Doctoral Training Partnerships: a range of postgraduate training is funded by the Research Councils. For information on current funding routes, see the common terminology at https://www.ukri.org/apply-for-funding/how-we-fund-studentships/. Training grants may be to one organisation or to a consortia of research organisations. This portal will show the lead organisation only.

Methacrylates are currently produced from petrochemical feedstocks and are used to manufacture a range of bulk and specialist polymers. For example, methylmethacrylate (2-methylpropenoic acid methyl ester) is used as the monomer for polymethylmethacrylate, a transparent, UV-resistant, biocompatible polymer which can easily be recycled. The polymer and its blends are used for numerous applications, such as construction, paints, coatings, automotive components, biomedical materials and as Perspex and Plexiglas, thus supporting a large, diverse supply chain. The acrylics industry requires 2000 kilotonnes of methylmethacrylate annually and the market size is 3 Billion USD. Lucite International has over 35% of the global market share for methacrylate monomers, methyl methacrylate and methacrylic acid, with 28% of their production in the UK. Therefore, methacrylate manufacturing and use provides an important contribution to the UK economy. The dependence on petrochemical feedstocks is an increasing risk factor for the future sustainability of the acrylics industry. Oil reserves are rapidly being depleted, and this is already causing increased feedstock costs. Longer term, there are concerns over the availability of feedstock supplies. Therefore, a transition to renewable feedstocks will be required to 'future-proof' the supplies of methacrylate monomers. Lucite is exploring the potential to introduce a new Hybrid Bio- and Chemocatalytic Process to produce methacrylic acid from renewable feedstocks. The proposed process involves production of organic acids by fermentation, followed by base-catalysed decarboxylation to produce methacrylic acid in near- or supercritical water. The great advantage is that both processes operate in water. This avoids the need to separate the organic acid from the fermentation broth, which would otherwise require a costly crystallization process. The chemocatalytic stage has already been developed successfully in an EPSRC-funded CASE project at the University of Nottingham, using itaconic acid and citramalic acid as substrates. The aim of this project is to develop an improved route to produce itaconic acid by fermentation and to demonstrate that raw fermentation broth can be fed directly into the hot water process, after removing the cells. The traditional itaconic acid fermentation depends on the use of filamentous fungi, and is reasonably efficient. However, there are mass transfer problems both within the fermentation process (because the fungi grow as pellets) and at the intracellular level, because aconitate has to be transferred from the mitochondria to the cytoplasm. Both problems contribute to limited productivity. Furthermore, acid pH is required in the fungal process, whereas the base-catalysed Hybrid Process requires the neutral salt. Therefore, we shall develop engineered E. coli strains to produce itaconic acid. The project will include overexpression of citrate synthase, aconitate hydratase, and aconitate decarboxylase in E. coli for initial proof of concept. Subsequently, a two stage fermentation process will be developed, with initial, rapid growth to produce the biocatalyst under aerobic conditions, followed by a switch to anaerobic conditions to produce itaconate using non-growing cells. Although this will automatically suppress the downstream reactions of the TCA cycle, further metabolic engineering will be needed to develop a robust manufacturing process. Therefore, metabolic modelling will be used to design strains which produce itaconic acid precursors efficiently, and which do not divert the precursors and product into unproductive metabolism. Some of the preliminary designs will be constructed and tested in the Hybrid Process for methacrylic acid production. This will provide a platform for future follow-on projects to construct metabolically engineered biocatalysts, based on the designs, and to develop a fully integrated Hybrid Process

Methoxycarbonylation is a process that converts cheap, widely available feedstocks (alkenes, carbon monoxide and methanol) into commercially-important intermediates for the chemicals industry. This process uses Pd-based catalysts and the best example is the reaction of the simplest alkene, ethene, to give the intermediate methyl methacrylate, which is used in the synthesis of plastics. More recently, alkenes such as vinyl acetate have been shown to undergo methoxycarbonylation to generate intermediates that are themselves useful as green solvents (low-volatility/biodegradable) or as monomers for the formation of biodegradable polymers. These have the potential to replace traditional materials such as polystyrene or polythene. Methoxycarbonylation of butadiene promises a new route to adipic acid, one of the co-monomers involved in the manufacture of nylon. As yet the methoxycarbonylation of vinyl acetate and butadiene have not been optimised and greater insight into these reactions is required before effective industrial processes are in place.A key issue that remains to be solved in the methoxycarbonylation reaction is the detailed mechanism by which the products are released - the so-called methanolysis step. There a several possibilities for this process, however, it is extremely difficult to obtain information on this from experiment as the reaction itself is incredibly fast. In these circumstances the use of computational modelling comes into its own, as this can readily provide information on the energies of the species involved in reactivity. The methanolysis reaction is, however, very complicated and is strongly dependent on the precise nature of the reacting species and the nature of the solvent being used. To obtain reliable modelling data these factors must be taken into account, a fact that makes the task of modelling these systems very challenging.This proposal seeks to use high level computational modelling to assess the mechanism of the methanolysis on the simplest methoxycarbonylation system - ethene/CO/MeOH - and the most effective Pd catalysts. Our approach will be to employ hybrid calculations where the catalyst and reacting molecules are dealt with at a high level of theory (density functional theory) but the solvent molecules (many 10s or hundreds) are treated at a lower level of theory based on classical force fields. Through this approach the effect of the solvent on the reactivity at the Pd catalyst will be taken into account and we aim to provide extremely reliable data to define the preferred mechanism. We will test our approach by comparing with an alternative catalyst which displays a different reactivity, thus giving a stringent test of our modelling approach.Once we have defined the correct way to treat these complicated reactions - as well as the mechanism by which methanolysis occurs - we will be in a position to tackle the new reactions of vinyl acetate and butadiene. We hope to provide sufficient insight into these processes that experimental chemists will be able to design new improved catalysts for more efficient methoxycarbonylation of these feedstocks on an industrial scale.

