Vinyl polyether alcohols

Vinyl polyether alcohols of formula I ##STR1## (R=C.sub.1 -C.sub.25 -alkyl, C.sub.2 -C.sub.25 -alkenyl or alkylaryl having a total of not more than 20 carbon atoms, PA0 A=1,2-alkylene having from 2 to 4 carbon atoms and n=1 to 20). These compounds serve as intermediates in the preparation of polyether sulfonates of formula III ##STR2## (M=hydrogen, alkali metal or ammonium). The vinyl polyether alcohols of formula I are useful as surface-active compounds for inclusion in surface-active compositions.

The present invention relates to novel vinyl polyether alcohols of the 
general formula I 
##STR3## 
in which R stands for C.sub.1 -C.sub.25 -alkyl, C.sub.2 -C.sub.25 -alkenyl 
or alkylaryl having a total of not more than 20 carbon atoms, 
A denotes a 1,2-alkylene group having from 2 to 4 carbon atoms and 
n is a number from 1 to 20, 
and to a process for the preparation of the compounds of formula I, to 
their use as surface-active components of surface-active compositions and 
to said surface-active compositions. 
The present invention further relates to a process for the preparation of 
polyether sulfonates of the general formula III 
##STR4## 
in which M denotes hydrogen, an alkali metal or ammonium, from said vinyl 
polyether alcohols I and to the use of compounds III as surface-active 
components in detergent, cleaning and cosmetic preparations and to said 
preparations. 
Polyglycol ether sulfonates, such as are described in DE-A 3,735,056 (1) 
for example, are important surface-active compounds which are used as 
surfactants in a wide variety of industrial applications. Usual methods of 
making such compounds include, for example, the chlorination of 
appropriate polyglycol ether alcohols with agents such as thionyl chloride 
or phosgene followed by reaction with alkali metal sulfites. This 
procedure is complicated and, furthermore, gives rise to problems relating 
to corrosion, waste disposal and toxicity. Thus novel, simpler methods for 
the synthesis of such polyether sulfonates are particularly welcome, 
especially when the resulting polyether sulfonate molecule additionally 
contains functional groups, such as hydroxyl, in a vicinal position to the 
sulfonate group. 
The use of vinyl oxirane as a synthesis unit for the preparation of 
hydroxy-hydrocarbyl ethers from alcohols or phenols and epoxides has been 
described in JP-AS 87/45,851 (2), for example. 
Polyether sulfonates III are recommended for use as auxiliaries in methods 
of tapping crude oil from underground reservoirs in specifications DE-A 
2,854,826 (3), U.S. Pat. No. 4,421,168 (4) and U.S. Pat. No. 4,463,806 
(5). 
Polyether sulfates, as described in Technische Information TI/P 2759d, June 
1983 (6) in a discussion on Lutensit.RTM.-AS brands of BASF 
Aktiengesellschaft, are frequently used as surfactants in detergent, 
cleaning and cosmetic preparations. 
It is an object of the present invention to provide a simple and efficient 
method of synthesizing polyether sulfonates III. 
Accordingly, we have found the vinyl polyether alcohols I defined above, 
which act as intermediates in the synthesis of polyether sulfonates III 
and which constitute per se surface-active compounds having valuable 
properties for industrial applications. 
The vinyl polyether alcohols I contain a hydrophobic radical R consisting 
of a straight-chain or branched-chain C.sub.1 -C.sub.25 -alkyl group, a 
straight-chain or branched-chain C.sub.2 -C.sub.25 -alkenyl group or an 
alkylaryl group containing a total of not more than 20 carbon atoms. 
Examples of C.sub.1 -C.sub.25 -alkyl groups are methyl, ethyl, propyl, 
butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, 
undecyl, dodecyl, tridecyl, isotridecyl, myristyl, cetyl, stearyl, and 
eicosyl. 
Examples of C.sub.2 -C.sub.25 -alkenyl groups are vinyl, 1-propenyl, 
2-propenyl, oleyl, linolyl, and linolenyl. 
