Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates. 2021

Philip B V Scholten, and Grégory Cartigny, and Bruno Grignard, and Antoine Debuigne, and Henri Cramail, and Michael A R Meier, and Christophe Detrembleur
Center for Education and Research on Macromolecules (CERM), CESAM Research Unit, Department of Chemistry, University of Liège, Sart-Tilman B6a, 4000 Liège, Belgium.

Partly or fully renewable (co)polymers are gaining interest in both academia and industry. Polyethylene is a widely used polymer, classically derived from fossil fuels, with a high versatility stemming from the introduction of comonomers altering the mechanical properties. The introduction of renewable functionalities into this polymer is highly attractive to obtain functional, tunable, and at least partially renewable polyethylenes. We herein report the introduction of biosourced cyclic carbonates into polyethylene using organometallic-mediated radical polymerization under mild conditions. Molecular weights of up to 14 600 g mol-1 with dispersities as low as 1.19 were obtained, and the cyclic carbonate content could be easily tuned by the ethylene pressure during the polymerization. As a proof of concept, the hydrolysis of the cyclic carbonates of a representative copolymer was explored, and it provided polyethylene-bearing vicinal diols, with a hydrolysis degree of 71%. Given the multitude of chemoselective modifications possible on cyclic carbonates as well as the fact that many allylic- and alkylidene-type cyclic carbonates are accessible from renewable resources, this work opens up an avenue for the design of functional and more sustainable polyethylenes.

UI MeSH Term Description Entries
D008970 Molecular Weight The sum of the weight of all the atoms in a molecule. Molecular Weights,Weight, Molecular,Weights, Molecular
D011108 Polymers Compounds formed by the joining of smaller, usually repeating, units linked by covalent bonds. These compounds often form large macromolecules (e.g., BIOPOLYMERS; PLASTICS). Polymer
D002254 Carbonates Salts or ions of the theoretical carbonic acid, containing the radical CO2(3-). Carbonates are readily decomposed by acids. The carbonates of the alkali metals are water-soluble; all others are insoluble. (From Grant & Hackh's Chemical Dictionary, 5th ed) Carbonate
D058105 Polymerization Chemical reaction in which monomeric components are combined to form POLYMERS (e.g., POLYMETHYLMETHACRYLATE). Polymerizations
D020959 Polyethylene A vinyl polymer made from ethylene. It can be branched or linear. Branched or low-density polyethylene is tough and pliable but not to the same degree as linear polyethylene. Linear or high-density polyethylene has a greater hardness and tensile strength. Polyethylene is used in a variety of products, including implants and prostheses. HDPE,High-Density Polyethylene,Polythene,LDPE,Low-Density Polyethylene,High Density Polyethylene,Low Density Polyethylene,Polyethylene, High-Density,Polyethylene, Low-Density

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