Patent Publication Number: US-3879526-A

Title: High energy oxidizers and method of synthesizing same

Description:
United States Patent 1 Christe HIGH ENERGY OXIDIZERS AND METHOD OF SYNTHESIZING SAME [75] Inventor: Karl 0. Christe, Calabasas, Calif.  
 [73] Assignee: Rockwell International Corporation, El Segundo, Calif.  
  22 Filed: Dec. 4, 1972 211 Appl.No.:3l2,0l4  
 [52] US. Cl. 423/277; 423/466; 423/592 [51] Int. Cl. C0lb 35/00; C0lb 7/24; COlg 55/00 [58] Field of Search 423/276, 466, 592, 277  
 [56] References Cited UNITED STATES PATENTS 3.320.031 5/l967 Grossc et al. 423/466 1 Apr. 22, 1975 Primary Eraminer-F. C Edmundson Attorney, Agent, or Firm-L. Lee Humphries; Robert M. Sperry [57] ABSTRACT 15 Claims, No Drawings HIGH ENERGY OXIDIZERS AND METHOD OF SYNTHESIZING SAME BACKGROUND OF THE INVENTION The invention herein described was made in the course of or under a contract with the Department of the Navy.  
 1. Field of the Invention This invention relates to compositions of matter and is particularly directed to compounds containing the cation ClO F and methods of synthesizing such compounds.  
 2. Prior Art Compositions of matter which contain oxygen and fluorine have been found to be extremely useful in formulating energetic materials, such as solid propellants, explosives and the like. Many simple compounds containing these elements have been disclosed heretofore. However, it has been recognized that more energetic compositions could be formulated by synthesizing more complex compositions containing multiple atoms of these elements. Unfortunately, it has been found that these more complex compositions cannot be produced from elementary fluorine by conventional methods. Accordingly, considerable effort has been expended to discover and find methods for producing these complex compositions.  
 BRIEF SUMMARY AND OBJECTS OF INVENTION These disadvantages of the prior art are overcome with the present invention and several compositions containing the cation C 1; have been synthesized by reacting FClO with PtF to produce ClO F PtF and employing displacement techniques to produce several additional salts containing this cation, such as CIO FJBFJ and ClO F AsF i Accordingly, it is an object of the present invention to provide new, highly-energetic compositions of matter.  
  Another object of the present invention is to provide methods of synthesizing new, highly-energetic compositions of matter.  
  An additional object of the present invention is to provide complex compositions containing multiple atoms of oxygen and fluorine.  
  A specific object of the present invention is to provide several compositions containing the cation ClO F by reacting FClO with PtF to produce C1O F PtF and employing displacement techniques to produce additional salts containing this cation, such These and other objects and features of the present invention will be apparent from the following detailed description.  
 DETAILED DESCRIPTION OF THE-INVENTION EXAMPLE I The FClO -PtF System Platinum hexafluoride (17.0 mmole) and FClO (46.1 mmole) were combined at l96 (all temperatures in this and other examples are degrees centrigrade) in a passivated (with ClF -ml stainless steel cylinder. The starting materials, platinum hexafluoride and FClO are available commercially from Ozark Mahoning Co., Tulsa, Oklahoma. The temperature of l96 was selected as one at which the starting materials have no volatility. The cylinder was placed at room temperature to allow the mixture contained therein to slowly warm up to 25 without the addition of external heat. This required approximately 30 minutes to one hour, after which, the mixture was kept at this tempera ture for three days. The cylinder was cooled to l96 and 3.75 mmole of material volatile at this temperature was removed and identified as F by its vapor pressure and mass spectrum. The products volatile at 25 were separated by fractional condensation through traps kept at 78, 126 and l96. The l26 fraction consisted of FCIO (28.7 mmole) and the l96 one of FClO (0.3 mmole), ClF (0.1 mmole), and a small amount of FClO The cylinder contained a stable canary yellow solid (6.618 g), which was identified by infrared spectroscopy as a mixture of ClO PtF and ClO F PtF Hence, PtF (17.0 mmole) had reacted with FCIO (17.1 mmole) in a 1:1 mole ratio yielding F (3.75 mmole), ClO PtF (12.2 mmole), and ClO F PtF (4.8 mmole) as the main products. It was found that PtF and FCIO when combined at 196 and allowed to slowly warm up to 25 by placing the container at room temperature for 30 minutes to one hour interacted according to:  
 This mixture may then be employed as a starting material for producing a plurality of pure salts containing the CIO F cation, as described in the following examples. The yield of ClO F was not 50 percent as expected from the above equation, but generally about 25 percent owing to the following competing reaction:  
