Патент USA US2411815код для вставки
2,411,815 Patented Nov. 26, 1946 UNITED STATES PATENT OFFICE 2,411,815 SOLUTIONS OF ORGANIC MERCURY COMPOUNDS Frank J. Sowa, Cranford, N. J. No Drawinga, Application May 31, 1943, Serial No. 489,244 (Cl. 167-30) 5 Claims. 1 This invention relates to solutions of organic mercury compounds and to methods for produc ing and using such solutions. It is well known that the aryl and aralkyl'mer 2 latex solutions, and they may be added to dis persions and emulsions of water proo?ng or fabric treating compositions. They also may be used in carrying out various chemical reactions wherein high concentrations of mercury com cury hydroxides and salts are relatively insolu pounds are desirable or of advantage. The solu ble in water. Thus, for example, phenyl mer tions may be caused to penetrate into ?bers, or curic acetate is soluble in water to the extent of pores in material or they may be applied as a about 1 part in 600 parts of water while phenyl constituent of ?lm forming, coating or impreg mercuric chloride only. dissolves to the extent of nating compositions. Furthermore, the concen about 1 part to 20,000 parts of water. All known 10 tration of organic mercury compounds in medic compounds having the general formula Rr—Hginal and industrial formulae may be materially X, wherein R is an aryl, aralkyl, alkaryl, or increased by practice in accordance with the heterocyclic group, Hg is mercury, and X is an present invention. ' anion, exhibit similar low solubility in water and The principal objects of the present invention in many water miscible solvents such as alco 15 are to increasethe solubility or concentration of hols, glycerols and the like.v organic mercury compoundsv in aqueous solu Many, if not all, of these organic mercury tions; to provide new types of mercury‘contain compounds have high toxicity to bacteria and ing germicidal compositions and products; to in fungi and have other important uses in indus crease the resistance of products to the action of try and medicine. However, because of their 20 bacteria, fungi, mildew and the like; and to pro relatively low solubility it is not economically practical to ship the product in the form of a vide novel methods of producing and using solu tions of organic mercury compounds having the solution and it frequently is di?icult or impos general formula R—Hg-X, in which R is an sible for the user to produce solutions having the aryl, aralkyl,‘ alkaryl or heterocyclic group, Hg is 25 desired concentration of the mercury compound mercury and X is an anion. therein. Moreover, in many applications of such Particular objects of the invention are to pro solutions it is impossible to use suf?cient water vide relatively concentrated solutions of phenyl or solvent for the mercury compound to obtain mercury compounds and to provide methods for the required concentration thereof in the product using such solutions in the treatment of fabrics, 30 without undesired dilution or unbalancing of a leather and other ?brous, porous or textile formula. products to render them bacterlostatic, fungi I have discovered that the solubility of mer static and mildew resistant. cury compounds of the R—Hg-X type, in water These and other objects and features of the and in mixtures of water with solvents such as present invention will appear from the following alcohols, glycerols and the like, can be materially description thereof in which speci?c examples increased provided ammonium hydroxide and a are cited to indicate the nature of the invention soluble ammonium salt are present in the solu and , typical applications and. embodiments tion. Some of the ammonium salts may be used thereof, but without intending to limit the scope for this purpose without adding ammonium hy of the invention thereby. 40 droxide to the solution, whereas in at least one My investigations indicate that all of the or instance I have found it possible to dissolve a ganic mercury compounds which have the gen relatively water insoluble organic mercury com eral formula R.—Hg-A-X will dissolve to a greater pound in a solution of ammonium hydroxide extent in aqueous solutions containing an am alone. However, in most instances it is necessary 45 monium compound than they will in water'or ammonium hydroxide and an am-_ to use both the solvent alone. It appears in most instances monium salt in order to dissolve substantial that the solubility of the mercury compound in amounts of the mercury compounds in aqueous aqueous solvents is markedly increased when the solutions. It is also found in general that the solution also contains both an ammonium salt pH value of the solution should be above 7 and and ammonium hydroxide. I am unable at this 50 preferably in the range of about ‘7.2 to 9.0. time to state exactly what chemical or physical Solutions of this character may contain up to reactions account for the increase in solubility of 50% or more by weight of the aryl, aralkyl or the mercury compound in aqueous solutions alkaryl mercury compound and can be used to when ammonium compounds are present, but it