Molecular Design,Synthesis And Properties Research Of Polymeric Ferrocenyl Absorbing-wave Materials

Ferrocenyl polymer served as a new class of functional polymer with lots of special electronic, electrochemical, optical and magnetic properties had extensive application prospects and important values in academic research. Then, we synthesized a series of polymeric ferrocenyl materials on the basis of molecular designs and functional designs, and its structures and some performances were studied too.In this paper, ferrocene was taken to be raw material, and the conjugated group bearing conductive function was introduced into ferrocenyl polymeric compound by means of special molecular designs. Then the conjugated group in molecular was coordinated with another metallic atom M(Fe,Cr,Mn). At the same time, there's certain electronic delocalization between the coordinated metallic atom M and the iron atom in the ferrocene. And therefore a new polymeric compound was synthesized containing both metallic atom delocalization structure of"magnetic"group and the great conjugated system consisted of cyclopentadienide ring and conjugated substituent of the"conductive"group. According to the above-mentioned analyses, we attempted to introduce groups of Fe(III)-phthalocyanine and 8-hydroxyquinoline which possessed distinguished photoelectric performances into structures of ferrocenyl polymer. So, three series of ferrocenyl polymeric materials were synthesized. They were coordination on ferrocenyl acylamide and thiosemicarbazide polycondensated, ferrocenyl polymer modified by phthalocyanine and the type of 8-hydroxyquinoline-ferrocenyl polymer. In the meanwhile, the structure and performance of the composite were characterized by means of infrared absorption spectrum(IR), nuclear magnetic resonance hydrogen spectrum (1HNMR), gel permeation chromatography(GPC), thermal gravimetry analysis(TGA), X-ray photoelectron spectroscopy(XPS) and so on. And the four important electromagnetic parameters and microwave reflecting properties of some compounds were studied under frequency 2~12GHz.Results showed that the chemical structures of the final products were comparatively complex, and many ways existed in the type of metallic coordinate linkage. While we couldn't conform their purity and chemical structure absolutely for the moment, because the polymer hardly cultivated single crystal restricted by our condition and technical level. The researches on molecular weight distributions have indicated that branching reaction must have been happened during the condensate polymerization caused by chain transference at high conversion rate. And the polymerization was impeded by the rigid group, which led to the lower molecular weight, but the degree of polymerization of 1,1'-divinylferrocenyl polymer could be controlled out of needs which had comparatively simple structure.In the meantime, we found that all series of compounds were provided with fine thermal stability. As to the type of phthalocyanine-ferrocene compounds, the thermal decomposition temperature of 1,1'-divinylferrocenyl polymer could be enhanced by means of introducing phthalocyanine into the polymer. However, the thermal stability of metallic coordination polymer hardly enhanced in comparison with the polymer never coordinated transitional metallic ions. The reason might be that the energy of coordinate bond formed between metallic ion and polymer was trival in comparison with that of covalent bond in polymer. It started with coordinate bond when the coordinate polymer decomposed under high temperature, so it engendered little for the thermal stability at high temperature.The researches on the electromagnetic parameters confirmed that these polymeric ferrocenyl absorbing-wave materials were different from the inorganic ferrite absolutely. Their parameters ofμ′andμ′′were horizontal lines practically, in other words, the magnetic parameter nearly never changed on frequency. Dielectric parameters demonstrated that the dielectric performances of the type of phthalocyanine-ferrocene compounds mixed with carbon fiber were remarkably increased, and its dielectric constantsε′andε′′raised obviously which attained to maximum at 7~10GHz, which was caused by intermediate state whose structure came down to"double electronic layer"existed between phase boundary surfaces after adulteration.On the whole, as an absorbing-wave material of electric attenuation in low-frequency of 4GHz, the coordination polymer was of great value of tgδu in frequency of 6~8GHz, which illustrated that the absorption microwaves included electric wastage and magnetic wastage, and the latter predominated. The reflected attenuation, moreover, had to do with the substituent and coordination metal. Nevertheless, so far as the type of phthalocyanine-ferrocenyl polymer was concerned, the phthalocyanine group brought into the side chains could provide moreπelectrons to participate conjugation, while the ferrocenyl polymer did not form a conjugated system itself, and the electronic delocalization structure scarcely came into being, so the result was that the electromagnetic attenuation hardly increased, and the absorbing-wave performance couldn't be excellent especially. But we strongly believed that a new type of ferrocenyl polymeric absorbing-wave material could be prepared which had characteristics of practical value, light weight, violent absorption and wide bandwidth by means of regulating structures of conjugated system and controlling metallic types and coordination angle.In addition, the researches on the type of 8-hydroxyquinoline-ferrocenyl polymer are still at the exploratory stage, and lots of testing works are on the march which will lay the groundworks for continued studies.