Chemical functionalization of graphene oxide for improving mechanical and thermal properties of polyurethane composites

Graphene oxide (GO) was chemically functionalized to manufacture polyurethane (PU) composites with improved mechanical and thermal properties. In order to achieve a well exfoliated and stable GO suspension in organic solvent, 4, 4′- methylenebis(phenyl isocyanate) and polycaprolactone diol – two monomers used to synthesize polyurethane – were employed to functionalize GO sequentially. The obtained functionalized GO (FGO) could form homogeneous dispersions in DMF solvent and the PU matrix, as well as provide a good compatibility with the latter. The most efficient improvement in mechanical properties was achieved when 0.4 wt% FGO was added into the PU matrix, corresponding to increases in the tensile stress, elongation at break and toughness by 34.2%, 27.6% and 64.5%, respectively (compared with those of PU). Regarding the thermal stability, FGO/PU 1 wt% showed the largest enhancement, with T2% and T50% 16 °C and 21 °C higher than those for PU, respectively. A significant improvement in both mechanical properties and thermal stability of FGO/PU composites should be attributed to homogeneous dispersion of FGO in the PU matrix and strong interfacial interaction between them

Effect of graphene-oxide enhancement on large-deflection bending performance of thermoplastic polyurethane elastomer

Thermoplastic polyurethane (PU) elastomers are used as shoe-sole materials due to many excellent properties but their inelastic deformation is a serious deficiency for such applications. Hence, graphene oxide (GO) was introduced into the synthesized thermoplastic PU to produce a GO/PU composite material with enhanced properties. Plastic behaviour of this composite was assessed in cyclic tensile tests, demonstrating reduction of irreversible deformations with the addition of GO. Additionally, in order to evaluate mechanical performance of PU and the GO/PU composite under conditions of large-deflection bending typical for shoe soles, finite-element simulations with Abaqus/Standard were conducted. An elastic-plastic finite-element model was developed to obtain detailed mechanical information for PU and the GO/PU composite. The numerical study demonstrated that the plastic area, final specific plastic dissipation energy and residual height for PU specimens were significantly larger than those for the GO/PU composite. Besides, the addition of GO into the PU matrix greatly delayed the onset of plastic deformation in PU in a large-deflection bending process. The average residual height and final specific plastic dissipation energy for PU were approximately 5.6 and 17.7 times as large as those for the studied GO/PU composite. The finite-element analysis provided quantification of the effect of GO enhancement on the large-deflection bending performance of PU for regimes typical for shoe soles and can be used as a basis for optimization of real composite products

Preparation, characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes <i>via</i> Photoclick Chemistry for Alkene Epoxidation

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide (<i>e</i>.<i>g</i>., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV–visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes <i>via</i> Photoclick Chemistry for Alkene Epoxidation

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide (<i>e</i>.<i>g</i>., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV–visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces