Internal Cross-linking Research Articles

Probing the influence of composition and cross-linking degree on single-chain nanoparticles from poly(tetrahydrofuran-ran-epichlorohydrin) copolymers: Insights from neutron scattering, calorimetry, and dielectric spectroscopy

The industrial sector has made significant strides in the development of multicomponent and multiphasic polymer materials, including polymer blends, composites (such as nanocomposites), and various copolymers. Random copolymers, characterized by their statistical arrangement of repeating units, are particularly noteworthy due to their tunability from amorphous to semicrystalline states. In this study, we focus on poly(tetrahydrofuran-ran-epichlorohydrin) (P(THF-ran-ECH)) copolymers, which serve as precursors for single-chain nanoparticles (SCNPs). These SCNP-based materials are of particular interest as they bridge the gap between traditional polymers and colloids. This research comprehensively investigates how the type and degree of internal cross-linking influence the structure and dynamics of P(THF-ran-ECH) copolymers and their SCNPs. Techniques such as quasielastic neutron scattering (QENS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS) were employed to study copolymers with varying compositions and levels of cross-linking. By analyzing two samples with different epichlorohydrin (ECH) contents (13 mol% and 27 mol%), we aim to control crystallization and explore its effects on dynamic behavior. Our results show that both the composition and the degree of cross-linking significantly impact the dynamics of the SCNPs, with SCNPs exhibiting slower dynamics compared to their precursor copolymers. Furthermore, semicrystalline samples display faster dynamics in SCNPs than amorphous samples. These findings provide valuable insights for the design and optimization of advanced multicomponent polymer systems.

Multiphase hydrogen bonding strategies room temperature self-healing, recyclable polyurethane elastomers for applications in flame retardant materials

Novel elastomers offer new opportunities to develop multifunctional materials in terms of combining mechanical strength, room-temperature self-healing properties and recyclability. However, self-healing polymers have high mechanical strength at high internal cross-linking density, but restrict the movement of molecular chain segments leading to reduced self-healing efficiency. The presence of microphase-separated structures makes the polymers poorly efficient for repair at room temperature. In this paper, a multiphase hydrogen bonding (H-bonding) strategy is used to introduce an aliphatic ring into the system to form a repeating unit with the hard segments, as well as a bis-benzene ring structure with a methylene linkage to disrupt the crystallization of the hard domains. Specifically, PUPI-M2I3 has a mechanical tensile strength of 17.93 MPa, an excellent tensile ratio of 1109.88 %, the sample can recover 95.93 % at room temperature after 24 h of fracture and stretching, with excellent room temperature self-healing performance and recyclability. Meanwhile, the self-healing flame-retardant material based on PUPI-M2I3 is developed by comprehensive consideration, which opens a new way for the research and development of flame-retardant materials.

A bio-based soy wood adhesive modified by dual-crosslinking strategy with excellent mechanical strength and water-resistance

Soy-based adhesives have garnered significant attention owing to their distinctive environmentally sustainable characteristics and low cost. However, they exhibit inadequate bonding strength and water-resistance, which can be attributed to the presence of polar groups in soy flours. Herein, a simple and eco-friendly dual-crosslinking strategy was proposed to manufacture a soy-based adhesive (SF/IO4/CA adhesive) with excellent mechanical properties and good water-resistance. Specifically, soy flours were treated with sodium periodate (NaIO4) for oxidization, which facilitated the soy flours' self-crosslinking process by converting carbohydrates into components having the cross-linking action (internal cross-linking agents). Then, incorporating the citric acid (CA) would promote to the carboxyl groups (-COOH) of CA to react with the hydrophilic hydroxyl groups (-OH) present in soy flours by esterification reaction. The findings demonstrated that a high-performance plywood using SF/IO4/CA adhesive was successfully produced, which shear strength of cold-water (20 °C for 24 h), hot-water (63 °C for 3 h), and boiling-water (93 °C for 3 h) reached 1.69 MPa, 1.68 MPa, 1.72 MPa, and 1.47 MPa, respectively. The soy-based adhesive has excellent mechanical strength and water-resistance due to its dual-crosslinking network system, which has significant promise for application use in the wood-based panels industry.