Examples of alkylaryl groups having a total of not more than 20 carbon 
atoms are tolyl, methylnaphthyl, xylyl, mesityl, cumyl, ethylphenyl, 
propylphenyl, butylphenyl, hexylphenyl, octylphenyl, 2-ethylhexylphenyl, 
nonylphenyl, decylphenyl, dodecylphenyl and myristylphenyl. The 
substituents on the aromatic ring system may be in any position. 
Preferred compounds I are those in which R stands for a relatively 
long-chain alkyl group, in particular a C.sub.8 -C.sub.20 -alkyl group. 
Such radicals R are based, for example, on natural fatty alcohols or 
synthesized alcohols, of which the latter are normally produced by oxo 
synthesis or Ziegler synthesis, in which case they are generally a mixture 
of various isomers and adjacent homologs, for example C.sub.9 /C.sub.11 - 
or C.sub.13 /C.sub.15 -oxo-alcohols and C.sub.8 /C.sub.10 -, C.sub.12 
/C.sub.14 - or C.sub.10 /C.sub.20 -Ziegler-alcohols. 
The 1,2-alkylene group A particularly stands for an ethylene group but may 
also denote a propylene, 1,2-butylene or 2,3-butylene group. 
The degree of alkoxylation n is between 1 and 20, preferably between 2 and 
15 and more preferably between 3 and 10. The value of n is usually an 
average value. 
The vinyl polyether alcohols I are advantageously prepared by reacting a 
polyether alcohol of the general formula II 
EQU R--(O--A).sub.n --OH II 
with vinyl oxirane in the presence of a base. 
The base used is generally an alkali metal or alkaline earth metal 
hydroxide, such as sodium hydroxide, potassium hydroxide, calcium 
hydroxide or barium hydroxide or an alcoholate of a low-boiling alcohol, 
such as sodium methylate, sodium ethylate or potassium t-butylate. 
Catalytic amounts are used, for example from 0.1 to 5% molar, based on II. 
In the case of higher-boiling alcohols II it is advantageous to distill 
off any solvent introduced with the base, e.g. water or alcohol, prior to 
carrying out the reaction with vinyl oxirane. 
The reaction with vinyl oxirane is usually carried out at a temperature of 
from 50.degree. to 180.degree. C. and preferably from 100.degree. to 
160.degree. C., at atmospheric pressure or an elevated pressure of up to 
about 10 bar. The alcohol II may be heated to the desired reaction 
temperature in admixture with the vinyl oxirane and base, or the vinyl 
oxirane may be metered to the heated reaction mixture, in which latter 
case the removal of the heat of reaction is less difficult to control. 
For each mole of alcohol II there will generally be used from 1 to 2 moles, 
preferably from 1 to 1.5 moles, of vinyl oxirane. Any residues of 
unconverted vinyl oxirane may be distilled off or removed by stripping 
with an inert gas such as nitrogen. 
Alternatively, the reaction between II and vinyl oxirane may be carried out 
in the presence of a solvent which is inert to vinyl oxirane and alkali, 
examples thereof being tetrahydrofuran, methyl-t-butyl ether, dioxane, 
toluene and xylene. 
The reaction between II and vinyl oxirane may be carried out batchwise or 
continuously in a cascade of stirred vessels or in a tubular reactor. 
The invention further relates to a process for the preparation of polyether 
sulfonates III from vinyl polyether alcohols I by reacting a compound I 
with an alkali metal sulfite, bisulfite or disulfite or ammonium sulfite, 
bisulfite or disulfite or a mixture thereof. The alkali metals involved 
are predominantly sodium and potassium. 
Particularly suitable compounds for this reaction are alkali metal 
bisulfites such as sodium or potassium bisulfite, for example in the form 
of a commercial solution, or mixtures of alkali metal bisulfites with 
alkali metal sulfites. If the reaction is carried out in the presence of 
atmospheric oxygen, a portion of the bisulfite will be oxidized to 
bisulfate, which reacts with sulfite to be reconverted to bisulfite. In 
this way, use may also be made of sulfite, which is less reactive under 
normal reaction conditions, to effect addition thereof to I. In this case, 
the molar ratio of sulfite to bisulfite is advantageously from about 1:2.5 
to about 1:1. 
