DE1934540B2 - PROCESS FOR PREPARING A DETERGENT RAW MATERIAL MIXTURE - Google Patents

Description

or several fatty acids at a temperature between 160 and 200 ⁰ C or one or more fatty acid esters of lower alkanols at a temperature between 80 and 180 ⁰ C at least partially esterified.

The hydroxyl compound used in the process of the invention serves not only as a solvent for sucrose in the condensation reaction, but also as a starting material for the formation of a nonionic surfactant, namely a fatty acid ester of an alcohol-alkylene oxide condensation product, which forms the second necessary component of detergent raw material mixtures that can be produced according to the invention. Using water as the hydroxyl compound or solvent, caused by the reaction with the alkylene oxide used in each case in situ, a corresponding the Atkylenoxyd glycol, ie, there is obtained the Urapid-cozy result as in use of the corresponding glycol as a solvent.

üei ücr practical implementation of the invention In the process, the sucrose is dissolved in a lower alkanol or a glycol. Therefore A variety of different primary, secondary and tertiary mono-, di-, tri- and polyols can be used graze. Typical examples of suitable alcohols are alkanols such as methyl, ethyl, propyl and butyl alcohol. Glycols, such as ethylene, diethylene, Triülhvlen-Lind Tetraethylene glycol, as well as higher oligomers of the polyethylene glycol series, propylene, dipropylene, Tripropylene and tetrapropylene glycol as well as higher oligomers of the polypropylene glycol series, glycerine, Sorbitol and sorbitan.

For economic and technical reasons as well as with a view to toxicity, preference is given to Ethyl alcohol, ethylene glycol, propylene glycol, ghzerin and sorbitol are used.

The sucrose should be dissolved in the alcohol used as the solvent at the lowest possible temperature to avoid any caramelization. Preferably one works at a temperature of at most 90'C. Under these temperature conditions, the ratio of sucrose to alcohol should be be at most 8: 2 in order to achieve a satisfactory solution without caramelization of 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 each active hydrogen atom of the sucrose used as the starting material and 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 ⁰ C and preferably between 100 and 200 C when using of ethylene oxide and between 80 and 15O ⁰ 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 used as esterifying agent or the lower fatty acid alkyl ester can be used in any proportions, based on the number of active hydrogen atoms in the condensation products. Preferably, about 1 to 5 moles of esterifying agent are used per mole of sucrose used. When using a fatty acid as the esterifying agent, the esterification temperature is preferably between 160 and 200 ⁰ C, while is preferably between 80 and 180 ° C in the esterification by transesterification, ie when using a fatty acid alkyl ester as the esterifying agent, the esterification temperature.

The esterifying agent used is preferably saturated and unsaturated fatty acids with 8 to

ίο 22 carbon atoms and their esters with lower alcohols. Typical examples of suitable esterification agents are caprylic, capric, lauric, myristic, palmitic, stearic, arachin, oil, sabin, juniper, 12-hydroxystearin, rijinolein, linden, physeterin, palmitolein -, gadoleic and erucic acids and their lower alkyl esters, such as the methyl, ethyl, propyl and butyesters, and the triglycerides of the acids mentioned.

The detergent raw material mixtures made from nonionic surfactants by the process of the invention Can be used as emulsifiers, dispersants, solubilizers, defoamers or foam inhibitors 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 mouth 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 achieved lowering of the surface tension, to the detergent effect, Toxicity, phytotoxicity and biodegradability than the previously known comparable Detergent raw materials, such as those made known, for example, by the process of Documents of Belgian patent 677 874 were obtained. This has been shown by comparative tests that 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 were carried out according to Examples 7, 14 and 18 of Belgian patent 677,874 were prepared. The applied Test methods are described below following the examples according to the application.

These comparative tests detergent ingredient mixtures of the invention in 0 showed l ° / ₀ strength aqueous solution has a lower surface tension than the known products, and their washing efficiency was partly twice as large 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. When testing the biodegradability, which is described below under (9), the detergent mixtures according to the invention were degraded significantly 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 examples below.

