Synthesis And Characterization Of Polyacene Quinone Radical Conducting Polymers

Polyacene quinone radical(PAQR)polymers are intrinsic semiconducting materials which are synthesized by the step-growth condensation polymerization of aromatic hydrocarbons or heterocycles with different anhydrides,using Lewis acid,a Friedel-Crafts catalyst.They are black solid powders and possess not only the nature of the semiconductor but the high dielectric constant while they could not dissolve or melt.They could be used to prepare the complex as high dielectric or conducting filler but also be used in the fields of the sensor or energy storage as one kind of pure organic conductive/dielectric material.Therefore the study has great practical significance.In this paper,we reported a solvothermal method to synthesize PAQR polymers and discussed the synthetic technology of polymerization conditions.The influences of the synthetic conditions on the morphologies and the properties were also studied.The main points in this paper are summarized as follows:1.PAQR polymers were prepared by using a variety of aromatics and anhydride,with different Louis acids as catalyst.The reaction mechanism was studied.The production rate,morphologies and properties were also discussed through changing aromatics,anhydride,catalyst,solvents and other process conditions.The results show that the yield of the product was the largest when choosing An and PMA as the monomers,zinc chloride as the catalyst,nitrobenzene as the solvent and the mole ratio of monomers and catalyst was 1:1:2.The yield of the product treated by high temperature was larger than that by purification.2.The products were characterized by scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),infrared spectrometer(IR),Raman spectrometer(Raman),and X-Ray Spectrometer(XPS).The results indicated that great differences existed in the morphologies of PAQR polymers which were prepared though different process technology and monomers.Some block? ball and rod-like structures were observed in the polymers using Aq or An as the reactive monomer,however,only slabs can be found in the polymers using Py as the monomer.The cyclization degree of PAQR polymers using cyclohexane as solvent was larger? the structure of microcrystalline graphite getting by purification was more.3.Thermal properties and conductivity were characterized by thermo gravimetric analyzer(TG),ultraviolet-visible spectrometer(UV-Vis),cyclic voltammetry(CV),electron spin resonance(ESR)and semiconductor powder conductivity meter.And the polymers synthesized by solid melting method were also compared.The results indicated that the thermal stability of PAQR polymers using PMA as anhydride was the best? the gap of PAQR polymers synthesized by solvothermal method and treated by high temperature was less than that by solid melting one.Conductivity of PAQR polymers treated by high temperature was greater than that by purification.