DE1132730B - Process for the production of surface-active substances by reacting organic compounds containing an active hydrogen atom with two different alkylene oxides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY KL.39c 30

INTERNAT. KL. C 08 g

GERMAN

PATENT OFFICE:

EXPLAINING EDITORIAL 1132 730

W 8712 IVd / 39 c

REGISTRATION DATE: MAY 31, 1952

NOTIFICATION OF REGISTRATION AND ISSUE OF EDITORIAL: JULY 5, 1962

The invention relates to a process for the preparation of surfactants. It enables the production of surface-active agents tailored to specific purposes, namely in that the hydrophobic and the hydrophilic components of the agent both in terms of their molecular weight as well as their type depending on the desired use of the Funds are granted.

It is an accepted principle that all surfactants that are both hydrophobic and also contain hydrophilic components, have relatively large molecules. The hydrophobic A component in the previous surface-active agents was always a hydrocarbon group, such as they are found in the long-chain fatty acids and alcohols, or an alkylaryl group as in the known cleaning agents of the alkylarylsulfonate type are present. The hydrophilic component was either ionic in nature, such as B. in the alkali metal salts of long-chain fatty acids, the quaternary ammonium compounds, the alkylarylsulf onates and the sulfates of long-chain fatty acids, or non-ionic, such as. B. in the long-chain hydrophilic polyethers obtained by condensation of alkylphenols with ethylene oxide or its Derivatives are obtained. It has been recognized that it is necessary to achieve the most favorable surface-active properties what is desired is that there is a suitable balance between the hydrophobic and hydrophilic Components.

A significant shortcoming of the previous surfactants is that their structure in the essential in each case and that it is difficult process of manufacture

of surfactants

Implementation of organic compounds containing an active hydrogen atom with two different alkylene oxides

Applicant:

Wyandotte Chemicals Corporation, Wyandotte, Mich. (V. St. A.)

Representative: Dr. W. Beil, lawyer, Frankfurt / M.-Höchst, Antoniterstr.

Claimed priority:

V. St. v. America of May 31, 1951 and March 26, 1952 (No. 229 128 and No. 278 632)

Donald Richard Jackson, Wyandotte, Mich., And Lester Gordon Lundsted, Gross He, Mich.

(V. St. A.) have been named as inventors

of surface-active substances by reaction of an active hydrogen atom have the organic Compounds with two different alkylene oxides is to change their molecular weight or their type. 35 in succession, with the indication that one is in the

For the production of a surfactant based on fatty acids and / or fatty alcohol with different Chain length of the hydrophobic component is the use of several different ones Starting materials necessary. Because of the different raw materials used when using several raw materials Difficulties encountered in reaction conditions, it is not possible to surface-active Manufacture means which differ from each other by small, uniform increases in chain length distinguish the hydrophobic component. Similar difficulties arise in manufacture of petroleum-based surfactants that differ from each other only by small, finite first stage 1 mole of a low molecular weight organic compound with only one reactive Hydrogen atom with an alkylene oxide of the formula

IV

condensed (R ₁ , R ₂ , R ₃ and R ₄ = hydrogen atoms or aliphatic ^ or aromatic groups, with at least one of these radicals not being a hydrogen atom increases in the chain length of the hydrophobic constituent 50), with at least 6.4 mol of alkylene oxide, partly differ. when the total number of carbon atoms in R ₁ ,

The invention relates to processes for the preparation of R ₂ , R ₃ and R ₄ = 1, or with at least 3 mol

209 618/359

Alkylene oxide when the total number of carbon atoms in these radicals is 2 or more, and that the process product obtained in the first stage in the second stage with 20 to 95% (based on the total weight of the end product) of an alkylene oxide, which has an oxygen-carbon ratio of at least 0.5 to form a surfactant mixture of polyoxyalkylene compounds of the formula of the present invention can be achieved according to the two-step process.

The group

R ₁ R ₂

—C — C — O

R3 R4

R ₁ R ₂

Y—

C —O— —X in the above general formula represents a hydrophobic one Polyoxyalkylene chain in the surfactant.

The group X of the general formula is hydrophilic and is a polyoxyalkylene chain with an oxygen-carbon ratio, which is different from that of the first polyoxyalkylene chain.

