Singapore

Sulfur-containing polymer is promising to the application of the optical, anti-corrosion and antifouling materials. Using sulfur-containing C1 building blocks [i.e. carbonyl sulfide (COS), carbon disulfide (CS2)] to copolymerize with epoxides have been rapidly developed in our group and others. This talk reports two metal-free routes for the reaction of COS with epoxides.
1) The inhibition of oxygen-sulfur exchange reaction (O-S ER)1 for synthesizing poly(monothiocarbonate)s. Two types of organocatalysts will present, one is the combination of Lewis bases including amidine, guanidine, or quaternary onium salts with triethyl borane.2 A highly transparent and colorless poly(monothiocarbonate)s are obtained with &gt; 99% tail-to-head content and high Mns of up to 92.5 kg/mol. O-S ER that would generate random thiocarbonate and carbonate units, were totally suppressed in most instances. The turnover frequency (TOF) of these Lewis pairs are as high as 240 h-1 at ambient temperature. The other is the combination of organic bases and thioureas via cooperative catalysis.3 Poly(monothiocarbonate)s are obtained with 100 % alternating degree, &gt; 99% tail-to-head content, high Mns of up to 98.4 kg/mol and narrow molecular weight distributions (1.13-1.23). TOFs of the catalysts are up to 112 h−1 at 25 °C. 
2) The utilization of O-S ER for synthesizing poly(thioether)s using COS and epoxides as the starting materials.4 This route undergoes the coupling reaction of COS with epoxides, decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing CO2(a little bit COS). And this method is also applied to the reaction of carbon disufide with epoxides, providing a new pathway to produce COS and poly(thioether)s simultaneously. 
Finally, we’ll present the transformation of poly(monothiocarbonate)s to poly(thioether)s by using O-S ER process, which is a polymer A to polymer B method for recycling the polymers.

MATERIALS FOR HUMANITY (MH 21)

Organocatalytic Synthesis of Sulfur-containing Polymers

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MH 21 is arranged around 6 themes that focus attention on pressing needs that should be addressed to enhance the well-being of communities and provide a forum for presenting breakthrough discoveries.

Sulfur-containing polymer is promising to the application of the optical, anti-corrosion and antifouling materials. Using sulfur-containing C1 building blocks [i.e. carbonyl sulfide (COS), carbon disulfide (CS2)] to copolymerize with epoxides have been rapidly developed in our group and others. This talk reports two metal-free routes for the reaction of COS with epoxides.
1) The inhibition of oxygen-sulfur exchange reaction (O-S ER)1 for synthesizing poly(monothiocarbonate)s. Two types of organocatalysts will present, one is the combination of Lewis bases including amidine, guanidine, or quaternary onium salts with triethyl borane.2 A highly transparent and colorless poly(monothiocarbonate)s are obtained with > 99% tail-to-head content and high Mns of up to 92.5 kg/mol. O-S ER that would generate random thiocarbonate and carbonate units, were totally suppressed in most instances. The turnover frequency (TOF) of these Lewis pairs are as high as 240 h-1 at ambient temperature. The other is the combination of organic bases and thioureas via cooperative catalysis.3 Poly(monothiocarbonate)s are obtained with 100 % alternating degree, > 99% tail-to-head content, high Mns of up to 98.4 kg/mol and narrow molecular weight distributions (1.13-1.23). TOFs of the catalysts are up to 112 h−1 at 25 °C. 
2) The utilization of O-S ER for synthesizing poly(thioether)s using COS and epoxides as the starting materials.4 This route undergoes the coupling reaction of COS with epoxides, decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing CO2(a little bit COS). And this method is also applied to the reaction of carbon disufide with epoxides, providing a new pathway to produce COS and poly(thioether)s simultaneously. 
Finally, we’ll present the transformation of poly(monothiocarbonate)s to poly(thioether)s by using O-S ER process, which is a polymer A to polymer B method for recycling the polymers.

