DE1934540C3 - Process for the production of a detergent raw material mixture - Google Patents

Description

or more fatty acids at a temperature between 160 and 200 C or one or more cn Feit acidification of lower alkenols at one temperature at least partially esterified between 80 and 180 ° C.

The one used when \ experiencing the invention \ Hydroxyl compound serves not only as a solvent for sucrose in the condensation reaction, but also as a starting nutlerial for the formation of a non-ionic Surfactant, namely a fatty acid ester of an alcohol-alkylene oxide condensation product, the forms the / wide hot-essential component of detergent raw material mixtures that can be produced according to the invention. Used if water is used as the hydroxyl compound or solvent, the reaction with the alkylene oxide used in each case a Cilycol corresponding to the alkylene oxide, d. i.e. it will be achieved the same result as with \ erwendun-j the corresponding one ·. ilykols al ·, solvent.

In the practical implementation of the inventive The sucrose is processed in one process dissolved lower alkanol or a glycol. For this, a variety of different, primary, secondary and tertiary mono-, di-, Tn- and polyols can be used; typical examples of suitable alcohols are Alkanoia. such as methyl, ethyl, propyl and bulyl alcohol, Glycols such as ethylene, diethylene, triethylene and tetraethylene glycol. as well as higher oligomers the polyethylene glycol series, propylene, dipropylene, fripropylene and tetrapropylene glycol and higher oligomers of the polyp, opylene glycol series, glycerine, Sorbitol and sorbilun.

For economic and technical reasons as well as in view of toxicity are preferred Ethyl alcohol, ethylene glycol, propylene glycol. Glycerin and sorbitol are used.

The sucrose should be kept at the lowest possible temple temperature be dissolved in the alcohol used as a solvent in order to avoid any caramelization. It is preferable to work at a temperature of at most 90 ° C. Under these temperature conditions the ratio of sucrose to alcohol should be at most 8: 2 to achieve a satisfactory solution without caramelizing the sucrose.

In the process of the invention, the alkylene oxide used as the starting material can be condensed in any number of molecules onto every active hydrogen atom of the sucrose used as the starting material and of the respective alcohol. A total amount of about 1 to 50 mol of alkylene oxide, based on the total amount of sucrose and alcohol used, is preferably used. The reaction with alkylene oxide may be generally at temperatures between 80 and 200 C and preferably between 100 and 200 ⁰ C with the use of ethylene oxide as well as between 80 and 150 C with the use of propylene oxide as alkylene oxide are carried out.

As already mentioned, the alkylene oxide condensation products can be esterified either with a fatty acid or by transesterification with a fatty acid ester of a lower alkanol. In the esterification, the fatty acid or lower fatty acid alkyl ester used as the esterifying agent can be used in any proportions, based on the number of active hydrogen atoms in the condensation products. Preferably, about 1 to 5 mol of esterifying agent are used per mol of sucrose used Fatty acid as esterification agent, the esterification temperature is preferably between 160 and 200 C, while in esterification by transesterification, ie when using a fatty acid alkyl ester as esterification agent, the esterification temperature is preferably between SO and 1 SO x ".

The esterification agents used are preferably saturated and unsaturated fatty acids with 8 to ίο 22 carbon atoms and their esters with lower alcohols. Typical examples of suitable esterifying agents are Kaprvl-, Kaprin-, Laiirin-, Myristin-, Palmitin-, Stearin-, Arachin-, Oil-, Sabin-, Juniper-, 12-hydroxystearin, ricinoline, linden, physettrin, Paimitolein, gadoleic and erucic acid and their lower alkyl esters, such as the methyl, ethyl, propyl and butyl esters, as well as the triglycerides of the said sugars.

The detergent raw material mixtures made from nonionic surfactants by the process of the invention Can be used as emulsifiers, dispersants, solubilizers. Defoaming agents or foam retarders and are generally used for the same purposes as the known nonionic Surfactants or wetting agents. They can also be used for various biochemical uses, e.g. B. as dishwashing detergent, for Vlund and Dental care and personal hygiene for children, and as a growth promoter in the manufacture of antibiotics and amino acids used microbiologically, as phytohormones and as wetting agents will.

