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Towards Next-generation Eco-efficient PHOTO and EMULSION Polymerisations Imparting Synergy to Process, Products and Applications

Periodic Reporting for period 1 - PHOTO-EMULSION (Towards Next-generation Eco-efficient PHOTO and EMULSION PolymerisationsImparting Synergy to Process, Products and Applications)

Reporting period: 2017-10-01 to 2019-09-30

The polymer industry is going through one of the most significant periods of change in its history. Driven by new environmental regulations, the development of eco-efficient processes and zero-VOC products has become an absolute necessity. In this field, 2 technologies stand out: Polymerisation in dispersed media and Photopolymerisation. To maintain EU leadership in this sector, PHOTO-EMULSION aims at training a next-generation of 8 Early-Stage Researchers (ESRs) who can push towards new eco-friendly polymerisation processes. Our primary strength is a demanding technical knowledge base bringing together, for the first time, all disciplines related to these 2 strategic fields. Secondly, we will broaden traditional doctoral training by targeting transferable and specialized skills sought after by the employers, and learned through innovative methods: tandem ESRs, distance language learning, ESR as itinerant science educator, online courses, ESR-led subproject, highly interactive meetings, and industrial secondments. In research, we will develop a “hybrid” next-generation technology based on thiol-ene photopolymerisation in dispersed media. Advanced manufacturing based on photoreactor promises a wave of high sulfur content dispersed products (films, nanoparticles, porous network). Their outstanding properties open the door to applications responding to current industrial needs such as non-leaching materials, O2 barrier and biobased waterborne coatings, biologically-active particles, hybrid nanosensors and monolithic chromatography column.
PHOTO-EMULSION is a EU-funded Innovative Training Network (ITN) project of the H2020 programme. Led by Institut de Science des Matériaux de Mulhouse in France (Coordinator: Dr. Abraham Chemtob), it involves a high-quality research network including 8 internationally reputed academic institutions, 5 leading companies and 2 non-profit organisations. Balanced & EU-wide, its diversity expresses through the participation of 8 countries (Austria, France, Germany, Ireland, Poland, Slovenia, Sweden & Spain), 50% female scientists-in-charge, and structures supporting gender equality.
During the first reporting period, PHOTO-EMULSION has established a range of novel zero-VOC technologies based on thiol-ene photopolymerisations in dispersed media. Miniemulsion and emulsion thiol-ene photopolymerisations have resulted in a new portfolio of waterborne sulfur polymer dispersions whereas conventional latexes are essentially based on acrylics. In these process, the ability to harness the inherent advantages of light over heat for creating the initiating radicals has enabled to achieve temporal control, and tune reaction rates and molecular weights through irradiation intensity, dose, and duration. In addition, thiol or ene functionalization of particle surface has opened the door to highly functional particles whose surface has been decorated by biologically-active ligands. The advantage of this ultrafast thiol-ene technology has gone beyond latex, surfactant-free powder nanoparticles were obtained via aerosol photopolymerisation while porous structures have derived from thiol-ene high internal phase emulsions (HIPE) via a templating approach. A final major innovation of PHOTO-EMULSION has been the development of novel LED photoreactors.
The next technological frontiers in green polymerisation will be opened by understanding and optimizing combinations of already well-established eco-efficient technologies ─ such as polymerisation in dispersed media and phototopolymerisation ─ and their synergistic function. The research and training program in PHOTO-EMULSION offers a holistic approach to improving photopolymerisation in dispersed media, leading to characterization and development that will enable engineering ‘smart’ dispersed sulfur materials with new functionalities and eco-efficient products and applications. The novel dispersed polysulfide materials will be able to provide answers to contemporary challenges in 6 different applications. As the monomer rapidly disappears in a step-growth mechanism far before high conversion, there is no residual (toxic) monomer in the final latex, opening the door to non-leaching waterborne coatings. Highly crystalline polysulfide films can become the next generation oxygen high barrier waterborne coating for plastic packaging. Compared to vinylidene chloride copolymer latex (PVDC), the industrial standard, our technology is chlorine-free and yields smarter coatings featuring not only passive barrier (crystalline domains), but also additional active barrier (self-healing action) due to intrinsic sulfur antioxidant properties. Novel biobased decorative coating can result from thiols’ addition across a host of internal polyunsaturated natural resources (terpene, fatty acid, natural latex), normally poorly reactive in a chain-growth process. Sulfur has a unique affinity for noble metals, which will create Ag@ and Au@ hybrid dry nanoparticle for diagnostics, such core-shell morphology is difficult to attain by conventional wet techniques. In the field of chromatography, emulsion templated macroporous sulfur-based polyHIPE can challenge the existing stationary phases based on packed silica particles thanks to, firstly, 3D printing (layer-by-layer photopolymerisation) as advanced manufacturing technology allowing on-demand production, and secondly, easy and reproducible functionalization so that the porous surface is varied to suit the individual separation application. Finally, biologically-active particles can be obtained by adsorbing or covalently binding proteins on the surface of the functionalized thiol-ene polymer nanoparticles.
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