The said sulfite addition is usually carried out at a temperature of from 
20.degree. to 130.degree. C. and preferably from 50.degree. to 100.degree. 
C., at atmospheric or slightly elevated pressure (up to about 2 bar). The 
reaction may be accelerated by adding a free-radical starter, for example 
an organic peroxide, e.g. dibenzyl peroxide, or an azo compound such as 
azodiisobutyronitrile or a water-soluble peroxo compound such as potassium 
peroxo disulfate, or by bubbling air through the reaction mixture. 
A high reaction rate is achieved, for example, by at least partially 
dissolving the vinyl compound I and the sulfite, bisulfite or disulfite in 
the reaction medium. A suitable solubilizer for this purpose is, in 
particular, water or a water-miscible alcohol such as methanol, ethanol, 
n-propanol, isopropanol, n-butanol, s-butanol and t-butanol. 
For each mole of I there will generally be used from 1 to 3 moles, 
preferably from 1 to 1.5 moles, of sulfite, bisulfite, disulfite or 
mixture thereof. 
Under the conditions used, the sulfite addition takes from 1 to 10 hours, 
in exceptional cases up to 50 hours. Completion of the reaction may be 
ascertained from redox titration findings, after which any precipitated 
salt is removed by filtration, and water and any solvent are distilled 
off. The polyether sulfonate III is thus obtained as a viscous to pasty 
substance. If it is desired to prepare the free sulfonic acid, it will be 
necessary to react the said salt with an acid. 
In a preferred embodiment, the two reaction stages - the reaction of a 
polyether alcohol II with vinyl oxirane to form a vinyl polyether alcohol 
I and the addition of sulfite to said compound I - are combined to form an 
overall process for the preparation of a polyether sulfonate III, which 
combined process is particularly significant economically, since it is not 
necessary to purify the intermediate I, which can be further reacted in 
situ. 
The vinyl polyether alcohols I of the invention have surface-active 
properties and are thus suitable for a variety of industrial applications. 
Possible fields of use include, for example, detergents and cleaners for 
domestic and industrial applications, electroplating, the photographic 
industry, the textile industry, the paper industry, oil production, the 
pharmaceutical industry, the cosmetic industry, the food industry and 
plant nutrition. 
The present invention also relates to surface-active compositions 
containing from 1 to 50% w/w, preferably 1 to 30% w/w, of a vinyl 
polyether alcohol I or a mixture of said vinyl polyether alcohols acting 
as surface-active ingredient and also containing conventional auxiliaries 
and possibly other conventional surfactants. 
The polyether sulfonates III are surface-active compounds useful for 
inclusion in detergents, cleaners and cosmetic preparations. 
The present invention further relates to detergents, cleaners and cosmetic 
preparations containing from 1 to 50% w/w, preferably 5 to 45% w/w, of a 
polyether sulfonate III or a mixture of said polyether sulfonates. 
The cosmetic preparations containing at least one compound III as 
emulsifier are for example skin creams, lotions, gels skin oils or 
shampoos, and these may contain other ingredients such as cosmetic oils, 
conventional emulsifiers, light stabilizers, preservatives, scents and 
other conventional adjuvants. 
The present invention reveals a simple and economically attractive method 
of manufacturing said polyether sulfonates III from commercially readily 
available starting products, which method is substantially free from the 
toxicological, environmental and disposal problems characteristic of 
conventional synthesis methods. 
The polyether sulfonates III are particularly useful for inclusion in 
detergents, cleaners and cosmetics by virtue of their favorable surfactant 
properties, particularly their good resistance to hard water and their 
high degree of stability of saponification under alkaline and weakly acid 
conditions.

SYNTHESIS EXAMPLES 
Example 1 
174 g (0.4 mole) of a C.sub.13 /C.sub.15 -oxo-alcohol which had been 
reacted with 5 moles of ethylene oxide, were mixed with 2.4 g of a 30% w/w 
methanolic sodium methylate solution (corresponding to 13 mmoles of 
NaOCH.sub.3), and methanol was distilled off at 60.degree. C. and 30 mbar. 