Fabrication of black wolfberry anthocyanin-based hydrogels for monitoring freshness and extending shelf-life of Dolang lamb

In this study, a black wolfberry anthocyanin-based indication label (BWIL) was developed using black wolfberry pigment (BWP) in combination with polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) (PVA:CMC = 4:3). The potential use of BWIL for monitoring the freshness of Dorang lamb was further investigated. As revealed, physical cross-linking occurred between PVA, CMC and BWP during the preparation of BWIL. The addition of BWP promoted the internal cross-linking, porosity, and thermal stability of BWIL significantly (p < 0.05). Specifically, BWIL showed a distinct color change when exposed to the refrigerated conditions of Dorang lamb. After 6 days, 12 days and 16 days of lamb refrigeration, the ΔE of BWIL was 26.3, 28.6 and 30.7, respectively, which far exceeded the human eyes' color threshold discernible (ΔE = 3.5). Besides, the ΔE of BWIL was significantly correlated with pH, fat oxidation, and TVB-N content of Dorang lamb (p < 0.05). This result indicated that BWIL could be used for identifying the freshness of lamb accurately. Importantly, the shelf-life of lamb with BWIL was extended from 6 days to 16 days, which suggests that BWIL would be an effective tool for real-time freshness monitoring and shelf-life extending of Dorang lamb.

Ultrasonic-microwave technique promotes the physicochemical structure of hydrogel and its release characterization of curcumin in vitro

In this study, soybean protein isolate and hawthorn pectin were mixed to prepare binary hydrogels using ultrasound and microwave techniques. Moderate treatment can not only significantly improve the mechanical strength of the hydrogel, but also increase the tightness of the internal cross-linking. The strengthening of interactions (hydrogen bonds, hydrophobic interactions, and disulfide bonds) was the main reason for this trend. Especially, the ultrasonic-microwave (80 s) treatment hydrogel possessed excellent hardness (33.426 N), water-holding capacity (98.26%), elasticity (G′ = 1205 Pa), and a more homogeneous and denser microstructure. In addition, the hydrogel minimized the extent of curcumin loss (21.23%) after 5 weeks of storage. In general, the ultrasonic-microwave technique could significantly promote the physicochemical structure and curcumin bioaccessibility of hydrogels, which showed excellent market prospects in the food industry.

Structural heterogeneity in tetra-armed gels revealed by computer simulation: Evidence from a graph theory assisted characterization.

Designing homogeneous networks is considered one typical strategy for solving the problem of strength and toughness conflict of polymer network materials. Experimentalists have proposed the hypothesis of obtaining a structurally homogeneous hydrogel by crosslinking tetra-armed polymers, whose homogeneity was claimed to be verified by scattering characterization and other methods. Nevertheless, it is highly desirable to further evaluate this issue from other perspectives. In this study, a coarse-grained molecular dynamics simulation coupled with a stochastic reaction model is applied to reveal the topological structure of a polymer network synthesized by tetra-armed monomers as precursors. Two different scenarios, distinguished by whether internal cross-linking is allowed, are considered. We introduce the Dijkstra algorithm from graph theory to precisely characterize the network structure. The microscopic features of the network structure, e.g., loop size, dispersity, and size distribution, are obtained via the Dijkstra algorithm. By comparing the two reaction scenarios, Scenario II exhibits an overall more idealized structure. Our results demonstrate the feasibility of the Dijkstra algorithm for precisely characterizing the polymer network structure. We expect this work will provide a new insight for the evaluation and description of gel networks and further help to reveal the dynamic process of network formation.

Camellia meal-based adhesive with synergistic crosslinking of physical and chemical interaction for preparing aldehyde-free, anti-mildew, water-resistant wood-based composites

Wood adhesives containing toxic aldehyde-based adhesives play a vital role in the performance of wood-based panels, while the mechanical properties and water and mildew resistance of aldehyde-free adhesives are lacking. In this study, a high-strength aldehyde-free adhesive was constructed via a combination of physical and chemical crosslinks. Inexpensive alum was used to ensure a high degree of crosslinking and to increase the crystallinity. Metal ions in alum opened the protein helix, exposed the active groups, increased the number of hydrogen bonds, and ultimately improved the internal physical crosslinking ability of the adhesive. The compound formed by the Schiff base reaction formed coordination bonds with metal ions, thus forming a covalently-crosslinked network. The high-strength polymer produced in this study contained multiple physical and covalent crosslinks, resulting in significantly improved mechanical properties of the adhesive. Its water-resistant adhesive strength reached 1.96 MPa, which was 180.2% higher than that of ordinary phytogenic protein adhesive (0.69 MPa), and it can still reach 1.28 MPa after hot water circulation soaking experiment. The adhesive also possessed antifungal properties and flame-retardant capabilities, achieving a V-1 rating in the UL-94 test. This strategy expanded the application of phytogenic protein adhesives in environmentally friendly wood composite materials by replacing synthetic resins that released formaldehyde and provided an economical and feasible industrial scale production method for the preparation of high strength, water, and mildew resistant, flame retardant indoor and outdoor wood-based panels.

