Note: Descriptions are shown in the official language in which they were submitted.
Our invention relates to the preparation of certain
types of novel unsymmetrical sulfosuccinate dlesters at least
most of which can be represented by the followinc, formula:
R--O--C--CH CH2--C-O--( R10) H ( I )
O SO 3M O
where R-O~ is the radical of a Cl-C20 aliphatic monohydric
alcohol, or of an ethoxylated or propoxylated alkyl phenol in
which there are not more than 2 nuclearly attached alkyl groups
each containing from 5 to 12 carbon atoms and in which the
number of ethoxy (-C2H40) or propoxy (-C3H60) groups is from
1 to 6; and R O- is the radical of an a-monoepoxide (hereafter
called ~-epoxide) radical containing from 3 ta 20 carbon atoms;
: . -- ]
`', .
.
:`
' .
.
:~ ; ,
. ~ -2
106~092
with the proviso that the sum of the number of carbon atoms in
R and Rl is from 7 to 35 and that there is a difference in the
number of carbon atoms in R and Rl which difference is at leàst
2; and M is a cation selected from the group of alkali metals
(including ammonium), alkaline earth metals, and organic sub-
:i stituted ammonium or amines. Most desirably, the difference
in the number of carbon atoms between R and Rl is from 4 to 14.
Again, most desirably, in the novel compounds of our present
invention, R is alkyl containing from 8 to 15 carbon atoms
and Rl contains 3 carbon atoms.
; ~ '
: It is particularly desirable that the novel sulfo-
:succinate compounds of our present invention be marketed and
used in the form of the aforementioned types of salts, that is,
where M in formula (l) 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
;1 or amines. These latter, which most advantageously are water-
1:
soluble lowerlmolecular weight amines, may be selected from a
wide:group~ typical examples of which are dimethylamine;
diethylamine; triethylamine; propylamine; monoisopropylamine,
diisopropylamine, triisopropylamine, and commercial mixtures
of said isopropylamines; butyl amine, amyl amine; monoisopro-
panolamine, diisopropanolamine, trLisopropanolamine and
` commercial mixtures of said isopropanolamines; ethanolamines
such as monoethanolamine, diethanolamine, triethanolamine,
and commercial mixtures thereof; polyamines such . . . . .
~::
- - 2 -
~ 3
~06709Z
as aminoethyl ethanolamine, ethylenediamine, diethylenetriamine,
hydroxyethyl ethylenediamine, and hexamethylenediamine; hexyl-
amine; cyclohexylamine; dimethylbenzylamine, benzylamine;
morpholine; etc. Such salts can be prepared from sodium or
potassium salts of the novel sulfosuccinate compounds of our
present invention by known metathesis techniques.
The aforesaid unsymmetrical sulfosuccinate diesters
are characterized by the fact that there is present in the
molecules thereof, connected through one ester linkage to one
of the carboxyl groups of maleic anhydride, a free hydroxyl
group in the ~-position resulting from the utilization of an
~-epoxide containing at least 3 carbon atoms in the production
of the compounds of our invention, all as is hereafter described
in detail and illustrated by the various disclosed embodiments
of our invention. The special combination of radicals in the
,
compounds of our inventions results in pàrticular properties
which effectively adapt various of the compounds to particularly
effective utilities in various environments.
In the usual case, the radical R-O- in formula (I) will
be derived from a long chain aliphatic monohydric alcohol, or an
ethoxylated or propoxylated alkyl phenol containing a nuclearly
attached alkyl group or groups each having a chain of from 5 to
12 carbon atoms, and the radical R10- in said formula (I) will
be derived from an~-epoxide such as propylene oxide or butylene
oxide, particular propylene oxide. However, as has been indicate
- 3 -
~ -4
~067092
,
compounds according to our invention are also obtained where
the R-O- radical of said formula (I) is derived from a Cl-C3
aliphatic monohydric alcohol such as methanol, ethanol or
propanols, and the R10- radical is derived from a C8-C12 or
C8-C20 a-epoxide such as octylene oxide or dodecylene oxide
or styrene oxide.