Examples of the group Y of the general formula of the second 20 are the radicals of compounds such as monovalent Alcohols, e.g. B. methanol and butanol; aliphatic acids such as formic acid, acetic acid and butyric acid; secondary amines such as diethylamine and ethylbutylamine; N-substituted amides such as methylacetamide;

(Y = remainder of the low molecular weight organic compound with only one reactive hydrogen atom; X = polyoxyalkylenes! according to Process stage).

In one embodiment of the invention is
they are non-ionic surface-active agents,
in which R ₁ , R ₂ and R _{3 are} H and R _{4 is} GH ₃
is, η is at least 6.4 and X is a polyoxy- 25 aliphatic mercaptan such as methyl and butylalkylene radical in which the oxygen-carbon mercaptan; N-substituted sulfonamides such as N-Pro-

pylethanesulfonamide and other compounds which, as described above, have a single active hydrogen atom. The group Y can be substituted by groups which do not have an active hydrogen atom which is able to react with a <%, /? - alkylene oxide, e.g. B. by Cl, Br, - NO ₂ and an alkoxy group.

When defining R ₁ , R ₂ , R ₃ and R ₄ in the

If it is a nonionic, surface-active 35 hydrophobic polyoxyalkylene chain, the terms means, in which R ₁ , R ₂ and R ₃ stand for H and R ₄ "aliphatic groups" and "aromatic groups"

used in their broad general meaning. The term "aliphatic group" includes both Open chain compounds as well as ring compounds that are free of benzene-like unsaturated Are bonds, but contain unsaturated bonds of the type of ethylene and / or acetylenes can.

This definition includes compounds such as the cyclopentyl and cyclohexyl groups. In this definition are included compounds in which two R groups are on adjacent carbon atoms Are members of a single alkylene ring; an example of such a compound is polyoxycyclohexene.

The term "aromatic group" includes mononuclear and polynuclear aromatic compounds, such as. B. the phenyl group, the naphthyl group and the biphenyl group.

As noted above with respect to Y, both

than 6.4 moles, according to the present invention, the aliphatic groups as well as the aromatic groups are required to make the polyoxypropylene groups substituted by radicals or groups to give hydrophobic character. which do not contain an active hydrogen atom, the

Furthermore, agents have also become known which are able to react with an a, /? - alkylene oxide, by reacting an active hydrogen. Examples of such usable hydrophobic poly-

Holding compound with a mixture of 60 oxyalkylene chains are those which are made from 1,2-propylene-propylene oxide and ethylene oxide. These oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene agents, however, do not have good surface-active oxide, arylene oxide, cyclohexene oxide, octene oxide, styrene properties, because they derive from the use of an oxide and butadiene monoxide.
Mixture of the hydrophobic and hydrophilic groups The use of substantially homogeneous

are randomly distributed in the molecule and not attached to 65 hydrophobic polyoxyalkylene chains is one

Ratio is at least 0.5 and which preferably has the formula

(CH ₂ -CH ₂ -O) ₇₁

has, the number m being chosen so that the remainder X makes up 20 to 95, preferably 50 to 70 percent by weight of the surface-active agent. In another embodiment of the invention

is C ₂ H ₅ , η is at least 3 and X is a polyalkylene radical in which the oxygen-carbon ratio is at least 0.5 and which preferably has the formula

(CH ₂ - CH ₂ - O) _m

has, the number m being chosen so that the remainder X makes up 20 to 95, preferably 50 to 70 percent by weight of the surface-active agent.

Surfactants consisting of an organic compound with a reactive hydrogen atom and two different alkylene oxides were already known. However, these substances are structured differently than the agents according to the invention and inferior to these in terms of their properties. In the known compounds, which also use propylene oxide and ethylene oxide to build up, are only 6 moles of propylene oxide used, d. H. so less

opposite ends of the molecule are located as this is used to produce the superior surfactant Means is required and due to the preferred embodiment of the present invention, However, the hydrophobic polyoxyalkylene chains can also be made from mixtures of monomeric components

γ__ | _c —C - ΟΙ

^R 3 R4 /

5 6

exist as long as essentially each monomer feeds as it reacts, an excess is avoided Unit corresponds to the definitions given above. an «, jß-alkylene oxide and facilitates the control of the Examples of such compounds with heterogeneous construction reaction.