The detergent raw material mixtures produced according to the invention show significantly more favorable effects, especially with regard to the reduction in surface tension achieved, to the detergent effect, Toxicity, PhytCioxicity and the biodegradability than the previously known comparable Detergent raw materials, such as those made known, for example, by the process of Documents of the Belgian "-η patent 677 874 received became. This could be shown by comparative tests with products according to the invention that according to Examples 1, 3, 4 and 5 of the present patent application on the one hand and with known products on the other hand, those according to Examples 7, 14 and 18 of the Belgian patent were carried out 677 874 were made. The test methods used are listed below following the Appropriate examples described.

In these comparative tests, the detergent raw material mixtures according to the invention in O ₁ L ⁰ Z ₀ aqueous solution showed a lower surface tension than the known products, and their washing effectiveness was in some cases twice as great as that of the known mixtures. _{The detergents according} to the invention showed higher LD 50 values, some of which indicated a toxicity that was reduced by half. The phytotoxicity of the detergents according to the invention has also proven to be significantly lower. In the test of biodegradability, which is described below under (9), the detergent mixtures according to the invention were degraded much faster and better than the products obtained according to the published documents of Belgian patent 677 874.

The invention is illustrated in more detail by the following examples.

example 1

A small autoclave equipped with a thermometer, a device for introducing nitrogen and alkylene oxide and a stirrer is charged with 684 g sucrose, 184 g glycerine and 0.8 g potassium hydroxide. A solution is prepared from this mixture by heating to 50 ° ^{C. to 85 ° C.} Then ν ird the air in the autoclave is displaced with nitrogen, whereupon the contents are ^{heated to about 100 =} C and within 3 hours under a pressure of 2 to

4 kp / cm ^{2 introduces} 440 g of ethylene oxide, a pale yellow oil being obtained. This oil (664.4 g) is added along ig ^he mil 284.4 g of stearic acid and 0.6 g of 36% hydrochloric acid in a .nit a thermometer, a nitrogen feed pipe, a cooler and a stirrer-equipped four-neck flask. The mixture is then reacted for about 8 hours at about INI) C ", before the acid number of the mixture is reduced

5 lies. The hydrochloric acid contained as an acidification catalyst in the reaction mixture with potassium hydroxide neutralized, whereupon the reaction mixture is dehydrated and filtered. You get as Product sucrose polyoxyethylene stearate and glyceryl polyoxyethylene stearate.

Example 2

The autoclave described in Example 1 is charged with 684 g of sucrose, 184 g of glycerol and 4 g of potassium hydroxide, whereupon the mixture is converted into a solution by heating to 80 to 85.degree. Qann displaces the air from the autoclave with nitrogen and the reaction mixture at 12O ⁰ C heated, followed by introducing 2320 g of propylene oxide in about 10 hours under a pressure of 2 to 4 kgf / cm ^2. The product obtained is a yellowish brown liquid.

This liquid (1592 g) is transferred to a as described in Example 1 equipped four-neck flask and reacted for 8 hours at about 180 C with 284.4 g of stearic acid and 0.6 g of 36 ° / _o hydrochloric acid, whereupon the acid number of the reaction mixture below 5 located. Potassium hydroxide is then added to the reaction mixture to neutralize the hydrochloric acid contained therein, and the mixture is dehydrated and filtered. The product obtained is a mixture of sucrose polyoxypropylene stearate and glyceryl polyoxypropylene stearate

Example 3

tion mixture contained hydrochloric acid neutralized, whereupon the reaction mixture is dehydrated and filtered. Al The product obtained is a mixture of sucrose poly oxyäthylenlaurat and Oxypropylenpolyoxyäthylen laurat.

