Detersive system and low foaming aqueous surfactant solutions containing a mono(C.sub.1-4 alkyl)-di(C.sub.6-20) alkylamine oxide compound

A C.sub.1-4 alkyl-di C.sub.6-20 alkylamine oxide surfactant composition can be used in detersive systems. The amine oxide can be used in effective surfactant concentrations in aqueous alkaline solutions (pH about 7 or greater) producing an aqueous solution having halogen stability, reduced surface tension and low foaming properties. The surfactants have properties that are useful in detersive systems for hard surfaces, warewashing, laundry, clean-in-place, and other applications.

FIELD OF THE INVENTION 
The invention relates to a novel class of surfactant compounds, to aqueous 
solutions containing an effective surface active amount of the novel 
surfactants and to detersive systems containing the surfactant as an 
active detergent ingredient. More particularly the invention relates to a 
class of low-foaming surfactants that, depending on pH can have both 
cationic and nonionic properties, can be stable in the presence of halogen 
bleaches, and can be used generally in detersive systems such as 
particulate, liquid and solid household and institutional warewashing 
detergents, laundry detergents, hard surface cleaners, clean-in-place 
agents, and others. 
BACKGROUND OF THE INVENTION 
Commonly a surfactant is an organic compound having at least one functional 
group that tends to be hydrophilic or water-seeking and at least one other 
functional group that tends to be hydrophobic or water hating. These 
functional groups can be assembled in surfactant molecules wherein the 
solubility, properties, location and relative sizes of the functional 
groups determines the surfactant properties of the compound. 
The practical application of surfactants generally depends upon the 
properties of the surfactant in aqueous solution. Important properties of 
surfactants include the wetting power of aqueous solutions of surfactants, 
the ability of surfactants to dissolve normally water insoluble 
substances, the ability of surfactants to stabilize dispersed systems such 
as emulsions or suspensions, the ability of detersive systems (systems 
containing a detergent) to clean, the ability of surfactants to foam or 
resist foaming in aqueous solutions, the ability of surfactants to 
sanitize and others. Many types of surfactant molecules are known and are 
broadly classified as anionic, cationic, nonionic and amphoteric. 
Surfactant molecules can contain one or more of a variety of hydrophilic 
functional groups such as hydroxyl groups, ether linkages, groups derived 
from alkylene oxides such as ethylene oxide and propylene oxide; 
quaternary amines, ester linkages, amino groups, amido groups, carboxylic 
acid groups, sulfonic acid groups, and can contain one or more of 
hydrophilic groups such as alkyl groups, unsaturated alkenyl or alkynyl 
groups, aromatic groups, fatty acid residues, and many others. Such 
functional groups can easily be classified by the skilled artisan into 
groups that tend to be hydrophilic and groups that tend to be hydrophobic. 
However, the properties of the resulting surfactant molecules are not 
directly predictable since the contribution of each functional group is 
not fully quantifiable. 
In general, high molecular weight tertiary amine oxide compounds have been 
recognized in the art. The prior art is primarily directed to two classes 
of surfactants which have been examined in great detail and have useful 
high-foaming surfactant properties. These compounds are typically the 
(C.sub.8-18 mono- alkyl)di(methyl) amine oxide compounds of the formula: 
##STR1## 
wherein R is a C.sub.8-18 alkyl group and the mono-(C.sub.8-18 
alkyl)di(C.sub.2-3 alkanol) amine oxide compounds of the formula: 
##STR2## 
The commercial use of such amine oxide classes are discussed in 
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 1, pp. 32-47, 
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 19, pp. 556-559. See 
also Burton, U.S. Pat. No. 4,421,740, Ando et al, U.S. Pat. No. 4,337,165, 
Yoshikawa, U.S. Pat. No. 4,320,033, Russell, U.S. Pat. No. 3,843,395, 
Olson et al, U.S. Pat. No. 3,808,311, Morton, U.S. Pat. No. 3,686,025, 
Heinz, U.S. Pat. No. 3,470,102, Drew, U.S. Pat. No. 3,441,612, Wakeman et 
al, U.S. Pat. No. 3,270,060, Lang, U.S. Pat. No. 3,086,943, Drew et al, 
U.S. Pat. No. 3,001,945, Pilcher et al, U.S. Pat. No. 2,999,068, and 
British Pat. No. 1,294,642. 
BRIEF DESCRIPTION OF THE INVENTION 
We have found a novel surfactant class that comprises at least one compound 
or a mixture of compounds of the formula: 
##STR3## 
wherein R is a C.sub.1-4 alkyl and each R.sub.1 is independently a 
branched or unbranched aliphatic hydrocarbon group having more than 6 
carbon atoms, and less than 20, preferably less than 14 carbon atoms. 