 In some of the experiments, small amounts of ClF &#34;PtF or ClF and FClO were observed, depending on the exact reaction conditions. The formation of some FClO is not surprising since it is known that FClO readily interacts with nascent oxygen to yield FCIO Further modification of the reaction conditions (rapid warm up of the FClO -PtF mixture from l96 to either 78 or 25 and completion of the reaction at 25) did not produce detectable amounts of either ClO F or ClFJ&#39;PtFf, but only ClOfPtF; and C11 F and 0 This indicates that the nature of the reaction products are more influenced by the warm-up rate of the starting materials from 1 96 to about -7 8 than by the final reaction temperature. Slow warm up favors the formation of C1O F whereas rapid warm up yields ClF or ClF and F EXAMPLE II Synthesis of ClO F Salts The synthesis of CIO FJPtF has been described in Example I. For the synthesis of ClO F BF{, a mixture 3 of ClO F PtF (4.8 mmole) and ClO PtF (12.2 mmole) was treated in a passivated (with ClF and BrF 75 ml stainless steel cylinder with FNO (25.3 mmole) at 78 for 48 hours. The reaction products volatile at 25 consisted of FClO ClF O and unreacted FNO and were separated by fractional condensation through a series of traps kept at 112&#34;, 126&#34;,  
 142 and l96. The 126 fraction contained most of the ClF O and some FClO Attempts to further separate the C1F O and FC1O mixture by fractional condensation were unsuccessful. Consequently, 2.76 mmole of this mixture was combined with BF (3.00 mmole) at 196 in a passivated ampoule formed of perfluoroethylenepropylene copolymer and the temperature was cycled several times between 196 and 25. The product was kept at 7 8 for several hours and unreacted BF (0.22 mmole) was removed at this temperature in vacuo. Removal of volatile material in vacuo was continued at 20. The volatile material (2.70 mmole) consisted according to its infrared spectrum of a 1:1 mixture of FClO and BF The white solid, nonvolatile residue (280 mg 1.46 mmole) was identified by infrared, Raman, and F nmr spectroscopy as ClO F BF{.  
  For the preparation of the AsF; salt, ClO F BF., (0.62 mmole) and AsF (1.43 mmole) were combined at -l96 in a passivated ampoule formed of perfiuoroethylenepropylene copolymer. The contents of the ampoule was kept at 78 for 30 minutes and at 25 for 1 hour. Volatile products were removed at 25C and consisted of unreacted AsF (0.79 mmole) and BF (0.59 mmole). The white, stable solid weighted 185 mg (weight calculated for 0.62 mmole of ClF OfAsF 183 mg) and was identified as ClF O AsF by infrared, Raman, and F nmr spectroscopy.  
 Syntheses and Properties of ClO F Salts The synthesis of ClO F PtF from FClO and PtF and its temperature dependence has been discussed above. The BF and AsF salts were prepared according to the following scheme:  
 Unreacted FNO and some of the FClO could be separated from ClF O by fractional condensation. The remaining F C was separated from ClE O by complexing with BF Since the resulting ClOfBF, has a dissociation pressure of 182 mm at 221, while ClO F B- F is stable, the former salt could be readily removed by pumping at 20. Conversion of CIO FJBFJ to the corresponding AsF salt was accomplished through displacement of BF; by the stronger Lewis acid AsF All three salts, synthesized with the (310,1 cation and fluorine-containing anions, ClO F PtF ClO F- AsF and ClO F BF are solids, stable at 24, and react violently with water or organic materials. The PtF compound is canary yellow, while those of ASP and BF are white. The salts dissolve in anhydrous HF without decomposing. They are crystallinic in the solid state and the x-ray powder diffraction patterns of ClF O BF.{ and ClO F AsF are listed in Table 1.  
 TABLE 1 X-Ray Powder Patterns for ClO FfBFf and ClO F AsF ClO F BF, C1O F AsF Continued d,A lntensity d,A lntensity d,A lntensity 5.47 s 7.49 w 2.12 w 5.06 m 5.50 ms 2.01 w 4.37 ms 4.98 w 1.94 mw 4.15 w 4.35 ms 1.90 mw 3.70 vs 4.02 w 1.86 w 3.56 s 3.86 s 1.80 w 3.00 m 3.70 w 1.76 mw 2.77 m 3.57 m 1.72 w 2.57 vs 3.40 mw 1.70 mw 2.41 m 3.02 mw 1.65 w 2.18 s 2.77 m 1.62 w 2.08 s 2.69 m 1.59 w 1.86 ms 2.60 w 1.54 w 1.80 w 2.41 w 1.50 w  
 2.30 w 1.41 w 2.20 w 1.37 w 1.34 w  
  The powder pattern of CIO FJBRI is much simpler than that of ClO F AsF This is not surprising since the anion and cation in the former salt are both approximately tetrahedral and of similar size. The powder pattern of ClO F BF{ can be indexed on the basic of an orthorhombic unit cell with a 5.45, b 7.23, and c 13.00A. Assuming four molecules per unit cell and neglecting&#39;contributions from the highly charged central atoms to the volume, a plausible average volume of 16 A per F or O atom is obtained. However, the agreement between the observed and calculated reflections is somewhat poor for &#39;several lines and, hence, the above unit cell dimensions are tentative.  