5 6

Example 1 tion mixture contained hydrochloric acid neutralized, whereupon

the reaction mixture is dehydrated and filtered. as

A small, with a thermometer, a Vorrich- product you get a mixture of sucrose poly-

device for introducing nitrogen and alkylenoxyd oxyäthylenlaurat and Oxypropylenpolyoxyäthens as well as a stirrer equipped autoclave is equipped with 5 laurate

684g sucrose, 184g glycerine and 0.8g potassium - Example 4 hydroxyd charged. This mixture becomes through

Heating aui 80 to 85 ⁰ C a solution. Then the autoclave used in Example 1 is with

if the air in the autoclave is displaced with nitrogen, 684 g sucrose, 184 g glycerine and 0.8 g potassium

whereupon the contents are heated to about 100 ° C and charged io hydroxide, whereupon from the mixture through

a solution is produced within 3 hours under a pressure of 2 to heating to 80 to 85 ^{° C.}

4 kp / cm ^{2 introduces} 440 g of ethylene oxide, whereby a pale yellow oil is then displaced, the air contained in the autoclave is obtained. This oil (664.4 g) is added with nitrogen and the contents of the autoclave are heated to about 284.4 g of stearic acid and 0.6 g of 36% 100 ° C., whereupon it is poured into a thermometer under hydrochloric acid within 3 hours , a pressure of 2 to 4 kp / cm ² initiates 440 g of ethylene oxide. Nitrogen supply line, a condenser and a pale yellow oil.

Given a four-necked flask equipped with a stirrer. Then this oil (657 g) is in a as described in the foreseen the mixture for about 8 hours with about going examples equipped four-180 ⁰ C, whereupon the acid number of the mixture is transferred under neck flask by adding 298.5 g

5 lies. Which converts as an esterification catalyst in the reaction methyl stearate S hours at about 10 OC, The hydrochloric acid contained in the mixture is mixed with potassium whereupon the hydroxyl number of the reaction mixture is 493 hydroxyd neutralized, whereupon the reaction is. The reaction mixture is then mixed with salt dehydrated and filtered. The acid used as a catalyst is added as the acid Product sucrose polyoxyethylene stearate and GIy potassium hydroxide to neutralize, dehydrated and zeryl polyoxyethylene stearate. 25 filtered. The product obtained is a mixture of

Sucrose polyoxyethylene stearate and glyceryl poly-

Example 2 oxyethylene stearate.

The autoclave described in Example 1 is identical to Example 5

684 g sucrose, 184 g glycerine and 4 g potassium 3 °

hydroxyd charged, whereupon the mixture through the same autoclave as in Example 1 is with

Heating to 80 to 85 ⁰ C converts into a solution. 684 g sucrose, 124 g ethylene glycol and 0.8 g ca-

Then the air from the autoclave is charged with nitrogen liumhydroxyd, whereupon the mixture through

displaced and the reaction mixture ^{heated to 120 0} C to 60 to 70 ^c transferred into a solution

heats up, going below 35 within about 10 hours. Then the one contained in the autoclave is displaced

a pressure of 2 to 4 kp / cm ² 2320 g propylene oxide air with nitrogen and heated the contents to 100 ⁰ C,

initiates. The product obtained is a yellowish-brown one whereupon within about 3 hours under a

Liquid. Pressure of 2 to 4 kp / cm ^{2 introduces} 440 g of ethylene oxide.

This liquid (1592 g) is poured into a pale yellow liquid,
Game 1 described equipped four-necked flask exceeded 40 This liquid (642 g) is dissolved in a like leads into and reacted for 8 hours at about 180 ⁰ C with 284.4 g previous examples equipped stearic acid and 0.6 g of 36% hydrochloric acid, Four-necked flask transferred and 8 hours at about whereupon the acid number of the reaction mixture is below 5 180 ^c C with 302 g of methyl ricinoleate and 1.1 g of potassium. The reaction mixture is then converted to the neutral carbonate, after which the base number of the cation of the hydrochloric acid contained therein with potassium reaction mixture is 307. The reaction hydroxide is added, dehydrated and filtered. The mixture is then mixed with sulfuric acid, in order to neutralize the product a mixture of sucrose poly- the potassium carbonate used as a catalyst to oxypropylene stearate and glyceryl polyoxypropylene stearate, dehydrate and filter, with arat. End product a mixture of sucrose polyoxy-

50 ethylene ricenoleate and polyoxyethylene glycol ricinoleate

Example 3 receives.

