Palladium-Catalyzed Living/Controlled Vinyl Addition Polymerization of Cyclopropenes
2021
Zhang, Zepeng | Gao, Yunpeng | Chen, Shufeng | Wang, Jianbo
Despite the various utilities of cyclopropenes (CPEs) in organic synthesis and ring-opening metathesis polymerization (ROMP), their vinyl addition polymerization has been sporadically explored, and the corresponding living/controlled polymerization remains a formidable challenge. The major obstacle is the intrinsic instability of the intermediate and the kinetic barrier for propagation. Herein a living/controlled vinyl addition polymerization of 3-methyl-3-carboxymethyl CPEs, catalyzed by [Pd(π-allyl)Cl]₂ ligated by a sulfinamide bisphosphine ligand, is demonstrated. A plot of the number-average molecular weight (Mₙ) versus the conversion was found to be linear during the polymerization, with the molecular weight dispersity (Mw/Mₙ) remaining narrow. The Mₙ values increased linearly with the increase in the initial feed ratio of monomer to catalyst. Furthermore, controlled block copolymerization via sequential monomer addition was successful. All of these points corroborate the living nature of this polymerization. The synergistic coordination action of the catalyst ligand and the lateral carbonyl group in the cyclopropene moiety plays a key role in achieving the efficient polymerization in a living/controlled manner.
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