A novel bottom-up approach to obtain polymer nanocomposites using cubic silsesquioxanes (POSS) nanoparticles as building blocks is reported. The design is based on associative interaction between particles to form ordered nanostructure and limited crystal growth to render anisotropic shapes. Specifically, the affinity between POSS units causes these particles to aggregate and closely pack into a crystalline lattice. The organic polymer, covalently connected to each POSS unit, limits the crystallization into a two-dimensional lattice as demonstrated in random copolymers of polybutadiene and cubic silsesquioxanes. The copolymers were synthesized by ring-opening metathesis copolymerization of cyclooctadiene and POSS bearing a polymerizable norbornene group. The polymers were characterized using NMR, DSC, TEM, WAXD, and SAXS. The data from TEM and X-ray diffraction clearly show the formation of two-dimensional lamellar-like nanostructures of assembled cubic silsesquioxanes.

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The effect of chain architecture on the morphological and tensile properties of series of multigraft copolymers, with regularly spaced tri-, tetra-, and hexafunctional junction points, was investigated using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and tensile testing. The materials were synthesized by coupling difunctional polyisoprene (PI) spacers and living polystyrene (PS) branches, made by anionic polymerization, with chlorosilanes of different functionalities. Since the coupling process is a step-growth polymerization, yielding polydisperse products, fractionation was utilized to separate each material into three fractions (high, middle, and low molecular weight), each of low polydispersity. All three fractions have the same chain architecture on a per junction point basis but differ in the number of junction point units per molecule. By applying the constituting block copolymer concept, the physical behavior of these molecules was compared with current theories. It was found that morphological behavior of these graft copolymers can be predicted using theoretical approaches and is independent on the number of junction points. The number of the junction points, however, greatly influences the long-range order of microphase separation. Additionally, two new parameters for adjusting mechanical properties of multigraft copolymers were found in this investigation: (1) functionality of the graft copolymerstri-, tetra-, or hexafunctionalsand (2) number of junction points per molecule. An increase in functionality causes a change in morphology, resulting in a high level of tensile strength for tetrafunctional (cylindrical) and hexafunctional (lamellae) multigraft copolymers, leading to about the twice the strength of the spherical trifunctional multigrafts of similar overall composition. Tetrafunctional multigraft copolymers show a surprisingly high strain at break, far exceeding that of commercial block copolymer thermoplastic elastomers (TPEs). Strain at break and tensile strength increase linearly with the number of junction points per molecule. Hysteresis experiments at about 300-900% deformation demonstrate that multifunctional multigraft copolymers have improved high elasticity as compared to commercial TPEs like Kraton or Styroflex.

In this study we demonstrate simple guidelines to generate a diverse range of fluorescent materials in both liquid and solid state by focusing on the most popular C-dots precursors, i.e. the binary systems of citric acid and urea. The pyrolytic treatment of those precursors combined with standard size separation techniques (dialysis and filtration), leads to four distinct families of photoluminescent materials in which the emissive signal predominantly arises from C-dots with embedded fluorophores, cyanuric acid-rich C-dots, a blend of molecular fluorophores and a mixture of C-dots with unbound molecular fluorophores, respectively. Within each one of those families the chemical composition and the optical properties of their members can be fine-tuned by adjusting the molar ratio of the reactants. Apart from generating a variety of aqueous dispersions, our approach leads to highly fluorescent powders derived from precursors comprising excessive amounts of urea that is consumed for the build-up of the carbogenic cores, the molecular fluorophores and the solid diluent matrix that suppresses self-quenching effects.