US 3055834 A
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3,055,834 ANHYDROUS ANItlN-ACIIVE DETERGENTS IV THE FORM OF AEROSOLS Roger Charle, Soisy-sons-Montmorency, and Jean Pomot,
Nenilly-sur-Seine, France, assignors to Societe Anonyrne dite: Societe Monsavon-lOreal, Paris, France, a cnrporation of France No Drawing. Filed June 2, 1958, Ser. No. 738,954 Claims priority, application France Apr. 14, 1958 3 Claims. (Cl. 252-90) It has already been suggested that a heterogeneous mixture comprising a liquified propellant (consisting usually of a group of substances commercially known as Freons) and detergents in the form of true aqueous solutions may be projected in aerosol form.
In the suggested embodiments the projection of the mixture under the pressure of the gaseous propellant produces a foam consisting of a gaseous emulsion of the solvent in the aqueous surface-active solution of the detergent.
In the processes heretofore known, contact between water and a propellant, such as one of the products com mercially known as Freons produces a more or less rapid hydrolysis of the halogenated hydrocarbon with formation of acids such as hydrochloric or hydrofluoric acid, which tend to attack the metallic parts of the casing. For this reason the heretofore proposed embodiments in which the detergent is carried in an aqueous medium have not given complete satisfaction.
In order to avoid such corrosion, we have discovered that it is advantageous to obtain true solutions of anhydrous anion-active detergents in gases which have been liquefied under pressure, thus avoiding the direct projection of the foam (which is undesirable in certain cases) and eliminating any risk of corroding the metallic containers holding the product.
An additional subsidiary advantage resides in the gain in useful weight obtained, because the transportation of an undesirable quantity of water is avoided.
Moreover, most of the anion-active detergents commonly heretofore employed (such as alkaline soaps, alkyl sulfates of alkaline metals, and the alkyl aryl sulfonates of alkaline metals) cannot be dissolved in the liquefied gases ordinarily used as propellants (which are usually of the type commercially known as Freons; methyl, ethyl or vinyl chlorides; butane, etc.), because of their pronounced insolubility in these mediums.
However, it is known that the ammonium salts of these same anion-active substances are slightly soluble in the gaseous propellants mentioned at an ordinary temperature, although this solubility is completely insuflicient to obtain solutions which may be commercially utilized for the production of aerosols.
The object of the present invention is, first, to provide a new article of manufacture which comprises true solutions of certain anhydrous anion-active detergents in gases which have been liquefied under pressure. These solutions are intended to permit these detergents to be dispensed in the form of aerosols and are true solutions characterized by the fact that they are obtained by dissolving, in a liquefied propellant gas or mixture of gases selected from the following group:
1) Fluorinated derivatives of ethane and methane of the type commercially known as Freons.
(2) Light hydrocarbons such as butane or pentane. Substances having the following general formula:
in which R may be either (1) A saturated or unsaturated straight chain comprising from 8-22 carbon atoms and corresponding to fatty alcohols;
(2) A branched chain comprising between 10 and 20 carbon atoms and corresponding to alcohols obtained by OXO synthesis;
(3) An alkyl phenyl radical such as octylphenyl or nonylphenyl.
According to the present invention it is preferable that the number n of Formula I fall between 1 and 6. These values permit products to be obtained which have good detergent qualities, and a good solubility in the liquefied propellant gases. The preferred value of it between these two extremes is a function of the nature of R in the general formula since, in general, a low value of n is conducive to starting the formation of the foam, to its abund; ance, and the detergent effect of the product obtained, whereas a high value of It improves the solubility of the sulfated product in the propellant.
However, it is possible to depart somewhat from these specific values Without thereby departing from the spirit of the invention.
The desired solubility may be obtained by using a mixtllre of slightly soluble products comprising, for example, one or two molecules of ethylene oxide in their molecules, with variable proportions of more soluble products comprising 5 or 6 molecules of ethylene oxide in their molecules.
