US3367877A - Detergent-hydriodic acid compositions - Google Patents

Description

United States Patent 3,367,877 DETERGENT-HYDRIUDIC ACll) COMPOSITIONS Abraham tCantor, Elkins Park, Pa, and William Schmidt,

Jamaica, N.Y., assigncrs to West Laboratories, Inc., Long island City, N.Y., a corporation of New York No Drawing. Filed Feb. 3, 1965, Ser. No. 430,203 4 Claims. (Cl. 252-106) ABSTRACT OF THE DESCLGSURE Compositions consisting of hydriodic acid containing about 0.5 to 2.0 parts of water per part by weight of H1, and a nonionic detergent, in which the weight percentages of detergent and HI vary from a low acid composition having about 1% HI and 97.8% detergent to a compatible high acid composition having not more than 40% HI and not less than detergent, said detergent being selected from the group consisting of nonionic surface active agents and mixtures of nonionic surface active agents which have the capacity to dissolve and complex with elemental iodine. These compositions exhibit markedly reduced corrosiveness facilitating safer storage, shipping and handling of H1. They provide useful concentrates from which to prepare germicidal detergent-iodine compositions by simple room temperature addition of elemental iodine.

compositions as starting components.

The value of hydriodic acid, HI, in germicidal detergentiodine compositions has been disclosed in United States .Patent No. 3,028,299 issued Apr. 3, 1962 jointly to Murray W. Winicov and William Schmidt, the present applicant. In said patent it is disclosed that formulation of detergent-iodine compositions to contain HI or alkali metal iodide providing a source of (1) in excess of about 0.25 part per part of iodine acts to stabilize the iodine and prevent the loss of available iodine on standing that is normally experienced with detergent-iodine composition. The patent also points to the separate advantage of HI, when combined in an aqueous iodineiodide solution, in that it permits rapid cold formulation of detergent-iodine compositions, whereas the direct combining of detergent and elemental iodine ordinarily requires extended heating.

Unfortunately, commercial aqueous HI (normally about 46% HI) and aqueous HI-iodine solutions are quite corrosive, presenting problems both in storage and shipment and in handling during formulating operations, requiring the use of special glass lined or other corrosion resistant equipment. Furthermore, the commercial grade (46%) aqueous HI is available from few sources in the United States, and is virtually unobtained in other countries, so that the problem of corrosiveness in storage and shipping constitutes a deterrent to more extensive use Of HI in detergent-iodine compositions.

It has now been discovered, in accordance with the present invention, that the advantages of HI in detergentiodine compositions can be fully utilized, while substan- 3,367,877 Patented Feb. 6, 1968 tially reducing the problem of corrosiveness, by combining aqueous hydriodic acid (suitably the commercial acid of about 46% concentration) with compatible nonionic detergents which are known to be iodine carriers. The proportions of hydriodic acid to detergent can be varied to provide, per parts by weight, about 1 to 40 (and preferably 3 to 30) parts of HI and 97.8 to 10 (and pref erably 93.3 to 33) parts of detergent, the balance to 100 parts being water introduced with the HI in the commercial or technical grade hydriodic acid. With the normal variation in concentration of technical aqueous hydriodic acid, the proportion of water to HI in the composition Will fall within the range of about 0.5 to 2.0 parts water per part by weight of HI.

The ability of nonionic detergent to reduce the corrosiveness of HI is surprising in view of the known practices of combining acid with detergent to enhance metal cleaning and etching actions; and it is thought that the corrosion inhibiting may be due to a type of binding or complexing of HI with the nonionic detergent. This theory would appear to be supported by the fact that the new nonionic detergent-HI compositions will readily dissolve elemental iodine by simple mixing at room temperature, whereas iodine can be dissolved in the detergent alone only by extended mixing, preferably at substantially elevated temperature. Solutions of iodide, diluted with water, dissolve iodine with difficulty, frequently taking as much as hours or days to dissolve the same amount of iodine which would have dissolved readily in a more concentrated iodide solution. The same solutions of iodide, diluted with nonionic detergents as herein described dissolve iodine readily.

