DK156274B - DIFFICULT TENSID CONCENTRATES - Google Patents

Description

DK 156274 B

The preparation of pumpable high-concentrated alkyl ether sulfates presents, as previously known, a problem which is difficult to solve. Alkyl ether sulphates are in this connection especially sulphates of alkoxylated non-aromatic alcohols containing from 8 to 24 carbon atoms, especially from 8 to 18 carbon atoms. Alcohols of this kind can be extracted from starting materials of natural origin, for example coconut or palm kernel oil, or available as synthetic material, e.g. in the form of the known Ziegler or oxo alcohols. The non-aromatic alcohols 10 with saturated or unsaturated, optionally also branched alkyl = groups of the aforementioned kind are made for the purpose of producing detergents to begin with alkoxylated with lower alkylene oxides, especially with ethylene oxide and / or with propylene oxide, and thereafter sulfated and then converted to the corresponding 15 water-soluble salts.

Detergents of this kind find many uses, for example in liquid cleaners, foam baths and hair washing agents.

Aqueous solutions having a relatively low content of alkyl ether sulphate - for example having a content of approx. 10 wt% 20 detergent (WAS) - exhibits the particular property of this detergent class again to be thickened by the addition of neutral salts, such as NaCl or Na 2 SO 4. In practice, this property is frequently used in the class of detergents in question.

25 A further peculiarity in the rheological conditions of corresponding surfactant concentrates, however, entails considerable difficulties in practical application. Highly concentrated aqueous surfactant concentrates having a WAS content of, for example, 50% by weight or more have consistency as a thick 30 gel or similar paste and are not pumpable. If one tries to dilute this gel with water, the thickening state does not decrease to any expected extent, but on the contrary increases initially. Understandably, this creates significant problems for the person who needs to process the material.

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DK 156274 B

There are the innumerable suggestions for overcoming this difficulty. Addition of limited amounts of the various components as viscosity regulators to the aqueous surfactant concentrate is known. Reference is made here to German Publication No. 2,251,405 (certain carboxylic acid salts, in particular salts of hydroxycarboxylic acids), German Publication No. 2,305,554 (addition of aromatic sulfonic acids or the water-soluble salts thereof), and German publication No. 32 32 or 10 sulphates or the corresponding water-soluble salts of unsaturated or unsaturated aliphatic hydrocarbon groups or hydrocarbon bonoxy-hydrocarbon groups having 1 to 6 c of carbon, which may also be substituted in a specific way). According to the disclosures in these printing presses, the addition of lower alcohols, such as isopropanol or ethanol, is known in practice to solve the above-mentioned problem. However, the lower alcohols cause significant disadvantages as a result of the high vapor pressure and their flammability.

The present invention is intended to provide 2.0 aqueous surfactant concentrates of said alkyl ether sulfates which are also pumpable at high concentrations and which, upon dilution with water, show no undesirable increase in viscosity or thickening of the gel state and yet in diluted state. in the case of low WAS-25 concentrations, it can be effectively thickened by the addition of neutral salts, such as sodium chloride or sodium sulfate.

The technical solution of this task is based on the finding that water-soluble salts of mono- and / or disulfates of lower polyalkylene glycols - especially of polyethylene glycol · 30 and / or polypropylene glycol. - are effective viscosity controllers for aqueous surfactant concentrates of the kind in question. It was thereby used to find that the effect of these viscosity regulators increases with the increase in the molecular weight of the basic polyether glycol.

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DK 156274 B

The present invention is concerned with aqueous surfactant concentrates containing 25-80% by weight of water-soluble salts of aliphatic alkoxylated and then sulfated alcohols (ether sulfate salts) together with small amounts of viscosity regulators. These surfactant concentrates are characterized in that the soin viscosity regulators contain 1-10% by weight of water-soluble alkali metal, ammonium and / or amine salts of disulfates of polyethylene glycol and / or of polypropylene glycol having a molecular weight of the polyalkylene ether glycol of 600-6000, on request. together with lower polyalkylene ether glycols having a molecular weight of 1500-6000 in a ratio of 1: 0 to 1: 3.

To improve the flow ratio of heavily moving aqueous surfactant concentrates of water-soluble salts of non-aromatic 15 alkoxylated sulfated alcohols of 8 to 24, preferably 8 to 18 carbon atoms, small amounts of viscosity regulator are added. In the process, water-soluble salts of disulfates of lower polyalkylene ether glycols having a molecular weight of at least 600, preferably 20 of at least 1000, are used as viscosity regulator. If desired, the non-sulfated free, lower polyalkylene ether glycols of at least 1500 molecular weight can be used.

