Патент USA US2406692код для вставки
Patented Aug. 27, 1946 " 2,406,692 UNITED STATES PATENT OFFICE 2,406,692 SOLID COIVIPLEX METAL AMMINE SALTS AND METHOD FOR THE PREPARATION THEREOF Grirmell 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. 447,470 5 ‘Claims. (cl. 167-46) plex’metal ammine salt and to methods for the preparation thereof. 2 multaneously. The product may The present invention relates to a solid com be ground to ' any desired particle size. In some cases it is desirable to heat the mix ' By the term "ammine” it is intended to in clude only ammonia and amines. Complex metal ammine salts very widely in chemical structure and also in physical proper solubility, ties, particularly depending withupon regard thetonature stability of and _the - ture to start the reaction. The heat is prefer ably moderate, of the order of 70-80" 0., although considerable variation in this temperature is permissible according to the ingredients and the ?nal product involved. -. Drying can be accelerated by the application of metal (and in some cases its state of oxidation) , 10 a vacuum. For a better understanding of our invention, the anion, the conditions of preparation and ' other factors. For these and other reasons, it is dif?cult to generalize in this ?eld and to deter mine in advance either the nature of the ?nal product or the essential or optimum ingredients or procedures to be employed. Many complex metal ammine salts are ex tremely soluble in water and for this reason it is di?icult to prepare them in the solid state, in the following speci?c examples of its application may be given, it being understood that these are illustrative only and are not to be construed - in a limiting sense. The proportions are by weight. Example 1.-45 parts of copper sulfate, 50 parts of ammonium carbonate and 16 parts of sodium ?uoride are mixed in dry form in a mortar and view of the dif?culty of precipitating them from 20 the mixture is agitated, as by stirring. The re action starts almost immediately and proceeds the solutions in which they are formed. Attempts with the liberation of carbon dioxide and water. to prepare these soluble salts in the solid state by After the reaction has gone to completion (as chilling the solutions are often ineffective and indicated by the fact that carbon dioxide is no give poor yields. Attempts to recover the salt by evaporation of the- liquid commonly result in 25 longer given off), the product may, if desired, be dried by spreading it in thin layers. It may loss of ammonia or of a volatile amine by volatili then be ground if desired. zation. Other complex metal ammine salts which The mixing and drying may be simultaneously are sparingly soluble are not subject to these accomplished. For instance, the reaction may be dimculties but involve other difficulties in precip itation, ?ltering, washing and drying. 30 carried out in a closed vessel to which a vac It is an object of our invention to provide an uum is applied during the reaction, the vessel improved product comprising a solid complex being heated in a water bath or otherwise. Evo lution of carbon dioxide and water vapor will reduce the ‘.acuum during the progress of the metal ammine salt and an improved method for the manufacture thereof. Our products are, for the most part, soluble in 35 reaction and completion of the reaction and formation of the desired dry product will be in water or in dilute aqueous ammonia solutions, dicated by decrease in and stabilization of the but, ‘upon evaporation of the solution and vola pressure. tilization of the, ammonia or volatile amine, in For example, in one experiment it was found soluble metal salts are deposited. -In general, our improved method comprises 40 that when 1 lb. of the product was formed in a ?ve litre, three-neck Pyrex ?ask, under a vacuum the dry mixing and agitation of a solid metal which ?nally went to about 22 millimeters of .' . compound (which may for purposes of identi?ca mercury, the ?ask being heated in a water bath tion be referred to as the primary metal com to approximately 100° C., the reaction was com pound or salt) which is soluble in water, with a source of ammine, preferably a solid ammine 45 plete in less than one hour. The exact nature of the ?nal produce is sub compound which is relatively unstable and which will form, with the primary metal compound, a ject to some speculation. , It is possible that the sodium fluoride‘ appears complex metal ammine salt, and also with a sec as such in the ?nal product, mixed with copper ond salt or salts, soluble in water and contain ing an anion which is capable of forming an in— 50 ammonia sulfate. Or there may be a double de composition reaction which results in the forma soluble salt with the primary metal compound. tion of copper ammonia ?uoride and also the When a source of ammonia such as ammonium formation of sodium sulfate simultaneously with carbonate, ammonium carbamate, or the like, is the formation of the complex copper ammonia used, carbon dioxide is liberated during the mix ing and agitation. In some cases‘color changes 55 salt.v A third possibility is that both of these re actions may take place to some extent; the ?nal characteristic of the metal appear. The mixture product maybe intermediate between the two becomes, Wet and in some cases pasty, almost ?rst indicated. comprising a mixture of copper ?uid. The solid complex metal compound may ammonia sulfate, copper ammonia ?uoride, so be dried after the reaction is complete, or the agitation and drying may be accomplished si 60 dium sulfate and sodium ?uoride.