The UK has long held a world-leading capability in acrylic technology. UK innovation in acrylic technology started with the world's first commercial production process in the 1930s. The earliest major application of acrylic materials was the substitution of glass with acrylic glazing in British World War II fighter planes, resulting in lighter weight and a significant improvement to pilot survivability when wounded by shrapnel. Lucite's UK presence includes an award-winning technology development capability at the Wilton Research Centre, and world scale manufacturing assets at Billingham and Newton Aycliffe. As durable materials, acrylic polymers have numerous advantageous properties, including excellent optical properties, resistance to weathering, imparting high performance to surface coatings, bio-compatibility, and the opportunity of recycling via depolymerisation. The increasing market size is due to both the heightened demand for acrylic glass and the expanding number of new applications. Given pMMA's versatility, the annual market will exceed $8 billion US dollars by 2025, growing at a rate of 8-9% per year. As demand continues to grow, the need for increased sustainability and fur-ther waste reductions is paramount. In 2012, the International Energy Agency designated meth-acrylic acid as a noteworthy target for the design of sustainable manufacturing [5]. Therefore, an extraordinary opportunity exists to decarbonise this value chain though UK technology leadership spanning the global stage. The two principal research challenges of the Prosperity Partnership are: (1) Decarbonise the acrylics value chain through resource circularity. (2) Maintain and extend the UK's technical and manufacturing leadership in this sector through 21st century manufacturing excellence in the North East of England. These UK advances in acrylic technology will have both national and global deployment capability, representing a first in class demonstration of decarbonisation through resource circularity in the bulk chemicals sector. This Prosperity Partnership will frame and catalyse further knowledge exchange, given that the anticipated global reduction in carbon intensity aligns with (1) UK legislation on attaining net zero carbon emissions by 2050, (2) the UK's Clean Growth grand challenge and (3) UKRI's Industrial Strategy policy of promoting decarbonisation, catalysing growth via resource circularity and the use of sustainable polymers.

Methoxycarbonylation is a process that converts cheap, widely available feedstocks (alkenes, carbon monoxide and methanol) into commercially-important intermediates for the chemicals industry. This process uses Pd-based catalysts and the best example is the reaction of the simplest alkene, ethene, to give the intermediate methyl methacrylate, which is used in the synthesis of plastics. More recently, alkenes such as vinyl acetate have been shown to undergo methoxycarbonylation to generate intermediates that are themselves useful as green solvents (low-volatility/biodegradable) or as monomers for the formation of biodegradable polymers. These have the potential to replace traditional materials such as polystyrene or polythene. Methoxycarbonylation of butadiene promises a new route to adipic acid, one of the co-monomers involved in the manufacture of nylon. As yet the methoxycarbonylation of vinyl acetate and butadiene have not been optimised and greater insight into these reactions is required before effective industrial processes are in place.A key issue that remains to be solved in the methoxycarbonylation reaction is the detailed mechanism by which the products are released - the so-called methanolysis step. There a several possibilities for this process, however, it is extremely difficult to obtain information on this from experiment as the reaction itself is incredibly fast. In these circumstances the use of computational modelling comes into its own, as this can readily provide information on the energies of the species involved in reactivity. The methanolysis reaction is, however, very complicated and is strongly dependent on the precise nature of the reacting species and the nature of the solvent being used. To obtain reliable modelling data these factors must be taken into account, a fact that makes the task of modelling these systems very challenging.This proposal seeks to use high level computational modelling to assess the mechanism of the methanolysis on the simplest methoxycarbonylation system - ethene/CO/MeOH - and the most effective Pd catalysts. Our approach will be to employ hybrid calculations where the catalyst and reacting molecules are dealt with at a high level of theory (density functional theory) but the solvent molecules (many 10s or hundreds) are treated at a lower level of theory based on classical force fields. Through this approach the effect of the solvent on the reactivity at the Pd catalyst will be taken into account and we aim to provide extremely reliable data to define the preferred mechanism. We will test our approach by comparing with an alternative catalyst which displays a different reactivity, thus giving a stringent test of our modelling approach.Once we have defined the correct way to treat these complicated reactions - as well as the mechanism by which methanolysis occurs - we will be in a position to tackle the new reactions of vinyl acetate and butadiene. We hope to provide sufficient insight into these processes that experimental chemists will be able to design new improved catalysts for more efficient methoxycarbonylation of these feedstocks on an industrial scale.