Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3197509 A
Publication typeGrant
Publication dateJul 27, 1965
Filing dateDec 21, 1961
Priority dateDec 21, 1961
Publication numberUS 3197509 A, US 3197509A, US-A-3197509, US3197509 A, US3197509A
InventorsHoward F Drew, Roger E Zimmerer
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Diamine dioxide compounds
US 3197509 A
Abstract  available in
Images(5)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent This invention relates to detergent compounds and compositions and more particularly to new and novel surface active diamine dioxides and compositions composed thereof.

In the constant improvement of organic detergent compounds, certain features have been found to be highly desirable. These features include resistance toward the ingredients imparting hardness to water, a high degree of detergency, and a capacity for solubilization of hard Water soaps, such as calcium soap. Although there are a number of organic detergents which have these characteristics, detergent compounds having additional desirable characteristics find a Wider scope of application.

An advantageous property for organic detergent is a low degree of hygroscopicity which results in improved crystallinity. vhen detergent active agents which are hygroscopic are used in bar or granular forms desirable physical properties are impaired. Bars become soft and slimy and granules tend to cake and lose their free flowing and quick dissolving characteristics. For example, trialkylamine oxides have been found to be excellent detergent compounds but are so hygroscopic that they can be effectively used only in liquid detergent compositions.

On the other hand, a high degree of aqueous solubility is desirable since some Well-known surface active agents such as allcylbenzenesultonate are very insoluble in Water in the presence of other electrolytes and can only be used in liquid detergent compositions in conjunction with a suitable hydrotrope such as toluene sulionate.

A high degree of detergency in cool or cold Water is also highly desirable. Many fabrics such as those containing crease resistant additives should be Washed in cool water to retain their crease resistant properties. Wool garments should be Washed in cool Water. In some locations Warm or hot Water is not available.

Detergent surface active agents which exhibit a high degree of mildness are particularly desirable.

It is a principal object or this invention to provide organic detergents and detergent compositions which have excellent detergency as Well as a high degree of mildness and a low degree or" hygroscopicity.

It is another important object to provide detergents and detergent compositions W ich have these characteristics and also have a high detergency in cool water.

it has been found that these and other objectives which will be apparent to those skilled in the art are achieved in the novel class of diamine dioxide compounds having the structure set forth below and in liquid and solid detergent compositions composed therefrom.

The diamine dioxides of this invention are:

In the above formula, R is an allzyl group having from it) to 18 carbon atoms; R R and R each are methyl, ethyl or propyl radicals and n is the whole number 2 or 3. The arrows are the conventional representation for semipolar bonds.

Examples of the compounds or tns invention are: N,N,N',-trimethyl-l=l-decyltrimethylenediarnine-Ndl',

dioxide,

tergents and surface active agents.

Bidifidh Patented July 27, E965 N,l l,N-triethyi-N-dodecylethylenediamine-N,N-

dioxide,

N,N ',N-tripropyl-N-tetradecylethylenediamine-bLN dioxide,

N,N' ,l l -trimetl1y1-l-I-hexadecyltrimethylene diamine- N,N'-dioxide, N,N',N'-tripropyl-N-octadecyltrimethylenediamine- N,N-di0Xide, N-rnethyl-N,N-diethyl-N-octadecylethylenediamine- N,N'-dioxide, N,N'-dimethyl-N'-propyl-N-decylethy1enediamine- NJW-dioxide and,

N,N-diethyl-l -methyl-N-d0decyltrimethylenediamine- N,N-dioxide.

Tertiary amine oxides as a broad class of compounds are known. However, diamine dioxides are new and novel. It is surprising to find in this new and novel class of compounds, compounds which have highly desirable properties as organic detergents.

it appears that only certain of the diamine dioxides have the aforementioned desired characteristics. If R is an alkyl group longer in chain length than 18 carbon atoms or shorter in chain length than 10 carbon atoms, desired detergency is not obtained. Likewise, if R R or R contain more than 3 carbon atoms, such characteristics are not obtained. Moreover, it has been found that the linkage between the amine groups must be no greater than three carbon atoms in order to realize the desired characteristics. A methylene linkage between the nitrogen atoms is diiiicult to achieve inasmuch as the parent compounds are unstable. This instability undesirably affects the corresponding diamine dioxides.