Example 4

The autoclave used in Example 1 contains 684 g of sucrose, 184 g of glycerol and 0.8 g of potassium

ίο hydroxide charged, whereupon a solution is made from the mixture by heating to 80 to 85 ° C. Then the air contained in the autoclave is displaced with nitrogen and the contents of the autoclave are heated to approx. 100 ^° C., whereupon 440 g of ethylene oxide are passed in under a pressure of 2 to 4 kp / cm ^{2 over the course of} 3 hours. A blue-pale oil is obtained.

This oil (657 g) is converted into a four-necked flask equipped as described in the preceding examples by reacting it with 298.5 ι methyl stearate 8 levels at about 100 ° C. whereupon the hydroxyl level of the reaction mixture is 49%. The reaction mixture is then ^{mixed with S-1} Z acid to use it as a catalyst! Neutralize potassium hydroxide, drained uik filtered. The product obtained is a mixture of sucrose polyoxyethylene stearate and glycerol polyoxyethylene stearate.

Example 5

In the same autoclave as in Example 1 mi 684 g sucrose, 124 g ethylene glycol and 0.8 g Ka is charged liumhydroxyd, Overfill and the mixture durcl heating at 60 to 70 ^c C into a solution '-. R. Then you displace the ones contained in the autoclave; Air with nitrogen and heated the contents at 100 ⁰ C after which within Eiwa j hours under a pressure of 2 to 4 kgf / cm ^2, 440 g of ethylene oxide is obtained initiates a blaügelbe liquid.

This liquid (642 g) is transferred to a as described in the previous examples equipped four-neck flask, and reacted for 8 hours at etwi carbonate 180 ^D C with 302 g of methyl ricinoleate, and 1.1 g of potassium, after which the base number de; Reaction mixture is 307. The reaction mixture is then treated with sulfuric acid, un neutralize the potassium carbonate used as a catalyst, dehydrated and filtered, giving a mixture of sucrose polyoxy ethylene ricenoleate and polyoxyethylene glycol ricinolea al: end product.

The small autoclave described in Example 1 is charged with 684 g of sucrose, 152.2 g of propylene glycol and 0.8 g of potassium hydroxide, whereupon a solution is prepared ^{from the mixture by heating to 60 to 70 ° C.} The air in the autoclave is then displaced with nitrogen and the reaction mixture is ^{heated to about 100 °} C., whereupon 88O g of ethylene oxide is introduced over the course of about 6 hours under a pressure of 2 to 4 kp / cm ^2. The product obtained is a yellowish-brown liquid.

This liquid (647 g) is unci transferred to a as described in Example 1 equipped four-neck flask for 8 hours at about 18O ⁰ C and 200,31g lauric acid and 0.7 g 36 ^c 7 ₀ hydrochloric acid reacted, whereupon the acid number of the reaction mixture below 5 located. Then, with potassium hydroxide, the reaction

Example 0

The autoclave used in the preceding examples is 684 g of sucrose, 364.4 g Sorbi un.J 0.8 g of potassium hydroxide were charged, whereupon au: the mixture by heating at 80 to 90 ⁰ C a! Solution. The air contained in the autoclave is then displaced with nitrogen and the contents of the autoclave are heated to about 120 ° C., whereupon 440 g of ethylene oxide are introduced under a pressure of 2 to 4 kp / cm ² within about 6 hours. A pale yellow liquid is obtained.

This liquid (702 g) is transferred to a four-necked flask equipped as described in the preceding examples and filled for 8 hours at about K) O ⁰ C with 891.5 g of stearic acid tricyclic acid and 1.7 t

Potassium carbonate implemented. The complete decline this reaction is caused by the disappearance of the stain of unreacted stearic acid triglyceride determined by thin layer chromatography.

A product is obtained by neutralizing, draining and filtering the reaction mixture Mixture of sucrose polyoxyethylene stearate and sorbitol polyoxyethylene stearate.

