US3816329A - Dispersing a water-immiscible liquid in an aqueous medium - Google Patents

Abstract

A method of dispersing a water-immiscible liquid in an aqueous medium is disclosed. At least one immiscible liquid is combined with a stable aqueous colloidal solution, formed by a controlled hydrolysis and nucleation reaction and comprising insoluble hydrous oxide particles of one or more selected elements, such solutions being exemplified in U.S. Pat. application Ser. No. 8,022, filed Feb. 2, 1970, now U.S. Pat. No. 3,657,003. The combined liquid source and colloidal solution are then subjected to a dispersive force to (1) fractionate the liquid source to form a plurality of immiscible liquid particles, and (2) disperse the liquid particles within the colloidal solution. Where the liquid source is initially fractionated in a suitable manner, the dispersive force then merely disperses the water-immiscible liquid particles.

Description

United States Patent 1191 1111 3,816,329

Kenney et a]. June 11, 1974 l l DISPERSING A WATER-IMMISCIBLE LIQUID IN AN AQUEOUS MEDIUM Primary Examiner-Richard D. Lovering [75] Inventors: John Thomas Kenney, Lawrence Attorney Agent or Flrm J Rqsenstock Township, Mercer County; Frederic Alan Litt, Cranford, both of NJ. [57] ABSTRACT A method of dispersing a water-immiscible liquid in an aqueous medium is disclosed. At least one immiscible liquid is combined with a stable aqueous colloidal so- [73] Assignee: Western Electric Company,

Incorporated, New York, NY.

[22] Filed: May 24, 1972 lutiOn, formed by a controlled hydrolysis and nucleation reaction and comprising insoluble hydrous oxide p 256,550 particles of one or more selected elements, such solutions being exemplified in US. Pat. application Ser. 52 us. c1 252/312, 44/51, 117/1355, 8,022, filed 2, 1970, now US 25 252 3 3,657,003. The combined liquid source and colloidal [5 l] Int. Cl B0lj 13/00 Solution are then subjected to a dispersive force to (1) [58 Field of Search 252/312, 314 fractionate the liquid Source to form a plurality of miscible liquid particles, and (2) disperse the liquid [56] References Cited particles within the colloidal solution. Where the liq- UNITED STATES PATENTS uid source is initially fractionated in a suitable;manl 44 35 l2/l922 Mona 252512 UX ner, the dispersive force then merely disperses the wa- 21755I194 7/1956 Volkmann et al. 252/312 x ter'lmm'sclble l'quld parades 3.657.003 4/1972 Kenney 252/313 R X 6 Claims, 2 Drawing Figures BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a method of dispersing a water-immiscible liquid in an aqueous medium and more particularly, to a method of dispersing waterimmiscible liquid organic compounds including hycrocarbons, silicones, etc.

2. Discussion of the Prior Art Emulsions, i.e., dispersions of a water-immiscible liquid in an aqueous medium, have been used for literally thousands of years. Emulsions are used in cosmetics, foods, polishes, paints, etc. An important application of emulsions is in impregnating paper, fabric, wood, etc., for ultimate use in electrical and heat equipment.

The appearance, glaze and shape-retaining properties of garments may be impaired by washing. A process termed finishing or dressing helps to restore garments after washing. The finishing or dressing processes comprise mechanical treatment and processing by chemicals to improve the glaze, shape-retaining properties, crease resistance, smoothness and drape of the particular material. Additionally, depending on the kind of material and the purpose for which it is to be used, it can be made shrinkproof, water repellant, supple, soft or heavy.

Mechanical finishing treatments may consist in mangling, pressing, rolling, milling, shearing, calendering, raising and/or singing. However, before undergoing these treatments, the material is passed through liquid baths in which various substances (textile auxiliaries) are applied to the fibres. Suspensions in water of starch, starch derivatives, vegetable gums, glues, gelatins, and mucilages improve the shape-retaining properties after the material has been dried and smoothed. Waterresistant synthetic substances such as emulsions or dis persions of silicones are employed to waterproof the material.

