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Patented Dec. 17, 1946 2,412,890 ‘ " UNITED} STATES PATENT "OFFICE PREPARATION OF METAL AMTMCINE SALTS Grinnell [Jones and Walter Juda, Cambridge,‘ Mass., assignors to Albi Chemical Corporation, ' New’York, N. Y., a corporation of New York No Drawing. ‘Application June 17, 1942, Serial No. 447,471 7 Claims. 1 The present invention relates to the prepara tion of complex metal ammine salts. ‘By the term "ammine" it is intended to include (Cl. 23-14) 2 A further object is to provide such a method which will be practical and economical for use in large scale manufacture. - ‘ only ammonia and amines. Yet another object is to provide a method for Complex metal ammine salts vary widely in .3 producing solid complex metal ammine salts of chemical structure and also in physical proper controlled stability and controlled solubility. ties, particularly with regard to stability and solu bility. depending upon the nature of the metal In general, our improved method comprises the dry mixing and agitation of a solid metal com (and in some cases its state of oxidation), the pound the anion of which is‘ derived from an acid anion, the conditions of preparation and other 10 strongerthan carbonic acid, with a solid ammine factors. For these and other reasons, it is dif compound which is relatively unstable and which ficult to generalize in this ?eld and to determine will form, with the solid metal compound, a com in advance either the nature of the ?nal product plex metal ammine salt. When a source of am or the essential or optimum ingredients or pro mine such as ammonium carbonate, ammonium cedures to be employed. Our invention provides carbamate, or an amine carbonate. or the like, is a practical and ?exible procedure by the use of used, carbon dioxide is liberated during the :mix which a-wide variety of useful products is obtained ing and agitation. In some cases color changes as hereinafter disclosed. characteristic of the metal appear. The mixture Ma'ny complex metal ammine salts are ex becomes wet and‘in some cases pasty, almost ?uid. tremely soluble in water and for this reason it is ~ The solid complex metal compound may be dried very di?icult to prepare them in the solid state, afterthe reaction is complete, or the agitation in view of the difficulty of precipitating them from and drying may be accomplished simultaneously. the solutions in which they are formed. Attempts The product may be ground to any desired par to prepare these soluble salts in the solidv state by ticle size. chilling the solutions are often ineifective and 25 In an alternate procedure, a metal salt and an give poor yields. Attempts to recover the salt ammine compound are mixed with a salt or salts by evaporation of the liquid commonly result in containing an anion which is capable of forming loss of ammonia or of a volatile amine by vola tilization. Other complex metal ammine salts which are sparingly ‘soluble are not subject to these di?lculties but involve other dif?culties in precipitation, ?ltering, washing and drying. an insoluble salt with one or more of the metal salts, as claimed in our co-pending application _ In some cases it is desirable to heat the mix ture to start the reaction. The heat is prefer 30 Serial No. 447,470, filed June 17, 1942. It has been proposed to form complex metal ably moderate, of the order of ‘70-80° C., although ammonia salts by exposing the solid metal salts to considerable variation in this temperature is per ammonia gas. However, with ‘this method the L3 LI missible according to the ingredients and the ?nal formation of the complex salt is apt to be merely product involved. superficial and may not penetrate thoroughly into Drying can be accelerated by the application of the inner part of the crystals. Thus the conver a vacuum. sion to the complex salt may be incomplete. As indicated above, a wide range of desirable It has also been proposed to react basic copper d products may be obtained by our invention. The carbonate with ammonium carbonate in the dry solubility and stability of the ?nal product may state to form solid copper ammonia carbonate, the be varied inaccordance with the requirements of reaction preferably being. carried out in the pres the particular purpose in mind. The chemical ence of lime to absorb the carbon dioxide which composition is also subject to variation in the light is liberated. It is di?icult, however, if not impos of the same considerations. sible to tell when this reaction. has gone to com For a better understanding of our invention. pletion, so that the nature of the ?nal product the following speci?c examples of its application and of solutions prepared therefrom are neces may be given, it being understood that these are sarily somewhat indeterminate. Furthermore,‘ illustrative only and are not to be construed in this proposal results in a product of extremely un- - a limiting sense. The proportions are by weight. stable character, which must be shipped and Example 1.