The small autoclave described in Example 1 becomes Example 6
with 684 g sucrose, 152.2 g propylene glycol and

0.8 g of potassium hydroxide are charged, whereupon 55 of the amounts used in the preceding examples

the mixture by heating at 60 to 70 ⁰ C a autoclave is charged with 684 g of sucrose, 364.4 g sorbitol

Solution. Then the in the autoclave is loaded and (J.s g potassium hydroxide, whereupon you from

Lent air is displaced with nitrogen and the reaction mixture by heating to 80 to 90 ⁰ C a

The mixture is heated to about 100 ° C, whereupon a solution is produced in the course of the process. Then the produced in the autoclave is

air kept under a pressure of 2 to 60 for about 6 hours is displaced with nitrogen and the autoclave

4 kp / cm ² 88Og ethylene oxide introduces. Obtained as content to about 12O ⁰ C heated, after which within

Product a yellowish brown liquid. about 6 hours 440 g of ethylene oxide under pressure

This liquid (647 g) is introduced into one as in the case of 2 to 4 kp / cm ² . A pale yellow one is obtained

Game 1 described equipped four-necked flask over-liquid.

leads and 8 hours at about 180 ° C with 200.31g 65 This liquid (702 g) is in a like in the

Lauric acid g 36 / reacted and 0.7 ° _o hydrochloric acid, previous examples equipped

whereupon the acid number of the reaction mixture transferred under 5 four-necked flasks and 8 hours at about

lies. Then with Kaliumhydroxyo is the reaction in the 100 ⁰ C with 891.5 g and 1.7 g Stearinsäuretriglyzerid

t 934

Potassium carbonate implemented. The complete abatement of this implementation is indicated by the disappearance of the Flecks 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 heating to 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 ² 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 18O ⁰ C and 200 g of lauric acid and 4.6 g of 36 ° / _o hydrochloric acid, after which the acid number of the reaction mixture below 5 lies. The hydrochloric acid contained in the reaction mixture as a catalyst is then 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 glycol monoethyl ether monolauric acid ester.

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, followed by converting the mixture by heating at 60 to 70 ^c C in a solution. 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 introduced under a pressure of 2 to 4 kp / cm ² within about 3 hours. A pale yellow liquid is obtained. This liquid (1165 g) is transferred to a four-necked flask equipped as in the previous examples and reacted for 8 hours with 200 g of lauric acid and 1.2 g of 36% hydrochloric acid at about 180 ° C. , after which the acid number of the reaction mixture is below 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.

To get the excellent properties of the detergent raw material produced according to the invention in comparison to known nonionic surfactants will show a series of comparative experiments carried out.

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

1. Foam test

According to the method of Ross - Miles the foaming ability of the samples of non-ionic surfactants listed in Table 1 below at 25 ⁰ C in the form of 0.257 _0. ig ^he tested aqueous solutions.

Table I.

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

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

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

2. Defoaming test

The defoaming 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 the Table III compiled.

Table II

sample

Composition of the test solution

0.025% product of Example 2;

0.25 ° / ₀ Nonylphenol-Ethylenoxyd-Kon-

densation product

(Molar ratio 1:10); Rest water.

B 0.025 ° / ₀ Polypropylene glycol (Molekulai

weight 2000);

0.25% nonylphenol-ethylene oxide condensation product (Molar ratio 1:10); Rest water.

