ESTER-AMIDES DE TYPE SULFOSUCCINATE

SULFOSUCCINATE ESTER-AMIDES

Abrégé anglais

SULFOSUCCINATE ESTER-AMIDES
Abstract of the Disclosure
Sulfosuccinate ester-amides in which one carboxyl
group of the sulfosuccinate is amidified with an aliphatic
non-tertiary amine, for instance, a C8-C12 aliphatic amine such
as octyl or dodecyl amine, and in which the other carboxyl group
of the sulfosuccinate is esterified by reaction with an .alpha. -mono-
epoxide such as propylene oxide, or higher .alpha. -monoepoxides, and
method of preparation of such sulfosuccinate ester-amides.
The said sulfosuccinate ester-amides have utility as surfactants,
such as detergents and emulsifiers.

Revendications

-16
We claim:
1. A sulfosuccinate surfactant according to the formula
<IMG>
where R-NX- is the radical of a C2-C20 aliphatic non-tertiary
monoamine in which X is hydrogen or lower alkyl; and R1O- is the
radical of an .alpha.-epoxide containing from 3 to 20 carbon atoms;
with the proviso that the sum of the number of carbon atoms in
R-NX- and R1 is from 7 to 35 and that there is a difference in
the number of carbon atoms in R-NX- and R1 which difference is
at least 2; and M is a cation selected from the group of alkali
metals, alkaline earth metals and organic substituted ammonium.
2. A surfactant according to claim 1, in which the
difference in the number of carbon atoms between R-NX- and R1
is from 4 to 14.
3. A surfactant according to claim 1, in which R is
alkyl containing from 8 to 15 carbon atoms, X is hydrogen, and
R1 contains 3 carbon atoms.
4. A surfactant according to claim 3, in which R is
a straight chain.
5. A surfactant according to claim 1, in which R
contains from 3 to 18 carbon atoms and is a branch chain.
- 16 -

6. A method of preparing certain sulfosuccinate ester-
amide surfactants which comprises
(a) reacting maleic anhydride with
(b) an aliphatic non-tertiary monoamine having the
formula R-NHX and in which R-NH- is the radical of a
C2-C20 aliphatic non-tertiary monoamine and X is hydrogen
or lower alkyl, in proportion to produce predominately
the monoamide of said monoamine,
(c) reacting said monoamide with an .alpha. -epoxide
having an R1O- radical containing from 3 to 20 carbon
atoms to produce the ester-amide, and
(d) then reacting said ester-amide with an aqueous
solution of a bisulfite to convert said ester-amide to
a sulfosuccinate ester-amide surfactant.
7. The method of claim 6 in which the difference in the
number of carbon atoms between R-NHX- and R1 is from 4 to 14.
8. The method of claim 6 in which R is alkyl containing
from 8 to 15 carbon atoms, X is hydrogen and R1 contains 3 carbon
atoms.
9. The method of claim 8 in which R is a straight chain.
10. The method of claim 8 in which R is a branch chain.
17

Description

O~r invention relates to the preparation of certain
types of novel sulfosuccinate ester-amides at least most of which
can be represented by the following formula:
R-~X-C-CH CH -C-O-~RlO~H (I)
~ 1 2 "
0 S03M 0
where R-~X is the radical of a C -C20, preferably a C3-C18,
aliphatic non-tertiary monoamine in which X is hydrogen or lower
(C -C ) alkyl; and R10- is the radical of an o~-monoepoxide
(hereafter called ~ -epoxide) containing from 3 to 20 carbon
atoms; with the proviso that the sum of the number of carbon
atoms in R-NX- and Rl is from 7 to 35 and that there is a
difference in the number of carbon atoms in R-~X- and Rl which
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1068Z93
difference is at least 2 and, better still, at least 4: and M
is a cation selected from the group of alkali metals (including
ammonium), alkaline earth metals, and organic substituted ammonium -
or amines. Most desirably, the difference in the number of
carbon atoms between R-~X- and Rl is from 4 to 14. Again,
generally speaking, the preferred novel compounds of our present
invention are those wherein, in the aforesaid formula, R is alkyl
containing from 8 to 15 carbon atoms, X is hydrogen, and R
contains 3 carbon atoms; and those wherein, in the aforesaid
formula, R is alkyl containing from 3 to 5 carbon atoms, X is
hydrogen and Rl contains from 8 to 12 carbon atoms.
~'
It is particularly desirable that the novel sulfosucci-
nate ester-amide compounds of our present invention be marketed
and used in the form of the aforementioned types of salts, that
is, where M in formula (I) is an alkali metal (which term is here
used to mean sodium, potassium, lithium and ammonium), or alkaline
earth metals, namely, calcium, magnesium, strontium and barium;
or, as noted above, organic substituted ammonium or amines.
These latter, which most advantageously are water-soluble lower
molecular weight amines, may be seIected from a wide group,
typical examples of which are dimethylamine; diethylamine; trieth-
ylamine; propylamine; monoisopropylamine, diisopropylamine,
.fi ~ ' .
triisopropylamine, and commercial mixtures of said isopropyl-
amines; butyl amine, amyl amine; monoisopropanolamine, diisopro-
panolamine, triisopropanolamine and commercial mixtures of said
-'1 `
isopropanolamines; ethanolamines such as monoethanolamine,
diethanolamine, triethanolamine, and commercial mixtures thereof;
. ~ .
il - 2 -
. .