Synthesis of phosphate hydrogels with excellent swelling behavior prepared by ascorbic acid -mediated ARGET ATRP

This manuscript explores the synthesis of hydrogels through reversible deactivation radical polymerization (RDRP) methods, specifically, activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and Cu0-mediated ATRP. These techniques are known to offer improved control over polymer network structures due to their slow polymerization kinetics. However, these methods have historically been challenging to apply to stimuli-responsive polymers, such as those with acidic or basic moieties. In this study, the direct synthesis of poly(2-(methacryloyloxy) ethyl phosphate) (PMOEP), a phosphate-pendant hydrogel, was investigated in aqueous media by both ascorbic acid (AsA)-mediated ARGET ATRP and Cu0-mediated ATRP. 2-(methacryloyloxy) ethyl phosphate (MOEP) was utilized as the active monomer with tris(2-pyridylmethyl) amine (TPMA) as the ligand. A unique feature of this work is that the diene moiety inherently present in the commercial monomer, bis[2-(methacryloyloxy) ethyl] phosphate (BMOEP), served as the crosslinking agent to obtain the novel PMOEP hydrogel. Formulations were tuned to optimize the swelling characteristics of the hydrogels, with the restriction that the hydrogels should swell homogeneously without fracture. Importantly, using AsA as the reducing agent in the ARGET ATRP reaction resulted in improved homogeneity and enhanced swelling properties of the hydrogel. Furthermore, tuning the target degree of polymerization (Dp) ([monomer]:[initiator]) had a significant impact on swelling characteristics. Specifically, PMOEP hydrogels synthesized via ARGET ATRP with a target Dp of 300 and 1 mM CuII catalyst demonstrated outstanding water absorption capacity of more than 2500% (relative to the dry mass) in phosphate buffer solution (PBS) at pH 7.4 and over 6000% in pure water. The morphology of these hydrogels was imaged using field emission environmental scanning electron microscopy (FE-ESEM) and the chemical composition was examined using Fourier transform infrared (FTIR) spectroscopy. Furthermore, nuclear magnetic resonance (NMR) analysis was performed to investigate the conversion rate of monomer during Cu0-mediated ATRP. To the authors’ knowledge, the synthesis of a 100% phosphate-pendant hydrogel using AsA-mediated ARGET ATRP and an internal phosphodiester crosslinking moiety without dilution or comonomer, has not been reported previously. This facile method for synthesizing and controlling phosphate-based hydrogel properties also provides an opportunity to include additional functional groups and holds significant promise for applications in biomedical engineering, agriculture, and membrane separations.

Utilization of composite particles with customizable cross-linked lignin patches for dental cleansing

Lignin, a natural polyphenol polymer, is a biocompatible, cost-effective and accessible material. To fully utilize the benefits of lignin, it is crucial to transform its complex macromolecules into nanoscale particles in a single solvent. In this research, an assembly-mediated internal cross-linking method in single solvent was proposed to manufacture cross-linked lignin colloidal particles with nanoscale particle size controlled to be around 50 nm. Then, cross-linked lignin composite particles with a unique “patchy” structure for dental cleansing were obtained by rapidly grafting the cross-linked lignin colloidal particles onto the surface of silica microspheres through the bridging effect of silane coupling agent. The resulting composite particles have rivets with adjustable hardness, significantly lower than traditional abrasives like silica in both hardness and modulus. Through the group cleansing behavior of soft interlocking, a breakthrough has been achieved in the high solid content agglomeration friction mode of traditional abrasives, which effectively reduces tooth wear and exhibits an excellent plaque removal effect.

Synthesizing Hypercrosslinked Polymers with Deep Eutectic Solvents to Enhance CO2 /N2 Selectivity.

