Aliphatic Hyperbranched Polycarbonates Solid Polymer Electrolytes with High Li-Ion Transference Number for Lithium Metal Batteries.

In this work, hyperbranched polycarbonate-poly(ethylene oxide) (PEO)-based solid polymer electrolytes (HBPC-SEs) are successfully synthesized via a straightforward organo-catalyzed "A1"+"B2"-ring-opening polymerization approach. The temperature-dependent ionic conductivity of HBPC-SEs, composed of different polycarbonate linkages and various LiTFSI concentrations, is investigated. The results demonstrate that HBPC-SE with an ether-carbonate alternating structure exhibits superior ionic conductivity, attributed to the solubility of Li salts in the polymer matrix and the mobility of the polymer segments. The HBPC1-SE with 30 wt% LiTFSI presents the highest ionic conductivities of 2.15  × 10-5, 1.78 × 10-4, and 6.07 × 10-4 Scm-1 at 30, 60, and 80 °C, respectively. Compared to traditional PEO-based electrolytes, the incorporation of polycarbonate segments significantly enhances the electrochemical stability window (5 V) and Li+ transference number (0.53) of HBPC-SEs. Furthermore, the LiFePO4/HBPC1-SE-3/Li cell exhibits exceptional rate capability and long-cycling performance, maintaining a discharge capacity of 130 mAh g-1 at 0.5C with a capacity retention of 95% after 300 cycles.

Chromium Complexes Supported by Salen-Type Ligands for the Synthesis of Polyesters, Polycarbonates, and Their Copolymers through Chemoselective Catalysis.

Salen, Salan, and Salalen chromium (III) chloride complexes have been investigated as catalysts for the ring-opening copolymerization reactions of cyclohexene oxide (CHO) with CO2 and of phthalic anhydride (PA) with limonene oxide (LO) or cyclohexene oxide (CHO). In the production of polycarbonates, the more flexible skeleton of salalen and salan ancillary ligands favors high activity. Differently, in the copolymerization of phthalic anhydride with the epoxides, the salen complex showed the best performance. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures from mixtures of CO2, cyclohexene oxide, and phthalic anhydride with all complexes. In addition, all chromium complexes were revealed to be very active in the chemical depolymerization of polycyclohexene carbonate producing cyclohexene oxide with high selectivity, thus offering the opportunity to close the loop on the life of these materials.

Biodegradable Polymers and Polymer Composites with Antibacterial Properties.

Antibiotic resistance is one of the greatest threats to global health and food security today. It becomes increasingly difficult to treat infectious disorders because antibiotics, even the newest ones, are becoming less and less effective. One of the ways taken in the Global Plan of Action announced at the World Health Assembly in May 2015 is to ensure the prevention and treatment of infectious diseases. In order to do so, attempts are made to develop new antimicrobial therapeutics, including biomaterials with antibacterial activity, such as polycationic polymers, polypeptides, and polymeric systems, to provide non-antibiotic therapeutic agents, such as selected biologically active nanoparticles and chemical compounds. Another key issue is preventing food from contamination by developing antibacterial packaging materials, particularly based on degradable polymers and biocomposites. This review, in a cross-sectional way, describes the most significant research activities conducted in recent years in the field of the development of polymeric materials and polymer composites with antibacterial properties. We particularly focus on natural polymers, i.e., polysaccharides and polypeptides, which present a mechanism for combating many highly pathogenic microorganisms. We also attempt to use this knowledge to obtain synthetic polymers with similar antibacterial activity.

Challenges and Opportunities in the Catalytic Synthesis of Diphenolic Acid and Evaluation of Its Application Potential.