—20 parts of copper sulfate and 23 stored in sealed containers. ‘ parts of ammonium carbonate are mixed in dry It is an object of our invention to provide an crystalline form in a mortar and the mixture is improved-process for the preparation of solid com “agitated as by stirring. ‘The reaction starts almost plex metal ammine salts. ' ' 55 immediately and proceeds with the liberation of 8,418,890 3 . carbon dioxide and of water. The water of crys tallization is partially substituted by NR1. Since 4 tion of copper ammonia ?uoride and alsopthe formation of sodium sulfate simultaneously with the formation of the complex copper ammonia the final product appears to have the composition salt. A third possibility is that both of these Cu(NI-11)4SO4H2O, it is likely that four molecules of water of crystallization are directly substituted CI reactions may take place to some extent; the ?nal product may be intermediate between the by four NH: groups while the ?fth molecule of water of crystallization cannot be replaced. two ?rst indicated, comprising a mixture of cop Since the copper ammonia sulfate is a fairly per ammonia sulfate, copper ammonia ?uoride, stable compound, the salt can be dried by heat. sodium sulfate and sodium ?uoride. A short exposure to a temperature of about 105° 10 In most cases it is immaterial which of these C. will dry the product if it is exposed to the heat conditions prevails, since in any event the ?nal in thin layers, without decomposing the copper ammonia complex. A continued exposure, how ever, will slowly decompose the complex, ammo nia being given on and the deep blue to violet color of the powder ‘becoming lighter. Mixing and drying may be facilitated by car rying out the mixing and agitation of the ingredi ents in a closed container or ?ask to which a product will contain ions which, when dissolved, deposited upon a base material such as a fab ric and the ammonia volatilized, will leave an insoluble metal compound. ’ \ If we assume the ?nal product to be a mixture of copper ammonia sulfate and sodium ?uoride. the theoretical amounts of copper, ammonia and ?uorine present will be: Cu, 19%, NHa, 20.3% and vacuum is applied, the ingredients being heated 20 F, 12%, based on the original amounts of cop during the agitation. The evolution of carbon per sulfate, ammonium carbonate and sodium > ?uoride given in Example 2. If complete double dioxide'and of water vapor during the reaction decomposition takes place and the ?nal product tends to reduce the vacuum but after the reac-_ tion has gone to completion, the vacuum will consists of copper ammonia ?uoride and sodium increase and then reach a constant value. This 25 sulfate, the relative amounts of copper, ammonia and ?uoride in the product still would not be gives a reliable indication of the completion of signi?cantly changed from the percentages just the desired reaction and the formation of the given. desired dry product. For example, in one experiment it was found If the number of ‘molecules of water of crys that when 1 lb. of copper ammonia sulfate was 30 tallization per molecule of copper ammonia ?u oride should be high, the above theoretical per formed in a ?ve litre, three-neck Pyrex ?ask, centages of copper, ammonia and ?uorine would under a vacuum which ?nally went to about 22 millimeters of mercury, the ?ask being heated no longer hold. This, however, seems unlikely, since water is obviously liberated during the in a water bath to approximately 100° 0., the reaction was complete in less than one hour. reaction. The product may be ground to any desired par Analysis of our product prepared in accordance with Example 2 has given ?gures closely com ticle size. parable to the theoretical percentages just given. Example 2.—16 parts of sodium ?uoride, 45 The complex ?nal product is quite stable. Only parts of copper sulfate and 50 parts of ammo nium carbonate are dry mixed and agitated to 40 one-?fth of the ammonia is lost when the powder is dried for thirty minutes at a temperature of gether, using the above orany convenient pro 106° C. If the product is to be used in solution, cedure, either with or without the application the loss of ammonia during drying (if any) does of vacuum and heating. After the reaction has gone to completion (as indicated by the fact that not render the product useless, since a small carbon dioxide is no longer given o?) , the prod 45 addition of ammonia to the solution will dissolve uct may, if desired, be dried by spreading it in any residue. thin layers. It may then be ground as previously The ?nal composition which contains the the oretical proportions within the limits given above is soluble in water, giving a deep blue solution accomplished, as in the case ofExample 1. For 50 characteristic of copper ammonia complex com instance, the reaction may be carried out in a pounds. If an excess of water is added, the solu ?ask to which a vacuum is applied during the tion turns to a lighter blue and a’ turbidity ap reaction, the ?ask being heated in a water bath pears which may be due to hydrolysis. A small or otherwise. Evolution of carbon dioxide and addition of ammonia, however, clears the solu indicated. ’ The mixing and drying may be simultaneously water vapor will reduce the vacuum during the 55 tion again and causes the deep blue color to re progress of the reaction and completion of the appear.‘ This indicates that an excess of am reaction will be indicated by decrease in and monia is required to obtain stable dilute solu stabilization of the pressure. tions of copper ammonia compounds. Example 2 is illustrative of a type of procedure Example 3.-—48 parts of copper sulfate and 48 in which a ?rst or primary water-soluble metal 60 parts of ammonium carbonate are mixed in dry salt is agitated with an ammonium compound crystalline form in a mortar or in a closed ?ask as and a second water-soluble salt, the anion of in Example 1 above.