When R R or R are alkyl radicals containing more than three carbon atoms, the compounds begin to lose their high solubility in the presence of an electrolyte. The nonhygroscopic properties of these compounds are also adversely aiiected. Surprisingly, those compounds containing one or more methyl groups have been found to exhibit especially outstanding sudsing properties.

in the diamine dioxides of this invention, the R alkyl group can be derived from naturally occurring fats and oils or from synthetic sources. Mixtures of diamine diOXides are very suitable wherein R varies in chain length from about C to C in the solid compositions, particularly granular products, an octadecylethylene or octadecyl trimethylene diamine dioxide or the tallow alkyl homologue thereof is preferred. The preferred compound for use in liquid compositions is the corresponding dodecyl or coco alkyl homologue thereof.

The diamine dioxides of this invention can be prepared by oxidizing corresponding diamines. A corresponding primary aliphatic dlamine, in general, can be prepared by the method disclosed in U.S.P. 2,754,330. Primary aliphatic diamines are prepared from glycols or amino alcohol by reacting the alcoholic compound with ammonia over a ruthenium catalyst.

Compounds of this invention are useful per so as de- Desirably, they are used With other materials to form built and unbuilt liquid and solid compositions, as for example, bar, flake, granular or tabletted granular compositions. it has been found in the liquid compositions built with a pyrophosphate compbhnd, that N,N',N'-trimethyl-N-dodecylethylenediamine-N,N'-dioxide gives the most unusual and desirable results. Do the other hand, N,N',N-trimethyl-N-octadecylethylenediarnine-N,N-dioxide gives unusual and outstanding results in a granular or other solid product.

The solid form detergent compositions of this invention can contain from about 5% to of the instant diarnine dioxides and from to about 20% of normally solid anionic organic detergents, nonionic organic these polycarboxylates are also suitable.

15 detergents, water soluble inorganic alkaline builder salts, water soluble organic alkaline sequestrant builder salts and mixtures thereof. The liquid compositions of this invention contain in addition to these other actives and additives from about 2% to about 30% of the diamine dioxides of this invention in a liquid vehicle.

Granular or flake detergents preferably contain about 5% to about 50% of the diamine dioxides of this invention and from about 95% to about 50% normally solid, Water soluble inorganic alkaline builder salts, or organic alkaline sequestrant builder salts. Bar formulations contains about 5% to about'50% of the diamine dioxides of this invention when used with anionic detergents such as a soap base, and, if desired, alkaline or organic builders or inert fillers. Bar formulations can contain about 40% to about 80% of the diamine dioxides of this invention as the only detergent component, if desired, and the balance inert fillers or builders.

Anionic organic detergents used alone or in admixture include both the soap and non-soap detergents. Ex-

amples of suitable soaps are the sodium, potassium, am-.

monium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; lalkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethiona tes; acyl N-methyl taurides; alkylbenzenesulfonates; alkyl phenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain to atoms. They are used in'the form of watersoluble salts, the sodium, potassium, ammonium and alkylolammonium salts, for example. Specific examples are: sodium lauryl sulfate; potassium N -methyl lauroyl tauride;triethanolammonium dodecylbenzenesuifonate.

The examples of nonionic organic detergents are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms e.g., 5-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to, alkyl phenol in a range of 10:1 to 1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensationproducts range from 5000 to 11,000; the condensation product of from about 5 to moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms.(e.g., lauryl alcohol) Water-soluble inorganic alkaline builder salts used alone or in admixture are alkaiimetal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted. ammonium saltscan also be used. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium sesqui-carbonate, sodium monoand di-ortho phosphate and potassium bicarbonate. vSuch inorganic builder salts enhance the detergency ofthe sub-. 1

ject diamine dioxides.

Examples of water-soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal,

ammonium or substituted ammonium amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, .sodium. and potassium N-(Z-hydroxyethyl)-ethyl- 'enediaminetriacetates, sodium and potassium nitrilotriacetates and sodium potassium, and triethanolamrnonium N-(Z-hydroxyethyl) .nitrodiacetates. Mixed salts of v The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic sequestering agent-s (see US. Patent 2,739,942).

The preferred solid form detergent compositions con i tain about 10% to about'30% of the diamine dioxides of the invention and at least an equal amount of sodium tripolyphosphate. Desirably the higher alkyl diamine dioxides wherein the alkyl radical ranges from 16 to 18 carbon atoms in chain length are used in such preferred compositions.