The various emulsions employed for the abovementioned applications, of course, comprise waterimmiscible liquids suspended or dispersed in an aqueous medium. In order to get the various immiscible liquids dispersed throughout the aqueous medium, organic surfactants (cationic, non-ionic and anionic) are employed. Eliminating the use of the various organic surfactants is desirable since the immiscible organic liquids are partially soluble in the organic surfactants. In the case of silicones, ordinary surfactants are not effective and special surfactants have to be employed which are expensive. A method whereby organic surfactants can be eliminated in dispersing water-immiscible liquids in an aqueous medium is therefore needed.

Within the past few years, pollution from oil spillage in the oceans of the world has become a major wildlife threat. When such an oil spillage occurs, organic surfactants and detergents have been employed to disperse or break up the oil spillage. A problem encountered, however, is that the surfactants and/or detergents may destroy ocean life. An alternative method of dispersing the oil spillage or hydrocarbon accumulation whereby organic surfactants and detergents are eliminated is therefore greatly needed.

SUMMARY OF THE INVENTION This invention relates to a method of dispersing a water-immiscible liquid in an aqueous medium, and more particularly, to a method of dispersing waterimmiscible liquid organic compounds including hydrocarbons, silicones, etc.

Briefly, the inventive technique involves combining a source of the immiscible liquid with a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of one or more selected elements, the particles having a size within the range of 10A to 10,000A. The hydrolysis reaction includes dissolution of a salt of the selected element in an aqueous medium and maintenance of the pH of the aqueous medium at a point where no flocculate results. The resultant combination or mixture is then subjected to a dispersive force to (1) break up or fractionate the liquid source into a plurality of discrete particles which may be of uniform size and shape, and (2) uniformly disperse the resultant waterimmiscible liquid particles through the colloidal solution. Where the liquid source is initially fractionated in a suitable manner, the dispersive force then merely disperses the water-immiscible liquid particles. The resultant dispersed immiscible liquid particles will not coalesce and/or settle for a relatively long period of time.

DESCRIPTION OF THE DRAWING The present invention will be more readily understood by reference to the following drawing taken in conjunction with the detailed description, wherein:

FIG. 1 is a cross-sectional view of a discrete source ofa water-immiscible liquid combined with an aqueous stable colloidal solution contained in a suitable container; and

FIG. 2 is a cross-sectional view of a plurality of waterimmiscible liquid particles fractionated from the liquid source of FIG. 1 and uniformly dispersed throughout the colloidal solution of FIG. 1 to form a stable dispersed mixture.

DETAILED DESCRIPTION The present invention has been described primarily in terms of forming and dispersing, in a selected aqueous colloidal solution, a plurality of discrete, noncoalescing water-immiscible liquid hydrocarbon and silicone particles. However, it will be understood that such description is exemplary only and is for purposes of exposition and not for purposes of limitation. It will be readily appreciated that the inventive concept described is equally applicable to forming and dispersing in the selected aqueous medium or solution a plurality of discrete, non-coalescing liquid particles of any water insoluble or water-immiscible liquid, provided, of course, that the selected immiscible liquid does not react with the aqueous solution selected.

Referring to FIG. 1, at least one discrete suitable water-insoluble or water-immiscible liquid source is combined with a suitable stable colloidal solution 61, contained in a suitable container 62, to form a mixture. A suitable liquid source 60 is one comprising a liquid which (I) will not react with the suitable stable colloidal solution 61 with which it is destined to be combined, (2) will not dissolve in the colloidal solution 61 to any appreciable extent, typically being soluble to an extent of less than one weight percent, and, of course, (3) is in the liquid state at a suitable temperature, i.e., at a temperature at which the colloidal solution 61 remains in a stable condition, such temperature typically being less than 100 C.

Some typical suitable immiscible liquid sources comprise organic oils, such as fixed oils, essential oils, mineral oils, fuel oils, lubricants (paraffins), silicone oils, creosote, solid organics dissolved in suitable organic solvents, e.g., CCl etc. In this regard, it is again to be pointed out and stressed that any immiscible liquid unreactive with the colloidal solution 61 may be employed and dispersed throughout the solution 61.

