USRE23863E - Solutions of organic mercury - Google Patents
Solutions of organic mercury Download PDFInfo
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- USRE23863E USRE23863E US23863DE USRE23863E US RE23863 E USRE23863 E US RE23863E US 23863D E US23863D E US 23863DE US RE23863 E USRE23863 E US RE23863E
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- Prior art keywords
- ammonium
- solution
- solutions
- mercury
- acetate
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title description 5
- 229910052753 mercury Inorganic materials 0.000 title description 5
- 239000000243 solution Substances 0.000 description 70
- 150000002731 mercury compounds Chemical class 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 24
- 239000000908 ammonium hydroxide Substances 0.000 description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 description 24
- 229940043379 ammonium hydroxide Drugs 0.000 description 24
- XEBWQGVWTUSTLN-UHFFFAOYSA-M Phenylmercury acetate Chemical compound CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 18
- 150000003863 ammonium salts Chemical class 0.000 description 15
- 229940100892 mercury compounds Drugs 0.000 description 12
- 150000003868 ammonium compounds Chemical class 0.000 description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 11
- 235000011130 ammonium sulphate Nutrition 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000005695 Ammonium acetate Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 8
- 235000019257 ammonium acetate Nutrition 0.000 description 8
- 229940043376 ammonium acetate Drugs 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 6
- RZOBLYBZQXQGFY-UHFFFAOYSA-N Ammonium lactate Chemical compound [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 description 6
- 239000004251 Ammonium lactate Substances 0.000 description 6
- 229940096826 Phenylmercuric Acetate Drugs 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 229960004418 Trolamine Drugs 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 6
- 229940059265 ammonium lactate Drugs 0.000 description 6
- 235000019286 ammonium lactate Nutrition 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- DCNLOVYDMCVNRZ-UHFFFAOYSA-N phenylmercury(.) Chemical class [Hg]C1=CC=CC=C1 DCNLOVYDMCVNRZ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 6
- 229940029612 triethanolamine Drugs 0.000 description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N Ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 5
- -1 aralkyl mercury hydroxides Chemical class 0.000 description 5
- KTXPGRSAPGCSGO-UHFFFAOYSA-Z dodecaazanium;tetraborate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KTXPGRSAPGCSGO-UHFFFAOYSA-Z 0.000 description 5
- 229940096825 phenylmercury Drugs 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N Ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N Ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N Ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 239000001166 ammonium sulphate Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940050410 gluconate Drugs 0.000 description 4
- XKUUMWKWUZRRPD-UHFFFAOYSA-N heptan-2-amine;sulfuric acid Chemical compound [O-]S([O-])(=O)=O.CCCCCC(C)[NH3+].CCCCCC(C)[NH3+] XKUUMWKWUZRRPD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006012 monoammonium phosphate Substances 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001450 anions Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 3
- MSYUMXXVCSLXMR-UHFFFAOYSA-N phenylmercury;hydrate Chemical compound O.[Hg]C1=CC=CC=C1 MSYUMXXVCSLXMR-UHFFFAOYSA-N 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 229940044197 Ammonium Sulfate Drugs 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N Ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000126 Latex Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 230000003385 bacteriostatic Effects 0.000 description 2
- AWGTVRDHKJQFAX-UHFFFAOYSA-M chloro(phenyl)mercury Chemical compound Cl[Hg]C1=CC=CC=C1 AWGTVRDHKJQFAX-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001408 fungistatic Effects 0.000 description 2
- 230000002070 germicidal Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002314 glycerols Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N Ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 244000233967 Anethum sowa Species 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L Mercury(II) acetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- VUXSPDNLYQTOSY-UHFFFAOYSA-N Phenylmercuric borate Chemical compound OB(O)O[Hg]C1=CC=CC=C1 VUXSPDNLYQTOSY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229960000247 phenylmercuric borate Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/10—Mercury compounds
Definitions
- This invention relates to solutions of organic mercury compounds [and to methods for producing and using such solutions] having in solution more of the organic mercury compound than the amount normally soluble in the same amount of solvent.
- aryl and aralkyl mercury hydroxides and salts are relatively insoluble in water.
- phenyl mercuric acetate is soluble in water to the extent of about 1 part in 600 parts of water while phenyl mercuric chloride only dissolves to the extent of about 1 part to 20,000 parts of water.