‘ The mixture is stirred con which second salt forms an insoluble salt with stantly and when it becomes pasty or ?uid, ap the metal of the ?rst or primary metal salt. This proximately 6.4 parts of a wetting agent (for ex process results in a ?nal product which is solu ample an ester of a sulfonated bi-carboxylic acid ble in water but which, when applied to a fabric, such as Aerosol M. A.) are added and uniformly for example, and the ammonia volatilized, will distributed throughout the mixture. In the case leave upon the fabric a deposit of a water-insolu of solid wetting agents, uniform distribution is ble metal compound. facilitated by dissolving said agent in a minimum The exact nature of the ?nal product of Exam 70 amount of hot water prior to introducing it into ple 2 is subject to some speculation. , the mixture. It is possible that the sodium ?uoride appears The reaction proceeds to completion as in Ex as such in the ?nal product, mixed with copper. ample 1 and the product maythen be used if de ammonia sulfate. or there may be a double de sired in the formation of various compositions. composition reaction which results in the forma 75 For example, an eifective ?re retarding compo sitlon may be made by mixing this product with starting materials because. in their absence, the diammonium phosphate in the proportions of ap completion of the reaction is indicated when car bon dioxide is no longer liberated. Thus when ~ monia product to ten parts of diammonium phosphate, The resulting mixture will be solu $1 ammonium carbonate is used as a source of am monia. the metal salt will be a salt with an anion ble in water and will have high penetrating and different from that of the ammonium salt. wetting qualities due to the presence of the wet We also prefer to avoid the formation of metal ting agent. When impregnated into combustible ammonia carbonates as final products. For a materials such as wood or fabric, this composi given metal the carbonate will be less stable than tion will impart to such material desirable pre salts containing anions derived from acids servative and ?reproof properties. . stronger than carbonic, acid. ' Example 4.—10 parts of cobaltous chloride, 20 In place of ammonium carbonate there may be parts of ammonium carbonate, and 4 parts of am used ammonium bicarbonate. ammonium carba monium chloride are mixed and stirred together mate, urea, amine compounds, such as carbon in the presence of air or other oxidizing agent. ates, for example guanidlne carbonate, and the The purpose of the oxidizing agent is to convert like. , the cobalt from the cobaltous to the cobaltic In place of sodium ?uoride mentioned in Ex state. The reaction goes as above. The mixture ample 2 there may be used monoammonium ‘becomes moist, carbon dioxide is liberated and phosphate, diammonium phosphate, sodium ar the color turns to brown, indicating the forma proximately one part of the complex copper am tion ‘of a cobaltic ammonia compound. senite, sodium arsenate, or other salt the anion of which will form, with the metal of the ?rst or primary salt, a compound which is relatively in soluble in water. For many purposes, water‘ soluble salts of this class are preferred. It is to be noted that salts which are strongly The color of the mixture after drying is red-violet. ' The final product'contains a sparingly soluble product, probably the chloro pentammonia co baltichloride, [C0(NH3)5CI]C1:. Example 5.--20 parts of copper ?uoride and 50 basic or acid are not suitable for admixture as in parts of ammonium carbonate are mixed and agi Example 2 with the primary metal salt and the source of ammine prior to reaction between these ingredients to form the complex metal ammine tated together as in the preceding examples. ' The reaction proceeds as above, the ?nal product be ing, for the greater part, readily soluble in water. ' Other insoluble copper salts, for example cop per phosphate or copper arsenite, may be used in stead of the ?uoride in Example 5, but in these cases the reaction proceeds with more dimculty 30 salt, because the strong alkalinity or acidity im parted thereby would prevent the formation of the complex salt. The ammonia or volatile amine will be driven oif from strongly basic mixtures and the complex formation cannot take place in strongly acid media. The compound selected as a third ingredient should, therefore, be one which is substantially neutral. As previously indicated, the proportions given above are merely convenient examples of opera stirred together in the presence of air or other 40 tive proportions. The proportionsof ingredients oxidizing agent, as‘in Example 4. Oxidation of usable in our process are subject to wide varia the cobalt and formation of a complex cobalt tion. If it is desired to eifect complete conversion guanidlne chloride proceeds and the ?nal prod of the metal salt to the complex metal ammine uct is violet-blue in color. compound, su?icient ammonia or amine must ob It will be noted that in Examples 4 and 6 the 45 viously be supplied for this purpose. metal is oxidized from the "ous" to the “ic" state By our novel process we may prepare solid com during the formation of the complexsalt. For plex metal ammine salts which are stable at nor maximum e?iciency it therefore becomes advisa mal temperatures and pressures under ordinary ble to furnish an additional supply of the anion of this metal salt. This may be done, as in Ex 50 conditions of manufacture, handling and storage. Such stability is possessed, for example, by the amples 4 and 6, by supplying this anion products obtained by the procedures given in Examples 1, 2 and 3, above. As illustrated by (51) Example 3, we may produce solid complex metal and it is advisable to heat the mixture in order to expedite the reaction. Example 6.