Ultrafast synthesis of dialkyne-functionalized polythioether and post-polymerization modification via click chemistry

Pektas, Bercis; Sagdic, Gokhan; Dağlar, Özgün; Luleburgaz, Serter; Gunay, Ufuk Saim; Hızal, Gürkan; Tunca, Ümit; Durmaz, Hakan

doi:10.1016/j.polymer.2022.124989

Cited by 9 publications

(7 citation statements)

References 62 publications

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“…[ 42 ] Then, they developed the TBD‐catalyzed polymerization of dithiols and disubstituted acetylenedicarboxylates in chloroform, quantitatively producing various linear polythioethers with high molecular weights in 1 min (Scheme 1F). [ 38,43,44 ]…”

Section: Progresses In X‐yne Click Polymerizationmentioning

confidence: 99%

“…[42] Then, they developed the TBD-catalyzed polymerization of dithiols and disubstituted acetylenedicarboxylates in chloroform, quantitatively producing various linear polythioethers with high molecular weights in 1 min (Scheme 1F). [38,43,44] Mono-addition polymerization could be realized by using the less basic catalyst. In 2010, Tang and coworkers reported an organobase-catalyzed thiol-yne click polymerization of ester-activated terminal alkynes and 4,4′-thiodibenzenethiol (Scheme 1G).…”

Section: S C H E M E 1 (A-m)mentioning

confidence: 99%

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X‐yne click polymerization

Qin

Tang

2023

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Alkyne‐based click polymerizations have been nurtured into a powerful synthetic technique for the preparation of new polymers with advanced structures and versatile properties. Among them, the emerging thiol‐yne, hydroxyl‐yne, and amino‐yne click polymerizations have made remarkable progress from reactions to applications. These polymerizations avoid the usage of inherently dangerous monomers and are safer to operate than the classical azide‐alkyne click polymerization (AACP), making them more prospective for diverse applications. To greatly promote the new alkyne‐based click polymerizations beyond AACP, a new concept of “X‐yne click polymerization” is proposed to unify them, where “X” denotes the monomers that can react with alkynes under mild reaction conditions, including thiols, alcohols, amines, and other promising ones. In this review, we mainly present a brief account of the progress of X‐yne click polymerization and discuss in detail the challenges and opportunities in this field.

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Section: Progresses In X‐yne Click Polymerizationmentioning

confidence: 99%

Section: S C H E M E 1 (A-m)mentioning

confidence: 99%

X‐yne click polymerization

Qin

Tang

2023

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“…When unsymmetrical alkynes, including terminal alkynes, were used, the double 1,4-addition occurred at the electron-deficient position, resulting in thio-acetal type polythioethers (Scheme 67). 219,220 Organocatalysts exhibit excellent tolerance to functional groups, allowing for the incorporation of reactive or functional units into monomers. For instance, alkyne esters were introduced for click reactions, 220 and phosphothioester-dithiols 221 were used to demonstrate their versatile application.…”

Section: S C H E M E 6mentioning

confidence: 99%

“…219,220 Organocatalysts exhibit excellent tolerance to functional groups, allowing for the incorporation of reactive or functional units into monomers. For instance, alkyne esters were introduced for click reactions, 220 and phosphothioester-dithiols 221 were used to demonstrate their versatile application. The team also showcased hyperbranched polymer synthesis using tri-thiol and alkyne, following the A3 + B2 mechanism.…”

Section: S C H E M E 6mentioning

confidence: 99%

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Triazabicyclodecene: A versatile catalyst for polymer synthesis

Kim,

Lee,

Lee

2023

Journal of Polymer Science

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This comprehensive review aims to provide an in‐depth analysis of the catalytic performance of 1,5,7‐triazabicyclo[4,4,0]dec‐5‐ene (TBD) in polymer synthesis. TBD, a well‐established organic superbase, possesses a distinctive bifunctional character that grants it exceptional capabilities, particularly in processes such as transesterification or transamidation. TBD has garnered considerable attention since its initial report by Hedrick and Waymouth in 2006, and it has played a pivotal role in diverse polymerization reactions. Its versatility spans various polymerization modes, including chain‐growth and step‐growth polymerization, post‐polymerization modification, and network thermoset formation. More recently, its utility has extended to the green chemical recycling of polymers. By providing an encompassing overview of TBD's historical journey, this review delves into its past accomplishments while shedding light on its present and future potential to organocatalysts in polymer science.

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Synthesis of PEGylated amphiphilic block copolymers with pendant linoleic moieties by combining ring‐opening polymerization and click chemistry

Porras,

Diaz,

Perez

2024

Biopolymers

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This study focused on synthesizing and characterizing PEGylated amphiphilic block copolymers with pendant linoleic acid (Lin) moieties as an alternative to enhance their potential in drug delivery applications. The synthesis involved a two‐step process, starting with ring‐opening polymerization of ε‐caprolactone (CL) and propargylated cyclic carbonate (MCP) to obtain PEG‐b‐P(CL‐co‐MCP) copolymers, which were subsequently modified via click chemistry. Various reaction conditions were explored to improve the yield and efficiency of the click chemistry step. The use of anisole as a solvent, N‐(3‐azidopropyl)linoleamide as a substrate, and a reaction temperature of 60°C proved to be highly efficient, achieving nearly 100% conversion at a low catalyst concentration. The resulting copolymers exhibited controlled molecular weights and low polydispersity, confirming the successful synthesis. Furthermore, click chemistry allows for the attachment of Lin moieties to the copolymer, enhancing its hydrophobic character, as deduced from their significantly lower critical micelle concentration than that of traditional PEG‐b‐PCL systems, which is indicative of enhanced stability against dilution. The modified copolymers exhibited improved thermal stability, making them suitable for applications that require high processing temperatures. Dynamic light scattering and transmission electron microscopy confirmed the formation of micellar structures with sizes below 100 nm and minimal aggregate formation. Additionally, 1H NMR spectroscopy in deuterated water revealed the presence of core‐shell micelles, which provided higher kinetic stability against dilution.

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Ultrafast synthesis of dialkyne-functionalized polythioether and post-polymerization modification via click chemistry

Cited by 9 publications

References 62 publications

X‐yne click polymerization

X‐yne click polymerization

Triazabicyclodecene: A versatile catalyst for polymer synthesis

Synthesis of PEGylated amphiphilic block copolymers with pendant linoleic moieties by combining ring‐opening polymerization and click chemistry

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