Diphenolic acid, or 4,4-bis(4-hydroxyphenyl)pentanoic acid, represents one of the potentially most interesting bio-products obtainable from the levulinic acid supply-chain. It represents a valuable candidate for the replacement of bisphenol A, which is strongly questioned for its toxicological issues. Diphenolic acid synthesis involves the condensation reaction between phenol and levulinic acid and requires the presence of a Brønsted acid as a catalyst. In this review, the state of the art related to the catalytic issues of its synthesis have been critically discussed, with particular attention to the heterogeneous systems, the reference benchmark being represented by the homogeneous acids. The main opportunities in the field of heterogeneous catalysis are deeply discussed, as well as the bottlenecks to be overcome to facilitate diphenolic acid production on an industrial scale. The regioselectivity of the reaction is a critical point because only the p,p'-isomer is of industrial interest; thus, several strategies aiming at the improvement of the selectivity towards this isomer are considered. The future potential of adopting alkyl levulinates, instead of levulinic acid, as starting materials for the synthesis of new classes of biopolymers, such as new epoxy and phenolic resins and polycarbonates, is also briefly considered.

Enabling New Approaches: Recent Advances in Processing Aliphatic Polycarbonate-Based Materials.

Aliphatic polycarbonates (aPCs) have become increasingly popular as functional materials due to their biocompatibility and capacity for on-demand degradation. Advances in polymerization techniques and the introduction of new functional monomers have expanded the library of aPCs available, offering a diverse range of chemical compositions and structures. To accommodate the emerging requirements of new applications in biomedical and energy-related fields, various manufacturing techniques have been adopted for processing aPC-based materials. However, a summary of these techniques has yet to be conducted. The aim of this paper is to enrich the toolbox available to researchers, enabling them to select the most suitable technique for their materials. In this paper, a concise review of the recent progress in processing techniques, including controlled self-assembly, electrospinning, additive manufacturing, and other techniques, is presented. We also highlight the specific challenges and opportunities for the sustainable growth of this research area and the successful integration of aPCs in industrial applications.

Bicyclic Guanidine Promoted Mechanistically Divergent Depolymerization and Recycling of a Biobased Polycarbonate.

We here report the organocatalytic and temperature-controlled depolymerization of biobased poly(limonene carbonate) providing access to its trans-configured cyclic carbonate as the major product. The base TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) offers a unique opportunity to break down polycarbonates via end-group activation or main chain scission pathways as supported by various controls and computational analysis. These energetically competitive processes represent an unprecedented divergent approach to polycarbonate recycling. The trans limonene carbonate can be converted back to its polycarbonate via ring-opening polymerization using the same organocatalyst in the presence of an alcohol initiator, offering thus a potential circular and practical route for polycarbonate recycling.

Exploiting the Use of the Decarboxylative S-Alkylation Reaction to Produce Self-Blowing, Recyclable Polycarbonate Foams.

Polymeric foams are widely used in many industrial applications due to their light weight and superior thermal, mechanical, and optical properties. Currently, increasing research efforts is being directed towards the development of greener foam formulations that circumvent the use of isocyanates/blowing agents that are commonly used in the production of foam materials. Here, a straightforward, one-pot method is presented to prepare self-blown polycarbonate (PC) foams by exploiting the (decarboxylative) S-alkylation reaction for in situ generation of the blowing agent (CO2 ). The concomitant formation of a reactive alcohol intermediate promotes a cascade ring-opening polymerization of the cyclic carbonates to yield a cross-linked polymer network. It is shown that these hydroxyl-functionalized polycarbonate-based foams can be easily recycled into films through thermal compression molding. Furthermore, it is demonstrated that complete hydrolytic degradation of the foams is possible, thus offering the potential for zero-waste materials. This straightforward and versatile process broadens the scope of isocyanate-free, self-foaming materials, opening a new pathway for next-generation environmentally friendly foams.

End Group Dye-Labeled Polycarbonate Block Copolymers for Micellar (Immuno-)Drug Delivery.

