Note: Descriptions are shown in the official language in which they were submitted.
1040~49
Addition products of sulfites on maleic acid mono- and
diesters of long-chain fatty alcohols and their use as surface-active
agents are already known.
It has now been found that compounds of the formula I -
RO-CO-CH2-CH~S03M)-CO-OR' '
R stands for a group of the formula II
Rf-(CH2)m-(OCH2CH2)n
wherein Rf stands for a straight-chain perfluoroalkyl radical or a terminally
methyl-branched perfluoroalkyl radical, i.e. a perfluoroalkyl group -~
carrying a trifluoro methyl group in the penultimate position, each group
having 2 to 8 carbon atoms, m is a number of from 1 to 4 and n is a number ~ `
of from 0 to 3, M is a hydrogen or alkali metal atom or an ammonium group ~ -
of the formula -
x 4-x
ln which R" is an alkyl group of 1 to 4 carbon atoms which is unsubstituted
or substituted by hydroxy, carboxy or sulfo, x is an integer of zero to 4,
and R' has the meaning of R or M, are obtained when maleic acid anhydride is
reacted with one or two mol equivalents of an alcohol of the formula II
ROH
in which R is as defined above, wherein in the reaction with 2 mols of
~cohol an acidic esterification catalyst is added,and to the maleic acid
ester thus obtained a--water-soluble sulfite is added in an aqueous medium in
the presence of a solubilizer, and optionally subsequently the cation M is -~
exchanged partly or completely.
The alcohols of the formula ROH are known (United States Patent
Specifications Nos. 2,666,797 and 3,171,861, German Offenlegungsschriften
Nos.2,028,459 and 1,468,253) and can be prepared easily. Alcohols of the
formula III having 1, 2 or 4 methylene groups (m = 1,2 or 4) are preferred,
since they are obtained in an industrial scale from perfluorocarboxylic acids
and the derivatives thereof by hydrogenation (m = 1) or from perfluoro-
i ~ ,' :'
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,.... ~
-. : . ~, : , . . . .
', . '` . .' '. ' ' ',' . ' :
:, . . .
- '
104~)649
alkyl iodides by reacting with 1 or 2 mols of ethylene and saponification of
the iodide thus obtained (m = 2 or 4). In the latter case the mixtures
obtained in the industrial process may be used directly, as well as, of
course, mixtures with other alcohols of the mentioned type (thus, m may be
a fraction).
In the case of the straight-chain compounds the perfluoroalkyl
radical of the alcohols ROH con~ains 2 to 8, preferably 4 to 6 carbon atoms
and in the case of the branched radicals, 3 to 8, preferably 5 to 7 carbon
atoms. Since the starting materials are often obtained by telomerization of
tetrafluoroethylene on to lower perfluoroalkyl iodides mixtures of such com-
pounds are especially interesting, that means the number of the carbon atoms
is not necessarily an integer.
By known oxethylation methods the corresponding oxethylates
(n = 1 to 3) are prepared from the starting materials having n = O. It is
known that the oxethylation products generally are mixtures having a different
content of oxethyl groups (i.e. n is an average value which represents i-a-
a fraction). These mixtures may be separated by distillation or chromato-
graphy; in general the mixtures are used directly since ~hey have the same
activity.
Alcohols to be reacted according to the invention of the formula ~ -~
III are for example
C2F5_CH2_CH2_0H :.
1CF3)2CF~CH2~CH2~-CH2~CH2~H
3 ( 2)3 2
CF3-(CF2?4~H2-(O-cH2 CH2)2'
( 3~2CF CF2-CF2-CH2-CH2-(OCH2CH2)3-OH ''
CF _(CF2) _(CH2~ ~H
3 5 3
3 ( 2)6 ( 2~4
(CF3~2CF(CF2~5_CH2_(0 CH2CH2)2
-- 2 --
CF3(CF2)7-(CH2~2 1040649
The alcohols of the formula III are reacted in known manner
(Houben-Weyl, Methoden der organischen Chemie, 3rd edition, volume 9, page - -
383 (1955) and K. Lindner~ Tenside, Hilfsmittel Waschrohstoffe; Wissen-
schaftliche Verlag~gesellschaft, Stuttgart 1965, page 747~ with 1 mol of
maleic acid anhydride to give the maleic acid monoester (maleic acid -
semiester) or with half a mol of maleic acid anhydride in the presence of an
acidic esterification catalyst to give the maleic acid diester. As acid
esterification catalysts may be used for example borontrifluoride or mineral
lo acids such as phosphoric acid, perchloric acid or preferably sulfuric acid.
