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Патент USA US2412945

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2,412,945‘
Patented Dec. 24, 1946
UNITED STATES PATENT OFFICE
2,412,945
DETERGENT COMPOSITION AND METHOD ’
OF PREPARING SAME
Frederick G. Bersworth, Verona, N. J.
No Drawing. Application July- 2'7, 1945,
Serial No. 607,481
.
16 Claims. (0]. 252-—117)
1
2
By the term “alkali metal salt of an amino
polyacetic acid" is meant an alkali metal salt of
an amino poiyacetic acid conforming to the for
This invention relates to detergents and deter
gent compositions and has for its object the pro
vision of a detergent that is soluble in water and
is miscible with alkali metal fatty acid soap com
pounds to form detergent compositions adapted
mula:
.
11000-011:
for use in saline and hard waters and a method
N-R
of producing the said detergent product.
noes-chi
Another object is to provide a soap composition
suitable for use in hard and saline (sea) waters.
A further object is to provide’ a detergent com 10
position of matter consisting of the reaction
product of a polyalcohol, such as glycerine and
an alkali metal salt of an amino polyacetic acid,
such as the tetrasodium salt of ethylene diamine
16
tetracarboxylic acid.
Other objects will be apparent as the inve tion
is more fully hereinafter disclosed.
In accordance with these objects I have dis
covered that by heating together a polyalcohol
and the alkali metal salt of an amino polyacetic 20
acid, each compound being either in the anhy
drous state or in aqueous solution, to a tempera
ture and for a time interval required to obtain a
wherein R is selected from the group consisting of
Example
—-CH2- C 0 0H
(Tn-glycine)
C H:- C 0 0 H
—0 H:- CH:
CH:- C 0 0H
(Ethylene diamine tetracarboxylic acid)
CH:- C 0 OH.
—-A—(NH-—-A) -—N
CH, C 0 0H
(Diethylene triamine tetracarboxylic acid)
substantially anhydrous reaction product, the
resultant reaction product is a detergent soluble 26 and
in water and having strong foaming Properties in
hard and saline or sea water and the additional
property of being substantially non-reactive with
CHrCOOH
--A--(N—A)—N
\
cnrcoon
soluble salts in hard and saline water to form in
soluble salts therewith. I have further discovered 30
( Hz-COOH).
’
that the reaction product is miscible with alkali
(Diethylene triamine pentacarboxylic acid)
metal fatty acid soap compounds in all propor
in which in is zero and any positive integer and Av
tions up to equal proportions without interfering
is a member of the group consisting of alkylene
with the normal bar, ?ake and powder forming
properties of the soap compounds and that when 35 and hydroxyalkylene.
Representative examples of the amino poly
added to, or incorporated in, said soap compounds
acids are ethylene diamine tetraacetic acid, pro
imparts thereto the property of foaming in hard
and saline (sea) water and inhibits or prevents ' pylene diamine tetraacetic acid, diamino pro
vpanol tetraacetic acid, diethylene triamino poly- .
the reaction of the said soap compounds with
soluble salts in the water to form insoluble soap v 40
compounds.
The relative proportions of the two compounds
may be varied widely without essential departure
acetic acid, dipropylene triamino polvacetic acid,'.
and triethylene tetramino polyacetic acid. 7
The detergent reaction product of the present .
invention is made by heating the alkali metal salt
of the polyacetic acid with at least 15%, by
equal amounts by weight to a considerable excess 45 weight, of the polyalcohol to elevated tempera-5
tures above the boiling point of water with thor
of one constituent over the other constituent. In
ough agitation and fOr an extended time interother words, the relative portions of the hydroxyl
from the present invention from approximately
groups of one and the sodium atoms of the other
may vary from a large excess of either to the
other.
-
By the term “polyalcohol” is meant any poly
alcohol containing at least two but not more than
six alcoholic (hydroxyl) groups. Typical exam
' ' '
val required to remove water to the ‘extent re- -'
quired to obtain a, reaction temperature of at
50 least 115° C. up to 200° C. Either one or both of
the reacting compounds may be employed inv the
anhydrous or hydrous condition. , The amount of
the polyalcohol may vary widely from a ‘15%, by
weight, minimum to a large excess over equiva
ples of such polyalcohols are glycerine, mannitol,
55 lent weights.
sorbitol and triethanol amine.
'
2,412,945
It is not known whether the reaction product
of the present invention is a chemical compound
or a mixture of chemical compounds. It is
known, however, that a mechanical mixture of
the two reactants in the same relative proportions
in either the hydrous or anhydrous state does
not exhibit the properties of a detergent when
added to hard and saline water and is not misci
ble with the alkali metal fatty acid soap com
4
peratures has the consistency of clear, soft soap
but at lower temperatures tends to congeal to a
product resembling putty.
