US2067674A - Germicidal composition and process for preparing the same - Google Patents

Description

Patented Jan. 12, 1937 UNITED STATES PATENT OFFICE GERMICIDAL COMPOSITION AND PROCESS FOR PREPARING THE SAME Harold B. Kimerlin, New York, N. Y.

No Drawing. Application November 25, 1935,

Serial No. 51,482

32 Claims. (Cl. 167-71) tion with a soap, and includes 'correlated.im-,

provements and discoveries whereby the germicidal properties of such a composition are en- 10 hanced.

Germicidal compounds as usually prepared are predicated upon the utilization of phenols, mercury compounds, chlorine products, and their derivatives. These three classes of compounds 15 are, and have been used, for the production of germicidal soaps. The phenols and their derivatives possess the disadvantage that they begin to lose their effectiveness as a germicide when the medium has a pH value of about 10.5. A dis- 20 advantage of the mercury compounds is that they are precipitated in alkaline solutions and, since the organic mercury compounds are usually derivatives of a phenol, they are affected in the same manner as the phenols. Furthermore, it

25 v is well known that the hypochlorites and organic chlorine-containing compounds are not reliable germicides, especially when in combination with soap or other organic matter, owing to the instability of such compounds.

30 Soaps which have been prepared and alleged topossess germicidal action have not been effective, inasmuch as the concentrations of the soap solutions resulting in the ordinary use of soaps, as in the washing of the hands, is about to 35 based upon the weight of the anhydrous soap,

and such solutions retard markedly, the germicidal action of practically all germicides, even though the soap solution functions as a surface tension depressor. The lack of efiectiveness of '40 such soap solutions is considered to be mainly germicidal agent of which is unaffected in an alkaline,medium, or, in other words, by an increase in pH value.

It is an object of the invention to provide a germicidal composition containing mercury and 5 iodine in combination with an organic compound.

Another object of the invention is to provide a germicidal composition having high bactericidal power, low toxicity, high penetration, quick action and being substantially odorless 10 and non-irritating.

A further object of the invention is to provide a germicidal composition which may be readily, eifectively and economically prepared on a com mercial scale and which may be utilized either perse of incompatible combinations.

A still further object of the invention is to provide a germicidal composition containing mercury and iodine in conjunction with a detergent.

A specific object of the invention is the provision of a; germicide containing a double iodide of mercury and hydrogen combined with diethylene glycol monobutyl ether in conjunction with a soap tincture containing said ether and a stabilizer.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the product possessing the features, properties, and the relation of constituents, which are exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

I have observed that the efiectiveness of various double iodides of mercury of the type HgIz.2RI, wherein R represents an alkali metal or hydrogen, as germicides, is largely dependent upon the atomic weight of the element R". The 40 lower the atomic weight, the more effective is the germicidal action. Hence, such compounds containing hydrogen are the most highly effective. However, the double iodide of mercury and hydrogen reverts rather easily in the presence of sodium and potassium compounds to the corresponding double iodides. The mercuric hydrogen iodide compound is quite unstable, corrosive, irritating and toxic, and, further, it is not readily admixed with or inducted. into a soap.

I have found that the double iodides of mercury, especially the double iodide of mercury and hydrogen, combine with various organic compounds under the influence of heat and pressure with the production of organic mercurial compounds or derivatives which have high bactericidal power.

In the practice of the invention a bactericidal composition containing mercury is produced by reacting a double iodide of mercury with a compound belonging to the group consisting of a glycol and a glycol-ether, at a temperature above atmospheric and under pressure; for example,

by heating the reactants in an autoclave.

More particularly, a combination may be effected by reacting a double iodide of mercury and hydrogen with a glycol-ether in the presence of an acid at a temperature in the neighborhood of about 140 C. The temperatures employed whereby reaction is effected may be from about C. to about 150 C., and the heating in an autoclave or other .suitable pressure vessel, may be for a period of from two to five hours. During such heating the pressure under which the reaction is taking place may be from about 5 to 55' lbs. gauge. As double iodides of mercury, utilization may be made of mercuric iodide in combination with iodides of sodium, potassium, lithium and hydrogen, and the organic compound with which the combination or reaction takes place may be, for example, the ethylene, propylene, diethylene and triethylene glycols, and the methyl, ethyl and butyl ethers of the glycols, preferably diethylene glycol monobutyl ether.