The maleic esters thus obtained in a high purity of more than 97% -
and in a pratically quantitative yield, are reacted with water-soluble
sulfites in~an aqueous medium, with the aid of a solubilizer. As solubilizer
are suitable water-soluble polar organic solvents, such as lower alcohols,
for example methanol~ ethanol, isopropanol; lower ketones, such as acetione;
ethers, such as tetrahydrofuran or dioxan etc. Water-soluble eulfites are
above all aIkalimetal and ammonium sulfites and the corresponding hydrogen
sulfites or disulfites- The easiest way is to react the semiesters with
sulfites and the diesters with disulfites, according to the following ~, `
! 20 equations:
ROOC-CH=~H~COOH + M2S03 ~ ROOC-CH2-CH-COOM
' 3
2 ROOC-CH¢ H-COOR ~ M2S205 + H20 2 ROOC CH2 IH
S03M
The cation M may be exchanged partly or completely by another
; cation by preparing from the s-~ats obtained the free acids with mineral acid
and by isolating them, if desired, and converting them, if des red, with
bases into other salts. Suitable bases are above all amines which carry
lower aIkyl groups, which may be substituted by solubilizing groups such as
.
. ~.
104~649
hydroxy, carboxy and sulfo groups. Such amines are especially mono-, di-and
triethanol amine, glycine, taurine and N-methyltaurine. Salts such as amines
are especially suitable for preparing high-percentage solutions of the
products of the invention.
Depending on the length of the fluoroalkyl chain, on the ethylene
oxide content and on the type of the ester the products of the invention are
obtained as highly viscous, colorless to slightly yellow masses or as white
powders.
The products of the invention are soluble in water and have the
property of strongly reducing the surface tension of water even in the case
of low initial concentrations (Table 1). The very low surface tension values,
combined with excellent wetting properties, open a large field of application
to the compounds of the invention. Thus, these compounds are excellent
wetting agents for fibre materials, which is particularly important in dyeing
processes, textile finishing processes, purification and washing processes.
~ .
Further possibilities for the technical application of the com-
pounds of the invention are their addition as levelling agents to dispersions
and their addition in order to increase the wetting properties of other
wetting agents, for example in the wetting of powdery materials such as
silica, chaIk and spray powders.
- Furthermore the compounds of the invention are characterized by
their excellent levelling capacity in the case of self gloss emulsions which
may b0 used for example for the polish of the floor. The addit1on of these
surface-active compounds brings about an exoellent distribution of wax
emulsions on very different su~faces, for example floor coverings, whereby,
when drying, the formation of undesired stains and rims is reduced or com-
pletely avoided. ~ -
The novel compounds are obtained as solutions. These solutions
may be incorporated as such into wa emulsions or the compounds are obtained
::
~, .. .
104~ 49
free from solvents by spray drying or evaporating. By extraction with ether
they may be freed, if desired, from small amounts of maleic ester or
fluoroalcohol.
It is significant that also the novel compounds ha~ing a short-
chain perfluoroaIkyl radical are surface-active. Thus, if starting materials
from a telomerization reaction are used, it is not necessary to separate the
compounds having short-chain radicals, since the corresponding products of
the invention do not represent a 'iballast" which would be inacceptably
expensive in the present case. m us, the compounds of the invention are
additionally superior to other fluo~oalkyl surfactants with regard to the
working up of the starting materials which is not necessary or easier.