The new compositions are therefore uniquely adapted for'use as commercial concentrates or starting components in the formulation of consumer products of the germicidal detergent-iodine type. Just as these consumer products vary widely in composition, depending on the germicidal job to be done (the formulations differing, for example in general purpose germicidal cleaners, dairy equipment cleaners, instrument cleaners for hospital use, germicidal rinses for commercial kitchen use, surgical scrub compositions, animal shampoos, and the like) so the formulation of the new detergent-HI concentrates can be widely varied to facilitate their use in the formulating of such consumer products. Suitably these concentrates can be utilized:

(a) By adding elemental iodine.

(b) By adding elemental iodine and then diluting with Water.

(c) By adding elemental iodine and then adding water plus an acid such as phosphoric acid, hydroxyacetic acid or mixtures thereof.

(d) by following any of (a), (b), or (c), above plus the addition of more (of the same or different) detergent.

All of these formulating procedures can be carried out at room temperature and with conventional mixing equipment (except as the added acid in procedure (c) may require special handling), thus for the first time making it commercially practical for the small formulator of environmental sanitation products to formulate detergentiodine consumer products starting with elemental iodine as one of the components.

The new corn-positions provide a further economic advantage, since formulators can purchase iodine at the World price and add it themselves, thereby avoiding the duties and handling charges on the most expensive constituent of ordinary concentrates. Since most detergents and HI are currently available in the United States at a lower price than in other countries, the new compositions can also be shipped economically to other countries.

Any nonionic detergent selected from the group consisting of nonionic surface active agents and mixtures of nonionic surface active agents which have the capacity to dissolve and complex with elemental iodine can be blended with hydriodic acid to form one or more new concentrates and formulating components in accordance with the present invention. From the standpoint of cost, availability and general usefulness, the following types of nonionic iodine carriers are of particular interest:

(a) Nonionic iodine carriers of the type disclosed in United States Patent No. 2,931,777 which are generally embraced by the formula:

wherein R represents the residue of a water insoluble organic compound containing at least 6 carbon atoms, and have an active hydrogen and x represents an integer within the range of 6 to about 100; and

(b) Nonionic iodine carriers of the type disclosed in US. Patent No. 2,759,869 and generally embraced by the formula:

where y equals at least 15 and (C H O) equals 20 to 90% of the total weight of said compound.

Within the preferred range of proportions, i.e. in concentrates containing up to about 30% HI most of the detergents embraced by the foregoing formulas form stable concentrates. As the proportion of HI approaches or exceeds 30%, with the amount of water introduced with the HI (as technical aqueous hydriodic acid of about 46% concentration), care must be taken to provide an appropriate hydrophobic-hydrophilic balance in the detergent. If a selected detergent will not form a stable solution with an amount of aqueous hydriodic acid to provide 30 to 40% by weight of HI, then a similar detergent having a longer ethylene oxide chain, and increased hydrophilic properties, should be employed.

The following examples will provide a fuller understanding of the various adaptations and embodiments of the present invention, but it is to be understood that these examples are given by way of illustration and not of limitation.

In the examples the iodine carriers identified by code or trade name have the following chemical compositions:

Pluronic L-62=25 to 30 mols of polyoxypropylene condensed with 8.5 to 10.2 mols of ethylene oxide.

Pluronic P65==25 to 30 mols of polyoxypropylene condensed with 33 to 40 mols of ethylene oxide.

Igepal CO-710=nonyl phenol condensed with -11 mols of ethylene oxide.

Igepal CO-730=nonyl phenol condensed with about mols of ethylene oxide.

EXAMPLE I Two sets of detergent aqueous hydriodic acid concentrates were prepared using in one set Pluronic L-62 (and Pluronic P-65 where indicated) and in the other Igepal CO-710 as the detergent component; and a similar set of control concentrates was prepared containing only water and HI. The compositions and properties of these concentrates are shown in the following tabulations:

At 40% HI, 50% water and 10% detergent Pluronic L-62 does not form a stable concentrate.

