Polymeric bis(triphenylphosphine)iminium chloride as a recyclable catalyst.

Metal-free catalysts have garnered considerable interest as an environmental and economical alternative to precious metal catalysts. Bis(triphenylphosphine)iminium chloride (PPNCl) has emerged as a prominent choice due to its air and thermal stability and broad reactivity, especially in applications where a bulky cation is needed. The high phosphorus content and synthetic effort required for catalyst synthesis increase environmental impact; the recyclability of PPNCl in catalytic processes remains largely unexplored. The potential development of a polymer-supported PPNCl catalysts therefore desirable to enable this recyclability. In this work, we synthesise polymeric PPNCl (poly(PPNCl)) for the first time. Poly(PPNCl) demonstrates a comparative catalytic reactivity to its small molecule variant when employed as a catalyst in halogen-exchange reactions and CO2/epoxide coupling. For the latter the effect of catalyst loading, CO2 pressure, reaction time and addition of co-catalyst on conversion and selectivity was investigated. Poly(PPNCl) was easily recovered from the crude product by simple precipitation and its catalytic reactivity was well-maintained over three reaction cycles, providing environmental and economic advantages for sustainable reaction development.

Mechanical Properties and Recyclability of Fiber Reinforced Polyester Composites.

Fiber reinforced polymer composites (FRPs) are valuable construction materials owing to their strength, durability, and design flexibility; however, conventional FRPs utilize petroleum-based polymer matrices with limited recyclability. Furthermore, fiber reinforcements are made from nonrenewable feedstocks, through expensive and energy intensive processes, making recovery and reuse advantageous. Thus, FRPs that use biobased and degradable or reprocessable matrices would enable a more sustainable product, as both components can be recovered and reused. We previously developed a family of degradable and reprocessable cross-linked polyesters from bioderived cyclic esters (l-lactide, δ-valerolactone, and ε-caprolactone) copolymerized with a bis(1,3-dioxolan-4-one) cross-linker. We now incorporate these networks into FRPs and demonstrate degradability of the matrix into tartaric acid and oligomers, enabling recovery and reuse of the fiber reinforcement. Furthermore, the effect of varying comonomer structure, catalyst, reinforcement type, and lay-up method on mechanical properties of the resultant FRPs is explored. The FRPs produced have tensile strengths of up to 202 MPa and Young's moduli up to 25 GPa, promising evidence that sustainable FRPs can rival the mechanical properties of conventional high performance FRPs.

Depolymerization within a Circular Plastics System.

The societal importance of plastics contrasts with the carelessness with which they are disposed. Their superlative properties lead to economic and environmental efficiency, but the linearity of plastics puts the climate, human health, and global ecosystems at risk. Recycling is fundamental to transitioning this linear model into a more sustainable, circular economy. Among recycling technologies, chemical depolymerization offers a route to virgin quality recycled plastics, especially when valorizing complex waste streams poorly served by mechanical methods. However, chemical depolymerization exists in a complex and interlinked system of end-of-life fates, with the complementarity of each approach key to environmental, economic, and societal sustainability. This review explores the recent progress made into the depolymerization of five commercial polymers: poly(ethylene terephthalate), polycarbonates, polyamides, aliphatic polyesters, and polyurethanes. Attention is paid not only to the catalytic technologies used to enhance depolymerization efficiencies but also to the interrelationship with other recycling technologies and to the systemic constraints imposed by a global economy. Novel polymers, designed for chemical depolymerization, are also concisely reviewed in terms of their underlying chemistry and potential for integration with current plastic systems.

Effect of Polymer Host on Aggregation-Induced Enhanced Emission of Fluorescent Optical Brighteners.

