42 research outputs found

    Closed-Loop Recyclable Poly(imine-acetal)s with Dual-Cleavable Bonds for Primary Building Block Recovery

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    Chemical recycling offers a promising solution for the end-of-life treatment of synthetic polymers. However, the efficient recovery of well-defined recycled building blocks continues to be a major challenge, especially for crosslinked thermosets. Here, we developed vanillin-based polymer networks functionalized with dual-cleavable imine and acetal bonds that facilitate chemical recycling to primary building blocks and their convenient separation at the molecular level. A library of crosslinked poly(imine-acetal)s was synthesized by combining the in-bulk synthesized liquid di-vanillin acetal monomer (DVA) with commercially available liquid di- and triamines under solvent-free conditions. These thermosets showed tailor-made thermal and mechanical properties along with outstanding chemical recyclability. Under aqueous acidic conditions, poly(imine-acetal)s selectively and completely disintegrate into small molecules. During the polymer design stage, these compounds were carefully selected to enable facile separation without tedious techniques. As a result, the primary building blocks were isolated in high yields and purity and immediately reused to produce fresh polymers with identical thermomechanical properties. Since our "design for recycling" concept aims at obtaining the primary building blocks rather than monomers after depolymerization, a plethora of possibilities are unlocked to utilize these chemical resources, including closed-loop recycling as portrayed

    Epoxy Thermosets Designed for Chemical Recycling

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    Epoxy thermosets constitute a significant portion of high-performance plastics, as they possess excellent thermal and mechanical properties that are applicable in a wide range of industries. Nevertheless, traditional epoxy networks show strict limitations regarding chemical recycling due to their covalently crosslinked structures. Although existing methods provide partial solutions for the recycling of epoxy networks, it is urgent to develop more effective, sustainable, and permanent strategies that will solve the problem at hand. For this purpose, developing smart monomers with functional groups that enable the synthesis and development of fully recyclable polymers is of great importance. This review highlights recent advancements in chemically recyclable epoxy systems and their potential to support a circular plastic economy. Moreover, we evaluate the practicality of polymer syntheses and recycling techniques, and assess the applicability of these networks in industry

    Photoredox-Catalyzed Reduction of Halogenated Arenes in Water by Amphiphilic Polymeric Nanoparticles

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    The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare the activity of two established organic photoredox catalysts, one based on 10-phenylphenothiazine (PTH) and one based on an acridinium dye (ACR), in the light-activated dehalogenation of aromatic halides in pure water. Both PTH and ACR were covalently attached to amphiphilic polymers that are designed to form polymeric nanoparticles with hydrodynamic diameter DH ranging between 5 and 11 nm in aqueous solution. Due to the hydrophobic side groups that furnish the interior of these nanoparticles after hydrophobic collapse, water-insoluble reagents can gather within the nanoparticles at high local catalyst and substrate concentrations. We evaluated six different amphiphilic polymeric nanoparticles to assess the effect of polymer length, catalyst loading and nature of the catalyst (PTH or ACR) in the dechlorination of a range of aromatic chlorides. In addition, we investigate the selectivity of both catalysts for reducing different types of aryl-halogen bonds present in one molecule, as well as the activity of the catalysts for C-C cross-coupling reactions. We find that all polymer-based catalysts show high activity for the reduction of electron-poor aromatic compounds. For electron-rich compounds, the ACR-based catalyst is more effective than PTH. In the selective dehalogenation reactions, the order of bond stability is C-Cl > C-Br > C-I irrespective of the catalyst applied. All in all, both water-compatible systems show good activity in water, with ACR-based catalysts being slightly more efficient for more resilient substrates

    Photocatalysis as an Effective Tool for Upcycling Polymers into Value-Added Molecules

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    Shaping a sustainable future is closely tied to the development of advanced plastic recycling technologies. As global recycling rates remain low, the lion's share of post-consumer plastics is either incinerated or disposed of in landfills. This unbalanced plastic waste management not only poses severe environmental risks, but also entails an irrevocable loss of chemical resources that are embedded in synthetic polymers. To give plastic waste a new life, a series of photocatalytic methods has recently been reported that convert polymers directly into value-added organic molecules. These approaches operate at ambient temperature, show high reactivity/selectivity, and provide alternative reaction pathways as compared to thermal depolymerizations. This Minireview highlights the scientific breakthroughs in upcycling polymers through state-of-the-art photocatalysis under environmentally benign conditions.</p