are the compounds that can be obtained by condensation.

a condensed temperature containing an active hydrogen atom depends on the particular one bond with a mixture of α, / 3-alkylene oxides, plant and in particular of the one used z. B. propylene and butylene oxides, amylene and catalyst concentration. In general, can Cyclohexene oxides obtained. the reaction with higher catalyst concentrations

From the general formula given above is at lower temperatures and accordingly it can be seen that at least one of the R groups is not subjected to 10 lower pressures. The too Hydrogen atom is so that the oxygen-carbon- any given reaction requires temperatures material ratio of the hydrophobic polyoxyalkylene chain and pressures change depending on the is equal to or less than 0.33. Compound with active hydrogen atom, the alkylene

X is a hydrophilic polyoxyalkylene chain whose oxide and the type and concentration of the oxygen-carbon ratio used is equal to or greater than 15 catalyst than 0.5. A preferred example of one
Chain is a polyoxyethylene chain. example 1

The water-solubilizing hydrophilic polyoxyalkylene chain must be present in an amount that is 180 g (3 moles) of distilled n-propanol and 12 g is sufficient to make the surface-active agent at least so 20 NaOH in flake form as a catalyst in water-soluble to the extent that it is commonplace - given a stainless steel autoclave to be used for loaned uses. with a stirrer, a thermocouple, in order to determine the value of η of the general formula to a pressure gauge and an inlet tube for the molecular weight of the intermediate reactants, the outlet of which connection 25 is located directly under the stirrer, is provided

is. The autoclave is initially filled with oxygen

R ₁ R ₂ cleans, whereupon the basic catalyst and the

n-propanol are heated ^{to 100 ° C. with stirring.} H 4510 g (78 mol) of 1,2-propylene oxide are then added

30 an average temperature of 14O ⁰ C and an average pressure of 4.2 kg / cm ² for 7 hours to the reaction vessel. The basic catalyst is _{neutralized with 50% H 2} SO ₄ , and it

according to the hydroxyl number, according to the procedure of, 4528 g of the intermediate product are obtained. Ogg et al. (See Ind. Eng. Chem. Anal, Issue 17, 35 The p. 395 [1945] determined on the basis of the hydroxyl groups). The molecular weight of the molecular weight of the product is 580, η is a compound with an active hydrogen atom, which means that it is equal to 9.0.

subtracted, and the resulting molecular weight.

the polyoxyalkylene chain is established by the molecular bond with the value = 11.7, dividing the weight of the monomeric oxyalkylene and 40,200 g (0.272 mol) of the intermediate compound gives the value n. 1,2-propylene oxide and n-propanol, with the value η

In the preparation of the intermediate compound der = 11.7, and 1 g of NaOH in flake form are used in The above formula is the condensation of a reaction vessel and filled with nitrogen compound containing active hydrogen atom with blown out. Then 202 g (4.6 mol) of ethylene in one suitable alkylene oxide normally with 45 oxide of the reaction mixture with an average higher Temperatures and pressures in the presence borrowed reaction temperature of 125 ° C during an alkaline catalyst such as sodium alkoxide, added for 7.1 hours. The final product contains a quaternary ammonium base or preferably 50 percent by weight hydrophilic polyoxyethylene. That Sodium hydroxide carried out. Surfactant is in at room temperature

Although the reaction is easily soluble by simply heating 5 ° water, a mixture of the reactants under pressure
and carried out at a sufficiently high temperature

this procedure is usually not Example 2

applied as the required temperatures and

Pressures are excessively high and the control of the 55 Example 1 is repeated, however, 222 g of reaction causes difficulties. Per mole of (3 moles) n-butanol converting in place of n-propanol alkylene oxide are estimated to be used. The 25 kilogram calories of heat released due to the hydroxyl groups, the molecular weight of the intermediate product of a large amount of alkylene oxide determined in the presence of the temperature and is 808, η is therefore equal to 12.6. the rate of reaction to such an extent that the reaction proceeds explosively. create a bond with the value «= 9.8.

