Synthesis and characterization of carboxylated PBAMO copolymers as promising prepolymers for energetic binders.

The carboxylated poly[3,3-bis(3-azidomethyl)oxetane] (PBAMO) copolymers (poly(BAMO-carboxylate)) were synthesized by substitution of poly[3,3-bis(3-chloromethyl)oxetane] (PBCMO) with potassium carboxylate and sodium azide in DMSO. The synthesized compounds were characterized using various analytical techniques, such as Fourier-transform infrared (FT-IR) spectroscopy, inverse-gated decoupling 13C-nuclear magnetic resonance (13C NMR) spectroscopy, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), calorimetry, friction, and impact sensitivity analysis. These poly(BAMO-carboxylate) compounds have better thermal properties, with lower glass transition temperatures (ranging from -43 °C to -51 °C) than PBAMO (-37 °C) and higher thermal decomposition temperatures (233-237 °C) than PBAMO (211 °C). Moreover, poly(BAMO0.80-octanoate0.20) and poly(BAMO0.78-decanoate0.22) have higher heats of combustion (5226 and 5665 kJ mol-1, respectively) and negative formation enthalpies (-0.17 and -0.55 kJ g-1, respectively), while PBAMO has lower heat of combustion (3125 kJ mol-1) and positive formation enthalpy (0.06 kJ g-1). The poly(BAMO-carboxylate) compounds have higher values (38-50 J) than that of PBAMO (14 J) in the impact sensitivities. This is a valuable study for improving the properties of PBAMO, which is a high energetic polymeric binder but difficult to handle because of its sensitivity. Therefore, poly(BAMO-carboxylate) could be a good candidate as a prepolymer for designing the energetic polymeric binder.

Highly ductile multilayered films by layer-by-layer assembly of oppositely charged polyurethanes for biomedical applications.

Multilayered thin films prepared with the layer-by-layer (LBL) assembly technique are typically "brittle" composites, while many applications such as flexible electronics or biomedical devices would greatly benefit from ductile, and tough nanostructured coatings. Here we present the preparation of highly ductile multilayered films via LBL assembly of oppositely charged polyurethanes. Free-standing films were found to be robust, strong, and tough with ultimate strains as high as 680% and toughness of approximately 30 MJ/m(3). These results are at least 2 orders of magnitude greater than most LBL materials presented until today. In addition to enhanced ductility, the films showed first-order biocompatibility with animal and human cells. Multilayered structures incorporating polyurethanes open up a new research avenue into the preparation of multifunctional nanostructured films with great potential in biomedical applications.

Ecofriendly synthesis and characterization of carboxylated GAP copolymers.

Carboxylated GAP copolymers (polyGA-carboxylate) compounds (1-7), were synthesized by the simultaneous substitution reaction with PECH, sodium azide, and sodium carboxylate in DMSO. The synthesized compounds (1-7) were characterized by various analysis tools, such as Fourier transform infrared (FT-IR), inverse gated decoupling 13C-nuclear magnetic resonance (13C NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), calorimetry, and friction and impact sensitivity. These poly(GA-carboxylate) compounds (1-7) have better thermal properties owing to their lower glass transition temperatures, from -48 °C to -55 °C, compared to glycidyl azide polymer (GAP) (-49 °C) and similar first thermal decomposition temperatures (228-230 °C) in comparison to GAP (227 °C), regardless of the introduction of the carboxylate group in GAP. Moreover, poly(GA0.8-butyrate0.2) and poly(GA0.8-decanoate0.2) have higher heats of combustion (2331 and 2976 kJ mol-1) and negative formation enthalpies (-0.75 and -2.02 kJ g-1), while GAP has a lower heat of combustion (2029 kJ mol-1) and positive formation enthalpy (1.33 kJ g-1). Therefore, poly(GA-carboxylate) could be a good candidate for the polymeric binder in solid propellants.

LBL assembled laminates with hierarchical organization from nano- to microscale: high-toughness nanomaterials and deformation imaging.

Layer-by-layer assembly (LBL) can generate unique materials with high degrees of nanoscale organization and excellent mechanical, electrical, and optical properties. The typical nanometer scale thicknesses restrict their utility to thin films and coatings. Preparation of macroscale nanocomposites will indicate a paradigm change in the practice of LBL, materials manufacturing, and multiscale organization of nanocomponents. Such materials were made in this study via consolidation of individual LBL sheets from polyurethane. Substantial enhancement of mechanical properties after consolidation was observed. The resulting laminates are homogeneous, transparent, and highly ductile and display nearly 3x higher strength and toughness than their components. Hierarchically organized composites combining structural features from 1 to 1 000 000 nm at six different levels of dimensionality with a high degree of structural control at every level can be obtained. The functionality of the resulting fluorescent sandwiches of different colors makes possible mechanical deformation imaging with submicrometer resolution in real time and 3D capabilities.