Fluorophores displaying concentration-dependent luminescence are becoming increasingly valuable in stress-sensing, tagging, and dyeing applications, including the quantification of recycled content in plastic packaging. In this work, we investigate the effects of the polymer matrix, dye structure, and crystallinity on aggregation-induced enhanced emission (AIEE). We demonstrate that the aggregation threshold required for successful quantification can be adjusted through modulation of guest-host (dye-polymer) interactions and monitored using an array of fluorescence characterization. Modification of guest-host interactions is realized through choice of host, change of guest, and tuning of the crystallinity of the host system. Increasing the number of guest-host interactions and solubility between guest and host, loosely predicted through the calculation of the solubility parameter, increases the aggregation threshold relative to other low-polarity and low-interacting systems. We demonstrate that issues, such as loading level and cost, associated with high aggregation thresholds, can be circumvented by increasing system crystallinity, improving spectral intensities, and subsequent quantification. These insights explore the fundamental understanding of supramolecular interactions that govern dye-polymer systems.

Sustainable formulation polymers for home, beauty and personal care: challenges and opportunities.

As society moves towards a net-zero future, the need to adopt more sustainable polymers is well understood, and as well as plastics, less visible formulation polymers should also be included within this shift. As researchers, industries and consumers move towards more sustainable products there is a clear need to define what sustainability means in fast moving consumer goods and how it can be considered at the design stage. In this perspective key challenges in achieving sustainable formulation polymers are highlighted, and opportunities to overcome them are presented.

Circularizing PET-G Multimaterials: Life Cycle Assessment and Techno-Economic Analysis.

The recycling of multimaterials such as payment or access cards poses significant challenges. Building on previous experimental work demonstrating the feasibility of chemically recyclable payment cards made from glycol-modified poly(ethylene terephthalate) (PET-G), we use life cycle assessment and techno-economic analysis to investigate two chemical recycling scenarios and evaluate their potential environmental and economic benefits. Recovering all components from the depolymerized products (Scenario 1) achieves substantial environmental benefits across most categories, reducing global warming by up to 67% compared to only recovering major components (Scenario 2). However, the environmental benefits in Scenario 1 incur 69% higher total annualized costs, causing its profitability to be dependent on a minimum selling price of £13.4/kg for cyclohexanedimethanol and less than a 10% discount rate. In contrast, Scenario 2 is less sensitive to discount rate variation and thus a lower risk and more economically feasible option, albeit less environmentally sustainable.

Light-Induced Polymeric Frustrated Radical Pairs as Building Blocks for Materials and Photocatalysts.

Polymeric frustrated Lewis pairs, or poly(FLP)s, have served to bridge the gap between functional polymer science and main group catalysis, pairing the uniqueness of sterically frustrated Lewis acids and bases with a polymer scaffold to create self-healing gels and recyclable catalysts. However, their utilization in radical chemistry is unprecedented. In this paper, we disclose the synthesis of polymeric frustrated radical pairs, or poly(FRP)s, by in situ photoinduction of FLP moieties, where their Lewis acidic and basic centers are tuned to promote single electron transfer (SET). Through systematic manipulation of the chemical structure, we demonstrate that inclusion of ortho-methyl groups on phosphine monomers is crucial to enable SET. The generation of radicals is evidenced by monitoring the stable polymeric phosphine radical cations via UV/vis and EPR spectroscopy. These new poly(FRP)s enable both catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations. These polymeric radical systems open new avenues to design novel functional polymers for catalysis and photoelectrical chemistry.

Biodegradable and conventional plastic packaging: Comparison of life cycle environmental impacts of poly(mandelic acid) and polystyrene.

Most of plastic packaging waste does not degrade over time, which can lead to harmful effects on aquatic life and humans, highlighting the need for packaging materials that are easily degradable. Poly(mandelic acid) (PMA) is a biodegradable polymer that has been proposed as an alternative to polystyrene for use in packaging. However, its potential to replace the existing packaging materials also depends, among other factors, on the environmental sustainability of its production. This study aims to estimate and compare the life cycle environmental impacts of the production of PMA via polymerisation of 5-phenyl-1,3-dioxolane-4-one (Ph-DOX) and o-carboxyanhydride (OCA) monomers. For each route, the impacts are evaluated for 18 ReCiPe categories for reported laboratory scales and potential scaled-up commercial production. The results suggest that most of the impacts of PMA production via the Ph-DOX route are significantly lower (≥20%) than that of the OCA route for both the laboratory and large scales. However, compared to polystyrene, the impacts of large-scale PMA production via the (better of the two) Ph-DOX route are more than five times higher. This is largely due to the use of benzaldehyde, enzymes, hydrocyanic acid and sodium phosphate in the production of mandelic acid and the solvents utilised in monomer synthesis. A sensitivity analysis shows that the bio-transformation of bio-glycerol to produce mandelic acid would reduce 16 out of 18 life cycle impacts of PMA by 6-77%. The impacts are also sensitive to the assumptions used in the scaling-up of laboratory data for solvents. However, the results indicate clearly that, despite all the uncertainties in the scaling-up method, the proposed production routes for PMA would still have several times higher environmental impacts than polystyrene. Therefore, further research would be needed to improve significantly the production process for (bio-)mandelic acid, synthesis of monomers and their polymerisation before PMA can be considered an environmentally sustainable option for packaging applications.