- All known compounds having the general formula RHgX, wherein R is an aryl, aralkyl, alkaryl, or heterocyclic group, Hg is mercury, and X is an anion exhibit similar low solubility in water and in many water miscible solvents such as alcohols, glycerols and the like.
- aqueous solutions It is also found in general that the pH value of the solution should be above 7 and preferably in the range of about 7.2 to 9.0.
- Solutions of this character may contain up to or more by weight of the aryl, 'aralkyl or alkaryl mercury compound and can be used to apply such compounds to fabrics, leather, paper, sheets or films, or for admixture with paints or latex solutions, and they may be added to dispersions and emulsions of water proofing or fabric treating compositions. They also may be used in carrying out various chemical reactions wherein high concentrations of mercury compounds are desirable or of advantage.
- the solutions may be caused to penetrate into fibers, or pores in material or they may be applied as a constituent of film forming, coating or impregnating compositions.
- concentration of organic mercury compounds in medicinal and industrial formulae may be materially increased by practice in accordance with the present invention.
- the principal objects of the present invention are to increase the solubility or concentration of organic mercury compounds in aqueous solutions; to provide new types of mercury containing germicidal compositions and products; to increase the resistance of products to the action of bacteria, fungi, mildew and the like; and to provide novel methods of producing and using solutions of organic mercury compounds having the general formula RHg-X, in which R is an aryl, aralkyl, alkaryl or heterocyclic group, Hg is mercury and X is an anion.
- Particular objects of the invention are to provide relatively concentrated solutions of phenyl mercury compounds a d to provide methods for using such solutions the treatment of fabrics, leather and other fibrous, porous or textile products to render them bacteriostatic, fungistatic and mildew resistant.
- ammonium salts I have used to increase the solubility of phenyl mercuric acetate in water
- I may mention specifically ammonium sulphate, ammonium carbonate, triamrnonium phosphate, di-ammonium phosphate, ammonium borate, ammonium tetraborate, ammonium citrate, ammonium oxalate, ammonium lactate, 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 ammonium hydroxide is also present in the solution and preferably is added in suflicient quantities to give a final solution having a pH value above 7 and preferably in the range of from about 7.2 to 9.0.
- ammonium carbonate, diammonium phosphate,- tri-ammonium phosphate and ammonium borate are capable of use by themselves in increasing the solubility of phenyl mercuric acetate. No ammonium hydroxide need be added when using these salts.
- phenyl mercuric hydroxide, phenyl mercuric borate, phenyl mercuric phthalate, phenyl mercuric gluconato, benayl mercuric acetate and pyridyl mercuric acetate are soluble to a creator extent in aqueous solutions of ammonium salts containing ammonium hydroxide, than they are in water alone.
- Phenyl mercuric hydroxide is soluble in solutions of ammonium acetate or ammonium sulphate alone but this probably is due to a reaction of the hydroxide with the acetate or sulphate to produce some ammonium hydroxide in the solution.
- phenyl mercuric aluconate is soluble in ammonium hydroxide alone. Solutions containing '15 grams of phenyl mercuric gluconats in 100 cc. oi water are obtained by simply adding enough lmrmmium hydroxide to keep the pH value around 8. Similarly, 20 grams of phenyl mercuric hydroxide may be dissolved in 100 cc. of water containing 40 grams or ammonimn alucunsto and having a pH value oi approaimatsly O.
- Inprcducingsolutiominaccordoncswithmy invention it is of course desirable to choose ammonium salts which will not react with the mercury compound to produce a more insoluble mercury compound.
- ammonium salts which will not react with the mercury compound to produce a more insoluble mercury compound.
- ammonium salts of nitrogen containing acids are much less effective than are other salts.
- the increase in solubility of phenyl mercuric acetate in an ammoniacal solution of ammonium nitrate is less than might have been expected.
- the action of a few other ammonium salts is limited and relatively poor or negligible results are obtained when using ammonium fluoride, ammonium flue-silicate, ammonium chloride and ammonium llnolate.
- the great majority of the ammonium salts appears to increase the solubility of the mercury compounds enormously and even the less active salts mentioned above appear to have some influence on the solubility of the R-Hg-x type of compounds.