Defined conjugation of functional molecules to block copolymer end groups is a powerful strategy to enhance the scope of micellar carriers for drug delivery. In this study, an approach to access well-defined polycarbonate-based block copolymers by labeling their end groups with single fluorescent dye molecules is established. Following controlled polymerization conditions, the block copolymers' primary hydroxy end group can be converted into activated pentafluorophenyl ester carbonates and subsequently aminolyzed with fluorescent dyes that are equipped with primary amines. During a solvent-evaporation process, the resulting end group dye-labeled block copolymers self-assemble into narrowly dispersed ∼25 nm-sized micelles and simultaneously encapsulate hydrophobic (immuno-)drugs. The covalently attached fluorescent tracer can be used to monitor both uptake into cells and stability under biologically relevant conditions, including incubation with blood plasma or during blood circulation in zebrafish embryos. By encapsulation of the toll-like receptor 7/8 (TLR7/8) agonist CL075, immune stimulatory polymeric micelles are generated that get internalized by various antigen-presenting dendritic cells and promote their maturation. Generally, such end group dye-labeled polycarbonate block copolymers display ideal features to permit targeted delivery of hydrophobic drugs to key immune cells for vaccination and cancer immunotherapy.

Non-Isocyanate Aliphatic-Aromatic Poly(carbonate-urethane)s-An Insight into Transurethanization Reactions and Structure-Property Relationships.

This study reveals insights into the transurethanization reactions leading to the aliphatic-aromatic non-isocyanate poly(carbonate-urethane)s (NIPCUs) and their structure-property relationships. The crucial impact of the alkyl chain length in 4,4'-diphenylmethylene bis(hydroxyalkyl carbamate) (BHAC) on the process of transurethanization reactions was proved. The strong susceptibility of hydroxyethyl- and hydroxybutyl carbamate moieties to the back-biting side reactions was observed due to the formation of thermodynamically stable cyclic products and urea bonds in the BHACs and NIPCUs. When longer alkyl chains (hydroxypentyl-, hydroxyhexyl-, or hydroxydecyl carbamate) were introduced into the BHAC structure, it was not prone to the back-biting side reaction. Both 1H and 13C NMR, as well as FT-IR spectroscopies, confirmed the presence of carbonate and urethane (and urea for some of the samples) bonds in the NIPCUs, as well as proved the lack of allophanate and ether groups. The increase in the alkyl chain length (from 5 to 10 carbon atoms) between urethane groups in the NIPCU hard segments resulted in the increase in the elongation at break and crystalline phase content, as well as the decrease in the Tg, tensile strength, and hardness. Moreover, the obtained NIPCUs exhibited exceptional mechanical properties (e.g., tensile strength of 40 MPa and elongation at break of 130%).

Efficient and Selective Chemical Recycling of CO2 -Based Alicyclic Polycarbonates via Catalytic Pyrolysis.

Chemical recycling of polymers to their constituent monomers is the foremost challenge in building a sustainable circular plastics economy. Here, we report a strategy for highly efficient depolymerization of various CO2 -based alicyclic polycarbonates to epoxide monomers in solvent-free conditions by a simple CrIII -Salen complex mediated catalytic pyrolysis process. The chemical recycling of the widely studied poly(cyclohexene carbonate) exhibits excellent reactivity (TOF up to 3000 h-1 , 0.1 mol % catalyst loading) and high epoxide monomer selectivity (>99 %). Mechanistic investigation reveals that the process proceeds in a sequential fashion via a trans-carbonate intermediate.

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO2 and Epoxides: From High Pressure and Temperature to Ambient Conditions.

Organophosphazenes combined with triethylborane (TEB) were selected as binary organocatalyts for the copolymerization of CO2 and epoxides. Both the activity and selectivity were highly dependent on the nature of phosphazenes. 2,4,6-Tris[tri(1-pyrrolidinyl)-iminophosphorane]-1,3,5-triazine (C3 N3 -Py-P3 ) with a relatively low basicity (pKa =26.5 in CD3 CN) and a bulky molecular size (φ=1.3 nm) exhibited an unprecedented efficiency (TON up to 12240) and selectivity (>99 % polymer selectivity and >99 % carbonate linkages) toward copolymerization of CO2 and cyclohexene oxide (CHO), and produced CO2 -based polycarbonates (CO2 -PCs) with high molar masses (Mn up to 275.5 kDa) at 1 MPa of CO2 and 80 °C. Surprisingly, this binary catalytic system achieved efficient CO2 /CHO copolymerization with TOF up to 95 h-1 at 1 atm pressure and room temperature.