C 0.25 ° / "Nonylphenol-ethylene oxide con-

Blind condensation 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. Direct
after adding
the sample 90 65 B. 80 C. 100 Blind test 100

3. Surface tension test

The surface tension of the samples listed in Table IV ax in the form of 0.1% aqueous solution

sample product
from
example 1 product
from
Example 3 product
from
Example 4 Trade
usual
Product*) surfaces
tension
(dyn / cm) .. 40 45 30th 40

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

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

^{Table IV} a) Test procedure

Bowls with a diameter of 13 cm on the concave side are used, each by dropping 2 ml of a prepared by mixing equal amounts of beef tallow and salad oil Dirt oil are soiled as evenly as possible, whereupon they are left to stand for 24 hours and then subject to the following test:

In each case a soiled bowl is immersed in a wash basin, the 41 of the as above described contains prepared, tested, 40 ± 2 ° C warm detergent solution, dipped and with washed with a common household sponge for 30 seconds, after which it is rinsed with water. 5 bowls at a time are washed in the same way. The so washed

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

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

hand):

2 ■ = slightly 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 calculated according to the equation

4. Dispersibility

i) First, the dispersing or washing capacity of the samples listed in Table V 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

Surfactant concentration 0.5 0.25 (%) Surfactant 52.7 59.4 1 63.3 66.1 0.1 Product of example 1 ... 66.4 75.5 57.9 51.5 Product of example 3 ... 66.4 63.3 Product of example 4 ... 81.2 61.5 70.0 51.8 Commercially available Product*) 70.6 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

average fat residue =

Number of bowls rated 5

calculated, in the α to e have the following meaning:

Number of bowls rated 1,. .

a- 100;

The flushing efficiency in percent is thus K. Number of bowls rated 2 (average residue).

ο = ■ ■ * 100;

Number of bowls rated 3

_{d =}

number

^^ ewerteteji ^ clrusseln

c) flushing efficiency

The determined in the above manner and ΐ ~ - · 100; calculated flushing efficiency of samples A, B, C, and E are compiled in Table VI.

Table VI

sample A. B. C. D. E. Flushing efficiency,
0 /
/O 90 60 80 70 75

6. Toxicity test

The toxicity of the samples listed in Table VI 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 VII

sample

Product of example 1

Product of Example 3 Product of
Example 4

Commercial product (1) *)

Commercially available product (2) **)

LD ₅₀ (g / kg) I 4.0 to 3.8 | 4.29 to 3.6

*) Sorbitan monoleate-ethylene oxide condensation product (molar ratio 1:23). **) Sorbitan monolaurate-ethylene oxide condensation product (molar ratio 1:20).

3.3 to 3.0 j 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 1 ml to 10 cm ^{2 of} the clean-shaven dorsal 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

Regarding appetite, change in body weight, spontaneous behavior, lack of muscle coordination, 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.

3 ° ii) Condition of the skin in the area of application

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

iii) blood and urine sample

During the blood test, the number of erythrocytes and leukocytes, the hemoglobin and hematocrit and liver function, as can be seen from Table VIII, are nothing unusual ascertain. The results of the urine sample are all as shown in Table IX Cases normal.

Table VIII

number of

Erythrocytes

(10 '/ mm »)

number of

Leukocytes

(mm ¹ )

Hemoglobin level Hematocrit wide

(Vo)

S-GPT (jug units)

Distilled water (Blank sample)

Product of example 1

Product of Example 3

Before, afterwards

Before, afterwards

Before, afterwards

648 ± 41 655 ± 35

648 ± 70 642 ± 69

645 ± 33 650 ± 35

S-GPT: Serum Glutamine Pirvin Transaminase. Before: Before applying the sample. After: After applying the sample.

