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European Joint Doctorate in Organocatalysis and Sustainable Polymers

Periodic Reporting for period 2 - SUSPOL (European Joint Doctorate in Organocatalysis and Sustainable Polymers)

Reporting period: 2017-01-01 to 2018-12-31

SUSPOL-EJD is an European Joint Doctorate in “Organocatalysis and Sustainable Polymers”. SUSPOL-EJD is set up by a consortium formed by four Academic beneficiaries: University of Bordeaux (FR), University of the Basque Country (SP), University of Mons (B) and University of Warwick (UK). Furthermore, six industrial organizations: BASF (D), Purac Corbion (NL), Critical Pharma (UK), Synthomer (UK), IBM (CH and USA) and FORESA (SP) will act as partners collaborating in the research and training activities. SUSPOL-EJD will offer to 10 early stage researchers the possibility of being awarded with double doctoral degrees in two different countries. SUSPOL-EJD will aim at excellence in developing high quality training opportunities for early stage researchers in the area of Sustainable Organocatalysis and Polymers. The final objective is to create scientists who will be the future leaders to make the transition of organocatalysis between the lab and sustainable industrial processes and products. Research and training areas include organic chemistry, catalysis, modelling, polymer engineering, green chemistry, sustainable processes, renewable products, polymer latexes, coatings, biomaterials, pharmaceutical and adhesives. The presence of a high number of industrial partners makes the project highly intersectoral. The research and training programme is very innovative combining frontier research projects and industrial developments.
Within this reporting period, the project has progressed smoothly and mostly according to Annex I, with some minor deviations. Within the first 12 months of the project and in line with Annex I, the ten ESRs had been recruited and all of them were enrolled in the PhD Programme of their respective Universities. One of the key parts of the project was the signature of an agreement to award joint doctorates, which was successfully signed before the end of the first year. In this agreement, the beneficiaries negotiated the requirements to deliver the double or joint doctorate. Hence, each ESR was first registered on the Doctoral programme at the Primary University and shortly thereafter registered at the Secondary University, within the first academic year and according to the procedure and registration periods established at each University. Thus, ESR1 has been successfully enrolled in the PhD program of the University of the Basque Country (UPV/EHU) and the University of Mons (UMons), ESR2 has been successfully enrolled in the PhD program of UPV/EHU and University of Bordeaux (UB); ESR3 and ESR 5 have been enrolled in the PhD program of UPV/EHU and Warwick University (Warwick), ESR 4 and ESR 10 have been enrolled in UMons and Warwick, ESR 6 and ESR 7 have been enrolled in UB and Warwick and ESR 8 and ESR 9 have been enrolled in UB and Mons. In this first 2 years of the project, some initial results have been obtained by the ESRs. The ESRs have progressed in the preparation of new organocatalysis for the polymerization of cyclic esters and amides based on frustrated ion pairs and bronsted acid and bronsted bases. In addition, they have been able to design new catalyst able to promote the stereocontrol polymerization from racemic mixture. The ESR´s using modelling tools have been able to investigate which factors are dominating the polymerization process, which can help to the design of more appropriate polymerizations. The ESRs have also progressed smoothly in the preparation of nanoreactors. These nanoreactors containing an organocatalysts can be used to promote different polymerization directly in aqueous media in the absence of organic solvents.
SUSPOL-EJD will offer a unique combination of local specialist training and network-wide interdisciplinary/intersectorial training to researchers in the first stage of their scientific careers in the emerging field of Organocatalysis and Sustainable Polymers. The final goal will be to improve the career prospects of the ESRs as quality researchers, by setting up a joint doctoral programme and to prepare them for positions in industry and academia. SUSPOL-EJD consortium brings together world leading European groups carrying out research at the frontier of knowledge and industrial players.

Different areas were identified where there was some existing state-of-the-art but the progress was not sufficient to address current challenges.

1) One of the limitations of organocatalysis is the low thermal stability of the organic catalyst to be used at high temperatures. Most of the industrial processes of commodity polymers require the utilization of temperature close to 200 ºC to be able to polymerize the monomers in efficient yields and to get appropriate viscosities for the preparation of different parts with different shape and morphologies. The ESRs of SUSPOL have gone beyond the state of the art because they have been able to use protic ionic liquids as catalysts able to resist temperatures above 200 ºC.

2) The second challenge in organocatalyzed polymerizations is to be able to prepare new catalyst families for the stereocontrol polymerization of polymers. Stereocontrol is an important feature of polymers; the stereoregularity is a necessary condition for crystalline polymers. Given the excellent performance and almost limitless opportunities of ligand/metal combinations, it is not surprising that transition metals and organometallic catalysts have dominated the field of stereocontrolled polymerization. In this sense, SUSPOL ESRs have been able to design two new catalyst families able to promote the stereochemical outcome from racemic mixture at room temperature.

3) Another important factor that has been raised by the society is the utilization of renewable feedstocks to prepare plastics. Most of the plastics are generated using fossil fuel resources, which is known that are limited. ESR from SUSPOL are designing new routes for the valorization of CO2. In the last decade many efforts have been made to use CO2 for the production of monomers and polymers but mainly employing metal catalysts. SUSPOL ESR have been able to design both new organocatalysis to improve the CO2 fixation into epoxides for the preparation of cyclic carbonates and also organocatalysts able to promote the copolymerization of epoxides and CO2 in situ to generate high added value polymers.

4) One of the open challenges in organocatalyzed polymerizations is to be able to efficiently promote polymerizations in aqueous media. Organic compounds such acids and bases are usually deactivated in aqueous conditions and therefore their utilization in water has been limited. One possibility to facilitate their utilization in aqueous media is the incorporation of an organocatalyst inside a polymer chain able to nano-assemble in aqueous media. In this way, hydrophobic nano-pockets dispersed in aqueous media can be generated, which can allow the direct polymerization in water.

All these being said, it is clear that ESRs from SUSPOL-EJD project are going beyond the state of the art in different areas related to organocatalyzed polymerizations and these results will have a tremendous socio economical impact.