The formation of the double iodides of mercury may be accomplished by precipitating mercuric iodide through the interaction of mercuric chloride and sodium iodide, followed by. a conversion of the mercuric iodide so obtained into the desired double iodide by treatment with sodium iodide, potassium iodide, lithium iodide or hydrogen iodide and hydriodic acid. Further, the double iodide of mercury and hydrogen may be produced by treating the double iodides of mercury with sodium, potassium orlithium, with a suitable acid, as hydrochloric, sulfuric and acetic acids. The formation of hydriodic acid in such manner is advantageously effected under the influence of heat and pressure, and when the double iodide of mercury and potassium together withacid and diethylene glycol monobutyl ether are reacted, e. g. in an autoclave. The pressure preferably is brought quickly to about 5 pounds and maintained for 30 minutes. The temperature is then brought to about -140 C. which represents a pressure of from about 25 to 40 lbs. and heating continued for a period of several hours. Furthermore, the mercuric iodide may be produced by reacting mercury and iodine directly. Moreover, the double iodide of mercury and hydrogen may be prepared by dissolving mercuric iodide in the least amount of hydriodic acid (40%), necessary to dissolve completely such iodide.

As an illustrative embodiment of a manner in which the novel organic mercury compounds may be produced, and a germicidal composition containing such a compound prepared, the following examples are presented. The parts are by weight.

Example I tilled water, and adding the solution thus prepared slowly and with constant stirring, and at a temperature of about 50 C. to about 30 parts mercuric iodide. When solution has been effected the volume is raised to 100cc. through the addition of distilled water.

The solution thus obtained may now be acidified by the addition thereto of a small amount of an acid, as hydrochloric, sulfuric or acetic acid, to give a pH value of from 4.0 to 4.5, whereupon the potassium iodide is converted into hydrogen iodide when heated under pressure, which in turn reacts with the mercuric iodide to form a double iodide of mercury and hydrogen, which may be represented by the following probable formula: HgI2.2HI. The acid is added to the double mercury potassium iodide solution at a temperature of about 30 0., and the additions may be made in the following amounts: 21 cc. hydrochloric acid (11%), 18 cc. sulfuric acid (30%), 21 cc. acetic acid (36%).

The mass is thoroughly mixed and to it is then added about 240 cc. of diethylene glycol monobutyl ether. This reaction mass is transferred to a pressure vessel, as an autoclave, the temperature raised to about 130140 C., and heating continued for a period of about four hours. When using hydrochloric and acetic acid, a layering of the solution following reaction, cooling and agitation, is not present, but theuse of sulfuric acid 1 tory vessel, from which the potassium sulfate solution is removed. Following removal of this solution any of' mercurial compound present therein may be extracted therefrom by repeated small washings with diethylene glycol monobutyl ether.

There is thus obtained a liquid composition containing a mercury compound formed by reaction of a double iodide of mercury and hydrogen with diethylene glycol monobutyl ether. A soap tincture is now prepared, preferably utilizing a potassium cocoanut oil soap, by dissolving 500 parts thereof in about 1350 cc. of diethylene glycol monobutyl ether at a temperature of about 70 C. The mass is permitted to stand for about 24 hours at room temperature and is then filtered. To 500 cc. of the solution so obtained there is now added about 60 cc. of a 30% solution of potassium iodide and the mass thoroughly mixed. After bringing the temperature of the mixture to about 40 C. there is added slowly, and with constant stirring, the solution containing the reaction product of the double iodide of mercury and hydrogen with diethylene glycol monobutyl ether, also heated to a temperature of about 40 C. I

Finally, the solution is brought to a pH value of from about 7.0 to 8.0, preferably about 7.0, by adding an alkaline substance thereto, e. g. a 2N. solution of sodium hydroxide. of the solution is raised to 1,000 cubic centimeters by a further addition of the soap tincture. This constitutes the composition of matter having germicidal properties, and may be used, either per se or in conjunction with other compatible substances, for example, a detergent, specifically a soap. Furthermore, the soap tincture may be prepared'by dissolving the soap in a glycol or a glycol-ether, other than diethylene glycol monobutyl ether, or a mixture of a glycol and a glycolether, or in an alcohol.

The volume Example II The organic mercurial compounds may be produced by first preparing a double iodide of potassium, or sodium or of lithium, as set forth in Example I, and the solution thus obtained, but without acidification, reacted with a compound belonging tothe group consisting of a glycol and a glycol-ether, as diethylene glycol monobutyl ether, in the manner described in Example I.

Following the preparation of the mercurial, it may then be incorporated with a soap solution to which a stabilizer, as potassium iodide or sodium iodide, may be added as above described.

The organic mercurial compounds prepared-in accordance with the foregoing procedure may be utilized as effective germicides, either per se or in conjunction with compatible compositions. A highly effective manner for the use of the germicides is through the incorporation thereof with a detergent, especially a soap. Such incorporation may be effected in various manners, as, for example, by a spraying of the germicide composition, i. e. the solution of. the mercurial in admixture with a tincture of soap containing a stabilizing agent, upon the soap in chip, flake or powder condition, or by inducing the germicidal composition into the soap stock following the saltingout operation, or, further, by introducing it into the soap during a milling thereof. The percentage of germicide to be incorporated may vary from 0.05% to 1.5%, preferably'0.1% to 0.2%, calculated as mercuric iodide and based on the total weight of the soap (not anhydrous).