Like the previous products described, however,
the reaction product is highly soluble in water,
has free-foaming properties in hard and saline
waters without forming insoluble compounds
with the soluble salts and electrolytes in the wa
ter, and is a strong detergent. The product is
pounds. By heating the mechanical mixture to 10 freely miscible in all proportions up to equal
elevated temperatures above the vaporization
weights with alkali metal fatty acid soap com
temperature of water for a time interval required
pounds to impart these desirable properties to
to obtain a substantially homogeneous liquid
such soap compounds without interfering with
phase reaction product, a chemical reaction oc
the desired bar, ?ake and powder forming prop
curs that results in the formation of a highly wa 15 erties ,of the said soap compounds.
ter soluble compound or mixture of compounds
IV. When 380 grams of the tetrasodium salt of
which have strongly detergent properties, strong
ethylene diamine tetraacetic acid in 500 c. c. of
deionizing properties and strong electrolyte carry
water and 200 grams of vtriethanol amine are
ing properties, which render the reaction product
heated to temperatures above the boiling point of
freely miscible with alkali metal fatty acid soap 20 water until the major portion of the water is
compounds in all proportions up to equal
removed by vaporization, a reaction product 15
amounts, by weight, to form soap mixtures of
obtained which is a heavy, clear yellow liquid
strong sudsing and foaming properties in hard
when hot and a waxy solid when cooled to atmos
and saline water without forming insoluble soap
pheric temperatures. This reaction product evi
compounds with the soluble salts in said hard and 25 dences the same properties in aqueous solution as
saline water.
the other products above described and imparts
As speci?c examples of the practice of the
these properties to alkali metal fatty acid soap
present invention with various polyalcohols and
compounds with which it is miscible in all pro
various salts of amino polyacetic acids the fol
portions up to about equal weights.
lowing are given:
V. Where the tetrasodium salt of propylene
30
I. Two (2) molar weights of the tetrasodium
diamine tetraacetic acid is substituted for the
salt of ethylene diamine tetraacetic acid (‘760
tetrasodium salt of ethylene diamine tetraacetic
grams), dissolved in 11/2 liters (1500 grams) of
acid in equivalent amounts in any of the above
water, are heated to the boiling point of the so
examples, lower viscosity reaction products are
lution in a container open to the atmosphere.
Three hundred (300) grams of mannitol
(CH2OH(CHOH) 4CH2OH)
are added to the boiling solution and boiling of
the solution is continued until approximately
1200 grams of water have been removed by evap
oration from the solution.
The resultant clear liquid reaction product, on
cooling to room temperatures, has the consist
ency of cold glycerine, is highly soluble in water,
has excellent detergent properties with good
foaming properties in hard and saline water and
does not react with soluble salts and electrolytes
in aqueous solutions to form insoluble compounds
therewith. The reaction product is miscible with '
obtained which otherwise evidence the same prop
erties.
VI. Where the tetra-sodium salt of diamino
propanol tetraacetic acid is substituted for the
tetrasodium salt of ethylene diamine tetraacetic
acid, in any of the above examples in equiva
lent amounts, lower viscosity reaction products
evidencing the same properties are also obtained.
VII. Where the sodium salt of diethylene tri
amine polyacetic acid is substituted for the tetra
sodium salt of ethylene diamine polyacetic acid
in Example I in equivalent amounts and glyc
erine is substituted for mannitol in equivalent
amounts, and the heating is continued until at
least 80% of the water present is removed by
evaporation, a reaction product is obtained which
alkali metal fatty acid soap compounds in all,
proportions up tov equal amounts by weight to
form a detergent composition adapted to be
formed into bar, ?ake and powder which is free
foaming in hard and saline water and non-reac
tive with soluble salts and electrolytes in the hard
ture. This product, however, is freely soluble
in water and in the liquid phase is freely miscible
with alkali metal soap compounds, and evidences
all of the desirable properties above noted.
and saline water to form insoluble soap com
propylene triainine polyacetic acid for the poly
pounds therewith.
on cooling to room temperatures is waxy in na
VIlI.~ The substitution of the sodium salt of di
acetic acid salt of Example VII produces a reac
II. Where sorbitol in an amount approximat
tion
product closely resembling the reaction prod
ing 300 grams is substituted for mannitol in the 60 uct obtained'in Example VI.