3D Printed CO2 -Based Triblock Copolymers and Post-Printing Modification.

We report the facile synthesis and 3D printing of a series of triblock copolymers consisting of soft and hard blocks and demonstrate that alkene pendant groups of the hard block can be covalently modified. The polymers are prepared using a salenCo(III)TFA/PPNTFA binary catalyst system and 1,2-propanediol as a chain transfer agent, providing an efficient one-pot, two-step strategy to tailor polymer thermal and mechanical properties. Thixotropic inks suitable for direct ink write printing were formulated by dissolving the block copolymers in organic solvent and dispersing NaCl particles. After printing, porous structures were produced by removing solvent and NaCl with water to give printed structures with surfaces that could be modified via UV-initiated thiol-ene click reactions. Alternatively, a tetra-thiol could be incorporated into the ink and used for cross-linking to give objects with high solvent resistance and selective degradability.

Exovinylene Cyclic Carbonates: Multifaceted CO2 -Based Building Blocks for Modern Chemistry and Polymer Science.

Carbon dioxide is a renewable, inexhaustible, and cheap alternative to fossil resources for the production of fine chemicals and plastics. It can notably be converted into exovinylene cyclic carbonates, unique synthons gaining momentum for the preparation of an impressive range of important organic molecules and functional polymers, in reactions proceeding with 100 % atom economy under mild operating conditions in most cases. This Review summarizes the recent advances in their synthesis with particular attention on describing the catalysts needed for their preparation and discussing the unique reactivity of these CO2 -based heterocycles for the construction of diverse organic building blocks and (functional) polymers. We also discuss the challenges and the future perspectives in the field.

Organocatalytic Synthesis of Alkyne-Functional Aliphatic Polycarbonates via Ring-Opening Polymerization of an Eight-Membered-N-Cyclic Carbonate.

The synthesis of well-defined propargyl-functional aliphatic polycarbonates is achieved via the organocatalytic ring-opening polymerization of prop-2-yn-1-yl 2-oxo-1,3,6-dioxazocane-6-carboxylate (P-8NC) using a wide variety of commercially available or readily made, shelf-stable organocatalysts. The resulting homopolymers show low dispersities and end-group fidelity, with the versatility of the system being demonstrated by the synthesis of telechelic copolymers and block copolymers with molar mass up to 40 kDa.

A Method for Identification and Assessment of Radioxenon Plumes by Absorption in Polycarbonates.

A method for the retrospective evaluation of the integrated activity concentration of 133Xe during radioxenon plumes and the moment of the plume's center is proposed and explored by computer modeling. The concept is to use a specimen of polycarbonate material (a stack of Makrofol N foils of thickness 120 µm and 40 µm in 1 L non-hermetic Marinelly beaker) that is placed in the environment or in a controlled nuclear or radiopharmaceutical facility. On a regular basis or incidentally, the specimen may be retrieved and gamma spectrometry in two consecutive time intervals with durations of 8 h and 16 h is performed. To assess the performance of the method, 133Xe plumes of various integrated activity concentrations and with a duration of up to 10 h are simulated and analyzed, assuming that the measurement starts with a delay of up to one day after the moment of the plume center. It is found that the deviation between the estimates by the method and their true values are within a few percent. Depending on the delay, events of integrated 133Xe activity concentration 250-1000 Bq h m-3 might be qualitatively identified. At levels >10,000 Bq h m-3, the uncertainty of the quantitative estimates might be ≤10%.

Poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) Amphiphilic Copolymers for Long-Acting Injectables: Synthesis, Non-Acylating Performance and In Vivo Degradation.