The preferred method of carrying out the An intermediate compound having a value of η - 9.8

The reaction is that the alkylene oxide becomes one with ethylene oxide, as described in Example 1, stirred, heated mixture of the desired implemented. The uptake of ethylene oxide through Connection with active hydrogen atom and the 65 the intermediate connection requires 5.3 hours, and alkaline catalyst in a closed re-the end product contains 50 percent by weight hydroaktionsgef äß is added. By using the phile polyoxyethylene. The product yields in water a, /? - Alkylene oxide to the reaction vessel to the extent that it is a good detergent solution.

Example 3

10 g (0.17 mol) of n-propanol and 0.7 g of NaOH catalyst in flake form are placed in a three-necked round bottom flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and a feed line for alkylene oxide. The flask is purged of oxygen by a stream of dry nitrogen and 39.3 g (0.55 mol) of 1,2-butylene oxide are charged into the flask over 5.5 hours at an average temperature of 98 ° C. The molecular weight of the epoxy hydrocarbon polymer is 280 as determined from the hydroxyl groups; As a result, η is 3.1.

Table I.

Moles added

Propylene oxide

per mole

n-propanol

3.98
5.0
10.2
24.9

η due to the

certain
Hydroxyl groups

3.95
4.5
7.17
10.3

η as a percentage

his calculated

Worth

99 90 70 42

It was also observed that the difference between the calculated and the determined value

19 g (0.07MoI) of the non-neutralized intermediate 15 of η with the reaction temperature, the concentration

Compounds with a molecular weight of 280 are placed in a reaction vessel. 13 g of 1,2-ethylene oxide are added at a temperature of 135 ° C over 4.5 hours. The product contains 41% Oxyethylene groups.

Example 4

48 g (0.5 mol) of phenol and 2 g of NaOH are filled into the device of Example 1, but with the The alkylene oxide is fed in through a dropping funnel. The reaction mixture is heated to 120.degree heated, and 52.6 g (0.44 mol) of styrene oxide are added dropwise over 5 hours. That The reaction mixture is then freed from unreacted phenol and styrene oxide in vacuo.

49 g (0.23 mol) of the phenol-styrene oxide addition product thus obtained and 1 g of NaOH in flake form are placed in the device described above. The reaction mixture is heated to 120 ⁰ C, and 147.3 g (1,2MoI) styrene oxide is added dropwise during 23 hours. The basic catalyst is neutralized with H ₂ SO _4, and unreacted styrene oxide and other volatile materials are removed at a pot temperature of 110 ⁰ C and a pressure of 1 mm Hg. The final product has a molecular weight of 532 as determined by the hydroxyl groups; As a result, η is 3.66.

56 g of the intermediate compound thus obtained and 1.3 g of NaOH are placed in a reaction vessel. 147 g of ethylene oxide are added to this compound over the course of 8 hours and at a temperature of 120.degree. The product contains 72% oxyethylene groups. At 14O ⁰ C, a 0, l% solution of this product has a cleaning value for carbon contamination of the 163rd

From the above examples it can be seen that although the, -alkylene oxide reacts completely, the value η determined on the basis of the hydroxyl groups is nevertheless lower than its calculated value. The 55 manufactured. Magnitude of the difference between the calculated and _an d R ₈ the observed value is influenced by a number of factors whose hauptsächlichster the total number α of the compound having active hydrogen atom added moles / 3 alkylene oxide is.

To illustrate this effect, various amounts of 1,2-propylene oxide were added after the Process of Example 1 implemented with n-propanol. The following Table I shows the number of moles of the catalyst and the water content of the reactants is greater.

It is likely that with the addition of larger amounts of α, α-alkylene oxide, the non-uniformity of the product increases and that the final product consists of many chains in which η is much greater than its average value and a relatively large number of low molecular weight chains. There is reason to believe that the chains in which η is relatively large cause the surface-active properties of the products according to the invention. Nonetheless, the η determined on the basis of the hydroxyl groups is an empirically determined value which corresponds fairly closely to the observed surface active properties, and it is a useful measure which can be relied upon in predicting surface active properties if the teachings of this invention are followed.

The properties of the surfactants are best described in accordance with those disclosed in the U.S. Patent 2 677 700 described test method for the removal of carbon contamination and for the determination of the degree of whiteness established.

