Polymer production is rapidly increasing, but there are no large-scale technologies available to effectively mitigate the massive accumulation of these recalcitrant materials. One potential solution is the development of a carbon-neutral polymer life cycle, where microorganisms convert plant biomass to chemicals, which are used to synthesize biodegradable materials that ultimately contribute to the growth of new plants. Realizing a circular carbon life cycle requires the integration of knowledge across microbiology, bioengineering, materials science, and organic chemistry, which itself has hindered large-scale industrial advances. This review addresses the biodegradation status of common synthetic polymers, identifying novel microbes and enzymes capable of metabolizing these recalcitrant materials and engineering approaches to enhance their biodegradation pathways. Design considerations for the next generation of biodegradable polymers are also reviewed, and finally, opportunities to apply findings from lignocellulosic biodegradation to the design and biodegradation of similarly recalcitrant synthetic polymers are discussed.

The development of degradable polymers has commanded significant attention over the past half century. Approaches have predominantly relied on ring-opening polymerization of cyclic esters (e.g., lactones, lactides) and N-carboxyanhydrides, as well as radical ring-opening polymerizations of cyclic ketene acetals. In recent years, there has been a significant effort applied to expand the family of degradable polymers accessible via olefin metathesis polymerization. Given the excellent functional group tolerance of olefin metathesis polymerization reactions generally, a broad range of conceivable degradable moieties can be incorporated into appropriate monomers and thus into polymer backbones. This approach has proven particularly versatile in synthesizing a broad spectrum of degradable polymers including poly(ester), poly(amino acid), poly(acetal), poly(carbonate), poly(phosphoester), poly(phosphoramidate), poly(enol ether), poly(azobenzene), poly(disulfide), poly(sulfonate ester), poly(silyl ether), and poly(oxazinone) among others. In this review, we will highlight the main olefin metathesis polymerization strategies that have been used to access degradable polymers, including (i) acyclic diene metathesis polymerization, (ii) entropy-driven and (iii) enthalpy-driven ring-opening metathesis polymerization, as well as (iv) cascade enyne metathesis polymerization. In addition, the livingness or control of polymerization reactions via different strategies are highlighted and compared. Potential applications, challenges and future perspectives of this new library of degradable polyolefins are discussed. It is clear from recent and accelerating developments in this field that olefin metathesis polymerization represents a powerful synthetic tool towards degradable polymers with novel structures and properties inaccessible by other polymerization approaches.

Polymer research is currently focused on sustainable and degradable polymers which are cheap, easy to synthesize, and environmentally friendly. Silicon-based polymers are thermally stable and can be utilized in various applications, such as columns and coatings. Poly(silyl ether)s (PSEs) are an interesting class of silicon-based polymers that are easily hydrolyzed in either acidic or basic conditions due to the presence of the silyl ether Si-O-C bond. Synthetically, these polymers can be formed in several different ways, and the most effective and environmentally friendly synthesis is dehydrogenative cross coupling, where the byproduct is H2 gas. These polymers have a lot of promise in the polymeric materials field due to their sustainability, thermal stability, hydrolytic degradability, and ease of synthesis, with nontoxic byproducts. In this review, we will summarize the synthetic approaches for the PSEs in the recent literature, followed by the properties and applications of these materials. A conclusion and perspective will be provided at the end.

Elemental sulfur, a waste product of the oil refinement process, represents a promising raw material for the synthesis of degradable polymers. We show that simple lithium alkoxides facilitate the polymerisation of elemental sulfur S8 with industrially relevant propylene oxide (PO) and CS2 (a base chemical sourced from waste S8 itself) to give poly(monothiocarbonate-alt-Sx) in which x can be controlled by the amount of supplied sulfur. The in situ generation of thiolate intermediates obtained by a rearrangement, which follows CS2 and PO incorporation, allows to combine S8 and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S8 ring opening and sulfur chain length equilibration represent the better nucleophiles for inserting the next PO if compared to the trithiocarbonates obtained from the competing CS2 addition, which causes the sequence selectivity. The polymers can be crosslinked in situ with multifunctional thiols to yield reprocessable and degradable networks. Our report demonstrates how mechanistic understanding allows to combine intrinsically incompatible building blocks for sulfur waste utilisation.

With the increasing use of pressure-sensitive adhesives (PSAs) in various industries, there is a need for greater sustainability, particularly in developing polymer materials from renewable resources, as well as the reuse and recycling of materials to reduce environmental impact, reduce waste, or extend their life. Here, we outlined the required properties of PSAs which are governed by the molecular parameters (molecular weights, dispersities, molecular weight between entanglement, molecular weight between cross-links and gel content) of polymer materials which subsequently define the physical properties (storage and loss moduli, glass transition temperature) that are required for good performance in peel, tack and shear tests. The sustainable approach discussed here is the development of degradable polymer materials featuring selectively degradable linkages in the backbone. This provides a viable alternative for the design of PSAs that could overcome the \'stickies\' problem and make the recycling of glass and cardboard more efficient.

