Synthesis, Characterization And Thermal Stability Of C₆₀-gap And Its Pb/cu Salts

To explore new burning rate catalyst, two energetic fullerene salts were synthesized for the first time and their thermal performance was investigated. Glycidyl azide polymer(GAP) was synthesized by propylene glycol, epichlorohydrin(ECH) and Na N3, 2,4,6-trinitrobenzoyl chloride(TNBC) was synthesized by 2,4,6-trinitrotoluene(TNT)and thionyl chloride(SOCl2), then GAP reacted with TNBC to get TNB-GAP. At the same time, methyl-glycidyl azide polymer(Me-GAP)was synthesized by epichlorohydrin, CH3 OH and Na N3. Both of the products were characterized by fourier transform infrared(FT-IR)spectoscopy, ultraviolet-visible(UV-Vis) spectroscopy, nuclear magnetic resonance spectroscopy(NMR). Results confirmed the successful preparation of TNB-GAP and Me-GAP. Differential scanning calorimetry(DSC) and differential thermal analysis(DTA)were used to study their thermal stability and thermal decomposition mechanism, results confirmed that Me-GAP had better thermal stability than TNB-GAP.Me-GAP reacted with malonyl chloride, bromine and C60 to get[60]fullerene glycidyl azide polymer(C60-GAP) by esterification reaction, substitution reaction and modified Bingel reaction successively for the first time. Simultaneously, FT-IR, UV-Vis, 1H NMR,13 C NMR, X-ray photoelectron spectroscopy(XPS) were used to characterize the product. Results confirmed the preparation of C60-GAP was successful. Moreover, the thermal decompositions of C60-GAP were analyzed by DSC, thermogravimetry-infrared spectrometry(TG-IR),and in situ FT-IR. Results showed the decomposition step of C60-GAP at approximately 150 °C was due to the reaction of the azide group and C60.[60]fullerene glycidyl azide polymer(C60-GAP) itaconic acid copolymer was synthesized by C60-GAP and itaconic acid, then theproduct reacted with Pb(NO3)2 and Cu(NO3)2 to obtain unreported C60-GAP Pb/Cu salt. The salts were characterized by FT-IR, XPS and X-ray diffraction(XRD) spectra. Results proved the successful preparation of C60-GAP Pb/Cu salts. Meanwhile, the thermal decomposition and thermodynamic parameters of C60-GAP Pb/Cu salts were analyzed by thermogravimetry(TG), DTA, and DSC. The results showed that C60-GAP Pb salt had two decomposition steps, and the top temperatures were 290 ℃ and 415 ℃, the Ea were 140.42 k J/mol and145.85 k J/mol; and there were three decomposition steps for C60-GAP Cu salt, the top temperatures were 230 ℃, 280 ℃ and 390 ℃, the Ea were 165.99 k J/mol, 199.96 k J/mol and 172.09 k J/mol. The results confirmed the good thermal stability of C60-GAP Pb/Cu salts.