Hypercrosslinked polymers (HCPs) are widely used in ion exchange, water purification, and gas separation. However, HCP synthesis typically requires hazardous halogenated solvents e. g., dichloroethane, dichloromethane and chloroform which are toxic to human health and environment. Herein we hypothesize that the use of halogenated solvents in HCP synthesis can be overcome with deep eutectic solvents (DES) comprising metal halides-FeCl3 , ZnCl2 that can act as both the solvent hydrogen bond donor and catalyst for polymer crosslinking via Friedel Crafts alkylation. We validated our hypothesis by synthesizing HCPs in DESs via internal and external crosslinking strategies. [ChCl][ZnCl2 ]2 and [ChCl][FeCl3 ]2 was more suitable for internal and external hypercrosslinking, respectively. The specific surface areas of HCPs synthesized in DES were 20-60 % lower than those from halogenated solvents, but their CO2 /N2 selectivities were up to 453 % higher (CO2 /N2 selectivity of poly-α,α'-dichloro-p-xylene synthesized in [ChCl][ZnCl2 ]2 via internal crosslinking reached a value of 105). This was attributed to the narrower pore size distributions of HCPs synthesized in DESs.

Preparation of multifunctional cellulose macromolecule blended fabrics through internal and external synergy by N1, N6-bis (ethylene oxide-2-ylmethyl) hexane-1,6-diamine

With the diversification of people's demand for textile functions, the preparation of multifunctional fabrics is still a current research hotspot. In this study, the water-soluble epoxy compound N1, N6-bis(oxiran-2-ylmethyl) hexane-1,6-diamine (EH) was introduced into cellulose macromolecule blended fabrics (cotton/modal) by two-phase vaporization technique, resulting in excellent wrinkle, hydrophobicity, and certain UV protection effects. It could be observed by electron microscopy that EH formed a polymer film on the fiber surface. In addition, the results of EDS scans and fiber swelling rate tests showed that EH was uniformly distributed and formed a cross-linked structure in the amorphous zones inside the fibers. Compared with the control fabrics, the wrinkle recovery angle of the EH-treated fabric was increased by 39.7 %. The fabrics could reach a contact angle of 136.9°, providing excellent hydrophobic effect. In addition, the fabrics achieved certain UV protection effects (UPF of 50+). The EH-treated fabrics were less stabilized in strong acid and alkali conditions, but exhibited greater durability in other environments. In summary, the internal and external synergistic effects of EH in forming polymer films on the fibers surface and internal cross-linking structures provided a cleaner, simple, and feasible method for the preparation of multifunctional cellulose macromolecule fibers textiles.

Bifunctional lignocellulose nanofiber hydrogel possessing intriguing pH-responsiveness and self-healing capability towards wound healing applications

Lignocellulose nanofibers (LCNF) obtained from agricultural waste are potential candidates for enhancing composite materials because of their excellent mechanical properties, abundant groups and high biocompatibility. However, the application of LCNF has received limited attention to date from researchers in the healthcare field. Herein, based on the bifunctional group (carboxyl and aldehyde groups) modified LCNF (DCLCNF) and chitosan (CS), we developed a multifunctional bio-based hydrogel (CS-DCLCNF). The addition of lignin-containing DCLCNF strengthened the internal crosslinking and the intermolecular interaction of hydrogels, and the presence of lignin and carboxyl groups increased the mechanical strength of the hydrogel and the adsorption of aromatic drugs. Results revealed that the hydrogels exhibited self-healing, injectable, and high swelling rates. The hydrogels had favorable mechanical strength (G'max of ~16.60 kPa), and the maximum compressive stress was 24 kPa. Moreover, the entire tetracycline hydrochloride (TH) release process was slow and pH-responsive, because of the rich noncovalent and π–π interactions between DCLCNF and TH. The hydrogels also exhibited excellent biocompatibility and antibacterial properties. Notably, the wound healing experiment showed that the hydrogels were beneficial in accelerating wounds healing, which could heal completely in 13 days. Therefore, CS-DCLCNF hydrogels may have promising applications in drug delivery for wound healing.

Self-Adhesive, Strong Antifouling, and Mechanically Reinforced Methacrylate Hyaluronic Acid Cross-Linked Carboxybetaine Zwitterionic Hydrogels.