8080 ± 3239 8280 ±

8420 ± 1088 8280 ±

8500 ± 8480 ±

67.6 ± 2.4
68.4 ± 1.3

67.6 ± 2.3
68.0 ± 2.3

67.0 ± 2.4
66.0 ± 2.2

41.0 ± 1.7 41.4 ± 1.2

41.8 ± 1.5 41.6 ± 1.0

40.6 ± 1.9 41.0 ± 0.9

35 ± 4

36 ± 3

38 ± 4

37 ± 2

39 ± 3 40 ± 6

13th

Table IX

Number of Experimental rabbit Before
Afterward 1 2 3 4th 5 comment Sucrose Before
Afterward (-)
(-) (-)
(-) (-)
(-) (-)
(-) (-)
(-) normal Distilled water
(Blank sample) protein Before
Afterward (-)
(-) (±)
(±) (-)
(±) (±)
(±) (-)
(-) normal Urobilinogen Before
Afterward (±)
(±) (±)
(±) (±)
(±) (±)
(±) (±)
(±) normal Sucrose Before
Afterward (-)
(-) (-)
(-) (-)
(-) (-)
(-) (-)
(-) normal Product of
example 1 protein Before
Afterward (-)
(i) (±)
(±) (-)
(-) (±)
U) (-)
(-) normal Urobilinogen Before
Afterward (±)
(±) (±)
(±) (±)
(i) (±)
(±) (±)
(±) Low turbidity at
Addition of the sample
normal Sucrose Before
Afterward (-)
(-) (-)
(-) (-)
(-) (-)
(-) (-)
(-) normal Product of
Example 3 protein Before
Afterward (-)
(±) (-)
(-) (±)
(±) (±)
(±) (-)
(-) normal Urobilinogen (±)
(±) (i)
(±) (i)
{-) (±)
(±) (±)
(±) normal

8. Phytotoxicity (determined by the seed dipping method)

In this test seeds of Brassica var. Komatsuna 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
Growth
index
(Control
attempt
= 100) Phyto
toxicity (2) Test sample XlOOO Growth
index UJ 97 0 Growth
index (1) 122 -1 Product of example 1 X2000 39.6 100 0 51.0 115 -1 Product of example 1 X5000 40.8 115 -1 48.5 95 1 Product of example 1 - 46.8 100 0 39.7 100 0 Control attempt
(Blank sample) 40.8 42.0

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

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

0 1 2 3 4 5

The growth index is derived from the valuation

5 N

calculated, in which N is the total number of seedlings i: and n Tj ₂ , n ₃ , W ₄ and n _{s are} the number of seedlings b valued in each case with d <their indices.

2) The phytotoxicity is determined according to the rating scale listed below, which is ai the relative growth index, d. h, the growth index set to de equal to 100 at the Kontroi

or blind test-related
index rated.

relative growth

Relative growth index Phytotoxicity 140 to 125
125 to 110
10 to 95
95 to 80
80 to 65 2
1
0
1
2

9. Biodegradability

surface water is placed in an agar nutrient broth Poured from a sewer system to grow bacteria. With the bacteria grown in this way will be inoculated the culture broths listed in Table XI, whereupon the respiratory metabolism of the Bacterial cultures, d. H. the uptake or release 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 ₄ , 0.04% MgSO ₄ 7 H ₂ O,

5TpM Fe and Mn
distilled water

as well as sterilized,

Culture broth No. 1 + 400 bacteria / mm ³ culture broth No. 1 + 0.1 percent by weight

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

+ 0.1 percent by weight product 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

Tabel Oxygen-
Recording 1 XII 3 4th 5 Kul or delivery
(ml) 1
0 ]
0 1
0 1
0 door
broth Submission
recording 0
0 0
0 0
0 0
0 1 Submission
recording 0
1 After X days 0
2 0
1 0
1 2 Submission
recording 0
3 2 0
10 0
3 0
3 3 Submission
recording 0
1 2
0 0
1 0
1 0
1 4th Submission
recording 0
2 0
0 0
4th 0
2 0
2 5 Submission
recording 0
1 0
3 0
2 0
1 0
1 6th Submission
recording 0
2 0
17th 0
6th 0
2 0
2 7th Submission
recording 0
2 8th 0
8th 0
3 0
12th

Claims (1)

