Functionalization And Electromagnetic Properties Of Ferrocenyl-bisphthalonitrile Resin And Its Composites Materials

The structure of polymeric materials can be designed according to different usage requirements. Therefore, abundant polymer resources can be obtained by the following methods. For example, adjusting the bonding sequence of carbon atoms between main chains and side chains, or replacing the carbon atoms with heteroatoms, or introducing functional group and so on. Meanwhile, compared with traditional inorganic materials, polymeric materials has its own advantages, such as easy processing, low density and recycle use, and so on. So functional polymeric materials, as the key component of modern information materials, will play an increasingly important role. Especially in electronic information field, magnetic polymeric materials have rapid growth in recent years. Thus the research in this thesis has mostly focused on this aspect.Ferrocene polymeric magnets, as the principal member of magnetic polymers, has become one of the most significant research topics in modern materials science according to low electromagnetic loss under higher frequency, low density, wide use temperature range and radiation resistant. Compared with other organic magnets, such as radical magnetic materials, fullerene magnetic materials, and conductive metal magnetic materials, ferrocene polymeric magnets process its own unique advantages and well application value. However, its microwave absorption property is weak, which limit the application in electromagnetic shielding(ES) area. Besides, the morphology of ferrocene polymeric magnets primarily is powder, which can’t meet the diversification requirements.Based on the shortages as above, a kind of ferrocene organic magnetic prepolymer(FOM) was prepared. The origin of magnetism of FOM, the mechanism of molecular-cluster with special morphology and the influence of thermal treatment on FOM were anylized. The electronic interaction between FOM molecules and the ES property both were improved by introducing metal phthalocyanine ring into FOM molecule and doping rare-earth oxide. Meanwhile, Furthermore, organic/inorganic composites with micro-nano structure were prepared by in-situ reaction, which benefited the structural diversity of FOM and improved the magnetic and ES properties according to enhancing the interface polarization among the hybrids microspheres and between organic phase and inorganic phase inside the microspheres. A novel magnetic film with excellent mechanical property was prepared by FOM and polyarylene ether nitrile(PEN) composite, which enlarged the application fields of FOM. Specific research contents are as follows:(1) Ferrocene-benzoxazine bisphthalonitrile monomer was synthesized by Mannich reaction. Then FOM was obtained by ring-opening reaction of oxazine ring in monomer. The relationship between the structure of FOM and the magnetism of it was analysized. The magnetism and electromagnetic properties of FOM and the samples after thermal treatment were studied by vibrating sample magnetometer and vector network analyzer, respectively. Besides, the molecular-cluster of FOM and magnetic film were obtained. The results showed that the the magnetism of FOM may come from the n-π*and π-π* electron interaction. It is very interesting that FOM possess a certain magnetism and ES properties, which can be further improved by high temperature treatment.(2) A series of ferrocene magnets with different metal phthalocyanine ring were prepared by introducing Cu+, Ni2+ and Co2+ ions under mild conditions. The results showed that the magnetism was enhanced greatly and samples showed better microwave absorption in higher frequency.(3) In order to further enhance the magnetism and ES property, organic magnet/Fe3O4 hybrid microspheres were prepared by one-step in-situ method. The morphology of hybrids was studied by scanning electron microscope and transmission electron microscopy. The diameter of hybrids can be adjusted from a few tens of nanometers to 300 nanometers by changing the reaction conditions. Furthermore, the hybrid microspheres exhibited high saturated magnetization, which could be beyond 70 emu/g. Meanwhile, the hybrids exhibited special electromagnetic properties different from FOM and FOM magnets with metal phthalocyanine ring(MPc-FOM), especially showing strong absorption in X-band.(4) PEN was selected as matrix and a series of magnetic films were prepared. Among them, the magnetic composite film from Co Pc-FOM/Fe3O4 and PEN by tape-casting showed good mechanical and heat resistance properties.