Non-isocyanate Synthesis of Covalent Adaptable Networks Based on Dynamic Hindered Urea Bonds: Sequential Polymerization and Chemical Recycling.

The development of environmentally sustainable processes for polymer recycling is of paramount importance in the polymer industry. In particular, the implementation of chemical recycling for thermoset polymers via covalent adaptable networks (CANs), particularly those based on the dynamic hindered urea bond (HUB), has garnered intensive attention from both the academic and industrial sectors. This interest stems from its straightforward chemical structure and reaction mechanism, which are well-suited for commercial polyurethane and polyurea applications. However, a substantial drawback of these CANs is the requisite use of toxic isocyanate curing agents for their synthesis. Herein, we propose a new HUB synthesis pathway involving thiazolidin-2-one and a hindered amine. This ring-opening reaction facilitates the isocyanate-free formation of a HUB and enables sequential reactions with acrylate and epoxide monomers via thiol-Michael and thiol-epoxy click chemistry. The CANs synthesized using this methodology exhibit superior reprocessability, chemical recyclability, and reutilizability, facilitated by specific catalytic and solvent conditions, through the reversible HUB, thiol-Michael addition, and transesterification processes.

A microcapsule-based reusable self-reporting system using a donor-acceptor Stenhouse adduct.

Self-reporting systems automatically indicate damaged or corroded surfaces via color changes or fluorescence. In this study, a novel reusable self-reporting system is developed by exploiting the reversibility of a donor-acceptor Stenhouse adduct (DASA). The synthesized DASA precursor exhibits a color change when damaged upon reaction with diethylamine, and returns to its colorless form upon irradiation with visible light. Microcapsules are synthesized with a core comprising styrene and the DASA precursor, along with a shell formed of urea and formaldehyde. The optimal particle size and shell thickness of the microcapsules are 225 µm and 0.17 µm, respectively. The DASA precursor-containing microcapsules are embedded in a PEG gel matrix with secondary amine groups. This coating system, initially colorless, exhibits a color change, becoming pink after being damaged by scratching due to the reaction between the DASA precursor released from ruptured microcapsules with the secondary amine groups of the PEG gel, thus demonstrating self-reporting characteristics. Furthermore, the colored surface is restored to its initial colorless state by irradiation with visible light for 1.5 hours, demonstrating the reusability of the self-reporting system.

Anti-counterfeiting fiber system with near-infrared wavelength selectivity based on photothermal and thermochromic dyes.

Anti-counterfeiting (ACF) technology plays a crucial role in distinguishing genuine products from counterfeits, as well as in identity verification. Moreover, it serves as a protective measure for safeguarding the rights of individuals, companies, and governments. In this study, a high-level ACF technology was developed using a color-conversion system based on the photothermal effect of near-infrared (NIR) wavelengths. Diimonium dye (DID), which is a photothermal dye, was selected because it is an NIR absorbing dye with over 98% transparency in the visible light (vis) region. Due to the photothermal properties of DID, the temperature increased to approximately 65 °C at 1064 nm and 39 °C at 808 nm, respectively. Additionally, we employed a donor-acceptor Stenhouse adduct dye, a thermochromic dye, which exhibits reversible color change due to heat (red color) and light (colorless). Our ACF technology was applied to the brand-protecting fiber utilizing the difference in photothermal temperature according to the NIR wavelength. We successfully implemented anti-counterfeit clothing using alphabet K labels that could distinguish between genuine and counterfeit products by irradiating with specific NIR wavelengths.

Clinical characteristics of juvenile systemic sclerosis in Korea: 31-year single-center study.