The preferred built liquid detergent compositions contain about 5% to about 30% of the diamine dioxides of the invention and about 5% to 40% of potassium pyrophosphate in a liquid vehicle. Desirably the lower alkyl diamine dioxides wherein the alkyl radical ranges from 10 to 12 or 14 carbon atoms in length are used in such preferred compositions.

The detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, ampholytic or zwitterion-ic detergents, cationic detergents, perfumes, anti-tarnishing agents, antiredeposition agents, bacteriostatic agents, dyes, fluorescers, oxygen orchlorine bleaches, suds builders, sud depressors, and the like.

The following examples illustrate the preparation of diamine dioxide compounds and compositions of this invention.

EXAMPLE I assembly, and a pressure compensated addition funnel.

The solution was stirred while 230 grams (1.05 moles) of lauroyl chloride were added at such a rate that a steady, moderate reflux was maintained. The reaction mixture was stirred and refluxed at 35 C. for 45 minutes after addition has been completed. The reaction mixture was then poured into a mixture of 48 grams (1.2 moles) of sodium hydroxide and 1500 grams of ice. The other layer was separated. The ether was evaporated, the residue taken up in acetone and dried with anhydrous sodium carbonate. The drying agent was removed by filtration and the acetone evaporated on a steam bath to yield 114 grams (42% of theory) N,N-dimethyl-N'-lauroylethylenediamine.

Calculated for C H N O: percent N, 10.4. Found: percent N, 10.1;

Thirty-eight grams (1.0 mole) of powdered lithium aluminum hydride were combined with 600 mls. of anhydrous diethyl ether in a 1-liter, glass, round-bottom flask surmounted with a .Soxhlet extraction apparatus containing 113 grams (0.41 mole) N,N-dimethyl-N'-lauroylethylenediamine in a paperextraction thimble. The apparatus was heated electrically to 35 C. Reaction proceeded by the gradual solution of the amide in the ether and periodic siphoning of this solution into the'reactor. Reflux was maintained at 35 C. for 6 hours, at which time the excess lithium aluminum hydride was decomposed with ethyl acetate. Themixture was acidified with dilute HCl to break up salts and complexes. After basification with dilute sodium hydroxide the resulting suspension was extracted with petroleum ether. The organic (ether) layer was separated, dried over anhydrous sodium sulfate, filtered, and the petroleum ether. removed on a stream bath to yield 105grams (100% of theory) of crude N,N'-dimethyl-N-dodecylethylenediamine.

One hundred and five grams (0.41 mole) of crude N,N'- dimethyl-N-dodecylethylenediamine were combined with 102. grams (2 moles) of %v formic acid in a 500ml. l-necked, glass, round-bottom flask. Sixty-three grams ing. This was controlled by periodic cooling to about 90 C. in a cold water bath. Reflux temperature C.) was maintained until the evolution of CO had almost ceased (3 /2 days). The mixture was combined with 150 mls. of concentrated HCl and heated to 100 C. on the steam bath to remove excess formaldehyde and formic acid. The solution was made basic with 30% aqueous sodium hydroxide solution, the layer of amine separated and distilled through a 1 foot Vigreux column at a pressure of 1 mm. of mercury. The fraction boiling from 130135 C. with 11 1.4475 was collected. This fraction weighed 71 grams representing a yield 64% of theory for N,N',t -trimethyl-N-dodecylethylenediamine.

Calculated for C H N percent N, 10.4. Found: percent N, 10.0.

Forty grams (0.15 mole) of N,l l',N'-trimethyl-N-dodecylethylcnediarnine were dissolved in a mixture of 150 mls. of formula 3A alcohol (ethanol denatured with methanol) and 50 mls. of water contained in a 500 ml. glass, round-bottom flask equipped with a mechanical stirring assembly, reflux condenser, and thermometer. To this solution were added 51 grams of 30% aqueous H (0.45 mole). The mixture was stirred and the temperature maintained at 50-60 C. for 5 hours. After standing overnight at room temperature the mixture was diluted with 300 mls. of water and the excess peroxide decomposed catalytically with platinum black. The spent catalyst was removed by filtration and the unreacted amine (1.3 grams) was removed by a triple extraction with petroleum ether. The alcohol was removed on the steam bath under a current of nitrogen. The residual solution was freeze-dried to yield 45 grams of hydrated N,N,N'- trirnethyl-N-dodccylethylenediamine N,N-dioxide representing a 94% yield.