The novel aqueous compositions of this invention comprise an effective 
amount, typically about 5 wt-% or less, of a mono-(C.sub.1-4 
alkyl)di(C.sub.6-20 alkyl)-amine oxide compound sufficient to produce 
surfactant properties in an aqueous solution. We have found that such 
solutions have chlorine stability, substantially reduced surface tension, 
have low foaming properties, defoaming properties and antimicrobial 
sanitizing activity in specific pH ranges. 
We have also found novel detersive systems that contain the novel 
surfactants of this invention in combination with other components. The 
unique properties of the surfactants of this invention provide warewashing 
detergents, hard surface cleaners and laundry detergents, clean-in-place 
compositions and other systems having novel and surprising properties. 
DETAILED DESCRIPTION OF THE INVENTION 
The mono-(C.sub.1-4 alkyl)-di- C.sub.6-20 alkyl)amine oxide surfactant 
compounds of the invention comprise a compound according to the formula: 
##STR4## 
wherein R comprises an alkyl group of 1 to 4 carbon atoms and R.sub.1 
comprises a linear, branched or cyclic aliphatic group having 6 to 20, 
preferably 6 to 12 carbon atoms. Specific examples of C.sub.6-20 linear or 
branched alkyl groups include hexyl, heptyl, 2-ethylhexyl, n-octyl, 
2,2,4-trimethylpentyl, cyclohexyl, methylcyclohexyl, decyl, dodecyl, 
tetradecyl, hexadecyl, octadecyl, etc. The C.sub.1-4 alkyl groups include 
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl. 
Specific examples of the preferred amine oxide surfactants for use in the 
novel aqueous solutions of the invention include dihexylmethylamine oxide, 
dioctylmethylamine oxide, didecylmethylamine oxide, octyldecylmethylamine 
oxide, decyldodecylmethylamine oxide, dodecyltetradecylmethylamine oxide, 
decyltetradecylmethylamine oxide, didodecylmethylamine oxide, 
dipentadecylmethylamine oxide, dihexadecylpropylamine oxide, 
dihexylisopropylamine oxide, dioctylethylamine oxide, didecylethylamine 
oxide, didodecylethylamine oxide, dipentadecylethylamine oxide, 
dihexadecylethylamine oxide, dioctylisopropylamine oxide, 
didecylisopropylamine oxide, didodecylisopropylamine oxide, 
dipentadecylisopropylamine oxide, dihexadecylisopropylamine oxide, and 
others. 
The most preferred amine oxide surfactants are compounds of the formulae I 
wherein either (1) R.sub.1 is octyl, decyl or mixtures thereof, (2) 
R.sub.1 is octyl, (3) R.sub.1 is decyl, or (4) R.sub.1 is a mixture of 
decyl, dodecyl and tetradecyl. The mixtures of the surfactant compositions 
comprise a mixture of dioctyl methylamine oxide and didecyl amine oxide or 
a mixture of compounds wherein R.sub.1 can be either octyl, decyl or a 
mixture of octyl and decyl. 
We have found, surprisingly in comparison with dimethyl higher 
(C.sub.18-24) alkylamine oxide that the aqueous solutions of the compounds 
of this invention exhibit excellent surfactant properties as shown in a 
substantial reduction in surface tension, surprising low foaming 
properties in view of the high foaming nature of the alkyl dimethylamine 
oxide surfactants, chlorine stability, excellent detersive properties and 
have a number of other properties not recognized in the prior art. 
Amine oxides are typically formed from tertiary amines by an oxidative 
reaction creating the amine oxide functional group. Typically amine oxides 
are made by oxidizing a tertiary amine with hydrogen peroxide or other 
oxygen source. Such preparatory methods are discussed by Lake and Hoh in 
J. Am. Oil Chemist Society. 40, 628 (1963), The higher alkyl C.sub.6-18 
dimethylamine oxides were first developed as foam builders in liquid 
handwashing formulations. In addition to foam boosting, the higher alkyl 
dimethylamine oxides have been shown to be effective in high foaming 
shampoos and other end uses where foaming is important, 
We have found that the amine oxide compounds of this invention are 
preferably made by oxidizing the di-C.sub.6-20 alkyl-C.sub.1-4 alkylamine 
with hydrogen peroxide or other common oxidant (oxygen yielding substance) 
at elevated temperature. The tertiary amine compound is typically placed 
in a reaction flask and heated to an elevated temperature. Into the heated 
tertiary amine is slowly added an aqueous solution of oxidant (30 to 50 
wt-%) over an extended period, At the end of the addition of the hydrogen 
peroxide, the reaction mixture is typically treated to dispel remaining 
hydrogen peroxide. The amine oxide compounds are formed at high yield with 
little residual amine. 