Example 7

The autoclave of Example 1 is charged with 684 g of sucrose, 460 g of ethanol and 0.4 g of potassium hydroxide, followed by up to 8O ⁰ C preparing a solution from the mixture by Hrhitzen on 70th The air contained in the autoclave is then displaced with nitrogen and the contents of the autoclave are heated to about 100 ° C., whereupon 880 g of ethylene oxide are injected under a pressure of 2 to 4 kp / cm ^a within about 3 hours. A pale yellow liquid is obtained.

This liquid (1267 g) is transferred to a as described in the previous examples equipped four-neck flask and reacted for 8 hours at about 180 "C and 200 g of lauric acid and 4.6 g of 36 ° / _o IGCR hydrochloric acid, after which the acid number of the reaction mixture below 5 Then the hydrochloric acid contained in the reaction mixture as a catalyst is neutralized by adding potassium hydroxide to the reaction mixture, and the reaction mixture is dehydrated and filtered, the product being a mixture of sucrose polyoxyethylene laurate and polyoxyethylene "! ^ koimonoäthyiäthcrmonolHurinsäureester receives.

Example 8

The small autoclave used in Example 1 is charged with 342 g of sucrose, 180 g of water and 4.3 g of potassium hydroxide, whereupon the mixture is converted into a solution by heating to 60 to 70 ° C. Then, the air contained in the autoclave is displaced by nitrogen and the Auloklavinhalt heated to about 100 ⁰ C, followed by g within about 3 hours Äthyienoxyd 880 initiates at a pressure of 2 to 4 kgf / cm ^2. A pale yellow liquid is obtained. This liquid (1165 grams) is transferred to a flask equipped as in the preceding examples Vierhalskolbtn and reacted for 8 hours with 200 g of lauric acid and 1.2 g of 36% IGCR hydrochloric acid at about 180 ³ C, after which the acid number of the reaction mixture is less than. 5 Potassium hydroxide is then added to the reaction mixture in order to neutralize the hydrochloric acid, dehydrated and filtered, a mixture of sucrose polyoxyethylene laurate and polyoxyethylene glycol laurate being obtained as the end product.

About the excellent properties of the detergent raw material mixtures produced according to the invention in comparison to known nonionic surfactants will show a series of comparative experiments accomplished.

The details of how the experiment was carried out and the results obtained in the comparative experiments are as follows:

1. Foam test

Using the Ross-Miles method, the foaming power becomes that in the table below I listed samples of non-ionic surfactants at 25 ° C in the form of 0.25% aqueous solutions checked.

Table I.

Foaming power 5 Product of example 1 Schuumhöhc To (mm) Product of example 3 Immediately 5 min. Product of example 4 cash after Commercially available Encore 30th Product (I) *) the sample 25th ¹ S Commercially available 40 50 Product (2) **) 35 60 90 195 90 190 To 10 min. 27 23 45 70 65

*) Lauric acid-ethylnoxide condensation product (molar ratio 1; 10).

**) Nonylphenol-ethylene oxide condensation product (molar ratio 1:10).

2. Defoaming test

The anti-foaming or foam-inhibiting effect of the product of Example 2 and a commercially available one Product in the form of aqueous solutions with the composition given in Table II is measured according to the Ross-Miles method. The results of these experiments are in Table III compiled.

Table Il

sample

Composition of the drug solution

0.025% product of Example 2; 0.25% nonylphenol ethylene oxide

densation product

(Molar ratio I: 10); Rest water.

0.025% polypropylene glycol (molecular

weight 2000);
0.25% nonylphenol ethylene oxide

Densationsprodiikt (molar ratio

1: 10); Rest water.

C 0.25% nonylphenol ethylene oxide con

Blind densation product (molar ratio!

attempt 1: 10); Rest water.

Table III

Defoaming ability To
5 min. To
10 min. 10 5 sample Foam height (mm) 30th 20th A. Right away
after adding
.the sample 90 65 B. 80 C. 100 Blind test 100

3. Surface tension test

The surface tension of those listed in Table IV Samples in the form of 0.1% aqueous solutions

309646/253

10

product

from
Example 3

Pnxlukt

from example 4

Commercial product »)

gen is measured according to the method of Du N o ü y and supplementing with water to 100 parts by weight. placed.