Calculated for C P N O QH O: percent C, 60.4; percent H, 12.5; percent N, 8.28; percent reducible O, 9.47; percent H 0, 10.6. Found: percent C, 61.6; percent H, 12.5; percent N, 8.37; percent 0 (SnCl reduction), 9.33; percent H O (vacuum oven), 10.0.

By substituting N,l l-diethylethylenediamine for N,N- dimethylethylenediamine as the starting material in this example, N',N-diethyl N methyl N dodecylethylenediamine-N,N-dioxide was obtained.

EXAMPLE H In a 5-liter, 3-necked, glass, round-bottom flask equipped with a reflux condenser, additional funnel, and mechanical stirring assembly were placed 300 grams (5 moles) ethylenediamine, obtained from Matheson, Coleman and Bell, dissolved in 150 mls. of formula 3A alco- 1101. This solution was stirred while 333 grams (1 mole) of octadecyl bromide dissolved in 2 liters of formula 3A alcohol were added over a period of 1 /2 hours. The temperature was raised to a reflux (77 C.) by means of an electric heating mantle. Stirring and heating were continued for about 6 hours. At this point 1000 mls. of alcohol were removed by distillation and 1 liter of l N sodium hydroxide added to the cooled concentrate. The resulting water/alcohol system was extracted with warm heptane. Upon evaporation of the heptane 300 grams of crude octadecylethylenediamine were obtained. This represents a yield of 96%.

Calculated for C H N Neutral equivalents, 313 and 156 for the first and second nitrogen, respectively. Found: neutral equivalents, 307 and 169.

Into a 2 liter, 3-necked, glass, round-bottom flask, equipped with reflux condenser and mechanical stirring assembly were placed 115 grams (0.37 mole) of octadecylethylenediamine, 225 grams (4.4 moles) 90% formic acid, and 122.5 grams formalin (1.47 mole formaldehyde). Gccasional cooling to about 90 C. with a cold water bath was required in the early stage of the reaction to reduce foaming. Stirring at reflux temperature (100 C.) was maintained for 3 days. The resulting solution was transferred to an evaporating dish, 150 mls. of concentrated HCl added and the excess formaldehyde and formic acid removed on a steam bath by heating to 100 C. The resulting solution was poured into a mixture of 1000 grams of crushed ice and 400 mls. of 30% aqueous sodium hydroxide solution. The solids were removed by filtration, taken up in ether, washed with water, and the ether removed by evaporation on a steam bath. The resulting dark brown product consisted of 51 grams of liquid and 62 grams of paste-like solid. Infrared spectra indicated the liquid was completely methylated (no NH bands were detected) while the solid was incompletely methylated. The liquid portion was distilled at 0.1 mm. mercury pressure through a 1 ft. Vigreux column to yield 30 grams boiling from 156l6l C. with n 1.4532.

30 grams (0.08 mole) of the ditertiaryamine prepared above were combined with 240 mls. of formula 3A alcohol, mls. of water, and 28 grams of 30% aqueous H 0 solution (0.25 mole) in a 500 ml. glass, roundbottom flask equipped with a mechanical stirring assembly, thermometer, and reflux condenser. The reaction was stirred for about 8 hours at 50-60 C. After cooling to room temperature, 150 mls. of water were added and the excess H 0 decomposed catalytically using platinum black. After removal of the spent catalyst by filtration, the solution was extracted with petroleum either to remove unreacted amine (1.5 grams). The alcohol was removed by evaporation on a steam bath under a stream of nitrogen and the product isolated from the remaining solution by freeze-drying. A yield of 29.5 grams (about 87% of theory) of hydrated Nil,N'-trimethyl-N-octadecylethylenediamine-N,N-dioxide was obtained.

Calculated for C l-l N 9 -H O: percent C, 68.2; percent H, 12.9; percent N, 6.92. Found: percent C, 67.8; percent H, 12.6; percent N, 6.94.

EXAMPLE Ill N,N-diethylethylenediamine, obtained from Eastman Kodak Co., was converted to N,N-diethyl-N-dodecylethylencdiamine following the procedure given in Example This amine was converted to N,N', '-triethyl- N-dodecyiethyleneidiamine in a manner analogous to the methylation in Example l except that acetaldchyde was used in place of formaldehyde. The oxidation was carried out in the same manner as above to give N,N,N- triethyl-N-dodecylethylenediamine-N,N'-dioxide.

