Project description:A new type of tetraphenylborate salts derived from highly basic and nucleophilic amines, namely 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU) and triazabicyclodecene (TBD), was applied to the preparation of networked poly(thiourethane)s (PTUs), which showed a vitrimer-like behavior, with higher stress-relaxation rates than PTUs prepared by using dibutyl thin dilaurate (DBTDL) as the catalyst. The use of these salts, which release the amines when heated, instead of the pure amines, allows the formulation to be easily manipulated to prepare any type of samples. The materials prepared from stoichiometric mixtures of hexamethylene diisocyanate (HDI), trithiol (S3) and with a 10% of molar excess of isocyanate or thiol were characterized by FTIR, thermomechanical analysis, thermogravimetry, stress-relaxation tests and tensile tests, thus obtaining a complete thermal and mechanical characterization of the materials. The recycled materials obtained by grinding the original PTUs and hot-pressing the small pieces in the optimized time and temperature conditions were fully characterized by mechanical, thermomechanical and FTIR studies. This allowed us to confirm their recyclability, without appreciable changes in the network structure and performance. From several observations, the dissociative interchange trans-thiocarbamoylation mechanism was evidenced as the main responsible of the topological rearrangements at high temperature, resulting in a vitrimeric-like behavior.
Project description:In the state-of-the-art membrane industry, membranes have linear life cycles and are commonly disposed of by landfill or incineration, sacrificing their sustainability. To date, little or no thought is given in the design phase to the end-of-life management of membranes. For the first time, we have innovated high-performance sustainable membranes, which can be closed-loop recycled after long-term usage for water purification. By synergizing membrane technology and dynamic covalent chemistry, covalent adaptable networks (CANs) with thermally reversible Diels-Alder (DA) adducts were synthesized and employed to fabricate integrally skinned asymmetric membranes via the nonsolvent-induced phase separation technique. Due to the stable and reversible features of CAN, the closed-loop recyclable membranes exhibit excellent mechanical properties and thermal and chemical stabilities as well as separation performance, which are comparable to or even higher than the state-of-the-art nonrecyclable membranes. Moreover, the used membranes can be closed-loop recycled with consistent properties and separation performance by depolymerization to remove contaminants, followed by refabrication into new membranes through the dissociation and reformation of DA adducts. This study may fill in the gaps in closed-loop recycling of membranes and inspire the advancement of sustainable membranes for a green membrane industry.
Project description:The modern materials economy is inefficient since most products are principally derived from non-renewable feedstocks and largely single-use in nature. Conventional thermoset materials are often inherently unreprocessable due to their irreversible covalent crosslinks and hence are challenging to recycle and/or reprocess. Covalent adaptable networks (CAN)s, which incorporate reversible or dynamic covalent bonding, have emerged as an efficient means to afford reprocessable crosslinked materials and increasing the feedstock sustainability of CANs is a developing aim. In this study, the biomass-derived lipoic acid, which possesses a dynamic cyclic disulfide moiety, was transformed into a series of bifunctional monomers via a one-step esterification or amidation reaction and reacted with a commercially available multi-valent thiol in the presence of an organobase catalyst to afford dynamically crosslinked networks. Large differences in material properties, such as storage modulus and glass transition temperature, were observed when the ratio of the lipoic acid-based monomer to thiol (from 1 : 1 to 16 : 1) and the composition of the monomer were changed to modify the network architecture. The thermomechanical properties of an optimised formulation were investigated more thoroughly to reveal a moderately strong rubber (ultimate tensile strength = 1.8 ± 0.4 MPa) possessing a large rubbery plateau (from 0 to 150 °C) which provides an adaptable material with a wide operational temperature range. Finally, the chemical recycling, or depolymerisation, of the optimised network was also demonstrated by simply solvating the material in the presence of an organobase catalyst.
Project description:Boronic esters prepared by condensation of boronic acids and diols have been widely used as dynamic covalent bonds in the synthesis of both discrete assemblies and polymer networks. In this study we investigate the potential of a new dynamic-covalent motif, derived from TetraAzaADamantanes (TAADs), with their adamantane-like triol structure, in boronic ester-based covalent adaptable networks (CANs). The TetraAzaADamantane-boronic ester linkage has recently been reported as a more hydrolytically stable boronic ester variant, while still having a dynamic pH response: small-molecule studies found little exchange at neutral pH, while fast exchange occurred at pH 3.8. In this work, bi- and trifunctional TetraAzaADamantane linkers were synthesised and crosslinked with boronic acids to form rubber-like materials, with a Young's modulus of 1.75 MPa. The dynamic nature of the TetraAzaADamantane networks was confirmed by stress relaxation experiments, revealing Arrhenius-like behaviour, with a corresponding activation energy of 142 ± 10 kJ/mol. Increasing the crosslinking density of the material from 10% to 33% resulted in reduced relaxation times, as is consistent with a higher degree of crosslinking within the dynamic networks. In contrast to the reported accelerating effect of acid addition to small-molecule TetraAzaADamantane complexes, within the polymer network the addition of acid increased relaxation times, suggesting unanticipated interactions between the acid and the polymer that cannot occur in the corresponding small-molecules analogues. The obtained boronate-TetraAzaADamantane materials were thermally stable up to 150°C. This thermal stability, in combination with the intrinsically dynamic bonds inside the polymer network, allowed these materials to be reprocessed and healed after damage by hot-pressing.