~068293
-3
polyamines such as aminoethyl ethanolamine, ethylenediamine,
diethylenetriamine, hydroxyethyl ethylènediamine, and hexamethyl-
enediamine; hexylamine; cyclohexylamine; dimethylbenzylamine,
benzylamine; morpholine; etc. Such salts can be prepared from
sodium or potassium salts of the novel sulfosuccinate ester-
amide compounds of our present invention by known metathesis
techniques.
The aforesaid sulfosuccinate ester-amides are character-~ -
ized by the fact that there is present in the molecules thereof,
connected through an ester linkage to one of the carboxyl groups
~, of maleic anhydride, a free hydroxyl group in the ~-position
3~ resulting from the utilization of an ~ -epoxide containing at
least 3 carbon atoms in the production of the compounds of our
invention, and an amide linkage connected through the other one
of the carboxyl groups of the maleic anhydride, all as is here-
after described in detail and illustrated by the various disclosed,~,
embodiments of our invention. The special combination of radicals
in the compounds of our invention results in particular properties
which effectively adapt various of the compounds to highly
effective utilities in various environments.
In certain cases, the radical R-NX- in formula (I) will
be derived from a long chain, for instance a C8-C20, aliphatic
: ~ ~
~ ~ prLm,ary monoam,ine, and the radical R10- in said formula (I) will
, ~
~ 3 ~
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1068Z93 4
be derived from an cC -epoxide such as propylene oxide or butylene
oxide, particular propylene oxide. However, compounds according
to and within the scope of our invention are also obtained where
the R-NX- radical of said formula (I) is derived from a C -C5
aliphatic non-tertiary amine such as ethyl amine, n-propyl amine,
isopropyl amine, n-butyl amine, isobutyl amine, n-pentyl amine
and isopentyl amine, and the Rl-0- radical is derived from a
C3-C20, particularly a C8-C20,a~-epoxide such as octylene oxide
or dodecylene oxide or styrene oxide.
~ The aforesaid compounds are useful in various fields
- where surfactant or wetting-out properties are a desideratum such
as, for instance, detergents, emulsifiers, penetrating agents,
stabilizing agents, dispersants, emollients, and the like.
Cert~in sulfosuccinate esters and certain sulfosuccinate
amides are known to the art, being disclosed, for instance, in
U.S. Patents Nos. 2,028,091; 2,252,401; 2,316,234; 2,507,030;
2,887,504; 2,976,208; 2,976,20g; 2,976,211; 3,002,994; 3,080,280;
3,123,640; 3,123,641; 3,141,905; 3,155,591; 3,404,164; 3,481,973;
French Patent of Addition No. 69,516: and C. R. Caryl, Ind. Eng.
Chem., 33,731-7 (1941). However, so far as we are aware, there
has been no prior suggestion or disclosure of any of the compounds
of our-invention.
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~068293
In the preparation of various of the novel compounds
of our invention, maleic anhydride is initially reacted with an
aliphatic (which term includes cycloaliphatic) primary monoamine
in proportions such as to produce predominately the maleic acid
monoamide, generally speaking, a mole ratio of 1 to about 1.2
moles of maleic anhydride to 1 mole of the long chain aliphatic
; primary amine, namely, a reaction product which contains upwards
of 90 or 95% of the monoamide. It is generally unnecessary to
purify the reaction product to separate the monoamide but this
can be done, if desired, by conventional purification techniques.
In one procedure for the production of the monoamide,
~ ~ particularly where the aliphatic non-tertiary amine reactant with
;',
;"~r' the maleic anhydride is an aliphatic non-tertiary amine, such as,
, for instance, long chain aliphatic primary amines, said primary
~X;
amines are initially admixed with the maleic anhydride and reacted,
~ for instance, at about 70 to about 100C, until the acid number
."~
reaches or approximates that of the desired monoamide. To said
monoamide is then added the selected ~-epoxide in amounts to drive
the desired esterification reaction to completion which, in the
usual cases, involves the employment of about 0.2 to 0.3 moles ex-
cess to effect completion of the reaction in a reasonable length of
~Y.:~ ~
time. To the resulting ester-amide there is then added slightly
~-~, more than 1 mole of the bisulfite per mole of maleic anhydride used
;~ and the resulting mixture is heated until the reaction is complete.
i
.