Hyaluronic acid and zwitterionic hydrogels are soft materials with poor mechanical properties. The unique structures and physiological properties make them attractive candidates for ideal hydrogel dressings, but the crux of lacking satisfying mechanical strengths and adhesive properties is still pendent. In this study, the physical cross-linking of dipole-dipole interactions of zwitterionic pairs was utilized to enhance the mechanical properties of hydrogels. The hydrogels have been prepared by copolymerizing methacrylate hyaluronic (HAGMA) with carboxybetaine methacrylamide (CBMAA) (the mass ratio of [HAGMA]/[CBMAA] is 2:5, 1:5, 1:10, or 1:20), obtaining HA-CB2.5, HA-CB5.0, HA-CB10.0, or HA-CB20.0 hydrogel. Therein, the HA-CB20.0 hydrogel with a high CBMAA content can generate a strong dipole-dipole interaction to form internal physical cross-links, exhibit stretchability and low elastic modulus, and withstand 99% compressive deformation and cyclic compression under strain at 90%. Moreover, the HA-CB20.0 hydrogel is adhesive to diverse substrates, including skin, glass, stainless steel, and plastic. The synergistic effect of HAGMA and CBMAA shows strong anti-biofouling, high water absorption, biodegradability under hyaluronidase, and biocompatibility.

Nanoscale Composite Lignin Colloids with Tunable Visible Colors Used for Anti-UV Cosmetics.

Nanoscale composite lignin colloids were prepared on a large scale with a process of assembly-mediated internal cross-linking in a good solvent, thus possessing absolutely nanoscale dimensions, excellent robustness, and less aggregation. The therefore prime UV resistance and various natural visible colors contribute to the preservation and beautification of skin.

Stabilization of emulsions prepared by ball milling and cellulase treated pomelo peel insoluble dietary fiber: Integrity of porous fiber structure dominates the stability

Emulsion gels from the pomelo peel insoluble dietary fiber (PIDF) were developed. The emulsification potentials of PIDFs subjected to various degrees of ball milling (M−PIDFs), cellulase hydrolysis (C-PIDF), and cellulase hydrolysis followed by ball milling (CM-PIDFs) were evaluated. Emulsions prepared by M−PIDFs for different lengths of ball milling time exhibited similar stability characteristics, confirming that M−PIDF emulsion stability might be determined by the three-dimensional structure formed by M−PIDF stacking and oil droplet capture. C-PIDF had characteristics resembling those of Pickering particles. CM-PIDF emulsions got destabilized with ball milling time prolongation. Interface tension and particle size of C/CM-PIDF decreased gradually during ball milling. Rheological and fluorescence microscopy results revealed that the intact internal crosslinking structure frameworks were disrupted in CM-PIDF emulsions. Therefore, intact fiber-based networks, rather than small particle size or low interfacial tension, determine the stability of PIDF emulsions. This study deepens the understanding of PIDF as a clean emulsifier.

Spectroscopic evidence and mechanistic insights on dehydrofluorination of PVDF in alkaline medium

This study presents newer insights on the dehydrofluorination of poly(vinylidene fluoride), PVDF, in alcoholic sodium hydroxide using infrared (IR), Raman and nuclear magnetic resonance (1H and 1H {19F}) spectroscopies. Details on the reactivity of phases and site selectivity of different orientations viz head-to-tail and tail-to-tail is comprehensively examined using IR/Raman and NMR (1D and 2D), respectively. The α-phase is prominently involved in dehydrofluorination and transforms into the more electroactive β-phase. 1H NMR spectra highlight that the tail-to-tail addition of PVDF is not disturbed and remains unaffected during dehydrofluorination reaction. Furthermore, 1H-19F heteronuclear correlation spectroscopy (Hetero COSY) clearly evidences the formation of the –(CH=CF)– double bond in dehydrofluorinated PVDF. Moreover, detailed mechanistic insights of dehydrofluorination reaction and possible internal crosslinking during the chemical transformation is presented.

Surface modification and interface strengthening strategies for fly ash and its application in anti-corrosion coatings

A robust anti-corrosive coating has been prepared by using functional fly ash with excellent interface binding strength. Molecular cross-linking design and surface augmentation techniques improve the anti-corrosion capabilities of functional fly ash coatings. The epoxy group produced by functional fly ash cross-links with the iminoamino group of isocyanate, resulting in prominent shielding functions and mechanical property improvements. In comparison with pure polyurea coating, it can improve the impedance modulus by 1000 times. This study is expected to provide new insights into the preparation of functional fly ash coatings with a unique internal cross-linking effect.

Enhanced Thermal and Dielectric Properties of Polyarylene Ether Nitrile Nanocomposites Incorporated with BN/TiO2-Based Hybrids for Flexible Dielectrics.