Detersive Systems 
The novel surfactant solutions of this invention can be used in the form of 
a detersive system. Detersive systems comprise a combination ingredients 
that when used primarily, but not always, in aqueous detergents can act to 
remove soil from a substrate. The detersive systems of this invention are 
typically liquids, gels, granular or particulate solids or cast solids. A 
detergent is a chemical compound that can weaken or break bonds between 
soil and a substrate. Detergents include surfactants, solvents, alkalis, 
and other compounds. A detersive system is typically used in a liquid 
cleaning bath which produces an enhanced cleaning effect that is caused 
primarily by the presence in the bath of a special solute (the detergent) 
that acts by altering the interfacial effects at the various phase 
boundaries (i.e. between soil, substrate and both) within the system. The 
action of the bath typically involves more than simply soil dissolution. 
The cleaning or washing process in a typical detersive system usually 
consists of the following sequence of operations. The soiled substrate is 
immersed or otherwise introduced into or contacted by a large excess of a 
bath containing a detergent solute. The soil and the underlying object or 
substrate typically becomes thoroughly wetted by the bath. The system is 
subjected to mechanical agitation by rubbing, shaking, spraying, mixing, 
or other action to provide a shearing action which aids in the separation 
of the soil from the substrate. The bath now containing the soil is 
typically removed from the object to be cleaned, the object is rinsed and 
often dried. 
Most typically detersive systems are used in cleaning hard surfaces such as 
sinks, tiles, windows, and other glass, ceramic, plastic or other hard 
surface dishware and laundry or other textiles. Soils removed from 
substrates by the detersive systems are extremely variable in composition. 
They may be liquid, solid or a mixture thereof. The soils typically 
consist of mixtures of proteinaceous, carbohydrate, and fatty materials 
typically in combination with inorganic components and some water. 
Detersive baths typically contain a detergent which is often an organic 
surfactant, an inorganic detersive component, or combinations of organic 
and inorganic components, and can typically be used in combination with 
other organic and inorganic components that provide additional properties 
or enhance the basic detersive property of the detersive component. The 
compositions dissolved or suspended in water to provide detersive systems 
are formulated to suit the requirements of the soiled substrate to be 
cleaned and the expected range of washing conditions. Few cleaning systems 
have a single component. Formulated detersive systems consisting of 
several components often out-perform single component systems. The 
materials which can be used independently in detersive systems are as 
follows: 
(a) surfactants including various synthetic surfactants and natural soaps; 
(b) inorganic builders, diluents, or fillers including salts, acids and 
bases; 
(c) organic builder additives which enhance detergency, foaming power, 
emulsifying power, soil suspension; 
(d) special purpose additives such as bleaching agents, brightening agents, 
enzymes, bactericides, anticorrosion agents, emollients, dyes, fragrances, 
etc.; and 
(e) hydrotrope solubilizers used to insure a compatible uniform mixture of 
components including alcoholic cosolvents, low molecular weight anionic 
surfactants, emulsifying agents, etc. 
Surfactants 
The detersive systems of this invention include the amine oxide surfactant 
composition disclosed herein. The properties of the amine oxide surfactant 
can be enhanced or augmented using a variety of other anionic, nonionic, 
cationic and amphoteric surfactants known in the art including soaps such 
as sodium or potassium salts of fatty acids, rosin acids, and tall oil; 
alkyl or alkyl benzene sulfonates; alkyl sulfates; long chain acid esters 
of polyethylene glycols; polyethylene glycol ethers of alkyl phenols; 
polyethylene glycol ethers of long chain alcohols and mercaptans; fatty 
acid diethanol amides; block copolymers of ethylene oxide and propylene 
oxide. 
Preferred surfactants are the low foaming nonionic or anionic surfactant 
compositions. Cationic surfactants such as quaternary ammonium compounds 
are frequently used in detersive systems but are typically not cleansing 
ingredients and are used for purposes such as sanitizing or fabric 
softening. 
Preferred surfactants for use with the amine oxide surfactants of this 
invention in the detersive systems comprise low foaming nonionic 
surfactants including block copolymers of ethylene oxide and propylene 
oxide, polyethylene glycol ethers of either alkyl phenols or long chain 
fatty alcohols. The ethylene oxide-propylene oxide block copolymers can 
contain from about 3 to about 50 moles of ethylene oxide in combination 
with about 3 to about 50 moles of propylene oxide. The alkoxylated alkyl 
phenols or the alkoxylated fatty alcohols can contain from about 3 to 
about 40 moles of the alkylene oxide, or mixtures thereof, in combination 
with 1 mole of the alkyl phenol or fatty alcohol. 
Inorganic Compounds 
Detersive systems can contain inorganic compounds which are typically 
grouped into the following six categories: alkalis, phosphates, silicates, 
neutral soluble salts, acids, and insoluble inorganic builders. The 
alkalis typically contains alkali metal hydroxides, alkali metal 
carbonates, alkali metal bicarbonates, alkali metal sesquicarbonate, and 
alkali metal borates. The carbonate and borate forms are typically used in 
place of alkali metal hydroxide when a higher pH is desired. 