- 1068293
It should be noted that, in the preparation of the novel compound~
of our present invention, whether by the preferred procedure
described in this paragraph or otherwise in accordance with our
invention, it is essential that maleic anhydride be utilized.
The preparation of the intermediate amides, to wit,
the ~-alkylmaleamic acid, by reaction of the aliphatic non-tertiary
monoamines with maleic anhydride is, per se, well known to the
art and no novelty is claimed therein. Various methods are f
known to the art and it is convenient, if desired, to utilize
procedures such as are disclosed by Mehta et al, J. Org. Chem. -
f25f,1012 (1960), utilizing an organic solvent reaction medium,
such as anhydrous diethylether.
,', .
, In the preparation of those of the compounds of our
i~'f,~ invention which are in the form of amine salts, it is sometimes
fif desirable to produce such in substantially anhydrous form, soluble
in organic solvents, particularly polar organic solvents such as
ethyl alcohol, propyl alcohol, isopropyl alcohol, methyl and `-
ethyl formamides, etc. To this end, for instance, the afore-
ff~ described intermediate ester-amides can be reacted with a solution
aontaining an organic amine, sufficient water to provide a reactiop
medium and containing dissolved sulfur dioxide to form a sulfite
of said organic amine, and a water-miscible alcohol, for instance,
methyl alcohol, ethyl alcohol, n-propanol or isopropyl alcohol,
whereby to produce a substantially anhydrous organic amine salt
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~068293 _7
of the said sulfosuccinic acid ester-amides. For best results,
in carrying out such reaction, for each mol of said intermediate
ester-amide, the solution reacted therewith should contain about
1 mole or slightly more of organic amine or amines, and about
1 mol of water containing about 1 mol of sulfur dioxide.
In the preparation of the novel compounds of our
invention by the foregoing method, it is important, in order to
obtain said compounds, that the sequence of steps noted above
be followed, that is, that the maleic acid monoamide of the
Cl-C20 aliphatic non-tertiary amine first be provided or prepared
after which the reaction with the ~ -epoxide is carried out,
followed by the reaction with the aqueous bisulfite to introduce
the sulfonic group into the molecule. Thus, for instance, if the
~ -epoxide is first reacted with the maleic anhydride and then
with (a) the C2-C20 aliphatic non-tertiary amine, followed by
the reaction with the aqueous bisulfite, or (b) the aqueous
bisulfite followed by the reaction with the C2-C20 aliphatic non-
tertiary amine, the products of or contemplated by the present
invention axe not obtained.
In the reaction of the monoamides with the o~-epoxides
containing at least 3 carbon atoms to produce the intermediate
ester-amides w~ich are then converted into the sulfosuccinate
ester-amides of our invention, said reaction is especially
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;