The nonionic surface-active agents prepared according to the invention are characterized by an extremely high cleaning power, as measured by the values which were achieved in the removal of carbon soiling. The preferred surfactants were obtained by condensing the intermediate compound with a κ, ß- alkylene oxide of the following formula

40

45

In this formula, R ₅ , R ₆ , R _{7 mean}

H, -CH ₂ OH or _-CH;

-CH ₉

where R ₅ , R ₆ , R ₇ and R ₈ are selected such that the oxygen-carbon ratio is equal to or greater than 0.5. In the surface

Propylene oxide, which was added 65 active agents per mole of n-propanol, the polyoxyalkylene chain was present in an amount sufficient to reduce the surface area and η as a percentage of its calculated active agent to about 0.1% i ^Q distilled water

agreed η
Value:

active means to about
to make it soluble.

Even if the radical X is generally any polyoxyalkylene chain can be in which the oxygen-carbon ratio is equal to or greater than 0.5, a polyoxyethylene chain is preferred because the surface-active properties achieved with it are unusually good, and the ethylene oxide condenses easily with the interconnection.

It has been empirically found that the hydrophilic polyoxyalkylene chain is more surface active for development Properties must make up at least 20% of the surfactant produced and that highly active products are obtained when the hydrophilic polyoxyalkylene chain is 20 to 95% of the surfactant produced. The best surface-active properties are obtained when the hydrophilic polyoxyalkylene chain constitutes 50 to 70% of the surfactant produced.

Example 5

Seven intermediate compounds are by the procedure of Example 1 by condensation of 1,2-propylene oxide produced with n-propanol, whereby the η values of the intermediate compounds 3.9, 6.4, 7.2, Are 8.0, 9.0, 9.8 and 11.7, respectively. Any of these interconnections is reacted with so much ethylene oxide that surface-active agents with 38 to 61 percent by weight Polyoxyethylene arise. The surfactants were prepared according to the above procedure in terms of their ability to remove carbon pollution and in terms of their whiteness examined. The results are recorded in Table II:

Table II Table III

Oxybutylene
groups:
η due to
the hydroxyl
groups Oxyethylene
groups
Weight
percent Value of
carbon
dirt
distance
0.1% at 6O ⁰ C Value of
Whiteness
0.1 ⁰ zo
at 6O ⁰ C 3.1
5.1
6.1 61
66
62 128
236
211 272
286
271

Oxyethylene Value of Value of Oxypropylene groups Carbon- Whiteness
η *) ε ο / groups:
η due to ver
dirty υ, / D 7o the hydroxyl Weight distance groups percent 0.25 ° / " at 6O ⁰ C 50 at 60 ⁰ C 3.9 38 78 - 6.4 44 82 _ 7.2 52 94 - 8.0 45 106 340 9.0 47 248 342 9.8 61 258 ■ 337 11.7 261

In a similar manner, three intermediate compounds are produced by the condensation of 1,2-butylene oxide with n-Propanol prepared according to the method of Example 3. Any of the epoxy hydrocarbon polymers so prepared is then condensed with such a large amount of ethylene oxide that the oxyethylene groups make up about 60% of the compound produced. The connections were then made according to the above Methods investigated regarding the removal of carbon soiling. The number of in higher oxyalkylene groups contained in the epoxy hydrocarbon polymer portion, the weight percentage the oxyethylene groups in the compound produced and the value of their carbon pollution removal are given in Table III.

The values in Table II are shown graphically in FIG. It can be seen that the curve is very flat at values below 6.4, that is, the change in carbon pollution removal capacity (CFU /) that takes place with chain length is small. This value is 1.6% KVE per unit of η between values from 3.9 to 6.4. With a «value of 6.4 the curve has a bend and the ratio KVE /« is ten times as large as below 6.4, ie 15% KVE per unit of «between κ values from 6.4 to 8, 0. When «reaches 8.0, the curve changes significantly. It rises almost vertically with a gradient almost 100 times greater than below 6.4, corresponding to 142% CVU per unit of κ between κ values from 8.0 to 9.0. Between = 9.0 and 9.8 the curve has a bend, and above = 9.8 the curve becomes flat, and the ratio KVE / becomes small again, ie 1.6% KVE per unit of between η Values from 9.8 to 11.7.

