| Item type |
学術雑誌論文 / Journal Article(1) |
| 公開日 |
2023-06-20 |
| タイトル |
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|
タイトル |
Statistical Analysis of Catalytic Performance in Ethylene/Methyl Acrylate Copolymerization Using Palladium/Phosphine-Sulfonate Catalysts |
|
言語 |
en |
| 言語 |
|
|
言語 |
eng |
| 資源タイプ |
|
|
資源 |
http://purl.org/coar/resource_type/c_6501 |
|
タイプ |
journal article |
| 著者 |
Akita, Shunpei
Guo, Jing Yao
Seidel, Falk W.
Sigman, Matthew S.
Nozaki, Kyoko
|
| 著者所属 |
|
|
言語 |
en |
|
著者所属 |
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo |
| 著者所属 |
|
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言語 |
en |
|
著者所属 |
Department of Chemistry, College of Science, The University of Utah |
| 抄録 |
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内容記述タイプ |
Abstract |
|
内容記述 |
For various types of palladium complexes bearing phosphine-sulfonate (PS) ligands used in the coordination–insertion copolymerization of olefins with polar monomers, characteristic features of the ligands, such as electronic and steric properties, have been discussed to describe their catalytic performance. Aiming at further analysis of the literature data, here we report the development of a statistical method for how the ligand impacts the performance of a Pd-catalyzed copolymerization of ethylene and methyl acrylate (MA). During our investigation, ligand features important for the resultant molecular weight of the obtained polymers were identified. Consistent with previously suggested important parameters, the electron density on the palladium center and maximum width of the substituents on the phosphorus atom (B5) were found to be significant for catalyst performance. We also found that additional features impact reaction outputs. As an example, the lower occupancy of the palladium dz2 orbital results in an increase of molecular weight and catalyst activity in both ethylene homopolymerization and ethylene/methyl acrylate copolymerization. Furthermore, it was predicted that a larger bite angle of the ligand increased the activity of ethylene/methyl acrylate copolymerization without impacting the molecular weight. On the basis of these machine learning predictions, three thiophene derived PS-type catalysts were synthesized and tested for MA/ethylene copolymerization. Unexpectedly, rather than the one predicted to enhance catalytic performance, a synthetic intermediate to this ligand exhibited higher activity albeit with the expense of molecular weight and MA incorporation. The inconsistency between the prediction and the experimental result is likely a result of insufficient training data for the catalyst with a different linker moiety. However, the unexpected finding that chlorination of the ligand backbone increases the overall catalyst performance will inspire an avenue for PS catalyst development. |
|
言語 |
en |
| 書誌情報 |
en : Organometallics
巻 41,
号 22,
p. 3185-3196,
発行日 2022-03-29
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| ISSN |
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収録物識別子タイプ |
PISSN |
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収録物識別子 |
02767333 |
| 権利 |
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|
権利情報 |
This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Organometallics], copyright [© 2022 American Chemical Society] after peer review and technical editing by the publisher. To access the final edited and published work see [https://doi.org/10.1021/acs.organomet.2c00066]. |
| 出版者 |
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出版者 |
American Chemical Society |
|
言語 |
en |
| 関係URI |
|
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関連タイプ |
isVersionOf |
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|
識別子タイプ |
URI |
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|
関連識別子 |
https://doi.org/10.1021/acs.organomet.2c00066 |
| 出版タイプ |
|
|
出版タイプ |
AM |
acs_organomet2c00066.pdf (1.5 MB)