The mixture was then kept at a temperature of from 138.degree. to 
140.degree. C. for 3.5 hours while 31 g (0.44 mole) of vinyl oxirane were 
metered thereto. There were obtained 206 g of vinyl polyether alcohol, 
this constituting a yield of 100%. The iodine number following 
hydrogenation was 50, and the cloud point was 52.degree. C., as measured 
according to DIN 53,917. 
The vinyl polyether alcohol thus obtained was dissolved in a mixture of 335 
ml of ethanol and 130 ml of water at room temperature. Air was bubbled 
through the solution while a solution of 30.3 g (0.29 mole) of sodium 
bisulfite and 17.8 g (0.14 mole) of sodium sulfite in 80 ml of water was 
added dropwise over a period of 2 hours. Stirring was continued for 1 hour 
at room temperature and for 2 hours under reflux. Following the removal of 
water and ethanol by distillation at 60.degree. C. and 20 mbar there 
remained 254 g of polyether sulfonate as a viscous oil. The yield was 
100%. 1 g of the sulfonate gave a clear solution in 100 ml of water. 
Example 2 
Following the procedure described in Example 1, 138 g (0.4 mole) of a 
C.sub.13 /C.sub.15 -oxo-alcohol which had been reacted with 3 moles of 
ethylene oxide were converted to the corresponding polyether sulfonate. 
There were obtained 218 g of product as a pasty substance, this 
constituting a yield of 100%. 
Example 3 
Following the procedure described in Example 1, 116 g (0.4 mole) of a 
C.sub.10 -oxo-alcohol which had been reacted with 3 moles of ethylene 
oxide were converted to the corresponding polyether sulfonate. There were 
obtained 196 g of product as a yellow paste, this constituting a yield of 
100%. 
Example 4 
Following the procedure described in Example 1, 129 g (0.4 mole) of a 
C.sub.13 -oxo-alcohol which had been reacted with 3 moles of ethylene 
oxide were converted to the corresponding polyether sulfonate. There were 
obtained 208 g of product as a light brown paste, this constituting a 
yield of 100%. 
Example 5 
Following the procedure described in Example 1, 164 g (0.4 mole) of a 
C.sub.13 -oxo-alcohol which had been reacted with 5 moles of ethylene 
oxide were converted to the corresponding polyether sulfonate. There were 
obtained 243 g of product as a brown paste, this constituting a yield of 
100%. 
APPLICATION TESTS 
A. Basic surfactant data 
The vinyl polyether alcohols I and polyether sulfonates III were tested for 
useful properties as regards the surface tension, foamability and wetting 
power of aqueous compositions containing the products obtained in Examples 
1 to 5. 
The surface tension was determined as specified in DIN 53,914. This test 
measures the force required, in mN/m, to pull a horizontally suspended 
ring or U-shaped wire from the surface of the liquid. 
The foamability was determined as specified in DIN 53,902 by measuring the 
volume of foam, in ml, one minute after foam-generating agitation had 
ceased. 
The wetting power was determined as specified in DIN 53,901 by submerging a 
piece of cotton fabric in the surfactant solution under test. This test 
measures the time taken, in seconds, for the fabric to lose its buoyancy 
(as caused by air enclosure) and to begin to sink. The shorter the time, 
the greater the wetting power. 
Table 1 below lists the results obtained with the products from Examples 1 
to 5. In each case, the surface tension was measured on an aqueous 
solution containing 0.1 g of anhydrous active ingredient per liter, while 
the wetting power was determined using an aqueous solution containing 1.0 
g of anhydrous active ingredient per liter. 
TABLE 1 
______________________________________ 
Surface tension, foamability and wetting power 
of vinyl polyether alcohols and polyether sulfonates 
Surface Wetting 
tension power 
at 20.degree. C. 
Foamability 
at 25.degree. C. 