Similarly, Figure 2 shows the values of Table III. As can be seen, the curve is relatively flat for values below about 3. When is 3 when the oxyalkylene chain contains 4 carbon atoms, the curve has a curvature showing that is 3 or more, good detergency is obtained.
It can be seen from FIGS. 1 and 2 that the chain length of the hydrophobic polyoxyalkylene is extremely critical. The surfactants of the present invention have values that are above the critical inflection points in FIGS.

It has been recognized that the exact critical chain length of the hydrophobic polyoxyalkylene is to a certain extent Way depends on the molecular weight of the monomeric oxyalkylene used. Especially when a relatively high molecular weight oxyalkylene is used, e.g. B. oxycyclohexene or Oxystyrene, a slightly shorter hydrophobic polyoxyalkylene chain can be used without affecting the surface-active ones Properties are seriously reduced. Higher molecular weight alkylene oxides and somewhat shorter hydrophobic polyoxyalkylene chains can be used, but it is preferred the z. B. to use polyoxyalkylenes derived from propylene and butylene oxides, their molecular weight is lower and whose «values are greater than 6.4 and 3, respectively, for the following reasons.

The low molecular weight organic compound has an active hydrogen atom that the polymerization des «, jS-alkylene oxide with formation of the Initiates interconnection. Any organic compound that has a single active hydrogen atom Contains to initiate the above polymerization, can be used to prepare the inventive Find surfactants use.

209 618/359

11 12

The preferred, an active hydrogen atom ent. While the previous nonionic surface-retaining compounds contain only aliphatic active agents, the usual dependence of the purity groups with 1 to 5 carbon atoms such. B. have power from the concentration, show aliphatic alcohols such as methanol, ethanol, the products prepared according to the invention over-propanol, isopropanol, butanol, secondary Bu- 5 surprisingly only an insignificant decrease tanol, tertiary butanol, η-amyl alcohol, the cleaning power Over a wide concentration of monomethyl ether of ethylene glycol, the monotration range of the active agent and have surface-active properties in nonethanol from methyl ether of diethylene glycol and 2-chlorine; properly diluted aqueous solutions. With many aliphatic carboxylic acids, such as formic acid, io industrial types of application, such as. B. with continuous acetic acid, mono-, di- and trichloroacetic acid, natural bleaching of cotton fabrics by propionic acid, butyric acid and valeric acid; Hypochlorites, it is desirable to use a nonionic secondary aliphatic amine such as dimethyl surfactant in concentrated salt amine, diethyl amine, dipropyiamine, dibutyl amine solutions. Because of the "salting out" it is N-methylethylamine and N-ethylpropylamine; It is difficult to maintain a sufficient concentration of the upper-N-substituted aliphatic carboxamide surfactant, such as N-methylformamide, N-methylacetamide, in the solution to achieve the desired wetting effect. N-ethylbutyric acid amide, N-butylpropionic acid- The remarkable effectiveness of the invention amide and N-methylvaleric acid amide; according to prepared surface-active agents at N-substituted aliphatic sulfonamides, such as 20 low concentrations makes them ideally suited for such N-methylethanesulfonamide, N-ethylpropane sulfonamide types of application, formamide, N-methylbutanesulfonamide and N-Pro- An advantageous feature of the invention pylpentanesulfonamide; The surface-active agent produced consists in aliphatic mercaptans, such as methyl mercaptan, that both the hydrophobic and the hydrophilic ethyl mercaptan, propyl mercaptan, tertiary Bu- 25 constituents of the same both with regard to their MoIetyl mercaptan, isobutyl mercaptan and amyl mercaptan and with regard to their type for the purpose of mercaptan. Production of means adapted for special purposes Any of these compounds with active hydrogen can be changed. By simply changing the atom can contain substituents, e.g. B. Cl, Br, I, the amount of hydrophobic alkylene oxide that contains the one - NO ₃ and alkoxy groups, but no compound containing water-active hydrogen atoms that is stored to react with «, ß-alkylene oxides, it is possible a large number of hydro assets. From FIG. 3 it can be seen that between 25 small, finite increases in the length of the hydro- and 95% polyoxyethylene content, bell-phobic polyoxyalkylene chains differ. Similar curves can be obtained which show region 35 can include different amounts of good detergency. Between the hydrophilic part, e.g. B. alkylene oxide, each of the polyoxyethylene contents 40% and 75% is attached to the hydrophobic parts described above, and "humps" of the curve that the preferred compound so surface-active agents are produced that fertilize the present invention, while each other only through small finite enlargement of the range between 50 and 70% polyoxyethylene 40 differ in the content of hydrophilic part. The content of the area of maximum cleaning power characterizes the structure of the surface. Above about 75% polyoxyethylene-active agent can be changed, the cleaning power is therefore reduced; This fact is particularly advantageous because the surface-active thing is balanced out by the fact that the surface-active agents suitable for performing special functions are solid bodies and can be produced for the purpose.

