Project description:A self-healable polyhydroxyurethane (S-PU) was synthesized from sorbitol, a biomass of polyhydric alcohol, by a simple process that is suitable for practical applications. In the synthesis, only two primary hydroxyl groups of sorbitol were considered for the chain extension of the polyurethane (PU) prepolymers to introduce free hydroxyl groups in PU. As a control, conventional PU was synthesized by hexane diol mediated chain extension. Relative to the control, S-PU showed excellent intrinsic self-healing property via exchange reaction, which was facilitated by the nucleophilic addition of the secondary hydroxyl groups without any catalytic assistance and improved tensile strength due to the enhanced hydrogen bonding. We also investigated the effect of the exchange reaction on the topological, mechanical, and rheological properties of S-PU. The suggested synthetic framework for S-PU is a promising alternative to the conventional poly hydroxyurethane, in which cyclic carbonates are frequently reacted with amines. As such, it is a facile and environmentally friendly material for use in coatings, adhesives, and elastomers.
Project description:Four linear polyurea elastomers synthesized from two different diisocyanates, two different chain extenders and a common aliphatic amine-terminated polyether were used as models to investigate the effects of both diisocyanate structure and aromatic disulfide chain extender on hard segmental packing and self-healing ability. Both direct investigation on hard segments and indirect investigation on chain mobility and soft segmental dynamics were carried out to compare the levels of hard segmental packing, leading to agreed conclusions that correlated well with the self-healing abilities of the polyureas. Both diisocyanate structure and disulfide bonds had significant effects on hard segmental packing and self-healing property. Diisocyanate structure had more pronounced effect than disulfide bonds. Bulky alicyclic isophorone diisocyanate (IPDI) resulted in looser hard segmental packing than linear aliphatic hexamethylene diisocyanate (HDI), whereas a disulfide chain extender also promoted self-healing ability through loosening of hard segmental packing compared to its C-C counterpart. The polyurea synthesized from IPDI and the disulfide chain extender exhibited the best self-healing ability among the four polyureas because it had the highest chain mobility ascribed to the loosest hard segmental packing. Therefore, a combination of bulky alicyclic diisocyanate and disulfide chain extender is recommended for the design of self-healing polyurea elastomers.
Project description:Azomethine diols (AMDs) were synthesized by condensation between a terephthalic aldehyde, polyether diamine, and ethanol amine. The synthesized AMDs were employed to introduce azomethine groups into the backbones of polyurethane elastomers (PUEs). Different AMDs were designed to control the concentration and distribution of azomethine groups in PUEs. In this study, we explored the intrinsic self-healing of AMD-based PUEs by azomethine metathesis. Particularly, the effects of the concentration and distribution of the azomethine groups on the AMD-based PUEs were considered. Consequently, as the azomethine group concentration increased and the distribution became denser, the self-healing properties improved. With AMD3-40, the self-healing efficiency reached 86% at 130 °C after 30 min. This represents a 150% improvement over the control PUE. Additionally, as the AMD content increased, the mechanical properties improved. With AMD3-40, the tensile strength reached 50 MPa. Therefore, we concluded that the self-healing and mechanical properties of PUEs can potentially be tailored for applications by adjusting the concentration and design of AMD structure for PUEs.
Project description:The possibility of exchange reactions and thermal self-healing in blends of thermoplastic polyurethane (TPU) and phenoxy resin was investigated herein. The analyses were based on characterization obtained via differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), and tensile test. A new phenoxy resin was synthesized from eugenol, and blends with different types of TPU were prepared to investigate the exchange reaction, thermal self-healing, and mechanical properties. The influence of phenoxy resin content on the mechanical behavior and healing efficiency was studied. Improvement of storage modulus owing to the increase of phenoxy resin content was observed. Results suggest that the exchange reaction between phenoxy- and ester-type TPU occurred during thermal treatment. However, little exchange occurred between phenoxy resin and ether-type TPU. Specifically, only ester-type TPU exhibited a significant exchange reaction in the phenoxy resin blend. Furthermore, in the presence of a catalyst (e.g., zinc acetate), the exchange reaction readily occurred, and the healing efficiency improved by the addition of the catalyst and increase in the phenoxy content.
Project description:Urethane groups formed by reacting phenolic hydroxyl groups with isocyanates are known to be reversible at high temperatures. To investigate the intrinsic self-healing of polyurethane via a reversible urethane group, we synthesized vanillyl alcohol (VA)-based polyurethanes. The phenolic hydroxyl group of vanillyl alcohol allows the introduction of a reversible urethane group into the polyurethane backbone. Particularly, we investigated the effects of varying the concentration of reversible urethane groups on the self-healing of the polyurethane, and we proposed a method that improved the mobility of the molecules contributing to the self-healing process. The concentration of reversible urethane groups in the polyurethanes was controlled by varying the vanillyl alcohol content. Increasing the concentration of the reversible urethane group worsened the self-healing property by increasing hydrogen bonding and microphase separation, which consequently decreased the molecular mobility. On the other hand, after formulating a modified chain extender (m-CE), hydrogen bonding and microphase separation decreased, and the mobility (and hence the self-healing efficiency) of the molecules improved. In VA40-10 (40% VA; 10% m-CE) heated to 140 °C, the self-healing efficiency reached 96.5% after 30 min, a 139% improvement over the control polyurethane elastomer (PU). We conclude that the self-healing and mechanical properties of polyurethanes might be tailored for applications by adjusting the vanillyl alcohol content and modifying the chain extender.