To illustrate this process, the case of a product having the following formula may be cited by way of example:
A solution of such a product II in the product commercially known as Freon 11, comprising 33% by Weight of the product of Formula II, and 67% by Weight of Freon 11, remain clear at 18 C., but begins to pre cipitate at 15 C., and is completely pasty at 10 C.
It has been established, however, that a solution in the product commercially known as Freon 11 containing 27% by weight of the product of Formula II (above) and 6% by weight of the following formula:
R-(O-CH CH OSO NH (III) in which R represents the same radical as Formula II, re-' mains liquid and limpid at 10 C.
It has moreover been established that a mixed solution of these same products comprising 20% by weight of the product of Formula II and 13% by weight of the product of Formula III in solution in the product commercially known as Freon 11 remains limpid at 5 C.
A further object of the invention is to provide a method for directly preparing the anhydrous detergent solutions hereinbefore defined in the midst of the liquefied propellant gases.
It is known that products according to the general formay be obtained by reacting the sulfamic acid with oxyethylenated alcohols or alkylphenols, the reaction taking place at a temperature of about 125 to 135 C. by simple agitation of the solid sulfamic acid in the oxyethylene alcohol or in the oxyethylenated alkylphenol, the reaction taking place according to the following formula:
It might at first be thought that the reaction product could be dissolved in the product known commercially as Freon 11 neutralizing the solution, by means of an ammonia gas, for example, until a pH of 7 is reached. But this mode of operation has proven impracticable, since by reason of the thickening of the reaction mass the difiiculty of agitating and homogenizing it render it practically impossible to complete the reaction according to Formula IV so that a substantial proportion of the alcohol or oxyethylenated alkylphenol do not take part in the reaction.
By reason of this incomplete reaction a large proportion of very finely divided insoluble materials are found in the solution, and these are difficult to separate by filtration.
The object of the present invention is to prepare true solutions of anhydrous anion-active detergents in gases which have been liquefied under pressure, the process being characterized by the fact that the sulfamic acid is reacted with oxyethylenated alcohol or oxyethylenated alkylphenol in a solvent, this solvent having the following characteristics:
(a) It comprises at least one compound in the following categories:
(1) The chlorofiuorinated derivatives of ethane and methane of the type commercially known as Freons; (2) Light hydrocarbons such as butane and pentane.
(b) This solvent preferably comprises those boiling at a temperature sufficiently high that the reaction temperature, which is situated at about 120 C., may be attained without developing too high a pressure.
It is a good solvent for the detergent obtained. The process is carried out in an autoclave which is resistant to corrosion while agitating the reacting compositions at a temperature between 110 C. and 130 C. and under a pressure equal to the vapor tension of the solvent or mixture of solvents at that temperature.
In accordance with the invention it is desirable to add to the reacting mass a certain quantity of urea, in order to avoid the coloration which results from the traces of sulfuric acid contained in the sulfamic acid, and to facilitate the filtration of the solution at the end of the operation. The quantity of urea used may run between 1 and by weight of the total of the alcohol and sulfamic acids used.
It is also preferable to select as a solvent the constituant of the propellant mixture having the highest boiling point, so as to operate at the lowest possible pressure. Thus, for example, one may operate under a pressure of 6 to 9 kg./crn. in the case of trichlorotrifluoroethane (a product known commercially as Freon 113), and under a pressure of from 12 to 16 kg./cm. in the case of trichloromonofiuoromethane (a product known commercially as Freon 11).
The proportion of the solvent to the reaction mixture is dependent on the concentration of detergent which it is desired to obtain. It is always desirable to utilize to the utmost the capacity of the autoclave and to employ the minimum quantity of solvent required to obtain at the end of the reaction a solution sufliciently fluid when cold. For example, from 150 to 350 grams of solvent may be used per 100 grams of oxyethylenated alcohol or oxyethylenated alkylphenol, according to the degree of oxyethylenation. The weight of solvent required is the less as the degree of oxyethylenation is greater, since it is the degree of oxyethylenation which determines the solubility of the detergent in the solvent.