A germicide in liquid form may he produced by admixing about one part of the germicidal composition containing the organic mercurial compound, with from 300 to 400 parts of diluent. The diluent may be a tincture of soap, a soap solution, an alcohol, or water. It is preferred to have the diluting agent warm at the time of. the admixture. v

When the germicide is to be incorporated with the soap, it isdesirable to have present a solvent having a relatively high boiling point and, commensurately, a relatively slow rate of evaporation. Further, there should be no unfavorable physiological action due to the presence of this compound, and it should be compatible with the soap and the organic mercurial constituting the active germicidal compound. The glycol ethers are especially well adapted for this purpose and, more particularly, diethylene glycol monobutyl ether, because of its capability to dissolve relatively large amounts of soap and themercurial.

When preparing a germicide for use in liquid form I prefer,to utilize the alcohols, especially isopropyl alcohol. Furthermore, I have found that employment of the mercurial in conjunction with a tincture of soap markedly increases the germicidal activity. This is believed to be due to the synergistic effect of the soap tincture. The effect is marked not only when the soap tincture is made with a solvent having germicidal power, but also and, as well, with tinctures containing a solvent having no germicidal power. Such soap tinctures are much more active than the aqueous solutions of the soap which contain the same percentage of anhydrous soap. Use of the glycol ethers are more particularly desirable, especially, diethylene glycol monobutyl ether, inasmuch as thereby the emulsifying properties of the soap solutions are increased, as well as thepoduction of a finer dispersion. The production of a fine dispersion is especially desirable in order to promote highly effective germicidal activity;

The high activity-of germicidal compositions prepared in accordance with the description contained herein, is shown by the following test. (This test is the standard F. D. A. procedure described in United States Department of Agriculture circular 198.)

1-200 (calculated as HgIz) l300 (calculated as HgIz) X Example I germicide I 5 min. l-20000 (calculated as H'gIz) l-24000 (calculated as HgIz) 1-30000 (calculated as HgIz) X Dilutions made with distilled water.

Key: X Growth -No growth While it is not definitely known, nevertheless it is believed that the mercury compounds formed by reaction between a double iodide of mercury and a compound belonging to the group consisting of a glycol and a glycol-ether, may

be represented by the probable general formula A.I.Hg'Iz.MI or A.I.HgIz.I .A, in which A represents a glycol or glycol -ether residue, and wherein M indicates an element having a positive valence of one, as sodium, potassium, lithium and hydrogen. Further, the residues A of the second of above given formulae may be simple or mixed. Thus, the organic; mercurial compound formed in accordance with Example I is considered to possess the following probable formula:

HOHzC CHOH H: CH1 6 HA 3H2 A germicidal composition containing an organic mercurial compound prepared as above described is characterized by the following properties: a high bactericidal power against all types of pathogenic organisms; low toxicity; maximum synergistic action in soap solutions; high degree of stability and activity in solutions having a high pH; odorless or nearly so;

non-irritant to tissue; high degree of penetration and exerts a moderate solvent effect on the body oils, perspiration and contaminants of the skin and pores; not susceptible to reversion reactions, and quick action.

Further, in regard to the germicidal activity ,tion

of the organic mercurials described herein, it may be added that such activity is markedly increased when in contact with a soap solution or tincture, even when the content of anhydrous soap is so low that the germicidal or bacteriostatic action is negligible. This is also the case when strong soap solutions are used having a high pH value.

ince certain changes in carrying out the above process, and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.

I claim:

1. A mercury compound obtainable by reaction of a double iodide of mercury and a comcund belonging 'to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric.

2. A mercury compound obtained by reaction of a double iodide of mercury and a compound belonging to the group consisting of a glycol and a glycol-ether, in an acid medium at a temperature and a pressure above atmospheric.

3. A' mercury compound obtained by reaction of a double iodide of mercury'and a glycol-ether at a temperature and a pressure above atmospheric.

4. A mercury compound obtainable by reacof a double iodide of mercury and diethylene glycol monobutyl ether at a temperature and .a pressure above atmospheric.

5. A mercury compound obtained by reaction of a double iodide of mercury and hydrogen, and a compound belonging to the groupconsisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric.

6', A mercury compound obtained by reaction of a double iodide of mercury and hydrogen, and a compound belonging to the group consisting of a glycol and'a glycol-ether, in an acid medium at a temperature and a pressure above atmospheric.

