Research On Synthesis And Performance Of Polyamino And Polynitro Benzofuroxan And Their Metal Complex

In this paper, two multi-amino, and multi-nitro benzofuroxan,7-Amino-4,6-dinitrobenzofuroxan (ADNBF) and5,7-diamino-4,6-dinitrobenzenfuroxan (DADNBF), and their alkali metal complex, were researched systematically, comprising their synthesis, characterization, property and application.ADNBF was prepared by three reaction, i.e. acylation reaction, nitration reaction and cyclization reaction, using3-nitroaniline as material, and the total yield was38.7%. The yield of nitration reaction was30%higher than the reported documents. Comparing the reported synthesis method, this method was more moderate and higher yield. The structure of ADNBF was studied by1HNMR, IR and MS. The crystal of ADNBF belongs to monoclinic system. Cell parameters are:a=0.71470(14) nm, b=0.9891(2) nm, c=1.1964(2) nm, a=90.00°, β=199.91(3)°, y=90.00°, V=0.8377(3) nm3, Z=4, Dc=1.912g·cm-3, F (000)=488.DADNBF was developed by a series reaction, i.e. oxidation reaction, nitration reaction, VNS amination and acidification, using2-nitroaniline as material, and the total yield was75.3%, which was higher than the reported yield47.2%. The new synthetic route was mile and easy to control, which is helpful the following enlarged experiment. The structure of DADNBF was identified by1HNMR, IR and MS.ADNBF was refined by recrystallization, and methanol, acetonitrile and N-methyl pyrrolidone(NMP) were respectively used as solvents. Compared the three refined samples, it showed that the average particle sizes of refined ADNBF when using NMP as solvent was biggest, and the impact sensitivity and friction sensitivity of ADNBF were22%and18%respectively.DADNBF, a newly refining technology was developed, i.e. potassium salt of DADNBF was first purified and then followed by acidification in high temperature. The sensitivity and heat stability of DADNBF before and after refined were measured then. The result showed that the pH value of the refined DADNBF was6.5, and the impact sensitivity and friction sensitivity were8%and8%respectively. The amount of gaseous products measured by Vacuum Stability Test (200℃,48h) was0.50mL·g-1. The exothermic peak temperature in DSC curve was313.7℃, which was13.7℃higher than that of unrefined counterpart. So the refined DADNBF by the new refining technology have lower acidity and better heat stability.The property, such as heat thermal sensitivity, impact sensitivity, friction sensitivity and detonation performance and so on, of ADNBF and DADNBF were studied carefully. The results showed that the detonation velocity of both the above two complex were higher than7900ms-1, the detonation pressure were higher than26.5GPa, and the impact sensitivity were higher than100cm. Two heat-resisting composite explosive respectively based on ADNBF and DADNBF were prepared in this paper, and the detonation performance and penetration of petroleum perforating charge were tested subsequently. The result were that the detonation velocity of ADNBF-based composite explosive and DADNBF-based composite explosive were7568m·s-1(p=1.81m·s-1) and7542m·s-1(p=1.81m·s-1) respectively, which are91.2%and94.5%of that of SH-931respectively. The penetration depth of DADNBF-based composite explosive was170mm, which approximate to that of SH-931.Based on the study of ADNBF alkali metal complex, Four DADNBF alkali metal complex, Na(DADNBF)(2H2O), K(DADNBF)(2H2O), Rb(DADNBF)(2H2O) and Cs(DADNBF)(2H2O), were then synthesized. The crystal diffraction results showed that both_Na(DADNBF)(2H2O) and K(DADNBF)(2H2O) were metal cluster compounds, and the metal ions were inserted into the molecular layers of DADNBF and formed a extended scalariform network structure. In addition, the influence of the four kind of DADNBF alkali metal complex on the thermal decomposition of AP were investigated, did also the catalysis of them on RDX-CMDB propellants. The result showed that all of the four complex showed good catalysis on the thermal decomposition of AP, and the temperature of exothermic peak of AP reduced34.2～74.2℃. K(DADNBF)(2H2O) and Cs(DADNBF)(2H2O) showed good catalysis ability in the aspects of improving the combustion behavior and decreasing pressure exponent of the RDX-CMDB propellants, and the pressure exponents of the propellants to0.283and0.572respectively in the pressure range of8-10MPa. The results suggest that DADNBF alkali metal complex be used in solid rocket propellant as novel energetic compounds catalysts.