EXAMPLE IV Nu ZN tripropyl-N-tetradecylethylenediamine N,N'- dioxide was prepared in a manner analogous to that given in Example ll except that tetradecyl bromide and propionaldehyde were substituted for octadecyl bromide and formaldehyde respectively.

EXAM-ILE V Following the procedure outlined in Example H but substituting 1,3-diarninopropane and dodecyl bromide for ethylenediamine and octadecyl bromide respectively, N,N',N' trim-ethyl N dodecyltrimethylenediamine-N, N-dioxide was obtained.

EMMPLE Vl N,N,N trimethy-l-N-dodecylethylenediamine-N,N'- dioxide, prepared in the manner described in Exmiple l, was determined to be substantially superior to sodium dodecylbenzenesulfonate wherein the dodecyl group was derived from tetrapropy-lene in the cloth-swatch detergency'test described below. Sodium dodecylbenzenesulfonate is a Widely used detergent active for laundering compositions and is, therefore, a reasonable standard for comparison.

This test involved washing naturally soiled cloth (desized print cloth) in a 0.1% aqueous solution of a composition comprising 20% organic detergent compound (diamine dioxide being tested or the alkylbenzenesulfonate standard), 50% sodium tripolyphosphate and 30% sodium sulfate. The composition had a pH of 10.0 and the Washing was done at F. for 10 minutes arouses pared withthe percentage after washing with the alkylbenzenesulfonate standard composition. On the basis of the percent residual lipid soils, the lower the percent, the better the detergericy performance. The test indicated that the percent residual lipid soil remaining on the test switch after washing with the N,N',N-tri-' methyl-N-dodecylethylenediamine-N,N-dioxide composition was substantially less than that remaining after washing with the sodium dodecylbenzenesulfonate stand ard composition.

The hygroscopicity of N,N',N-trimethyl-l l-dodecylethylenediamine-N,N'-dioxide was determined by exposing dry recrystallized material in a constant 50% relative humidity chamber at 70 F; it had weight increases of about 4.0% after 2 days and about after 7 days in this hygroscopicity test. Dimethyldodecylamine oxide, 'a lmown detergent active, had weight increases of 32% after 1 day and 30% after 7 days. It is apparent that the former compound is much less hygroscopic than the latter.

N,N',N' trimethyl-N-dodecylethylenediamine-N,N'-dioxide has been found to exhibit an unexpectedly high degree of mildness. It is also an effective mildness additive for other detergents. On a comparative basis in a standard, but exaggerated, mildness test; using guinea pigs with shaved undcrsides, partially immersed in aqueous test solutions, N,N',N'-trimethyl-N-dodecylethylenediamine-N,N'-dioxide was scored as an 8 on a scale or" 1 to 10 wherein the highest score indicates the highest degree of desirable mildness and l is severe irritation. Sodium dodecylbenzenesulfonate was scored as 4. At least three or more test solutions of 0.2% etergent active were averaged in tabulating the results. An aqueous test solution consisting of 0.2% of sodium dodecylbenzenesulfonate plus 0.1% of N,N',N-trimethyl-N- dodecylethylenediamine-N,N'-dioxide was scored as 9, showing the additive rnildness eifect of the diamine dioxides and the sulfonate.

The solubility of N,N',N-trimethyl-N-dodecylethylene-diamine-N,N-dioxide in aqueous electrolyte solutions was determined by adding knownamounts of diamine dioxide to known amounts of tetrapotassium pyroph-osphate and tetrapotassium ethylenediamine tetraacetate (K4: EDTA). No hydrotroping agents were used. It was found that more than 21 grams of diamine dioxide were soluble in 100 grams of aqueous K EDTA at room temperature. In the case of K pynophosphate, the results showed that more than 16 grams of diamine dioxide were soluble in 100 grams of 20% aqueous electrolyte. The generally high solubility of the :diamine dioxide in aqueous solutions of electrolyte is apparent from the solubility of other known detergents in such test solutions. For example, only up to 2.0 grams of dodecyldimethy'lamine oxide are soluble in an aqueous solution of 20% K pyrophosphate at room temperature. Less than 0.25 grams of sodium dodecylbenzenesulfonate can be solubiliz'ed in an'aque-' ous solution of 20% K pyrophosphate at room temperature.