In particular, of the sulfates, the disulfates of lower polyalkylene ether glycols, namely, of polyethylene oxide and / or of polypropylene oxide, have been found to be particularly effective viscosity regulators, as well as to high-concentration aqueous surfactant concentrates of alkyl ether sulfates. The viscosity-lowering or reducing effect on the thickness range of the gel of these regulators increases with increasing molecular weight or increasing polycondensation degree of the alkylene ether glycol. Preferably, the molecular weight of the base material for the viscosity regulator is approx. 1000. Molecular weights of up to 6000 or more may be considered. Particularly preferred are disulfates of polyalkylene ether glycols of the present 4

DK 156274B

species with molecular weights in the range of 1500 to 4000 or 1500 to 3000. The disulfates used in the invention as a viscosity regulator are thus usually derived from polyglycols which differ from polyalkylene ether glycols, 5 which - caused by low traces of water - can be formed by the oxalkylation of fatty alcohols. According to the invention, the viscosity controllers can be used in a predetermined manner according to the nature and amount thereof, so that desired effects which can be predetermined are possible with respect to the reduction of the gel state. The viscosity regulators used in accordance with the invention are themselves effective detergents. An unwanted load with inactive components is avoided. The surfactant compositions of the invention are not only pumpable as such in highly concentrated form, since, when diluted with water, no increase in the gel state occurs, but the desired dilution effect. Nevertheless, after lowering the surfactant content to the practically desired lower values of e.g. 10 to 25 wt.% By the addition of neutral salts, they now thicken easily moving liquid aqueous solutions.

Desired water-soluble salts of the viscosity regulators used in the invention can be used. For the practical application, especially alkali salts, soluble soil alkali salts, for example magnesium salt, ammonium salt and / or salts with organic amines, for example alkylolamine salts, are considered. The most important site for practical use is the sodium salt of the disulfate of polyethylene glycol and / or 1,2-polypropylene glycol - with the minimum molecular weights indicated.

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The viscosity regulators are present in the aqueous surfactant concentrates in amounts from 1 to 10% by weight. Particularly preferred may be amounts from 2 to 5% by weight. In detail, the amount of viscosity regulator is determined by the desired lowering of the gel point and / or by the thickening effect of the current 5.

DK 156274 B

ether sulfate. Finally, the degree of polyalkoxylation of the alcohol may be significant. Thus, lower alkoxylated alcohols may also be effective at high concentrations, usually with 2 to 5% by weight of the viscosity regulator, while somewhat higher amounts of the viscosity regulator may be necessary in conjunction with high polyalkoxylated alcohols (degree of polymerization of the polyalkoxy group above 10). .

As noted above, if desired, with the sulphates of the polyethylene glycol and / or polypropylene glycol, free polyethylene glycol and / or free polypropylene glycol can be used as viscosity regulating components. Here, too, it has been found that the effect of these non-sulfated polyalkylene ether glycols appears the more pronounced the higher the molecular weight of the polyalkylene-ether glycol. These free polyalkylene ether glycols, which may be used together, must have at least a molecular weight of 1500 and preferably their molecular weight at least 2000 and are, for example, in the range of 2000 to 20,000, especially in the range of 3000 to 5000.

The mixing ratio between the sulfates of the lower polyalkylene ether glycols - especially the disulfates - and the free polyalkylene len ether glycols is advantageously in the range of 1: 0 to 1: 3. The mixing range from 1: 0 to 1: 1 is generally preferred.

The viscosity controller can be added within the scope of the invention to the aqueous surfactant concentrate as a pre-formed compound or as a pre-formed compound mixture. Hereby, the viscosity regulator is suitably used as concentrated aqueous solution (content of WAS from 50 to 90%).

DK 156274 B

and mixed with the aqueous solution of the alkyl ether sulfate.

However, in a particular embodiment of the invention, it is also possible to prepare the viscosity regulator by sulfating the lower polyalkylene ether glycols in situ in the vicinity of the non-aromatic alkoxylated alcohol. In this embodiment, the alkoxylation of both the non-aromatic alcohols as well as the previously formed lower polyalkylene = ether glycols is conveniently carried out in conjunction with one another. Thus, the desired mixing ratios of 10 non-aromatic alcohol to lower polyalkylene ether glycol are adjusted in a simple manner, after which this compound is subjected to the sulfation known per se. Finally, the resulting sulfates are converted to the desired water-soluble site. Hereby the same cation is introduced into the alkyl ether = the sulfate and in the viscosity regulator. In general, this may be a preferred embodiment of the invention.