Inorganic phosphate compositions include monomeric phosphate compounds such 
as sodium orthophosphate and the higher condensed phosphates including 
tetraalkali metal pyrophosphates, sodium tripolyphosphate, glassy 
phosphates and others. Phosphates are typically used as sequestering, 
suspending and cleaning agents. Sodium tripolyphosphate is the most widely 
used builder in heavy detergents. 
Silicates (Na.sub.2 O:SiO.sub.2 compounds) which are typically a reaction 
product between sodium hydroxide and silica, have a variety of Na.sub.2 
O:SiO.sub.2 reaction ratios. Silicates are primarily used as alkalis as 
builders in both warewashing and laundry formulations. 
Neutral soluble salts which are typically the reaction product of a strong 
acid and a strong base including sodium sulfate, sodium chloride, and 
others are typically used as builders or diluents in synthetic surfactant 
based detersive compositions. 
Acids are often incorporated into hard surface detergents for the purpose 
of dissolving or loosening by chemical action soils which otherwise can be 
difficult to remove. Such soils include calcium and magnesium hardness 
components of service water and other mildly alkaline soil. Both organic 
and inorganic acids can be used. Inorganic acids include hydrochloric 
acid, sulfuric acid, phosphoric acids, and others. Organic acids that can 
be used include acetic acid, lactic acid, oxalic acid, citric acid, 
benzoic acid, and others. Insoluble organic builders are often used in 
both liquid, gel and solid detersive systems. The insoluble inorganics 
including clays, both natural and synthetic, montmorilonite clay, 
bentonite clay, can have a detersive effect in certain systems. Further, 
they can be used as suspending agents to maintain a liquid or gelled 
system. 
Organic Builders and Additives 
Further, the detersive systems can contain organic builders and other 
special purpose additives. This class of compounds are typically organic 
molecules having little detersive nature but containing many other 
desirable properties including antiredeposition additives, sequestrants, 
antifoaming or foaming additives, whiteners and brighteners, additives for 
maintaining the solubility of components, and additives for protecting 
both the substrate and the washing apparatus. The most common organic 
additives include organic sequestrants and organic antiredeposition 
agents. Organic sequestrants include compositions such as polyacrylic acid 
and methacrylic acid polymers, ethylene diamine tetraacetic acid, nitrilo 
triacetic acid, etc. and others. Antiredeposition agents include alkali 
metal carboxymethyl cellulose and others. 
Common detersive systems in use today are laundry systems, industrial, 
institutional and household dishwashing or warewashing compositions, 
clean-in-place and hard surface cleaning compositions. 
In aqueous dishwashing, detersive solutions are prepared from typically 
liquid, gelled, granular or cast solid detersive systems by the action of 
water within a warewashing machine. The surfactant of this invention can 
be used in detersive compositions prepared from solid cast, granular, 
particulate, powdered, gelled or liquid warewashing cleaners. The 
surfactant solutions must show effective soil removing properties, be 
resistant to any halogen source present in the cleaner, and should be low 
foaming or preferably defoaming. 
Dishwashing detersive systems typically comprise a source of alkali in the 
form of an alkali metal hydroxide, alkali metal carbonate, or alkali metal 
silicate in combination with a hardness sequestering agent, optional 
surfactants, a source of halogen bleach, and other optional chemical 
substances. The amine oxide surfactant composition of this invention can 
be used in warewashing detersive systems since they are low-foaming, 
chlorine stable, and are useful at typical alkaline pH's found in 
dishwashing detersive systems to augment or enhance the soil removal 
properties of the alkali components. 
The aqueous surfactant solutions of this invention are often used in a 
clean-in-place-cleaning environment in which the chemical properties of an 
aqueous solution pumped into a site requiring cleaning are relied on to 
the exclusion of mechanical soil removing processes in order to clean 
pipelines, process equipment, storage tanks, and other enclosed easily 
soiled locations. Such applications require significant detergency and 
stability to chemical soils. In most end uses, the novel surfactant 
compositions of the invention can be used in the form of an aqueous 
solution, prepared by diluting a concentrate, containing typically less 
than about 5,000 parts per million of the amine oxide surfactant, 
preferably for purposes of reducing cost of use, the surfactant 
compositions of this invention will contain less than 500 parts per 
million surfactant, and most preferably, as a result of the nature of 
surfactant compounds, optimum surfactant properties will be found in 
aqueous solutions containing the surfactants of this invention at a 
concentration of about 1 to 200 parts per million surfactant. 