N',N diethyl-N-methyl-N-dodecylethylenediamine N,

N'-.dioxide has performance characteristics substantially similar in all respects to those of N,N',N'-trimethyl-N- dodecylethylenediamine-N,N'-dioxide. The other diamine dioxides of this invention will have substantially equivalent hygroscopicity characteristics, mildness characteristics, and detergent efficacy. The solubility in electrolyte solutions is slightly less for the homologues above the dodecyl compounds.

I EXAMPLE Vii In addition to the performance tests of Example VI, NJ? ',N' -trimethyl-N-octadecylethylenediamine N,N'- dioxide was evaluated in an extensive wash-wear test by Washing naturally soiled white dress shirts worn by male subjects under ordinary conditions for two normal days. The degree to which a detergent composition containing a detergent compound to be tested cleaned the collars and cuffs of the soiledshirts, relative to the cleaning degree of a similar composition containing a standard detergent compound, was considered a measure of the detergency eifectiveness of the test compound.

The washing solutions used in the wash-wear test contain 0.03% organic detergent compound and 0.06% sodium tripolyphosphate. (No fluorescers, bleachers, or anti-redeposition agents are used.) The pH of the washing solution is 10 and water of 7 grains per gallon hardness is used. A conventional, agitator-type washer and Wash water of 130 F. are used. The detergent compound in the standard detergent composition is sodium dodecyloenzenesulfonate, the most commonly used organic detergent surface active agent in heavy duty laundry detergent compositions. The test detergent composition contains the detergent compound to be compared with the detergent compound in the standard compositions.

In the instant test, N,N,N'-trirnethyl-N-octadecyl 'ethylenediamine-N,N'-dioxide was preferred over the standard test composition in general detergency eitectiveness.

The surprising cool water detergency powers of the dia'mine dioxides of this invention was demonstrated by the results obtained in the swatch test of Example Vi wherein the test swatches were washed in aqueous solution containing sodium dodecylbenzenesulfonate at 140 F. for lt) minutes an aqueous solution containing N,N,N trimethyl N-octadecylethylenediamine-N,l l-dioxide at F. for 10 minutes. The percentage of lipid soil remaining on the swatches after washing with the diamine dioxide solution at low temperature is found to be about equivalent to that remaining after washing with the sodium dodecylbenzenesulfonate standard composi tion at 140 F. and is substantially superior to that of the standard composition at 80 F. A further comparison of N,N,N' trimethyl N-octadecyl-ethylenediam-ine-N,N'- d-ixoide with dimethyldodecy-lamine oxide shows that both of these amine oxide compounds have substantially equiva- Granular detergent lent cool to tepid water (40 F. to F.) washing characteristics.

The diamine dioxides of this invention can be used in effective solid form detergent compositions having improved hygroscopicity, desirable mildness and detergency eflicacy. The following formulations have these characteristics:

, Percent N,N,N' trimethyl -octadencylethylene-diain-ine- N,N'-dioxide 17.5 Sodium sulfate 23 Sodium tripolyphosphate 50 Sodium silicate 6 Water 3.5 N,1\l diethyl N methyl N dodecylethy-lene-diamine-N,N'-dioxide 10 Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetrapropylene) 10 Sodium nitrilotriacetate 50 Sodium sulfate 30 N,N,N tripropyl N tetradecylethylene-d-iamine- N,N'-dioxide 10 Condensation product of one mole of nonyl phenol and nine moles of ethylene oxide l0 Sodium pyrophosphate 50 Percent Sodium carbonate 3 Tr-isodium phosphate 3 Sodium sulfate 24 Milled toilet bar N,N',l trimethyl N alkyltrimethylenediamine- N,N'-dioxide (the alkyl group being derived from coconut fatty alcohol) 10 Sodium coconut oil soap 15 Sodium tallow soap 65 Moisture 10 N,N,N' triethyl-N-tetradecyltrimethylenediamine- N,N'-dioxide 50 Tallow fatty acid 25 Moisture 15 Cornstarch 5 Triethanol ammonium ethylenediaminetetraacetate 5 Securing cleanser Silica flour 85 Detergent consisting of 85% trisodium phosphate and 15% N,N',N'-trimethyl-N-octadecylethylenediamine-N,N'-dioxide 15 The diamine dioxides of this invention find particularly desirable utilization in liquid form detergent compositions. Liquid form detergent compositions provide convenience in use, particularly for measurement and dispensing operations. Liquid detergent compositions can be in the form of solutions, dispersions or emulsions. Preferably, they can contain from about 5% to about 30% of the diamine dioxides of this invention and from about 5% to about 40% of a water-soluble inorganic alkaline builder salt or an organic alkaline sequesttant builder salt, the balance of the composition being a solvent, such as water, and/ or other liquid vehicles.

