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Патент USA US3021294

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United States Patent O?icc
3,021,284
Patented Feb. 13, 1962
2
1
The heavy duty concentrated liquid detergent composi
3,021,284
LIQUID DETERGENT COMPOSITIONS
Robert B. Doan, Drexel Hill, Pa., assignor to The Atlantic
Re?ning Company, Philadelphia, Pa., a corporation of
Pennsylvania
No Drawing. Filed Oct. 30, 1958, Ser. No. 770,583
6 Claims. (Cl. 252-110)
tion of this invention contains the following active ingredi
ents in aqueous solution with the range of concentration
of each ingredient being based on the total weight of the
solution:
This invention relates to liquid detergent compositions
and more particularly to liquid detergent compositions 10
Trisodium phosphate ____________________ __ 2.5-5.0
Sodium tripolyphosphate ________________ .__
0-2.5
Potassium tripolyphosphate ______________ __ 5.0-7.5
Alkyl benzene sulfonate _________________ __ 7.5-l5.0
containing inorganic salts and alkylated aryl sulfonates.
Laurylethanolamide _____________________ __
The use of the various water soluble salts of the alkylat
ed benzene sulfonic acids wherein the alkyl group con
tains from 9 to 15 carbon atoms as synthetic detergents
percent by weight of morpholine is included in the solu
2.5-7.5
These ingredients are soluble when 1.0 percent to 2.5
has become increasingly important in the past several 15 tion. It has been found that from 5.0 percent to 12.0
percent by weight of morpholine oleate may be used in
years. Detergent manufacturers have long recognized,
stead of the morpholine with equal success.
however, that not only may cost savings be realized but
Instead of trisodium phosphate, tripotassium or triam
also improved detergent properties be obtained if these
monium phosphate may be utilized in the same quantities
synthetic detergents are mixed with certain inorganic salts
to produce what is known as “built” formulations. These 20 and instead of sodium tripolyphosphate, potassium tri—
polyphosphate or ammonium tripolyphosphate may be
“built” formulations are particularly useful for heavy
utilized so that all of the tripolyphosphate is the potassium
duty requirements in cleaning heavily soiled cotton cloth
materials but at the same time they may be employed in
or ammonium salt.
It has been found, however, because of the somewhat
formulations consisted primarily of a mixture of solid in 25 lower solubility of the sodium salt that it is not possible
to use sodium tripolyphosphate instead of the potassium
organic chemicals with solid synthetic detergents to pro
tripolyphosphate in the formulation set forth above.
duce a built material in the form of a ?ake or powder.
These tripolyphosphates have the general formula:
These solid built formulations were found objectionable
less severe uses such as dishwashing.
The early built
by the consumer primarily for two reasons—one reason
being that they were not readily soluble either in cold or 30
hot water and required an appreciable time to go into
solution, and the second reason being that the dust which
arose from these ?akes or powders was often times ex
wherein the M represents either sodium, potassium or the
ammonium group.
tremely irritating and caused violent sneezing by anyone 35 The alkyl benzene sulfonate portion of the formulation
consists of a mixture of 95 percent to 70 percent by weight
standing in the'vicinity of its use. The most obvious solu
tion to this problem was to produce a liquid detergent
which would be readily soluble in water and which would
of a water soluble salt of a mono-alkylated benzene sul
fonic acid in which the alkyl group contains from 9 to. 15
carbon atoms and 5 percent to 30 percent by weight of
be free of any irritating dustiness.
In attempting to produce liquid built detergent formula 40 a water soluble salt of xylene sulfonic acid or ethyl ben
zene sulfonic acid. The preferred salts are the sodium,
tions it was found that only rather small amounts of solids
potassium and ammonium salts of these sulfonic acids.
would go into solution with the result that the amount of
The alkylated benzene hydrocarbons which are sulfona
active ingredients in the liquid detergent composition was
ted and neutralized to produce the sulfonates containing
rather small, generally less than about 20 percent by
weight and usually 10 to 12 percent by Weight. While 45 from 9 to 15 carbon atoms in the alkyl group may be
produced by any one of a number of well known methods;
these formulations overcame the objectionable character
for example, the alkylation may be accomplished by
istics of solid formulations, they were expensive since it
treating an excess of the benzene with a halogenated ali
was necessary to ship dilute solutions, thus a large part
phatic hydrocarbon of 9 to 15 carbon atoms in the pres
of their cost was simply the cost of transporting water.