~ ~068Z93
--8
desirably carried out in the presence of a catalyst, particularly
a basic organic material such as, by way of example; tertiary
amines such as triethylamine and triisopropylamine; tris
dimethylamino methyl phenol; and quaternary ammonium salts such
as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide,
benzyl trimethyl ammonium hydroxide and benzyl triethyl ammonium
hydroxide. Inorganic basic catalysts such as sodium hydroxide
or potassium hydroxide can be used but are not preferred. The
catalysts can be used in variable proportions, generally in the
range of 0.1 to 2 or 3%, based on the weight of the monoamide,
depending generally on the basicity of the catalyst.
The radicals represented by R-NH- in formula (I) or
in the formula R-NX can be straight chain or branch chain and
include, by way of illustration, radicals derived from such
non-tertiary amines as ethyl amine, n-propyl amine, isopropyl
amine, n-butyl amine, isobutyl amine, cyclopropyl amine, cyclo-
butyl amine, cyclopentyl amine, cyclohexyl amine, n-amyl amine,
isoamyl amine, n-hexyl amine, isohexyl amine, 2-ethyl hexyl amine,
r~ ~
~ 2-ethyl octyl amine, n-nonyl amine, isononyl amine, n-decyl amine,
~J~
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` ~o68293
isodecyl amine, undecyl amine, n-dodecyl amine, isododecyl amine,
tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl
amine, heptadecyl amine and octadecyl amine, and mixtures thereof
as in commercial mixtures of fatty and other non-tertiary amines.
The non-tertiary amines include the secondary amines corresponding ~
to the primary amines mentioned above, as, for example, di-n- ~:
propyl amine, di-n-butyl amine, etc.
The oC-epoxides which are utilized in the preparation
of the novel compounds of the present invention and from which
the radical Rl-O- of formula (I) is derived include, by way of
illustrative examples, propylene oxide; butylene, pentylene,
hexylene, heptylene, octylene, nonylene, decylene, dodecylene,
tetradecylene, pentadecylene, hexadecylene and octadecylene
oxides, as well as styrene oxide and similar oC-epoxides derived
from analogous alkenyl benzenes.
Illustrative examples of chemical compounds falling
~ ~ .
within the scope of our invention are the following:
(1) C H -~H-C-CH - CH -C-O-CH -CH-CH
12 25 2. 2 3
O S03~a o OH
;"s~
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~(~68293 -lo
(2) C12H25NH-C-CH CH2-C-O-CH2-cH-cH3
3 2 4 3 OH
(3) C14H29-NH-C-CH CH2-C--CH2-CH-CH3
3 4 OH
.
( ) 8 17 ~ I CH -C-O-CH -CH-CH
O SO K O OH
15 31 .. , CH -C-O-CH -CH-CH -CH
O S03Na O OH
,
(6) CH3-(CH2)10-CH-NH-C-CH~ CH2-C-O-CH2-cH-cH3
3 0 SO Na o OH
.,
:i
~A~ ~ ( ) 3 2 10 . " ' 2 " 2 , 3
C2H5 S03K OH
(8) Cl8H37-NH-c-cH CH -C-O-CH -CH -CH2-CH
O SO Na O OH
; (g) H2 H2
C C
H2C ~NH-C-CH - CH2-c-o-cH2-cH-cH3
:~ H H - S03H N(C2H4H)3 o OH
`"'
-- 1 0
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~o6~293 -11 -
.
16 33 " ,CH -C-o-cH2-cH-cH3 .,
O S03NH4O OH
12 25 - CH -C-O-CH2-CH-(CH2) -CH3
O 503Na OH
(12) C H -NH-C H -O-C-CH CH -C-O-CH -CH-CH
12 25 2 4 ll ' 2 ll 2 ' 3 :`
3 OH
( 14 29 " , CH-C-CH -CH-CH3
O SO H. H N-HC=(CH ~ O OH
: 3 2 3 2
":
' (14) C3 ~-NH-C-CH CH -C-O-CH -CH-(CH2) -CH3
~: O SO3Na O OH
~ :
,,
(15) C2H -NH-C-CH CH -C-O-CH -CH-(CH ) -CH3
~:-` O SO K O OH ~ "
..,; ,
(16) CU3 .CH-~H-C-CH CH -C-O-CH -CH-(CH j -CH
CH ~ " l 2 ll 2 ~ 2 10 3
3 O SO NH4 OH
12 25 " , CH -C-O-CH2-CH
O SO Na O OH
~ '`? ' ''
-- 1 1 --
: _ ..... , . ~ , , .

