Supramolecular polymers, as a type of dynamic polymers, are subordinate to the interdisciplinary field of polymer chemistry and supramolecular chemistry, whose development has greatly promoted the prosperity of new materials. Notably, molecular weight is one of the most important parameters of supramolecular polymers, which affects the physical/chemical properties and processing applications of materials. Developing new methods for characterizing the molecular weight of supramolecular polymers is crucial for advancing the development of supramolecular polymers. In this review, we elaborate and summarize three strategies for characterizing the molecular weight of supramolecular polymers that recently reported by our research group according to the characteristics of supramolecular polymers, including (1) the molecular weight distinction corresponding to variable fluorescence colors, (2) matching different molecular weights with different fluorescence lifetime, (3) transforming supramolecular polymers into mechanically interlocked polymers or covalent polymers. Besides, we also discuss the limitations of current methods for characterizing supramolecular polymers. We hope that this review can promote the development of supramolecular polymers and significantly inspire to exploit new methods to characterizing molecular weight of supramolecular polymers.
Poly(butylene succinate) (PBS) exhibits many advantages, such as renewability, biodegradability, and impressive thermal and mechanical properties, but is limited by the low melt viscosity and strength resulted from the linear structure. To address this, vitrimeric network was introduced to synthesize PBS vitrimers (PBSVs) based on dynamic imine bonds through melt polymerization of hydroxyl-terminated PBS with vanillin derived imine containing compound and hexamethylene diisocyanate using trimethylolpropane as a crosslinking monomer. PBSVs with different crosslinking degrees were synthesized through changing the content of the crosslinking monomer. The effect of crosslinking degree on the thermal, theological, mechanical properties, and stress relaxation behavior of the PBSVs was studied in detail. The results demonstrated that the melt viscosity, melt strength, and heat resistance were enhanced substantially without obvious depression in crystallizability, thermal stability, and mechanical properties through increasing crosslinking degree. In addition, the PBSVs exhibit thermal reprocessability with mechanical properties recovered by more than 90% even after processing for three times. Furthermore, PBSV with improved melt properties shows significantly improved foamability compared to commercial PBS. This research contributes to the advancement of polymer technology by successfully developing PBS vitrimers with improved properties, showcasing their potential applications in sustainable and biodegradable materials.
Elastomers with high mechanical toughness can guarantee their durability during service life. Self-healing ability, as well as recyclability, can also extend the life of materials and save the consuming cost of the materials. Many efforts have been dedicated to promoting the mechanical toughness as well as the self-healing capability of elastomers at the same time, while it remains a challenge to balance the trade-off between the above properties in one system. Herein we proposed a molecular design driven by dual interactions of acylsemicarbazide hydrogen bonding and Cu2+-neocuproine coordination simultaneously. By introducing the reversible multiple hydrogen bonds and strong coordination bonds, we successfully fabricated an extremely tough and self-healing elastomer. The elastomer can achieve an impressive top-notch toughness of 491 MJ/m3. Furthermore, it boasted rapid elastic restorability within 10 min and outstanding crack tolerance with high fracture energy (152.6 kJ/m2). Benefiting from the combination of dynamic interactions, the material was able to self-repair under 80 °C conveniently and could be reprocessed to restore the exceptional mechanical properties.
The incorporation of dynamic covalent bonds into thermosets facilitates the reprocessing of polymer networks, thereby meeting the sustainable requirements for polymer recycling. However, the mechanical properties of many materials often decline significantly upon reprocessing due to side reactions caused by harsh processing conditions. In this work, we find that the aromatic dithiocarbamate bond can undergo dissociation under mild conditions without the need for a catalyst, enabling the efficient reprocessing of the corresponding polydithiourethane. As a consequence, the mechanical properties of the polydithiourethane can be largely preserved after reprocessing. The discovery of this dynamic chemistry is anticipated to broaden the potential for material design in dynamic covalent polymer networks.
Realizing multiple locked shapes in pre-oriented liquid crystal elastomers (LCEs) is highly desired for diversifying deformations and enhancing multi-functionality. However, conventional LCEs only deform between two shapes for each actuation cycle upon liquid crystal-isotropic phase transitions induced by external stimuli. Here, we propose to regulate the actuation modes and the locked shapes of a pre-orientated epoxy LCE by combining dynamic covalent bonds with cooling-rate-mediated control. The actuation modes can be adjusted on demand by exchange reactions of dynamic covalent bonds. Derived from the established actuation modes, such as elongation, bending, and spiraling, the epoxy LCE displays varied locked shapes at room temperature under different cooling rates. Various mediums are utilized to control the cooling rate, including water, silicone oil, and copper plates. This approach provides a novel way for regulating the actuation modes and locked shapes of cutting-edge intelligent devices.