- ammonium sulphate and ammonium hydroxide overcomes this difliculty and not only increases the amount of the mercury compound which may be dissolved but greatly speeds up solution and results in the formation of solutions which are clear and very stable.
- Solutions produced in accordance with; the present invention may be applied directly or after dilution with water, to fabrics, leather, paper or the like by spraying the solution thereon or by dipping or immersing material therein and the solution may be applied under pressure to insure the desired penetration of the solution into the pores or fibers of the articles being treated. They also may be added to textile treating baths or finishes such as alkaline solutions of cellulose ethers, suspensions of waxes, resins or other similar materials.
- the ammoniacal or alkaline nature of solutions embodying my invention renders them particularly suitable for admixture with latex dispersions, and suspension of rubber, colloids, waterproofing or fireproofing agents, or products such as casein paints and aqueous coating and impregnating compositions.
- Products thus treated are rendered bacteriostatic, fungistatic, mildew resistant and germicidal by reason of the mercury compound deposited on or in the product or admixed therewith.
- the amount of the solution used in any particular application will vary considerably but when employed to treat textile fabrics the weight of the mercury compound in the treated material should generally equal about 0.02 to 1.0% and preferably about 0.5% of the weight of the fabric.
- a salt selected from the group consisting of ammonium sulfate, ammonium carbonate, tri-ammonium phosphate, diammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetrabor
- an ammonium salt selected from the group consisting of ammonium sulfate, ammonium carbonate, tri-ammonium phosphate, di-ammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetra-borate, ammonium citrate, am
- a method of increasing the stability of an aqueous solution containing phenyl mercury acetate and triethanolamine which comprises the step of adding ammonium hydroxide and ammonium sulfate thereto until the solution has a pH value of not less than 7.
- ammonium hydroxide being present in an FOREI N PATENTS amount to produce a pH value above 7 and in Number country t the range of from about 7.2 to 9.0, the amount of 546,493 Great England July 1 1943 phenyl mercury acetate in solution being in excess of that normally soluble in the water of 5 OTHER, REFERENCES the solution and the said phenyl mercury acetate being chemically uncombined with the ammonium hydroxide and the ammonium acetate.
Description
Reiuued Aug. 31, 1954 SOLUTIONS OF ORGANIC MERCURY COMPOUNDS Frank J. Sowa, Oranford, N. J.
No Drawing. Original No. 2,411,815, dated No-' vember 26, 1946, Serial No. 489,244, May 31, 1943. Application for reissue April 22, 1953,
Serial No. 350,536
6 Claims.
This invention relates to solutions of organic mercury compounds [and to methods for producing and using such solutions] having in solution more of the organic mercury compound than the amount normally soluble in the same amount of solvent.
It is well known that the aryl and aralkyl mercury hydroxides and salts are relatively insoluble in water. Thus, for example, phenyl mercuric acetate is soluble in water to the extent of about 1 part in 600 parts of water while phenyl mercuric chloride only dissolves to the extent of about 1 part to 20,000 parts of water. All known compounds having the general formula RHgX, wherein R is an aryl, aralkyl, alkaryl, or heterocyclic group, Hg is mercury, and X is an anion, exhibit similar low solubility in water and in many water miscible solvents such as alcohols, glycerols and the like.
Many, if not all, of these organic mercury compounds have high toxicity to bacteria and fungi and have other important uses in industry and medicine. However, because of their relatively low solubility it is not economically practical to ship the product in the form ofa solution and it frequently is difllcult or impossible for the user to produce solutions having the desired concentration of the mercury compound therein. Moreover, in many applications of such solutions it is impossible to use suflicient water or solvent for the mercury compound to obtain the required concentration thereof in the product without undesired dilution or unbalancing of a formula.
I have discovered that the solubility of mercury compounds of the R--Hg--X type, in water and in mixtures of water with solvents such as alcohols, glycerols and the like, can be materially increased provided ammonium hydroxide and a soluble ammonium salt are present in the solution. Some of the ammonium salts may be used for this purpose without adding ammonium hydroxide to the solution, whereas in at least one instance I have found it possible to dissolve a relatively water insoluble organic mercury compound in a solution of ammonium hydroxide alone. However, in most instances it is necessary to use both ammonium hydroxide and an ammonium salt in order to dissolve substantial amounts of the mercury compounds in Matter enclosed in heavy brackets I: appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
aqueous solutions. It is also found in general that the pH value of the solution should be above 7 and preferably in the range of about 7.2 to 9.0.
