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Synergic Main Group Catalysis for Degradable Main Group Polymers

Alternating ring-opening copolymerisation (ROCOP) is a highly modular polymerisation methodology which offers straightforward access to polymer structures which are not easily accessible otherwise. Commonly, transition metal-based catalysts are used to copolymerise oxygenated monomers such as epoxides and CO2. Although main group catalysts are an attractive alternative due to their low toxicity, cost and colourlessness, their overall catalytic performance is still lacking behind leading transition metal systems. Moving towards main group catalysts could be particularly important when turning to heavier main-group monomers in order to avoid catalyst poisoning and facilitate polymer purification. Although there are select examples (e.g. CS2 ROCOP), this area of polymer chemistry is largely overlooked in chemical literature. However, incorporating main group elements such as sulphur or phosphorus into polymers already shows promise, in their application as high refractive index polymers, polymeric electrodes as well as flame retardant materials and might even lead to more facile degradation.

The overarching aim of research in the Plajer group is to design and investigate new polymerisation methodologies based on main-group elements for the synthesis of degradable and recyclable main group polymers. The copolymerisation of waste materials such as CO2 will be of particular interest. Moreover, fundamental questions will be targeted, as to how exactly polymerisation mechanisms and material properties change through the introduction of main group elements. We will also study the polymerisation behaviour of monomer mixtures comprising more than two monomers, i.e. whether three, four or even five monomers can be enchained in a regular fashion through intrinsic chemoselectivity of the reaction mechanism.

Research in the Plajer group lies between inorganic chemistry, catalysis and material science. The work we do spans from synthesis, mechanistic investigations to material applications and also involves computational studies. Students can expect to receive broad training and dive into many different areas of exciting chemistry.

For a general review of the area see:
“Heterocycle/Heteroallene Ring-Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers”
A. J. Plajer, C. K. Williams; Angew. Chem. Int. Ed. 2022, 61, 1 ;
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