Preparation, Morphology Control And Properties Of Functional Nanomaterials Based On Iron Polyphthalocyanines

Phthalocyanines and metallophthalocyanines have recently received considerable attention due to their unique properties, such as high thermal and chemical stability, excellent photoconductivity, intense optical absorptions in visible-near infrared optical region, and the well-defined coupling of the electronicp-systems. Since the synthesis of phthalocyanines in the early 1930 s, a rich and varied chemistry and technology has developed around these interesting materials. There are more than thousands of publications and patents related to phthalocyanine and its analogs. Since 1983, metal polyphthalocyanines, which were first synthestized in 1983, have been paid much attention. Metal polyphthalocyanines can offer a unique combination of good properties of polymers and Pcs/Mt Pcs. Furthermore, Metal polyphthalocyanines can show more excellent performances than that of Pcs/MtPcs. Polyphthalocyanines having various, for example, stacked polyphthalocyanine for electrical conductors, thermally stable polymers containing metallphthalocyanines, copolymerized phthalocyanine polymers for organic photoconductors, phthalocyanine polymers for catalysts and so on.The metal polyphthalocyanines have many excellent performances: excellent electric conductivity, high dielectric response, versatile reactivity of phthalocyanine with metal, self-assembly and so on. Based on the above excellent features, we prepared metal polyphthalocyanines funcationa functional magnetic Fe3O4 microspheres, which show outstanding microwave absouption properties and act as nanoparticle-reinforced composites. We also explored the self-assembly of metal polyphthalocyanine and combined the electrospinning technology to prepare the 3D micro/nano fibers with controlled morphology.Specific research contents are as follows:(1) The novel nano-scale Fe-phthalocyanine oligomers/Fe3O4(FePc/Fe3O4) hybrid microspheres were synthesized from bis-phthalonitrile and FeCl3·6H2O through a simple solvent-thermal route. The hybrids were monodispersed solid microspheres and the morphology can be adjusted by controlling the addition of bis-phthalonitrile. After introducting the FePc, the dielectric loss of the hybrid microspheres was larger and a new magnetic loss peak appeared at high frequency. Furthremore, The microwave absorbing properties enhanced with increasing the addition of bis-phthalonitrile and a maximum reflection loss of-31.1dB was obtained at 8.6 GHz with 15 wt% bis-phthalonitrile, when the matching thickness was 3.0 mm. The novel hybrid materials are believed to have potential applications in the microwave absorbing performances.(2) Based on the high dielectric response of hyperbranched copper phthalocyanines(HBCuPc), HBCuPc funcational Fe3O4 microspheres were prepared by a simple solvent-thermal method. HBCuPc molecules were not only attached to the surface of Fe3O4 in the form of beads, but also embedded in the interior. Importantly, after introducing the HBCuPc, the HBCuPc/Fe3O4 composites exhibit excellent microwave absorbability. The wider and stronger microwave absorption can be obtained. The composites with a coating layer thickness of 4.0 mm exhibit a maximum absorption of-30.3 dB at 10.2 GHz and the bandwidth below-10.0dB reaches up to 10.6 GHz, which covers the whole X-band and Ku-band(7.4-18.0 GHz). The as-prepared hierarchical HBCuPc/Fe3O4 is shown to be lightweight, strong absorption, and broad frequency bandwidth microwave absorbers.(3) FePc/Fe3O4 nano-hybrid particles not only showed excellent excellent microwave absorbability, but also can act as nanoparticle-reinforced composites. The hybrids exhibited better dispersion and compatibility with polyarylene ether nitriles(PEN) matrix, and the mechanical properties and thermal stability of FePc-Fe3O4/PEN nanocomposites had a significant improvement. Furthermore, the prepared PEN nanocomposites presented soft magnetic properties.(4) Combining the self-assembly of phthalocyanines and electrospinning, the special morphology 3D micro/nano fibers can be prepared. The novel “rose thorns” like fiber, composed of PEN ??stems?? and FePc ??Rose thorns??, was prepared by combining electrospinning and temperature-induced self-assembly. Especially, the FePc thorns-like structures can be grown on PEN nanofibers by a post-temperature treatment, and the lengths of the thorns could be finely controlled by the processing time and temperature, respectively. More importantly, after the thorns-like fibers were embeded into epoxy resin, the “thorns” could tie molecules and interlock with the surrounding epoxy resin. Thus, the flexural properties of composites reinforced with these thorn-like fibers further increased in comparison with that of neat and untreated fiber-reinforced epoxy resin, respectively. The functional fibers can be used as an effective composite reinforcement to polymer resinsBesides, novel flowers-like PEN/FePc fibers can be formed via combining electrospinning with solvent-induced selfassembly. The morphology of nanoflowers grown on PEN fibers can be well controlled by solvent, hyperbranched degree. Furthermore, these nanoflowers-like micro/nanofibers treated in ethanol indicated stronger fluorescent properties.