Degradable and Reprocessable Resins from a Dioxolanone Cross-Linker.

Chemically cross-linked polymers offer excellent temperature and solvent resistance, but their high dimensional stability precludes reprocessing. The renewed demand for sustainable and circular polymers from public, industry, and government stakeholders has increased research into recycling thermoplastics, but thermosets have often been overlooked. To address this need for more sustainable thermosets, we have developed a novel bis(1,3-dioxolan-4-one) monomer, derived from the naturally occurring l-(+)-tartaric acid. This compound can be used as a cross-linker and copolymerized in situ with common cyclic esters such as l-lactide, ε-caprolactone, and δ-valerolactone to produce cross-linked, degradable polymers. The structure-property relationships and the final network properties were tuned by both co-monomer choice and composition, with properties ranging from resilient solids with tensile strengths of 46.7 MPa to elastomers with elongations up to 147%. In addition to exhibiting properties rivalling those of commercial thermosets, the synthesized resins could be recovered at end-of-life through triggered degradation or reprocessing. Accelerated hydrolysis experiments showed the materials fully degraded to tartaric acid and the corresponding oligomers from 1 to 14 days under mild basic conditions and in a matter of minutes in the presence of a transesterification catalyst. The vitrimeric reprocessing of networks was demonstrated at elevated temperatures, and rates could be tuned by modifying the concentration of the residual catalyst. This work develops new thermosets, and indeed their glass fiber composites, with an unprecedented ability to tune degradability and high performance by creating resins from sustainable monomers and a bio-derived cross-linker.

Recycled Plastic Content Quantified through Aggregation-Induced Emission.

The linearity of the plastics economy is wasteful and polluting. To encourage recycling and decrease diversion to landfill, new legislation within the EU and UK will tax single-use plastic products made with less than 30% recycled plastic. At present, quantitative determination of recycled content is elusive and existing methods are inconsistent. We present a fluorescence-based analytical technique to determine recycled content in plastic and (single use) packaging. Bathochromic shifts resulting from aggregation of the fluorescent brightener 4,4'-bis(2-benzoxazolyl) stilbene (BBS) in three commodity plastics [high-density polyethylene, polypropylene, and poly(ethylene terephthalate)] at loadings ≤0.5 wt % were used to systematically quantify simulated recycled contents as low as 10 wt %. Linear correlations were found between recycled content and three fluorescence-based properties: emission, lifetime, and resulting color. We demonstrate how this multi-branched verification system is completely independent of sample dimensions and processing conditions, has a negligible effect on polymer properties, and is inexpensive and highly compatible with existing recycling infrastructure.

Sustainability and Polyesters: Beyond Metals and Monomers to Function and Fate.