Laundry detersive systems typically in the form of liquid, gelled, 
granular, particulate or cast solid compositions can be used in both 
household and institutional laundry equipment to clean and destain 
typically soiled fabric articles. Cleaning of such articles is typically 
accomplished by removing soil that is physically associated with the 
fabric and by destaining or bleaching soils that cannot be removed by 
typical detersive systems. Laundry compositions typically comprise anionic 
or nonionic surfactants, water, softening or hardness sequestering agents, 
foam stabilizers, pH buffers, soil suspending agents, perfumes, 
brighteners, opacifiers, and colorants. If the laundry detersive system is 
in liquid form typically the components are dissolved or suspended in 
water, while if in a gelled form the water solution is typically combined 
with a gelling agent. 
Further, the amine oxide surfactant compositions of this invention can be 
used in a variety of liquid detergent compositions that can be used in a 
variety of environments including hard surface cleaning, hand cleaning, 
general household cleaning, car washing, recreational equipment cleaning, 
etc. Such detersive systems are used in the form as shown below or in 
aqueous solution prepared from the compositions as shown below. 
TABLE A 
______________________________________ 
Warewashing Composition 
Most 
Useful Preferred Preferred 
Component Wt % Wt % Wt % 
______________________________________ 
Sequestrant 1-80 20-60 25-50 
Source of alkalinity 
1-80 20-60 25-50 
Source of halogen bleach 
1-10 2-8 3-7 
Amine oxide 0.01-10 0.1-8 0.5-7 
Water 0-10 0-10 0-10 
______________________________________ 
TABLE B 
______________________________________ 
Preferred Warewashing Composition 
Most 
Useful Preferred Preferred 
Component Wt % Wt % Wt % 
______________________________________ 
Alkali metal 20-80 30-70 25-50 
tripolyphosphate 
Alkali metal 20-80 30-70 25-50 
metasilicate 
Alkali metal 0-20 1-20 2-20 
carbonate 
Source of chlorine 
1-10 2-8 3-7 
di C.sub.6-20 alkyl methyl 
0.01-10 0.1-8 0.5-7 
amine oxide 
______________________________________ 
TABLE C 
______________________________________ 
Laundry Composition 
Most 
Useful Preferred Preferred 
Component Wt % Wt % Wt % 
______________________________________ 
Hardness sequestrant 
10-50 15-45 25-45 
Source of alkalinity 
0.5-30 1-25 5-20 
Cosurfactant (anionic) 
5-50 10-45 15-30 
Inorganic builder salt 
10-50 15-45 20-30 
Amine oxide surfactant 
0.1-20 1-15 1-10 
Water 0-5 0-5 0-5 
______________________________________ 
TABLE D 
______________________________________ 
Preferred Laundry Composition 
Most 
Useful Preferred 
Preferred 
Component Wt-% Wt-% Wt-% 
______________________________________ 
Alkali metal 5-50 10-45 15-40 
tripolyphosphate 
Alkali metal 0.5-25 1-20 5-15 
silicate 
Sulfonate surfactant 
10-50 15-45 20-40 
Alkali metal sulfate 
5-50 10-45 15-40 
builder salt 
di C.sub.6-20 alkyl methyl 
0.1-20 0.5-15 1-10 
amine oxide 
______________________________________ 
TABLE E 
______________________________________ 
Concentrated* Clean-in-Place Composition 
Most 
Useful Preferred 
Preferred 
Component Wt-% Wt-% Wt-% 
______________________________________ 
Strong base 
50-90 50-85 50-80 
Sequestrant 
10-50 15-45 20-40 
Amine oxide 
0.1-10 0.5-8 1-5 
Water 0-5 0-5 0-5 
______________________________________ 
*Use at about 0.5 to 5 wt% active base. 
TABLE F 
______________________________________ 
Preferred Concentrated** Clean-in-Place Composition 
Most 
Useful Preferred 
Preferred 
Component Wt-% Wt-% Wt-% 
______________________________________ 
Alkali metal 50-90 50-85 50-80 
hydroxide 
Alkali metal 10-50 15-45 20-40 
tripolyphosphate 
di C.sub.6-20 alkyl methyl 
0.1-10 0.5-8 1-5 
amine oxide 
Water 0-5 0-5 0-5 
______________________________________ 
**Use at about 0.5 to 5 Wt% active alkali metal hydroxide. 
TABLE G 
______________________________________ 
Liquid Hard Surface Cleaner 
Most 
Useful Preferred 
Preferred 
Component Wt-% Wt-% Wt-% 
______________________________________ 
Nonionic surfactant 
0.1-25 0.5-20 1-15 
Hydrotrope 0.1-25 0.5-20 1-15 
Amine oxide 0.5-15 1-12 2-10 
Water Balance Balance Balance 
______________________________________ 
TABLE H 
______________________________________ 
Preferred Liquid Hard Surface Cleaner 
Most 
Useful Preferred Preferred 
Component Wt-% Wt-% Wt-% 
______________________________________ 
C.sub.1-12 alkyl phenol 
5-15 6-14 7-12 
alkoxylate 
C.sub.1-12 alkyl benzene 
5-20 7-15 8-12 
sulfonate hydrotrope 
di C.sub.6-20 alkyl methyl 
1-10 2-9 3-8 
amine oxide 
Water Balance Balance Balance 
______________________________________

The foregoing provides a detailed discussion of the surfactant compositions 
of the invention, their manufacture and use. The following Examples 
further illustrate the invention and contain a best mode. 