The following ~xamples illustrate the invention. Percentages and
parts are by weight unless speclfied otherwise, the ratio of parts by welght
to parts by volume being that of the kilogram to the litre. -
E X A M P L E 1:
19.5 g of 1.1.2.2-tetrahydroperfluoro-butanol (=119nmol9)~ 5.8 g
of maleic acid anhydride (=59.2 mmols) and 0~1 g of concentrated sulfuric
acid (=o.5% calculated on fluoroalcoholl)were introduced into a 100 ml flask -
and stirred for 16 hours under inert gas (nitrogen) at 140 C, while 0.5 ml
of water (=28 mmols) was distilled off. The maleic acid diester was distilled
at 0.2 torr/40 C - 188C.
In a 250 ml flask 5.6 g of sodium disulfite (=29.5 mmols), 80 ml
.
of water and 40 ml of isopropanol were added to the distillate (24.3 g = 59.3
mmols) and refluxed for 16 hours at 80C until a clear solution resulted from
the two phases. Subsequently the solventwas evaporated in the vacuum drying
cabinet at 50 C/ 12 to~r. 23 g of a white product having a m~lting point of
269 C (decomposition) were obtained. The yield was 95.4%.
E X A M P_L E 2:
50 g of 1.1.2.2-tetrahydroperfluoro-hexanol (=189 mmols) and 18.6
- 5 -
, . ~ ~ ' : . '
~040649
g of maleic acid anhydride (=190 mmols) were introduced into a 100 ml flask
and stirred for 20 hours at 140C. The acid number of the monoester was
determined: AN = 149 (calculated = 155). The monoester was filled into a
250 ml flask and 23.9 g of sodium sulfite (=lgo mmols)~ 100 ml of water and
50 ml of isopropanol were added and the whole was refluxed for 8 hours at
80 C. It was boiled until a clear solution resulted from the two phases.
Then the solvent was removed. 91 g of a yellow product in the form of a
; paste were obtained which had the following elementary analysis:
Found: Calc:
C: 24.8% 24.6%
H: 1-4% 1-4%
The yield was 98.5%.
E~X A M P L E 3:
171 g of 1.1.2.2-tetrahydroperfluorohexyl-glycol ether (=555 mmols)
and 54.7 g of maleic acid anhydride (=555 mmols~ were introduced into a 500
ml flask and stirred for 16 hours at 140 C. The acid number of the ester was
determined: AN = 137 (calculated 135). The monoester was filled into a 1
liter flask, and 70.5 g of sodium sulfite (=555 m~ols), 400 ml of water and
200 ml of isopropanol were added and the mixture was refluxed until a clear
solution resulted from the two phases. The solvent was removed. The yield
wa~ 280 g (=94% of the theory).
In the same manner 20 g of 1,1,2,2-tetrabydroperfluorohexyl-
triglycol ether (=50 mmols) and 5 g (=50 mmols) of maleic acid anhydride were
reacted. After refluxing with sodium sulfite solution (6.5 g = 50 mmols) and
removing the solvent, 26 g (--80% of the theory) of a slightly yellow-colored
paste were obtained.
X A ~I P L E 4:
600 g of 1.1.2.2-tetrahydroperfluoro-hexanol (=2.27 m~ols), 115.5 g
of maleic acid anhydride (=1.14 mols) and 1.2 g of concentrated sulfuric acid -
-- 6 --
1040649
(=0.2% calculated on fluoroalcohol) were introduced into a 500 ml flask and
stirred for 24 hours under inert gas (nitrogen~ at 140C, while 15 ml of
water (=834 mmols3 were distilled off. After cooling the acid number was
determined (AN = 5). 107.8 g of sodium disulfite (=567 mmols), 1.0 liter
of water and 500 ml of isopropanol were add~d to the maleic acid diester and
the mixture was refluxed for 24 hours at 80C until a clèar solution result-
ed from the two layers.
Subsequently the solvent was removed. The yellowish solid sub-
stance obtained was extracted with diethyl ether. 600 g of the extraction
residue were obtained with the following elementary analysis:
Found: Calculated:
C: 26.8% 27.0%
H: 1.9% 1-55%
7 Melting ppint: 244 c (decomposition)
The yield was 75%.