Poor waste management and unchecked consumption underpin our current paradigm of plastics use, which is demonstrably unsustainable in the long term. Nonetheless, the utility and versatility of plastics suggest that the notion of a plastic-free society is also unsustainable. Responses to this conundrum are increasing, and among these are research efforts focused on the development of more sustainable plastics. This Account, written by trained chemists, reflects an academic research journey culminating in an appreciation of the importance of improving and enabling the overarching systems that plastics exist within. Our primary initial focus was on catalyst development because catalysts are key drivers of sustainability by improving the efficiency and ease of polymerization. Metal catalysts ranging in ligand structure and the incorporated metal(s) were developed for the preparation of traditional polyesters such as poly(lactic acid) and polycaprolactone. The central themes in these works were stereocontrol (tacticity), efficiency (polymerization rate), and versatility (monomer scope). Alongside insights gained by systematically varying catalyst structure came impressive results gained through collaboration, including the remarkably high activity of novel heterometallic zinc catalysts toward various cyclic esters.This catalysis work was complemented by and slowly transitioned to a focus on polymer functionality and monomer design. Several fundamental studies focus on polymer topology, specifically star-shaped polyesters, tuned arm number, length, and tacticity. These reports feature emphases on the end of life (solvolysis) and physical properties of polymers, which were increasingly important themes as work shifted toward new methods of incorporating functionality in polymers produced by ring-opening polymerization. Three key highlights demonstrate this shift: the first two rely upon the exploitation of olefin metathesis (cross- and ring-closing) to functionalize polyesters or polyethers, and the third involves the manipulation of ring-opening polymerization equilibrium to enable selective monomer recovery from a polyester. Our foundational work on 1,3-dioxolan-4-one (DOX) monomers is then discussed because this emerging class of molecules offers a distinct synthetic pathway toward functional polyesters, both conventional and novel. With this DOX framework, polyesters that are usually challenging to synthesize (e.g., poly(mandelic acid)) are accessible because polymerization is driven by the concomitant, controlled extrusion of small molecules (acetone or formaldehyde).After these polyester-focused highlights, the foundation of our ongoing work is presented, namely, that polymer sustainability must be viewed from a systems-level perspective, including economic and social components alongside the environmental considerations. Material design must be driven by practice, and we have to involve key players in academia, industry, and government in a concerted effort to enable positive and robust change. The key goal is to develop sustainable systems that retain plastics in their highest value state for as long as possible by designing materials and products for a particular (and assured) end-of-life fate, whether that be reuse, recycling, (bio)degradation, or energy recovery.

Polymeric frustrated Lewis pairs in CO2/cyclic ether coupling catalysis.

Frustrated Lewis pairs (FLPs) are now ubiquitous as metal-free catalysts in an array of different chemical transformations. In this paper we show that this reactivity can be transferred to a polymeric system, offering advantageous opportunities at the interface between catalysis and stimuli-responsive materials. Formation of cyclic carbonates from cyclic ethers using CO2 as a C1 feedstock continues to be dominated by metal-based systems. When paired with a suitable nucleophile, discrete aryl or alkyl boranes have shown significant promise as metal-free Lewis acidic alternatives, although catalyst reuse remains illusive. Herein, we leverage the reactivity of FLPs in a polymeric system to promote CO2/cyclic ether coupling catalysis that can be tuned for the desired epoxide or oxetane substrate. Moreover, these macromolecular FLPs can be reused across multiple reaction cycles, further increasing their appeal over analogous small molecule systems.

Low Formaldehyde Binders for Mineral Wool Insulation: A Review.

Insulating materials are ubiquitous in a built environment and play a critical role in reducing the energy consumed to maintain habitable indoor environments. Mineral wool insulation (MWI) products, including glass, stone, and slag variants, are the most widely used class of insulating materials in Europe and account for more than 50% of the total market by volume. MWI typically consists of two key components: a mesh of inorganic fibers that are several micrometers in diameter, and an organic thermosetting adhesive commonly referred to as the "binder." Traditional phenol-formaldehyde-urea (PFU) binders used in the manufacture of MWI are increasingly being scrutinized for the formaldehyde released during their manufacture and service lifetime. The recent classification of formaldehyde as a carcinogen by various safety organizations has accelerated a paradigm shift within the industry toward alternative binder technologies that minimize or indeed eliminate formaldehyde emissions. This review examines more recent strategies for achieving low- or zero-added formaldehyde binders for MWI, with a particular focus on the patent literature. The chemistry underpinning traditional PFU binders is presented and compared to new strategies involving scavenging molecules that decrease formaldehyde emissions, as well as zero-added formaldehyde binder technologies such as polyester, Maillard, and epoxide thermosets.

Cyclic Ether Triggers for Polymeric Frustrated Lewis Pair Gels.