apply such compounds to fabrics, leather, paper, is my belief that some addition compound or co sheets or films, or for admixture with paints or 55 2,411,815 4 ordination complex is produced during solution, acetate so that the apparent result when using ammonium chloride and ammonium thiocyanate or similar compounds, is to decrease the amount of the phenyl mercury acetate in solution. Such reactions, however, are to be avoided in the prac_ and that the resulting compound or complex is itself relatively soluble or exerts an in?uence on the mercury compound which serves to increase its solubility in water. v Among the ammonium salts I have used to in crease the solubility of phenyl mercuric acetate in water, I may mention speci?cally ammonium tice of my invention and ammonium salts se lected which will not react with the mercury com sulphate, ammonium carbonate, tri-ammonium phosphate, di-ammonium phosphate, ammonium borate, ammonium tetraborate, ammonium ci trate, ammonium oxalate, ammonium lactate, pound. pound to produce a less soluble mercury com- ' 10 ammonium formate and ammonium acetate. A 5% solution of any one of these salts has been found to be capable of dissolving from 4 to 12% of phenyl mercuric acetate provided some am monium hydroxide is also present in the solution and preferably is added in sufficient quantities In choosing an ammonium salt to increase the solubility of ammonium compounds ‘of the R-Hg—-X type it also appears that the action of ammonium salts of nitrogen containing acids are much less eifective than are other salts. Thus the increase in solubility of phenyl mercuric acetate in an ammoniacal solution of ammonium nitrate is less than might have been expected. Similarly, the action of a few other ammonium to give a ?nal solution having a pH value above 7 salts is limited and relatively poor or negligible and preferably in the range of from about ‘7.2 20 results are obtained when using ammonium ?uo to 9.0. Of these salts it has been found that am ride, ammonium ?uo-silicate, ammonium chlo monium carbonate, di-ammonium phosphate, tri ride and ammonium linolate. Nevertheless, the ammonium phosphate and ammonium borate are great majority of the ammonium salts appear to capable of use by themselves in increasing the increase the solubility of the mercury compounds solubility of phenyl mercuric acetate. No am enormously and even the less active salts men monium hydroxide need be added when using tioned above appear to have some in?uence on these salts. the‘ solubility of the R--Hg-X type of com Other compounds having the general formula pounds. R—Hg-—X exhibit the same property of in In order to indicate typical and preferred solu creased solubility in water containing ammonium 30 tions using ammonium salts in ammoniacal water compounds. Thus, phenyl mercuric hydroxide, solutions, having a pH valve above 7 the follow phenyl mercuric borate, phenyl mercuric ing examples are cited. phthalate, phenyl mercuric gluconate, benzyl 100 cc. of 5% salt mercuric acetate and pyridyl mercuric acetate are soluble to a greater extent in aqueous solutions 35 solution: of ammonium salts containing ammonium hy droxide, than they are in water alone. Phenyl mercuric hydroxide is soluble in solu tions of ammonium acetate or ‘ammonium sul phate alone but this probably is due to a reaction 40 of the hydroxide with the acetate 'or sulphate to produce some ammonium hydroxide in the solu tion. I have also discovered that phenyl mercuric gluconate is soluble in ammonium hydroxide - alone. Solutions containing 75 grams of phenyl mercuric gluconate in 100 cc. of water are ob tained by simply adding enough ammonium hy droxide to keep the pH value around 8. Similarly, Grams of phenyl mer curic acetate dissolved (NHUzSO-i __________________________ __ 8-12 NH4H2PO4 _ 6-8 (NH4)2HPO4 ________________________ _._ 6-8 (NH4)3PO4 __ ‘ 6-8 NHdHCOG ___________________________ __ 4-6 (NH4) 3B0: __________________________ __ 6-8 (NH4)HB4O7 ________________________ __ 8-10 Ammonium oxalate______-._.._.______.____ 7-9 Ammonium citrate ___________________ __ M Ammonium lactate _______ ._‘_ __________ __ 8-12 Ammonium formate __________________ __ 6-7 Ammonium acetate __________________ -_ 6-8 Alcoholic solutions and mixtures of water with 20 grams of phenyl mercuric hydroxide may be other water miscible solvents such as triethanol dissolved in 100 cc. of water containing 40 grams 50 amine also exhibit the same ability to dissolve of ammonium gluconate and having a pH value increased amounts of organic mercury com of approximately 9. _ pounds of the R-Hg-X type provided an am The amount of the ammonium salt used ap monium compound is present. Thus, for example, pears to influence the solubility of the mercury when forming solutions of phenyl mercuric ace compound and solutions containing from 1 to 20% 55 tate in water and triethanol amine in accordance of ammonium sulphate indicate that the maxi with the process of my copending application Se mum solubility of the mercury compound in such rial No, 443,304, ?led May 16, 1942, it is sometimes solutions is possible when about 4 % of ammonium di?lcult to produce solutions of the desired con sulphate is used. centration. The addition of ammonium sulphate In producing solutions in accordance with my 80 and ammonium hydroxide to such solutions over invention it is of course desirable to choose am comes this di?lculty and not only increases the monium salts which will not react with the mer amount of the mercury compound which may be cury compound to produce a more insoluble mer dissolved but greatly speeds up solution and re cury compound. Thus, when endeavoring to in sults in the formation of solutions which are clear crease the solubility of phenyl mercuric acetate. 