technical paper

Composites, and especially carbon fibre reinforced plastics (CFRP), have impressively demonstrated their mechanical performance in several applications in the last years, starting from aerospace, finding their way into sports and commodities and just recently having a significant increase in the wind energy sector. These materials are often referred to as “a material with high potential”. The question is: potential to what? The potential to be a solution to the CO2-problem due to lightweight construction capabilities and the possibility to contribute to fuel savings during the lifetime of an aircraft, a truck or a car, to provide clean energy with more efficient next-gen wind turbines? Or is it the potential to be part of the problem, as the material is very difficult to recycle and currently causes trouble in waste incineration plants and in many cases just ends up in landfills. The presented talk will address the state of the art of recycling CFRP-materials: in a first step the different components of the materials (fibres and plastics, the so called matrix) need to be separated. This can be done via pyrolysis on a commercial scale, or by different alternatives with lower TRL levels. After that the recovered fibres are processed into semi-finished products, such as nonwovens, that are suitable to replace the first-gen materials in terms of handling and processing. All along the way, it is necessary to monitor the properties of the materials, in order to be able to identify correlations of process-parameters and resulting properties, both for quality assurance in a future supply chain, as well as identification of further demand for continuing R&D-activities. Finally, the stakeholders in a circular economy are adressed: why should a company invest in the improvement of recycle-ability of their products? This discussion is not limited to CFRP-materials only, but is open to interaction with other material classes with emerging circularity.

Recycling of fibre reinforced plastics - state of the art and outlook

Flexible electronics are of critical importance for medical devices, portable electronics, smart textiles, energy storage, communication and sensor systems [1,2]. However, the lifetime of electronics is becoming shorter, which poses a growing ecological problem. Therefore, it is urgent and necessary to find sustainable and cost-efficient materials to replace the crude oil-derived polymers that are commonly used in flexible electronics. To this end, fish gelatin (FG) extracted from fish scales could provide an eco-friendly and biodegradable alternative to plastic for use in flexible electronics. Fish scales are inedible and malodorous kitchen waste, and >2 million metric tons of fish scales are discarded each year. This talk will introduce our recent works on FG-based flexible electronics, including flexible electroluminescent devices and triboelectric nanogenerators (TENGs) [3-6]. The properties of FG films, the structure design and the performance of flexible electronic devices will be briefly discussed. These works may pave a new way to green and sustainable flexible electronics.

References
1. S. Xu, A. Jayaraman, J. A. Rogers. Skin sensors are the future of health care. Nature, 2019, 571, 319-321.
2. G.-H. Lee, H. Moon, H. Kim, G. H. Lee, W. Kwon, S. Yoo, D. Myung, S. H. Yun, Z. Bao, S. K. Hahn. Multifunctional materials for implantable and wearable photonic healthcare devices. Nat. Rev. Mater., 2020, 5, 149–165.
3. X. P. Zhang, T. Y. Ye, X. H. Meng, Z. H. Tian, L. H. Pang, Y. J. Han, H. Li, G. Lu, F. Xiu, H. D. Yu, J. Q. Liu, W. Huang. Sustainable and transparent fish gelatin films for flexible electroluminescent devices. ACS Nano, 2020, 14, 3876-3884.
4. T. F. Jiang, X. H. Meng, Z. Zhou, Y. Y. Wu, Z. H. Tian, Z. D. Liu, G. Lu, M. Eginlidil, H. D. Yu, J. Q. Liu, W. Huang. Highly flexible and degradable memory electronics comprised of all-biocompatible materials. Nanoscale, 2021, 13, 724-729.
5. Y. J. Han, Y. F. Han, X. P. Zhang, G. Lu, H. D. Yu, W. Huang. Fish gelatin-based triboelectric nanogenerator for harvesting biomechanical energy and self-powered sensing of human physiological signals. ACS Appl. Mater. Interfaces, 2020, 12, 16442-16450.
6. Q. Z. Sun, H. C. Wang, L. Wang, X. P. Yue, L. R. Zhang, G. Z. Ren, D. H. Li, Y. J. Han, L. L. Xiao, G. Lu, H. D. Yu, W. Huang. Fully sustainable and high-performance fish gelatin-based triboelectric nanogenerator for wearable movement sensing and human-machine interaction. Nano Energy, in revision.