^{Table IV} a) Test procedure

Hs bowls with a diameter of 13 cm on the concave side are used, the respective by dropping 2 ml of a prepared by mixing equal amounts of beef tallow and salad oil Dirt OK are soiled as evenly as possible, whereupon it is left for 24 hours and then subjected to the following test:

In each case a soiled bowl is immersed in a wash basin, the 4 l of the 40 ± 2 ″ C to be tested, produced as described above

J5 contains warm detergent solution, dipped and with washed with a common household sponge for 30 seconds, after which they are rinsed with water. 5 bowls at a time are washed in the same way. The so washed

λο Bowls are then stained with oil red dye to determine the amount of fat residue.

sample product
from
example 1 surfaces
voltage
(dyn / cm) .. 40

30th

40

*) Nonylphenol-Ethylcnoxyd condensation product (molar ratio 1: 10).

4. Dispersibility

i) First, the dispensing or washing capacity of the samples listed in Table V is determined according to the Washing test for a standard soiling according to that of the Japan Oil washing board Chemists Society's adopted soiling method tested cotton fabric, whereby one the results listed in Table V were achieved.

Table V

Tcnsid Tens
1 dkonze
0.5 nt rat ion
0.25 Cn)
0.1 Product of example 1 ... 66.4 52.7 59.4 51.5 Product of example 3 ... 66.4 63.3 66.1 63.3 Product of example 4 ... 81.2 75.5 57.9 51.8 Commercially available
Product*) 70.6 61.5 70.0 43.6

*) Sodium dodecylbenzenesulfonate.

5. Dispersibility

ii) In this test the products of the examples 1, 3 and 4 as well as the commercially available products used to test foaming capacity 1 and 2 used as samples A, B, C, D and E. The samples are made by adding 20 parts each of the product to be tested with 2.3 parts of ethyl alcohol

b) Evaluation of the test results

The amount of fat residues stained in this way is assessed visually according to the following rating scale:

0 = not colored (no oily residue present);

1 = very weakly colored (oily residue before

handen);

2 = weakly colored (oily residue present);

3 - colored (oily residue present);

4 = strongly colored (oily residue present):

5 = very strongly colored (oily residue present).

The average fat residue is determined according to de ι equation

average fat residue = I ¹ ^

calculated, in which α to e have the following meaning: Number of bowls rated with 1

a =

_ Number of bowls rated with 2

O - ~~ ~~~ - .. - ■

■ 100 ;.

_ Number of bowls rated 5 _{1 / v} .

The flushing efficiency in percent is thus (average residue).

Number of bowls rated 3 ^ _- c) Flushing efficiency

5 and E are summarized in Table VI.

3601

Vl 1 934 540 12th H 6. Toxicity test Γ dragonfly

sample

Flushing efficiency,

C. D. E. 80 70 75

The toxicity of the samples listed in Table VII below is determined in each case by injecting the sample into the abdomen of mice, the LD _{50 being} determined as the test results.

Table VIl

sample

Product V (M Example 1

Product of example 3

Product of Example 4

Commercially available Product (1)

Commercially available
Product (2) * ·)

LD ₅₀ (g / kg) 4.0 to 3.8 4.29 to 3.6 3.3 to 3.0

·) Sorbitan monolocate-ethylnoxide condensation product (molar ratio I: 23). ♦ ^ Sorbitan monolaurate ethyl oxide coidation product (molar ratio 1:20).