EXAMPLE I 
Into a 1 liter resin flask equipped with a heater, mechanical stirrer, 
thermometer and addition funnel was placed 147.3 grams (0.74 mole) of 
dihexylmethylamine. The flask and its contents was heated and into the 
heated stirred tertiary amine was added 82.6 grams (0.845 mole) of 35 wt-% 
aqueous hydrogen peroxide in a drop-wise fashion from the addition funnel 
over a 1 hour and 15 minute period. At the beginning of the peroxide 
addition the temperature of the amine was 29.0.degree. C. which slowly 
increased during addition to 70.degree. C. At the end of 58 hours the 
mixture was cooled and transferred to a separatory funnel at 65.degree. C. 
Into the funnel was added 280 grams of water and 13.1 grams of sodium 
sulfite. After dissolution of the sodium sulfite and shaking the solution, 
the contents of the flask formed two layers, the upper layer comprising an 
aqueous solution of the dihexyl methylamine oxide product, and the lower 
layer an aqueous salt. The bottom was removed and 131.3 grams of water 
were added to the amine oxide layer remaining in the separatory funnel. A 
moderate excess of sodium sulfite was treated with hydrogen peroxide. The 
product was analyzed and found to comprise 24.86% dihexylmethylamine oxide 
and 0.36% dihexylmethylamine. 
EXAMPLE II 
Into a 2 liter resin flask equipped with a heater, stirrer, and dropping 
addition funnel was placed 255 grams (1 mole) of dioctylmethylamine. The 
resin flask and its contents was heated to a temperature of 63.degree. C. 
and into the heated stirred amine was added 120 grams (1.23 moles) of a 35 
wt-% aqueous hydrogen peroxide solution over a period of 3 hours. An 
additional 30 grams (0.26 mole) of 35 wt-% aqueous peroxide was added 3 
hours into the reaction. The reaction was continued for an additional 14 
hours. At the end of that time the reaction mixture was treated with 0.13 
grams of a 10% platinum on activated carbon catalyst to discharge excess 
hydrogen peroxide. 
The amine oxide product was dissolved in an equal volume of CH.sub.2 
Cl.sub.2 and was filtered. The CH.sub.2 Cl.sub.2 was stripped and the 
product was found to contain 87.2% dioctyl methylamine oxide and 1.2% free 
amine. 
EXAMPLE III 
Into a 2 liter resin reaction flask equipped with a heater, stirrer and 
dropping addition funnel was placed 283.1 grams of a tertiary amine 
comprising a mixture of 50% octyl decyl methylamine, 25% dioctyl 
methylamine, and 25% didecyl methylamine (1.0 moles, DAMA 810, Ethyl 
Corp.). The resin flask and its contents were heated to a temperature of 
about 70.degree. C. and into the heated stirred tertiary amine was added 
120 grams (1.23 moles) of a 35 wt-% aqueous hydrogen peroxide solution at 
an addition rate of 15 milliliters per each 10 minutes. Three hours into 
the reaction an additional 30 grams (0.26 moles) of hydrogen peroxide was 
added. At the end of a total reaction time of 21 hours, 0.10 grams of a 
10% platinum on activated carbon catalyst was added to discharge excess 
hydrogen peroxide. The product was filtered, dissolved in an equal volume 
of CH.sub.2 Cl.sub.2 and again filtered. The CH.sub.2 Cl.sub.2 solvent was 
removed by stripping and the product was analyzed showing 87.6 wt-% amine 
oxide and 2.0 wt-% free amine. 
EXAMPLE IV 
Into a 2 liter resin reaction flask equipped with a heater, stirrer and 
dropping addition funnel was placed 311.0 grams of a didecyl methylamine 
(1.0 moles DAMA 10, Ethyl Corp.). The resin flask and its contents were 
heated to a temperature of 65.degree. C. and into the heated amine was 
added 120 grams (1.23 moles) of a 35 wt-% aqueous hydrogen peroxide 
solution at a rate of 15 milliliters per each 10 minutes. 3 hours into the 
reaction time an additional 30 grams (0.26 moles) of a 35 wt-% aqueous 
hydrogen peroxide solution was added slowly to the reaction mixture. The 
reaction was continued for a total of 31 hours at 65.degree. C. At the end 
of the reaction 0.10 grams of a 10% platinum on activated carbon catalyst 
was added to discharge excess hydrogen peroxide. The amine oxide product 
was dissolved in an equal volume of CH.sub.2 Cl.sub.2 and filtered. The 
solvent was removed by stripping and the product contained 85.6 wt-% amine 
oxide and 2.05 wt-% free amine, indicating a 97.65% conversion. 
