Biomass derived synthetic polymers

Polymers are produced on a multi-million tonne scale per annum and are a high priority to move from non-sustainable petroleum based to sustainably based starting materials. Itaconic acid 1 and hydroxymethylfuran 2 are both available by fermentation or pyrolysis of sugars. We have recently shown that treatment of the cyclic anhydride of 1 with 2 led to oxa-norbornene derivative 3 via a tandem ring-opening Diels-Alder sequence. Subsequent esterification of 3 with methanol (sustainably available by hydrogenation of carbon dioxide) gave monomer 4 which we have shown will undergo ring-opening metathesis polymerisation (ROMP) when treated with Grubbs second generation catalyst (Green Chemistry 2016, 18, 3945–3948).

Unfortunately, the ROMP homopolymer of 4 was found to be rather insoluble which has prevented its full characterisation, though copolymers with other norbornene derivatives could be prepared and characterised. Therefore, the first aim of this project is to replace the methyl ester in monomer 4 with esters derived from other sustainably sourced alcohols to obtain more soluble polymers. Examples of suitable alcohols are shown in structures 5-9. The resulting polymers will be characterised by GPC, Maldi-MS, TGA/DSC and IR and NMR studies will be used to demonstrate the living nature of the polymerisation and to investigate the regiochemistry and tacticity associated with the polymerisation. The synthesis of amides rather than esters will also be investigated as will the synthesis and polymerisation of related monomers from furan derivatives and other biomass derivable cyclic anhydrides.

All research students follow our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills. All research students take the core training package which provides both a grounding in the skills required for their research, and transferable skills to enhance employability opportunities following graduation. Core training is progressive and takes place at appropriate points throughout a student’s higher degree programme, with the majority of training taking place in Year 1. In conjunction with the Core training, students, in consultation with their supervisor(s), select training related to the area of their research.

The student appointed to this project will receive broad based training in the areas of organic synthesis, polymer chemistry and green chemistry.

The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel. Chemistry at York was the first academic department in the UK to receive the Athena SWAN Gold award, first attained in 2007 and then renewed in October 2010 and in April 2015.