—5 parts of cobaltous chloride, 10 parts of guanidine carbonate, and one to two parts of ammonium chloride are mixed and as a part of the source of ammonia. Or some ammine salts which can be mixed with other in , other source of this anion may be provided. 55 gredients to form products useful for a variety of Both the speci?c ingredients and the relative purposes. amounts thereof given in the foregoing examples are subject to wide variation. In place of the copper sulfate mentioned. salts of cobalt, nickel, silver, zinc, cadmium and others For some uses less stable products may be un ' objectionable or even desirable. Products of varying degrees of ~solubility, as desired. may be prepared by our process. Thus the process of Example 4 above utilizes an initial be used. mixture of ingredients all of which are readily In the appended claims, we use the term "am soluble in water to form a ?nal product which mine complexogen metal” to designate metals contains a complex metal ammine salt which is which are capable of forming ‘complex metal 65 only sparingly soluble. In Example 5, on the amine salts or metal ammonia salts, when mixed other hand. the initial metal salt is relatively in the solid state with a solid source of ammine. insoluble in water but the ?nal product is for the capable of forming complex ammine salts may . As previously indicated, theanions combined greater part readily soluble in water. ' with the metals in these salts will be anions de will thus be seen that by our invention there rived from acids stronger than carbonic acid. In 70 is It provided a novel and improved process for the determining the relative strengths of acids, the preparation of solid complex metal ammine salts. dissociation constant is to be taken into consid which‘ process is practical and economical for eration, in accordance with well established large scale manufacture and results in a greatly principles. , _ - It is desirable to avoid metal carbonates as improved yield of desirable products having a wide range of commercial applications. l 2,412,890 7 .We claim: 1. A method for the preparation of a solid com . plex metal ammine salt, which comprises the steps _ l monia salt, and continuing said agitation until said salt is substantially converted to a complex of mixing and agitating together a solid salt of an ammine complexogen metal, said salt having an anion derived from an acid stronger than car metal 5. Aammonia method for salt. the preparation of a solid com plex copper ammonia salt, said method compris ing mixing and agitating together a solid copper bonic acid, and a solid ammine salt which is un ' stable and which will form, with the solid metal salt which has an anion derived from an acid stronger than carbonic acid, and ammonium car bonate, until the mixture becomes moist and car compound, a complex metal ammine salt, con tinuing said mixing and agitation until the mix--. 10 bon dioxide is evolved, then continuing said agi tation until the evolution of carbon dioxide'and ture becomes moist and the metal salt is substan water vapor substantially ceases, and drying the tially converted into a complex metal ammine resulting complex salt. salt, and drying the complex salt. 6. In a method for the preparation of solid 2. A method for the preparation of a solid com plex metal ammonia salt, which comprises the 15 complex metal ammonia salts. the steps'which comprise mixing, agitating and heating together, steps of mixing and agitating together a solid salt in the solid state and under a vacuum, a'metal of an ammine complexogen metal, said salt hav-_ salt selected from the group consisting of those ing an anion derived from an acid stronger than carbonic acid, and ammonium carbonate, con salts of copper, cobalt and silver having an anion salt is substantially converted into a complex and a solid ammonium compound which is un tinuing said mixing and agitation until the metal 20 derived from an acid stronger than carbonic acid, stable and which will form, with the solid metal compound, a complex metal ammonia salt, and continuing said agitation until the metal salt is plex metal guanidine salt, which comprises the steps of mixing and agitating together a solid 25 substantially converted into a complex metal am monia salt. salt of an ammine complexogen metal, said salt 7. A method for the preparation of a solid having an anion derived from an acid stronger complex metal ammonia compound, which com than carbonic acid, and guanidine carbonate, and ’ metal ammonia ‘salt, and drying the complex salt. 3. A method for the preparation of a solid com continuing said mixing and agitation until the prises the steps of mixing and agitating together 30 a solid salt of an ammine complexogen metaLsald salt having an anion derived from an acid stronger than carbonic acid, and a solid ammoni 4. In a method for the preparation of a solid um compound which is unstable and which will complex metal ammonia salt, the steps which form, with the metal compound, a complex metal ' comprise mixing and agitating together a solid metal salt is substantially convertedinto a com plex metal guanidine salt. salt of a metal selected from the group consisting of copper, cobalt, and silver, said salt having an anion derived from an acid stronger than car bonic acid, and a solid ammonium compound which is relatively unstable and which will form, with the said metal salt. a complex metal am 40 ammonia salt, agitating the mixture until it be comes pasty or ?uid, and continuing the agitation until said metal salt is substantially converted into a solid complex metal ammonia compound. ’ GRINNELL JONES. WALTER JUDA.