly explores the current challenges and potential future developments associated with polysulfides. Additionally, it provides a cursory examination of the role of simulations, modeling, and artificial intelligence in advancing the understanding and applications of polysulfides.

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Section: Polysulfide Preparation Techniquesmentioning

confidence: 99%

A Comprehensive Exploration of Polysulfides, From Synthesis Techniques to Diverse Applications and Future Frontiers

Amna,

Alhassan

2024

ACS Appl. Polym. Mater.

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“…High-sulfur content polymers are widely used in various applications including Li–S batteries, , heavy metal adsorption, − high refractive index ( n ) materials, − and infrared (IR) transmissive materials − thanks to the unique characteristics of the sulfur atom. In 2013, inverse vulcanization, a compelling process to prepare high sulfur content polymers using elemental sulfur and organic cross-linker, was established.…”

Section: Introductionmentioning

confidence: 99%

Structural Effect of Cyclic Olefin Cross-Linkers on Long-Wave Infrared-Transmitting Sulfur Polymers

Lee,

Jang,

Yeo

et al. 2024

Macromolecules

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The structural characteristics of the organic crosslinker greatly affect the potential infrared (IR) optics applications of sulfur polymers synthesized through the inverse vulcanization reaction. Unlike elemental sulfur, organic cross-linkers induce various absorptions in the IR region and leave organic moieties that affect the IR transmittance, even after inverse vulcanization. Most of the cyclic olefin cross-linkers [e.g., dicyclopentadiene (DCPD)] investigated so far are expected to produce side reactions and form byproducts during inverse vulcanization. The side reactions caused by differences in reactivity between the reaction sites can result in the deterioration of the optical properties of sulfur polymers. In this study, thiol groups were introduced as a cross-linker to effectively control the side reactions and byproducts that may occur in inverse vulcanization. The sulfur and thiol cross-linkers reacted rapidly and uniformly at all reaction sites to form sulfur polymers without unwanted side reactions. Optical windows prepared with the sulfur polymer exhibited enhanced IR transparency and achieved thermal imaging of the human body in the long-wave IR (LWIR) region. By design of a cross-linker for LWIR transparent sulfur polymers, these results provide a useful solution for IR optics applications.

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“…Sulfur-containing polymers can exhibit improved semicrystallinity, recyclability and degradability in comparison to their all-oxygen-containing counterparts, as well as unique properties such as high refractive indices rendering them, for example, as useful components in optical applications. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] In this regard ring-opening copolymerization (ROCOP) of a strained heterocycle with a heteroallene such as carbon disulfide (CS 2 ), carbonyl sulfide (COS), or isothiocyanates (RNCS) can provide access to sulfur-containing polymers, which are otherwise difficult to obtain with common synthetic strategies. [15] Much work has focused on the copolymerization of substituted epoxides to produce polythiocarbonates.…”

Section: Introductionmentioning

confidence: 99%

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

Stephan,

Olmedo‐Martínez,

Fornacon‐Wood

et al. 2024

Angew Chem Int Ed

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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 and phenyl isothiocyanate quantitatively yields polythioimidocarbonates as a new class of sulfur containing polymer, with narrow molecular weight distributions (Mn = 5–80 kg/mol with Đ ≤ 1.2; Mn,max = 124 kg/mol) and high melting points of up to 181 ºC. The method tolerates different substituent patterns on both the oxetane and the isothiocyanate. Self‐nucleation experiments reveal that π‐stacking of phenyl substituents, the presence of unsubstituted polymer backbones, and the kinetically controlled linkage selectivity are key factors in maximising melting points. The increased tolerance to macro‐chain transfer agents and the controlled propagation allows the synthesis of double crystalline and amphiphilic block copolymers, which can be assembled into micellar‐ and worm‐like structures with amorphous cores in water. While in ethanol, crystallization driven self‐assembly gives cylindrical micelles or platelets.

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Base-Assisted Polymerizations of Elemental Sulfur and Alkynones for Temperature-Controlled Synthesis of Polythiophenes or Poly(1,4-dithiin)s

Cited by 10 publications

References 59 publications

A Comprehensive Exploration of Polysulfides, From Synthesis Techniques to Diverse Applications and Future Frontiers

A Comprehensive Exploration of Polysulfides, From Synthesis Techniques to Diverse Applications and Future Frontiers

Structural Effect of Cyclic Olefin Cross-Linkers on Long-Wave Infrared-Transmitting Sulfur Polymers

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

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