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Plastics have become indispensable in modern life and the material of choice in packaging applications, but they have also caused increasing plastic waste accumulation in oceans and landfills. Although there have been continuous efforts to develop biodegradable plastics, the mechanical and/or transport properties of these materials still need to be significantly improved to be suitable for replacing conventional plastic packaging materials. Here we report a class of biorenewable and degradable plastics, based on copolymers of γ-butyrolactone and its ring-fused derivative, with competitive permeability and elongation at break compared to commodity polymers and superior mechanical and transport properties to those of most promising biobased plastics. Importantly, these materials are designed with full chemical recyclability built into their performance with desired mechanical and barrier properties, thus representing a circular economy approach to plastic packaging materials. Biodegradable plastics usually have poorer mechanical or transport properties compared to conventional plastics. Here the authors show a class of biorenewable and chemically recyclable plastics based on copolymers of γ-butyrolactone and its ring-fused derivative, with competitive properties compared to conventional plastics.

Thermosets—polymeric materials that adopt a permanent shape upon curing—have a key role in the modern plastics and rubber industries, comprising about 20 per cent of polymeric materials manufactured today, with a worldwide annual production of about 65 million tons 1 , 2 . The high density of crosslinks that gives thermosets their useful properties (for example, chemical and thermal resistance and tensile strength) comes at the expense of degradability and recyclability. Here, using the industrial thermoset polydicyclopentadiene as a model system, we show that when a small number of cleavable bonds are selectively installed within the strands of thermosets using a comonomer additive in otherwise traditional curing workflows, the resulting materials can display the same mechanical properties as the native material, but they can undergo triggered, mild degradation to yield soluble, recyclable products of controlled size and functionality. By contrast, installation of cleavable crosslinks, even at much higher loadings, does not produce degradable materials. These findings reveal that optimization of the cleavable bond location can be used as a design principle to achieve controlled thermoset degradation. Moreover, we introduce a class of recyclable thermosets poised for rapid deployment. A method of endowing thermoset plastics with a degree of recyclability and reprocessability by incorporating cleavable chemical linkages in the strands of the polymer, rather than in the crosslinks, is presented.

The emergence of wearable electronics puts batteries closer to the human skin, exacerbating the need for battery materials that are robust, highly ionically conductive, and stretchable. Herein, we introduce a supramolecular design as an effective strategy to overcome the canonical tradeoff between mechanical robustness and ionic conductivity in polymer electrolytes. The supramolecular lithium ion conductor utilizes orthogonally functional H-bonding domains and ion-conducting domains to create a polymer electrolyte with unprecedented toughness (29.3 MJ m −3 ) and high ionic conductivity (1.2 × 10 −4 S cm −1 at 25 °C). Implementation of the supramolecular ion conductor as a binder material allows for the creation of stretchable lithium-ion battery electrodes with strain capability of over 900% via a conventional slurry process. The supramolecular nature of these battery components enables intimate bonding at the electrode-electrolyte interface. Combination of these stretchable components leads to a stretchable battery with a capacity of 1.1 mAh cm −2 that functions even when stretched to 70% strain. The method reported here of decoupling ionic conductivity from mechanical properties opens a promising route to create high-toughness ion transport materials for energy storage applications. Typically, ion conducting polymers exhibit a trade-off between mechanical robustness and ionic conducting performance. Here, the authors utilize supramolecular chemistry obtaining extremely tough electrolytes with high ionic conductivity and enabling stretchable lithium-ion batteries.

Unlike their more common linear counterparts, cyclic polymers have a ring-like structure and a lack of chain ends. Because of their topology, cyclic polymers exhibit a unique set of properties when compared with linear or branched macromolecules. For example, cyclic homopolymers exhibit a reduced hydrodynamic volume and a slower degradation profile compared with their linear analogues. Cyclic block copolymers self-assemble into compact nanostructures, as illustrated by their reduced domain spacing when cast into thin films and their reduced micellar size in solution. Although methods for preparing well-defined cyclic polymers have only been available since 1980, the extensive utilization of the cyclic topology in nature highlights the vital role that a cyclic architecture can play in imparting valuable physical properties, such as increased chemical stability or propensity towards self-assembly. This Review describes the major developments in the synthesis of cyclic polymers and provides an overview of their fundamental physical properties. In this context, preliminary studies exploring potential applications will be critically assessed and the remaining challenges for the field delineated.Cyclic polymers have a ring-like architecture and one of the most important consequences of this topology is the absence of any chain ends, which typically have a substantial impact on the physical properties of macromolecules. This Review Article discusses advances in the synthesis, purification and characterization of cyclic polymers and the potential applications they may prove useful for.

The development of polymers with switchable glass transition temperatures ( T g ) can address scientific challenges such as the healing of cracks in high- T g polymers and the processing of hard polymers at room temperature without using plasticizing solvents. Here, we demonstrate that light can switch the T g of azobenzene-containing polymers (azopolymers) and induce reversible solid-to-liquid transitions of the polymers. The azobenzene groups in the polymers exhibit reversible cis – trans photoisomerization abilities. Trans azopolymers are solids with T g above room temperature, whereas cis azopolymers are liquids with T g below room temperature. Because of the photoinduced solid-to-liquid transitions of these polymers, light can reduce the surface roughness of azopolymer films by almost 600%, repeatedly heal cracks in azopolymers, and control the adhesion of azopolymers for transfer printing. The photoswitching of T g provides a new strategy for designing healable polymers with high T g and allows for control over the mechanical properties of polymers with high spatiotemporal resolution. Reversibly inducing solid-to-liquid transitions of polymers at room temperature represents a challenge for enhanced processability and applications of polymers. Now, three azopolymers have been shown to exhibit photoswitchable glass transition temperatures, resulting in reversible solid-to-liquid transitions. Light exposure can heal cracks in hard azopolymers, reduce surface roughness of azopolymer films and control azopolymer adhesion.