Moreover, attempts to make built formulations in slurry 50 ence of a suitable alkylation catalyst of the Friedel-Crafts
type, i.e. AlCl3, to obtain substantial yields of mono
form were unsuccessful since stratification and settling
alkylated benzenes. These alkylated benzenes may also
occurred giving a non-homogeneous mixture.
be
produced by alkylating benzene with an alcohol or
A method now has been found, however, whereby su
mono-ole?in of 9 to 15 carbon atoms using either sulfuric
perior amounts of alkyl benzene sulfonates and inorganic
builders may be contained in an aqueous solution to pro 55 acid or a Friedel-Crafts catalyst as the case may be.
vide a heavy duty concentrated liquid detergent composi
tion.
It is an object of this invention to provide a heavy duty
concentrated liquid detergent composition.
A further method for producing the alkylated benzene
or mixture of alkylated benzenes having 9 to 15 carbon
atoms in the alkyl group is to polymerize an ole?n such
as propylene, or a gas stream containing propylene, with
an acid catalyst such as a supported phosphoric acid cata
It is a further object of this invention to provide a 60
lyst or boron tri?uoride catalyst at elevated temperatures
heavy duty concentrated liquid detergent composition con
sisting of a built formulation wherein superior quantities
of inorganic salts and synthetic alkyl benzene sulfonates ’
are contained in aqueous solution.
and pressures according to well known methods thereby
obtaining a mixture of propylene polymers which are
ractionated to produce polymers of from 9 to 15 carbon
Further objects of this invention will be apparent from 65 atoms or intermediate fractions of a narrower molecular
weight range. The benzene is then alkylated with the
the description and claims that follow.
propylene
polymer fraction in the presence of a Friedel
In accordance with this invention it has been found
Crafts catalyst or with a sulfuric acid catalyst to produce
that if morpholine or its salt with oleic acid, commonly
the alkylated benzene or mixture of alkylated benzenes.
called morpholine oleate, is included in certain built de
tergent formulations superior quantities of the inorganic 70
salts and alkylated benzene sulfonates will be retained in
aqueous solution.
The xylenes to be employed may be one or a mixture
of the isomeric xylenes, all of which are commercially
available or the xylenes may have admixed therewith
nuances
3
4»
various proportions of ethyl benzene including the case
where the only 8 carbon atom alkylated benzene is ethyl
Example I
Three aqueous compositions were prepared containing
the following ingredients in Weight percent based on the
total weight of the composition:
benzene.
' 'Ir‘he alkylated benzene having an alkyl ‘group of from
9 .to 15 ‘carbon atoms or a mixture of alkylated benzenes
within this range may be mixed with 5 percent to 30
percent by weight of xylene or the other 8 carbon atom
| A l B | O
alkylated benzene mixtures described heretofore. The
entire mixture is then subjected to sulfonation with an
agent such as sulfuric acid of 98 percent to 100 percent
concentration preferably at temperatures of from 150° F.
