Tailor-made poly(vinylidene sulfide)s by Rh(I)–NHC catalyzed regioselective thiol-yne click polymerization

Hermosilla, Pablo ; Funes-Hernando, Daniel ; Castarlenas, Ricardo ; Di Giuseppe, Andrea ; Azpíroz, Ramón ; Vispe, Eugenio ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza)

Resumen: The [Rh(μ-Cl)(IPr)(η2-coe)]2/pyridine system efficiently catalyzes the polyhydrothiolation of a series of dialkynes with dithiols, producing sulfur-rich poly(vinylidene sulfide)s with a typical Mw in the range 20.000–124.000 and vinylidene content of 75–87%. A combination of flexible aliphatic dithiols, including 1,6-hexanedithiol and 2,2′-(ethylendioxy)diethanethiol, and the rigid aromatic dithiol 4,4′-thiobisbenzenethiol, with rigid aromatic dialkynes, 1,3-diethynylbenzene and 1,4-diethynylbenzene, and flexible dialkynes, including propargyl ether and 1,7-octadiyne, have been used to prepare poly(vinylidene sulfide)s. The copolymerization of flexible dithiols with rigid aromatic dialkynes or vice versa results in high molecular weight polymers, Mw up to 259.000, with low polydispersities. However, polyhidrothiolation of flexible dialkynes with flexible dithiols is much less efficient and usually results in the formation of oligomers. The interplay of the IPr and pyridine ligands on the RhCl(IPr)(py)(η2-coe) catalyst, which controls the regioselectivity of the alkyne insertion step towards the branched vinyl sulfide, is key in the preparation of these poly(vinylidene sulfide)s.

Idioma: Inglés

DOI: 10.1016/j.eurpolymj.2023.112117

Año: 2023

Publicado en: European Polymer Journal 194 (2023), 112117 [10 pp]
ISSN: 0014-3057

Factor impacto JCR: 5.8 (2023)

Categ. JCR: POLYMER SCIENCE rank: 9 / 95 = 0.095 (2023) - Q1 - T1

Factor impacto CITESCORE: 9.9 - Polymers and Plastics (Q1) - Organic Chemistry (Q1) - Materials Chemistry (Q1) - Physics and Astronomy (all) (Q1)

Factor impacto SCIMAGO: 0.982 - Materials Chemistry (Q1) - Polymers and Plastics (Q1) - Physics and Astronomy (miscellaneous) (Q1) - Organic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)