.~
Particularly preferred embodiments of the novel com-
pounds of our invention comprise unsymmetrical sulfosuccinate
diesters one carboxyl group of the sulfosuccinate of which is
esterified with a C8-C20 aliphatic monohydric alcohol, and the
other carboxyl group of the sulfosuccinate of which is reacted
with propy]ene oxide to form a propylene glycol ester group.
The aforesaid compounds are useful in various fields
~ where surfactant or wetting-out properties are a desideratum
I such as, for instance, detergents, emulsifiers, penetrating
agents, stabilizing agents, dispersants, emollients, and the like
Sulfosuccinate surfactants and, more specifically,
sulfosuccinate diesters, are known to the art, being disclosed,
for instance, in U. S. Patents Nos. 2,028,091; 2,507,030;
2,887,504; 3,002,994 and 3,481,973. However, so far as we are
, aware, there has been no prior suggestion or disclosure of any
of the compounds of our invention.
In the preparation of the novel compounds of our in-
vention, maleic anhydride is initially reacted with an aliphatic
(which term includes cycloaliphatic) monohydric alcohol, or
1067Q9Z -s
with an ethoxylated or propoxylated alkyl phenol, in proportions
such as to produce predominately the maleic'acid monoester.
Generally speaking, a mole ratio of 1 to about 1 2 moles of
maleic anhydride to 1 mole of the aliphatic monohydric alcohol
or of the alkyl phenol or of the ethoxylated or propoxylated
alkyl phenol results in the production of a'reaction product
which contains upwards of 90 or 95% of the monoester. It is
generally unnecessary to purify the reaction product to separate
the monoester but this can be done, if desired, by conventional
purification techniques.
. , .
¦ In a particularly preferred procedure for the production
~' of the monoester, particularly where the alcoholic reactant with
the maleic anhydride is an aliphatic monohydric alcohol, such
as, for instance, long chain aliphatic monohydric or fatty alco-
hols, said alcohols are initially admixed with a small proportion
~I commonly from about 0.05 to 0.5%, by weight of said alcohol, of
, an inorganic hydroxide or a basic catalyst, such as sodium hydrox-
,~
ide or potassium hydroxide in strong aqueous solution, and heated
to a somewhat elevated temperature, for'instance about 109-115C
under vacuum while purging with an inert gas, such as nitrogen,
, .
`
argon or helium, whe'reby to remove all or essentially all water
from the system, after which the vacuum is released and the
alcoholic reactant, at the selected temperature, is 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 monoester or half ester. To said monoester is
then added the selected ~-epoxide to drive the reaction to com-
'
_ 5
_
, ~6
~06709Z
pletion which, in the usual cases, involves the employment ofabout 0.2 to 0.3 moles excess to effect completion of the reaction
in a reasonable length of time. To the resulting unsymmetrical
diester there is then added slightly more than i mole of the
bisulfite per mole of maleic anhydride used and the resulting
mixture is heated until the reaction is complete. It should be
noted that, in the preparation of the novel compounds of our
present invention, whether by the preferred procedure described
in this paragraph or otherwise in accordance with our invention,
it i8 essential that maleic anhydride be utilized.
~ .
In the pr~paration of those of the compounds of our
invention which are in the form of amine salts, it is sometimes
desirable to produce such in substantially anhydrous form, soluble
I ~ in organic solvents, particularly polar organic solvents such
` as ethyl alcohol, propyl alcoholi isopropyl alcohol, methyl and
ethyl formamides, etc. To this end, for instance, the afore-
.;, , .
,I descrlbed diesters can be reacted with a soIution containing an
organic amine, sufficient water to provide a reaction 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 al~ohol,
whereby to produce a substantially anhydrous organic amine salt
of the said sulfosuccinic acid diesters. For best results, in
carrying out such reaction, for each mol of said diester, the
solution reacted therewith should contain about 1 mole or slightl~
more of organic amine or amines, and about 1 mol of water con-
taining about 1 mol of sulfur dioxide.