Project description:In this study, the self-healing properties of waterborne polyurethane (WPU) were implemented by chitosan as a chain extender of polyurethane prepolymers. The physical properties and self-healing efficiency of WPU were studied by changing the molar fractions of chitosan from 0.1 to 0.3. After thermal treatment for 24 h at 110 °C, the self-healing efficiency for the tensile strength of the highest chitosan content (WPU-C3) was found to be 47%. The surface scratch was also completely restored. The efficiency of the sample with the lowest chitosan content (WPU-C1) was found to be 35%, while that of the control sample without chitosan (WPU-C0) was 4%. The self-healing properties of the as-prepared films were attributed to the exchange reactions between the hydroxyl groups of chitosan and the urethane groups in the films at elevated temperature. It is inferred that self-healing WPU can be synthesized by chain extension with chitosan.
Project description:Polyurethane (PU) is a versatile polymer used in a wide range of applications. Recently, imparting PU with self-healing properties has attracted much interest to improve the product durability. The self-healing mechanism conceivably occurs through the existence of dynamic reversible bonds over a specific temperature range. The present study investigates the self-healing properties of 1,4:3,6-dianhydrohexitol-based PUs prepared from a prepolymer of poly(tetra-methylene ether glycol) and 4,4'-methylenebis(phenyl isocyanate) with different chain extenders (isosorbide or isomannide). PU with the conventional chain extender 1,4-butanediol was prepared for comparison. The urethane bonds in 1,4:3,6-dianhydrohexitol-based PUs were thermally reversible (as confirmed by the generation of isocyanate peaks observed by Fourier transform infrared spectroscopy) at mildly elevated temperatures and the PUs showed good mechanical properties. Especially the isosorbide-based polyurethane showed potential self-healing ability under mild heat treatment, as observed in reprocessing tests. It is inferred that isosorbide, bio-based bicyclic diol, can be employed as an efficient chain extender of polyurethane prepolymers to improve self-healing properties of polyurethane elastomers via reversible features of the urethane bonds.
Project description:Polymeric nanocarriers have been extensively used in medicinal applications for drug delivery. However, intravenous nanocarriers circulating in the blood will be rapidly cleared from the mononuclear macrophage system. The surface physicochemical characterizations of nanocarriers are the primary factors to determine their fate in vivo, such as evading the reticuloendothelial system, exhibiting long blood circulation times, and accumulating in the targeted site. In this work, we develop a series of polyurethane micelles containing segments of an anionic tripeptide, hydrophilic mPEG, and disulfide bonds. It is found that the long hydrophilic mPEG can shield the micellar surface and have a synergistic effect with the negatively charged tripeptide to minimize macrophage phagocytosis. Meanwhile, the disulfide bond can rapidly respond to the intracellular reduction environment, leading to the acceleration of drug release and improvement of the therapeutic effect. Our results verify that these anionic polyurethane micelles hold great potential in the development of the stealth immune system and controllable intracellular drug transporters.
Project description:Inspired by the growing demand for smart and environmentally friendly polymer materials, we employed 2,2'-disulfanediyldianiline (22DTDA) as a chain extender to synthesize a waterborne polyurethane (WPUR). Due to the ortho-substituted structure of the aromatic disulfide, the urea moieties formed a unique microphase structure in the WPUR, its mechanical strength was enhanced more 180 times relative to that of the material prepared without 22DTDA, and excellent self-healing abilities at body temperature in air or under ultrasound in water were obtained. If the self-healing process was carried out at 37 °C, 50 °C or under ultrasound, the ultimate tensile strength and elongation at break of the healed film could reach 13.8 MPa and 1150%, 15.4 MPa and 1215%, or 16 MPa and 1056%, respectively. Moreover, the WPUR films could be re-healed at the same fracture location over three cutting-healing cycles, and the recovery rates of the tensile strength and elongation at break remained almost constant throughout these cycles.
Project description:Following severe spinal cord injury (SCI), dysregulated neuroinflammation causes neuronal and glial apoptosis, resulting in scar and cystic cavity formation during wound healing process and ultimately atrophic nerve regrowth inhibitory microenvironment. Because of this complex and dynamic nature of SCI pathophysiology, a systemic solution for scar and cavity free wound healing while remodeling microenvironment for nerve regrowth has been rarely explored. To address this challenge, we provided a one-step solution through a self-assembly, multifunctional hydrogel depot punctually releasing the anti-inflammatory drug methylprednisolone sodium succinate (MPSS) and growth factors locally according to its pathophysiology to repair severe SCI. We found release of growth factors alone could only provide some tissues/axons protection, but failed to eliminate all cystic cavity formation. Sustained release of MPSS is sufficient to modulate dysregulated neuroinflammation and eliminate almost all cystic cavity but unable to alleviate impenetrable scar boundaries, which are largely responsive for nerve regrowth failure. Strikingly, synergically releasing anti-inflammatory drugs MPSS and growth factors in the hydrogel depot along SCI pathophysiology protected spared tissues/axons from secondary injury, promoted scar boundary and cavity free wound healing and made permissive bridges for remarkable axonal regrowth. Behavior and electrophysiology studies indicated that the remnant of spared axons but not regenerating axons mediated functional recovery, strongly suggesting that additional interventions are still required to make the rebuilt neuronal circuits perform functions. Taken together, these findings pave the way to develop a systemic solution to treat acute SCI.