When the reaction has been completed, the mixture is cooled below the boiling point of the solvent at atmospheric pressure so that the overpressure in the autoclave is zero.
The residual acidity is neutralized either by introducing a measured quantity of gaseous ammonia into the autoclave or by adding a specific weight of an anhydrous amine, such as mono-, di-, or triethanolamine, so as to adjust the pH to a value of at least 7 and not more than 8.
The solution is then discharged under pressure through a filter which removes those solid impurities which could block the expansion valves of the dispensing containers.
The solution obtained in this manner may be introduced directly into the dispensing containers. The concentration and vapor pressure may be brought to the desired value by adding under pressure certain products known commercially as light Freons such as Freon 12" or a mixture of light Freons and other liquefied gases, such as butane.
In order that the object of the invention may be better understood, several specific methods of carrying out the invention will now be described, purely by way of illustration, without limiting the scope of the invention to the details thereof.
Example 1 Into an autoclave made of stainless or enamelled steel, provided with an agitator and tested under a pressure of 30 kg./cm. the following ingredients are introduced:
ular weight being 478 5O Sulfamic acid 78 Urea 10 Product commercially known as Freon 11 550 The autoclave is rapidly heated to C. while stirring. This temperature is then held for 30 minutes. The inner pressure is of the order of 13 kg./cm. The autoclave is then cooled at 20 C. without stopping the stirring. Ammonia gas is then introduced to obtain a pH between 7 and 8.
The product is then filtered under pressure to separate out the urea and impurities.
The filtrate serves as the mother liquor A.
Into a pressure resistant container provided with an expansion valve the following ingredients are introduced:
Solution A, obtained as above 87.5
Product commedcially known as Freon 11.. 10 Product commercially known as Freon,
A true solution is thus obtained which contains 25% by weight of anhydrous detergent. This solution may be perfumed as desired to provide a shampoo which may be sprayed onto the hair.
Example 11 The following ingredients are introduced into the autoclave described in connection with Example I:
The autoclave is brought to a temperature of C. while stirring, and kept at this temperature for about thirty minutes, with the pressure at about 13 kg./cm.
The autoclave is then cooled to 20 C. and the contents neutralized with a current of ammonia gas until a pH of 7.5 is obtained. Thecontents are then filtered under pressure to produce product B.
Into a pressure-resistant container provided with an expansion valve the following ingredients are introduced:
Gr. Product B 64.5 Product commercially known as Freon 11 10.5 Product commercially known as Freon 12 25 The product thus prepared in the container and sprayed on the hair results in the application of a detergent in a finely divided form which constitutes an excellent shampoo when water is added.
Example 111 Into an autoclave such as used to carry out the process of Example I, the following ingredients are introduced:
Octylphenol oxyethylenated with 2.5 moles of ethylene oxide, average molecular weight 311 311 Sulfamic a id 100 Product commercially known as Freon ll 816 The temperature is brought to 125 C. while stirring and this temperature is maintained for 40 minutes, at a pressure of about 13 kg./cm.
The contents are cooled to 20 C. and then neutralized by the addition of monoethanolamine so as to obtain a pH of 7. Finally, they are filtered under pressure to obtain product C.
Into a pressure resistant metallic container provided with an expansion valve the following ingredients are introduced:
Gr. Product C 75 Product commercially known as Freon 12 12.5 Butane 12.5
The product prepared and treated in this manner provides, when sprayed, a very porous film of detergent, which may be used to wash windows and Windshields of automobiles.