Solutions of this character may contain up to or more by weight of the aryl, 'aralkyl or alkaryl mercury compound and can be used to apply such compounds to fabrics, leather, paper, sheets or films, or for admixture with paints or latex solutions, and they may be added to dispersions and emulsions of water proofing or fabric treating compositions. They also may be used in carrying out various chemical reactions wherein high concentrations of mercury compounds are desirable or of advantage. The solutions may be caused to penetrate into fibers, or pores in material or they may be applied as a constituent of film forming, coating or impregnating compositions. Furthermore, the concentration of organic mercury compounds in medicinal and industrial formulae may be materially increased by practice in accordance with the present invention.
The principal objects of the present invention are to increase the solubility or concentration of organic mercury compounds in aqueous solutions; to provide new types of mercury containing germicidal compositions and products; to increase the resistance of products to the action of bacteria, fungi, mildew and the like; and to provide novel methods of producing and using solutions of organic mercury compounds having the general formula RHg-X, in which R is an aryl, aralkyl, alkaryl or heterocyclic group, Hg is mercury and X is an anion.
Particular objects of the invention are to provide relatively concentrated solutions of phenyl mercury compounds a d to provide methods for using such solutions the treatment of fabrics, leather and other fibrous, porous or textile products to render them bacteriostatic, fungistatic and mildew resistant.
These and other objects and features of the present invention will appear from the following description thereof in which specific examples are cited to indicate the nature of the invention and typical applications and embodiments thereof, but without intending to limit the scope of the invention thereby.
My investigations indicate that all of the orcases ganic mercury compounds which have the general formula R-Hg-x will dissolve to a greater extent in aqueous solutions containing an ammonium compound than they will in water or the solvent alone. It appears in most instances that the solubility of the mercury compound in aqueous solvents is markedly increased when the solution also contains both an ammonium salt and ammonium hydroxide.
It has been found that in solutions according to the invention the phenyl mercury acetate or other organic mercury compound remains in stable aqueous solution uncombined with ammonium compound and that the use of ammonium compounds other than ammonium hydroxide ea:- erts a buflerin action. In those solutions in which triethanolamine is present, however, a reaction occurs between the organic mercury compound and the triethanolamine to form a reaction product in solution.
Among the ammonium salts I have used to increase the solubility of phenyl mercuric acetate in water, I may mention specifically ammonium sulphate, ammonium carbonate, triamrnonium phosphate, di-ammonium phosphate, ammonium borate, ammonium tetraborate, ammonium citrate, ammonium oxalate, ammonium lactate, 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 ammonium hydroxide is also present in the solution and preferably is added in suflicient quantities to give a final solution having a pH value above 7 and preferably in the range of from about 7.2 to 9.0. Of these salts it has been found that ammonium carbonate, diammonium phosphate,- tri-ammonium phosphate and ammonium borate are capable of use by themselves in increasing the solubility of phenyl mercuric acetate. No ammonium hydroxide need be added when using these salts.
Other compounds having the general formula RHg--X exhibit the same property of increased solubility in water containing ammonium compounds. Thus, phenyl mercuric hydroxide, phenyl mercuric borate, phenyl mercuric phthalate, phenyl mercuric gluconato, benayl mercuric acetate and pyridyl mercuric acetate are soluble to a creator extent in aqueous solutions of ammonium salts containing ammonium hydroxide, than they are in water alone.
Phenyl mercuric hydroxide is soluble in solutions of ammonium acetate or ammonium sulphate alone but this probably is due to a reaction of the hydroxide with the acetate or sulphate to produce some ammonium hydroxide in the solution. I have also discovered that phenyl mercuric aluconate is soluble in ammonium hydroxide alone. Solutions containing '15 grams of phenyl mercuric gluconats in 100 cc. oi water are obtained by simply adding enough lmrmmium hydroxide to keep the pH value around 8. Similarly, 20 grams of phenyl mercuric hydroxide may be dissolved in 100 cc. of water containing 40 grams or ammonimn alucunsto and having a pH value oi approaimatsly O.