Vinylogous urethane based vitrimers are polymer networks that have the intrinsic property to undergo network rearrangements, stress relaxation and viscoelastic flow, mediated by rapid addition/elimination reactions of free chain end amines. Here we show that the covalent exchange kinetics significantly can be influenced by combination with various simple additives. As anticipated, the exchange reactions on network level can be further accelerated using either Brønsted or Lewis acid additives. Remarkably, however, a strong inhibitory effect is observed when a base is added to the polymer matrix. These effects have been mechanistically rationalized, guided by low-molecular weight kinetic model experiments. Thus, vitrimer elastomer materials can be rationally designed to display a wide range of viscoelastic properties. Vitrimers are malleable networks based on thermally triggered associative exchange reactions and thus can be used for processing, recycling and self-healing materials. Here the authors show how acids and bases affect the exchange kinetics and in turn rationalize these effects mechanistically.

Rational designs of solid polymer electrolytes with high ion conduction are critical in enabling the creation of advanced lithium batteries. However, known polymer electrolytes have much lower ionic conductivity than liquid/ceramics at room temperature, which limits their practical use in batteries. Here we show that precise positioning of designed repeating units in alternating polymer sequences lays the foundation for homogenized Li+ distribution, non-aggregated Li+-anion solvation and sequence-assisted site-to-site ion migration, facilitating the tuning of Li+ conductivity by up to three orders of magnitude. The assembled all-solid-state batteries facilitate reversible and dendrite-mitigated cycling against Li metal from ambient to elevated temperatures. This work demonstrates a powerful molecular engineering means to access highly ion-conductive solid-state materials for next-generation energy devices.Solid polymer electrolytes are crucial for the development of lithium batteries, but their lower ionic conductivity compared with liquid/ceramics at room temperature limits their practical use. Precise positioning of designed repeating units in alternating polymer sequences now allows the Li+ conductivity to be tuned by up to three orders of magnitude.

Vitrimers are one kind of covalently crosslinked polymers that can be reprocessed. Topology freezing transition temperature (T v ) is vitrimer’s upper limit temperature for service and lower temperature for recycle. However, there has been no proper method to detect the intrinsic T v till now. Even worse, current testing methods may lead to a misunderstanding of vitrimers. Here we provide a sensitive and universal method by doping or swelling aggregation-induced-emission (AIE) luminogens into vitrimers. The fluorescence of AIE-luminogens changes dramatically below and over T v , providing an accurate method to measure T v without the interference of external force. Moreover, according to this method, T v is independent of catalyst loading. The opposite idea has been kept for a long time. This method not only is helpful for the practical application of vitrimers so as to reduce white wastes, but also may facilitate deep understanding of vitrimers and further development of functional polymer materials. Detecting and understanding the topology freezing transition temperature of vitrimers has been very limited in the past. Here the authors use a sensitive and universal method by doping or swelling aggregation-induced-emission luminogens into vitrimers as probes to monitor the topology freezing transition temperature

Living organisms share the ability to grow various microstructures on their surface to achieve functions. Here we present a force stamp method to grow microstructures on the surface of hydrogels based on a force-triggered polymerisation mechanism of double-network hydrogels. This method allows fast spatial modulation of the morphology and chemistry of the hydrogel surface within seconds for on-demand functions. We demonstrate the oriented growth of cells and directional transportation of water droplets on the engineered hydrogel surfaces. This force-triggered method to chemically engineer the hydrogel surfaces provides a new tool in addition to the conventional methods using light or heat, and will promote the wide application of hydrogels in various fields. Living organisms are able to grow structures on their surface for specific applications. Here, the authors report on a force-triggered polymerisation mechanism of double-network hydrogels which allows for the growth of structures on polymer surfaces within seconds and demonstrate the creation of different functionalities.

New approaches are needed to both reduce and reuse plastic waste. In this context, poly(vinyl chloride) (PVC) is an appealing target as it is the least recycled high-production-volume polymer due to its facile release of plasticizers and corrosive HCl gas. Herein, these limitations become advantageous in a paired-electrolysis reaction in which HCl is intentionally generated from PVC to chlorinate arenes in an air- and moisture-tolerant process that is mediated by the plasticizer. The reaction proceeds efficiently with other plastic waste present and a commercial plasticized PVC product (laboratory tubing) can be used directly. A simplified life-cycle assessment reveals that using PVC waste as the chlorine source in the paired-electrolysis reaction has a lower global warming potential than HCl. Overall, this method should inspire other strategies for repurposing waste PVC and related polymers using electrosynthetic reactions, including those that take advantage of existing polymer additives.The facile release of corrosive HCl gas and plasticizers from poly(vinyl chloride) (PVC) makes it a challenging material to recycle. Now, it has been shown that PVC waste can be directly used as a halogen source to synthesize chloroarenes. This paired electro(de)chlorination is mediated by a phthalate plasticizer already contained in PVC waste.