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Quantitative comparison of the copolymerisation kinetics in catalyst-transfer copolymerisation to synthesise polythiophenes
https://oist.repo.nii.ac.jp/records/2000631
https://oist.repo.nii.ac.jp/records/200063104937475-2659-403c-b431-3489200675c3
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He-2024-Quantitative comparison of the copolym.pdf (1.2 MB)
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| Item type | 学術雑誌論文 / Journal Article(1) | |||||||||
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| PubDate | 2024-09-24 | |||||||||
| Title | ||||||||||
| Title | Quantitative comparison of the copolymerisation kinetics in catalyst-transfer copolymerisation to synthesise polythiophenes | |||||||||
| Language | en | |||||||||
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| Language | eng | |||||||||
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| Resource Type Identifier | http://purl.org/coar/resource_type/c_6501 | |||||||||
| Resource Type | journal article | |||||||||
| Access Right | ||||||||||
| Access Rights | open access | |||||||||
| Access Rights URI | http://purl.org/coar/access_right/c_abf2 | |||||||||
| Author |
He, Yifei
× He, Yifei
× Luscombe, Christine K.
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| Bibliographic Information |
en : Polymer Chemistry Volume Number 15, Issue Number 25, p. 2598-2605, Issue Date 2024-05-10 |
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| Abstract | ||||||||||
| Description Type | Abstract | |||||||||
| Description | Polythiophenes are one of the most widely studied conjugated polymers. With the discovery of the chain mechanism of Kumada catalyst-transfer polymerisation (KCTP), various polythiophene copolymer structures, such as random, block, and gradient copolymers, have been synthesized via batch or semi-batch (sequential addition) methods. However, the lack of quantitative kinetic data for thiophene monomers brings challenges to experimental design and structure prediction when synthesizing the copolymers. In this study, the reactivity ratios and the polymerisation rate constants of 3-hexylthiophene with 4 thiophene comonomers in KCTP are measured by adapting the Mayo–Lewis equation and the first-order kinetic behaviour of chain polymerisation. The obtained kinetic information highlights the impact of the monomer structure on the reactivity in the copolymerisations. The kinetic data are used to predict the copolymer structure of equimolar batch copolymerisations of the 4 thiophene derivatives with 3-hexylthiophene, with the experimental data agreeing well with the predictions. 3-Dodecylthiophene and 3-(6-bromo)hexylthiophene, which have higher structural similarity to 3-hexylthiophene, show nearly equivalent reactivity to 3-hexylthiophene and give random copolymers in the batch copolymerisation. 3-(2-Ethylhexyl)thiophene with a branched side chain is less reactive compared to 3-hexylthiophene and failed to homopolymerize at room temperature, but produced gradient copolymers with 3-hexylthiophene. Finally, the bulkiest 3-(4-octylphenyl)thiophene, despite its ability to homopolymerize, failed to maintain chain polymerisation in the copolymerisation with 3-hexylthiophene, possibly due to the large steric hindrance caused by the phenyl ring directly attached to the thiophene center. This study highlights the importance of monomer structures in copolymerisations and the need for accurate kinetic data. | |||||||||
| Language | en | |||||||||
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| Publisher | Royal Society of Chemistry | |||||||||
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| Source Identifier Type | PISSN | |||||||||
| Source Identifier | 1759-9954 | |||||||||
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| Source Identifier Type | EISSN | |||||||||
| Source Identifier | 1759-9962 | |||||||||
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| Relation Type | isIdenticalTo | |||||||||
| Identifier Type | PMID | |||||||||
| Related Identifier | 38933685 | |||||||||
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| Relation Type | isIdenticalTo | |||||||||
| Identifier Type | DOI | |||||||||
| Related Identifier | 10.1039/d4py00009a | |||||||||
| Rights | ||||||||||
| Rights | © 2024 Authors. | |||||||||
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| Rights Resource | https://creativecommons.org/licenses/by-nc/3.0/ | |||||||||
| Rights | Creative Commons Attribution-NonCommercial 3.0 Unported | |||||||||
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| Relation Type | isIdenticalTo | |||||||||
| Identifier Type | URI | |||||||||
| Related Identifier | https://pubs.rsc.org/en/content/articlelanding/2024/py/d4py00009a | |||||||||
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| Version Type | VoR | |||||||||
| Version Type Resource | http://purl.org/coar/version/c_970fb48d4fbd8a85 | |||||||||