The source 60 can be added in any amount ranging from a minimum, which represents a concentration at which the source 60 becomes immiscible or insoluble in the colloidal solution 61, to 74 percent by volume. It is to be noted that the minimum concentration is dependent on the source 60, the colloid solution, the temperature of addition, i.e., all factors which are known by one skilled in the art or are easily ascertained. It is, of course, understood that a suitable container is one which will not react with either the source 60 or the solution 61 at the temperature employed. Some typical suitable containers comprise glass, polytetrafluoroethylene, etc. Although the liquid source 60 has been shown in the form of a layer in FIG. 1, this is for illustrative purposes only and the liquid source may comprise at least one pool," droplet, etc. In this regard, it is, of course, understood that if the selected immiscible liquid has a specific gravity greater than that of the selected colloidal solution 61, then the source 60 will not be floating" atop the colloidal solution 61, but rather the reverse will be true.

A suitable colloidal solution 61 includes at least one aqueous wetting solution revealed in Kenney, US. Pat. Ser. No. 8,022, filed Feb. 2, l970 now US. Pat No. 3,657,003, assigned to the assignee hereof and incorporated by reference herein. The wetting solution is generally described as a stable colloidal solution formed by a controlled hydrolysis and nucleation in an aqueous medium wherein the colloidal-particles 63 (FIG. 1, greatly enlarged for illustrative purposes only) of the colloidal solution 61, (1) have a size within the range of A to 10,000A, and (2) are an insoluble hydrous oxide of one or more selected elements. The hydrolysis reaction includes dissolving a salt of the selected element in the aqueous medium and maintaining the pH of the aqueous medium at a point where no flocculate results. Some suitable elements include Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th and U. Specifically, the wetting solutions include Examples IA' to XXXIll-L, inclusively, revealed in Kenney.

The resultant mixture comprising the liquid source 60 and the colloidal wetting solution 61 is then subjected to dispersionby means of a dispersive force created by .any conventional dispersive device (not shown). Such devices are well known in the art, some typical ones being conventional stirrers (magnetic, mechanical) and vibrators (sonic, mechanical). Referring to FIGS. 1 and 2, the resultant dispersive force breaks up or fractionates the liquid source 60 into a plurality of discrete liquid particles 64 (enlarged for illustrative purposes only). The discrete immiscible liquid particles 64 are uniformly dispersed throughout the colloidal wetting solution 61 and will not coalesce, i.e., fuse or unite together, while under the influence of the dispersive force. By selecting proper dispersion conditions, including the quantum of the dispersive force, the size of the particles 64 can be maintained uniform. The proper dispersion conditions are well known in the art or can be easily ascertained experimentally by one skilled in the art. It is, of course, understood that the water-immiscible liquid source 60 may be combined with colloidal solution 61 prior to initiating the dispersive force or after initiating the dispersive force. It is also, of course, understood that where the source 60 EXAMPLE I A colloidal wetting solution was prepared in a suitable container by dissolving one weight percent SnCl2-2H2O in ml. of deionized water. Two weight percent of SnCl4-5H2O was then dissolved in an resultant solution. Finally, 1.5 weight percent SnCl2'2I-I O was added and dissolved therein to form a yellow colloidal wetting solution. Five weight percent of a commercially obtained, water-immiscible, liquid silicone oil was added to the wetting solution to form a mixture. The resultant mixture was stirred at room temperature with a mechanical stirrer for 5 minutes. A plurality of discrete spherical, non-coalescing silicone oil particles or droplets of uniform size and shape formed and were uniformly dispersed throughout the colloidal solution. There was no coalescence or settling of the resultant dispersion after one week. i

As a measure of stability of the resultant dispersion, the resistance to drop coalescence of the resultant dispersion was compared to that of a dispersion obtained using a commercially available surfactant. The resultant dispersion exhibited a greater resistance resistance to drop coalescence than that derived from the surfactant.

EXAMPLE II EXAMPLE Ill The procedure of Example I wasrepeated except that a commercially obtained heavy paraffin oil was employed as the water-immiscible liquid. The resistance to drop coalescence was good.