2.8 to 2.5

2.0 to 1.7

7. Toxicity upon percutaneous ingestion

Three samples are used in this test, namely the product of Example 1, the product of Example 3 and distilled water as a blank. Each sample is applied once a day on 5 consecutive days in an amount of I Γίϊΐ aiii 10 CiTr of the giiiti shaved back skin of five healthy rabbits with a body weight of 3 kg. 24 hours after the last application of the sample to be tested, blood and urine are taken from the test animal for examination. The test results are as follows:

a) Observation of the general condition

With regard to appetite, change in body weight, spontaneous behavior, a deficiency in Mjjskelkoordinatioii, paralysis, convulsion, the atonicity of the muscles, the excitement, the calming, the mucous membrane of the eyes, the formation of tears, salivation, urine output and hair loss are not changes in general condition ascertain.

ii) Condition of the lhiut in the application area

'There are no changes, for example regarding the inflammatory reaction, allergic reaction or a thickening.

iii) blood and urine sample

When the blood test is hit. -visible by the number the erythrocytes and leukocytes, the hemoglobin and hematocrit values and the liver function, such as from Table VIII it can be seen that nothing unusual is found. The results of the urine sample are, as can be seen from Table IX, normal in all cases.

Table VIII

Before
Afterward number of
Erythrocytes
(107mm ³ ) number of
Leukocytes
(mm ¹ ) Hemoglobin level Hematocrit value S-GPT
(Came
Units) Distilled water
(Blank sample) Before
Afterward 648 ± 41
655 ± 35 8080 ± 3239
8280 ± 467 67.6 ± 2.4
68.4 ± 1.3 41.0 ± 1.7
41.4 ± 1.2 35 ± 4
36 ± 3 Product of
example 1 Before
Afterward 648 ± 70
642 ± 69 8420 ± 1088
8280 ± 542 67.6 ± 2.3
68.0 ± 2.3 41.8 ± 1.5
41 φ ± 1.0 38 ± 4
37 ± 2 Product of
Example 3 645 ± 33
650 ± 35 8500 ± 498
8480 ± 392 67.0 ± 2.4
66.0 ± 2.2 40.6 ± 1.9
41.0 ± 0.9 39 ± 3
40 ± 6

S-GPT: Serum Glutamine Pirvin Transaminase.
Pre-animal: Before application of the sample.
After: After applying the sample.

3601

Table IX

Number of Experimental rabbit Before
Afterward t 2 3 4th 5 comment Sucrose Before
Afterward (-)
(-) (-)
(-) (-)
(-) (-)
(") (-)
(-) normal Distilled water
(Blank sample) protein Before
Afterward (-)
(-) (J)
(J =) (-)
(±) (J :)
(J) (-)
(-) normal Urobilinogen Before
Afterward (t)
(±) U)
(±) U)
(±) (±)
U) "(: t)
U) normal Sucrose Before
Afterward (-)
(~) (-)
(-) (-)
ι \ U)
(...) (-)
() normal Product of
example 1 protein Before
Afterward (-)
(t) (:H)
(J :) (-)
(-) (H)
(I) (-)
(-) normal Urobilinogen Before
Afterward (J :)
(! :) U)
(J :) (-1:)
(l ·) (J :)
(I) (1)
(J :) Low turbidity at
Addition of the sample
normal Sucrose Before
Afterward ()
(-) (-)
(-) (-)
(-) (-)
(-) (...)
() normal Product of
Example 3 protein Before
Afterward (-)
(i) (-)
(-) (J =) (i)
(I) (-)
(-) normal Urobilinogen (J =)
U) (J-)
(±) U)
U) (I.)
U) (L-)
(J :) normal

8. Phytotoxicity (determined by the seed dipping method)

In this test seeds of Brassica var. Koniatsuna in an aqueous solution of the product are immersed in Example 1, followed by sowing 50 of the thus-treated seeds per test unit and, after the seedlings for 3 days at 25 ⁰ C has grown, the size of the Measures plants to determine the phytotoxicity of the product under study. The blank test is carried out in the same way using water as a control substance. The results of this test are shown in Table X.