Theamountoitbelfltmdappears to influence the mm; or the "our, compound and solutions containing from i to 20% of ammonium sulphate indicate that the maximum solubility of the mercury compound insuchsolutionsisposaiblewhenaboutieb of sulphate is used.
Inprcducingsolutiominaccordoncswithmy invention it is of course desirable to choose ammonium salts which will not react with the mercury compound to produce a more insoluble mercury compound. Thus, when endcavoring to increase the solubility at phenyl mercuric acetate, if ammonium chloride is used the relatively less wiuble phenyl mercuric chloride will be prodnced and may even precipitate from the solution. similarly, if ammonium thiocyanate is used the almost completely insoluble phenyl mercuric thiocyanate will precipitate. while these less soluble compounds are themselves dissolved to some extent in the ammoniacal ammonium salt solution, although almost completely insoluble in water, they are not soluble to the same extent as the 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 practice of my invention and ammonium salts selected which will not react with the mercury compound to produce a less soluble mercury compound.
In choosing an ammonium salt to increase the solubility of [ammonium] compounds of the R,I-IgX type it also appears that the action of ammonium salts of nitrogen containing acids are much less effective 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 salts is limited and relatively poor or negligible results are obtained when using ammonium fluoride, ammonium flue-silicate, ammonium chloride and ammonium llnolate. Nevertheless, the great majority of the ammonium salts appears to increase the solubility of the mercury compounds enormously and even the less active salts mentioned above appear to have some influence on the solubility of the R-Hg-x type of compounds.
In order to indicate typical and preferred solutions using ammonium salts in ammoniacal water solutions, having a pH value above 7 the following examples are cited.
cc. of 5% salt Grams of phenyl mercuric Ammonium lactate 8-12 Ammonium iormate 8-? run acetate Alcoholic solutions and mixtures of water with other water miscible solvents such as triethanol amine also exhibit the same ability to dissolve increased amounts of organic mercury compounds of the R-Hr-X type provided an ammonium compound is present. Thus, for ea- I. will: train: solutions at phenyl mersons acetate in water and methanol mine in accordance with the procem of my [copending] application mrial No. 443,304, tiled May 16, 1942, now Patent 2,623,121, it is sometimes diillcult to produce solutions oi the desired concentration. The addition of ammonium sulphate and ammonium hydroxide to such solutions overcomes this difliculty and not only increases the amount of the mercury compound which may be dissolved but greatly speeds up solution and results in the formation of solutions which are clear and very stable.
Solutions produced in accordance with; the present invention may be applied directly or after dilution with water, to fabrics, leather, paper or the like by spraying the solution thereon or by dipping or immersing material therein and the solution may be applied under pressure to insure the desired penetration of the solution into the pores or fibers of the articles being treated. They also may be added to textile treating baths or finishes such as alkaline solutions of cellulose ethers, suspensions of waxes, resins or other similar materials. The ammoniacal or alkaline nature of solutions embodying my invention renders them particularly suitable for admixture with latex dispersions, and suspension of rubber, colloids, waterproofing or fireproofing agents, or products such as casein paints and aqueous coating and impregnating compositions.
Products thus treated are rendered bacteriostatic, fungistatic, mildew resistant and germicidal by reason of the mercury compound deposited on or in the product or admixed therewith. The amount of the solution used in any particular application will vary considerably but when employed to treat textile fabrics the weight of the mercury compound in the treated material should generally equal about 0.02 to 1.0% and preferably about 0.5% of the weight of the fabric.
While I have suggested numerous compositions and uses for solutions produced in accordance with the present invention it will be understood that many other uses and formulae will suggest themselves to those skilled in the art and be apparent from the foregoing description of the invention. In view thereof it is intended that the particular composition and uses of solutions specifically described above be considered as illustrative only since the scope of my invention is defined by the following 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, ammonium carbonate, tri-ammonium phosphate, diammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetraborate, ammonium citrate, ammonium oxalate, ammonium lactate, ammonium formate, ammonium acetate, and ammonium gluconate, together with sufficient ammonium hydroxide to maintain the pH value of the solution above 7, the amount of the phenyl mercury compound in solution exceeding the amount soluble in the aqueous solvent of the solution] [2. A solution containing phenyl mercury acetate dissolved in an aqueous solvent containing an ammonium salt selected from the group consisting of ammonium sulfate, ammonium carbonate, tri-ammonium phosphate, di-ammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetra-borate, ammonium citrate, ammonium oxalate, ammonium lactate, ammonium formate, ammonium acetate, and ammonium gluconate, together with sufficient ammonium hydroxide to maintain the pH value of the solution above '1, the amount of the phenyl mercury acetate in solution exceeding the 3. An aqueous solution having a pH value not less than 7 and containing a phenyl mercury compound, triethanolamine, ammonium hydrox ide and ammonium sulfate, the amount of the phenyl mercury compound in solution being in excess of that soluble in the water of the solution.