1068293
-12
.
The following examples are illustrative of the prepara-
tion of typical compounds of the present invention. All temp-
eratures recited are in degrees Centigrade.
EXAMPLE I:
To 98 g (1 mole) of molten maleic anhydride at 70
there is added 106 g (1.05 moles) of di-n-propyl amine over a
period of 1 hour, then stirring an additional 15 minutes at this
temperature. To the di n-propyl maleamide so formed there is
added 239 g of a Cll-C ~ -olefin epoxide (1.1 mole "Neodox 1114"-
Viking Chemical) over a period of 1 1/2 hours at 100-110, then
maintaining at this temperature for an additional 6 hours. At
the end of this period, the acid value is 0.027 meq/g. There is
., .
then added 327 g (1.1 mole) of 41% sodium bisulfite solution at
90. The reaction is very rapid and is complete within about
~,~
15 minutes. The product, a clear, dark amber viscous solution,
clearly soluble in water in all proportions with excellent foaming
and line soap dispersant properties, corresponds to the formula
'~l
~r
: ~
3 2 2 N-C-CH CH2-C-0-(R O)H
CH3-CH2-CH2 0 S0 Na 0
(where R10- is the radical of said ~ -olefin epoxide)
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. 1068293
EXAMPLE II:
To 139 g (0.5 mole) of ~-cocomaleamide, having an acid
valve of 3.6 meq/g, are added 0.3 g of tris dimethy~amino methyl
phenol, and then 50 g (0.86 mole) of propylene oxide are added
gradually over a period of about 3 hours while the reaction mixture
is heated at 100C, and the reaction mixture is maintained at
said temperature for an additional approximately 5 hours or until
an acid value is reached of about 0.13 meq/g. The resulting
` reaction product is stripped in vacuo, and to it are gradually
added, with stirring, 118 g of a 44% aqueous solution of sodium
bisulfite (0.5 mole) at 100C over a period of about 1 hour,
and stirring is continued for an additional 1/2 hour at a temp-
erature of about 100C. The final product is a clear, amber
liquid completely soluble in water, and corresponds to the formula
R-HN-C-CH CH2-c-o-cH2-cH-cH3
O SO3Na O OH
(where R-NH- is the radical of coco
fatty primary amines)
ll~ The product has moderate foaming properties; and it possesses
~ foam stabilizing properties for various surfactants such as
J ~ alkylaryl sulfonates such as dodecylbenzene sodium sulfonates and
dodecylbenzene triethanolamine sulfonates, and long chain aliphat~c
alcohol sulfates such as lauryl sodium sulfates and lauryl
~`'5.~ . triethanolamine sulfates.
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~068293 -14
EXAMP].E III:
The procedure described in Example I is carried out
except that, in place of the di-n-propyl amine, 91 g (about 1.05
moles) of n-amyl amine is used. The sulfosuccinate ester-amide
product obtained corresponds to the formula
C Hll--~H-C-CH CH2--C-O-(Rl())H `;'
(where R 0- is the radical of the said ~ -olefin epoxidel)
EXAMP~E IV:
The procedure described in Example II is carried out
except that, in place of the propylene oxide, 62 g (0.86 moles)
of butylene oxide is used. The sulfosuccinate ester-amide
product obtained corresponds to the formula
R-~H-C-CH- 2 ,C, O CH2-cH-cH2-cH
O S03Na O OH
EXAMPLE V:
The procedure described in Example II is carried out
except that, in place of the ~-cocomaleamide, there is used 114 g
(0.5 molel a monoamide of 2-ethylhexyl amine prepared by reacting
2-ethylhexyl amine with maleic anhydride. The sulfosuccinate
ester-amide product obtained corresponds to the formula
. i
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; , .

:1068293
-15
R-NH-C-CH- CH -C-O-CH -CH-CH
,l 2 " 2 3
O SO3Na O OH
(where R-NH is the radical of 2-e~hylhexy~ amine)
EXAMPLE VI:
To 400 ml of water are added 34 g of the sulfosuccinate
ester-amide surfactant prepared in Example II, 1.25 g of potassium
persulfate, 7 g of hydroxyethyl cellulose ("Cellosize WP-O9",
Union Carbide Corporation), and 1.3 g of sodium bicarbonate.
,, This solution is heated to 70 and to it is added at 70-75, in
' separate streams, over a period of 4 hours, 550 g of vinyl acetate
,,
'i and a solution of 1.25 g of sodium persulfate in 50 ml of water.
When the addition is complete, the temperature is raised to 90
~;, for 1~2 hour. The resulting vinyl acetate latex contains 55%
~ solids,and shows no separation after prolonged standing.
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