_ 6
~ 7
~Q67092
.
: . In the preparation of the novel compounds o our in-
vention by the foregoing method, is important, in order to obtain
:~ said compounds, that the sequence of steps noted above be followed
:~ that is, .that the maleic acid monoester of the Cl-C20 aliphatic
monohydric alcohol, or of the ethoxylated or propoxylated alkyl
1: :
~ phenol, 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 i~to the
molecule. Thus, for instance, if the ~-epoxide is first reacted
;with the maleic anhydride and then with (a) the Cl-C20 aliphatic
monohydric alcohol or ethoxylated or propoxylated alkyl phenol,
followed~by the reaction with the aqueous bisulfite, or (b) the
aqueous bisulfite followed by the reaction with the Cl-C
. ~ aliphatic monohydric alcohoil or the ethoxylated or propoxylated
" ~
; alkyl phenol, the.products of or contemplated by the present
; invention are not obtained.
In:the reaction of the monoesters with the ~-epoxides
containlng:at least 3 carbon atoms-to produce the intermediate
~ :diesters~ ich are then converted into the unsymmetrical sulfosuc-
!: : ~ .
~ : :cinate esters of our invention, said reaction is especially
'' 1 ' ~ ~ ' ~ ' '
désirably carried out in the presence of a catalyst, particularly
a basic inorganic or organic material such as, by way of example,
sodium hydroxide, potassium hydroxide, sodium carbonate, potas-
~ sium carbonate; tertiary amines such as triethylamine and tri-
;,il~ isopropylamine, and quaternary ammonium salts such as tetramethyl
:~i: ~ .~ ammonium hydroxide, tetraethyl ammonium hydroxide, benzyl tri-
:: .
-- 7
-- `
.. .
~0 6 7 0 9 2 -8
methyl ammoniurn hydroxide and benzyl triethyl ammonium hydroxide.
Such catalysts can be used in variable proportions, generally in
the range of 0.1 to 2 or 3%, based on the weight of the monoester,
depending generally on the basicity of the catalyst.
No novelty is claimed ln the monoesters of maleic an-
hydride with certain of the alcohols as such, namely with Cl-C10
aliphatic monohydric alcohols, since such compounds and various
procedures for their preparation are known to the prior art, and
the same is true with respect, per se, to certain of the reaction
products of such half esters or monoesters with ~-epoxides such
aæ ethylene oxide and propylene oxide.
,, .
The radicals represented by R-O-in formula (I) can be
derived from straight chain or branch chain aliphatic monohydric
alcohols ha~ing the formula RlOH where R10-is the radical of a
Cl-C20 aliphatic monohydric alcohol, or of an ethoxylated or
,
propoxylated phenol in which there are not more than 2 nuclearly
attached alkyl groups each contai~ing fro~ 5 to 12 carbon atoms
and in which the number of ethoxy (-C2H40) or propoxy (-C3H60)
groups is from 1 to 6.
The radicals represented by RO- in formula (I) or by
R 0- in the formula RlOH can be straight chain or branch chain
and include, by way of illustration, radicals derived from such
alcohols as methyl alcohol, ethyl alcohol, n-propyl alcohol,
isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohex-
anol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, isohexyl
_ _ . . _ . .... _ . _ .