Regarding the specific chemical nature of the alkyl ether sulfates, reference is made to the disclosures made in the disclosure of the prior art. Here, in principle, there is much concern about sulfates of 20 alkoxylated C 9 -C 20 alcohols, preferably about such derivatives having a carbon atom chain of 8 to 18 carbon atoms. Particularly preferred are non-aromatic alcohols with 10 to 16 membered carbon atom · The carbon atom chain may be straight and / or branched as well as saturated and / or unsaturated. Alcohols 25 of the kind mentioned can, as already stated, be obtained from natural products as well as by synthetic route.

The alcohols are alkoxylated with lower alkylene oxides in the first step. Hereby the two major groups of the low alkoxylated and the high alkoxylated derivatives can be distinguished.

In the low alkoxylated derivatives, up to 10, preferably 1 to 4, and especially 2 to 3 alkoxy groups are added to the alcohol group. In the highly alkoxylated derivatives there are polyalkoxy groups having a number greater than 10, for example up to 1Q0, and especially from 20 to 80. The most important alkoxylating agents are ethyl

DK 156274B

7 lenoxide and / or 1,2-propylene oxide.

As the group of suitable water-soluble salts of the sulfated polyalkoxylated compounds, the former group of cations mentioned in connection with the viscosity regulator is suitable.

Suitable salts are, in particular, the alkali salts, soluble alkaline earth salts, ammonium salts and salts with organic amines.

The most important site in practice is the sodium salt of; alkyl ether = the sulfate.

In addition to these alkyl ether sulfate salts, the aqueous surfactant concentrates of the invention may also contain other surface active agents. Suitable are, for example, nonionic, e.g., WAS, for example, alkyl phenol ethers. Further possibilities for co-used detergents are apparent from the prior art mentioned above.

From the preparation of the alkyl ether sulfates and / or the viscosity regulators used in the invention, usually small amounts of salts, such as sodium chloride and / or sodium sulfate, are usually present in the aqueous concentrates. Here, too, reference is made to the references in the prior art referred to.

20 Examples.

Example 1.

In a series of comparative experiments, the viscosity-regulating properties of polyethylene glycol disulfate and 1,2-polypropylene glycol disulfate are determined on aqueous 70% alkyl ether = 25 sulfate concentrates. Thus, the viscosity-regulating effect dependence of the different parameters is found.

The products used in this example are characterized as follows:

DK 156274 B

8 (abbreviated C12 / 14-2 sulfate) 70% by weight detergent (ethanol soluble amounts) 0.4% by weight NaCl 0.9% by weight Na2SO4.

2. Na-C 12/14 fatty alcohol-3-EO sulfate, (abbreviated C12 / 14-3 sulfate) 70% by weight detergent (ethanol-soluble amounts) 0.4% by weight NaCl 0.9% by weight Na2SO4 .

.10 3. Polyethylene glycol disulfates on the basis of polyethylene glyco = 1s having molecular weights 60Q, 1550, 2000 and 3000 obtained by direct slurry fumigation with chlorosulfonic acid and available in approx. 70% by weight of aqueous solution.

4. Polypropylene glycol disulfates on the basis of polypropylene = 15 glycols having molecular weights 620, 1020 and 2020, also prepared according to the usual method by direct sulfation of the corresponding polypropylene glycols and available as approx. 70% solutions in water.

a) In a first test series, the dependence of the viscosity (determined according to Hoppler on ball drop viscometer at 20 ° C) of the molecular weight of the polyethylene = glycol disulfate used is determined. Therefore, in the following Table I and in the additional tables in this example, the numerical values of the viscosity are given in mPas.

As surfactant, Na 2 Cl 2/14 ~ fatty alcohol-2-EO'S sulfate is used in the starting solution.

DK 156274B

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Table I.

WAS Contents Without added molecular weight of basic weight% of PGS +) statement polyethylene glycols' __ __weight% ___ 6Ôa | 1550 .2000 ~ 3000 5 70 3 150 000 120 000 60 000 SD 000 60 000 4 80 000 65 2.8 not 50 000 3.7 measurable 30 0Q0 + PGS = polyglycol disulfate.

(B) In a further test series, the viscosity dependence of the nature of the basic alkyl ether sulfate is determined using polypropylene glycol disulfate (molecular weight 15500-

Table II.

15 WAS Content C12 / 14-2 sulphate C12 / 14-3 sulphate wt% of PGS + without addition with- without addition- with- __weight% sentence statement sentence statement. Statement_ 70 3 150000 60000 180000 '35000 4 80000 - 40000 20 65 2.8 not 50000 not> 150000 3/7 ^ leU-ç, 300QO measurable 150000 J · PGS = polyglycol disulfate.

c) In a further series of experiments, the dependence of the viscosity on the nature of the polyglycol or the corresponding water-soluble sulfate salt is determined.