EXAMPLE IV The procedure of Example III was repeated except that the wetting solution of Example [I was employed. The results of Example II were obtained.

It is to be understoood that the above-described embodiments are simply illustrative of the principles of the invention. Various modifications and changes may be devised by those skilled in the art which embody the principles of the invention and fall within the spirit and scope thereof.

What is claimed is:

l. A method of dispersing a water-immiscible liquid in an aqueous medium to form a stable aqueous dispersion comprising a plurality of discrete particles of the liquid, which comprises:

a. combining a discrete source of the immiscible liquid with a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of one or more selected elements, said particles having a size within the range of A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium, and (2) maintenance of the pH of said aque ous medium at a point where no flocculate results; and

b. subjecting said combined liquid source to a dispersive force to (l) fractionate said discrete source to form the plurality of discrete, immiscible liquid particles, and (2) disperse the plurality of discrete particles within said colloidal solution.

2. The method as defined in claim 1, wherein said one or more elements is selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, ln, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U and mixtures thereof.

3. A method of dispersing a water immiscible liquid in an aqueous medium to form a stable aqueous dispersion comprising a plurality of discrete particles of the liquid, which comprises:

a. combining a discrete source of immiscible liquid with a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of an element selected from the group consisting of Sn and Fe, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results; and

b. subjecting said combined liquid source to a dispersive force to (l) fractionate said discrete source to form the plurality of discrete, immiscible liquid particles, and (2) disperse the plurality of discrete particles within said colloidal solution.

4. A method of forming a stable aqueous dispersion comprising a plurality of dispersed water-immiscible liquid particles, which comprises:

dispersing the plurality of water-immiscible liquid particles in a stable aqueous colloidal solution,

formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of one or more selected elements, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected elements in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results. 5. The method as defined in claim 4 wherein said one or more elements is selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U and mixtures thereof.

6. A method of forming a stable aqueous dispersion comprising a plurality of dispersed water-immiscible liquid particles, which comprises:

dispersing the plurality of water-immiscible liquid particles in a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction comprising insoluble hydrous oxide particles of an element selected from the group consisting of Sn and Fe, said particles having a size within the range of lOA to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected elements in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.

Q UNITED STATES PATENT OFFICE QERHFEQATE 0F CORRECTION Patent Nov 5,816,529 W Dated June 11, 197A I an T. Kenney and A0 Litt Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the title section, "Dispersing a Water-Immisoible Liquid in an Aqueous Medium" should read -.-Method of Dispersing a Water-Immisoible Liquid in an Aqueous Medium--.

I in the specification, oolumnl, line 10, "hycro" should read hydro Signed and sealed this 19th day of November 1974.

(SEAL) 4 Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM po'mso I uscoMM-Dc 603764 69 LS/GOVERNMENT PRINTING OFFICE: 869- 93 o

Claims (5)

1. 2. The method as defined in claim 1, wherein said one or more elements is selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U and mixtures thereof.
2. 3. A method of dispersing a water immiscible liquid in an aqueous medium to form a stable aqueous dispersion comprising a plurality of discrete particles of the liquid, which comprises: a. combining a discrete source of immiscible liquid with a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of an element selected from the group consisting of Sn and Fe, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results; and b. subjecting said combined liquid source to a dispersive force to (1) fractionate said discrete source to form the plurality of discrete, immiscible liquid particles, and (2) disperse the plurality of discrete particles within said colloidal solution.
3. 4. A method of forming a stable aqueous dispersion comprising a plurality of dispersed water-immiscible liquid particles, which comprises: dispersing the plurality of water-immiscible liquid particles in a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of one or more selected elements, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected elements in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.
4. 5. The method as defined in claim 4 wherein said one or more elements is selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U and mixtures thereof.
5. 6. A method of forming a stable aqueous dispersion comprising a plurality of dispersed water-immiscible liquid particles, which comprises: dispersing the plurality of water-immiscible liquid particles in a stable aqueous colloidal solution, formed by a hydrolysis and nucleation reaction comprising insoluble hydrous oxide particles of an element selected from the group consisting of Sn and Fe, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected elements in an aqueous medium, and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.

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