Objective: To evaluate the clinical and laboratory characteristics, therapeutic drugs, and prognosis of juvenile systemic sclerosis (JSSc) at a single center in Korea. Methods: This study was a retrospective analysis of patients with JSSc aged <16 years at disease onset and who were treated at our hospital between January 1992 and April 2023. All patients met the Pediatric Rheumatology European Society/American College of Rheumatology/European League against Rheumatism provisional classification criteria for JSSc, and those with localized scleroderma (morphea) were excluded. Results: Among the 13 patients, proximal skin sclerosis (100%), Raynaud's phenomenon (RP) (84.6%), and sclerodactyly (69.2%) were present at the time of diagnosis. The most common symptom before diagnosis was RP, which was present in 10 patients (76.9%), whereas proximal skin sclerosis was observed in only five patients (38.5%). Thirteen patients had positive anti-nuclear antibody (ANA). At the time of diagnosis, five individuals had findings suggestive of interstitial lung disease (ILD) on a pulmonary function test (PFT) or chest computed tomography (CT), two of whom were asymptomatic. During follow-up, three patients developed ILD, one developed renal dysfunction, one developed heart disease, and none died. Conclusion: This study was the first descriptive analysis of clinical features of JSSc in South Korea. Clinical suspicion is essential for diagnosing JSSc in patients with RP, especially if ANA is positive; however, proximal skin sclerosis, which is crucial for diagnosing JSSc, was unrecognized in the early phase of the disease. PFT should be considered even if a patient is asymptomatic or has normal chest CT.

Solvent-Triggered Chemical Recycling of Ion-Conductive and Self-Healable Polyurethane Covalent Adaptive Networks.

Given the substantial environmental challenge posed by global plastic waste, recycling technology for thermosetting polymers has become a huge research topic in the polymer industry. Covalent adaptive networks (CANs), which can reversibly dissociate and reconstruct their network structure, represent a key technology for the self-healing, reprocessing, and recycling of thermosetting polymers. In the present study, we introduce a new series of polyurethane CANs whose network structure can dissociate via the self-catalyzed formation of dithiolane from the CANs' polydisulfide linkages when the CANs are treated in N,N-dimethylformamide (DMF) or dimethyl sulfoxide at 60 °C for 1 h. More interestingly, we found that this network dissociation even occurs in tetrahydrofuran-DMF solvent mixtures with low DMF concentrations. This feature enables a reduction in the use of high-boiling, toxic polar aprotic solvents. The dissociated network structure of the CANs was reconstructed under UV light at 365 nm with a high yield via ring-opening polydisulfide linkage formation from dithiolane pendant groups. These CAN films, which were prepared by a sequential organic synthesis and polymerization process, exhibited high thermal stability and good mechanical properties, recyclability, and self-healing performance. When lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt was added to the CAN films, the films exhibited a maximum ion conductivity of 7.48 × 10-4 S cm-1 because of the contribution of the high concentration of the pendant ethylene carbonate group in the CANs. The ion-conducting CAN films also showed excellent recyclability and a self-healing performance.

Development of radical initiator based on o-imino-isourea capable of photo/thermal polymerization.

Using o-imino isourea, three photo- and thermal dual-responsive radical initiators dicyheDCC, CyheDCC, and BnDCC were systematically developed and synthesized. By adding an aromatic ring to the free radical initiators, the ultraviolet-visible absorption was redshifted, and the absorption coefficient was increased. Compared with other initiators, BnphDCC exhibited an exceptional photoinitiation rate under photo-differential scanning calorimetry (DSC) and a high absorption coefficient (ε = 15 420 M-1 cm-1). Therefore, it is an appropriate potential photoinitiator. DicyheDCC, which was composed of a cyclic hydrocarbon, exhibited rapid thermal initiation (Tpeak = 82 °C) during thermal DSC, making it a valuable thermal radical initiator. Because of the low stiffness of the N-O link in radical initiators, density functional theory predicts that the aliphatic ring has a significantly lower enthalpy than the aromatic ring. Moreover, in this study, CyhephDCC and BnphDCC, as dual-responsive radical initiators, indicated the potential for a photo- and heat dual-curing system through the universal free-radical polymerization of acrylates. These significant discoveries may be useful for developing efficient and diversified polymer network systems that require synergistic photo- and thermal effects.