Surfactant used: Na-C12 / 14 fatty alcohol-2-EO-sulfate Polyglycol disulfate amount; 2 "8% WAS: 65%,

Table III.

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Addition Viscosity (mPas.)

Without addition not measurable

Polyethylene Glycol 600 Disulfate 80,000 5 "-1550-" 50,000 "-3000-" 40,000

Polypropylene glycol-620-disulfate 90,000 "-1020-" 40,000. "-2020-" 40 000 10 d) In a final series of experiments, the re-thickening of dialkyl ether sulfate solutions which were made more liquid by water addition was determined.

Na-C12 / 14-2 sulfate is liquefied with 3 wt.% Or 6 wt.% Of the viscosity regulator and tested for its ability to be again thickened with boiling salt after dilution with water to a WAS content of 10 wt.%. In the following tabular composition, the results of the present invention are compared with the results obtained with similar solutions containing as a viscosity regulator butyl glycol sulphate or cumene sulphonate.

Table IV.

NaCl Without Addition Polyethylene Glycol Butyl Glycol = Cumensul = (S) to Make Fly 1550 Sulfate Sulfate Phonate __ ending__3% 6% 3% {6% 3% I 6% 25 3 47 47 29 33 26 14 14 5 5470 5440 6200 4030 1490 670 670 7 28170 20500 22600 18290 12380 9520 282Q0 9 14780 5230 5200 8800 8900. 9640 9600

The tables on a} and b) show that already small amounts of the viscosity regulators of the invention affect high-concentration fatty alcohol ether sulfates with respect to 11

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to make them more fluid. When switching to smaller concentrations, ie. by dilution, the viscosity is not jump-like, but a reduction results.

Compared to short chain alkyl ether sulphates (butylglycol sulph = 5 barrels) the re-thickening of the diluted surfactant solutions becomes less affected. To a greater extent this applies to the comparison with cumensulfonate.

Example1 2.

The aqueous solution of a Na-C12 / 14 fatty alcohol-50 EO-sol = 10 barrels containing an active material content of 25% by weight has a gel point of + 12 ° C. To reduce the gel point, disodium polyethylene glycol disulfates on the basis of polyethylene glycols having a molecular weight of 155Q, 3000 and 4000 are used.

Table V.

Addition Gel point (° C)

Without addition + 12 20 Polyethylene glycol-1550 disulfate + 2

Polyethylene glycol-3000 ~ disulfate - 1

Polyethylene glycol-4000-disulfate ^ 3

This series of experiments shows that already the slight addition of 1.2% by weight, calculated in relation to fatty alcohol'-EO sulfate, causes a gel point reduction of the order of 10 ° C.

Example 3

An adhesive product of 50 moles of ethylene oxide to one mole of C12 / 14

DK 156274 B

12 fatty alcohols are sulfated alone and in the mixtures listed in Table VI with polyethylene glycol under usual conditions with chlorosulfonic acid. Thus, 1.05 moles of chlorosul = phonic acid per ml are used. moles of hydroxyl groups (calculated by OH number).

5 After neutralization with baking soda and setting a concentration of active material at 25% by weight, the gel points listed in Table VI are found.

Table VI.

Starting material OH- Point of point ______ number__fç_ 10 C12 / 14 fatty alcohol + 50 EO 25 + 12 100 parts by weight C12 / 14 fatty alcohol + 50 EO 29 - 3 3.9 parts by weight polyethylene glycol 4000 100 parts by weight C12 / 14 fatty alcohol + 50 EO 29 - 2 1 , 3 parts by weight of polyethylene glycol 1550 15 2.6 parts by weight of polyethylene glycol 5000-6000

Claims (3)

1. Aqueous surfactant concentrates containing 25-80% by weight of water-soluble salts of aliphatic alkoxylated and sulfated alcohols (ether sulfate salts) together with high amounts of viscosity regulators, characterized in that the soin viscosity regulators contain 1-10% by weight of water-soluble alkaline metal -, ammonium and / or aminase 1 tea of diisulfates of 10 polyethylene glycol and / or polypropylene glycol having a molecular weight of the polyalkylene ether glycol of 600-6000, if coincident with lower polyalkylene ether glycols having a molecular weight of 1500-6000 in a ratio of 1: 0 - 1: 3. 2. Aqueous surfactant concentrates according to claim 1, characterized in that the molecular weight of the polyalkylene ether glycols underlying the viscosity regulator present is in the range 1500-4000. 3. Aqueous surfactant concentrates according to claim 1 or 2, characterized in that the viscosity regulators are present in amounts of 2-5% by weight and that the ether sulfate salts are present in amounts of 50 to 80% by weight, both of which are calculated relative to aqueous surfactant concentrates. 25 30 35