Thermochromic polymers with tunable thermochromism, high stretchability and mechanical strength are of interests for optical information storage and encryption. In this work, we demonstrate a new design of thermo-fluorochromic carboxylated nitrile butadiene rubber (XNBR) elastomer cross-linked by Eu3+-COOH dynamic coordination with deprotonated imidazole (DPIm) as the ancillary ligand. The presence of DPIm not only improves the mechanical strength and stretchability, but also dramatically intensifies the fluorescence emission and lifetime of the Eu-containing elastomer. The elastomer behaves reversible thermo-fluorochromism with easily tunable transition temperature and emission intensity by the simple change of the deprotonation degree of imidazole. The facile tunable thermo-fluorochromism, exceptional mechanical strength, and high stretchability (up to about 5000%) enable the Eu-containing XNBR elastomer with potential applications in soft electronics where optical information storage and encryption are required.
A series of novel side-chain liquid crystalline (SCLC) copolymers were synthesized by attaching two distinct mesogenic units, namely a chiral cholesteryl-based monomer (M1) and an achiral biphenyl-based monomer (M2), to a poly(3-mercaptopropylmethylsiloxane) (PMMS) backbone via thiol-ene click chemistry. The influence of side chain composition on the self-assembly behavior and phase structures of these SCLC copolymers was systematically investigated using different instrument. Results indicate that three distinct liquid crystalline phases and four unique molecular configurations were identified within the polymer series, with the emergence of the liquid crystalline phase being a synergistic outcome of the two distinct side chains. This study underscores the critical influence of side chain dimensions, rigidity, and spatial volume on the self-assembly structures and phase characteristics of liquid crystalline polymers, providing valuable insights for the rational design and development of advanced functional materials with tailored properties.
Developing hydroscopic actuators with simultaneous high elasticity, shape programmability and tunable actuating behaviors are highly desired but still challenging. In this study, we propose an orthogonal composite design to develop such a material. The developed composite elastomer comprises carboxyl group-grafted polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS-g-COOH) as the elastic substrate, and a synthesized azobenzene derivative as the functional filler (Azo12). By surface treatment using acidic and base solutions, the carboxyl groups on the surface can reversibly transform into carboxylate groups, which render the composite tunable hygroscopic actuating functionality. On another aspect, the added filler undergoes trans-to-cis isomerization when exposed to UV light irradiation, leading to liquefaction of the crystalline aggregates formed by Azo12 molecules. The liquefied Azo12 molecules can autonomously resotre their trans form and reform the crystalline structure. This reversible change in crystralline structure is utilized to realize the shape memory property, and 5 wt% of Azo12 addition is adequate for the composite to exhibit photo-responsive shape memory behavior without compromising much of the elasricity. The regualtion of external geometry by shape memory effect is effective in altering the actuating behavior. The proposed method can be extend to designing different composites with the demonstrated functionalities.
Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility. Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.
Crystal polymers or liquid crystal elastomers undergo a phase transition that results in a change in the corresponding optical properties, which has the potential to be applied in areas such as information encryption and anti-counterfeiting. The utilization of these materials for patterning purposes requires different phase transition temperatures. However, once prepared, altering the phase transition temperature of them presents significant challenges. Herein, a poly(oxime-ester) (POE) network is developed to achieve high-resolution and multilevel patterning by photo-induced isomerization. The as-prepared POE exhibits the ability to transition from an opaque state to a transparent state under temperature stimuli, with the transition temperature and kinetics dependent on UV light exposure time. Thus, complex patterns and information can be encrypted through different selective regional exposure time and decrypted under specific temperature or cooling time. Furthermore, we illustrate an example of temporal communication, where cooling time or temperature serves as the encoded information. This research expands the application scope of advanced encryption materials, showcasing the potential of POE in dynamic information encryption and decryption processes.