EXAMPLE V 
Following the procedure of Example IV except that a dicocomethylamine was 
substituted for the didecyl methylamine, a dicocomethylamine oxide product 
was formed having 83.3% dicocomethylamine oxide and 1.6 wt-% free amine in 
the product. 
EXAMPLE VI 
Into a 1 liter resin flask equipped with a heater, mechanical stirrer, 
thermometer and additional funnel was placed 226.6 grams of a distearyl 
methylamine (0.5 moles ADOGEN 349). The flask and its contents was heated 
to a temperature of about 70.degree. C. and into the heated amine was 
added 60 grams of a 35 wt-% aqueous hydrogen peroxide solution drop-wise 
at a rate of 15 milliliters per each 10 minutes. The reaction was 
continued at 70.degree. C. for 28 hours. At 5 hours, 13 hours, 21 hours, 
and 25 hours into the reaction an additional 15 grams (0.15 mole) of 35 
wt-% hydrogen peroxide was added to the reaction mixture. The final 
product contained 45.7 wt-% amine oxide and 0.6 wt-% free amine. 
The amine oxide surfactants of the invention were tested for dynamic 
foaming, surface tension and straight line gardner detergency. The 
following Tables summarize the data. The surface tension was measured in 
dynes per square centimeter on a Fisher Model 21 tensiometer with the 
indicated concentration of the amine oxide surfactant dissolved in 
deionized water measured at 70.degree.-80.degree. F. 
TABLE 1 
__________________________________________________________________________ 
Dynamic Foaming Dialkyl Methylamine 
Temperature vs. Foam Height 
C.sub.14 Alkyl 
C.sub.12 Alkyl 
Dimethylamine 
Dimethylamine 
Foam Height Oxide Oxide 
Temp. .degree.C. 
diC.sub.6 
diC.sub.8 
diC.sub.10 
diC.sub.12 
diC.sub.14 
NINOX-M NINOX-L Pluronic L-62 
__________________________________________________________________________ 
78 3 2 1.5 
1.75 
1 9 9 2 
88 2 1.75 
1 1.25 
0.25 
9 9 1.8 
92 1.5 
1.5 
0.8 
1 0.25 
9 9 1.7 
100 1.25 
1.5 
0.75 
0.75 
0 9 9 1.25 
108 1 1.25 
0.5 
0.6 
0 9 9 0.50 
124 1 0.8 
0 0 0 9 9 0 
136 1 0.33 
0 0 0 -- -- 0 
150 1 0.25 
0 0 0 9 9 0 
156 1 0.25 
0 0 0 -- -- 0 
160 1 0.25 
0 0 0 9 9 -- 
176 1 0 0 0 0 -- -- -- 
180 1 0 0 0 0 9 9 -- 
184 1 0 0 0 0 -- -- -- 
190 1 0 0 0 0 -- -- -- 
194 1 0 0 0 0 -- -- -- 
__________________________________________________________________________ 
TABLE 2 
______________________________________ 
Surface Tension* Dynes/cm.sup.2 
Concentration 
C.sub.8 Dialkyl 
C.sub.10 Dialkyl 
C.sub.12 Dialkyl 
______________________________________ 
5 55.1 39 33.1 
10 53.5 34 28 
20 49.9 29.5 24.9 
50 41.25 24.7 24.7 
100 36 23 24 
150 34 -- -- 
200 32 -- -- 
1000 23 -- -- 
______________________________________ 
TABLE 3 
______________________________________ 
Surface Tension Dynes/cm.sub.2 
Concentration 
C.sub.12 Alkyl C.sub.14 Alkyl 
______________________________________ 
5 57.1 57 
10 53.3 46.9 
20 43.2 40.1 
50 38.2 36.9 
100 35.3 37.3 
______________________________________ 
*Measured by Fisher Model 21 Teniometer deionized water at 70-80.degree. 
F. 
The dynamic foaming data relating to the sufactant of the reaction were 
generated in a foam test device which is a cylindrical container 8 liters 
in volume, 15 centimeters in diameter, and 50 centimeters in height, 
equipped with an electric hot plate for temperature control, and a pump to 
recirculate the test solution at 6 p.s.i. via a means to direct a spray of 
the test solution onto the surface of the contents of the solution to 
generate foam. Three liters of test solution were prepared in soft water 
which contains 50 p.p.m. of the aqueous amine oxide surfactant. The tests 
were performed by recirculating the detergent solution through the spray 
means in the dynamic foam tester while the temperature was gradually 
increased 2.degree.-3.degree. F. per minute. At regular intervals the foam 
height above the water was observed. 