‘ 2,406,692 4 Example 4 in most cases it is immaterial which of these conditions prevails, since in any event the ?nal product will contain ions which, when dissolved, Silver nitrate_ deposited upon a base material such as a fabric Ammonium carbonate ____________________ __ 40 and the ammonia volatilized, will leave an insolu Disodium hydrogen arsenate ble metal compound. Parts (Na2HASO4.7H20) 50 ____________________ .._ 35 If we assume the ?nal product to be a mixture When preparing unstable complex metal am of copper ammonia sulfate and sodium fluoride, monia salts as in Examples 3 and 4, it may be the theoretical amounts of copper, ammonia and necessary to take precautions to prevent decom ?uorine present will be: Cu, 19%, NHz', 20.3% and 10 position of the complex salt during and after its F, 12%, based on the original amounts of copper formation. sulfate, ammonium carbonate and sodium ?u Example 5.—45 parts of copper sulfate and 16 oride given in Example 1. If complete double parts of sodium ?uoride are mixed together and, decomposition takes place and the ?nal product while being agitated, ammonia gas in amount consists of copper ammonia ?uoride and sodium 15 of the order of 12-15 parts is passed through the sulfate, the relative amounts of copper, am mass. monia and ?uoride in?the, product still would not If avacuum is applied to the mixture of Ex be signi?cantly changed from the percentages ample 5, it should not be applied until the am just given. monia gas has reacted with the salts, since other“ If the number of molecules of water of crys 20 wise the ammonia gas might be drawn oil? with talli'zation per molecule of copper ammonia ?u out reacting. oride should be high, the above theoretical per While ammonia gas will react with soluble centages of copper, ammonia and?uorine would metal salts such as copper sulfate, to form com ‘no longer hold. This, however, seem unlikely, plex copper ammonia salts, it will not so react since water is obviously liberated during the re 25 with insoluble salts such as copper ?uoride, cop action. ' per phosphate and copper arsenite. Analysis of our product prepared in accord Both the speci?c ingredients and the relative ance with Example 1 has given ?gures closely amounts thereof given in the foregoing examples comparable to the theoretical percentages just are subject to wide variation. given. 30 ‘ As primary metal salts, salts of cobalt, nickel, The complex ?nal product is quite stable. silver, zinc, cadmium and others capable of Only one-?fth of the ammonia is lost when the forming complex ammine salts, or mixtures of powder ‘is dried for thirty minutes at a temper such metal salts, may be used. One or more of ature of 106° C. If the product is to be used in such compounds may be used. solution, the loss of ammonia during drying (if 35 In the appended claim we use the term “am any) does not render the product useless, since mine complexogen metal” to designate metals a small addition of ammonia to the solution will which are- capable of forming complex metal dissolve any residue. 1 The ?nal composition which contains the the oretical proportions within the limits given above is soluble in water, giving a deep blue solution characteristic of copper ammonia complex com amine salts or metal ammonia salts, when mixed in the solid state with a solid source of ammine. In Place of ammonium carbonate there may be used ammonium bicarbonate, ammonium car bamate, urea, amine compounds, such as car pounds. If an excess of water is added, the solu bonates, for example guanidine carbonate, and tion turns to a lighter blue and a turbidity ap the like. Ammonia gas may be used with cop pears which may be due to hydrolysis. A small 45 per sulfate and like soluble salts. addition of ammonia, however, clears the solu For the secondary metal salt there may be used tion again and causes the deepv blue color to re-' appear. This indicates that an excess of am essentially neutral, water soluble salts, the anion of which will form, with the metal of the pri monia is required to obtain stable dilute solu mary compound or salt, a compound which is 50 relatively insoluble in water. One or more of tions of copper ammonia compounds. Since the copper ammonia compound is a fairly such salts may be used. , stable compound, the product can be dried by It is to be noted that salts which are strongly heat. A short exposure to,a temperature of basic or acid are not suitable for admixture with about 105° C. will dry the product if it is exposed the primary metal salt and the source of ammine to the heat in thin layers, without decomposing 55 prior to reaction between these ingredients to the copper ammonia complex. A continued ex form the complex metal ammine salt, because the posure, however, will slowly decompose the com strong alkalinity or acidity imparted thereby plex, ammonia being given off and the deep blue would prevent the formation of the complex salt. to violet color of the powder becoming lighter. The ammonia will be driven off from strongly Additional examples of operative ingredients 60 basic mixtures and the complex formation can and proportions of ingredients are given below. not take place in strongly acid media. The com The mixing and agitation may be carried out ' pound selected as a secondary salt should, there as in Example 1. ' fore, be one which is substantially neutral, As previously indicated, the proportions of in Example 2 65 gredients usable inour process are subject to Parts considerable variation. If it is desired to effect Copper sulfate 45 complex conversion of the metal salt to the com Ammonium carbonate _______________ _l______ 60 plex metal ammine compound, sufficient