Product [mN/m] [ml] [sec] 
______________________________________ 
Vinyl polyether alcohol 
28.8 20 200 
of Example 1 
Polyether sulfonate of 
Example 1 28.4 170 35 
Example 2 33.2 120 125 
Example 3 34.7 110 187 
Example 4 28.8 200 21 
Example 5 28.1 400 16 
For comparison: 
Polyether sulfate* 
42.1 &gt;800 45 
______________________________________ 
*having the formula C.sub.12 H.sub.25 /C.sub.14 H.sub.29 --O--(CH.sub.2 
CH.sub.2 O).sub.2.5 --SO.sub.3 Na as described in (6) 
It is seen from Table 1 above that the vinyl polyether alcohols and 
polyether sulfonates show an advantageous reduction of surface tension and 
a marked drop in foaming propensity, which is an advantage in all 
industrial cleaning processes involving high mechanical agitation. The 
wetting power of the tested products is in some cases better, and in 
others poorer, than that of the prior art product, depending on the length 
of the ethylene oxide chain and on the alcohol radical. 
B. Washing efficiency 
The primary washing efficiency (dirt removal) was determined by laundering 
various soiled fabrics in test detergent formulations containing the 
polyether sulfonates. An increase in reflectance value (whiteness) 
indicates an improvement in the primary washing effect. 
The test washes were conducted in an Atlas Launder-O-meter. 
The washing conditions were as follows: 
______________________________________ 
Number of tests 
3 
per fabric: 
Temperature: 
60.degree. C. and 30.degree. C. 
Water hardness: 
16.8.degree. dH .congruent. 3 mmoles/1 (Ca:Mg = 4:1) 
Duration 30 minutes 
of wash: 
Detergent 5 g/l 
concentration: 
Liquor ratio: 
1:25 
Soiled fabrics: 
WFK 10 D [Test fabric standardized by 
the Waschereiforschung Krefeld 
(Laundry Research Institute, 
Krefeld), soiled with a mixture 
of skin grease and pigment] 
EMPA 104 [Test fabric standardized by 
the Eidgenossische Materialpruf- 
anstalt St. Gallen (Confederate 
Material Testing Laboratory, 
St. Gallen), soiled with a mix- 
ture of mineral oil and pigment] 
______________________________________ 
The detergents were formulated as follows: 
30% of polyether sulfonate as obtained in Examples 1 to 5, as surfactant, 
15% of potassium coconut soap, 
1% of polypropylene glycol (molar mass 600), 
1% of ethanol and 
water to make 100%. 
The reflectance values of the soiled fabrics were measured with a Zeiss 
Elrepho. 
Table 2 below lists the test results. The findings show that primary 
washing efficiency of the polyether sulfonates is in some cases distinctly 
better than that of the prior art products. 
TABLE 2 
______________________________________ 
Washing efficiency of polyether sulfonates 
Primary washing 
efficiency in % reflectance 
Fabric Fabric 
WFK 10 D EMPA 104 
Product 60.degree. C. 
30.degree. C. 
60.degree. C. 
30.degree. C. 
______________________________________ 
of Example 1 59.7 59.2 24.7 19.9 
of Example 2 64.7 59.2 23.7 19.2 
of Example 3 51.6 49.6 19.4 15.0 
of Example 4 63.7 58.8 22.2 18.5 
of Example 5 60.9 58.6 24.6 19.6 
for comparison: 
polyether sulfate* 
57.4 55.2 22.1 17.7 
polyether sulfonate** free 
52.4 48.4 19.0 16.5 
from hydroxyl groups 
prelaundering reference 
45.0 45.0 12.9 12.9 
values 
______________________________________ 
*having the formula C.sub.12 H.sub.25 /C.sub.14 H.sub.29 --O--(CH.sub.2 
CH.sub.2 O).sub.2.5 --SO.sub.3 Na as described in (6) 
**having the formula C.sub.10 H.sub.21 --O--(CH.sub.2 CH.sub.2 O).sub.3 
--CH.sub.2 CH.sub.2 SO.sub.3 Na as described in (1)