to 160° B. using about one volume of acid to one volume
Trisodium phosphate _____________________________ __
5. 0
5. 0
5. 0
Sodium trlpolyphosphate ____ __
Potassium tripolyphosphate _____ __
2. 5
7. 5
2. 5
7. 5
2. 5
7. 5
_._ 15.0
__
__
15.0
15. 0
_ . . __
7. 5
7. 5
15.0
Morpholinc oleate ________________________________ __
Sodium alkyl benzene sulfonate 1._
7. 5
0
0
Laurylethanolamide _ . _ _ _ r _ _ _ _ _ _ _
.of the 'alkylated benzene-xylene mixture. If desired the
sulfonation may be carried out with 20 percent fuming
sulfuric acid at slightly lower temperatures, i.e. 135° F. 15
with about one part by weight of acid toa'oout one part
“by weight of hydrocarbon. After the sulfonation is
completed the reaction mixture is diluted with a solvent
such as benzene or hexane and the spent sulfuric acid is
settled out leaving the alkylated benzene sulfonic acids in 20
solution in the immiscible benzene layer. The benzene
solution of sulfonic acids may be extracted with water
1 80 percent by Weight sodium mono-alkyl bcnzene‘sulfonates wherein
the alkyl group contains between 9 and 15 carbon atoms with the major
portion containing from 10 to 12 carbon atoms and 20 percent by weight
sodium xylene sulfonate. These sulfonates were prepared by the joint
sult'onetion of the corresponding alkyl benzene fraction and commercial
xylene which had a typical analysis in weight percentas follows:
ortho-xylem>
24
meta-xylene _ _
para-xylene
45
_ _ __ __
_ _ _ _ _ _l
8
____
19
other hydrocarbons. ______________________________ . -'_ _________ _ _
ethyl hen one
4
Formulations B and C did not produce a clear homo
geneous solution but instead separated into two phases.
acids, the water or alcohol solution is separated from the
benzene, neutralized with a suitable base such as aqueous 25 Formulation A, however, containing the morpholine ole
ate was a clear single phase homogeneous solution.
sodium hydroxide and resulting sulfonate solution evapo
or aqueous alcohol to dissolve and remove the sulfonic
rated to remove water or alcohol. Alternatively, the ben- _
zene solution of sulfonic acids may be treated with an
‘aqueous alcohol solution containing a basic reagent to
neutralize the mixture to form two immiscible liquid
Example vII
A liquid detergent composition was prepared having
the same ingredients in the same concentrations in
aqueous solution as set forth in composition “A” of EX
phases. The phase comprising the alcohol solution of
ample I except that the morpholine oleate was replaced
sulfonates is separated from the benzene and this sulfo
by 1.5 percent by weight of morpholine. A clear, homo
nate solution thereafter is washed with additional ben
geneous liquid detergent composition was obtained.
zene to remove traces of unsulfonated material and ?
nally heated to remove the alcohol, Water and traces of 35
Example III
hydrocarbon solvent from the sulfonate. Instead of sul
fonating the higher alkylated benzenes and the xylenes
7 A number of aqueous detergent compositions were pre
together, the higher alkylated benzenes may be separately
pared in which the ingredients and their concentrations
sulfonated and the xylene hydrocarbons separately sul
were the same as in composition “A” of Example I ex
40 cept that the concentration of morpholine oleate was
fonated and the resulting products mixed.
Although the preferred sulfonate is the sodium salt,
varied from solution to solution. It was found that if
the morpholine oleate was present in less than 5 percent
or more than 12 percent by weight of solution, phase
instead of the sodium salt the potassium or ammonium
salts or mixtures of these salts of the alkylated benzene
sulfonic acids may be used. The triethanolamine salts
separation occurred and non-homogeneous compositions
of the higher alkylated benzenes sulfonic acids also may 45 were obtained. These trials demonstrated the criticality
of the concentration'of the morpholine oleate.
be used in the formulation of this invention.
'The laurylethanolamide which functions as a sudsing
Example IV
agent is commercially ‘available and therefore the de
scription of its production is unnecessary. Morpholine
A number of aqueous detergent compositions were pre
and'morpholine oleate likewise are commercially avail 50 pared which were similar to those of Example III except
able chemicals.
that morpholine was employed instead of morpholine
In order to prepare the'novel formulations of this:v
oleate. It was found that at concentrations .below about
invention the trisodium phosphate, sodium tripolyphos
phate and the potassium tripolyphosphate salts are added
one percent by weight and above about 2.5 percent by
weight, phase separation occurred and non-homogeneous
to water withrheating to approximately 180° F. to 190° F. 55 compositions were obtained.
until they are dissolved. At this temperature they will
dissolve rather readily and thereafter the solution is cooled
to about 100° F. and the alkyl benzene sulfonate is added.