In this study, we synthesized a series of ABA-type vitrimers by crosslinking the short A moieties of precursors with a bifunctional crosslinker and evaporating the small molecular byproduct. The vitrimer samples thus prepared exhibit linear viscoelasticity dependent on the length of A moiety as well as the content of the crosslinks. When the average number of A monomers per end moiety m=1.1, the crosslinker can only extend the chain but not crosslink the chain. When m becomes 2.8 or higher, introducing a crosslinker first leads to the gelation, whereas excess in crosslinker molecules leads opening of the crosslinking sites and accordingly reentry into the sol regime. Surprisingly, a further increase in the length of the A moieties increases the relaxation time much weaker than the exponential increase seen for the physically crosslinked ABA-type ionomers. We attribute this difference to the distinct relaxation mechanisms: the relaxation of the vitrimer samples is based on relatively independent exchange reactions, which contrasts with the ABA-type ionomers that relax through the collective hopping of connected ionic groups from one ion aggregate to another.
Poly(butylene adipate-co-terephthalate) (PBAT), a widely studied biodegradable material, has not effectively addressed the problem of plastic waste. Taking into consideration the cost-effectiveness, upcycling PBAT should take precedence over direct composting degradation. The present work adopts a chain breaking-crosslinking strategy, upcycling PBAT into dual covalent adaptable networks (CANs). During the chain-breaking stage, the ammonolysis between PBAT and polyethyleneimine (PEI) established the primary crosslinked network. Subsequently, styrene maleic anhydride copolymer (SMA) reacted with the hydroxyl group, culminating in the formation of dual covalent adaptable networks. In contrast to PBAT, the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa, alongside an inherent resistance to creep and solvents. Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups, the PBAT-dual-CANs exhibited fast stress relaxation. Additionally, they could be recycled through extrusion and hot-press reprocessing, while retaining their biodegradability. This straightforward strategy offers a solution for dealing with plastic waste.
Recycling of carbon fiber reinforced composites is important for sustainable development and the circular economy. Despite the use of dynamic chemistry, developing high-strength recyclable CFRPs remains a major challenge due to the mutual exclusivity between the dynamic and mechanical properties of materials. Here, we developed a high-strength recyclable epoxy resin (HREP) based on dynamic dithioacetal covalent adaptive network using diglycidyl ether bisphenol A (DGEBA), pentaerythritol tetra(3-mercapto-propionate) (PETMP), and vanillin epoxy resin (VEPR). At high temperatures, the exchange reaction of thermally activated dithioacetals accelerated the rearrangement of the network, giving it significant reprocessing ability. Moreover, HREP exhibited excellent solvent resistance due to the increased cross-linking density. Using this high-strength recyclable epoxy resin as the matrix and carbon fiber modified with hyperbranched ionic liquids (HBP-AMIM+PF6−) as the reinforcing agent, high performance CFRPs were successfully prepared. The tensile strength, interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) of the optimized formulation (HREP20/CF-HBPPF6) were 1016.1, 70.8 and 76.0 MPa, respectively. In addition, the CFRPs demonstrated excellent solvent and acid/alkali-resistance. The CFRPs could completely degrade within 24 h in DMSO at 140 °C, and the recycled CF still maintained the same tensile strength and ILSS as the original after multiple degradation cycles.
Polyimides are a family of high-tech plastics that have irreplaceable applications in the fields of aerospace, defense, and opto-electronics, but polyimides are difficult to be reprocessed and recycled at the end of their service life, resulting in a significant waste of resources. Hence, it is of great significance to develop recyclable polyimides with comparable properties to the commercial products. Herein, we report a novel polymer-to-monomers chemically recyclable poly(imide-imine) (PtM-CR-PII) plastic, synthesized by cross-linking the amine-terminated aromatic bisimide monomer and the hexa-vanillin terminated cyclophosphazene monomer via dynamic imine bonds. The PtM-CR-PII plastic exhibits comparable mechanical and thermal properties as well as chemical stability to the commercial polyimides. The PtM-CR-PII plastic possesses a high Young’s modulus of ≈3.2 GPa and a tensile strength as high as ≈108 MPa, which also exhibits high thermal stability with a glass transition temperature of ≈220 °C. Moreover, the PtM-CR-PII plastic exhibits outstanding waterproofness, acid/alkali-resistance, and solvent-resistance, its appearance and mechanical properties can be well maintained after long-term soaking in water, highly concentrated acid and base, and various organic solvents. Furthermore, the cyclophosphazene moieties endow the PtM-CR-PII plastic with excellent flame retardancy. The PtM-CR-PII plastic exhibits the highest UL-94 flame-retarding rating of V-0 and a limiting oxygen index (LOI) value of 45.5%. Importantly, the PtM-CR-PII plastic can be depolymerized in an organic solvents-acid mixture medium at room temperature, allowing easy separation and recovery of both monomers in high purity. The recovered pure monomers can be used to regenerate new PtM-CR-PII plastics, enabling sustainable polymer-monomers-polymer circulation.
