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United States Patent Office Patented Dec 3,780,162 United States Patent Office Patented Dec. 18, 1973 1. 2 relatively short reaction times are realized, and the prod 3,780,162 uct has a low molecular weight without the low yields PREPARATION OF PHOSFONITRILIC CHLORIDE heretofore associated therewith. Charles R. Bergeron and James T. F. Kao, Baton Rouge, La., assignors to Ethyl Corporation, Richmond, Va. SUMMARY OF THE INVENTION No Drawing. Filed June 5, 1972, Ser. No. 259,669 This invention provides a process for the manufacture Int, C, COb 2.5/10 of phosphonitrilic chloride mixtures of the general for U.S. C. 423-300 11. Claims mula (PNCl3.J. wherein x is at least 3, said process com prising introducing ammonia into a slurry of phosphorus ABSTRACT OF THE DISCLOSURE O pentachloride in an inert solvent, said process being Process for the preparation of phosphonitrilic chloride carried out in the presence of an initially added amount from phosphorus pentachloride and ammonia in the pres of HCl. In a preferred aspect of this invention, the process ence of hydrogen chloride by carrying out the process is carried out by introducing the ammonia at the begin under a pressure of hydrogen chloride ranging from 10 ning of the reaction into the slurry at a rate of not less to about 40 p.s.i.g. The reaction product produced in good 5 than about 0.13 liter per minute per mole of phosphorus yield is a low molecular weight polymeric mixture pri pentachloride until an amount corresponding to about Ao to about /2 of the total ammonia has been added. Fur marily of cyclic trimer and tetramer. ther, the reaction is preferably carried out under slight preSSure of HCl to facilitate formation of ammonium BACKGROUND OF THE INVENTION chloride in situ. The formation of phosphonitrilic chlorides by the reac 20 tion of phosphorus pentachloride with ammonium chlo DESCRIPTION OF THE PREFERRED ride has been known since about 1897; Stokes, Am. Chem. EMBODIMENTS J., vol. 19, page 782 (1897); Schenck et al., Berichte, The starting material for this process is phosphorus vol. 57b, page 1343 (1924). In spite of the length of pentachloride. Preparation of PCls is known and de time the reaction has been known its "mechanism is still scribed in early literature. It can be prepared from phos not completely understood'; Enesley et al., J. Chem. Soc. phorus and chlorine generally by reacting through an (A), page 768 (1971). The use of monochlorobenzene as intermediate PCl3 stage. The process can be conducted the solvent is also known; Jaszke et al., U.S. 3,367,750. by combining PCl3 with liquid or gaseous chlorine in the U.S. 3,656,916 to Schiedermaier et al. teaches the absence of a solvent; Marsh, U.S. 1,914,750; Inorganic reaction of ammonia with phosphorus pentachloride to 30 Synthesis, vol. 1, page 99 (1939). The process can be produce phosphonitrilic chlorides using a specific feed conducted using carbon tetrachloride as the solvent. Kirk rate of ammonia such that the first A0 to 3 of the total Othmer, "Encyclopedia of Chemical Technology,' Inter ammonia is added to a solution of not more than 5 moles science Encyclopedia, Inc., New York, N.Y., vol. 10, page of phosphorus pentachloride per liter of inert solvent 479 (1953). In a co-pending application, Ser. No. 174,129, at a rate not exceeding 0.12 liter/minute-mole phosphorus 35 filed Aug. 23, 1971, of Braxton, there is disclosed a pentachloride present in the solution. The remainder is process for preparation of phosphorus pentachloride added at a rate higher than the initial amount of am which teaches the reaction of PCl and gaseous chlorine monia. The advantage indicated for the specific ammonia using a halogenated aromatic solvent. This process is addition rate is to obtain a low molecular weight product advantageous because the PCls in monochlorobenzene is having a high percentage of cyclic trimeric and tetrameric 40 to be further reacted to phosphonitrilic chlorides. phosphonitrilic chloride in the reaction product. Higher The amount of phosphorus pentachloride is not critical feed rates of ammonia produce high molecular weight and can be conveniently selected according to general phosphonitrilic chlorides which are only partially soluble engineering practices and economics of investment and in hydrocarbons, for example cyclohexane or petroleum 45 operation. Generally, from about 1 to about 5 moles of ether. PCls per liter of solvent can be employed. For purposes The Jaszka patent also teaches the use of finely divided of this discussion, the concentration of PCls will be 1. ammonium chloride of increased surface area for reaction mole of PCls as the basis for the reactants involved. with the phosphorus pentachloride in the solvent. The AS indicated above, the solvent does not appear to be ammonium chloride is not soluble in the reaction mixture critical. Several solvents are known for the reaction to and the reaction takes place on the surface of the ammo 50 produce phosphorus pentachloride