[en] 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.
Research Center/Unit :
Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Scholten, Philip Benjamin Vincent ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium > Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Cartigny, Grégory ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Grignard, Bruno ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Debuigne, Antoine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Cramail, Henri; University of Bordeaux, Laboratoire de Chimie des Polymères Organiques (LCPO), France
Meier, Michael A. R.; Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Germany
Detrembleur, Christophe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Language :
English
Title :
Functional polyethylenes by organometallic-mediated radical polymerization of biobased carbonates
Publication date :
16 March 2021
Journal title :
ACS Macro Letters
eISSN :
2161-1653
Publisher :
American Chemical Society, United States - District of Columbia
Volume :
10
Issue :
3
Pages :
313-320
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
EC - European Commission EOS - The Excellence Of Science Program F.R.S.-FNRS - Fonds de la Recherche Scientifique FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen
Funding text :
We thank the European Commission in the framework of the ITN-Marie Curie Program “EJD-FunMat” (grant number 641640). C.D. thanks the “Fonds National pour la Recherche Scientifique” (F.R.S.-FNRS) and the Fonds Wetenschappelijk Onderzoek − Vlaanderen (FWO) for financial support in the frame of the Excellence of Science (EOS) project no.
O019618F (ID EOS: 30902231). C.D. is a Research Director and A.D. is a Senior Associate Researcher, both financed by the F.R.S.-FNRS. We also thank Rebecca Seim for her help with the elemental analysis.
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