Supramolecular polymer networks (SPNs) are celebrated for their dynamic nature, yet they often exhibit inadequate mechanical properties. Thus far, the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge. Herein, we introduce [2]rotaxane into SPN to serve as another cross-link, which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties. Compared with SPN, the dually cross-linked network (DPN) demonstrates superior breaking strength, Young’s modulus, puncture force and toughness, underscoring its superior robustness. Furthermore, the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals, and in some cases surpasses, that of SPN, owing to the efficient energy dissipation pathway facilitated by [2]rotaxane. In addition, benefiting from stable topological structure of [2]rotaxane, DPN exhibits accelerated recovery from deformation, indicating superior elasticity compared to SPN. This strategy elevates the performance of SPNs across multiple metrics, presenting a promising avenue for the development of high-performance dynamic materials.
Covalent adaptive networks (CANs) are capable of undergoing segment rearrangement after being heated, which endows the materials with excellent self-healing and reprocessing performance, providing an efficient solution to the environment pollution caused by the plastic wastes. The main challenge remains in developing CANs with both excellent reprocessing performance and creep-resistance property. In this study, a series of CANs containing dynamic covalent benzopyrazole-urea bonds were developed based on the addition reaction between benzopyrazole and isocyanate groups. DFT calculation confirmed that relatively low dissociation energy is obtained through undergoing a five-member ring transition state, confirming excellent dynamic property of the benzopyrazole-urea bonds. As verified by the FTIR results, this nice dynamic property can be well maintained after incorporating the benzopyrazole-urea bonds into polymer networks. Excellent self-healing and reprocessing performance is observed by the 3-ABP/PDMS elastomers owing to the dynamic benzopyrazole-urea bonds. Phase separation induced by the aggregation of the hard segments locked the benzopyrazole-urea bonds, which also makes the elastomers display excellent creep-resistance performance. This hard phase locking strategy provides an efficient approach to design CANs materials with both excellent reprocessing and creep-resistance performance.
Vitrimers have emerged as a prominent research area in the field of polymer materials. Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures, while the impact of chemical structure on aggregate structure of vitrimers, particularly during polymer processing, remains insufficiently investigated. The present study employed commercial maleic anhydride-grafted-high density polyethylene (M-g-HDPE) as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process. Through chemical structure characterization, morphology observation, thermal and mechanical properties investigation, as well as aggregate structure analysis, this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing. A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing, resulting in a lower orientation of the PE chains. However, lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation. The uneven morphology of fiber-shaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding, which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.
Polydimethylsiloxane (PDMS) is an electron-withdrawing material that is widely used in triboelectric nanogenerators (TENGs). However, PDMS has poor mechanical properties after curing and is easily damaged when subjected to long-term workloads. Thus, the long-term stable operation of TENGs under mechanical deformation cannot be guaranteed. In this work, multiple hydrogen bonds and aromatic disulfide bonds were introduced into PDMS elastomers. These elastomers exhibited high toughness (a tensile strength of 1.91 MPa and an elongation at break of 340%), good recyclability, and room-temperature self-healing properties (healing efficiency of 96.4% in 24 h). Recyclable sandwich-like triboelectric nanogenerators with excellent electrical output performance (13.5 V) and room-temperature self-healing performance (24 h, 98% recovery of self-generating performance) were prepared by utilizing the hydrogen bonding between the PDMS elastomer and MXene. The work reported herein offers theoretical guidance and a compelling strategy for developing high-performance TENG negative friction layers.