- ~067Q92
alcohol, 2-ethyl hexyl alcohol, 2-ethyl octyl alcohol, n-nonyL
alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol,
undecyl alcohol, n-dodecyl alcohol, isododecyl alcohol, tridecyl
alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl al-
cohol, heptadecyl alcohol and octadecyl alcohol,-and mixtures
thereof as in commercial mixtures of fatty and other alcohols;
oxo alcohols such as the primary monohydric saturated aliphatic
C1o-C20 alcohols as, for instance, oxo tridecyl alaoho~ and oxo
hexadecyl alcohol (see U. S. Patent No. 2,965,678), and they can
be derived from grain sources, fatty triglycerides, and petroleum
sources including kerosene fractions and polymerized olefins such
as polypropylenes, for instance, propylene trimers and tetramers,
from oxo alcohol proaedures, and by Ziegler catalytic and other
chemical procedures. Also included in such aliphatic monohydric
alcohols are those derived by adducting 1 mole of such alcohols
as octyl, decyl and dodecyl alcohols, or analogous branched chain
alcohols, with 1 to 4 moles of ethylene oxide, or by adducting 1
mole of such alcohols as hexyl, octyl, decyl or dodecyl alcohols,
or analogous.branched chain alcohols, with from 1 to 4 moles of
propylene oxide.
Where R-O- ln formula (I)~ or R10- in the formula RlOH
is the radical of an ethoxylated or propoxylated alkyl phenol in
which there are not more than 2 alkyl groups each containing
from 5 to 12 carbon atoms, said alkyl phenol radicals can con-
veniently be represented by the formula
.
g _
1067Q92 -10
- (OR )yO~ (~II)
(R )n
where R2 and R3 are the same or dissimilar C5-C12 alkyl radicals,
R4 is a Cl-C3 alkyl radical, R5 is C2H4 or C3H6; each of w,m and
n is zero to 1, subject to the proviso that, when w is zero, m is
1 or 2; and y is 1 to 6.
Illustrative examples of such ethoxylated and propoxy-
,
lated alkyl phenols from which compounds of our invention can be
prepared are the adduct of 1 mole of octyl phenol with 2 moles
of ethylene oxide; the adduct of 1 mole of nonyl phenol with 3
moles of ethylene oxide; the adduct of 1 mole of nonyl phenol
with 1 mole of propylene oxide; th`e adduct of 1 mole of diamyl
phenol with 3 moles of ethylene oxide; the adduct of 1 mole of
dodecyl phenol with 2 moles of ethylene oxide; the adduct of
1 mole of dioctyl phenol with 2 moles of propylene oxide; the
adduct of 1 mole of dinonyl phenol with 3 moles of ethylene oxide;
the adduct of 1 mole of nonyl toluene with 2 moles of ethylene
oxide; the adduct of 1 mole of isopropyl nonyl phenol with 2 moles
ofethylene oxide; and the adduct of 1 mole of dinonyl isopropyl
phenol with 3 moles of ethylene oxide.
.~
The DC-epoxides which are utilized in the preparation of
the novel compounds of the present invention and from which the
radical R10- of formula (1) is derived include, by way of illus-
trative examples, propylene oxide; butylene, pentylene, hexylene,
heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene
-- 10 --
~)67092
pentadecylene, hexadecylene and octadecylene oxides, as well as
styrene oxide and similaro~-epoxides derived from analogous
alkenyl benzenes.
.
Illustrative examples of chemical compounds falling
within the scope of our invention are the following:
(I) C12H25--C-CH- CH2-C-O-cH2 !CH 3
O SO Na 0 OH
~ ' : ' ' ' ' ' '' '
15 31 1! I CH -C-O-CH -CH-CH
O S03K O OH.
;~ (3) CgH17--C-CH CH -C-O-CH2-CH-CH2-CH3
l ~ 3 OH
.'1, ' .
12 25 ll l 2 11 2 1 3,
O S03H-N(C2~40H)3 o OH
, ~, , ' ', .
(5) Cl4H29--l-fH~ _ CH -C-O-CH2-'CH-cH3 - .
O SO NH O OH
~. "
.
-- 11 --
``` -12
~067092
(6) Cl H -O-C~CH CH2-C-O-CH2-CH-(CH2)2-CH
0 S03Na O OH
,
(7) C12H25-0-C2H4-o-cj-fH - CH -C-O-CH -CH-CH
O S3Na OH-
- 12 25 1I f CH-C-CH2- IcH-cH3
3H.,H2N_HC=(CH3) o OH
14 29 (0c2H4)2-c2H4-o-c-cH CH2-C-O-CH -fH-CM3
. O SO Na O OH .