more convenient packaging and use into flakes The solid nonionic surfactants, can be processed. as prepared in accordance with the present invention. The surfactants as prepared in accordance with the present invention can be made with quaternary ammo invention described are prepared, sodium compounds are mixed and result as wetting and dispersing agents in textile, 50 marked cleaning agents for sanitary applications, leather, Paper, lacquer and rubber industries and in dung types. The cation-active nature of the quaternary related industries. They are making use of alkaline ammonium compounds and acidic media are very stable and keep their properties - a non-ionic cleaning agent is required, The previously available, known compounds centered ionic solutions. The combination 55 were not suitable because they did not have any after mixing chemical stability and high cleaning performance resulted in free flowing powder.

like make them particularly suitable in preparations, the surfaces produced according to the invention the In hard water oxidizing and reducing active agents are excellent for use in Media, etc. can be used. pharmaceutical preparations, e.g. B. in toothpastes ge-Die surfaces produced according to the invention are suitable because they are colorless, odorless, tasteless active means that are at least 70% from one and non-toxic. An extremely unusual and over-hydrophilic Polyoxyalkylene chains are hard, surprising characteristics of the inventively hergefeste Products and can e.g. B. for the production of fixed non-ionic products is that they are red Bars can be used for washing purposes. Blood cells do not dissolve and those in the blood pre-one do not attack the very desirable property of the lipoproteins in question. Because of surfactants prepared according to this property, it is obvious to these products in Their excellent cleaning ability is to be used in extra-cleaning devices that are located in blood stores properly diluted aqueous solutions. etc. are used, and these products can

possibly used as a stabilizer to increase the life of the stored blood raise.

. In that the non-ionic products as they are produced according to the invention described herein which have the structure of polyethers results in a very satisfactory use as a softening agent in binders based on dextrin, vinyl resins, phenolic resins and synthetic resins Types of rubber. The liquid nonionic products produced according to the invention possess extremely low vapor pressures, good lubricating properties and exceptionally good temperature resistance; They can therefore be used as lubricants, hydraulic fluids, heat transfer media and in other industrial applications where a combination these properties is desirable.

Claims (2)

PATENT CLAIMS: 1. A process for the preparation of surfactants by reacting organic compounds containing an active hydrogen atom with two different alkylene oxides in succession, characterized in that in the first stage 1 mol of a low molecular weight organic compound having only one reactive hydrogen atom with an alkylene oxide of the formula R ₁ R ₂ R ₃ -C CR ₁ atoms or aliphatic or aromatic groups, where at least one of these radicals is not a hydrogen atom), with at least 6.4 mol of alkylene oxide if the total number of carbon atoms in R ₁ , R ₂ , R ₃ and R ₄ = 1, or with at least 3 moles of alkylene oxide when the total number of carbon atoms in these radicals is 2 or more, and that the process product obtained in the first stage in the second stage with 20 to 95% (based on the total weight of the end product) of an alkylene oxide, which is a Has an oxygen-to-carbon ratio of at least 0.5, with the formation of a surface-active mixture of polyoxyalkylene compounds of the formula Y— C — C — O— - X (Y = remainder of the low molecular weight organic compound with only one reactive hydrogen atom; X = polyoxyalkylene radical according to the second process stage). 2. The method according to claim 1, characterized in that the _{alkylene oxide used in the first process stage is a compound in which R 1} to R _{3 are} hydrogen atoms and R _{4 is} a methyl or ethyl group, and ethylene oxide is used as the alkylene oxide in the second process stage. References considered: 35 U.S. Patent Nos. 2174,761, 2,203,883, condensed (R ₁ , R ₂ , R _3, and R ₄ = hydrogen-2,213,477, 2,425,755. 1 sheet of drawings © 209 618/359 6.