Sterically hindered Lewis acid and base centers are unable to form Lewis adducts, instead forming frustrated Lewis pairs (FLPs), where latent reactivity can be utilized for the activation of small molecules. Applying FLP chemistry into polymeric frameworks transforms this chemistry into responsive and functional materials. Here, we report a versatile synthesis strategy for the preparation of macromolecular FLPs and explore its potential with the ring-opening reactions of cyclic ethers. Addition of the cyclic substrates triggered polymer network formation, where the extent of cross-linking, strength of network, and reactivity are tuned by the steric and electronic properties of the ethers. The resultant networks behave like covalently cross-linked polymers, demonstrating the versatility of FLPs to simultaneously tune both small-molecule capture and mechanical properties of materials.

Mechanical Recycling of Packaging Plastics: A Review.

The current global plastics economy is highly linear, with the exceptional performance and low carbon footprint of polymeric materials at odds with dramatic increases in plastic waste. Transitioning to a circular economy that retains plastic in its highest value condition is essential to reduce environmental impacts, promoting reduction, reuse, and recycling. Mechanical recycling is an essential tool in an environmentally and economically sustainable economy of plastics, but current mechanical recycling processes are limited by cost, degradation of mechanical properties, and inconsistent quality products. This review covers the current methods and challenges for the mechanical recycling of the five main packaging plastics: poly(ethylene terephthalate), polyethylene, polypropylene, polystyrene, and poly(vinyl chloride) through the lens of a circular economy. Their reprocessing induced degradation mechanisms are introduced and strategies to improve their recycling are discussed. Additionally, this review briefly examines approaches to improve polymer blending in mixed plastic waste streams and applications of lower quality recyclate.

Combining alkali metals and zinc to harness heterometallic cooperativity in cyclic ester ring-opening polymerisation.

Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver "best of both" in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (k obs = 1.7 × 10-2 s-1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.

Alkyne-Tagged PLGA Allows Direct Visualization of Nanoparticles In Vitro and Ex Vivo by Stimulated Raman Scattering Microscopy.

Polymeric nanoparticles (NPs) are attractive candidates for the controlled and targeted delivery of therapeutics in vitro and in vivo. However, detailed understanding of the uptake, location, and ultimate cellular fate of the NPs is necessary to satisfy safety concerns, which is difficult because of the nanoscale size of these carriers. In this work, we show how small chemical labels can be appended to poly(lactic acid-co-glycolic acid) (PLGA) to synthesize NPs that can then be imaged by stimulated Raman scattering microscopy, a vibrational imaging technique that can elucidate bond-specific information in biological environments, such as the identification of alkyne signatures in modified PLGA terpolymers. We show that both deuterium and alkyne labeled NPs can be imaged within primary rat microglia, and the alkyne NPs can also be imaged in ex vivo cortical mouse brain tissue. Immunohistochemical analysis confirms that the NPs localize in microglia in the mouse brain tissue, demonstrating that these NPs have the potential to deliver therapeutics selectively to microglia.

Morpholino Oligonucleotide Cross-Linked Hydrogels as Portable Optical Oligonucleotide Biosensors.

Morpholino Oligonucleotides (MOs), an uncharged DNA analogue, are functionalized with an acrylamide moiety and incorporated into polymer hydrogels as responsive cross-links for microRNA sequence detection. The MO cross-links can be selectively cleaved by a short target analyte single-stranded DNA (ssDNA) sequence based on microRNA, inducing a distinct swelling response measured optically. The MO cross-links offer significant improvement over DNA based systems through improved thermal stability, no salt requirement and 1000-fold improved sensitivity over a comparative biosensor, facilitating a wider range of sensing conditions. Analysis was also achieved using a mobile phone camera, demonstrating portability.

Correction: Polymeric hole-transport materials with side-chain redox-active groups for perovskite solar cells with good reproducibility.

Correction for 'Polymeric hole-transport materials with side-chain redox-active groups for perovskite solar cells with good reproducibility' by Rosinda Fuentes Pineda et al., Phys. Chem. Chem. Phys., 2018, 20, 25738-25745.