7. A mercury compound obtained by reaction of a double iodide of mercury and hydrogen, and a compound belonging to the group consisting of a glycol and a glycolether, in an acid medium, at a temperature of about 110150 C. and at a pressure of about 5 to 55 lbs.

8. A mercury compound obtainable by reaction of a double iodide of mercury and hydrogen and a glycol-ether at a temperature and a pressure above atmospheric.

9. A mercury compound obtained by reaction of a double iodide of mercury and hydrogen and diethylene glycol monobutyl ether at a temperature and a pressure above atmospheric.

10. A mercury compound obtained by reaction of a double iodide of mercury and hydrogen and diethylene glycol monobutyl ether, in the presence of acetic acid, at a temperature of 130-140 C. and at a pressure of about to 40 lbs.

' 11. A composition adapted for use as a germicide, comprising a detergent and a mercury compound obtainable by reaction of a double iodide of mercury and a compound belonging to the group consisting of a glycol and a glycol-ether 12. A composition adapted for use as a germi.

cide, comprising a detergent and a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and a glycol-ether at a temperature and a pressure above atmospheric.

13. A composition adapted for use as a germicide, comprising a soap and a mercury compound obtained by reaction of a double iodide of mercury and a compound belonging to the group consistingof a glycol and a glycol-ether at a temperature and a pressure above atmospheric.

14. A composition adapted for use as a germicide, comprising a, soap and a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and a glycol-ether at a temperature and a pressure above atmospheric. 15. A composition adapted for use as a germicide, comprising a -soap and a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and diethylene glycol monobutyl ether at a temperature and a pressure above atmospheric.

16. A soap containing a mercury compound obtained by reaction of a double iodide of mercury and a compound belonging to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric, said mercury compound being present in an amount of from 0.05% to 1.5%, calculated as mercuric iodide and based on the total Weight of the soap.

17. A soap containing a mercury compound obtained by reaction of a double iodide of mercury and diethylene glycol monobutyl ether at a temperature and a pressure above atmospheric, said mercury compound being present in an amount of from 0.1% to 0.2%, calculated as mercuric iodide and based on the total weight of the soap.

18. A liquid containing a mercury compound obtained by reaction of a double iodide of mercury and a compound belonging to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric, and a solution of soap. l

19. A liquid containing a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and a compound belonging to the group consisting of a glycol and a glycolether at a temperature and a pressure above atmospheric, and a solution of soap.

20. A liquid containing a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and a compound belonging to the group consisting of a glycol and a glycolether at a temperature and a pressure above atmospheric, and a solution of soap containing a compound belonging to the group consisting of a glycol and a glycol-ether.

21. A liquid containing a mercury compound containing diethylene glycol monobutyl ether and potassium iodide. v

23. A liquid containing a mercury compound obtained by reaction of a double iodide of mercury and hydrogen and a compound belonging to the group consisting of a glycol and a glycolether at a temperature and a pressure above atmospheric, and a solution of potassium soap containing diethylene glycol monobutylether and potassium iodide, and having a pH value. of about 7.0 to 8.0.

24. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury with a compound belonging to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric.

25. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury with diethylene glycol monobutyl ether at a temperature and a pressure, above atmospheric.

26. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury and hydrogen with a glycol ether at a temperature and a pressure above atmospheric.

27. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury and hydrogen with diethylene glycol monobutyl ether, in an acid medium at a temperature of 130-140 C. and a pressure of from about 25 to 40 lbs.

28. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury with a compound belonging to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric, and admixing the compound thus obtained with a soap solution containing a compound belonging to the group consisting of a, glycol and a glycol-ether.

29. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury and hydrogen with a glycol-ether in an acid medium at a temperature and a pressure above atmospheric, and admixing the compound thus obtained with a potassium soap tincture containing a glycolether.

30. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury and hydrogen with a glycol-ether in an acid medium at a temperature and a pressure above atmospheric, and admixing the compound thus obtained with a potassium soap tincture containing diethylene glycol monobutyl ether and potassium iodide.

31. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury with a compound belonging to the group consisting of a glycol and a glycol-ether at a temperature and a pressure above atmospheric, admixing the compound thus obtained with a soap tincture, and finally adding an alkaline substance to give a pH value of about 7.0 to 8.0

32. A process for the preparation of a germicide containing mercury, which comprises combining a double iodide of mercury and hydrogen with a glycol-ether in an acid medium at a temperature and a pressure above atmospheric, admixing the compound thus obtained with a potassium soap tincture containing diethylene glycol monobutyl ether and potassium iodide, and finally adding an alkaline substance to give a pH value of about 7.0.

HAROLD B. KIMERLIN.