Reference : UMR5069-BLAMAR-001
Nombre de Postes : 1
Workplace : TOULOUSE
Date of publication : Friday, January 6, 2023
Scientific Responsible name : Blanca Martin Vaca
Type of Contract : PhD Student contract / Thesis offer
Contract Period : 36 months
Start date of the thesis : 1 March 2023
Proportion of work : Full time
Remuneration : 2 135,00 € gross monthly
Description of the thesis topic
A major challenge in polymer science today is to develop new functional materials with a minimal environmental footprint. Most polymers used in everyday life have a skeleton composed exclusively of carbon-carbon bonds, which makes their degradation extremely long. The current challenge is to find alternatives to these polymers by synthesizing polymers capable of degrading either in the natural environment (biodegradable polymers) or under chemically controlled conditions (circular polymers). For this, cleavable C-E bonds (E = heteroatom) must be inserted into the polymer chains. Heterocycles are the monomers of choice for doing this, either by homopolymerization via ring-opening polymerization (ROP) or by copolymerization with vinyl monomers via radical polymerization (rROP). This last option allows the preparation of degradable polyolefins, and the first results are very promising.
In this thesis project, we will initially focus on thionolactones (TnL) which have been shown to be effective partners in rROP with certain vinyl monomers (mainly acrylates). However, very few structures have been studied so far. In order to improve the efficiency of copolymerization with a wider range of vinyl monomers, we have identified promising targets by playing on the structural parameters of these heterocycles. A series of TnL will be prepared by the PhD student by varying the ring size (seven/six membered rings) and the substitution pattern (electron donating/attractor groups, condensed benzo rings). The strong experience of our group in molecular chemistry (including main group chemistry and organometallic catalysis) will be an asset for this part of the project. We will rely on known methodologies but also develop new ones to increase structural diversity.
In addition to the rROP of the new TnLs, which will be investigated by a collaborator, their organocatalyzed ROP will be studied, an area in which our group is internationally recognized. The structure and properties of the resulting polythioesters will be studied in depth.
The work will combine heterocyclic synthesis, polymerization studies and a range of analytical techniques for the characterization of small molecules as well as polymer stitched cyclic monomers to render plastics degradable.
Environment: The LHFA is affiliated to CNRS and UPS. It is located in the chemistry building of UPS, 118 route de Narbonne, Toulouse.
The LHFA gathers 6 research teams (about 70-80 people). Its core activity is the synthesis and study of original molecules, highly reactive species.
Host team: LBPB, see the corresponding website for more details
Constraints and risks
Nothing to report
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