Examples of liquid detergent compositions including the diamine dioxides of this invention are as follows:

Liquid detergent Percent Sodium dodecylbenzenesulfonate 6 N,N',N' trimethyl N-dodccylethylenediarnine- As many apparently different embodiments of this invention may be made Without departing from the spirit and scope thereof, it is understood that this invention is not limited to the specific embodiments or specific examples thereof except as defined in the appended claims.

What is claimed is:

1. N,N'N trimethyl-N-alkylethylenediamine-N,N-dioxide wherein said alkyl ranges in chain length from 10 to 18 carbon atoms.

2. N,N','N trimethyl-N-dodecylethylenediamine-N,N'- dioxide. 7

3. N,N',N' trimethyl N octadecylethylenediamine- N,N'-dioxide.

References Cited by the Examiner UNITED STATES PATENTS 2,060,568 11/36 Graenachcr et al. 260583 2,169,976 8/39 'Guenther et al 260-404.5 2,769,824 11/56 Schneider et al 260583 2,983,684 5/61 Langdon 2521 17 3,043,779 7/62 Parke et al. 252-117 3,047,579 7/62 Witman 260583 X OTHER REFERENCES Jerchel et al.: Chem. Abstracts, vol. 48 (1954), p. 1246. Websters 3rd New International Dictionary, 1963., G. & C. Merriam Co., Springfield, Mass, p. 1189, col. 3.

CHARLES B. PARKER, Primary Examiner.

I. GREENWALD, Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2060568 *Jun 20, 1935Nov 10, 1936Soc Of Chemical IndAssisting agents for the textile industry
US2169976 *Jan 17, 1935Aug 15, 1939Ig Farbenindustrie AgProcess of producing assistants in the textile and related industries
US2769824 *Apr 26, 1954Nov 6, 1956Upjohn CoHydroxylation of delta-pregnenes
US2983684 *Nov 28, 1956May 9, 1961Wyandotte Chemicals CorpSoap composition containing lime soap dispersant
US3043779 *Mar 13, 1958Jul 10, 1962Lever Brothers LtdDetergent tablets
US3047579 *Jul 18, 1958Jul 31, 1962Shell Oil CoProcess for preparing n-oxides
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3312626 *Sep 3, 1965Apr 4, 1967Procter & GambleToilet bar
US3312627 *Sep 3, 1965Apr 4, 1967Procter & GambleToilet bar
US3410903 *Jan 6, 1965Nov 12, 1968Phillips Petroleum CoPreparation of aliphatic amine oxides
US3412155 *Sep 15, 1965Nov 19, 1968Armour Ind Chem CoFatty branched amine dioxides
US3642506 *Nov 28, 1969Feb 15, 1972Swift & CoMethod for improving the properties of hydraulic cementitious mixtures
US4085144 *Nov 8, 1976Apr 18, 1978Sterling Drug Inc.N,N'-Bridged-bis(2-alkyl-2-hydroxyethylamine) dioxides
US4588522 *Apr 13, 1983May 13, 1986Hoechst AktiengesellschaftBetaine-amine oxides, a process for their preparation and their use as surfactants
US6417401 *Jan 22, 2002Jul 9, 2002Nova Molecular Technologies IncEther diamines amine oxides
USRE30796 *Sep 14, 1978Nov 17, 1981The Dow Chemical Co.Scale removal, ferrous metal passivation and compositions therefor
WO2013053770A1 *Oct 10, 2012Apr 18, 2013Eco Inhibitors AsMethod of inhibiting the formation of gas hydrates using amine oxides
Classifications
U.S. Classification564/297, 564/468, 510/503, 564/298, 510/395, 564/488, 510/154, 510/350, 510/433, 510/351
International ClassificationC07C291/04, C07C291/00, C11D1/75, C11D3/00
Cooperative ClassificationC07C291/04, C11D1/75
European ClassificationC11D1/75, C07C291/04