Convenient syntheses of fullerynes for 'clicking' into fullerene polymers.

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition 'click' chemistry to form two fullerene polymers: one with C60 tethered to the end of a PS chain (C60-1PS) and the other with C60 tethered at the junction point of two PS chains of identical molecular weight (C60-2PS). The fullerene polymers were characterized by 1H NMR, 13C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C60 in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV-Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C60. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C60 content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.

Preparation of a Fluorocarbon Polymerizable Surfactant and Its Application in Emulsion Polymerization of Fluorine-Containing Acrylate.

A novel polymerizable fluorocarbon surfactant, perfluoro (4⁻methyl⁻3, 6⁻dioxaoct⁻7⁻ene) sodium sulfonate (PSVNa), was synthesized and characterized. The fluorocarbon surfactant PSVNa and its mixture PSVNa/SDS were used as emulsifiers during the emulsion polymerization of DFHMA/MMA. The investigation of polymerization kinetics, particle size, and stability of the emulsions revealed that PSVNa has excellent emulsifying properties. The NMR spectrum of the copolymer and the detection of residual PSVNa show that more than 95% of the fluorocarbon surfactants have been linked to the polymer chains by radical polymerization, which will greatly reduce the environmental pollution caused by fluorinated surfactants.

γ-Fe2O3-MWNT/poly(p-phenylenebenzobisoxazole) composites with excellent microwave absorption performance and thermal stability.

Ferromagnetic γ-Fe2O3 nanoparticles were successfully loaded into multi-walled carbon nanotubes (MWNTs) as probed by transmission electron microscopy. Upon incorporation of the γ-Fe2O3-MWNTs into poly(p-phenylenebenzobisoxazole) (PBO), a conjugated polymer with high mechanical strength and outstanding thermal and oxidative stability, microwave absorbing materials were obtained. Attributed to the special structure of the γ-Fe2O3-MWNTs, synergistic effects on dielectric loss and magnetic loss, and a better matched characteristic impedance of the composites were achieved. The optimal minimum reflection loss reached -32.7 dB at 12.09 GHz on a composite containing 12 wt% γ-Fe2O3-MWNTs with a thickness of 2.7 mm, and the corresponding bandwidth below -5 dB was 6.2 GHz. This demonstrated its potential applications as a low-density microwave absorbing material operating under extreme environments.

Preparation of thermostable PBO/graphene nanocomposites with high dielectric constant.

In this study, poly(p-phenylene benzobisoxazole) (PBO)/graphene composites were prepared using PBO and poly(4,6-dihydroxymetaphenylenediamine terephthalamide) (PHA)-modified graphene oxide (GO-PHA). PHA is the precursor of PBO. GO-PHA was obtained via chemical coupling reaction of amino-terminated PHA and acyl-chloride-functionalized GO. Partially reduced graphene nanosheets and benzoxazole rings were formed after heating. GO-PHA could be stably dispersed in methane sulfonic acid (MSA), which facilitated its uniform distribution in the PBO matrix. The PBO/graphene nanocomposites were obtained by the dissolution of GO-PHA and PBO in MSA. The thermogravimetric analysis results showed that the PBO/graphene composites had good thermal stability below 400 ° C. The dielectric constant of the composites increased as the amount of GO-PHA increased, and the percolation threshold was f(c) = 0.037. The nanocomposite had a dielectric constant of 15.8, which was approximately five times larger than that of pure PBO polymer.

Synthesis, crystal structures, and optical/electronic properties of sphere-rod shape amphiphiles based on a [60]fullerene-oligofluorene conjugate.

A series of sphere-rod shape amphiphiles, in which a [60]fullerene (C60) sphere was connected to the center of an oligofluorene (OF) rod through a rigid linkage (OF-C60), were designed and synthesized. Alkyl chains of various lengths were attached onto the OFs on both sides of the C60 spheres. These compounds, denoted as alkyl-OF-C60, were fully characterized by (1)H NMR, (13)C NMR, and FTIR spectroscopy and by MALDI-TOF mass spectrometry. The morphologies and structures of their crystals were elucidated by wide-angle X-ray diffraction (WAXD) and by electron diffraction in transmission electron microscopy (TEM). Butyl-OF-C60 forms a monoclinic unit cell (a=1.86, b=3.96, c=2.24 nm; α=γ=90°, ß=68°; space group P2), octyl-OF-C60 also forms a monoclinic unit cell (a=2.21, b=4.06, c=1.81 nm; α=γ=90°, ß=75.5°; space group C2m), and dodecanyl-OF-C60 forms a triclinic structure (a=1.82, b=4.35, c=2.26 nm; α=93.1°, ß=94.5°, γ=92.7°; space group P1). The inequivalent spheres and rods were found to pack into an alternating layered structure of C60 and OF in the crystals, thus resembling a "double-cable" structure. UV/Vis absorption spectroscopy revealed an electron perturbation between the two individual chromophores (C60 and OF) in their ground states. Fluorescence spectroscopy exhibited complete fluorescence quenching of their solutions in toluene, thus suggesting an effective energy transfer from OF to C60. Cyclic voltammetry indicated that the energy-level profiles of C60 and OF remained essentially unchanged. This work has broad implications in terms of understanding the self-assembly and molecular packing of conjugated materials in crystals and has potential applications in organic field-effect transistors and bulk heterojunction solar cells.