Following addition of the sulfonate the laurylethanol
lowing ingredients in weight percent based on the total
amide and the morpholine or morpholine oleate are 60
weight of the composition:
Example V
7 An aqueous composition was prepared having the fol
-
a
-
'
added to the solution at a temperature of 100° F. or lower,
i.e. ambient temperatures. Upon standing and cooling to
Trisodium phosphate _____________ __. ________ _.'_
5.0
Sodium tripolyphosphate ____________________ __ 2.5
room temperature a clear homogeneous solution is ob
Potassium tripolyphosphate __________________ __ 7.5
tained. If desired, the amount of water originally em
ployed may be somewhat less than the amount desired 65 Sodium alkyl benzene sulfonate 1 _____________ __ 10.0
Triethanolamine alkyl benzene sulfonate 2- ______ __ 5.0
in the ?nal product so that after the addition of all of
Laurylethanolamide ________________________ __
5.0
the ingredients additional water may be added to adjust
the concentration to that desired. After the phosphate
_1_'l‘he sodium alkyl benzene sulfonate‘had the same compo
salts have been put into solution the actual order of addi—
sition as in Example I.
.
'
tion of the remaining ingredients may be varied from that 70 2 The triethanolamine alkyl benzene'sulfonate was prepared
by neutralizing with triethanolamine the mono-alkyl benzene
set forth although the preferred order of addition is that
sulfonic acid fraction of Example I wherein the alkyl group
Morpholine
given.
>
'
_ _ _ __
_
1.5
contained from S to 15 carbon atoms with the major portion
having from 10 M12 carbon atoms.
The examples which follow will serve to illustrate cer
tain speci?c embodiments of the invention.
_ _ _ ___
75
A clear, homogeneous solution was obtained.
8,021,284
6
built detergent. These tests demonstrated that by this in
vention it is possible to obtain concentrated heavy duty
liquid built detergent compositions which are equal to
standard powdered built detergent formulations.
Example VI
There was prepared an aqueous solution having the
same composition as that of Example V except that 6
weight percent instead of 5 weight percent of methanol
I claim:
amine mono-alkyl benzene sulfonate was employed and
5 weight percent of morpholine oleate was substituted for
1. An improved heavy duty liquid detergent composi
tion consisting essentially of an aqueous solution of the
following ingredients in weight percent based on the total
the 1.5 weight percent of morpholine. As in Example V,
a clear homogeneous solution was obtained.
weight of the solution:
Example VII
Trisodium phosphate ____________________ __ 2.5- 5.0
An aqueous composition was prepared identical with
that of composition “A” of Example I except that instead
of including the low molecular weight xylene and ethyl
benzene sulfonates in the sodium alkyl benzene sulfonate
portion of the composition, 15 percent by weight of the
Sodium tripolyphosphate _________________ __ 0
- 2.5
Potassium tripolyphosphate _______________ __ 5.0— 7.5
Alkyl benzene sulfonate _________________ __ 7.5-15.0
15 Laurylethanolamide ____________________ __ 2.5- 7.5
Mo'rpholine
1.0- 2.5
higher molecular weight sulfonate was used, i.e. wherein
wherein the alkyl benzene sulfonate consists of a mixture
the alkyl group contained from 9 to 15 carbon atoms with
of 95 percent to 70 percent by weight of a water soluble
the major portion having from 10 to 12 carbon atoms.
salt of a mono-alkylated benzene sulfonic acid in which
Phase separation occurred and a non-homogeneous com
20 the alkyl group contains from 9 to 15 carbon atoms and
position resulted. This demonstrated the necessity of
5 percent to 30 percent by weight of a water soluble salt
using the mixed high and low molecular weight sodium
of ‘at least one alkylated benzene sulfonic acid from the
alkyl benzene sulfonates rather than the sodium alkyl
group consisting of the isomeric xylene sulfonic acids and
benzene sulfonate wherein the alkyl group contained from
ethyl benzene sulfonic acid.
9 to 15 carbon atoms only.
