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Doctoral thesis (Dissertations and theses)
Organocobalt complexes as sources of radicals for macromolecular engineering
Demarteau, Jérémy
2017
 

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Keywords :
radical polymerization; cobalt-mediated radical polymerization (CMRP)
Abstract :
[en] Organocobalt(III) complexes (R-Co) have an excellent propensity to produce carboncentered radicals by the cleavage of their C-Co bond under mild conditions and, thereby, proved their huge interest in both organic and polymer chemistries. In particular, the cobalt mediated radical polymerization (CMRP) demonstrated its ability to control the polymerization of various monomers, especially the challenging less-activated monomers (LAMs) like vinyl esters or vinyl amides, and to produce the corresponding well-defined (co)polymers. In spite of these progresses, huge challenges are still pending in the controlled synthesis of functional LAMs-containing polymers, particularly those based on ethylene or a-olefins.The present thesis aims to address these challenges and develop a CMRP platform using novel bisacetylacetonato alkylcobalt(III) (R-Co(acac)2) as initiators for the controlled synthesis of α-olefin based (co)polymers by including functional ones. First, well-defined ethylene/vinyl acetate (EVA) copolymers are prepared using a previously reported nonfunctional oligopoly( vinyl acetate)-Co(acac)2 but also from a novel halomethyl-cobalt(III) (XCH2-Co(acac)2) paving the way to the corresponding functional EVAs. This end-chain functionalization route is notably exploited for the design of novel telechelic EVAs and unprecedented ethylenecontaining macrocycles. Finally, the cobalt-mediated radical (co)polymerization of α-olefins having perfluorinated side chains is considered in order to produce innovative well-defined fluorinated polymer structures with various compositions and architectures. Overall, this work aspires to increase the understanding and broaden the scope of the CMRP of LAMs, in particular of α-olefins.
Research center :
CESAM Complex and Entangled Systems from Atoms to Materials (CESAM)
Disciplines :
Materials science & engineering
Chemistry
Author, co-author :
Demarteau, Jérémy ;  University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Organocobalt complexes as sources of radicals for macromolecular engineering
Defense date :
20 December 2017
Institution :
ULiège - Université de Liège
Degree :
Docteur en Sciences
Promotor :
Detrembleur, Christophe ;  Université de Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM)
Debuigne, Antoine  ;  Université de Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM)
President :
Duwez, Anne-Sophie  ;  Université de Liège - ULiège > Molecular Systems (MolSys)
Secretary :
Monbaliu, Jean-Christophe  ;  Université de Liège - ULiège > Département de chimie (sciences) > Center for Integrated Technology and Organic Synthesis
Jury member :
Junkers, Tanja
Gigmes, Didier
Améduri, Bruno
Name of the research project :
Center for Education and Research on Macromolecules (CERM)
Funders :
FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE]
Available on ORBi :
since 17 January 2018

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