Table X

dilution Above-ground growth Relative
Growth
index
(Control
attempt)
= 100) Phyto
toxicity (2) Underground growth Relative
'S waxed
index
(Control
attempt
= 100) Phyto
toxicity (2) Test sample xlOOO Growth
index (1) 97 0 Growth
index (1) 122 -y Product of example 1 x2000 39.6 100 0 51.0 115 -1 Product of example 1 X5000 40.8 115 j 48.5 95 1 Product of example 1 - 46.8 100 0 39.7 100 0 Control attempt 40.8 42.0 (Blank sample)

1) The growth index is obtained from the results 55 digits according to the equation the evaluation of the test plant size is calculated:

Growth ■, 1 i_

index (%) = ^ _T _ ^? _

Size of the plant

0 to 0.5,
0.5 to 1.0
1.0 to 1.5
1.5 to 2.0
2.0 to 2.5
2.5 to 3.0

Valuation number

60

⁴ " ^{4 + 5} " ⁸

0 1 2 3 4 5

65

The growth index is derived from the valuation

5ΛΓ

calculated, in which N is the total number of seedlings and n 2, M ₃ , 4 and n _s denote the number of seedlings each evaluated with the evaluation number corresponding to their indices.

2) The phytotoxicity is determined according to the rating scale listed below, which is based on the relative growth index, d. H. the growth index set to 100 for the control

3601

15th

or blind test
index rated.

related relative growth

Relative growth index

Phytotoxicity

up to 125

to 110

to 95

up to 80

up to 65

- 2nd

-1

9. Biodegradability

Surface water from a sewer system is poured into an agar nutrient broth to keep bacteria away to breed. The culture broths listed in Table XI are inoculated with the bacteria cultivated in this way, whereupon the respiratory metabolism of the bacterial cultures, d. H. the admission or the delivery of oxygen, using a Warburg manometer determined in the course of time. The results are shown in Table XII.

Table XI

Culture broth

No.

composition

0.1% KH ₂ PO ₁ , 0.04% MgSO ₁ · 7 H ₂ O,

5TpM Fe and Mn as well as sterilized,

distilled water

Culture broth No. 1 -J- 400 bacteria / mm ³ Culture broth No. 1 - ^L 0.1 percent by weight

Product of example 1
Culture broth No. 1 + 400 bacteria / mm ³

+ 0.1 percent by weight Pr Jukt of

example 1
Culture broth No. 1 + 0.1 percent by weight

Product of example 3
Culture broth No. 1 + 400 bacteria / mm ³

+ 0.1 percent by weight of the product from Example 3
Culture broth No. 1 + 0.1 percent by weight

Product of example 4
Culture broth No. 1 + 400 bacteria / mm ³

+ 0.1 percent by weight product of

Example 4

table Oxygen
admission
or delivery
(ml) 1 XII h XTa
3 gene
4th 5 Kul
door
broth Submission
admission 1
0 Nac
2 1
0 1
0 1
0 1 Submission
admission 0
0 2
0 0
0 0
0 0
0 2 Submission
admission 0
1 0
0 0
2 0
1 0
1 3 Submission
admission 0
3 0
3 0
10 0
3 0
3 4th Submission
admission 0
1 0
17th 0
1 0
1 0
1 5 Submission
admission 0
2 0
2 0
4th 0
2 0
2 6th Submission
admission 0
1 0
8th 0
2 0
1 0
1 7th Submission
admission 0
2 0
3 0
6th 0
2 0
2 8th 0
12th

Claims (1)