Concentrates 13 Legend 1 2 3 4 5 6 Percent Igepal CO-710 97. 8 93. 3 77.8 55.0 33.0 10.0 Percent III 1.0 3. 0 10.0 20. 0 30.0 40. 0 Percent H O i. 1.2 3.7 12.2 25. 0 37.0 50. 0 Viscosity at 50 C. (cps.) 220 370 70 5 Controls C Legend 1 2 3 4 5 6 Percent Water 99. 0 97.0 00.0 80.0 70.0 60.0 Percent HI 1. 0 3. 0 10. 0 20. 0 30. 0 40. 0 Viscosity at 50 C. (cps) 2 2 2 2 2 2 Concentrates A, B, and C were subjected to comparative tests using metal samples measuring approximately 1" x 2" x /e" and warranted to meet A.S.T.M. D-1384 requirements (for antifreeze corrosion testing).

In conducting the tests, the metal strips were scrubbed with a wire brush in detergent solution, rinsed with water and then acetone, dried and weighed to the nearest milligram. The strips were then immersed in 50 ml. portions of the test solutions for a period of 24 hours at 50 C. The strips were then removed, flushed with water, rinsed in acetone, dried and weighed. All tests were run in duplicate. The results in the following tabulation shows the weight loss with concentrates A and B and controls C on five test metals:

WEIGHT LOSS (MG.)

Steel Alun Cast Iron Solder ri- Copper num Composition:

The test results tabulated above clearly indicate that in most instances, particularly at hydriodic acid concentrations of 1 to 30%, the compositions containing detergent (the A and B samples) caused much less corrosion (weight loss) under the test conditions than the samples C which contained no detergent.

In part, the corrosion inhibiting effect may be attributable to the viscosity increasing effect of the detergent, but separate tests have shown that viscosity increase alone can account for only a portion of the corrosion reduction. By way of illustration, a solution was prepared containing 10% HI, 88.15% water, and thickened to a viscosity of 280 cps. (at 50 C.) by the presence of 1.85% of carboxy polymethylene (Carbopol 941). In separate corrosion tests on aluminum according to the above described procedure, this solution gave results of 113 mg. and 111 mg. weight loss. These results are considerably greater than the weight loss values of 44 and 46 mg. for the comparable samples A-3 and B-3, as shown in the foregoing table.

In other comparative tests, a solution containing 20% HI, 78.1% water and 1.9% carboxy polymethylene having a viscosity of 320 cps. (at 50 C.) showed a weight loss on aluminum of 260 and 210 mg. Here again the results are significantly different from the weight loss of 5 112 and 116 for the comparable samples A-4 and B-4 in the foregoing tabulation.

At the higher HI concentrations of 30% and 40%, the viscosities of the detergent-HI solutions become so low that very little corrosion reduction can be attributed to a viscosity effect, and in the foregoing tabulations, the lower values for A-5 and B-5 compared with C-5, and for A6 and B6 compared with C-6, reflect primarily the detergent effect on corrosion reduction.

In summary, the corrosion reduction effected by the detergent in the new compositions is generally of the order of 50% or higher, and can be as high as 80 to 90% on some metals, particularly at the lower HI concentrations.

The following additional examples show the preparation of typical detergent-HI concentrates suitable for commercial distribution and the novel methods by which formulators may convert the same to different types of consumer products.

EXAMPLE II 887 grams of Igepal CO-730 (paste), warmed to 35 C., was placed in a 1500 ml. beaker, equipped with a laboratory stirrer. 113 grams'of (46% active) hydriodic acid was added, with stirring. After addition was complete, mixing was continued for an additional 10 minutes. The finished composition was analyzed and found to contain 5.0% hydriodic acid.