(10) C15H31 (OC2H4) -C2H4-0-C-fH CH2-C-O-CH2-CH-CH3
O S03Na 0 ON
(11) C8H17 (0C3H6) 3--cH2--fH--cH2--o--lcl--cH--cH2--c--o--cH2--cH--cH3
OH O so3Na O 0
(12) CH3-0-C-fH --CH2-C-O-CH -
-O SO Na O OH-
(13) C H -O-C-fH ¦I f
. O S03Na O 011
(14) C H -O-C-fH - CH -C-O-CII -CH-(CH ~ -CH
O S03Na O OH
~ -13
` ~ 1067~92
15) C12H2 ~ -O-C3H6-O-C-fH CH2-C-O-CH2-CH-CH3
O SO3Na O OH
16) CgHl ~ -O-C H -O-C-CH CH2-~-O-CH2-1CH-CH3
O SO3Na O OH
,
17) C12H2 ~ 2 4( 2 4)32 4 11 1
O S03N2
-; CH2-1CI-O-CH2-CH-CH3
;~ O OH
;~ ~
18) CgHl ~ -O-C H -O-f-fH CH2-~C-O-CH2-fH-CH3
-T-- O SO K O OH
~l 3
.~
The following examples are illustrative of the pre-
paration of typical compounds of the present invention. A11
temperatures recited are in degrees Centigrade.
EXAMPLE I:
(a) To 1242g (6.06 moles) of "NEODOL 25" (a commercial
product consisting mainly of a mixture C12-C15aliphatic mono-
hydric alcohols having an average molecular weight of about 205)
are added 1.4g of KOH in 3 ml of water, and the mixture is heated
o
to about 105 under a vacuum 25mm. of Hg while purging with
gaseous nitrogen, and then held at such temperature for about
1/2 hour. It is then cooled to about 75, the vacuum is released
and to it is added 600g (6.12 moles) of maleic anhydride, and
the reaction mixture is maintained at about 75 for approximately
* trade mark
- 13 -
-14
:1~67Q92
2 hours at the end of which time the acid value is 3.47 meq/g,
`~ indicating formation of the maleic acid monoester of said mix-
. . .
ture of alcohols.
(b) The monoester produced in part (a) hereof is
placed in an autoclave heated to 100 and to it is added 456 g
(7.85 moles) of propylene oxide over a period of 5 hours, at
the end~of which time the acid value is 0.001 meq/g. The
resulting di-ster contains, in the molecule, approximately
2-L.: 3~oxypropylene or~propoxy groups.
(c)~To~the dlester produced in part ~b) hereof there
18;addod~600 ml of~water and~1530 g of 42% aqueou,3 sodium
bifiulfate~solution ~`(6;.18~moles)~and heated to 90. An almost
immediate~exother~mLc reaction occurs~and the pressure in the
autoclave rise8 to of the~order of 5~to~10 pounds per square
inch. The reaction~is~complete in about 1/2 hour. A somewhat
vi8co~u,s;, light yellow~solution is obtained containing approx-
imately 0.5% free sodium~su}fite and 67%~solids. On the basis
of~the~ 801ids content~, the~sulfosuccinate surfactant produced
sh ~s tAe~following;~propeeties~
'Wëight '~In Water~Solution Draves Wetting Test
Slnk Time-Séc~,nds
0.168
0 335~ 12
e surface tension of a 0.05% water solution is
32.1 d nes/cm.~
~ 14 -
`'l :
~:
-15
1()6709?
EXAMPLE II:
A To SOOg (3.7 moles) of "ALFOL 610" (C6-C10 synthetic
alcohol, mean mol.wt. 136) is added lg of NaOH dissolved in 2ml
of water, and this mixture is heated to 85 in vacuo for 1/2
hour. To it is then added 361g (3.7 moles) of maleic anhydride
at 70 and the resulting reaction mixture is maintained at this
temperature for 1 hour. At the end of this period, the acid
; value is 4.25 meq/g. The resulting monoester is placed in a
stirred autoclave heated to 100 and to it is added 285g (4.9
: ,
moles~ of propylene oxide over a period of 2 hours at 3bpsi
- pressure, then stirred an additional 3 hours at this temperature.