above Example I, a closely similar reaction prod
uct is obtained exhibiting substantially the same
IX. Where the tetrasodium salt of ethylene di
amine tetraacetic acid and glycerine are reacted
in aqueous solution, as in Example I instead of
III. Where glycerine is substituted for man
as in Example III, and the amount of water re
nitol in the above Example I, I prefer to employ
moved by vaporization is anywhere within the
about 440 grams of the glycerine for each 200
range 40-90% of that present in the solution a
grams of the polyacetic acid salt, and to employ
reaction product liquid at 100° C. but solidifying
the salt in its substantially anhydrous condition.
to a putty-like semi-crystalline solid at room tem
With this modi?cation of the method of Exam
ple I it is necessary to heat the glycerine-salt 70 peratures is obtained where the reacting con
. mixture to temperatures approximating 140-145°
stituents are present in approximately equal
C. with good agitation for an extended period of
amounts. The amount of water present in the
time approximating 10 hours to form the reac
reaction product varies the kind of solid obtained
tion product of the present invention. So heat
at room temperatures, but the solid appears capa
ed, the reaction product on cooling to room tem 75 ble of holding large amounts of water in crystal
properties.
‘
8,419,945
6
line form at room temperatures. In general, in
this aqueous solution reaction, a reaction product
.
reaction product of an aliphatic polyhydroxy‘
alcohol and an alkali metal salt of a lower alhl
amino polyacetic acid, said reaction product be
containing as high as 3 parts of the sodium salt
in: formed by heating the said salt in aqueous
to one part glycerine may be formed, all of which
solution with at least 15% by weight of said ai
evidence the same general properties herein de
cohol to temperatures within the range 115-200‘
scribed.
C. for an extended time interval eiiective to va
In the practice of the above invention it is
porize the major portion of the water therefrom,
desirable for the purpose of forming detergent
said reaction product thereby obtained being
mixtures with alkali metal soap compounds to
continue heating until a reaction product con 10 characterized by being highly soluble in water, by v '
being non-reactive with salts and electrolytes
taining not over 10% water is obtained to facili
present in the water to form insoluble compounds
tate the subsequent admixture of the reaction
therewith, by being a strong detergent in aque
, product while in its liquid phase with fatty acid
ous solutions, and by being miscible in all pro
soap compounds while in their liquid phase.
Where the reaction product is not desired for 15 portions up to equal amounts by weight with al
kali metal fatty acid soap compounds without
admixture with fatty acid soap compounds, how
detriment to the bar, ?ake and powder iorm~
ever, the amount of water present may be varied
ing properties of the said soap compounds,
v widely without essential departure from the pres
,
by imparting to said soap compounds stron
ent invention, depending upon whether a reaction
product in the solid or liquid phase is desired. 20 foaming properties in the presence of dissolve
salts and electrolytes without the formation of
In all such reactions conducted in the presence
insoluble soap compounds therewith.
of water, however, an extended time interval of
2. A product of manufacture consisting of a
heating at temperatures approximating the boil
detergent consisting of a reaction product be
ing point of water appears necessary ‘to induce
or promote the formation of the reaction product 25 tween an- aliphatic polyhydroxy alcohol and a
neutral alkali metal salt of a lower alkyl amino
of the present invention. In most instances, a
polyacetic acid, the two said compounds being
time interval of heating at least approximating
present in the reaction product in the relative
10 hours appears to be required, although shorter
amounts ranging from approximately equal
or longer time intervals may be employed without
essential departure from the invention.
30 amounts up to and including a large excess of
Where the two reactants in the non-aqueous ‘
either constituent, said reaction product having
quired and precautionary measures to prevent
been formed by heating said salt and alcohol to
gether in aqueous solution to temperatures with—
in the range 115-200° C. for an extended time in
is preferred and ordinarily heating is continued
4. The product of claim 2 in its substantially
phase are brought together, higher temperatures
than the boiling point of water normally are re
the loss of the more volatile constituent must be 35 terval effective to vaporize the major portion of
the water therefrom.
taken, as by the use of a re?ux condenser. For
3. The product of claim 2, said product being
this reason, the performance of the reaction in
in its substantially anhydrous phase.
the presence of water at the boiling point of water
until the water content of the mixture is reduced 40 anhydrous phase in admixture with alkali metal
fatty acid soap compounds in amounts up to ap
to an amount not over about 20% and to an
proximately equal amounts, by weight.
amount producing a substantially anhydrous
5. The product of claim 2, wherein said alcohol
liquid phase at the temperature of heating. This
consists of glycerine.
'
normally requires the use of temperatures above
6. The product of claim 2, wherein said alkali
100° C. as the water content falls below 20% with
metal salt of an amino polyacetic acid consists
re?uxing to prevent the loss of volatile constit
of the tetrasodium salt of ethylene diamine tetra
uents as the product approaches the substantially
acetic acid.
water-free state.