Sustainable Flexible Electronics Based on Fish Gelatin

Chitin is the second most abundant biopolymer, after cellulose. It is present in the shell of crustaceans, in the cuticle of insect and even in some fungi. Chitin can be converted into chitosan, a highly praised material in the biomedical sector for its antibacterial properties, which finds also important application as a fertilizer, water treatment flocculant and food additive. Yet today's technologies for chitosan production from biomass rely on the use of corrosive treatments, high energy input and large quantities of by product effluents. Herein we are presenting our group's effort to tackle this question. We showed that mechanochemistry and aging could be used effectively for the deacetylation of chitin.1 This process yielded high molecular weight chitosan with minimal use of energy and solvent. This method is versatile and applicable to a number of chitin sources, including crude crustacean and insect shells, yielding deacetylation up to 98% and remarkably high molecular weights. This process affords chitosan in a safer fashion and with less materials and energy usage compared to the classic hydrothermal one. We have also extended this method to the fabrication of chitosan nanocrystals from chitin nanocrystals.2 Chitin and chitosan nanocrystals featured enhanced properties are nanocatalysts supports.3,4 We have also developed hydrogels from chitosan and chitin nanocrystals, with exceptional gelling properties and demonstrated their applicability for slow drug release.

Upcycling biomass: from crustacean waste to functional materials

Biopolymers such as chitosan, cellulose and alginate from biomass have demonstrated huge potential in many important and rapidly growing applications, it is always challenging to create advanced biopolymer materials cost-effectively. Herein, we present our progress in preparing a series of biopolymer composite materials with unexpected properties using a facile “dry”, thermomechanical method. Chitosan/CMC composite films created in this way showed much better hydrolytic stability, compared to chitosan-only films. This is so despite inclusion of the CMC in the chitosan matrix even increasing the surface hydrophilicity. We propose that our processing method led to the polyelectrolyte complexation between chitosan and CMC generating physical crosslinking points in the materials. These crosslinks stabilised the films in water although hydration disrupted hydrogen bonding between polysaccharide chains leading to dramatically decreased tensile strength and increased elongation at break. 
Besides, we found chitosan/silk peptide (SP) polyelectrolyte-complexed materials prepared in the same way had extraordinary mechanical properties. Moreover, we prepared chitosan/alginate composites using the same processing protocol and demonstrate that inclusion of graphene oxide could enhance polysaccharide plasticisation, leading to enhanced mechanical properties and surface hydrophobicity. 
The method of materials hybridisation without chemical reactions demonstrated in this work could provide an insight into the development of cost-effective biopolymer materials with competitive properties as plastic replacements in certain applications, where biodegradability, biosafety, and biocompatibility are indeed required (e.g. functional food packaging and antimicrobial wound healing).

Thermomechanically Processed, Polyelectrolyte-Complexed Polysaccharide Composites with Enhanced Hydrolytic Stability and Mechanical Properties

Plastics have become indispensable in the modern society. However, plastics pollution has also become a global environmental crisis that is projected to grow. The most common approaches to manage plastics pollution include mechanical recycling and pyrolytic waste-to-energy processes, but these methods inevitably lead to the increase in greenhouse gas emissions. In this presentation, I will summarize my team’s early contributions to using exclusively Earth-abundant elements and renewable energy to upcycle plastics. In particular, I plan to focus on our efforts at applying molecular vanadium complexes for selective, ambient condition, photoredox C-C cleavage reactions.1 We conducted detailed kinetic measurements to identify the fastest catalyst and the critical functional groups required in the substrates.2 The vanadium photocatalysts were then utilized for the C-C bond cleavage and oxygenation of over 30 substrates, including unactivated, commercially sourced alcohols and even non-biodegradable plastics.3-6 

Figure 1. Photocatalytic upcycling of non-biodegradable polyethylene to formic acid, a liquid organic hydrogen carrier as a fuel.

References
1. Gazi, S.; Ng, W. K. H.; Ganguly, R.; Moeljadi, A. M. P.; Hirao, H.; Soo, H. S. Chem. Sci. 2015, 6, 7130-7142.
2. Gazi, S.; Dokić, M.; Moeljadi, A. M. P.; Ganguly, R.; Hirao, H.; Soo, H. S. ACS Catal. 2017, 7, 4682-4691.
3. Gazi, S.; Dokić, M.; Chin, K. F.; Ng, P. R.; Soo, H. S. Adv. Sci. 2019, 6, 1902020.
4. Dokić, M.; Chin, K. F.; Soo, H. S. Trends Chem. 2020, 2, 485-488.
5. Zhao, X.; Boruah, B.; Chin, K. F.; Dokić, M.; Modak, J. M.; Soo, H. S. Adv. Mater. 2021, in press.
6. Estahbanati, M. R. K; Kong, X. Y.; Eslami, A.; Soo, H. S. ChemSusChem, 2021, in press.