_ X AMM P L E 5:
100 g of 1,1,2,2-tetrahydroperfluorohexyl-glycol ether (=308 mmols),
15.9 g of maleic acid anhydride (=162 mmols) and 0.2 g of concentrated
sulfuric acid (=0.2% calculated on fluoroalcohol) were introduced into a ~;
250 ml flask and stirred for 24 hours under iner* gas (nitrogen3 at 140C,
, while 3 ml of water (=160 mmols) were distilled off. From time to time the
.~ .
acid number was determined~ After 8 hours the acid number was 33.4; after
16 hours 24.03, after 24 hours it was 10.0 and after 40 hours the acid number
was 4Ø
After cooling 15.4 g of sodium disulfite (=79 mmols)~ 300 ml of
water and 150 ml of isopropanol were added to the maleic acid diester and the
mixture was refluxed for 16 hours until a clear solution resulted from the
3 two phases. Then the solvent was removed in the vacuum drying cabinet at
50 C/ 12 torr. 114 g (~ 89% of the theory) of a slightly yellow paste were
_ 7
~: . . . :
- . ,. . : , .. .
.
,
: 1040649
obtained.
In similar manner 100 g (=285 mmols) of 1~1,2,2-tetrahydroper-
fluorohexyl-diglycol ether and 61 g (=155 mmols) of 1,1,2,2-tetrahydroper-
; fluoroalkyl-triglycol ether were reacted with maleic acid anhydride and then
with sodium disulfite. 112 g (=89% of the theory) and 60 g (=80~ of the
theory), respectively, of slightly yellow pastes were obtained.
E X A M P L E 6:
50 g of 1.1.2.2-tetrahydroperfluoro-octanol (=137 mmols) and 13.5
g of maleic acid anhydride (=137 mmols) were introduced into a 250 ml flask -
and stirred for 16 hours at 140 C. The acid number of the ester was
determined: AN = 110.2 (calc. 121). 17.3 g of sodium sulfite (=137 mmols),
100 ml of water and 50 ml of isopropanol were added to the ester, the mixture
was refluxed for 16 hours until a clear solution was obtained and then the
solvent was removed. 77 g of a white product (=95.5% of the theory) were ~ ~
obtained with the following elementary analysis: -
; Found: Calculated:
C: 23.4% 24.5%
H: 1.7% 1.2%
E X A M P L E 7:
40 g of 1.1.2.2-tetrahydroperfluoro-diglycol ether (=~8.4 mmols)
and 8-7 g of maleic acid anhydride (=88-4 mmols~ were introduced into a 250
ml flask and stirred for 24 hours at 140 C. The ester was introduced into a
500 ml flask and m;Yed with 11.2 g of sodium sulfite (=88.6 mm~ls), 200 ml
o~ water and 100 ml of isopropanol and refluxed for 24 hours at 80 C, until
a clear solution was obtàined from the two phases. The solvent was removed.
;~ 56 g of the product (=93.5% of the theory) were obtained.
E X ~i~ P L E 8:
600 g of 1.1.2.2-tetrahydroperfluoro-octanol (=1.65 mols), 80.8 g
of maleic acid anhydride (=o.8 mol) and 1.0 g of concentrated sulfuric acid
- 8 -
. : - . : ~ . . , , . -
:. , . : : .
1040649
(=0-2% calculated on fluoro-alcohol) were introduced into a 500 ml flask and
stirred for 16 hours under inert gas (nitrogen) at 140C, whereby 14 ml of
water (=o.8 mol) were distilled off. The acid number of the ester was
determined: AN = 5.5; 65.7 g of sodium disulfite (345 mmols), 1.0 1 of water
and 0.5 1 of isopropanol were added to the Daleic acid d}ester and refluxed
for 20 hours at 80 C, until a clear solution resulted from the two phases;
then the solvent was evaporated. 628 g (=86% of the theory) of the product
were obtained with the following elementary analysis:
Found: Calculated~
C: 26.8% 26.3%
H: 1.4% 1.2%
Melting point: 252 C.
