Note: Descriptions are shown in the official language in which they were submitted.
EXPR~SS M~L Nl~ 00089s
CASE: 6050
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HEAVY DUTY LAUNDRY DETERGENT
Backqround
Trialkylamine oxides are known to be effective surfac-
tants. Such amine oxides are made commercially by reacting a
suitable trialkylamine with aqueous hydrogen peroxide. In this
process the water content must be controlled to be at least 70
weight percent of the final composition or the reaction mass will
gel and cannot be stirred. Such dilute aqueous solutions of
trialkylamine oxide cannot be used to make a free-flowing
granular laundry detergent by dry blending.
Esposita et al. U. S. 4,299,739 mention the desirability ,
of including tert-amine oxides in laundry detergents but offer no
suggestion of how to tolerate the high water content.
Inamorato et al. U. S. 3,489,687 describe an attempt to
make a granular free-flowing laundry detergent containing an
amine oxide by adding an amount of an anhydrous salt, e.g.,
sodium sulfate and sodium tripolyphosphate to react with all the
water in the amine oxide solution to form a friable mixed
hydrated salt/amine oxide composition. However this necessitates
20 the addition of a salt composite rather than a discrete solid
,-amine oxide.
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According to the present invention, free-flowing
granular heavy duty laundry detergent cor.taining a trialkylamine
oxide surfactant can he macle by dry mixing a detergent alkylamine
oxide dihydrate with a suitable laundry detergent builder and
optionally other laundry detergent components.
2~2~973
Description of the Preferred Embodiments
A preferred embodiment of the invention i5 a free-
flowing heavy duty granular laundry detergent, said laundry
detergent comprising (i) 1-30 weight percent of a discrete
tert-amine oxide dihydrate having the formula
RlR2R3No 2H2
wherein Rl is a C8_24 alkyl, R2 is methyl, ethyl or a
C12_24 alkyl and R3 is methyl or ethyl and (ii) 10-50 weight
percent o, a detergent builder.
An essential ingredient of the present heavy duty
laundry detergent is the trialkylamine oxide dihydrate having the
above formula RlR2R3NO-2H20. Such solid tert-amine
dihydrates comprise about 1-50 weight percent of the detergent
composition. More preferably the detergent comprises about 5-30
weight percent and most preferably 10-25 weight percent of the
formulation.
The essential trialkylamine oxide dihydrates can be made
by the process described in Application Serial No. 344,275, filed
April 26, 1989. According to that process, the appropriate amine
is reacted with at least a stoichiometric amount of concentrated
~(e.g., 50-70 weight percent active) hydrogen peroxide in an
organic ester solvent (e.g., ethyl acetate) in an amount suffi-
cient to maintain a fluid reaction mixture. Reaction
temperatures of about 25-100C can be used. A preferred range is
60-75~C. Carbon dioxide can be injected to promote the
reaction. Use of about 1.2 theories of 70 weight percent
hydrogen peroxide results in a final reaction mixture which
contains about 2 moles of water per mole of amine oxide. If more
water than this is present, it should be distilled out to obtain
a 2/1 water/amine oxide mole ratio. The organic ester solution
can then be cooled causing the amine oxide dihydrate to
- 2 -
2~5~73
crystallize. Alternatively, the organic ester can be distilled
out at atmospheric pressure or under vacuum to obtain the amine
oxide dihydrate as the residue. It was surprisingly found that
the tert-amine oxide dihydrate was not hygroscopic.
S Trialkylamines useful in making the tert-amine oxide
dihydrate are those having the formula RlR2R3N wherein
R1, R2 and R3 are as previously defined. Representative
examples of these are:
octyl dimethylamine
decyl dimethylamine
dodecyl dimethylamine
dodecyl diethylamine
tetradecyl dimethylamine
hexadecyl diethylamine
octadecyl dimethylamine
eicosyl dimethylamine
docosyl dimethylamine
tetracosyl dimethylamine
dioctyl methylamine
octyldecyl ethylamine
didecyl methylamine
decyl dodecyl methylamine
didodecyl ethylamine
ditetradecyl methylamine
dihexadecyl methylamine
eicosyldecyl methylamine
ditetracosyl methylamine
and the like including mixtures thereof.
Of the above, a still more preferred class of tert-
amines consists of those in which Rl ic a linear C12_24
2~25~73
primary alkyl, R2 and R3 are methyl. Examples of these are:
n-dodecyl dimethylamine
n-tetradecyl dimethylamine
n-hexadecyl dimethylamine
n-eicosyl dimethylamine
n-docosyl dimethylamine
n-tetracosyl dimethylamine
and the like including mixtures thereof.
The following Examples show how to make the required
trialkylamine oxide dihydrate.
Exam~le 1
In a 250 milliliter glass reaction flask was placed 100
grams of tetradecyldimethylamine (0.41 mole; amine value 230.0 mg
KOH/g amine) and 0.5 gram (1.27 mmol) of diethylenetriaminepenta-
acetic acid. This was heated with stirring to 65C and then 23
grams (0.47 mole) of 70 weight percent aqueous hydrogen peroxide
was~added dropwise over a 15-minute period. The mixture was then
heated to 76C and stirred at that temperature for seven hours.
As needed, ethyl acetate (34 mL) was added dropwise to the
reaction mass in order to maintain a clear, gel-free liquid.