25
2. The liquid detergent composition of claim 1 wherein
the water-soluble salts of the alkyl benzene sulfonic acids
Example VIII
An aqueous composition was prepared having the fol
lowing ingredient in weight percent based on the total
weight of the composition:
Trisodium phosphate _______________________ .._
Sodium tripolyphosphate ____________________ __
are the sodium salts.
30
5
2.5
7.5
Potassium tripolyphosphate __________________ .._.
Triethanolamine alkyl benzene sulfonate 1 ______ __ 15.0
Laurylethanolamine ________________________ ..
7.5
Morpholine oleate _________________________ __
7.5
3. The liquid detergent composition of claim 1 wherein
the alkyl benzene sulfonate is the triethanolamine salt of
the mono-alkylated benzene sulfonic acids in which the
‘alkyl group contains from 9 to 15 carbon atoms.
4. An improved heavy duty liquid detergent composi
tion consisting essentially of an aqueous solution of the
35 following ingredients in weight percent based on the total
1 The same triethanolamine salt as that of Example V.
A clear, homogeneous solution was obtained demon
strating that because of the greater solubility of the tri 40
ethanolamine sulfonate it may be substituted directly for
weight of the solution:
Trisodium phosphate ____________________ __ 2.5- 5.0
Sodium tripolyphosphate ________________ __ O
Potassium tripolyphosphate ______________ __
Alkyl benzene sulfonate _________________ __
Laurylethanolamide ____________________ __
Morpholine oleate ______________________ .._
— 2.5
5.0- 7.5
7.5-45.0
2.5- 7.5
5.0-12.0
the mixed sulfonates of composition “A” of Example I.
Example IX
wherein the alkyl benzene sulfonate consists of a mixture
A series of aqueous compositions similar to those of 45 of 95 percent to 70 percent by weight of a water soluble
the preceding examples were prepared using various con
salt of a mono-alkylated benzene sulfonic acid in which
centrations of the inorganic salts. It was found that clear,
homogeneous solutions were obtained when the inorganic
salt content did not exceed 20 weight percent and with
that amount of salt, only the potassium salts could be
employed. When, however, the less costly and less solu
ble sodium salts were employed, the upper limits set forth
hereinbefore could not be exceeded.
the alkyl group contains from 9 to 15 carbon atoms and
5 percent to 30 percent by weight of a water soluble salt
of an alkylated benzene sulfonic acid from the group
consisting of xylene sulfonic acid and ethyl benzene sul
fonic acid.
5. The liquid detergent composition of claim 4 wherein
the water-soluble salts of the alkyl benzene sulfonic acids
The ef?cacy of composition “A” of Example I and of
are the sodium salts.
the compositions of Examples II, V, VI and VIII was 55
6. The liquid detergent composition of claim 4 wherein
measured by use of the Atlas Launderometer, in the man
the alkyl benzene sulfonate is the triethanolamine salt of
ner described in “Soap and Sanitary Chemicals,” Septem
the mono-alkylated benzene sulfonic acids in which the
ber 1948, page 42. This test procedure by S. Machlis and
alkyl group contains from 9 to 15 carbon atoms.
E. B. Michaels was modi?ed by using cotton cloth in place
of the glass ?bre and maintaining a temperature of 120° 60
References Cited in the ?le of this patent
F. during the washing cycle. A detergent concentration
of 0.3 percent solids was employed in test comparisons.
UNITED STATES PATENTS
A detailed description of the testing device is found in
2,418,909
Skinner ______________ .._ Apr. 15, 1947
the “Technical Manual and Year Book of the American
2,560,839
Ayo et a1 _____________ __ July 17, 1951
Association of Textile Chemists and Colorists,” for 1947 65 2,581,677
Machlis et a1 ___________ __ Jan. 8, 1952
1948, on page 98.
It was found that the detergencies of the clear, homo~
geneous solutions of this invention were comparable to
those of a recognized commercial standard powdered
2,607,740
Vitale et a1 ___________ .._ Aug. 19, 1952
2,859,182
Carroll _______________ -._ Nov. 4, 1958
2,877,185
Krumrei ____________ __ Mar. 10, 1959
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