ammine Monoammonium phosphate _________ __,-______ 20 must obviously be supplied for this purpose. Our product comprises a solid water-soluble 70 Example 3 complex‘metal ammine salt, in combination with ‘ Zinc chloride _ Parts another soluble salt, said combination being 25 either chemical or mechanical. This product is adapted to a variety of uses. For instance, it may 75 be dissolved in water and applied to a fabric. Ammonium carbonate ____________________ __ 50 Monoammonium phosphate _______________ __ 20 2,406,692 6 5 Upon drying and volatilizing the ammonia or volatile amine, there will be deposited upon the fabric a relatively insoluble metal salt which may have desirable preservative and/or other proper ties. ' contains an anion capable of forming a water insoluble compound with the metal or the said first salt, and continuing said agitation until the formation of a complex metal salt is substantially complete. Products or highly 2. The process for forming solid compositions containing a complex metal salt, which process comprises mixing together a water-soluble salt will clear the solution immediately instead .of carbonate, ammonium bicarbonate, ammonium plexogen metals. The stability of the metal ammonia complex salt depends upon the metal of the primary salt ?nely divided state a solid complexogen metal ' Products of varying degrees of stability may be prepared by our process. Thus the product of Example 1 is quite stable. of a metal selected from the group consisting of unstable character can also be prepared by our method, as in Examples 3 and 4. These prod 10 copper, cobalt, nickel, silver, zinc, and cadmium, a second solid substantially neutral salt which ucts may contain so low an ammonia content as is soluble in water and which contains an anion to necessitate their solution in dilute aqueous capable of forming an insoluble compound with ammonia rather than in water. However, even in the metal of the said ?rst salt, and a substance these cases a small amount of ammonia added to selected from the group consisting of ammonium a turbid aqueous solution of the unstable product carbamate and non-aqueous ammonia, and agi causing ?rst a temporary precipitate of metal tating said mixture until the formation of a com hydroxide (soluble only in an excess of ammo plex metal salt is substantially complete. nia) which is obtained in the case of aqueous 3. The method which comprises reacting in a solutions of non-complex salts of ammine com 20 salt which is soluble in water, a second solid wa ter-soluble salt which is substantially neutral and which contains an anion capable of forming a and upon the anion of the essentially neutral secondary salt. Thus the product of Example 3 25 water-insoluble salt with the metal of the said ?rst solid salt, and passing ammonia gas through is relatively unstable because it contains the un said mixture while agitating the same. stable zinc ammonia complex ion which gives 4. The method which comprises reacting in a salts having a comparatively high vapor pressure ?nely divided state a primary solid complexogen of ammonia, and the product of Example 4 is unstable because there is a'strong tendency to 30 metal salt which is soluble in water, a non-aque ous source of ammonia and a second solid salt form the highly insoluble silver arsenate (solu which is soluble in water and substantially neu bility: 0.00085 g. in 100 cc. water at 20° 0.). tral and which contains an anion capable of form Obviously, the more unstable the product, the ing a water-insoluble salt with the metal of the more dimcult it is to give exact figures of its am monia content. Thus the products of Examples 35 primary salt, thereby forming a composition con taining a solid water-soluble complex metal am 3 and 4 may contain varying amounts of ammo monia salt, dissolving the composition in water, nia according to the precautions taken in their applying the dissolved salts to a fabric and then preparation, and they may therefore be more or treating the fabric to volatilize the ammonia, less soluble in water. ‘ It will thus be seen that by our invention there 40 whereby a water-insoluble metal compound is deposited on the fabric. is provided a novel and improved product hav 5. A solid composition of matter comprising the ing a wide ?eld of utility and also a novel proc complex copper ammonia ion, an anion which will ess for the formation of products comprising com form a sparingly soluble salt with the copper of plex metal ammine salts. 45 said complex ion upon decomposition of the com We claim: plex, and ions which will combine to form a wa 1. The process of forming solid compositions ter-soluble secondary salt, said composition con containing a complex metal salt, which process taining copper and ammonia in approximately comprises mixing and agitating together a wa equal quantities. ter-soluble solid complexogen metal salt, a non GRDINELL JONES. aqueous source of ammine, and a second solid, 60 WALTER JUDA. water-soluble and substantially neutral salt which Certi?cate of‘ Correction Patent No. 2,406,692. GRINNELL JONES ET AL. August 27, 1946. _ It is hereby certi?ed that errors appear in the printed speci?cation of the above numbered patent requiring correction as follows: Column 1, line _ 6, for “very” read vary ; column 2, line 46, for “produce” read product; column 4, hue 67 for “complex” read com lete ; and that the said Letters Patent should be read with t ese corrections therein at the same may conform to the record of the case in the Patent O?ice. Signed and sealed this 22nd day of October, A. D. 1946. [ml First Assistant Uommz'asiomr of Patents.