85 and very stable. if ammonium chloride is used the relatively less Solutions produced in accordance with the soluble phenyl mercuric chloride will be produced present invention may be applied directly or after and may even precipitate from the solution. Sim dilution with water, to fabrics, leather, paper or ilarly, if ammonium thiocyanate is 'used the al the like by spraying the solution thereon or by most completely insoluble phenyl mercuric ,thio 70 dipping or immersing material therein and the cyanate will precipitate. While these less soluble solution may be applied under pressure to insure compounds are themselves dissolved to some ex the desired penetration of the solution into the tent in the ammoniacal ammonium'salt solution, pores or ?bers of the articles being treated. They although almost completely insoluble in water, also may be added to textile treating baths or‘ they are not soluble to the same extent as the 75 ?nishes such as alkaline solutions of cellulose 2,411,815 , ethers, suspensions of waxes, resins or other sim ilar materials. The ammoniacal or alkaline vna ture of solutions embodying my invention renders them particularly suitable for admixture with latex dispersions, and suspension of rubber, col loids, waterproo?ng or fireproo?ng agents; or products such as casein paints and aqueous coat ing and impregnating compositions. Products thus treated are rendered bacterio static, fungistatic, mildew resistant and germicid 6 - acetate, and ammonium gluconate, together with sufficient ammonium hydroxide to maintain the pH value of thesolution above '7, the amount of the phenyl mercury compound. in solution ex ceeding the amount soluble in the aqueous sol vent of the solution. ‘ 2. A solution containing phenyl mercury ace tate dissolved in an aqueous solvent containing an ammonium salt selected from the group con 10 sisting of ammonium sulfate, ammonium car bonate, tri-ammonium phosphate, di-ammonium phosphate, mono-ammonium phosphate, ammo nium borate, ammonium tetra-borate, ammoni The amount of the solution used in any partic um citrate,‘ ammonium oxalate, ammonium lac ular application will vary considerably but when employed to treat textile fabrics the weight 01' 15 tate, ammonium formate, ammonium acetate, and ammonium gluconate, together with sufli the mercury compound in the treated material cient ammonium hydroxide to maintain the pH should'generally equal about 0.02 to 1.0% and value of the solution above 7, the amount of the preferably about 0.5% of the weight of the fabric. phenyl mercury acetate in solution exceeding the While I have suggested numerous composi tions and uses for solutions produced in accord 20 amount soluble in the aqueous solvent of the so al by reason of the mercury compound deposit ed on or in the product or admixed therewith. ance with the present invention it will be under stood that many other uses and formulae will suggest themselves to those ‘skilled in the art and » lution. » Y 3. An aqueous solution having a pH value not less than 7 and containing a phenyl mercury compound, triethanolamine, ammonium hydrox be apparent from the foregoing description of the invention. In view thereof it is intended that 25 ide ‘and ammonium sulfate, the amount of the phenyl mercury compound in solution being in the particular composition and uses of solutions excess'of that soluble in the water of the solution. speci?cally described above be considered as il 4. An aqueous solution having a pH value not lustrative only since the scope of my invention is less than 7 and containing phenyl mercury ace de?ned by the followim claims. I claim: ' 1. A solution of a phenyl mercury compound in an aqueous solvent containing from about 1 to 20 parts by weight of a salt selected from the group consisting of ammonium sulfate, ammo tate,,triethanolamine, ammonium hydroxide and ammonium sulfate, the amount of the‘ phenyl mercury compound in solution being in excess of that soluble in the water of the solution. 5. A method of increasing the stability of an nium carbonate, tri-ammonium phosphate, (11 35 aqueous solution containing phenyl mercury ace tate and triethanolamine which comprises the ammonium phosphate, mono-ammonium phos step of adding ammonium hydroxide and ammo phate, ammonium borate, ammonium tetra-b0 nium sulfate thereto. . rate, ammonium citrate, ammonium oxalate, am monium lactate, ammonium formate, ammonium FRANK J. SOWA.