EXAMPLE III To 695 grams of Pluronic P-65 (paste), warmed to 40 C., was added 305 grams of (46% active) hydriodic acid, with stirring. After completing the addition, the batch was stirred for an additional l rninutes. The finished composition was analyzed and found to contain 14.0% hydriodic acid.

EXAMPLE IV To 804 grams of Igepal CO-710 at 23 C., was added, with stirring, 196 grams of (46% active) hydriodic acid. After completing addition, the batch was stirred for an additional 10 minutes. The finished composition was analyzed and found to contain 9.0% hydriodic acid.

EXAMPLE V To 565 grams of Pluronic L62 at 23 C., was added, with stirring, 435 grams of (46% active) hydriodic acid. After completing the addition, the batch was stirred for an additional minutes. The finished composition was analyzed and found to contain 20% hydriodic acid.

EXAMPLE VI To 870 grams of (46% active) hydriodic acid, at 23 C., was added, with stirring, 130 grams of Pluronic P-65 (paste-warmed to 40 C.). After completing the addition, the batch was stirred for an additional 5 minutes. The finished composition was analyzed and found to contain 40% hydriodic acid.

Commercial hydriodic acid frequently contains traces of elemental iodine which is formed primarily as a result of the action of atmospheric oxygen on the highly acidic iodide solution. It is common practice to add a very small amount of hypophosphorous acid (H PO to hydriodic acid solutions to prevent this formation of free iodine. It has been found that hypophosphorous acid has a similar effect in preventing the formation of elemental iodine in the new detergent HI compositions, when included in such compositions at the rate of about 0.05 to 0.5% and preferably about 0.1 to 0.25% based on the weight of said compositions. It should be noted, however, that neither the small amount of iodine which may form in a detergent-HI composition, nor the small amount of hypophosphorous acid which may be employed to inhibit its formation have any appreciable effect on subsequent use of the detergent-HI compositions in the formulation of detergent-iodine products.

The following examples are illustrative of detergent-HI compositions containing hypophosphorous acid:

EXAMPLE VII To 695 grams of Pluronic P-65 (paste), warmed to 40 C., was added 305 gm. of (40% active) hydriodic acid, with stirring. After completing the addition, the batch was stirred for an additional 10 minutes during which time 2 grams of 50% aqueous HQPOZ was added providing 0.1% H PO in the product. The finished composition was analyzed and found to contain 12.2% HI.

EXAMPLE VIII To 695 grams of Pluronic P-65 (paste), warmed to 40 C., was added 305 gm. of (57% active) hydriodic acid, with stirring. After completing the addition, the batch was stirred for an additional 10 minutes during which time 5 gm. of 50% aqueous H PO was added providing 0.25% H PO in the product. The finished composition was analyzed and found to contain 17.4% HI.

The following examples illustrate the novel formulating procedure or method which can be utilized in preparing detergentdodine concentrates and consumer products utilizing the new detergent-HI compositions as starting components:

EXAMPLE TX 127 grams of the composition prepared. in Example II was placed in a 250 ml. beaker, equipped with a laboratory stirrer. 18.7 grams of elemental iodine was added, with stirring, at an initial temperature of 21 C. Mixing was continued for an additional 10 minutes at which time solution of the iodine was complete. The temperature of the batch was noted to increase from 21 C. to 28 C. after addition of the iodine.

After dissolving the iodine, the mixture was added to a 1500 ml. beaker containing 854 grams of water and stirred until batch was homogenous. The finished product was found to contain 1.88% available iodine and 2.54% total iodine (by Volhard).

EXAMPLE X 46.8 grams of the composition prepared in Example III was placed in a 250 ml. beaker equipped with a laboratory stirrer. 18.7 grams of elemental iodine and 116.5 grams of Igepal CO-730 (paste-warmed to 30 C.) were added, with stirring. After solution of iodine was complete (approximately 10 minutes mixing time is required) the mixture was added, with stirring, to a 1500 ml. beaker containing 818 grams of a 19.5% phosphoric acid solution. After completing the addition, stirring was continued for an additional 10 minutes.