    Eisenreich, Fabian

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    Biorenewable circularity aids sustainability of plastics

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    Closed-loop recycling of plastics is a key technology for a sustainable future. Researchers have now created biorenewable plastics that outperform fossil-based analogues and meet criteria for circularity

    Direct C-H trifluoromethylation of (hetero)arenes in water enabled by organic photoredox-active amphiphilic nanoparticles

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    Photoredox-catalyzed chemical conversions are predominantly operated in organic media to ensure good compatibility between substrates and catalysts. Yet, when conducted in aqueous media, they are an attractive, mild, and green way to introduce functional groups into organic molecules. We here show that trifluoromethyl groups can be readily installed into a broad range of organic compounds by using water as the reaction medium and light as the energy source. To bypass solubility obstacles, we developed robust water-soluble polymeric nanoparticles that accommodate reagents and photocatalysts within their hydrophobic interior under high local concentrations. By taking advantage of the high excited state reduction potential of N-phenylphenothiazine (PTH) through UV light illumination, the direct C−H trifluoromethylation of a wide array of small organic molecules is achieved selectively with high substrate conversion. Key to our approach is slowing down the production of CF 3 radicals during the chemical process by reducing the catalyst loading as well as the light intensity, thereby improving effectiveness and selectivity of this aqueous photocatalytic method. Furthermore, the catalyst system shows excellent recyclability and can be fueled by sunlight. The method we propose here is versatile, widely applicable, energy efficient, and attractive for late-stage introduction of trifluoromethyl groups into biologically active molecules

    Compartmentalized Polymers for Catalysis in Aqueous Media

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    The field of polymer science has advanced to a point where precise control over a polymer's chain length, dispersity, and microstructure permits to access compartmentalized polymers that catalyze a range of reactions efficiently and selectively in aqueous media. We here summarize how we unveiled the relation between the primary structure of amphiphilic polymers and their folding/collapse processes into compartmentalized structures in water. In addition, we discuss how these insights allowed us to access active catalysts that function in water and complex cellular media. After obtaining profound knowledge, we achieved enzyme-like activity and selectivity in these synthetic catalytic systems and improved their stability in complex media. We envisage that polymer-based catalytic systems will become accessible that cooperate in concert with enzymes for multistep cascade catalysis in water or induce novel ways to activate drugs in diseased tissue.</p

    Electronic Activity Tuning of Acyclic Guanidines for Lactide Polymerization

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    Novel aromatic guanidine-based organocatalysts for the ring-opening of l-lactide were synthesized and applied in comprehensive polymerization experiments and kinetic studies. The introduction of electronically active substituents led to a significant change in activity by 2 orders of magnitude. The formed polylactide is featured with narrow polydispersity and high end-group fidelity, both characteristics that are typical for living polymerizations. Besides that, using linear free-energy relationships and DFT calculations revealed new insights into the polymerization mechanism. The formation of an adduct consisting of the catalyst and initiator/chain end turned out to be the rate-limiting step

    Closed-Loop Recyclable High-Performance Polyimine Aerogels Derived from Bio-Based Resources

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    Organic aerogels are an intriguing class of highly porous and ultralight materials which have found widespread applications in thermal insulation, energy storage, and chemical absorption. These fully cross-linked polymeric networks, however, pose environmental concerns as they are typically made from fossil-based feedstock and the recycling back to their original monomers is virtually impossible. In addition, organic aerogels suffer from low thermal stability and potential fire hazard. To overcome these obstacles and create next-generation organic aerogels, a set of polyimine aerogels containing reversible chemical bonds which can selectively be cleaved on demand is prepared. As precursors, different primary amines and cyclophosphazene derivatives made from bio-based reagents (vanillin and 4-hydroxybenzaldehyde) to elevate the thermal stability and reduce the environmental impact are used. The resulting polyimine aerogels exhibit low shrinkage, high porosity, large surface area, as well as pronounced thermal stability and flame resistance. More importantly, the aerogels show excellent recyclability under acidic conditions with high monomer recovery yields and purities. This approach allows for preparation of fresh aerogels from the retrieved building blocks, thus demonstrating efficient closed-loop recycling. These high-performance, recyclable, and bio-based polyimine aerogels pave the way for advanced and sustainable superinsulating materials
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