Outstanding high-temperature resistance, thermal stability, and dielectric properties are fundamental for dielectric materials used in harsh environments. Herein, TiO2 nanoparticles are decorated on the surface of BN nanosheets by internal crosslinking between polydopamine (PDA) and polyethyleneimine (PEI), forming three-dimensional novel nanohybrids with a rough surface. Then, an ether nitrile (PEN) matrix is introduced into the polyarylene to form polymer-based nanocomposite dielectric films. Meanwhile, the structure and micromorphology of the newly prepared nanohybrids, as well as the dielectric and thermal properties of PEN nanocomposites, are investigated in detail. The results indicate that TiO2 nanoparticles tightly attach to the surface of BN, creating a new nanohybrid that significantly enhances the comprehensive performance of PEN nanocomposites. Specifically, compared to pure PEN, the nanocomposite film with a nanofiller content of 40 wt% exhibited an 8 °C improvement in the glass transition temperature (Tg) and a 162% enhancement in the dielectric constant at 1 kHz. Moreover, the dielectric constant-temperature coefficient of the nanocomposite films remained below 5.1 × 10-4 °C-1 within the temperature range of 25-160 °C, demonstrating excellent thermal resistance. This work offers a method for preparing highly thermal-resistant dielectric nanocomposites suitable for application in elevated temperature environments.

Self-assembled superhydrophilic MOF-decorated membrane for highly efficient treatment and separation mechanism of multi-component emulsions

Complex multi-component pollutant-oil-water emulsions have caused serious environmental problems and increased the difficulty of purification treatment in the last few decades. The membrane based on two-dimensional (2D) materials can rationally control the interlayer distance, thus improved the separation performance of the membrane for complex wastewater. We herein reported a composite membrane, in which 2D metal-organic frameworks (MOFs) Co-CAT-1 with super-hydrophilicity cross-linked by polyethylene imine (PEI) was integrated into graphene oxide (GO) and then coated on polyvinylidene fluoride (PVDF) membrane (CPG membrane). The CPG membrane exhibited highly efficient in separating oil-water (including crude oil) emulsions, achieving a flux of 219 L∙m−2∙h−1∙bar−1 and a separation efficiency of 99.2 %. Moreover, the separation efficiency for complex emulsions after several cycles was maintained >99 % for dyes and 76 % for heavy metal ions (Ni2+, Pb2+, Zn2+). The remarkable fouling resistance and reusability of CPG membrane in purifying complex oil-in-water emulsions can be attributed to their internal cross-linking, electrostatic interactions, hydrogen bonding attraction, and π-π stacking. Molecular dynamics simulations were employed for in-depth studies on the separation processes of dye- and heavy metal ions-emulsions, revealing the mechanisms of mass transfer within the membrane. This work aims to construct stable and multifunctional membranes for separating pollutant-oil-water emulsions with multi-component.

NIR light-induced functionalized MXene as a dynamic-crosslinker for reinforced polyurethane composites with shape memory and self-healing

Near infrared (NIR) light-driven shape memory can expand the potential of polyurethane as advanced materials. Herein, polyurethane composites (PU/B-THDI/FMXene) with Diels-Alder (D-A) reversible crosslinking feature were fabricated in combination with internal crosslinker bis(2-hydroxyethyl) terephthalate (BHET) modified hexamethylene-diisocyanate trimer (B-THDI), and functionalized MXene (FMXene). FMXene was prepared via 3-isocyanatopropyltriethoxysilane (IPTS) as a coupling agent between MXene and furfuryl alcohol (FA) through covalent bonds, thereby enabling dynamic crosslinking. FMXene can not only form D-A dynamic-crosslinked network with PU chain, but also retain excellent thermal conductivity. Only containing 2 wt% FMXene endows PU/B-THDI/FMXene2 composites with fast shape memory (<15 s, shape-fixity and recovery rates are 88.1 % and 97.8 %, respectively), self-healing (<100 s, the healing efficiency for tensile strength and elongation at break are 88.0 % and 91.0 %, respectively), good self-healing repeatability (79.1 %) and thermal conductivity (0.661 W m−1 K−1). Moreover, PU/B-THDI/FMXene2 exhibits remarkable mechanical performances (tensile strength of 16.9 MPa and elongation at break of 233.9 %) and thermal stability. In addition, B-THDI with crosslinking and toughening effects provides certain strength and flexibility for PU. Thus, this work may open new approaches for developing photothermal-induced shape memory polyurethane.