Diverse functional polyethylenes by catalytic amination

• 成果类型: Article
• 署名作者: Ciccia, Nicodemo R.; Shi, Jake X.; Pal, Subhajit; Hua, Mutian; Malollari, Katerina G.; Lizandara-Pueyo, Carlos; Risto, Eugen; Ernst, Martin; Helms, Brett A.; Messersmith, Phillip B.; Hartwig, John F.
• 署名单位: University of California System; University of California Berkeley; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; University of California System; University of California Berkeley; University of California System; University of California Berkeley; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory; BASF; BASF; United States Department of Energy (DOE); Lawrence Berkeley National Laboratory
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12080
• DOI: 10.1126/science.adg6093
• 发表日期: 2023-09-29
• 页码: 1433-1440
• 关键词: c-h bonds; free-radical copolymerization; reactivity ratios; vinyl monomers; ethylene; polymerization; polyolefins; copper; amidation; acetate

摘要

Functional polyethylenes possess valuable bulk and surface properties, but the limits of current synthetic methods narrow the range of accessible materials and prevent many envisioned applications. Instead, these materials are often used in composite films that are challenging to recycle. We report a Cu-catalyzed amination of polyethylenes to form mono- and bifunctional materials containing a series of polar groups and substituents. Designed catalysts with hydrophobic moieties enable the amination of linear and branched polyethylenes without chain scission or cross-linking, leading to polyethylenes with otherwise inaccessible combinations of functional groups and architectures. The resulting materials possess tunable bulk and surface properties, including toughness, adhesion to metal, paintability, and water solubility, which could unlock applications for functional polyethylenes and reduce the need for complex composites.