and these would also nium chloride. Therefore, a small particle ammonium be useful for the production of phosphonitrilic chlorides. chloride is highly reactive. Generally, the halogenated hydrocarbon solvents are suit The Jaszka patent, however, teaches the production of able for the process of this invention. Particularly, the ammonium chloride by reacting ammonia and hydrogen chlorinated hydrocarbons are useful. Typical of these are chloride in an inert solvent and introducing the phospho 55 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachlo rus pentachloride to the dispersion of small particle am ride, and the like. Similarly, the aromatic halogenated monium chloride. In contrast to both the Jaszka and the Solvents, particularly the chlorinated solvents, are also Schiedermaier et al. patents, it has now been found that useful in this invention. Preferably monochlorobenzene is an advantageous process for producing low molecular employed. The amount of solvent required is not critical. weight phosphonitrilic chloride polymers is provided by 60 Generally, enough solvent should be used to maintain a a process which includes one step reaction with a high Substantially fluid mixture. It has generally been found ammonia feed rate to phosphorus pentachloride in a sol that from about 0.2 to about 1 liter of solvent per mole vent in the presence of hydrogen chloride. This process of PCls may be used. Both lower and higher amounts of has the advantage of a one-step reaction to produce phos Solvent may also be employed. However, at the lower phonitrile chloride in contrast to the Jaszka patent and, 65 range of solvent used, the reaction mixture becomes thick additionally, employs a higher feed rate than is indicated and the slurry may not be readily agitated. On the other to be possible in the Schiedermaier et al. patent. hand, at higher solvent volumes, too much of the reactor By operating according to the process of this inven space is taken up with the solvent thus requiring larger tion, by-product reaction of PCls with ammonia is reactors and accessory equipment for the same amount of reduced, the thick practically unstirrable reaction mixture 70 product produced. formed by unknown reaction intermediates is avoided, According to this invention, hydrogen chloride is dis losses of ammonium chloride as fine dust are minimized, Solved in a slurry of phosphorus pentachloride in a solvent 3,780,162 3. 4 under slight pressure. The hydrogen chloride can be in ammonia feed rate is from about 0.13 to about 0.4 liter any form which does not cause deleterious side reactions per minute per mole of PCls. during subsequent processing, however gaseous hydrogen On introducing ammonia into the reactor, the reaction chloride is preferred. Particularly preferred is anhydrous mixture is heated to 110° to 150° C., preferably, from hydrogen chloride gas because any water present reacts 5 120 to 130° C. The reaction between ammonia and hy to form undesirable by-products during further reaction. drogen chloride takes place and ammonium chloride is Pressure and stirring are used to dissolve the hydrogen formed when ammonia is introduced. This then reacts chloride in the halogenated hydrocarbon solvent. General with the PCls to produce an insoluble intermediate when ly, nominal pressures are used so that expensive high the reaction mixture is heated to about 60° C. Continuing pressure reaction equipment is not necessary. Only suf O heating to 110° C. to 150 C. is necessary so that the in ficient pressure to dissolve an amount of hydrogen chlo termediate reacts further with ammonium chloride to pro ride necessary to initiate the reaction is necessary. Typical duce phosphonitrilic chloride. On reaction to form phos ly, this can be less than about 3 atmospheres. Preferably, phonitrilic chloride, about 4 equivalents of hydrogen chlo the reactor is pressurized to from about 10 to about 40 ride are evolved. This hydrogen chloride is available to p.s.i.g. of HC1. On introduction of the hydrogen chloride react with further ammonia beginning the reaction se into the reactor, the system is agitated so that more hy quence again. Since not all of the hydrogen chloride drogen chloride can be dissolved. A most preferred pres evolved is utilized, a portion is vented from the reactor. sure is from about 15 to about 30 p.s.i.g. of hydrogen However, the reactor is maintained under suitable pres chloride. Although higher pressures can be used they sure of from about 10 to about 40 p.s.i.g. of hydrogen tend to retard the reaction. Further, lower pressures may 20 chloride, during the entire time that ammonia is fed. This be used but less HCl is dissolved in the solvent. hydrogen chloride pressure not only guarantees that there The hydrogen chloride serves as an initially available will always be sufficient hydrogen chloride to quickly re reactant with ammonia for producing ammonium chlo act with all the ammonia, but it also greatly reduces the ride in situ.
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