Degradable polymers (both biomacromolecules and several synthetic polymers) for biomedical applications have been promising very much in the recent past due to their low cost, biocompatibility, flexibility, and minimal side effects. Here, we present an overview with updated information on natural and synthetic degradable polymers where a brief account on different polysaccharides, proteins, and synthetic polymers viz. polyesters/polyamino acids/polyanhydrides/polyphosphazenes/polyurethanes relevant to biomedical applications has been provided. The various approaches for the transformation of these polymers by physical/chemical means viz. cross-linking, as polyblends, nanocomposites/hybrid composites, interpenetrating complexes, interpolymer/polyion complexes, functionalization, polymer conjugates, and block and graft copolymers, are described. The degradation mechanism, drug loading profiles, and toxicological aspects of polymeric nanoparticles formed are also defined. Biomedical applications of these degradable polymer-based biomaterials in and as wound dressing/healing, biosensors, drug delivery systems, tissue engineering, and regenerative medicine, etc., are highlighted. In addition, the use of such nano systems to solve current drug delivery problems is briefly reviewed.

Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) is exploited to access azomethine-containing copolymers via a benign acid-catalyzed polycondensation protocol. Polymerizations involve reacting a dialdehyde-functionalized dihydropyrrolopyrrole with p-phenylenediamine as the comonomer using p-toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV-vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally-conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end-of-life management or/and recyclability.

Pressure-sensitive adhesives (PSAs) are made from soft, irreversibly lightly crosslinked polymers. Even after removal from surfaces, they retain insoluble networks which pose problems during the recycling of glass and cardboard. Herein, degradable PSAs are presented that provide the required performance in use but have networks that can be degraded after use. A series of copolymers was prepared through radical copolymerization of n-butyl acrylate, 4-acryloyloxy benzophenone (ABP) photo-crosslinker, and dibenzo[c,e]oxepin-5(7H)-thione (DOT) to provide degradable backbone thioesters. The optimum tack and peel strengths were found for molar contents of 0.05 mol% ABP and 0.25 mol% DOT. Degradation of the backbone thioesters through aminolysis or thiolysis led to the full dissolution of the networks, loss of adhesive properties of films (decreases in the measured tack and peel strengths), and the quick detachment of model labels from a substrate. Inclusion of DOT into PSAs offers a viable route toward degradable and recyclable packaging labels.

Synthetic polymers are indispensable in biomedical applications because they can be fabricated with consistent and reproducible properties, facile scalability, and customizable functionality to perform diverse tasks. However, currently available synthetic polymers have limitations, most notably when timely biodegradation is required. Despite there being, in principle, an entire periodic table to choose from, with the obvious exception of silicones, nearly all known synthetic polymers are combinations of carbon, nitrogen, and oxygen in the main chain. Expanding this to main-group heteroatoms can open the way to novel material properties. Herein the authors report on research to incorporate the chemically versatile and abundant silicon and phosphorus into polymers to induce cleavability into the polymer main chain. Less stable polymers, which degrade in a timely manner in mild biological environments, have considerable potential in biomedical applications. Herein the basic chemistry behind these materials is described and some recent studies into their medical applications are highlighted.

Cryogel formation is an effective approach to produce porous scaffolds for tissue engineering. In this study, cryogelation was performed to produce boron-containing scaffolds for bone tissue engineering. A combination of the synthetic polymer, poly(vinyl alcohol) (PVA), and the natural polymers, chitosan and starch, was used to formulate the cryogels. Boron was used with a dual purpose: as an additive to alter gelation properties, and to exploit its bioactive effect since boron has been found to be involved in several metabolic pathways, including the promotion of bone growth. This project designs a fabrication protocol enabling the competition of both physical and chemical cross-linking reactions in the cryogels using different molecular weight PVA and borax content (boron source). Using a high ratio of high-molecular-weight PVA resulted in the cryogels exhibiting greater mechanical properties, a lower degradation rate (0.6-1.7% vs. 18-20%) and a higher borax content release (4.98 vs. 1.85, 1.08 nanomole) in contrast to their counterparts with low-molecular-weight PVA. The bioactive impacts of the released borax on cellular behaviour were investigated using MG63 cells seeded into the cryogel scaffolds. It was revealed that the borax-containing scaffolds and their extracts induced MG63 cell migration and the formation of nodule-like aggregates, whilst cryogel scaffolds without borax did not. Moreover, the degradation products of the scaffolds were analysed through the quantification of boron release by the curcumin assay. The impact on cellular response in a scratch assay confirmed that borax released by the scaffold into media (~0.4 mg/mL) induced bone cell migration, proliferation and aggregation. This study demonstrated that boron-containing three-dimensional PVA/starch-chitosan scaffolds can potentially be used within bone tissue engineering applications.