The development of physically crosslinked hydrogels with excellent mechanical and sensing properties is of importance for expanding the practical applications of intelligent soft hydrogel materials. Herein, after copolymerization of hydroxyl-containing amino acid derivative N-acryloyl serine (ASer) with acrylamide (AM), we introduce Zr4+ through an immersion strategy to construct metal ion-toughened non-covalent crosslinked hydrogels (with tensile strength of up to 5.73 MPa). It is found that the synergistic coordination of hydroxyl and carboxyl groups with Zr4+ substantially increases the crosslinking density of the hydrogels, thereby imparting markedly superior mechanical properties compared to hydroxyl-free Zr4+-crosslinked hydrogels, such as N-acryloyl alanine (AAla) copolymerized with AM hydrogels (with tensile strength of 2.98 MPa). Through the adjustment of the composition of the copolymer and the density of coordination bonds, the mechanical properties of the hydrogels can be modulated over a wide range. Additionally, due to the introduction of metal ions and the dynamic nature of coordination bonds, the hydrogels also exhibit excellent sensing performance and good self-recovery properties, paving the way for the development of flexible electronic substrates with outstanding comprehensive performances.
Adhesives play an important role in modern society's production and daily life. Developing robust and sustainable adhesives remains a great challenge. Here we report a sustainable epoxy-vitrimer adhesive with high adhesive strength (about 10 MPa) and reusability (82% strength after 3 times). This adhesive can be fabricated from commercially available products through a straightforward hot-pressing method without the need of solvents. The adhesive process is also simple, requiring only 30 min at 180 °C. In addition, the vitrimer adhesive has the advantages of both erasability for reuse and excellent water resistance. This work provides a facile strategy to fabricate high-strength adhesive that ensures reusability, recyclability, low cost of raw materials, and simple processing technology. Simultaneously, it expands the range of potential applications for epoxy vitrimers.
Achieving versatile room temperature phosphorescence (RTP) materials, especially with tunable mechanical properties and shape memory is attractive and essential but rarely reported. Here, a strategy was reported to realize multi-functional RTP films with multicolor fluorescence, ultralong afterglow, adjustable mechanical properties, and shape memory through the synergistic dynamic interaction of lanthanide (LnIII)-terpyridine coordination, borate ester bonds, and hydrogen bondings in a poly(vinyl alcohol) (PVA) matrix. By varying the amount of borax, the mechanical properties of the films could be finely controlled due to the change of crosslinking degree of dynamic borate ester bonds in PVA. The assembly and disassembly of borate ester bonds upon the trigger of borax and acid were applied as reversible linkage to achieve programmable shape memory behavior. In addition, the films displayed both fascinating multicolor fluorescence and ultralong afterglow characteristics due to the presence of LnIII doping and confinement of terpyridine in PVA. This study provides a new avenue to impart modulable mechanical strength and shape memory to RTP materials.
The incorporation of molecular switches into polymer networks has been a powerful approach for the development of functional polymer materials that display macroscopic actuation and function enabled directly by molecular changes. However, such materials sometimes require harsh conditions to perform their functions, and the design of new molecular photoswitches that can function under physiological conditions is highly needed. Here, we report the design and synthesis of a spiropyridine-based photoswitchable hydrogel that exhibits light-driven actuation at physiological pH. Owing to its high pKa, spiropyridine maintains its ring-open protonated form at neutral pH, and the resulting hydrogel remains in a swollen state. Upon irradiation with visible light, the ring closure of spiropyridine leads to a decrease in the charge and a reduction in the volume of the hydrogel. The contracted gel could spontaneously recover to its expanding state in the dark, and this process is highly dynamic and reversible when the light is switched on and off. Furthermore, the hydrogel shows switchable fluorescence in response to visible light. Bending deformation is observed in the hydrogel thin films upon irradiation from one side. Importantly, the independence of this spiropyridine hydrogel from the acidic environment makes it biotolerant and shows excellent biocompatibility. This biocompatible spiropyridine hydrogel might have important biorelated applications in the future.
Elastomers with high strength and toughness, excellent self-healing properties, and biocompatibility have broad application prospects in wearable electronics and other fields, but preparing it remains a challenge. In this work, we propose a highly adaptable strategy by introducing the small molecule crosslinking agent of triethanolamine (TEA) to the poly(thioctic acid) (PTA) chains and preparing the PAxEy elastomers using a simple synthesis step. This strategy stabilizes the PTA chains by constructing multiple non-covalent cross-linked dynamic networks, endowing materials with excellent strength and toughness (tensile strength of 288 kPa, toughness of 278.2 kJ/m3), admirable self-healing properties (self-healing efficiency of 121.6% within 7 h at 70 °C), and good biocompatibility. The PAxEy elastomers can also be combined with MWNTs to become flexible strain sensors, which can be used to monitor human joint movements with high sensitivity, repeatable responses, and stability.