Air‐tolerant poly(3‐hexylthiophene) synthesis via catalyst‐transfer polymerization. Issue 3 (28th December 2020)

• Record Type: Journal Article
• Authors: Kubo, Tomohiro; Young, Morgan S.; Souther, Kendra D.; Hannigan, Matthew D.; McNeil, Anne J.
• Is Part Of: Journal of polymer science. Volume 59:Issue 3(2021)
• Page Start: 268
• Page End: 273
• Publication Date: 2020-12-28
• Subjects: catalysis -- catalyst‐transfer polymerization -- chain‐growth polymerization -- conjugated polymers -- palladium; Polymers -- Periodicals; Polymerization -- Periodicals; Polymerization; Polymers; Periodicals; 547.7
• DOI: 10.1002/pol.20200788
• Languages: English
• ISSNs: 2642-4150

Abstract

Abstract: The discovery of catalyst‐transfer polymerization and its further developments have led to unprecedented control over the length and sequence of conjugated polymers. However, the methods themselves are technically challenging to perform due to the air‐ and moisture‐sensitivities of the monomers and catalysts. Herein, we report a catalyst‐transfer polymerization method that affords poly(3‐hexylthiophene) in high yields without using an inert atmosphere. The synthesis capitalizes on a rapid Negishi cross‐coupling using a moisture‐tolerant organozinc monomer mediated by an air‐stable Pd precatalyst. This simple method should make conjugated polymer synthesis more accessible to a broader range of researchers and may be generalizable to other monomer scaffolds. Abstract : Transition metal‐mediated cross‐coupling polymerizations typically require inert atmospheres to attenuate premature monomer quenching and/or catalyst deactivation. Herein, poly(3‐hexylthiophene) is synthesized without the need for an inert atmosphere by using bench‐stable Pd precatalysts and organozinc pivalates. The reaction yields polymers with specified molar masses and end‐group identities, as well as with narrow dispersities, consistent with a living, chain‐growth polymerization.