Synthesis of megadalton stereoregular ring-substituted poly(phenylacetylene)s by a rhodium(<scp>i</scp>) catalyst with a N-functionalized hemilabile phosphine ligand
Angoy, Marta ; Jiménez, M. Victoria ; Vispe, Eugenio ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza)
Resumen: The cationic compound [Rh(nbd){κ2P,N-Ph2P(CH2)3NMe2}][BF4] efficiently catalyzes the polymerization of a series of ring-substituted phenylacetylene derivatives, R-C6H4–C[triple bond, length as m-dash]CH with groups of different electronic and steric properties at the para (R = F, CF3, Me, Bu, tBu, OMe, OBu) and meta (R = OMe) positions to give highly stereoregular ring-substituted poly(phenylacetylene)s with a cis-transoidal configuration of very high molar mass and moderate dispersities. The polymers have been characterized by size exclusion chromatography (SEC-MALS), NMR, DSC and TGA. The polymerization of phenylacetylene and 1-ethynyl-3-methoxybenzene gives megadalton poly(phenylacetylene)s, while the polymerization of 1-ethynyl-4-methoxybenzene and 1-(tert-butyl)-4-ethynylbenzene gives ultra-high molecular weight poly(phenylacetylene)s with Mn of 1.70 × 106 and 2.72 × 106, respectively. The electronic effect of the substituent strongly influences the catalytic activity. Phenylacetylene derivatives with an electron-withdrawing substituent in para position polymerize faster than those with an electron-donating substituent.
Idioma: Inglés
DOI: 10.1039/d4py00259h
Año: 2024
Publicado en: POLYMER CHEMISTRY 15, 20 (2024), 2028-2039
ISSN: 1759-9954
Factor impacto JCR: 3.9 (2024)
Categ. JCR: POLYMER SCIENCE rank: 34 / 94 = 0.362 (2024) - Q2 - T2
Factor impacto SCIMAGO: 0.842 - Organic Chemistry (Q1) - Polymers and Plastics (Q1) - Bioengineering (Q2) - Biochemistry (Q2) - Biomedical Engineering (Q2)
Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/AEI/10.13039/501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes.
Exportado de SIDERAL (2025-09-22-14:41:16)
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Idioma: Inglés
DOI: 10.1039/d4py00259h
Año: 2024
Publicado en: POLYMER CHEMISTRY 15, 20 (2024), 2028-2039
ISSN: 1759-9954
Factor impacto JCR: 3.9 (2024)
Categ. JCR: POLYMER SCIENCE rank: 34 / 94 = 0.362 (2024) - Q2 - T2
Factor impacto SCIMAGO: 0.842 - Organic Chemistry (Q1) - Polymers and Plastics (Q1) - Bioengineering (Q2) - Biochemistry (Q2) - Biomedical Engineering (Q2)
Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/AEI/10.13039/501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. Exportado de SIDERAL (2025-09-22-14:41:16)
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Record created 2024-05-22, last modified 2025-09-23