Photocatalytic Upcycling to Sustainably Reuse Plastics

High dielectric constant and low dielectric loss are desirable electrical properties for next generation polymer films for capacitive energy storage. Unfortunately, the dielectric constant of polymers is often limited to 2-5, much lower than that of inorganic dielectrics, because of the nature of hydrocarbon covalent bonds for electronic and atomic polarizations. It is essential to understand the fundamental physics of different types of polarization and the associated loss mechanisms in polymers. Among various approaches for high dielectric constant and low loss polymers, the multilayer film technology is of particular interest because a multilayer film is a unique one-dimensional system with tailored material choices, layer thicknesses, and interfaces. By minimizing the disadvantageous polarizations and enhancing the advantageous polarizations, multilayer films hold promise as advanced dielectrics for future polymer film capacitors.

High Energy Density and High Temperature Multilayer Polymer Films for Capacitive Energy Storage

The continuing growth of membrane technologies for water, solvent and gas separations, as well as other applications, has advanced significantly in the past few decades. However, the short durability of polymeric membranes, which wear out due to continuous fouling cycles and chemical cleaning, is increasingly becoming a waste disposal issue. The purpose of this presentation is to provide an overview of the environmental, energy and economic challenges and possible advantages of implementing sustainable processes in membrane manufacturing, evaluating the sustainability of membrane life-cycle and defining some end-of-life approaches such as reuse, repurposing and recycling. A bird’s eye review of the existing membrane challenges, state-of-art and potential sustainable solutions will be discussed in this presentation with examples from the literature.

Perspectives of sustainable development, life cycle and end of life in polymeric membranes

Membrane separations consume less than 90% of the energy required in incumbent industrial separation processes (absorption, distllation etc), and is widely considered as a "green" alternative for industrial separations. However, the manufacturing process of polymer membranes negates the "green" benefits of low energy. This is due to the mandatory use of oil-derived plastics and hazardous solvents e.g. NMP and n-hexane. At the Scale-Up Lab at The University of Edinburgh, we have deployed Green Chemistry concepts in tandem with additive manufacturing to imbue sustainability into polymer membrane fabrication. In this presentation, I will share with you key aspects of our work, including recycling plastic waste into high performance additives for mixed matrix membranes and replacing oil-derived plastics and overcoming the use of hazardous solvents in thin-film composite membrane fabrication.

Replacing plastics and hazardous solvents in polymer membrane fabrication

Repurposing of FRP Composites Using Next-Generation Technology


The needed massive deployment of lithium ion batteries (LIBs), in particular to satisfy the demand from the Electric Vehicle sector, encourage battery manufacturers to multiply the number of giga-factories to reduce the cost of production. Such a production consists of a complex process involving multiple steps, such as the slurry preparation, its coating, drying, calendering, electrolyte filling and formation. The choice of the manufacturing parameters along the process strongly impact the overall LIB cell performance. However, the optimization of the manufacturing parameters to obtain the desired characteristics of LIB cells is currently based on a forward "trial and error" approach. This approach is inefficient in terms of time and cost due to the infinite number of possibilities for adjusting the manufacturing parameters. The integration of Industry 4.0 concepts into giga-factories such as Artificial Intelligence (AI) and multiscale modeling is essential to accelerate the manufacturing process optimization and significantly raise the work efficiency of scientists, engineers and production line operators. Here I present our efforts in developing a digital twin of battery manufacturing [1], supported on a combination of physical and AI/machine learning models trained with data arising from in house high throughput characterizations. This digital twin allows simulating the different steps along the manufacturing process, predicting the resulting electrode properties and evaluating the associated electrochemical performance upon battery cell cycling. The predictive capabilities of this digital twin are illustrated with results for different electrode formulations, paving the way towards manufacturing digital optimization. Finally, data standardization challenges to ease the wide use of these tools in the battery field will be briefly discussed.

[1] www.erc-artistic.eu 


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