Claim: Method ιίιγ production of a detergent oil mixture from at least one fatty acid ester of a sucrose-alkylene oxide condensation product, characterized in that sucrose in a known manner in Water and / or one or more monohydric or polyhydric alcohols dissolves in the so-formed Solution 1 to 50 moles of ethylene or propylene oxide, based on the total amount of sucrose and Alcohol, initiates at a temperature between 80 and 200 C and the condensation product mixture obtained with one or more fatty acids at a temperature between 160 and 200C or one or more fatty acid esters of lower alkanols at a temperature between 80 and 180 C at least partially esterified. The previously known and widely used non-ionic surface-active substances or surfactants, in particular those used as wetting agents or detergents have an overall satisfactory quality Dispersing or washing power, satisfy but with regard to the foaming agent, the toxicity and biodegradability not yet, although various attempts have been made to improve them with regard to these properties, e.g. By introducing end groups or straight chain Fatty alcohol alkyl groups. Detergent raw materials based on sucrose fatty acid esters are also known as nonionic surfactants which are reasonably satisfactory with regard to the properties mentioned above. However, these surfactants are produced by adding alkylene oxides to sucrose in a two-phase reaction system, namely by means of a solid-vapor phase reaction (method for reaction under atmospheric pressure) or by solid-liquid reaction (method with reaction under elevated pressure). Because of the heterogeneous reaction system, these processes are extremely unsuitable and can only be transferred to an industrial scale with difficulty. To overcome these difficulties, attempts have been made to employ a more favorable one or two liquid phase reaction system by liquefying the sucrose used as a starting material or dissolving it in a solvent. The liquefaction of sucrose is not possible in practice because sucrose inevitably decomposes when heated to the melting point. Therefore, in numerous known processes, the reaction between sucrose and alkylene oxide is carried out in the presence of a solvent for sucrose, which facilitates the addition of the alkylene oxide and the subsequent esterification of the reaction product in that a reaction system consisting of one or two liquid phases is present. Due to the use of a solvent, however, the previously known processes for the production of detergent raw materials based on sucrose fatty acid esters are disadvantageous in that the synthesis has to be carried out in several stages, some of which are difficult to carry out, al> the end product because of its solvent residue content smells bad and the usability of the end product is limited due to the toxicity of the residual solvent it contains. Furthermore, the sucrose esters produced in this way are inevitably expensive because of the high production costs.
One of these known processes is that in the ίο published documents of the Belgian patent specification 677 874 described method for the preparation of a surfactant in which at the same time one or more mono- or polyhydroxy compounds, including sucrose, with one or more fatty acid esters of aliphatic Alcohols od polyols and an alkylene oxide reacted in the presence of an alkaline catalyst will. In this case too, a heterogeneous reaction mixture is formed. _2J E.ρ Process for the production of a surface-cooling agent is also described in the published documents of the Belgian patent 687 223. In this process, an alcohol or polyol, including sucrose, a fatty acid ester and an alkylene oxide are converted at the same time. A heterogeneous reaction mixture is also achieved in this known process. A similar procedure is used in the French Patent publication 1 546 261 described in which a surface-active Means by simultaneous reaction of a compound with labile hydrogen, among others Sucrose, a fatty acid and a salt eiü'.T fatty acid and an alkylene oxide produced will. This process also belongs to the state of the art already mentioned, according to which the implementation can only be carried out incompletely in a heterogeneous reaction system. From your German Auslegeschrift 1 125 168 was already known that an intermediate containing hydroxyl groups for the production of polyurethanes by reacting a mixture of carbohydrates with an alcohol can be obtained with alkylene oxide. However, this interpretative document does not give any teaching in soft A detergent mixture with advantageous properties can be achieved on the basis of sucrose could. The invention is therefore based on the object of a method for producing a detergent raw material composition from non-ionic surfactants based on sucrose derivatives with a satisfactorily low Foaming power, low toxicity and high biodegradability as well as high dispersibility or to provide detergency available in a simple manner and with low manufacturing costs can be carried out. The invention relates to a process for the production of a detergent raw material mixture from at least one fatty acid ester of a sucrose-alkylene oxide condensation product and at least one fatty acid ester of an alcohol-alkylene oxide condensation product, which is characterized in that sucrose in a known manner in Water and / or one or more monohydric or polyhydric alcohols dissolves in the solution thus formed 1 to 50 moles of ethylene or propylene oxide, based on the total amount of sucrose and alcohol ei ier temperature between 80 and 200 ° C and the resulting condensation product mixture with a