Project description:Polymer networks built out of dynamic covalent bonds offer the potential to translate the control and tunability of chemical reactions to macroscopic physical properties. Under conditions at which these reactions occur, the topology of covalent adaptable networks (CANs) can rearrange, meaning that they can flow, self-heal, be remolded, and respond to stimuli. Materials with these properties are necessary to fields ranging from sustainability to tissue engineering; thus the conditions and time scale of network rearrangement must be compatible with the intended use. The mechanical properties of CANs are based on the thermodynamics and kinetics of their constituent bonds. Therefore, strategies are needed that connect the molecular and macroscopic worlds. In this Perspective, we analyze structure-reactivity-property relationships for several classes of CANs, illustrating both general design principles and the predictive potential of linear free energy relationships (LFERs) applied to CANs. We discuss opportunities in the field to develop quantitative structure-reactivity-property relationships and open challenges.
Project description:Covalent adaptable networks (CANs) are polymer materials that are covalently cross-linked via dynamic covalent bonds. The cross-linked polymer network is generally expected to be insoluble, as is seen for traditional thermosets. However, in recent years, it has become apparent that-under certain conditions-both dissociative and associative CANs can be dissolved in a good solvent. For some applications (e.g., those that require long-term (chemical) stability), the solubility of CANs can be problematic. However, many forget that (selective) solubility of CANs can also be applied advantageously, for example, in recycling or modification of the materials. In this work, we provide results and insights related to the tunable solubility of imine-based CANs. We observed that selected CANs could be fully dissolved in a good solvent without observing dissociation of imines. Only in an acidic environment (partial) dissociation of imines was observed, which could be reverted to the associated state by addition of a base. By adjusting the network composition, we were able to either facilitate or hamper solubility as well as control the size of the dissolved particles. DLS showed that the size of dissolved polymer particles decreased at lower concentrations. Similarly, decreasing cross-linking density resulted in smaller particles. Last, we showed that we could use the solubility of the CANs as a means for chemical recycling and postpolymerization modification. The combination of our studies with existing literature provides a better understanding of the solubility of CANs and their applications as recyclable thermosets.
Project description:Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO2-facilitated recyclability without sacrificing performance. The presence of CO2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability.
Project description:Covalent adaptable networks (CANs) are being developed as future replacements for thermosets as they can retain the high mechanical and chemical robustness inherent to thermosets but also integrate the possibility of reprocessing after material use. Here, covalent adaptable polyimine-based networks were designed with methoxy and allyloxy-substituted divanillin as a core component together with long flexible aliphatic fatty acid-based amines and a short rigid chain triamine, yielding CANs with a high renewable content. The designed series of CANs with reversible imine functionality allowed for fast stress relaxation and tailorability of the thermomechanical properties, as a result of the ratio between long flexible and short rigid amines, with tensile strength (σb) ranging 1.07-18.7 MPa and glass transition temperatures ranging 16-61 °C. The CANs were subsequently successfully reprocessed up to three times without determinantal structure alterations and retained mechanical performance. The CANs were also successfully chemically recycled under acidic conditions, where the starting divanillin monomer was recovered and utilized for the synthesis of a recycled CAN with similar thermal and mechanical properties. This promising class of thermosets bearing sustainable dynamic functionalities opens a window of opportunity for the progressive replacement of fossil-based thermosets.
Project description:The introduction of dynamic covalent bonds into cross-linked polymer networks enables the development of strong and tough materials that can still be recycled or repurposed in a sustainable manner. To achieve the full potential of these covalent adaptable networks (CANs), it is essential to understand-and control-the underlying chemistry and physics of the dynamic covalent bonds that undergo bond exchange reactions in the network. In particular, understanding the structure of the network architecture that is assembled dynamically in a CAN is crucial, as exchange processes within this network will dictate the dynamic-mechanical material properties. In this context, the introduction of phase separation in different network hierarchies has been proposed as a useful handle to control or improve the material properties of CANs. Here we report-for the first time-how Raman confocal microscopy can be used to visualize phase separation in imine-based CANs on the scale of several micrometers. Independently, atomic force microscopy (AFM) confirmed the phase-separated domains inside the polymer. Remarkably, the materials were found to undergo phase separation despite being built up from miscible monomers, which arguably should yield homogeneous materials. We found that the phase separation not only affected the appearance of the material but-more notably-also had a noticeable effect on the thermal-mechanical properties of the material: CANs (of equal aliphatic/aromatic monomer composition) that displayed phase separation had both a higher crossover temperature (T cross, where tan(δ) = 1, and where the material transits from a rubbery to a viscous state) and an increased elastic modulus (G'). By modifying the CAN architecture, we were able to either suppress or enhance the phase separation, and we propose that the phase separation is driven by favorable π-π interactions between the aromatic components. Our work further shows the importance of phase separation in CANs, including in networks built from miscible components, and provides a handle to control the dynamic material properties. Moreover, our work underlines the suitability of Raman imaging as a method to visualize phase separation in CANs.
Project description:The development of sulfur-rich polymers derived from elementary sulfur provides an innovative approach to industrial waste valorization. Despite significant advancements in polymerization techniques and promising applications beyond traditional polymers, polysulfide networks are still primarily stabilized by diene crosslinkers, forming robust C-S bonds that hinder the degradation of sulfur-based polymers. In this study, the anionic ring-opening copolymerization of chemically homologous S8 and cyclic disulfides was explored to yield robust sulfur-rich copolymers with high molecular weight. The incorporation of polysulfide segments not only efficiently activated the crosslinked networks for excellent reprocessability and mechanical adaptability but also endowed the resulting copolymer with high optical transparency in the near-infrared region. More importantly, the dynamic disulfide crosslinking sites promoted the chemical closed-loop recyclability of the polysulfide networks via reversible S-S cleavage. This innovative inverse vulcanization strategy utilizing dynamic disulfide crosslinkers offers a promising pathway for the advanced applications and upcycling of high-performance sulfur-rich polymers.