The finished product was found to contain 1.89% available iodine, 2.55% total iodine (by Volhard) and 16.0% phosphoric acid.

EXAMPLE XI To 796 grams of the composition prepared in Example IV at 23 C. was added 204 grams of elemental iodine, with stirring. After completing the addition, the batch was stirred for an additional 15 minutes to complete solution of the iodine.

The finished product was found to contain 20.9% available iodine and 27.8% total iodine (by Volhard).

EXAMPLE XII To 33.5 grams of the composition prepared in Example V at 23 C. was added, with stirring, 18.7 grams of elemental iodine and 130 grams of Igepal CO-730 (pastewarmed to 30 C.). After solution of the iodine was complete (approximately 10 minutes mixing time is required) the mixture was added, with stirring, to a 1500 ml. beaker containing 817.8 grams of water. After completing the addition, stirring was continued for an additional 10 minutes. The finished product was found to contain 7 1.88% available iodine and 2.54% total iodine (by Volhard).

EXAMPLE XIII To 17.0 grams of the composition prepared in Example VI at 23 C. was added, with stirring, 18.7 grams of elemental iodine, 75 grams of Igepal CO-71O and 75 grams of Igepal CO730 (paste-warmed to 30 C.). After completing the additions, the batch was stirred for an additional 10 minutes to complete solution of the iodine.

The above mixture was then added, with stirring, to a 1500 ml. beaker containing 814.3 grams of a 19.6% phosphoric acid solution. After completing the addition, stirring was continued for an additional 10 minutes.

The finished product was found to contain 1.89% available iodine, 2.55% total iodine (by Volhard) and 16.0% phosphoric acid.

The products of Examples IX and XII are typical detergent-iodine consumer products for general environmental sanitation purposes. The products of Examples X and XIII are typical high acid detergent-iodine consumer products suitable for use in the dairy industry and other areas characterized by high concentrations of organic soil. The product of Example XI can be used as an intermediate concentrate to be combined with added detergent and/ or acid and suitably diluted with water to form consumer products. While the products of Examples IX to XIII can be prepared by other formulating procedures, and no novelty is asserted in these products, per se, it is considered that the new techniques using the novel detergent-HI compositions as starting components constitute an important advancement of the detergentiodine art.

Various changes and modifications in the new compositions and methods herein described may occur to those skilled in the art, and to the extent that such changes and modifications are embraced by the appended claims, it is to be understood that they constitute part of the present invention.

We claim:

1. A detergent-aqueous hydriodic acid composition consisting essentially of water, HI, and a nonionic detergent selected from the group consisting of nonionic surface active agents and mixtures of nonionic surface active agents which have the capacity to dissolve and complex with elemental iodine, water being present in the amount of about 0.5 to 2.0 parts per part by weight of HI, the weight percentages of detergent and HI in said compositions varying from a low acid composition having about 1% HI and 97.8% detergent to a compatible high acid composition having not more than HI and not less than 10% detergent, and all of the iodine present in said compositions being in the iodide form.

2. A detergent aqueous hydriodic acid composition as defined in claim 1, wherein the detergent and HI are present in the preferred range defined by a low acid composition having about 3% HI and 93.3% detergent and a compatible high acid composition having not more than 30% HI and not less than 33% detergent.

3. A detergent aqueous hydriodic acid composition as defined in claim 1, containing as a stabilizer for the HI an amount of H PO equivalent to about 0.05 to 0.5% based on the weight of said composition.

4. A detergent aqueous hydriodic acid composition as defined in claim 1, containing as a stabilizer for the HI an amount of HgPO equivalent to about 0.1 to 0.25% based on the weight of said composition.

References Cited UNITED STATES PATENTS 3,159,096 9/1964 Schmidt et al. 252-l06 3,028,299 4/1962 Winicov et al. 167-l7 3,220,951 11/1965 Cantor et al. 252-106 LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN SCHNEIDER, Assistant Examiner.