  The thermal stability of CIO FJBFJ is higher-than those of ClOfBFf, ClFf&#39;BFf, or other similar salts. This is in good agreement with the previously made correlations between the stability of an adduct and the structure of the parent molecule and its ions. Thus, tetrahedral ClO F (see below) should be energetically much more favorable than trigonal bypyramidal ClF O F-nmr Spectra A broad singlet at 310 ppm relative to external CFCl has been observed for ClO F PtF in anhydrous HF. The spectrum of CIF OJBR, in HF shows a strong temperature dependence. At 30 it consists of a single peak at 185 ppm relative to external CFCl With decreasing temperature the peak at first becomes broader, then separates at about 0 into signals at-301 (ClO Ff), 146 (BF.{), and 194 ppm (HF) which become narrower with further decrease in temperature. The observed peak area ratio of approximately 2:1 for the 146 and 301 ppm signals confirms their assignment of BF., and ClO F respectively, and proves the ionic nature of the ClF O .BF adduct in HF solution.  
  The spectrum of ClF O AsF in HF (which was acidified with AsF consists of two resonances at 307 (ClO Ff) and ppm (HF, AsF AsF respectively. Rapid exchange between HF, AsF and AsFf preempted the measurement of the CIO F to AsF peak area ratio.  
  Obviously, numerous variations and modifications may be made without departing from the present invention. Accordingly, it should be clearly understood that the forms of the present invention described above are illustrative only and are not intended to limit the scope of the present invention.  
 What is claimed is:  
  l. The composition of matter consisting of a salt having the cation ClO F and an anion selected from the group consisting of AsF BF. and PtF 2. The composition of claim 1 wherein the anion of said salt is PtF 3. The composition of claim 1 wherein the anion of sald salt is BF{.  
  4. The composition of claim 1 wherein the anion of said salt is AsF 5. The method of synthesizing a salt having a difluoroperchloryl cation, said method comprising the steps of:  
 combining PtF and FClO in a container at a starting temperature at which these materials have no volatility,  
 gradually increasing the temperature of said materials without the addition of external heat until the reaction is complete,  
 separating the volatile products, and  
 removing the resulting ClO F PtF salt from said container.  
  6. The method of claim 5 wherein said starting temperature is -l96C.  
  7. The method of claim 5 wherein said gradually increasing step comprises exposing said container to room temperature.  
  8. The method of claim 7 wherein said container is exposed to room temperature for a period of approximately 30 minutes to 1 hour.  
  9. The method of claim 7 wherein said room temperature is 25C.  
  10. The method of claim 5 comprising the further steps of:  
 combining said clO FfPtF f salt with FNO at a reaction temperature such that said FNO is in a liquid state, maintaining said reaction temperature until the reaction is complete, separating the volatile products by fractional condensation in a series of traps kept at -l 12C and 126C, respectively, combining the condensate of the 126C trap with BF at a temperature at which the materials have no volatility, raising the temperature of said condensate to 20C and removing all volatile materials, and recovering the resulting ClO- F BF{ salt as a nonvolatile solid. II. The method of claim 10 wherein said reaction temperature is 78C.  
  12. The method of claim 10 wherein said maintaining step is continued for approximately 48 hours.  
  13. The method of claim 10 comprising the further steps of:  
 combining said ClOJfBFf salt and AsF in a container at a temperature at which these materials have no volatility, raising the temperature of said container to a temperature at which said AsF is liquid, maintaining said container at said temperature at which AsF is liquid until the reaction is complete, raising the temperature of said container to ambient temperature, removing the volatile materials, and recovering the resulting ClO F AsF salt as a nonvolatile solid. 14. The method of claim 13 wherein said temperature at which Aslfiis liquid is -78C.  
 15. The method of claim 13 wherein said maintaining step is continued for approximately 30 minutes.