E X A M P L E ~:
66.5 g of 1.1.2.2-tetrahydroperfluorooctyl-diglycol ether (=147
mmols), 7.2 g of maleic acid anhydride (=73.5 mmols) and 0.1 g of concentrat-
ed sulfuric acid (=0.2% calculated on fluoro-alcohol) were introduced into a
250 ml flask and stirred for 20 hours under inert gas (nitrogen) at 140 C;
thereby 1 ml of water (=55 mmols) were distilled off. The acid number of the
ester was determined: AN = 6.5. 7~1 g of sodium disulfite (=37.5 mmols),
` 20 150 ml of water and 75 ml of isopropanol were added to the maleic acid diester
and the mixture was refluxed for 14 hours at 80 & until a clear so}ution
resulted from the two phases- Then the solvent was remo~ed. 72 g of the
product (=90.5% of the theory) were obtained.
E X A M P L E 10:
200 g of 1.1.2.2-tetrahydroperfluoro-decanol (=431 mmols) and 42.6
g of maleic acid anhydride (=434 mmols) were introduced into a 500 ml flask
and stirred for 20 hours at 140 C. The acid number of the ester was
determined: AN = 83.8 (calculated: 100). 55.2 g of sodium sulfite (438
mmols), 400 ml of water and 200 ml of isopropanol were added to the reaction
_ 9 _
'
.. . . . .
.
~04V649 ~
product, the whole was refluxed until a clear solution was obtained. The
solvent was removed. 257 g of the product ~=86.5% of the theory~ were
obtained.
Melting point: > 300 C.
X A M P L E 11:
100 g of 1.1.2.2-tetrahydroperfluoro-decanol (=216 mmols), 10.6 g
of maleic acid anhydride (=108 mmols) and 0.2 g of concentrated sulfuric acid
(=0.2% calculated on fluoroalcohol) were introduced into a 250 ml flask and
stirred for 24 hours under inert gas and at 140C; 1 ml ( =55 mmols) of water
was distilled off. The acid number of the ester was determined (AN = 7.0).
10.3 g of sodium disulfite (=54.2 mmols), 300 ml of water and 150 ml of -
isopropanol were added to the maleic acid diester, and the mixture was
refluxed for 24 hours at 80 C until a clear solution was obtained from the ~ -
two phases. Then the water/isopropanol mixture was removed. 106 g of the
product (=89% of the theory~ were obtained.
Melting point: 186 C.
E X A M P L E 12:
1304 g of 1.1.2.2-tetrahydroperfluoro-octanol (=3.6 mols), 326 g
of 1.1.2.2-tetrahydroperfluoro-hexanol (=1.3 mols) and 461.7 g of maleic
acid anhydride (=4.7 mols) were introduced into a 2 1 flask and stirred for
22 hours at 140C. The acid number of the ester was determined: AN = 139
(calculated 127). 594 g of sodium sulfite (4.7 mols), 2.2 1 of water and
1.1 1 of isopropanol were added to the ester and the mixture was refluxed
for 16 hours at 80 C until a clear solution resulted. The solvent was
' removed. 1954 g of the product (=73% of the theory) were obtained.
E X A M P L ~ 13:
1600 g of 1.1.2.2-tetrahydroperfluoro-octanol ~=4.4 mols), 400 g
of 1.1.2.2-tetrahydroperfluoro-octanol ~=1.5 mols), 284 g of maleic acid
anhydride (2.9 mols) and 4.5 g of concentrated sulfuric acid (0.2% calculated
,
-- lo --
..
. . .
1040649
on fluoro-alcohol) were introduced into a 2 1 flask and stirred for 22 hours
under inert gas (nitrogen) at 140C, while 34 ml of water (=1.9 mols) were
distilled off (acid number 6.o). 275.3 g of sodium disulfite (=1.45 mols),
1.8 1 of water and 0.9 1 of isopropanol were added to the ester and refluxed
for 16 hours at 80 C until a clea. solution was obtained. The solvent was
removed. 2130 g of the produc* (=84.4% of the theory) were obtained.
E X A M P L E 14:
To a wax emulsion basic preparation consisting of a montan wax
having a dropping point of 83 to 89 C, an acid number of 85 to 95 and a
saponification number of 120 to 145 (15 parts), of diethanol amine (3.0 parts)
and water (82.0 parts), the substances to be examined were added in such
-~ amounts as to obtain a concentration of fluorine of 0.02 to 0.05~. The
surface tension values of these test emulsions were measured.