Example IV Into an autoclave of the type used to carry out the processes of Example I and II the following ingredients are introduced:
Gr. Nonylphenol oxyethylenated with 4.5 moles of ethylene, the average molecular weight being 42l Oxo alcohol (chains from C to C oxyethylenated with 2 moles of ethylene oxide, the average molecular weight being 184 142 Sulfamic acid 80 Urea 3 Product commercially known as Freon 113 250 Gr. Product D 57 Product commercially known as Freon l1 18 Product commercially known as Freon 12 12.5 Butane 12.5
A true solution is thus obtained which contains 32% of a detergent which, when sprayed, gives a finely divided aerosol'that produces a porous film on surfaces to be washed.
It will be seen that in accordance with the invention an anhydrous solution of an anion-active detergent in a liquefied gas propellant, such for example, as one or more of the products commercially known as Freons may be obtained. This anhydrous solution is enclosed in a pressure-resistant metallic container provided with a valve for projecting the detergent in aerosol form onto objects to be washed.
At the time of this projection the solvent which serves as a liquified propellant evaporates and only a layer of detergent in finely divided form remains on the object to be washed, so that the addition of water quickly produces an abundant and persistent foam of good quality.
Detergents which are thus applied in finely divided form have many uses, particularly for cosmetic purposes such as washing the skin and shampooing. For this purpose any suitable subsetnces such, for example, as fatty bodies, mineral oils, waxes, essences, perfumes, colorants, antiseptics, insecticides, etc., may be added to the solution.
What we claim is:
1. An anhydrous detergent containing composition in a pressure container, said composition being a true solution consisting essentially of:
(a) at least one liquefied propellant gas selected from the group consisting of butane trichloromono-fluoromethane, dichlorodifluoromethane, and trichlorotrifluoroethane and their mixtures and (b) a detergent product having the formula in which R represents a radical selected from the group consisting of straight chains having not less than 8 nor more than 22 carbon atoms, corresponding to fatty alcohols; branch chains having not less than 10 nor more than 20 carbon atoms and corresponding toalcohols obtained by the 0x0 synthesis; octyl phenyl; and nonylphenyl; and n represents a number between 1 and 6, said liquified propellant gas being present in said combustion in major proportion, and said detergent product being present in said composition in minor proportion.
2. A method of preparing anhydrous detergent containing compositions in pressure containers, said compositions being true solutions, said method consisting essentially of the following steps:
(a) reacting sulfamic acid with (b) a substance chosen from the group consisting of oxyethylenated alcohols and alkyl phenols having the general formula in which R represents a radical selected from the group consisting of straight chains having not less than 8 nor more than 22 carbon atoms, corresponding to fatty alcohols; branch chains having not less than 10 nor more than 20 carbon atoms and corresponding to alcohols obtained by the 0x0 synthesis; octyl phenyl; and nonylphenyl; and n represents a number between 1 and 6.
(c) in a solvent selected from the group of trichloro monofluoromethane, trichloro trifiuoromethane, pentane and mixtures thereof, at a temperature between C. and C. under a pressure equal to the vapor pressure of said solvent at said temperature.
(11) and introducing the thereby obtained solution into a pressure container together with a liquified propellant gas which is a solvent for the thereby obtained reaction product and which is selected from the group consisting of butane and dichlorodifluoromethane,
(e) and the residual acidity of the reaction product being reduced to a pH of 7 to 8, by subjecting it to an alkaline agent selected from the group consisting of ammonia gas, monocthanolamine, diethanolamine,
7 and triethanolamine, said reacting substances being 2,655,480 present in minor proportion, and said solvents being 2,758,977 present in an amount forming the major proportion of 2,766,212 said compositions. 3. The method of claim 2 in which from 1% to 10% 5 by weight of urea is added to the reacting ingredients.
References Cited in the file of this patent UNITED STATES PATENTS 8 Spitzer et a1. Oct. 13, 1953 Knowles et al. Aug. 14, 1956 Grifo Oct. 9, 1956 FOREIGN PATENTS Great Britain May 23,1938 Belgium Oct. 13, 1955 OTHER REFERENCES Drug and Cosmetic Industry, October 1949; 65, 4, Kosmin July 7, 1953 10 article by Lesser, pp. 396-8, 4704.