At this point the pressure in the autoclave is about 10 pounds
1::: .
l ~ per square inch. The acid value of the diester, which contains,
i .
~ .
in tbe molecuie, approximately 1.3 propoxy groups, is 0.01
~ ~; meq/g. The said diester is stripped in vacuo at 9S-100 and
1 `: `,
to it~at this temperature is added 970 g.of a 40% aqueous sodium
bisulfite solution (3.7-moles) over a period of 1 hour, and to
thls solutLon is then added 345ml of 95 water. The final
sulfosuccina~te product is a mobile liquid at room temperature
which iS completely soluble in water.
EXAMPLE III:
To 316g ~2.02 moles) of the isopropyl alcohol monoester
o~ maleic anhydr:ide is added 0.5g of sodium methylate and 300g
(2.17 moles) of a technical yrade 1,2-octene oxide (M W. 136)
having an epoxide content of 7.25 meq/g. The reaction mixture
is heated to 100 for 10 hours, at the end of which period the
.i .
6rrk
.
-- 15 --
~~ . 1~7092 -16
acid value is 0.05 me~/g. The resulting diester lS stripped at
Looo and 0.1 mm pressure, and to it is added 550g. of a 42%
-aqueous sodium bisulfite solution (-2.22 moles) at 100. After
1 hour, the reaction is complete and an additional 500 parts of
95 water is added. The final sulfosuccinate productfiis a clear,
slightly amber, solution, which is completely miscib~e with
water.
. . . .
;1 EXAMPLE IV:
~I To 400ml of water are added 34g of the sulfosuccinate
surfactant prepared in Example II, 1.25g of potassium persulfate,
7g of hydroxyethyl cellulose ~"Cellosize~WP-09", Union Carbide
Corporation), and 1.3g 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, 550g of vinyl acetate and a solution
!
of 1.25g of sodium persulfate in 50ml 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
I andlshows no separation after standing for 6 months.
EXAMPLE V:
The sulfosuccinate surfactant product of Example III
is used in an emulsion polymerization process as described in
Example IV with similar results.
.J
EXAMPLE VI:
The procedure described in Example I is carried out
except that, in part (a), in place of the 1242g of "~EODOL 25,"
~r~ ?arks
.
- - 16 -
.
` 1067092
there is used 1664 g (6.06 moles) of an adduct of 1 mole of nonyl
phenol with 1.2 moles of ethylene oxide. The balance of Example
I is carried out using the same amounts of the specified in-
gredients. The sulfosuccinate product obtained corresponds
essentially to the formula ~;
A 9 19~--o--c H ~O--C-CH--CH2--C--O--CH2-CH--CH3
O S03Na O OH
EXAMPLE VII:
The procedure described in Example II is carried out
except that, in place of the 500 g of "ALFOL 610", there is used
,.
,~ 1133 g (3.7 moles) of an adduct of 1 mole of nonyl phenol with 2
moles of ethylene oxide. The sulfosuccinate product obtained
corresponds to the formula
CgHl~ 2 4 2H4 O oC Cl H CH2--CI--O--CH2-CH--CH,3
O SO3NaO OH
i EXAMPLE VIII:
j , .
The procedure described in Example II is carried out
except that, in place of the 500 g of "ALFOL 610", there is used
, 482 g (3.7 moles) of 2-ethyl hexanol. The sulfosuccinate product
' obtained, containing 69.6% solids, has a critical micelle con-
centration of 1. 2% which renders it especially desirable for use
in emulsion polymeriza~ion procedures such as are shown in
Example IV above.
~r~e~arks
.
- 17 -
.. , , . . .... , . , . , . _ ., ...... . _ _ .. , .. _ .. , . . , . . _, ... . .