The cleaning efficiencies of the surfactant compositions of this invention 
were measured using the gardner straight line detergency evaluation 
procedure in which a Gardner apparatus model WG6700 machine was used to 
clean standard soiled tiles with standard pressure and stroke of a sponge 
using use-dilution concentrations of surfactants on standard soiled tiles 
using an oily soil comprising 50% deodorized kerosene, 5% mineral oil, 5% 
#10 W motor oil, 2.5% of a dispersion of graphite in petroleum, and 37.5% 
black clay. 
TABLE IV 
______________________________________ 
Gardner Straight Line Detergency Evaluation 
Surfactant Soil Removal (%) 
______________________________________ 
Nonylphenol ethoxylate (9.5 moles EO) 
37.7 
di C.sub.6 alkyl methylamine oxide 
9.9 
di C.sub.8 alkyl methylamine oxide 
36.0 
di C.sub.10 alkyl methylamine oxide 
8.9 
di C.sub.12 alkyl methylamine oxide 
7.4 
C.sub.8 alkyl dimethylamine oxide 
8.9 
C.sub.10 alkyl dimethylamine oxide 
19.6 
C.sub.12 alkyl dimethylamine oxide 
22.5 
C.sub.14 alkyl dimethylamine oxide 
24.3 
______________________________________ 
The above tables of data indicate that the dialkyl methylamine oxide 
surfactants of the invention have significant surface tension, low foaming 
properties and detergency. 
The following exemplary detersive compositions are made using the amine 
oxide surfactant similar to those prepared in the above Examples. 
EXAMPLE A 
A granular laundry system was prepared comprising 40.0% sodium 
tripolyphosphate, 20.0% didodecylmethylamine oxide (75% active in water), 
10% sodium metasilicate, and 30% sodium carbonate by adding the sodium 
tripolyphosphate to a 1.5 liter ribbon blender. The amine oxide was 
absorbed on the tripolyphosphate and the balance of the particulates were 
added until blended. 
EXAMPLE B 
A granular laundry system was prepared according to Example A except that 
nonylphenol 9.5 mole ethoxylate was used to entirely replace the amine 
oxide. 
A tergotometer device was used to evaluate the two compositions. The 
following conditions were used: 
______________________________________ 
RPM rate 150 
Wash time 5 minutes 
Wash volume 800 mls. 
Detergent 2 grams (0.25 wt/wt) 
concentration 
Temperature 50.degree. C. 
Water type Distilled 
Soil fabric type 
Dacron 54 W/cotton polyester 65/35 
Shirting material with durable press 
Finish soiled with clay, lamp black, 
iron oxide and lanolin soil 
supplied by Test Fabrics, Inc., 
Middlesex, N.J., U.S.A. 
______________________________________ 
Under the above test conditions Example B gave a soil removal of 42.3%, 
whereas Example A gave a soil removal of 46.0%. Each value is the average 
of three separate experiments. Soil removal was measured using a Hunter 
Lab D2504 color difference meter. 
EXAMPLE C 
A granular warewashing system was prepared comprising 35 wt-% sodium 
tripolyphosphate, 3.0% didodecylmethylamine oxide, 40% sodium 
metasilicate, 20% sodium carbonate, and 2% sodium dichlorodiisocyanurate 
dihydrate by adding the sodium tripolyphosphate to a 1.5 liter ribbon 
blender. The didodecylmethylamine oxide surfactant was added to and 
absorbed onto the sodium tripolyphosphate and the balance of the 
particulate ingredients were added and blended until uniform. 
EXAMPLE D 
Hard Surface Cleaner 
A liquid, aqueous hard surface cleaner was prepared comprising 6% 
didodecylmethylamine oxide, 10% nonyl phenol 9.5 ethoxylate, 10% sodium 
xylene sulfonate hydrotrope, and 74% water by adding to water contained in 
a glass beaker the recited ingredients. 
EXAMPLE E 
Clean-in-Place Composition Concentrate 
A granular, clean-in-place concentrate composition was prepared comprising 
3 wt-% dioctylmethylamine oxide, 2% water, 25% sodium tripolyphosphate, 
and 70% solid pellet sodium hydroxide. The composition was prepared by 
adding the dioctylmethylamine oxide in the water to the sodium 
tripolyphosphate in a 1.5 liter ribbon blender. After the amine oxide was 
absorbed on the tripolyphosphate, the sodium hydroxide was slowly added 
and blended until uniform. 
The above specification, Examples and data provide a detailed discussion of 
the surfactants, detersive systems, and methods of the invention. However, 
since the invention can be present in a variety of embodiments that 
contain the spirit and scope of the invention, the invention is found 
within the claims hereinafter appended.