If 0.13 ml of the wax emulsions which contained 0.025 part of fluoro
surfactant was applied onto a purified polyvinylchloride (PVC) plate having
a size of 7 x 10 cm, the distribution and spreading capacity were the better,
and after drying the formation of stain~ and rims was the smaller (visual
estim~¢~dn~ the lower the surface tension value of the emulsions used was
(see Table 2).
E X A M P L E 15:
To a wax emulsion basic preparation consisting of a polyethylene
wax having a dropping point of 97 to 102C, an acid number of 14 to 18 and
a saponif1cation number of 20 to 35 (12 parts), of oleic acid (1.6 parts),
diethylamino ethanol (1.6 parts) and water (84.6 parts), the substances were
added in such amounts as to obtain a concentration of fluorine of 0.02 or
o.o5%. The surface tension values of these test emulsions were measured.
If 0.15 ml of the wax emulsions which contained 0.025 part of
fluoro-surfactant was applied onto a purified PVC plate having a size of
7 x 10 cm, the distribution and spreading capacity were the better~ and after
.
-- 11 --
.
:
- 1040649
drying the formation o stains and rims was the smaller (visual estimiati~n~
the lower the surface tension value of the emulsion used was (see Table 2).
E X A M P L F 16:
For the application of biocides, spray powders are used in practice.
These powders must have a good floating capacity in water with short wetting
time~s and low foam values. As dispersants are used commercial long-chain
alkylphenol-formaldehyde-condensation products. By addition of 0.15~ of the
substances according to the invention the wetting capacity of the powders is
considerably improved without the floating capacity (D) being reduced and the
foam values (S) being increased (Table 3).
In comparative tests the floating capacity was determined according
to the cyclinder method of Fischer (see "Handbuch der landwirtschaftlichen
Versuchs- und Untersuchungsmethodik~ (Methodenbuch~ Volume VII ~IDie
Untersuchungen von Pflanzenschutzmitteln" von W. Fischer (1941) page 53 and
~ page 12~ corresponding to the WHO method described in Specifications for
; Pesticides, 1967, pages 76, 77, 80 and 81 (Column D in Table)
The wetting capacity was determined as follows: A 500 ml beaker
(diameter of 8 cm) was filled with tap water of 20 C and 12 dH (German degree
of hardness), and one gram of the spray powder to be tested was sprayed onto
the surface. m e time required in order to wet the powder was measured and
indicatèd in seconds as wetting time (column N in Table~
The examination of the foaming capacity was carried out according
to J. Ross and G.D. Mlles (see Oil and Soap 18 (1941), 99): 4 grams per
liter of the spray powders to be tested were introduced into water. In e~ch
case the height of the foam after shaking was measured in cm in the beginning
and after a dwelling time of 5 minutes (column S in Table3.
For the comparative tests with the wetting agents and dispersants
to be tested the ollowing spray powder compositions were used.
.. ~
~ .
- 12 -
: . . . . . . . :, . , : .
~ ~, - ' - , : .. . .
1049649
A.50 Parts of ~-hexachloro-cyclohexane -:
47 Parts of siliceous chalk
2.85 Parts of dispersing agent (cresol - formaldehyde -
reaction product~ *
0.15 Parts of test product .
B.50 Parts of bis-(p-chlorophenyl)-trichloro-ethanol
10 Parts of silicic acid
36 Parts of siliceous chaIk
3.80 Parts of dispersing agent (see above)
0.20 Part. of test product
C.30 Parts of hexachloro-endomethylene-bicyclo-
heptene(oxymethylene-sulfite)
3 Parts of silica
64 Parts of siliceous chaIk
2.85 Parts of dispersing agent (see above~
0.15 Part of test product
D.50 Parts of trichloromethyl-thiophthalimide
47 Parts of siliceous chaIk
2.85 Parts of dispersing agent (see above) ~:
0.15 Part of test product
'
*~ according to German Offenlegungsschrift No. 1,945,100, ~xample 3
(consisting~ of 80% of the condensation product of 1 mol of cresol, 0.025
mol of nonyl phenol, 1.78 mols of formaldehyde and 0.75 mol of sodium
sulfite, residual 20~: sodium sulfate and water).
:
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