Analysis of the crude reaction mass showed 99 percent amine
conversion by proton NMR. The crude reaction mass was added to
400 mL additional ethyl acetate. The solution was then cooled to
15C forming a non-hydroscopic white crystalline solid tetradecyl-
dimethylamine oxide dihydrate in 86% recovered yield melting at
about 41C.
- 4 -
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Example 2
In a glass- reaction flask was placed 100 g tetradecyl
dimethylamine and 0.5 g diethylenetriamine pentaacetic acid.
Carbon dioxide sparge into the liquid phase was started and the
mixture was stirred and heated to 65C. The CO2 sparge was
stopped and a CO2 gas phase was maintained over the reaction
mixture. Dropwise feed of 70 weight percent aqueous hydrogen
peroxide was started. At the same time, addition of ethyl acetate
was commenced. After 10 minutes all the hydrogen peroxide and 28
mL of ethyl acetate had been added. Cooling was required to
maintain the temperature under 75C. Heat was applied and the
reaction continued for two more hours. Dropwise addition of ethyl
acetate was continued for the first 19 minutes of the two-hour
period. Total ethyl acetate feed was 43 mL. The reaction mixture-
was a clear gel-free solution. The reaction mixture was analyzed
by NMR showing a 100 percent amine conversion. The reaction
mixture was poured into a flask containing 300 mL of ethyl acetate
and cooled to 15C. Needle-like crystals of tetradecyl dimethyl-
amine oxide dihydrate form (106 g) indicating a 87 percent yield.
The other essential ingredient in the present laundry
detergent is at least one detergent builder. Detergent builders
include sodium aluminum silicates (e.g. Zeolite A), sodium
tripolyphosphate (STPP), sodium salt of nitrilotriacetic acid,
sodium carbonate, sodium bicarbonate, sodium citrate, potassium
carboxymethyloxymalonate, sodium carboxymethyloxy succinate,
sodium salt of ethylenediaminepentaacetic acid (EDTA), sodium
pyrophosphate and the like. Of the above the most preferred
detergent builders are sodium carbonate, STPP and Zeolite A.
The amount of builder can vary from about 10 weight
percent to 85 weight percent or more. A preferred amount is about
20-80 weight percent and most preferably 30-50 weight percent.
-- 5 --
2 ~ 7 3
The laundry detergent can contain an additional
surfactant other than the present tert-amine oxide dihydrate.
Examples of such surfactants are anionic, nonionic, amphoteric and
cationic detergents.
Anionics include sodium, potassium, ammonium or alkyl-
olammonium fatty acid soaps such as sodium salts of tallow fatty
acids, coco fatty acids, oleic acid, stearic acid and the like.
Other very useful anionics are the sodium, potassium, ammonium and
alkylolammonium salts of C10_16 alkyl benzenesulfonic acids such
as sodium tridecylbenzenesulfonate. Likewise the sodium,
potassium, ammonium and alkylolammonium salts of C12_16
alpha-olefin sulfonates and C12_16 alkylsulfates are useful.
Still another class of useful anionic surfactants
comprises the alkali metal alkyl glyceryl ether sulfonates such as
the C12_16 alkyl monoglyceride sulfonates and sulfates. Like-
wise the alkali metal salts of C8_12 alkylphenyl polyethoxy-
sulfonates and sulfates which contain about 5-10 ethyleneoxy units
per molecule.
Other useful anionics include the water-soluble salts of
2-10 alkyl esters of C12_16 alpha-sulfonated fatty acids. Also
water-soIuble salts of 2-acyloxyalkane-1-sulfonic acid which
contain 2-9 carbon atoms in the aryl group are useful. Likewise
fatty alcohol sulfates and ether sulfates are effective anionic
surfactants. Also C12_18 alkyl polyethoxysulfates are useful
co-surfactants.
Useful nonionics include polyethyleneoxy (5-10 units)
C12_16 alcohols or C5_10 alkylphenols. Examples are poly-
ethoxylated (5-9 units) dodecanol and polyethoxylated (5-9 units)
nonylphenol. Cationic surfactants include quaternary ammonium,
phosphonium and sulfonium compounds having at least one detergent
2 ~ 7 3
range, e.g. C12_18, alkyl group such as dodecyl dimethyl
ammonium chloride.
Useful amphoteric surfactants include the C12_18 alkyl
dimethyl betaines such as hexadecyl dimethylbetaine.
Other formulation components can include optical
brightening agents, e.g.4,4'-bis(triazin-2-ylamino) stilbene-
2,2'disulfonic acid, 2-(stilben-4-yl) napthotriazole, 2-(4-
phenylstilben-4-yl)benzosazole, 1,4-bis(styryl)benzene, 1,3-di-
phenyl-2-pyrazoline, and the like. The laundry detergent may also
be formulated to contain dry peroxygen bleaches, e.g. sodium
perborate; bleach activators, e.g. sodium Cg acyloxybenzene-
sulfonate; and anti-redeposition agents, e.g. sodium polyacrylate.
Water soluble bulk fillers are routinely included in
laundry detergents such as sodium sulfate. A typical laundry
detergent formulation will contain about 5-50 weight percent
filler to aid in handling.
A series of heavy duty laundry detergents formulations
containing the present tert-amine oxide dihydrates is shown in the
following table.
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