4. An aqueous solution having a pH value not less than 7 and containing phenyl mercury acetate, 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 aqueous solution containing phenyl mercury acetate and triethanolamine which comprises the step of adding ammonium hydroxide and ammonium sulfate thereto until the solution has a pH value of not less than 7.
6. A stable aqueous solution of an organic mercury compound having the formula wherein R is monophenyl, Hg is mercury and X is an anion, the said solution containing from about 1 to 20 parts by weight of an ammonium compound unreacted with the said organic mercury compound to avoid formation of an organic mercury compound having, in the presence of ammonium hydroxide, a lesser solubility in water than the initial organic mercury compound employed in forming the solution and which ammonium compound is selected from the group consisting of ammonium sulfate, ammonium carbonate, tri-ammonium phosphate, di-ammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetra-borate, ammonium citrate, ammonium oxalate, ammonium lactate, ammonium jormate, ammonium acetate and ammonium gluconate, together with sulficient ammonium hydroxide to maintain the pH value of the solution above 7 and in the range of from 7.2 to 9.0, the amount of the organic mercury compound in solution being in excess of the amount normally soluble in the same volume of aqueous solvent of the solution in the absence of ammonium compound.
7. A stable aqueous solution containing phenyl mercury acetate dissolved in an aqueous solvent containing from about 1 to 20 parts by weight of an ammonium compound unreacted with the phenyl mercury acetate to avoid formation of an organic mercury compound having, in the presence of ammonium hydroxide, a lesser solubility in water than phenyl mercury acetate and which ammonium compound is selected from the group consisting of ammonium sulfate, ammonium carbonate, tri-ammonium phosphate, di-ammonium phosphate, mono-ammonium phosphate, ammonium borate, ammonium tetra-borate, ammonum citrate, ammonium oxalate, ammonium lactate, ammonium formate, ammonium acetate and ammonium gluconate together with suflicient ammonium hydroxide to maintain the pH value of the solution above 7 and in the range of from about 7.2 to 9.0, the amount of the organic mercury compound in solution being in excess of the amount normally soluble in the same volume of aqueous solvent of the solution in the absence of ammonium compound.
8. A stable aqueous solution containing phenyl mercury acetate, ammonium hydroxide and 1 to 20 parts by weight of ammonium acetate, the
7 8 ammonium hydroxide being present in an FOREI N PATENTS amount to produce a pH value above 7 and in Number country t the range of from about 7.2 to 9.0, the amount of 546,493 Great Britain July 1 1943 phenyl mercury acetate in solution being in excess of that normally soluble in the water of 5 OTHER, REFERENCES the solution and the said phenyl mercury acetate being chemically uncombined with the ammonium hydroxide and the ammonium acetate.
Pesci: Gazz. Chim. ItaL, vol. 29 (1), page 394 (1899).
Pesci: Gazz. Chim. ItaL, vol. 39, page 148 References Cited in the me of this patent 10 (1909)- or the original patent Ilia/1:133; zm'ggeligigal Dictionary, Felice Le Mon- UNITED STATES PATENTS Chem. Abstracts. vol. 13, p. 1450 (1919).
Number Name Date 2,423,121 Sowa July 1, 1947 15
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USRE23863E true USRE23863E (en) | 1954-08-31 |
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US23863D Expired USRE23863E (en) | Solutions of organic mercury |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3089811A (en) * | 1959-02-24 | 1963-05-14 | Gillette Inhibitor Co | Aryl mercuric fungicidal compositions |
-
0
- US US23863D patent/USRE23863E/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3089811A (en) * | 1959-02-24 | 1963-05-14 | Gillette Inhibitor Co | Aryl mercuric fungicidal compositions |
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