7
7. The product ofclaim 2, wherein said al~
All of the above noted reaction products are
freely soluble in water, and evidence free foaming 50 cohol consists of glycerine and said alkali metal
properties with strong detergent properties even- , salt of an amino polyacetic acid consists of the
tetrasodium salt of ethylene diamine tetraacetic
in relatively hard or strong electrolyte-carrying
acid.
solutions, such as sea water, without the precipi
8. The product of claim 2, wherein said alcohol
tation of insoluble salts or compounds by reaction
with the salts and electrolytes present in the 55 consists of mannitol.
water. All of the reaction products in the liquid
anhydrous phase are freely miscible in all pro
portions and to equal amounts by weight with
', alkali metal fatty acid soap compounds in their
liquid phase without detriment to the bar, ?ake
or powder forming properties of the soap com
pounds and impart to such soap mixtures strong
foaming properties in hard and electrolyte-carry
ing water without the formation of insoluble soap
compounds‘. ,.
9. The product of claim 2, wherein said alcohol
consists of triethanol amine.
10. The method of forming a detergent com
position of matter which is soluble in water and
miscible in alkali metal fatty acid soaps and
adapted for use in saline and hard waters which
comprises heating an aliphatic polyhydroxy al
cohol and a neutral alkali metal salt of a lower
alkyl amino polyacetic acid, while in the liquid
phase and in the relative proportions within the
such are contemplated as may fall within the
range of approximately equal amounts up to a
large excess of either constituent over the other
constituent, for an extended time interval with
in the range 115-200“ C. until the major portion
terms “polyalcohoP’ and “amino polyacetic acid"
reaction therebetween completed.
Various modi?cations, adaptations and depar
tures .will occur'to those skilled in the art from
the invention as hereinabove disclosed, and all
scope of the following claims. In the claims the 70 of the water present has been evaporated and the
are to be construed in accordance with the deli
nitinn of these termsrgiven above.
What I claim is:
~
Y
'
11. The method of forming a detergent com
position which is soluble in water and miscible in
. alkali metal fatty acid soaps and adapted for use
1. A product or manufacture consisting of the 75 in saline and hard waters which comprises heat
2,412,945
ing an aqueous solution containing an aliphatic
polyhydroxy alcohol and a neutral alkali metal
salt of a lower alkyl amino polyacetic acid in
the relative proportions ranging from approxi
proximately equal amounts by weight, to the fatty
acid soap compounds to impart the desired strong
sudsing properties to the mixture in hard and in
hard saline waters.
15. A detergent composition of matter consist
mately equal amounts. up to a large excess of
either constituent over the other constituent, for
ing of a mixture of alkali metal fatty acid soap
an extended time interval at temperatures above
compounds and a reaction product between an
the boiling point or water but not over about 200°
aliphatic polyhydroxy alcohol and a neutral al
C. e?'ective to remove the major portion oi’ the
kali metal salt of a lower alkyl amino polyacetic
said water.
10 acid admixed in the relative proportions provid
12. The method of claim 11, wherein the heat
ing an excess of the hydroxyl groups in the al
ing is continued at a temperature in said range
and for a time interval required to obtain a sub
stantially anhydrous liquid phase reaction prod
uct.
13. A detergent composition of matter consist
ing of a mixture of alkali metal fatty acid soap
compounds and a reaction product between an
cohol over the alkali metal atoms of the said salt,
the amount of said reaction product being from
relatively small amounts up to approximately
equal amounts, by weight, to the fatty acid soap
compounds, said reaction product being that
formed vby the process of claim 10.
16. A detergent composition or matter consist
ing of a mixture of alkali metal fatty acid soap
aliphatic polyhydroxy alcohol and a neutral al
kali metal salt of a lower alkyl amino polyacetic 20 compounds and a reaction product between an
acid, the amount of said reaction product be
aliphatic polyhydroxy alcohol and a neutral alkali
ing from relatively small amounts up to approxi
metal salt of a lower alkyl amino polyacetic acid
mately equal amounts, by weight, to the fatty acid
admixed in the relative, proportions providing
soap compounds, said reaction product being that
an excess of alkali metal atoms in the salt over
formed by ‘the process of claim 10.
[6 GI the hydroxyl groups of the alcohol, the amount
14. A detergent composition of matter consist
of said reaction product being from relatively
ing of a mixture of alkali metal fatty acid soap
small amounts up to approximately equal
compounds and a reaction product between glyc
amounts, by weight, to the fatty acid soap com
erine and the tetrasodium salt of ethylene di
pounds, said reaction product being that formed
amine tetraacetic acid formed by the method of 30 by the process of claim 10.
claim 10, the amount of said reaction product
being from relatively small amounts up to ap
FREDERICK C. BERSWORTH. ‘
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