1 2 ρ, must, which are sometimes difficult to carry out, as ratentansnrucn: _{the end product} smells bad because of its content of solution process for the production of detergent residues and the usability of raw material mixture of at least one fatty acid of the end product due to the toxicity of the esters in it Sucrose-alkylene oxide condensation 5 contained solvent residues is limited. Further product, characterized in that the sucrose produced in this way is in a known manner sucrose in ester because of the high production costs incessantly water and / or one or more one or more expensive. polyhydric alcohols dissolves, in the so formed To these known processes belongs the m the solution 1 to 50 moles of ethylene or propylene oxide, io published documents of the Belgian patent based on the total amount of sucrose and writing 677 874 described process for Her alcohol, at a Temperature between 80 and position of a surface-active substance at which 200 ⁰ C initiates and the condensation obtained at the same time one or more mono- or polyproduct mixture with one or more fatty acids hydroxy compounds, including sucrose, at a temperature between 160 and 200 ⁰ C 15 one or more Fettsäureestern of aliphatic or one or more lower alcohols or polyols Fettsäureestern and an alkylene oxide in alkanols at a temperature between 80 and the presence of an alkaline catalyst reacted 180 ⁰ C at least partially esterified. will. In this case , too, will be a heterogeneous one Reaction mixture formed. ao A process for producing a surface active agent is also described in the published documents of Belgian patent 687 223. at this process will also be an alcohol The previously known and widely used or polyol, including sucrose, a fatty acid non-ionic surface-active substances or ten esters and an alkylene oxide. Even with this one side, especially those known as wetting agents or detergents, a heterogeneous reaction gentien used, achieved an overall positive mix. A similar process is described in the French patent specification 1 546 261, however, with regard to the foaming power, in which a surface-active agent is not yet obtained, although various attempts have been made were to improve a compound with labile hydrogen, among ansie in view of these properties, whose sucrose, a fatty acid and a salt z. B. by introducing end groups or straight chain fatty alcohol alkyl groups produced by a fatty acid and an alkylene oxide. will. This process also belongs to the already mentioned state of the art, according to which the UmBasis of sucrose fatty acid esters as non-ionic setting in a heterogeneous reaction system is only known to non-surfactants, which are carried out completely with respect to the above can. Reasonably satisfying from the named properties. This German Auslegeschnft 1125 168 was already known that surfactants are known through the addition of alkylene that a hydroxyl group-containing oxydene is produced on sucrose in a two-phase reaction system for the production of polyurethane, namely by means of a solid by converting carbohydrates in a mixture with vapor phase reaction (process for reacting an alcohol with alkylene oxide can be obtained under atmospheric pressure) or by solid- This interpretation does not give any teaching in which liquid reaction (process with reaction under way on the basis of sucrose a detergent increased Pressure). These processes are achieved with advantageous properties due to the heterogeneous reaction system being extraordinarily capable. inexpedient and can only be achieved with difficulty- The invention is therefore based on the object transferred to the industrial scale. a process for the production of a detergent raw To overcome these difficulties, a mixture of non-ionic surfactants was used on the is looking for a cheaper reaction system with one or 50 bases of sucrose derivatives with satisfactorily low to apply two liquid phases, by the as rigem foaming power, low toxicity and high Sucrose used as the starting material liquefies biodegradability and high dispersibility or dissolved in a solvent. To provide the capacity or washing capacity that is available in However, liquid sucrose separates in a simple manner and with low production costs Practice because sucrose can be carried out at the time of er-55. heat to the melting point inevitably decomposes. The invention relates to a process for the production of a detergent raw material mixture from reaction between sucrose and alkylene oxide in at least one fatty acid ester of a sucrose-presence of a solvent for sucrose alkylene oxide condensation product and at least carried out through which the addition of the alkylene 60 a fatty acid ester of an alcohol-alkylene oxide conoxide and the subsequent esterification of the reaction product, which is characterized, is facilitated by the fact that a reaction system is made up of one of the two liquid phases in front of water in a manner known per se and / or one or more is one or more. Due to the use of a solvent, valuable alcohols dissolve in the solution thus formed, however, are the previously known processes for the preparation of 65 1 to 50 mol of ethylene or propylene oxide, based on detergent raw materials based on the total amount of sucrose and alcohol Sucrose fatty acid esters disadvantageous insofar as the temperature between 80 and 200 ⁰ C initiates and synthesis is carried out in several stages, the condensation product mixture obtained with a