This article presents the evaluation of diblock and triblock poly(ethylene glycol)-b-poly(1,3-trimethylene carbonate) amphiphilic copolymers (PEG-PTMCs) as excipients for the formulation of long-acting injectables (LAIs). Copolymers were successfully synthesised through bulk ring-opening polymerisation. The concomitant formation of PTMC homopolymer could not be avoided irrespective of the catalyst amount, but the by-product could easily be removed by gel chromatography. Pure PEG-PTMCs undergo faster erosion in vivo than their corresponding homopolymer. Furthermore, these copolymers show outstanding stability compared to their polyester analogues when formulated with amine-containing reactive drugs, which makes them particularly suitable as LAIs for the sustained release of drugs susceptible to acylation.

Biodegradable Polymersomes with Structure Inherent Fluorescence and Targeting Capacity for Enhanced Photo-Dynamic Therapy.

Biodegradable nanostructures displaying aggregation-induced emission (AIE) are desirable from a biomedical point of view, due to the advantageous features of loading capacity, emission brightness, and fluorescence stability. Herein, biodegradable polymers comprising poly (ethylene glycol)-block-poly(caprolactone-gradient-trimethylene carbonate) (PEG-P(CLgTMC)), with tetraphenylethylene pyridinium-TMC (PAIE) side chains have been developed, which self-assembled into well-defined polymersomes. The resultant AIEgenic polymersomes are intrinsically fluorescent delivery vehicles. The presence of the pyridinium moiety endows the polymersomes with mitochondrial targeting ability, which improves the efficiency of co-encapsulated photosensitizers and improves therapeutic index against cancer cells both in vitro and in vivo. This contribution showcases the ability to engineer AIEgenic polymersomes with structure inherent fluorescence and targeting capacity for enhanced photodynamic therapy.

Randomly Distributed Sulfur Atoms in the Main Chains of CO2 -Based Polycarbonates: Enhanced Optical Properties.

Polymeric materials possessing both high refractive indices and high Abbe numbers are much in demand for the development of advanced optical devices. However, the synthesis of such functional materials is a challenge because of the trade-off between these two properties. Herein, a synthetic strategy is presented for enhancing the optical properties of CO2 -based polycarbonates by modifying the polymer's topological structure. Terpolymers with thiocarbonate and carbonate units randomly distributed in the polymers' main chain were synthesized via the terpolymerization of cyclohexene oxide with a mixture of CO2 and COS in the presence of metal catalysts, most notably a dinuclear aluminum complex. DFT calculations were employed to explain why different structural sequence were obtained with distinct bimetallic catalysts. Varying the CO2 pressure made it possible to obtain terpolymers with tunable carbonate linkages in the polymer chain. More importantly, optical property studies revealed that terpolymers with comparable thiocarbonate and carbonate units exhibited a refractive index of 1.501 with an enhanced Abbe number as high as 48.6, much higher than the corresponding polycarbonates or polythiocarbonates. Additionally, all terpolymers containing varying thiocarbonate content displayed good thermal properties with Tg >109 °C and Td >260 °C, suggesting little loss in the thermal stability compared to the polycarbonate. Hence, modification of the topological structure of the polycarbonate is an efficient method of obtaining polymeric materials with enhanced optical properties without compromising thermal performance.

A Novel [OSSO]-Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides.

A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers.

Progress in the Preparation of Functional and (Bio)Degradable Polymers via Living Polymerizations.

This review presents the latest developments in (bio)degradable approaches and functional aliphatic polyesters and polycarbonates prepared by typical ring-opening polymerization (ROP) of lactones and trimethylene carbonates. It also considers several recent innovative synthetic methods including radical ring-opening polymerization (RROP), atom transfer radical polyaddition (ATRPA), and simultaneous chain- and step-growth radical polymerization (SCSRP) that produce aliphatic polyesters. With regard to (bio)degradable approaches, we have summarized several representative cleavable linkages that make it possible to obtain cleavable polymers. In the section on functional aliphatic polyesters, we explore the syntheses of specific functional lactones, which can be performed by ring-opening copolymerization of typical lactone/lactide monomers. Last but not the least, in the recent innovative methods section, three interesting synthetic methodologies, RROP, ATRPA, and SCSRP are discussed in detail with regard to their reaction mechanisms and polymer functionalities.